Preform and methods of manufacturing the preform and a bottle

[0001] The present invention relates to articles having a formable material, more particularly mono- and multi-layer articles having a formable material, and methods for making such articles.

Description of Related Techniques [0002] Products are commonly used for storing beverages and food products. The use of products, such as plastic containers, as replacements for all-glass or metal containers for beverage packaging is becoming increasingly popular. The advantages of plastic packaging include lower weight, reduced breakage compared to glass, and potentially lower costs. The plastic most commonly used today for making beverage containers is polyethylene terephthalate ("PET"). Pure PET has been approved by the FDA for use in contact with food products. Containers made of PET are generally transparent, thin-walled, light and have the ability to retain their shape by resisting the force exerted on the container walls by pressurized contents such as carbonated beverages. PET resins are also quite cheap and easy to process.

[0003] Most PET bottles are made by a process that includes blow molding of plastic preforms made by methods involving injection molding or extrusion. A PET bottle may not provide a suitable thermal barrier to limit thermal communication through the walls of PET bottles. To maintain the temperature of the liquid inside the bottles, it may be desirable to reduce the heat transfer between the liquid in the bottle and the environment surrounding the bottle. Similarly, the cheapest food storage containers do not provide an effective thermal barrier to reduce heat transfer through the container. It may be desirable to reduce heat transfer through containers or packaging.

[0004] In addition, articles in the form of conduits, food packaging and the like may have inappropriate structural, barrier, or other characteristics. Often, liquids, foods or drinks, such as sparkling water, are stored in a container that can adversely affect their contents. Unfortunately, when food contacts the surface of some materials of known products, the taste of the food may change adversely. It may be desirable to maintain the taste of the food products in contact with the product.

[0005] GB 1 362 133 discloses an injection blow molding process for laminar structure preforms having an outer layer of a first injection moldable synthetic resin material that completely surrounds the core of a second injection moldable synthetic resin material. This reference further discloses that the finished product may include a foamed core layer.

[0006] US2001 / 132100A1 describes a method for producing lightweight objects, including calendering, extrusion, blow molding or injection molding of polypropylene, polystyrene, HD polyethylene or copolymers, and thermally expanded microspheres admixed thereto.

[0007] US2001 / 0038014A1 discloses a cradle base for receiving the bottom of the container body and for reducing the temperature rise of the liquid content of the container body. The skull base is made of foam and has a reflecting layer on most of its outer surface.

[0008] US 6,276914 discloses a method and apparatus for injection molding plastics, using a new needle valve to control the opening and closing of at least two injection holes in one injection nozzle. In addition, US Patent 6,276914 mentions that one of the two layers of the multilayered article contains foamed material.

[0009] Publication No. US2001 / 0040002 discloses a method of producing a tubular preform using the injection molding method.

[0010] It is an object of the present invention to provide a preform for blow molding PET bottles with a suitable barrier to limit thermal communication through the walls of the resulting PET bottles.

[0011] Furthermore, it is an object of the present invention to provide a method for producing such a PET bottle. Furthermore, it is an object of the present invention to provide a method for producing such a preform and to provide a method for producing a bottle from such a preform.

[0012] These and other objectives are achieved in accordance with independent claims 1, 19 and 21.

[0013] Advantageous embodiments can be derived from the dependent claims.

[0014] In a preferred embodiment, a method of forming a preform is provided. At least part of the preform is an expandable material that can expand to form a thermal barrier or a desired finish. The preform is heated to a temperature suitable for blow molding and at least part of the expandable material expands. The preform is blow molded into a container. In one embodiment, the preform is a monolayer preform. In another embodiment, the preform is a multilayer preform.

[0015] In another embodiment, a method of making a foam-coated polymer article is provided, comprising the steps of providing a foam-coated polymer preform and blow molding the preform into a container of the desired shape. In one embodiment, the method includes preheating the preform from the foam-coated polymer prior to blow molding, which causes the microsphere-containing foam coating to start expanding the microspheres. The microspheres can expand before blow molding, during blow molding, and / or after blow molding.

[0016] In one embodiment, the foam-coated polymer article comprises at least one foam layer surrounding at least a portion of another layer, substantially comprising polyester. The foam contains a polymeric carrier material and a foaming agent.

[0017] In another embodiment, a method of making a foam-containing article is provided. The foam may have a first component and a second component. The first component can expand when thermally activated. Optionally, the first component contains microspheres that are generally in the first state of expansion. In one embodiment, the second component is a carrier material mixed with the first component. When the mixture is heated, the mixture expands to form foam with generally closed cells.

[0018] In one embodiment, the mixture is formed into a preform having microspheres that are expanded from the first state of expansion to the second state of expansion. The preform is formed into a container having microspheres that are expanded from a second expansion state to a third expansion state. In one variant, the major part of the microspheres is generally not expanded in the first position. Optionally, a substantial portion of the microspheres are generally partially expanded in a second position. Optionally, a substantial portion of the microspheres are generally expanded in the third position.

[0019] In one embodiment, the preform comprises a plurality of layers and one of the layers comprises an expandable material. Preform a is optionally molded into a container. In one embodiment, the inner layer of the preform or container contains material suitable for contact with food products and / or a liquid and defines a storage chamber for the preform or container. In one embodiment, the inner layer comprises a thermoplastic material. The second layer of the preform or container contains expandable material comprising polymer and microspheres. Alternatively, the expandable material may form an inner layer or liner of the preform or container.

[0020] In one embodiment, the expandable material comprises a carrier material and a foaming agent. The support material is preferably a material that can be mixed with the microspheres to form an expandable material. The support material may be a thermoplastic or polymeric material, including, but not limited to, ethylene acrylic acid copolymer ("EAA"), ethylene vinyl acetate copolymer ("EVA"), linear low density polyethylene ("LLDPE"), ρoli (hydroxyaminoethers) ("PHAE"), polyethylene terephthalate ("PET") and other copolymers, including polyethylene terephthalate with glycol (PETG), polyethylene ("PE"), polypropylene ("PP"), polystyrene ("PS "), cellulose materials, pulp, mixtures thereof, and similar. In one embodiment, the foaming agent is microspheres that expand when heated and interact with the carrier material to form a foam. In one embodiment, the expanding agent is EXPANCEL® microspheres.

[0021] In preferred embodiments, the expandable material has insulating properties to inhibit heat transfer through the walls of the container containing the expandable material. The expandable material can therefore be used to maintain the temperature of food, liquids or the like. In one embodiment, when the liquid is in the container, the expandable material of the container reduces heat transfer between the liquid in the container and the environment surrounding the container. In one variant, the container can store the cooled liquid, and the container expandable material is a thermal barrier that inhibits heat transfer from the environment to the cooled fluid. Alternatively, the container may contain heated liquid, and the container expandable material is a thermal barrier that reduces heat transfer from the liquid to the environment surrounding the container. Although use in combination with food or drink is one of the preferred applications, these containers can also be used with non-food items.

[0022] In one embodiment, the foam material is extruded to form sheets that are formed into food storage containers, trays, bottles, and the like. Optionally, the sheets are formed into "clamshell" packaging that is adapted for food storage. The foam sheets can be pre-cut and shaped to form a container for storing food products. The sheets can be formed into a container by one or more processes, e.g. thermoforming or thermoforming process.

[0023] In another embodiment, an article is provided comprising foam material that forms a coating on a paper or pulp based material or container. In one variant, the foam material is mixed with the pulp. Optionally, foam material and pulp can be mixed to form a generally homogeneous blend that can be formed into any shape. The blend may be heated before, during, and / or after shaping the blend to cause expansion of at least part of the foam material included in the blend.

[0024] In another embodiment, the preform comprises at least a first layer containing a material suitable for contacting food products, and a second layer comprising a thermoplastic material, such as polypropylene. Optionally, the first layer comprises a thermoplastic material, such as PET, and the second layer comprises

EP 1 742 785 B1 foam material having polypropylene and microspheres. Optionally, the first layer contains PET and the second layer contains mainly or entirely polypropylene. Optionally, the first layer contains a phenoxy type thermoplastic and the second layer contains another material such as polypropylene. The preform can be formed into a container by one or more processes, e.g., a blow molding process.

[0025] In one embodiment, the method of making a bottle includes providing a preform comprising an inner layer of PET and an outer layer comprising PP. The preform is heated to a temperature that is not typically suitable for processing PP. After heating the preform, the preform is blow molded into a bottle. In one embodiment, the outer layer comprises foam material. In one variant, the outer layer mainly or completely contains PP.

[0026] In another embodiment, the preform comprises an inner layer that has a collar defining at least a portion of the preform opening. The outer layer surrounds the inner layer and defines a substantial part of the neck of the preform and forms the outer surface of the body of the preform.

[0027] Another embodiment is a pipe comprising a first layer and a second layer. In one embodiment, the first layer comprises a thermoplastic material, such as PET, and the second layer contains the same or different thermoplastic material, such as PP, and a foaming agent. Optionally, the first layer contains primarily PET and the second layer contains foam material based on PP. In one embodiment, the pipe is formed by a co-extrusion process. Optionally, the pipe can be blow molded into a container. Optionally, the pipe can be used as a fluid line for supplying food liquids.

[0028] In another embodiment, the preform comprises an inner layer and an outer layer. The outer layer surrounds the inner layer and defines an essential part of the cervical end of the preform. The outer layer also forms the outer surface of the body portion of the preform. [0029] In another embodiment, the preform forming apparatus comprises a mold core section and a mold matrix section. The mold matrix section has a delivery system. The mold core section and the mold matrix section work together to define the empty space when the mold core section and the mold matrix section are in the closed position. The delivery system is configured to deliver the binding material to the void. Optionally, the apparatus also includes an exhaust system in fluid communication with the voids.

[0030] In another embodiment, the method of forming a preform includes placing a portion of the preform on a mold mandrel. Binding material is supplied from the outlet of the delivery system formed in the matrix section defining the matrix. At least a portion of the preform is coated with a binding material.

[0031] In some embodiments, the preform comprises a neck portion and a body portion. The body portion has a wall portion and a bottom, and includes a first layer and a second layer, the first layer comprising expandable material. In some variants, the expandable material is adapted to expand by heat treatment.

[0032] In some embodiments, the preform comprises a threaded neck portion and a body portion. The body part includes a wall part and a bottom. The body portion contains expandable material constituting less than about 40% by weight of the preform. In some embodiments, the expandable material contains less than 20% by weight of the preform. The expandable material may optionally contain microspheres and preferably

Thermoplastic support material, including those selected from the group consisting of polypropylene, PET, and combinations thereof.

[0033] In some embodiments, the method of making the preform comprises forming the first layer of the preform. The second layer of the preform is molded and includes controllable expandable material. In some embodiments, the first layer is formed by injection of a first material, preferably containing polyester, through an injection opening into the space defined by the mold half matrix and core form half, to form the article. The product comprises an inner surface and an outer surface. The second layer is formed by injecting expandable material into a second space defined by the outer surface of the article formed by the first injected material and the second matrix half of the mold to form a second layer of the preform.

[0034] In some embodiments, the method of making a bottle includes providing a preform having a neck portion and a body portion. The preform is heated so that part of the preform at least partially expands to form foam. The preform is blow molded into a bottle containing foam material.

[0035] In some embodiments, the product includes a neck portion having threads and a body portion. The body part includes a first layer and a second layer. The first layer has an upper end that ends below the tapping of the neck portion and includes foam material. The second layer is placed inside the first layer. In some embodiments, the product is a preform, bottle, container or the like. The second layer may optionally contain material suitable for contacting food products. For example, the second layer may comprise a material comprising at least one material selected from the group consisting of polyester, polypropylene, a thermoplastic phenoxy type material, and combinations thereof.

[0036] In some embodiments, the bottle includes a neck portion and a body portion. The body portion includes an inner layer containing polyester and an outer layer containing foam material. The foam material contains polypropylene. The inner layer and the outer layer define at least a part of the wall of the body part.

[0037] In some embodiments, a method of making a multilayer preform comprises providing a substrate preform that has been produced by any of a variety of methods as are known in the art. The substrate preform is placed in the die cavity defined between the first mold part and the second mold part. From the outlet in the first part of the mold, the first material is injected into the die cavity for the substrate preform. The first material is adapted to form a layer on the preform as a substrate. From the alloy injection hole of the first mold part, a second material is injected onto the substrate preform. In some embodiments, the first material comprises a binder material. In some embodiments, the first material coats at least a portion, preferably a substantial portion, of the body portion of the substrate preform. The second material can be injected directly onto the first material, forming an outer layer. Optionally, the unused portion of the first material may be removed from the matrix via the exhaust system. In some embodiments, the first part of the mold is a die section and the second part of the mold is a core section.

[0038] In some embodiments, the method of injecting material into a mold for forming an article includes providing an injection mold capable of moving between an open position and a closed position. The form includes a core section and a matrix section. The material is supplied through the first injection hole of the die section. The alloy is supplied through the second injection section of the core section. In some variants,

The article is a preform or closure. The material delivered through the first injection opening may optionally contain a fluid containing the binding material.

[0039] In some embodiments, the mold for forming preforms or containers includes a core section and a die section that is able to move between an open position and a closed position. The core section and matrix section designate the matrix seat when the core section and matrix section are in the closed position. The injection opening in the core section is shaped to inject alloy into the die cavity. The outlet in the die section is positioned and shaped to inject the first material from the inlet conduit into the die seat. The inlet in the matrix section is positioned and shaped to draw material into the matrix cavity and deliver material to the exhaust duct. In some embodiments, the injection opening is located in the area of ​​the die section for forming the preform bottom. Optionally, the injection opening, outlet and inlet are separated from each other and are formed in the forming surface of the die section.

[0040] In some embodiments, the mold for molding articles includes a first mold section that defines a first molding surface. The second mold section defines a second forming surface. The first mold section and the second mold section cooperate to form a product-shaped die cavity. The mold delivery system has a fluid source and a power cord. The power cord is in fluid communication with the fluid source and outlet. The outlet is positioned along one of the first mold section and the second mold section. The outlet system has an inlet positioned along one of the first mold section and the second mold section. The exhaust system includes an exhaust line in fluid communication with the matrix socket. The injection opening for melt injection is positioned along one of the first mold section and the second mold section and is shaped to supply alloy to the die cavity. In some embodiments, the delivery system further includes a valve system configured to selectively regulate the amount of fluid delivered to the die seat. Optionally, the die seat is preformed or closed.

[0041] In some embodiments, the mold for making the article includes a core half and a die half that are matched to form a die cavity for forming the preform. The matrix half has an injection port. The mold has a means for supplying the coating material to the matrix cavity and a means for removing from the matrix cavity the coating material supplied by the coating material delivery means. Optionally, the article can be a preform or closure. The injection opening may be separated from the coating material supply and the coating material removal means.

[0042] In preferred embodiments, laminates, preforms, containers and articles containing PETG and polypropylene, and methods for their preparation are disclosed. In one embodiment, the polypropylene may be grafted or modified with maleic anhydride, glycidyl methacrylate, methyl methacrylate and / or similar compounds to improve adhesion. In another embodiment, the polypropylene further comprises "nanoparticles" or "nanoparticle material." In another embodiment, the polypropylene contains nanoparticles and is grafted or modified with maleic anhydride, glycidyl methacrylate, methyl methacrylate and / or similar compounds.

[0043] Preferred articles, preforms, containers and articles can be made using various techniques. For example, laminates, preforms, containers and articles can be formed by injection molding, overmoulding, blow molding, blow molding, extrusion, co-extrusion, and stretch blow molding, and other methods disclosed and / or known to those skilled in the art.

[0044] In some non-limiting embodiments, the articles may include one or

More layers or parts having one or more of the following preferred features: insulating layer, gas barrier layer, UV protective layers, protective layer (e.g. Vitamin protective layer, anti-abrasion layer, etc.), food contact layer, aroma-preventing layer, dye-preventing layer, high-strength layer, compatibilization layer, binding layer, gas capture layer (e.g. oxygen, carbon dioxide, etc.), a layer or part suitable for hot-filling applications, a layer having high melt strength suitable for extrusion, strength, recyclable (post-consumer and / or post-industrial), transparency, etc. In one embodiment, the monolayer or multilayer material comprises one or more of the following materials: (including recycled and / or unused PET), PEtG, foam, polypropylene, phenoxy type thermoplastics, polyolefins, polyolefin blends and phenoxy type thermoplastics, and / or combinations thereof.

Brief Description of the Drawings [0045] FIGURE 1 shows the preform used as starting material for forming containers.

[0046] FIGURE 2 is a cross-section of the preform of FIGURE 1.

[0047] FIGURE 3 is a cross-sectional view of a blow molding apparatus of the type that can be used to make a preferred container. [0048] FIGURE 4 is a side view of a container made of a preform.

[0049] FIGURE 5 is a cross-section of a multilayer preform.

[0050] FIGURE 6 is a cross-sectional view of the multilayer container made of the multilayer preform of FIGURE 5.

[0051] FIGURE 7 is an enlarged view of the container of FIGURE 6 taken along 7.

[0052] FIGURE 8 is a cross-sectional view of the multilayer preform.

[0053] FIGURE 8A is an enlarged view of the preform of FIGURE 8 taken along 8A.

[0054] FIGURE 9 is a cross-section of a multilayer preform having a multilayer neck portion.

[0055] FIGURE 10 is a cross-sectional view of the multilayer preform according to another embodiment.

[0056] FIGURE 11 is a cross-sectional view of a multilayer preform having an inner layer defining the interior of the preform.

[0057] FIGURE 12 is a cross-sectional view of a multilayer preform having an inner layer and an outer layer defining a neck portion.

[0058] FIGURE 12A is a cross-sectional view of a multilayer preform having an inner layer and an outer layer defining the neck portion.

[0059] FIGURE 12B is a cross-sectional view of a multilayer preform having an inner layer and an outer layer defining a neck portion.

[0060] FIGURE 13 is a cross-sectional view of a multi-layer flange preform having an inner layer.

[0061] FIGURES 13A and 13B are enlarged cross-sections of parts of multilayer preforms according to some embodiments.

[0062] FIGURE 14 is a cross-sectional view of a multi-layer preform having

An outer layer with a connecting structure.

[0063] FIGURE 14A is a cross-sectional view of the container made of the preform of FIGURE 14, the closure is attached to the container.

[0064] FIGURE 14B is an enlarged view of a portion of the container and closure of FIGURE 14A taken along 14B.

[0065] FIGURE 14C is an enlarged view of a portion of the container and closure according to another embodiment.

[0066] FIGURE 15A is a cross-sectional view of a portion of the preform having a neck portion without threads.

[0067] FIGURE 15B is a cross-section of the preform of FIGURE 15A.

[0068] FIGURE 15C is a cross-section of a portion of a multi-part preform.

[0069] FIGURE 16 is a cross-section of a preform according to another embodiment.

[0070] FIGURE 17 is a cross-section of a preform according to another embodiment.

[0071] FIGURE 18 is a perspective view of a closure suitable for closing a container.

[0072] FIGURE 19 is a cross-sectional view of a multilayer closure having an inner layer.

[0073] FIGURE 20 is a cross-sectional view of a multilayer closure having an inner layer extending along the sides of the closure.

[0074] FIGURES 21A-21E are cross-sections of multi-layer closures. [0075] FIGURES 22A-22B are cross-sections of sheets.

[0076] FIGURE 23 is a perspective view of one preferred embodiment of the profile.

[0077] FIGURE 24 is a side view of one preferred embodiment of the package, including a container having a label and a closure.

[0078] FIGURE 25 is a side view of the container and closure according to another embodiment.

[0079] FIGURE 26A is a perspective view of a container.

[0080] FIGURE 26B is a perspective view of the tray.

[0081] FIGURE 27 is a schematic view of an embodiment of a system for generating a lamellar melt stream.

[0082] FIGURE 27A is a cross-sectional view of the lamellar material produced in the lamellar melt stream generation system of FIGURE 27.

[0083] FIGURE 28 is a cross-section of a mold of the type that can be used to make the preform of FIGURE 1.

[0084] FIGURE 29 is a cross-section of a mold of the type that can be used to make the outer layer of the preform of FIGURE 5.

[0085] FIGURE 30 is a cross-section of a mold of the type that can be used to make the inner layer of the preform of FIGURE 11.

[0086] FIGURE 31 is a cross-section of a mold of the type that can be used to produce the outer layer of FIGURE 11.

[0087] FIGURE 32 is a cross-section of a mold of the type that can be used to make the closure.

[0088] FIGURE 33 is a cross-section of a mold of the type that can be used to form the outer layer of the closure of FIGURE 20.

[0089] FIGURE 34 is a mold system shaped for producing multi-layer preforms having tie layers.

[0090] FIGURE 35 is a cross-section of the mold of the mold system of FIGURE 34.

[0091] FIGURE 36 is a cross-section of the mold of FIGURE 35 taken along lines 36-36.

[0092] FIGURE 37 is a close-up perspective partial cross-section of the surface of FIGURE 35 along 37-37.

[0093] FIGURE 38 is a cross-sectional view of the modified mold of FIGURE 35 taken along lines 36-36.

[0094] FIGURE 39 is a close-up partial perspective view of the modified mold of FIGURE 35 along 37-37.

[0095] FIGURE 40 is a cross-section of a layered material.

Detailed Description of Preferred Embodiments [0096] All patents and publications mentioned herein are hereby incorporated in their entirety by reference. Except as described hereinafter, certain embodiments, features, systems, devices, materials, methods and techniques described herein may in some embodiments be similar to one or more of one of the embodiments, features, systems, devices, materials, methods and techniques described in US Patent Nos. 6,109,006; 6,808,820; 6,528,546; 6,312,641; 6,391,408; 6,352,426; 6,676,883; U.S. Patent Application Nos. 09 / 745,013 (Publication No. 2002-0100566); 10 / 168.496 (publication no. 2003-0220036); 09 / 844,820 (2003-0031814); 10 / 090,471 (publication no. 2003-0012904); 10 / 395.899 (publication no. 2004-0013833); 10 / 614,731 (publication no. 2004-0071885), provisional application 60 / 563,021, filed on April 16, 2004, provisional application 60 / 575,231, filed on May 28, 2004, provisional application 60 / 586,399, filed on July 7, 2004, provisional application 60 / 620,160, filed October 18, 2004, provisional filing 60 / 621,511, filed October 22, 2004, and provisional filing 60 / 643,008, filed January 11, 2005, Patent Application No. of the US Patent Application No. APTPEPl.090A entitled MONO- AND MULTILAYER PRODUCTS AND METHODS OF THEIR MANUFACTURE OF THEM, filed on the same day as this application, Patent Application No. EXTRUSION, filed the same day as this application, which are hereby incorporated in its entirety by reference. In addition, the embodiments, features, systems, devices, materials, methods and techniques described herein may in some embodiments be used for or in combination with one or more of the embodiments, features, systems, devices, materials, methods and techniques described above. listed patents and applications.

A. Articles [0097] In preferred embodiments, the articles may include one or more moldable materials. The articles described herein may be monolayer or multilayer (i.e., have two or more layers). In some embodiments, the articles may be packaging, such as for beverages (including preforms, bottles, closures, etc.), boxes, cartons and the like.

[0098] Multilayer products may include an inner layer (e.g., a layer in contact with the contents of the container) of material approved by a regulatory authority (e.g., the US Food and Drug Association) or officially food-approved material (including beverages), drugs, cosmetics, etc. In other embodiments, the inner layer comprises material (s) that are not officially approved for contact with food. The second layer may comprise a second material, which may be material similar to or different from the material forming the inner layer. Products can have as many layers as needed. It is contemplated that products may contain one or more materials forming different parts that are not "layers".

1. Detailed description of the drawings [0099] With reference to FIGURES 1 and 2, a preferred monolayer preform 30 is illustrated. In general, the preform 30 has a neck portion 32 and a body portion 34. The illustrated preform 30 may have a single layer formed of a material that can be blow molded. . The preform 30 is preferably blow molded into a container for storing liquids such as non-carbonated liquids such as fruit juice, water and the like. Optionally, the preform 30 may be formed into a container for storing other liquids, such as carbonated liquids. The illustrated preform 30 may be suitable for forming a 16 oz. Beverage bottle, which is particularly well suited for storing carbonated drinks. The term "bottle," as used herein, is a broad term and is used in its usual sense and may include, without being limited to, a container (typically glass and / or plastic, having a comparatively narrow neck or opening), a bottle-shaped container for storing liquids (preferably liquids), etc. The bottle may or may not have a handle.

[0100] The illustrated preform 30 has a neck portion 32 that begins at the opening 36 (FIGURE 2) into the interior of the preform 30 and extends into the support ring 38 and embraces it. The term "neck portion" as used herein is a broad term and is used in its usual sense and may include, without limitation, a portion of the preform attached to the body portion. The cervical portion may include the end of the neck. The end of the neck, together with the neck cylinder, can form what is referred to as the "neck portion". The neck portion 32 in the illustrated embodiment is further characterized by the presence of threads 40 that provide a way of attaching the lid or closure member to the bottle made of the preform 30. Alternatively, neck portion 32 may not be shaped to engage with the closure or may have other means than the thread to engage with the closure. The body portion 34 is an elongated and generally cylindrical shaped structure extending downward from the neck portion 32 and ending in bottom 42. The illustrated bottom 42 is rounded; however, the bottom may have other suitable shapes. The thickness of the preform 44 will depend on the total length of the preform 30 and the desired wall thickness and the total size of the container obtained.

[0101] With reference to FIGURE 3, in this blow molding process the preform 30 is placed in a mold having a die cavity corresponding to the desired shape of the container. The preform 30 is then heated and expanded by introducing air or other suitable fluid into the preform so as to stretch the preform so that it fills the die cavity, thus forming a container 37 (FIGURE 4). This blow molding process is described in detail below. A tension rod or other similar means may be used to assist the blow molding process, as is known in the art.

[0102] In some embodiments, to aid the blow molding process, the blow molding machine may receive heated articles (e.g.

EP 1 742 785 B1 profiles such as sleeves, preforms, etc.) as is known in the art. The mold 28 can receive heated preforms from an injection molding machine, such as the injection molding machines described herein. The preforms produced by the injection molding machine can be quickly transported to the mold 28 through the feed system. The internal heat of the preforms can provide one or more of the following effects: reduced blow molding time, reduced energy required to heat the preforms to a temperature suitable for blow molding, and / or the like.

[0103] Optionally, one or more delivery systems can be used to transport preforms and / or bottles from the mold. For example, the delivery system may include a swinging system (e.g., a linear or rotary swinging system) for transporting preforms to and / or from the mold 28. The swinging system may periodically feed the mold 28 into the preforms or remove blow molded bottles from the mold 28. Alternatively, the system the delivery may include a reciprocal and / or disc delivery system. In some embodiments, a disc delivery system is used to immediately deliver preforms to or remove bottles from the mold 28. Preferably, the disc delivery systems can continuously transport products to and from the mold 28, thereby increasing efficiency.

[0104] It is contemplated that the delivery system can be used in conjunction with a forming machine suitable for preform blow molding, extrusion blow molding, extrusion profiles, and the like. In addition, the delivery system may include a plurality of systems, such as a disc delivery system and a swinging delivery system, which cooperate in transporting products.

[00105] Referring to FIGURE 4, an embodiment of a container 37 that can be formed from the preform 30 is disclosed. The container 37 has a neck portion 32 and a body portion 34 corresponding to the neck and body portions of the preform 30. As described above with respect to the preforms, the neck portion 32 may be adapted to engage with closures. The illustrated neck portion 32 is characterized by the presence of a thread 40, which provides a method of attaching the cap to the container. Optionally, the wall of the container 37 may inhibit, preferably substantially prevent, gas migration (e.g., CO₂) through the wall of the container 37. In some embodiments, the container 37 comprises a substantially closed foam cell that can inhibit fluid migration through the foam.

[0106] The blow molding operation is normally limited to the body portion 34 of the preform, and the neck portion 32, including any threads, retaining ring and / or retaining ring, retains the original shape as in the preform. However, each part of the preform 30 can be stretch blow molded. The container 37 may also be formed by other processes, such as extrusion processes or process combinations (e.g. overmoulding). For example, container 37 may be formed by a blow molding process. Thus, the containers described herein can be made of preforms, extruded profiles, etc.

[0107] With reference to FIGURE 5, a cross section of one type of multilayer preform 50 has been disclosed having features in accordance with the preferred embodiment. The preform 50 preferably includes the uncoated (monolayer) preform 39, coated with the outer layer 52. Preferably, the uncoated preform 39 comprises a polymeric material, such as polypropylene, polyester, and / or other thermoplastic materials, preferably suitable for contacting food. In one embodiment, for example, the uncoated preform 39 substantially comprises polypropylene. In another embodiment, the uncoated preform 39 comprises substantially polyester, such as PET.

[0108] The multilayer preform 50 has a neck portion 32 and a body portion 34, as does the preform 30 of FIGURES 1 and 2. In the illustrated embodiment, the outer layer 52 is

EP 1 742 785 B1 disposed around at least a body portion 34. In one embodiment, the outer layer 52 is disposed around a substantial portion, preferably the entire portion, of the surface of the body portion 34 of the inner layer (illustrated as the preform 39 of Figure 1) ending at the bottom of the support ring 38. The outer layer 52 in the illustrated embodiment does not extend to the neck portion 32, nor is it present on the inner surface of the inner layer 39, which is preferably made of a material suitable for contacting the contents of the obtained container. The outer layer 52 may comprise either one material or several layers (e.g., microlayers) of one or more materials. In addition, the outer layer 52 may be generally uniform, generally heterogeneous, or sometimes intermediate between these possibilities. Although not illustrated, the outer layer 52 may form other parts of the preform 50. For example, the outer layer 52 may form at least part of the inner surface of the preform 50 (such as when the outer layer is sprayed around the tube or open profile at both ends) or part of the neck portion 32. The outer layer 52 may or may not be suitable for contact with food products.

[0109] The total thickness 56 of the preform is equal to the initial thickness of the uncoated preform 39 (i.e. the inner layer 54) plus the thickness 58 of the outer layer 52, and is dependent on the overall size and the desired coating thickness of the obtained container. However, the preform 50 may have any thickness depending on the desired thermal, optical, barrier and / or structural properties of the container formed from the preform 50. If a tie layer is present, the total thickness will include any tie layer thickness. Preforms and containers can have layers with a wide selection of relative thicknesses. In light of the present disclosure, the thickness of a given layer and total preform and container, both at a given point and throughout the container, can be selected to suit the manufacturing process or specific end use of the container. In the illustrated embodiment, the outer layer 52 has generally a uniform thickness. However, the outer layer 52 and / or the inner layer 54 need not be uniform and may have, for example, a thickness varying along the longitudinal axis of the preform 50.

[0110] Multi-layer preforms can be used to make containers. For example, the preform 50 may be used to form the container 83 (FIGURE 6). In one embodiment, the outer layer 52 cooperates with the inner layer 54 to provide a layer or space 85 between them, as shown in FIGURES 6 and 7. Layer 85 can allow air to pass between layers 52, 54 and can preferably further insulate the container 83 . Transitions between the layer 52 that loosely surrounds the inner layer 54 may be formed. Alternatively, the outer layer 52 may be of such a size and shaped to tightly hold the inner layer 54 and so that the inner surface of layer 52 contacts the outer surface of layer 54. In some embodiments, the layer 85 may be a foam layer that is similar or unlike one of the layers 52, 54. In yet another embodiment, the layer 85 may be a layer that connects the layer 52 to the inner layer 54. For example, the layer 85 is a contact or tie layer that inhibits, preferably substantially prevents, relative movement between layers 52, 54. For example, the layer 85 may be an adhesive layer that limits relative movement between layers 52, 54. It is contemplated that some or none of the layers of the embodiments disclosed herein may be joined together by a tie layer or similarly.

[0111] In one embodiment, at least one of the layers 52, 54 may be treated to assist or reduce adhesion between the layers 52, 54. For example, the inner surface of the inner layer 54 may be chemically treated such that the outer layer 52 adhered to the inner layer 54. Na

For example, a binder material can be applied to react and chemically treat one or more layers 52, 54. However, it is contemplated that any of the layers may be modified to achieve the desired interaction between the preform layers. Optionally, layers 52, 54 may adhere directly to each other.

[0112] In some embodiments, the container comprises foam material that preferably has insulating properties to inhibit heat transfer through the container walls. When the liquid is in the container, as for example in the container 83 of FIGURE 6, the foam material forming the wall 84 of the container 83 can reduce heat transfer between the liquid contents and the environment surrounding the container 83. For example, the container 83 can store cooled contents, such as a carbonated drink, and foam insulates the container 83, inhibiting temperature changes of the cooled fluid. Thus, the content may remain cooled for the desired period of time despite the fact that the external ambient temperature is higher than the liquid temperature. Alternatively, the container 83 may contain heated material, such as a hot drink, and the wall 84 may insulate the container 83, inhibiting heat transfer from liquid to the environment surrounding the container 83. In addition, the container foam material 83 may cause the surface temperature of the container 83 is in the desired temperature range, so that a person can conveniently grip the container 83 containing the heated or cooled liquid. The thickness of the foam layer and the size and shape of the foam portion of the container can be varied to achieve the desired thermal properties of the container.

[0113] With reference to FIGURE 8, a preferred embodiment of the multi-layer preform 60 is shown in cross section. One difference between the coated preform 60 and the preform 50 of FIGURE 5 is the relative thickness of the two layers in the bottom region. In the preform 50, the outer layer 52 is generally thinner than the thickness of the initial preform from beginning to end of the entire body portion of the preform. However, in preform 60, the outer layer 52 is thicker at point 62 near the bottom 42 than at point 64 at wall portion 66, and vice versa, the thickness of the inner layer 54 is greater at point 68 at wall portion 66 than at point 70, at the bottom region 42. This design of the preform is particularly useful when, to produce the multilayer preform, the outer coating is applied to the initial preform in an overmolding process as described below, which has some advantages, including the advantage of shortening the molding cycle time. Each of the layers may be homogeneous or may consist of multiple microlayers. In other embodiments of the preform 60, which are not illustrated, the outer layer 52 is thinner at point 62 near the bottom 42 than at point 64 at wall portion 66, and vice versa, the thickness of the inner layer 54 is smaller at point 68 at wall portion 66 than at at 70, in the bottom region 42. At least one of the layers 52, 54 may optionally include barrier material.

[0114] FIGURE 8 A is an enlargement of the wall section of the preform showing the layering of the layers made using the LIM overmoulding technique. Layer 54 is the inner layer of the preform, and layer 52 is the outer layer of the preform. The outer layer 52 contains many microlayers (i.e. lamellar material) of the material that will be produced when the LIM system is used. Of course, not all of the preforms of FIGURE 8 will be of this type.

[0115] With reference to FIGURE 9, another embodiment of the multilayer preform is shown in cross section. The basic difference between coated preform 76 and preforms 50 and 60 in FIGURES 5 and 8, respectively, is that the outer layer 52 is disposed on both neck portion 32 and body portion 34.

[0116] The preforms and containers may have layers that have a wide range of relative thicknesses. In light of the present disclosure, the thickness of a given layer and of the entire preform or container, whether at a given point or from beginning to end through the entire container, can be selected to suit the coating process or the particular final

EP 1 742 785 B1 to the use of the container. In addition, as discussed above with respect to the layers (s) in FIGURE 8, the layers in the embodiments of the preform and container disclosed herein may contain one material, more than one material, or several materials.

[0117] The apparatus and methods disclosed herein can also be used to create preforms with three or more layers. FIGURE 10 shows a three-layer embodiment of preform 132. The preform shown here has two coating layers, a middle layer 134 and an outer layer 136. The relative thickness of the layers shown in FIGURE 10 can be changed to suit a specific combination of materials or to allow bottles of different sizes to be made. As will be understood by one of ordinary skill in the art, the procedure disclosed herein would be followed, except that the starting preform would be a preform that has already been coated with one of the methods for producing coated performances described herein, including overmolding.

[0118] FIGURE 11 illustrates a cross-section of one type of multi-layer preform 160 having the features of the preferred embodiment. The preform 160 preferably includes an outer layer 162 and an inner layer 164.

[0119] The multi-layer preform 160 has a neck portion 132 and a body portion 134, as do the preforms described above. Preferably, the outer layer 162 forms the outer surface 165 of the body portion 134 and the inner surface 166 of the neck portion 132. The outer surface 166 can be shaped to engage with the closure. The outer layer 162 is disposed around the body, preferably the entire part, of the inner layer 164.

[0120] The illustrated outer layer 162 extends from the upper end 168 of the inner layer 164 to the aperture 169 of the preform 160. The inner layer 164 in the illustrated embodiment does not extend along the neck portion 132. Thus, the outer layer 162 can form substantially the entire neck portion 132, as shown in FIGURE 11. In other embodiments, the upper end 168 of the inner layer 164 may be located at a certain point along the neck portion 132. Thus, the inner layer 164 and the outer layer 162 may both define the neck portion. In one non-limiting embodiment, the outer layer 162 comprises at least about 70% by weight of the neck portion (or neck finish) of the neck portion 132. In another, non-limiting embodiment, the outer layer 62 comprises at least about 50% by weight of the neck portion 132. In yet another, non-limiting embodiment, the outer layer 162 comprises more than about 30% by weight of the neck portion 132.

[0121] The total thickness 171 of the preform 160 is equal to the thickness 172 of the outer layer 162 plus the thickness 174 of the inner layer 164, and is dependent on the total size of the container obtained. In one embodiment, the thickness 172 of the outer layer 162 is substantially greater than the thickness 174 of the inner layer 164. The outer layer 162 and the inner layer 164, as illustrated, are generally uniform in thickness. However, outer layer 162 and inner layer 164 may not have uniform thicknesses. For example, one or both of the layers 162, 164 may have a thickness varying along the length of the preform 160.

[0122] The outer layer 162 comprises the first material, and the inner layer 164 preferably comprises another material. For example, the outer layer 162 may contain foam material and the inner layer 164 may contain non-foamed polymeric material, such as PET (e.g., unused or post-consumer / recycled PET), phenoxy plastic, etc. Preferably, a substantial portion of the outer layer 162 comprises a first material and a substantial portion of the inner layer 164 comprises a second material. The first and second materials may be different or similar to each other.

[0123] FIGURE 12 is a cross-sectional view of the multilayer preform 180. The preform 180 is generally similar to the preform 160, and thus many aspects

EP 1 742 785 B1 will not be described in detail. The preform 180 includes an inner layer 184 and an outer layer 183. The inner layer 184 defines a substantial portion of the inner surface 173 of the preform 180. The inner layer 184 has an end 188 that is close to the opening 191 of the preform 180. In the illustrated embodiment, the outer layer 183 defines the outer surface 186 of the part neck portion 132, and the inner layer 184 defines the inner surface 187 of the neck portion 132. Of course, the outer layer 183 may be shaped to engage with the closure. In the illustrated embodiment, the outer surface 86 is defined by a thread 189 adapted to receive a threaded cap (e.g., a screw cap).

[0124] Although not illustrated, the preforms 160 and 180 may include more than two layers. For example, the outer layer 162 of the preform 160 may comprise a plurality of layers, including one or more of the following: lamellar material, foam material, PP, PET, and / or the like. Similarly, the inner layer 164 may include a plurality of layers. One skilled in the art can determine the dimensions and number of layers forming the preform described herein. Layers 183, 184 may be made of materials similar or other than layers 162, 164 described above.

[0125] Optionally, the layer may be coated on at least part of the preform to prevent abrasion or wear, especially if at least part of the preform is made of foam material. For example, the coating layer may surround the threads of the neck portion made of foam and may include PET, PP, combinations thereof or other thermoplastic materials.

[0126] FIGURE 13 is a cross-sectional view of the preform 190. The preform 190 is similar to the preform 180 illustrated in FIGURE 12, except for the further details given below.

[0127] The preform 190 includes an inner layer 194 that extends downwardly from the opening 191 and defines the interior of the preform. The inner layer 194 includes a collar 193. The term "collar", as used herein, is a broad term and is used in its usual sense and may include, without limitation, one or more of the following: spout, elongated portion, crown, protruding ridge, projection, and combinations thereof. The flange can act as a locking structure. In addition, the preform may optionally include multiple flanges.

[0128] Flange 193 defines a portion of the inner surface 201 and at least a portion of the top surface 195 of the preform. The flange 193 may have a constant or variable thickness F depending on the desired properties of the neck portion 132. In some embodiments, including the illustrated embodiment, the flange 193 is positioned above the structure (s) (e.g., threads 192) for receiving the closure. In some embodiments, the collar 193 defines a portion of one or more threads, projections, recesses, and / or other structures for engaging the closure.

[0129] Still with reference to FIGURE 13, the collar 193 extends around at least part of the periphery of the opening 191 and defines a layer of material. The flange 193 preferably extends around the entire periphery of the opening 191. Thus, the flange 193 may be a generally annular flange. When the closure is attached to the neck portion 132 of the container made of the preform 190, the upper surface of the collar 193 may form a seal with the closure to inhibit or prevent food from escaping from the container. Flange 193 may inhibit or prevent separation between inner layer 194 and outer layer 199.

[0130] One or more of the blocking structures 197 of FIGURE 13 may inhibit or prevent relative movement between the inner layer 194 and the outer layer 199. The term "blocking structure," as used herein, is a broad term and used in its usual meaning and may include, but without

Limited to them, one or more of the following: protrusions, surface treatments (e.g., rough surfaces), teeth, protrusions, spikes, flanges, recesses, humps, textured patterns or the like, preferably for inhibiting or reducing movement between layers 194 and 199. The locking structure 197 may be formed by the inner layer 194 and / or the outer layer 199. In the illustrated embodiment, the blocking structure 197 is a protrusion extending from and around the surface of the outer inner layer 194. In some embodiments, the blocking structure 197 is an annular protrusion extending circumferentially around the surface of the outer inner layer 194. The blocking structure 197 may be a continuous or discontinuous structure. The inner layer 194 may have one or more blocking structures, such as a textured pattern (e.g. series of grooves, protrusions, and the like).

[0131] In addition, the blocking structure 197 may be shaped to give a positive or negative pull direction. For example, the inner layer 194 may include a slightly elastic material (e.g., PET) and a locking structure 197 that can give a positive pull direction during mold removal. In some embodiments, the outer layer 199 includes a slightly rigid material (e.g., olefins) that can give a positive or negative pull direction when removing the mold.

[0132] The outer layer 199 is shaped to receive a blocking structure 197. The blocking structure 197 effectively blocks the outer layer 199 to the inner layer 194. Although not illustrated, there may be a plurality of blocking structures 197 defined by layers 194, 199 and may be they are arranged in the neck portion 132 and / or the body portion 134 of the preform 190. In some embodiments, a tie layer can be used to couple the inner layer 194 to the outer layer 199. In one embodiment, the inner layer 194 and the outer layer 199 are formed of materials that directly bind or adhere to each other. In other embodiments, the inner layer 194 is associated with the outer layer 199, such that layers 194 and 199 can be easily separated during e.g. a recycling process. However, in some embodiments, the article containing the tie layer can be recycled.

[0133] The upper end of the outer layer 199 is spaced from the upper surface 195 of the preform. One skilled in the art can choose the thickness of layers 194, 199 to obtain the desired structural properties, thermal properties, durability, and / or other preform properties.

[0134] FIGURES 13A and 13B illustrate modified embodiments of a portion of the preform 190 of FIGURE 13. The preform 190 of FIGURE 13 A has a collar 193 that extends along a portion of the upper surface 195 of the preform. In some non-limiting embodiments, the LF length of the collar 193 is less than about 95% of the wall thickness T of the neck portion 132. In one non-limiting embodiment, the LF length of the collar 193 is about 50% to 90% of the wall thickness T of the neck portion. In some non-limiting embodiments, the LF length of the 193 collar is about 60%, 70%, 75%, or 80%, or ranges including such percentages, of the wall thickness T of the neck portion. In another non-limiting embodiment, the length LF of the collar 193 is about 40% to 60% of the wall thickness T of the neck portion. In yet another embodiment, the length LF of the collar 193 is less than about 40% of the wall thickness T of the neck portion.

[0135] FIGURE 13B illustrates a portion of a preform having an outer layer 203 that defines a collar 223. The collar 223 extends inwardly and defines an upper surface 225. The collar 223 may define the inner surface of the preform, or be away from it. The collar 223 may have a similar or different length to the collar 193. The neck portion 132 has threads for receiving a closure. However, the neck part may have other structures (e.g. grooves, ridges, grooves, etc.) for attaching the closure. The preforms described above can be modified by adding one or more

Layers to obtain the desired properties. For example, a barrier layer may be formed on the body parts of the preforms.

[0136] FIGURE 14 illustrates a modified embodiment of preform 202. The preform 202 has a neck portion 132 that defines a coupling structure 207 shaped to receive a closure. The term "coupling structure," as used herein, is a broad term and is used according to its usual meaning, and may include, but is not limited to, features such as positive features (e.g. protrusion, convexity and the like) or features negative (e.g. indentation, recess, and the like). The engaging structure may be shaped to engage the closure so as to hold the closure in a desired position.

[0137] The illustrated coupling structure 207 is in the form of a recess fit to receive parts of the closing device. The coupling structure 207 may extend around one or more parts of the preform 202. In other embodiments, the coupling structure 207 extends around the entire circumference or periphery of the preform 202. The coupling structure 207 may have a V-shaped, curved (e.g., semi-circular) profile in U-shaped, or any other cross-sectional profile. Although not illustrated, the structure 207 may be a projection, such as an annular projection, defined by the outer layer 203. Optionally, the preform 202 may have a plurality of coupling structures 207 so that closures of different shapes can be attached to the container made of the preform. The distance between the upper surface 205 and the structures 207 and the shape of the structure 207 are determined by the geometry of the closure used to seal and close the container formed from the preform 202.

[0138] FIGURE 14A illustrates a container 211 made of the preform 202 of FIGURE 14. The closure 213 is attached to the neck portion 132 of the container 211. The closure 213 can be a one-part or multi-part closure. The closure 213 can be attached to the container 211 temporarily or permanently. The entire closure 213 can be removed from the container 211 when liquid is consumed. In other embodiments, part of the closure 213 can be removed, while the other part of the closure 213 remains attached to the container 211 during consumption. The closure 213 can be attached to the container temporarily or permanently. If the closure 213 is temporarily attached to the container 211, the closure 213 can be removed from the container 211. In one embodiment, if the closure 213 is permanently attached to the container 211, the closure 213 and container 211 may form a generally uniform body.

[0139] As shown in FIGURE 14B, the upper surface 205 of the preform and closure 213 may form a seal 231, preferably forming either an airtight seal or other seal that inhibits or prevents fluid from escaping between the container 211 and the closure 213. Optionally, the container 211 may have a seal or removable seal. For example, the container 211 may have a removable seal, such as a membrane adjacent the upper edge of the container, or a portion of the closure 213 that can be removed. The removable seal may have a flap or ring for convenient gripping and removal of the seal. Alternatively, the seal 231 can be formed by a membrane or sheet that can be broken or divided into parts to open the container 211. In some embodiments, the outer layer 203 of the container 211 is formed of generally high strength material or a rigid material (e.g. PP), so that the collar 209 can be compressed between the closure 213 and the outer layer 203 to ensure the integrity of the seal 231.

[0140] As shown in FIGURES 14A and 14B, the closure 213 has a body 215 and a cover 218. The body 215 can be connected to the cover 218 by a hinge 221 (e.g., molded material acting as a flexible hinge or other structure enabling

EP 1 742 785 B1 movement). Hook or tab 217 (FIGURE 14A) may attach cover 218 to body 215. Hook 217 may be moved to release cover 218 to open closure 213. Alternatively, cover 218 and body 215 may be separate parts so that cover 218 can be removed from the body 215. When the closure 213 is in the open position, the content can be delivered outside the container 211, preferably delivered while the body 215 remains attached to the neck portion. After removing the desired amount of food product from container 211, lid 218 can be returned to the closed position to reseal the container.

[0141] The body 215 of the closure 213 can be releasably connected to the neck portion. For example, the body 215 may be latched onto the neck portion 132. Alternatively, the body 215 may be permanently coupled to the neck portion 132. The neck portion 132 includes one or more structures connecting the closure 227, so that the closure 213 can be latched onto the container and from the container . The neck portion 132 in the illustrated embodiment has a structure connecting the closure 227 in the form of a negative feature, such as a recess or cut. The body 215 can be permanently coupled to the outer layer 203 by means of a welding or soldering process (e.g., induction welding), glue, friction interactions, and / or the like. Container 211 may be shaped to receive different types of closures, such as BAP® closures manufactured by Bapco Closures Limited (England) (or similar closures), screw caps, snap closures, and / or the like. A person skilled in the art can design the neck finish of the container 211 so that it can receive closures of various shapes.

[0142] Still with respect to FIGURE 14A, container 211 is particularly well suited for hot-fill applications. The container 211 can generally maintain its shape during hot-fill processes. After blow molding or hot filling, the final dimensions of the neck portion of the container 211 are preferably substantially identical to the initial dimensions of the preform. In addition, this results in a reduction in thread size deviations at the neck finish. For example, the inner layer 284 may be formed of a material for contacting food products, such as PET. The outer layer 203 may contain moldable materials (e.g., PP, foam material, crystalline or semi-crystalline material, lamellar material, homopolymers, copolymers, combinations thereof, and other heat resistant materials described herein) suitable for hot filling. The outer layer 203 provides dimensional stability of the neck portion 132 even during and / or after hot filling. The width of the outer layer 203 can be increased or decreased to increase or decrease, respectively, the dimensional stability of the neck portion 132. Preferably, one of the layers forming the neck portion 132 comprises a material having high temperature stability; however, the neck portion 132 may also be made of materials having low temperature stability, especially for non-hot filling applications.

[0143] In addition, the dimensional stability of the outer layer 203 ensures that the closure 213 remains attached to the container 211. For example, the outer layer 203 may contain high strength material (e.g. PP) and may maintain its shape, thereby preventing unintentional detachment of the closure 213 from container 211.

[0144] With reference to FIGURE 14C, the container has a neck portion that includes closure attaching structures by a snap fit. The neck portion in the illustrated embodiment has a structure connecting the closure 227 in the form of a positive feature, such as a protrusion, flange or the like, suitable for engaging the closure 213. The structure connecting the closure 227 may form an annular projection that extends around the periphery of the neck portion. Closure 213 may have

EP 1 742 785 B1 single-part or multi-part structure. The illustrated container 211 has a downwardly tapering wall forming a neck finish. The downwardly tapering portion of the cervical end can support the closure 213, forming a seal.

[0145] FIGURE 15A illustrates part of the preform 220 according to another embodiment. The preform 220 has a support ring 222 and a body portion 224 extending downward from it. The preform 220 has an opening 226 at its upper end. The neck finish of the preform may have or may not have threads. In some embodiments, the threads are attached to the cervical region 225 of the preform. It is contemplated that the preform 220 may be formed without a support ring. The support ring and / or threads may optionally be formed on the preform 220 in subsequent processes.

[0146] FIGURE 15B illustrates the preform 220 after attachment of the structures connecting the closure 228 to the cervical region 225. It is contemplated that thread structures, latch cap engagement structures, or other type of attachment or attachment structure may be attached to the cervical region 225 before or after processing the preform 220 into a container. For example, closure fastening structures 228 can be attached to the preform 220 after the preform has been formed into a container, preferably after blow molding.

[0147] The preforms may have other parts that are attached or coupled to each other. FIGURE 15C illustrates the preform 234, which has at least a portion of the neck end 240 coupled to the preform body 242. The illustrated preform 234 has a portion 238 that is coupled to the upper end 250 of the lower portion 252 of the preform 234. Part 238 may include materials and / or microstructures other than the lower portion 252. In some embodiments, portion 238 comprises crystalline material. Thus, the preform 230 may be suitable for hot fill applications. The lower portion 252 may be amorphous to facilitate the blow molding process. In some embodiments, the upper portion 238 includes a different material than the lower portion 252. A person skilled in the art may choose a preform forming material. In some embodiments, the upper end 250 is located at or below the support ring. The preforms illustrated in FIGURES 15A to 15C may have monolayer or multilayer walls.

[0148] The preforms, including the monolayer and multilayer preforms described above, may have other shapes and configurations. FIGURE 16 illustrates the preform 270 having a downwardly tapering body portion 272 and neck portion 274. The preform 270 can be blow molded to form a container in the form of, for example, a jar. The jar or other similar container may have an outlet or opening larger than the opening of the bottle. The preform 270 has a support ring 278 and one or more structures connecting the closure 279, preferably shaped to interact with a snap closure or other type closure. FIGURE 17 illustrates the implementation of a preform with a neck finish without threads. The preform 280 includes a body portion 281 that has a bottom 283 and a neck finish 282. The preform 280 may be suitable for blow molding into a container. The preforms illustrated in FIGURES 16 and 17 may be monolayer or multilayer preforms (e.g. having the layers described above). The preforms described above can be formed without a neck finish.

[0149] Preforms such as those depicted in FIGURES 1-18 may be subjected to a stretch blow molding process. The blow molding process is described primarily for monolayer preform 30, although multilayer preforms (e.g., 50, 60, 76, 80, 132, 160, 180, 290, and 216 preforms) can be processed in a similar manner. The containers described above can be formed, for example, by various molding processes (including molding by

EP 1 742 785 B1 extrusion blow-molding).

2. Detailed description of the closures [0150] As described above, the closures can be used to seal containers. The term 'closure', as used herein, is a broad term and is used in its usual sense and may include, without being limited to, a cap (including a clamp cap, a removable cap, a bottle cap, a threaded bottle cap, an anti-theft cap) , crown cap, cork (natural or artificial), perforated seal, lids (e.g. cup lid), multi-part closure (e.g. BAP® closures manufactured by Bapco Closures Limited (England) or similar closure), snap closures, and / or the like.

[0151] Generally, closures may have one or more features providing further advantages. Some closures may have one or more of the following: tamper-evident feature, tamper-evident feature, seal reinforcement, storage compartment, handle structures for facilitating removal / placement of the closure, spill-proof feature, and combinations thereof.

[0152] The closures may have a one-part or multi-part structure and may be shaped so that they can be connected to the container permanently or temporarily. For example, the closure illustrated in FIGURE 14A has a multi-part structure. The closure illustrated in FIGURE 18 has a one-piece structure. The terms "closure" and "cap" can be used interchangeably here. It is contemplated that closures may be used with bottles, boxes (especially boxes used for storing food products, such as, for example, juices), cartons, and other packaging or products. The term "bottle cap", as used herein, is a broad term and is used in its usual sense, and may include, without limitation, a cap suitable for being put on a bottle, such as a glass or plastic bottle (e.g. a typically shaped bottle for storing alcoholic beverages or juices) and may have threads or no threads. Bottle caps are typically removed in a manner known in the art using a bottle opener. The term "threaded bottle cap" is a broad term used in its usual sense and may include, without being limited to, a cap (e.g., a screw cap) suitable for attachment to bottles having threads. In light of the present disclosure, embodiments of closures having threads can be modified to form bottle caps or other types of closures for containers of various shapes. In some embodiments, the closures may engage the container by means of a thread or be attached to the container by various methods such as ultrasonic welding, induction welding, multi-stage molding process, adhesives, thermoforming, and the like.

[0153] FIGURE 18 illustrates one embodiment of a closure 302 that can be connected to an article, such as the neck portion of a container. In the illustrated embodiment, the closure 302 has internal threads 306 (FIGURE 19) that are shaped to match the threads of the neck portion so that the closure 302 can be connected to the container in a separable manner. The closure 302 may be attached to a container (e.g., bottle) to close the opening or outlet of the bottle. The closure 302 has a main body 310 and an optional tamper-evident structure or tamper-proof structure, such as tape 313 (or sheath) attached to the body 310 by means of one or more connectors 312. Connectors 312 may be of such a size and size that the connectors break during removal of the closure 302 from the container, thereby causing the body 310 to separate from the strip 313, indicating removal of the closure 302 from the container associated therewith. Although not illustrated, other types of tamper-evident structures can be used. The surface 316 of the body 310 may have surface treatment, such as grooves, ridges, machining

Texturizing, and / or similar, to facilitate interaction by friction with closure 302.

[0154] With reference to FIGURE 19, the closure 302 includes a body 310 and may or may not have an insert. The illustrated closure 302 includes an optional inner closure layer 314. The illustrated inner closure layer 314 is in the form of an insert contained in the outer portion 311 of the body 310. The insert 314 may be selected to contact food or liquid and may form a seal with the edge that forms the opening bottle. Thus, the insert 314 forms a significant part or all of the contact area of ​​the closure 304.

[0155] The insert 314 may be a barrier insert, such as an active or passive barrier insert. Insert 314 may act as a fluid barrier (e.g., liquid or gas), an aroma barrier, and combinations thereof. For example, the insert 314 may be a gas barrier that inhibits or prevents oxygen, carbon dioxide, and the like from passing through it. In some embodiments, the liner 314 may have absorption capabilities, such as gas absorption (e.g., oxygen absorption).

[0156] The insert 314 may be pressed against the edge of the bottle to prevent liquid from escaping from the container sealed with the closure 302. In one embodiment, the insert 314 is a gas barrier that prevents or inhibits the escape of gas from the container. In another embodiment, the liner 314 is an aroma barrier that can prevent or limit the change in taste of the liquid in the container. For example, the insert 314 may be formed of a polymer (e.g. thermoplastic material), which can act as an aroma barrier to ensure that the food product in the container retains the desired aroma. Thus, insert 314 can help ensure that the body 310 does not give flavor or odor to the food product in the container.

[0157] Often, a material having some ability to impart and / or reduce aroma or absorb (e.g. polyolefins, such as polypropylene or polyethylene) is used to manufacture a container or closure, such as a bottle cap, due to its physical properties (e.g. durability, hardness, impact strength and / or strength). In some embodiments, polypropylene may exhibit one or more physical properties that are advantageous over the physical properties of polymers such as PET. Unfortunately, under certain circumstances, polypropylene tends to reduce or absorb the aroma of the bottle contents or to remove the desired aromas or aromas from the contents. Thus, a person consuming a food product previously in contact with PP may believe that there has been a change in aroma. Preferably, the liner 314 may contain aroma-preserving material, such that it generally does not affect the food product in the container when the food product contacts the liner 314. Preferably, the aroma-preserving material is FDA approved material for contacting food products.

[0158] In some non-limiting embodiments, the aroma preserving material is PET (such as unused PET), phenoxy type thermoplastic, and / or the like. The body 310 can thus be made of an aroma-absorbing material, such as polypropylene, to give the desired physical properties, and the liner 314 contains PET as an effective aroma barrier to ensure that the contents of the container maintain the desired taste. It is contemplated that the liner 314 may be formed of any material suitable for contacting the food product in the container. In some embodiments, the inserts 314 may be formed of foam material described herein, which may substantially or not change the taste of the contents of the container. In addition, the thickness of the liner 314 may be increased to inhibit the passage of gas or other fluids through the liner. Optionally, the insert 314 may be a monolayer or multilayer structure. For example, the liner 314 may include an inner layer of PET (i.e., a layer contacting the contents of the container) and an outer layer of material

EP 1 742 785 B1.

[0159] The liner 314 may have a layer suitable for contact with food products and one or more layers acting as a barrier, like the preforms described herein. In some embodiments, for example, the liner 314 may include a first layer and a second layer, the first layer comprising foam material and the second layer comprising barrier material. Thus, the second layer may reduce or inhibit fluid migration through the insert 314, and the first layer isolates the closure 302. In some embodiments, the insert 314 comprises a PET layer and a layer comprising a second material. The PET layer is preferably the lowest layer so that it forms a seal with the container edge. The second material may be EVA or other suitable material for forming part of the insert.

[0160] In some embodiments, the insert 314 of FIGURE 19 may be pre-formed and slipped into the body 310. For example, the body 310 may be shaped as a typical cap used to seal the bottle. Insert 314 is formed by cutting out a portion of the sheet, described below. The pre-cut insert 314 may then be inserted into the body 310 and positioned as shown in FIGURE 19. Alternatively, the insert 314 may be formed within the body 310. For example, the insert 314 may be formed by a molding process, such as an overmolding process. At least a portion of the liner 314 may be formed by a spray coating process. For example, the single-layer liner may be sprayed and coated with a polymer (e.g., PET, a phenoxy type thermoplastic polymer, or other materials described herein), thereby obtaining a multilayer liner.

[0161] A further advantage is optionally obtained when the liner 314 can be retained in the body 310 or can be attached to the container. The insert 314 may be attached to the body 310 so that the insert 314 remains attached to the body 310 after the body has been separated from the container. Alternatively, the liner 314 may be attached to the container such that the body 310 and the liner are separable. For example, the insert 314 can be transferred to the body 310 to the container opening by means of a welding process, such as an induction welding process.

[0162] A further advantage is optionally obtained when at least part of the closure 302 is formed of a material providing a comfortable gripping surface, so that the user can conveniently grip the closure 302. The body 310 may include material to provide sufficient rigidity (e.g. PP), compressibility for comfortable grip (e.g. foam material), and / or the like. In some embodiments, the outer portion 311 of the body 310 may include foam to increase the space occupied by the outer portion 311 and may provide the user with a greater leverage for easy opening and closing of the closure 302. For example, the closure 302 may have an internally threaded surface that is shaped so to fit the thread into the externally threaded surface of the container. The enlarged outer portion 311 can provide increased leverage so that the user can easily screw and unscrew the closure 302 to and from the container. Preferably, a similar or the same amount of material forming a plain cap may be used to form the enlarged diameter closure.

[0163] In some embodiments, at least a portion of one of the parts 311 and the insert 314 may be formed of foam material for a very light closure due to the low density of the foam material. The reduced weight of the closure 302 can desirably reduce the cost of transporting the closure 302. In addition, the foam material of the closure 302 can reduce the amount of material that is used to form the closure because the foam material can have a significant number of bubbles.

[0164] The closures described below may be similar or different to the closure illustrated in FIGURE 19. With reference to FIGURE 20, the closure 330 has a body 331 which includes an inner part 332 and an outer part 334. The illustrated wall 335 includes parts 332, 334. Inner portion 332 may define at least a portion of the interior of the closure 330 and may optionally define one or more of threads 336. The inner portion 332 may be formed by an injection process, spray coating process, or other processes described herein to form parts of the article. In some non-limiting embodiments, the inner portion 332 comprises a polyolefin (e.g., PET), a phenoxy type thermoplastic, and / or other materials described herein. FIGURES 21A to 21E illustrate non-limiting embodiments of the closures. FIGURE 21A illustrates a closure 340 that has an outer portion 342 and an inner portion 344 that forms at least a portion of the interior of the closure 340. That is, each of the outer portion 342 and the inner portion 344 may define a portion (e.g., threads) of the inner surface of the closure 340. Inner portion 344 is inserted into outer portion 342; however, in other embodiments, the inner portion 344 is not inserted into the outer portion 342. FIGURE 21B illustrates a closure 350 that includes an inner portion 354 comprising a plurality of layers 356, 358. FIGURE 21C illustrates a closure 360 ​​comprising a plurality of layers. The outer layer 362 forms the outer surface (including the top and wall) of the closure 360. Intermediate layer 364 may include one or more layers. The inner layer 366 defines a threaded contact surface 368.

[0165] The closures may have parts or layers of different thicknesses. As shown in FIGURE 21D, at least one of the closure parts or layers 370 includes a thickened portion. The illustrated closure 370 has an inner portion 374 with a thickened top portion 372 that has a thickness greater than the thickness of the wall portion 376.

[0166] FIGURE 21E illustrates a multilayer closure 380 that includes a band 382 attached to the inner portion 383 of the closure 380 by one or more connectors 384. The closures illustrated in FIGURES 18 to 21E may have any suitable structures or patterns for attachment to containers. For example, the closures of FIGURES 18 to 21E may have a similar configuration as the closure 213 (FIGURE 14A). It is contemplated that the closures of FIGURES 18-21E described herein can be attached to containers by means of a threaded joint, welding or soldering process (e.g., induction welding), glue, friction interaction, or the like. The closures of FIGURES 18-21E are illustrated with bands. However, the closures may not have bands, or they may have other tamper-proof indicators or structures. Although the closures of FIGURES 18-21E are illustrated as screw closures, other types of closures (e.g., closures with multiple parts, such as closures with lids that open and close, closures with nipples, and the like) may have similar designs.

[0167] The closures may have one or more compartments shaped for storage. Compartments may contain additives that can be added to the contents of the accompanying container. Additives may affect the characteristics of the contents of the container and may be in solid, gas and / or liquid state. In some embodiments, the additives may affect one or more of the following characteristics: aroma (e.g., additives may contain perfumed gases / liquids), aroma, color (e.g. additives may contain dyes, pigments, etc.), nutrient content (e.g. additives may contain vitamins, proteins, carbohydrates, etc.), and combinations thereof. Additives can be provided from the closure to the contents within the container for later consumption and advantageously increase the attractiveness of the content and the consumer experience. The compartment may release additives when removing the closure so that the mix is ​​fresh. However, the compartment may be opened before or after removal of the closure from the container. In some embodiments, the closure has a compartment that can be broken (e.g., punctured) after

By separating the closure from the container. The compartment may be broken by means of a piercing, tearing, and similar process. The compartment may have a structure for releasing its contents. This structure may be a pull-out plug, a push-in latch, or other suitable structure to release the contents of the compartment.

[0168] The containers can also be closed with a seal that is separate from the closure. The seal can be applied to the container before the closure is attached. The sealing process can be used to attach the seal to the neck of the container after filling the container. The seal may be similar or different to the inserts that attach to the closures. The seals may be hermetic seals (preferably spill-proof) that ensure the integrity of the container contents. In some embodiments, the seal may comprise a foil (preferably containing a metal, such as aluminum foil) and is applied to the container by means of a welding process such as induction welding. However, the seal may be attached to the container using other suitable attachment processes, for example adhesive may be used.

[0169] The closures may have an internal surface suitable for connecting to the mounting mounted structures (e.g., threads, snap caps, and the like). The inner surface may have a slightly slippery surface to facilitate removal of the closure from the container. For example, the closures may have slippery or low-friction material (e.g. olefin polymers) for attachment to the container forming material. If the closure is formed of, for example, PET, the closure may adhere or lock with the PET container. Thus, the closure (including snap caps, twist caps, and the like) may require a relatively high removal torque. Advantageously, a closure with slippery or low friction material may reduce the removal moment to facilitate removal of the closure. Slippery or low-friction material preferably provides sufficient friction, so that the closure can remain attached to the associated container while allowing convenient removal of the closure. Thus, slippery or low friction materials can be chosen to achieve the desired removal moment.

[0170] With reference to FIGURE 20, the closure 330 may include an inner portion 332 containing slippery or low friction material (e.g., olefin or other material having a low friction coefficient) and an outer portion 334 containing a polymer, such as an olefin polymer, material foam, PET, and other materials described herein. The closures described here may contain slippery or low-friction material that can adhere to the container and provide the desired removal time. The closure forming a slippery or low friction material can be selected depending on the material forming the container to produce the desired friction interaction. It is contemplated that the molds described herein can be modified with a septum at the edge to form the innermost layer of the closure for connecting the container.

3. Detailed description of mono- and multilayer profiles and sheets [0171] FIGURES 22A and 22B are sectional views of the sheets. The sheets can have a uniform thickness or different thicknesses. The sheet of FIGURE 22A is a monolayer sheet 389. The sheet of FIGURE 22B is a multilayer sheet 390, comprising two layers. The sheets can have any number of layers of any desired thickness, depending on, for example, the use of the sheets. For example, sheets 389, 390 can be used to produce packaging, such as as a label. At least a portion of sheets 389, 390 may include foam material. For example, sheets 389, 390 may contain foam material to provide insulation to the packaging to which the label is attached. Optionally, sheet 390 may include one or more tie layers. For example, sheet 390 may include a tie layer between layers 392, 394.

[0172] The sheets can be used in various applications and can be formed into various shapes. For example, the sheets can be cut, formed (e.g., by thermoforming or casting), and / or similarly, to the desired shape. A person skilled in the art can choose the desired shape, size and / or configuration of the sheets, depending on the desired application.

[0173] FIGURE 23 illustrates multilayer profiles 402. Profile 402 is in the form of a conduit having a generally tubular shape. Profile shape 402 can be generally circular, elliptical, polygonal (including rounded polygonal), combinations thereof, and the like. The illustrated profile 402 has a generally circular profile in cross section.

[0174] In some embodiments, the profile 402 may be a conduit adapted to deliver liquids, preferably adapted to drinking liquids. Profile 402 may have an inner layer 404 and an outer layer 406. In some embodiments, at least one of the layers 404, 406 may include multiple layers (e.g., lamellar material).

[0175] Profile 402 may be a conduit that contains material suitable for contact with food products and one or more additional materials having the desired physical properties (e.g., structural and thermal properties). Preferably, the inner layer 404, which is in direct contact with the fluid, preferably does not substantially change the taste and aroma of the food product with which it contacts. For example, fluid dispensing systems often have polyolefins that absorb aromas and flavors. Preferably, the inner layer 404 preferably does not substantially change the taste and aroma of the fluid passing through the light 408 of the profile 402. In some embodiments, the outer layer 406 may provide improved physical characteristics of the profile 402. In another embodiment, the outer layer 406 may provide enhanced insulating and / or structural profile 402. For example, in one embodiment, the outer layer 406 can provide increased impact strength. In some embodiments, the outer layer 406 can reduce heat transfer through the walls of the profile 402. In some embodiments, the outer layer 406 can have high tensile strength, such that high pressure fluid can be passed through the profile 402. Thus, the inner layer serves as a substantially inert surface for contact with food, while the outer layer / outer layers serve as insulation and / or to resist external influences.

[0176] Of course, profile 402 can be used in various other applications. For example, profile 402 can be used in hospitals (e.g., as a transmission line for medical fluids, in manufacturing processes, equipment, in fluid systems (e.g., food fluid metering systems), and / or similarly.

4. Detailed Description of the Packaging [0177] One or more of the articles described herein can be used alone or in combination in various applications such as packaging. FIGURE 24 illustrates a packaging system 416 including a container 420 that can be made of the preforms described herein. A closure 422 may be attached to the neck portion 432 of the container 420 to close the container.

[0178] FIGURE 24 also illustrates a label 440 attached to the container 420 in the form of a bottle. Label 440 may include bottle 420 and may be monolayer or multilayer. The label 440 may optionally include foam material.

[0179] The label 440 is preferably attached to the outer surface 442 of the container 420. The label 440 can be attached to the outer surface 442 in a removable manner. Label 440 may be attached during and / or after manufacturing container 420. In the illustrated embodiment, label 440 is generally a tubular sleeve that surrounds

At least a portion of the bottle 420. The label 440 may have any shape or configuration suitable for attachment to the bottle and displaying information. Although not illustrated, label 440 may be attached to glass bottles, metal cans, or the like. In addition, label 440 may be attached to other structures or packages. For example, label 440 may be attached to the box, carton, bottle (plastic bottle, glass bottle, and the like), and other items discussed herein. In addition, label 440 may be printed. Optionally, the outer surface 446 of label 440 may be treated to obtain a surface suitable for printing.

[0180] An adhesive may be used to attach label 440 to the product. In one embodiment, after the label has been attached to the article, the foam material of the label 440 can be expanded to provide a thermal barrier, fluid barrier, protective layer, and / or desired structural properties. The foam material is preferably expanded by heating the label 440. The label material 440 can be foamed before and / or after placing the label 440 on the container 420. Of course, the foam material of the label 440 can directly adhere to the product without the use of adhesives.

[0181] FIGURE 25 illustrates another embodiment of a container containing mouldable material. The container 450 may be similar or different to the containers described above. In the illustrated embodiment, the container 450 includes a closure 452, a body 454, and a handle 456 attached to the body 454. The body 454 can be substantially rigid or flexible. The handle 456 is preferably shaped and sized so that it can be comfortably gripped by the user. The wall of the body 454 can be a single-layer or multi-layer wall. The container 450 can have any shape, including a shape similar to typical containers used to store food liquids. The container 450 may be formed by a blow molding process.

[0182] Referring to FIGURE 26A, container 460 is a package (e.g., food package) that preferably includes foam material. In one embodiment, a sheet (e.g., sheets 389 or 390) is used to form at least a portion of the container 460 by, e.g., a thermoforming process. The container 460 may be in the form of a flexible pouch, food container, or any other suitable structure.

[0183] For example, in one embodiment, the sheets are formed into "clamshell" packages that are adapted to hold food, such as hamburgers. In another arrangement, the sheets are shaped into boxes (e.g., pizza boxes). In another embodiment, the material and dimensions of the container 460 may be determined based on the desired structural properties, thermal properties, and / or other characteristics. For example, the container 460 may contain foam material for effective thermal insulation of the container 460. In another example, the container 460 may have thick walls, such that the container 460 is generally rigid.

[0184] FIGURE 26B illustrates another article comprising moldable material. In one embodiment, the product 462 is in the form of a tray that is shaped to receive a food product. Tray 462 can be formed from a sheet by thermoforming. Optionally, tray 462 can be fitted into the interior of the container or box.

[0185] Tray 462 (or other articles described herein) may be shaped for heat treatment. In some embodiments, tray 462 can be used for heating and heating. Food tray may be held in tray 462 so that these food products may be heated, e.g., by a heat lamp, microwave oven, oven, toaster, hot water and the like. The microstructure of the tray 462 can be selected depending on the type and method of heat treatment. For example, tray 462

EP 1 742 785 B1 may contain crystalline material (e.g. crystalline PET) to increase thermal stability. During the thermoforming process, one or more of the layers of the tray may be heated above a certain temperature to cause crystallization of at least part of one of the layers. Thus, at least part of the tray 462 can be crystallized during the manufacturing process. In some embodiments, tray 462 may include a mono- or multi-layer sheet. Tray 462 may have a first layer of thermoplastic material and a second layer (e.g., foam layer). The first layer may contain crystalline material (e.g., amorphous, partially crystallized or completely crystalline). Tray 462 can be used to store food for use in the microwave. Of course, other products, such as containers, such as pizza boxes, may have a similar shape.

[0186] The articles may also be in the form of a can. The can may contain polymeric materials as disclosed herein. The can may contain a metal layer and one or more layers of another material. In some embodiments, the metal can (e.g., aluminum can) may be coated with a foam material, such as a thermoplastic material. At least part of the outside and / or the inside of the can may be coated with foam material.

B. Crystalline neck ends [0187] In some embodiments, plastic bottles and containers preferably include in the neck, neck end and / or neck cylinder one or more materials that are at least partially in a crystalline state. Such bottles and preforms may also contain one or more layers of materials.

[0188] In some embodiments, the bottles are made by a process that includes blow molding plastic preforms. Under certain circumstances, it is preferred that the material in the plastic preforms is in an amorphous or semi-crystalline state, since materials in such a state can easily be blow molded, while fully crystalline materials generally cannot. However, bottles made entirely of amorphous or semi-crystalline material may not have sufficient dimensional stability during the standard hot-filling process. In such circumstances, a bottle containing crystalline material will be preferred because it will retain its shape during hot-fill processes.

[0189] In some embodiments, a plastic bottle has the advantages of both a crystalline bottle and an amorphous or semi-crystalline bottle. By making at least a portion of the highest part of the crystalline preform, while maintaining the amorphous or semi-crystalline preform body (sometimes referred to herein as "non-crystalline"), you can make a preform that will easily blow-mold while maintaining the necessary dimensions in a key neck area during the hot-filling process Some embodiments have both crystalline and amorphous or semi-crystalline regions. In this way, a preform is obtained that has sufficient strength for use in a wide range of commercial applications.

[0190] In one or more of the embodiments described herein, crystalline neck preforms are generally produced, which are typically then blow molded into beverage containers. Preforms can be monolayer; that is, they consist of one layer of basic material, or can be multi-layered. The material in such layers may be a single material or may be a mixture of one or more materials. In one embodiment, an article is provided that includes a neck portion and a body portion. The neck portion and the body portion are the monolithic first layer of material. The body portion is primarily amorphous or semi-crystalline, and the neck portion is primarily crystalline.

[0191] With reference to FIGURE 1, a preferred preform 30 is depicted. The preform 30 can be made by injection molding by a method known in the art or the method disclosed herein. The preform 30 has a neck portion 32 and a body portion 34, monolithically formed (i.e. as a single or unitary structure). Preferably, in some embodiments, the monolithic shape of the preform provides greater dimensional stability and improved physical properties in the blow molding of the bottle compared to a preform constructed of a separate neck portion and a separate body portion that are bonded together.

[0192] By obtaining the crystalline state in the neck portion of the preform during the forming step, the final dimensions are substantially identical to the initial dimensions, unlike when additional heating steps are used. Thus, dimensional variations are minimized and dimensional stability is obtained. The result is better predictable behavior of closures such as threads at the cervical end and reduction of the defect rate in the forming process.

[0193] While a non-crystalline preform is preferred for blow molding, a bottle having more crystalline character is preferred because of its dimensional stability during the hot-filling process. Accordingly, a preform constructed in accordance with some embodiments has a generally non-crystalline body portion and a generally crystalline neck portion. To create a generally crystalline and generally non-crystalline part in the same preform, different levels of heating and / or cooling are needed in the mold in the regions where the crystalline parts will be formed compared to those regions where the generally non-crystalline parts will be formed. Different levels of heating and / or cooling can be maintained by thermal insulation of regions having different temperatures. This thermal insulation between the mold threaded element, the core and / or the matrix contact surface can be obtained by using a combination of materials with low and high thermal conductivity as inserts or separate elements on the surfaces of the mating parts.

[0194] In some preferred processes, the preform is made at favorable time cycles for uncoated preforms of similar size using standard methods currently used to make preforms. In addition, beneficial processes are possible by designing process tools and techniques so that they enable the simultaneous production of crystalline regions and amorphous regions at specific locations of the same preform.

[0195] In one embodiment, a mold for making a preform is provided, comprising a neck portion having a first mold temperature control system (e.g. cooling / heating channels), a body portion having a second temperature control system, and a core having a third control system temperature, where the first temperature control system is independent of the second and third temperature control systems, and the neck portion is thermally insulated from the body portion and core.

[0196] Cooling the mold in areas forming the preform surfaces, for which it is preferred that the material be generally amorphous or semi-crystalline, can be accomplished by means of a cooled circulating fluid through the matrix and the mold core. In some embodiments, a mold system similar to typical injection molding applications is used, except that there is an independent fluid circuit or electric heating system for those mold parts from which the crystalline preform molds will be formed. Thermal insulation of the mold body, neck finish of the mold and core section can be obtained with inserts having low thermal conductivity. The neck portion, neck end and / or neck cylinder are preferably maintained at a higher temperature to achieve slower cooling, which promotes crystallinity of the material during cooling.

[0197] The above embodiments and further embodiments and techniques for preforms that have both crystalline and amorphous or semi-crystalline regions are described in US Patent Nos. 6,217,818, Collette et al; 6,428,737, Collette et al .; U.S. Patent Publication No. 2003 / 0031814A1, Hutchinson et al .; and PCT Publication No. WO 98/46410, Koch et al.

C. Detailed description of some beneficial materials

1. General Description of Preferred Materials [0198] In addition, the articles described herein may be described in detail with reference to specific materials such as polyethylene terephthalate (PET) or polypropylene (PP), but preferred methods apply to many other thermoplastics, including polyesters and polyolefins. Other suitable materials include, but are not limited to, foam materials, various polymers and thermosetting materials, thermoplastic materials such as polyesters, polyolefins, including polypropylene and polyethylene, polycarbonates, polyamides, including nylons (e.g., Nylon 6, Nylon 66, MXD6) , polystyrenes, epoxy materials, acrylic materials, copolymers, blends, graft polymers and / or modified polymers (monomers or parts thereof having a different group as a side group, e.g. olefin modified polyesters). These materials can be used alone or in combination with each other. More specific examples of materials include, but are not limited to, a copolymer of ethylene vinyl alcohol ("EVOH"), ethylene and vinyl acetate ("EVA"), ethylene and acrylic acid ("EAA"), linear low density polyethylene (" LLDPE "), poly (2,6- and 1,5-ethylene naphthalene) (PEN), glycol modified polyethylene terephthalate (PETG), poly (cyclohexylene dimethylene terephthalate), polystyrene cycloolefin copolymer, poly-4-methylpentene-1, poly (methyl methacrylate), acrylonitrile, poly (vinyl chloride), poly (vinylidene chloride), styrene-acrylonitrile, acrylonitrile-butadiene-styrene, polyacetal, polyethylene terephthalate, ionomer, polysulfone, polytetrafluoroethylene, 1,2-dioxybenzoate, polytetramethylene ethylene terephthalate and copolymers of ethylene terephthalate

[0199] The term "glycol-modified polyethylene terephthalate" (PETG), as used herein, refers to a PET copolymer in which significant amounts (e.g., about 40% by weight or more) are added to the PET mixture as additional cyclohexanedimethanol comonomer (CHDM). In one embodiment, the preferred PETG material is substantially amorphous. Suitable PETG materials can be purchased from various sources. One suitable source is Voridian, a division of Eastman Chemical Company. Other PET copolymers contain lower levels of CHDM, so that the resulting material remains crystallizable or semicrystalline. One example of a PET copolymer containing low levels of CHDM is Voridian 9921 resin.

[0200] In some embodiments, grafted or modified polymers may be used. In one embodiment, polypropylene or other polymers may be grafted or modified with polar groups to improve adhesion, including, but not limited to, maleic anhydride, glycidyl methacrylate, acrylic methacrylate, and / or similar compounds. In other embodiments, polypropylene also refers to clarified polypropylene. The term "clarified polypropylene," as used herein, is a broad term and is used in its usual sense, and may include, without limitation, polypropylene containing nucleation inhibitors and / or clarifying additives. Clarified polypropylene is a generally transparent material compared to a polypropylene homopolymer or block copolymer. The inclusion of nucleation inhibitors helps prevent and / or reduce crystallinity within polypropylene, which contributes to turbidity of polypropylene. Clarified polypropylene can be purchased from various sources, such as Dow Chemical Co. Alternatively, nucleation inhibitors can be added to the polypropylene. One suitable source of additives - nucleation inhibitors is Schulman.

[0201] Optionally, the materials may contain microstructures, such as microlayers,

Microspheres, and combinations thereof, In some embodiments, preferred materials may be unused, pre-consumer, post-consumer, milled, recycled, and / or combinations thereof.

[0202] The term "PET" as used herein includes, but is not limited to, modified PET and PET mixed with other materials. One example of modified PET is "PET with high IPA content" or IPA modified PET, which refers to PET in which the IPA content is preferably greater than about 2% by weight, including about 2-10% IPA by weight, also including about 5 -10% IPA by weight. PET may be unused, pre- or post-consumer, recycled or milled, and / or combinations thereof, PET copolymers and combinations thereof.

[0203] In preferred methods and processes, one or more layers may include barrier layers, UV protection layers, oxygen scavenging layers, oxygen barrier layers, carbon dioxide scavenging layers, carbon dioxide barrier layers and other layers, depending on needs for the application. The terms "barrier material," "barrier resin," and the like are broad terms and are used herein in their usual sense, and refer, without limitation, to materials that, when used in preferred methods and processes, have lower oxygen permeability and carbon dioxide than one or more layers. The terms "UV protection" and the like are broad terms and are used in their usual sense, and refer, without limitation, to materials that have a higher UV absorption coefficient than one or more layers of an article. The terms "oxygen scavenging" and the like, as used herein, are broad terms and are used in their usual sense, and refer, without limitation, to materials that have a higher oxygen absorption coefficient than one or more layers of an article. The terms "oxygen barrier" and the like, as used herein, are broad terms and are used in their usual sense, and refer, without limitation, to materials that are passive or active in nature and slow down oxygen transmission to and / or from a product. The terms "carbon capture" and the like, as used herein, are broad terms and are used in their usual sense, and refer, without limitation, to materials that have a higher carbon absorption coefficient than one or more layers product. The terms "carbon dioxide barrier" and the like, as used herein, are broad terms and are used in their usual sense, and refer, without limitation, to materials that are passive or active in nature and slow down carbon dioxide transmission to and / or from the product. Without wishing to be bound by theory, applicants believe that in applications in which the carbonated product contained in the product, e.g. carbonated non-alcoholic drink, is over-gassed, the introduction of a carbon dioxide capture substance into one or more layers of the article allows an excess gas saturation of the layer that contains the carbon dioxide capture substance. Thus, when carbon dioxide escapes from the product into the atmosphere, it first leaves the product layer and not the product contained therein. The terms "cross-linked", "cross-linked" and the like, as used herein, are broad terms and are used in their usual sense, and refer, without limitation, to materials and coatings that vary in degree of cross-linking from small to and including fully crosslinked materials, such as thermosetting epoxy. The degree of crosslinking can be adjusted to provide a degree of chemical or mechanical resistance appropriate to the circumstances. The term "binding material" is a broad term, as used herein in its usual sense, and refers, without limitation, to gas, liquid or suspension containing material that helps to bond two materials physically and / or chemically, including adhesives, surface modifying agents, reactive materials and the like, but not limited to them.

EP 1742 785B1

2. Preferred materials [0204] In a preferred embodiment, the materials are thermoplastic materials. A further preferred embodiment includes "phenoxy type thermoplastics". The term "phenoxy type thermoplastics," as used herein, covers a wide range of materials, including those discussed in WO 99/20462. In one embodiment, the materials include thermoplastic epoxy resins (TPE), a subgroup of phenoxy type thermoplastics. Another subgroup of phenoxy type thermoplastics and thermoplastic materials are preferred hydroxyphenoxy ether polymers, of which further preferred material are polyhydroxyamine ether copolymers (PHAEs). See, for example, US Patent Nos. 6,455,116; 6,180,715; 6,011,111; 5,834,078; 5,814,373; 5,464,924; and 5,275,853; see also publications in PCT applications no. WO 99/48962; WO 99/12995; WO 98/29491; and WO 98/14498. In some embodiments, the PHAE materials are TPE.

[0205] Preferably, the phenoxy type thermoplastics used in preferred embodiments include one of the following types:

(1) poly (amidoethers) substituted with a hydroxyl function, having repeating units represented by one of the formulas Ia, Ib or Ic:

<img file="PL1742785T3_D0001.tif" />

<img file="PL1742785T3_D0002.tif" />

or

<img file="PL1742785T3_D0003.tif" />

(2) poly (hydroxyamidoethers) having repeating units represented independently by one of the formulas IIa, IIb or IIc:

<img file="PL1742785T3_D0004.tif" />

EP 1 742 785 B1

<img file="PL1742785T3_D0005.tif" />

Ilb or

<img file="PL1742785T3_D0006.tif" />

(3) amido and hydroxymethyl functional polyethers, having repeating units represented by formula III:

<img file="PL1742785T3_D0007.tif" />

(4) hydroxyfunctional polyethers having repeating units represented by formula IV:

<img file="PL1742785T3_D0008.tif" />

R (5) hydroxyfunctional poly (ether sulfonamides) having repeating units represented by the formula Va or Vb:

<img file="PL1742785T3_D0009.tif" />

<img file="PL1742785T3_D0010.tif" />

<img file="PL1742785T3_D0011.tif" />

OH OH

II

OCH₂CCH₂-N-CH₂ECH₂OAr

RO = S = OR

R² (6) poly (hydroxyestroethers) having repeating units represented by formula VI:

EP 1 742 785 B1

<img file="PL1742785T3_D0012.tif" />

(7) hydroxyphenoxy ether polymers having repeating units represented by formula VII:

<img file="PL1742785T3_D0013.tif" />

(8) poly (hydroxyaminoethers) having repeating units represented by formula VIII:

<img file="PL1742785T3_D0014.tif" />

wherein each of the symbols Ar individually represents a divalent aromatic grouping, a substituted divalent aromatic or heteroaromatic grouping, or a combination of different divalent aromatic groups, substituted aromatic groups, or heteroaromatic groups; R is single hydrogen or a monovalent hydrocarbon group; each of Ar₁ is a divalent aromatic moiety or a combination of divalent aromatic moieties substituted with amide or hydroxymethyl groups; each of Ar₂ is the same as or different from Ar and is a single divalent aromatic grouping, a substituted aromatic group or heteroaromatic grouping, or a combination of different divalent aromatic groups, substituted aromatic groups, or heteroaromatic groups; R₁ is individually a predominantly hydrocarbon moiety such as a divalent aromatic grouping, a substituted divalent aromatic grouping, a divalent heteroaromatic grouping, a divalent alkylene grouping, a substituted divalent alkylene grouping, or a divalent heteroalkylene grouping; or a combination of such a heteroalkylene grouping; R₂is a single monovalent hydrocarbon moiety; A is an amino moiety or a combination of different amino moieties; X is an amino, arylenedioxy, arylene disulfonamide or arylene dicarboxyl moiety or a combination of such moieties; and Ar₃ is a "cardo" grouping represented by any of the following formulas:

EP 1742 785B1

<img file="PL1742785T3_D0015.tif" />

<img file="PL1742785T3_D0016.tif" />

[0206] wherein Y is nothing, a covalent bond, or a linking group, wherein suitable linking groups include, for example, an oxygen atom, a sulfur atom, a carbonyl atom, a sulfonyl group, or a methylene group, or similar bond; n is an integer from about 10 to about 1000; x has a value of 0.01 to 1.0; ay has a value of 0 to 0.5.

and [0207] The term "predominantly hydrocarbon" means a divalent radical that is predominantly hydrocarbon but which optionally contains a small amount of a heteroatom moiety such as oxygen, sulfur, imino, sulfonyl, sulfoxy, and the like.

[0208] Poly (amidoethers) substituted with a hydroxyl functional group represented by formula I are preferably prepared by contacting N, N'-bis (hydroxyphenylamido) alkane or arene with diglycidyl ether as described in US Patent Nos. 5,089,588 and 5,143,998.

[0209] Poly (hydroxyamidoethers) represented by formula II are prepared by contacting a bis (hydroxyphenylamido) alkane or arene or a combination of 2 or more of these

Compounds, such as N, N'-bis (3-hydroxyphenyl) adipinamide or N, N'-bis (3-hydroxyphenyl) glutaramide, with epihalohydrin as described in US Patent No. 5,134,218.

[0210] Amido and hydroxymethyl functionalized polyethers represented by Formula III can be prepared, for example, by reacting diglycidyl ethers, such as bisphenol A diglycidyl ether, with a dihydric phenol having side amide groups,

N-substituted amide and / or hydroxyalkyl, such as 2,2-bis (4-hydroxyphenyl) acetamide and 3,5-dihydroxybenzamide. These polyethers and their preparation are described in US Patent Nos. 5,115,075 and 5,218,075.

[0211] Hydroxy-functional polyethers represented by Formula IV can be produced, for example, by reaction of diglycidyl ether or a combination of diglycidyl ethers with

Of dihydric phenol or a combination of dihydric phenols using the method described in US Patent No. 5,164,472. Alternatively, hydroxyfunctional polyethers are obtained by reacting dihydric phenol or a combination of dihydric phenols with epihalohydrin using the method described by Reinking, Barnabeo and Hale in the Journal of Applied Polymer Science, Vol. 7, p. 2135 (1963).

[0212] Hydroxy-functional poly (ether sulfonamides) represented by the formula V are prepared, for example, by polymerizing N, N'-dialkyl- or N, N'-diaryldisulfonamide with diglycidyl ether, as described in US Patent No. 5,149,768.

[0213] Poly (hydroxyestroethers) represented by Formula VI are prepared by reacting diglycidyl ethers of aliphatic or aromatic diacids, such as diglycidyl terephthalate, or diglycidyl ethers of dihydric phenols with aliphatic or aromatic diacids such as adipic acid or isophthalic acid. These polyesters are described in US Patent No. 5,171,820.

[0214] Hydroxyphenoxy ether polymers represented by formula VII are prepared, for example, by contacting at least one dinucleophilic monomer with at least one diglycidyl ether of cardo bisphenol, such as 9,9-bis (4-hydroxyphenyl) fluorene, phenolphthalein, or phenolphthalimidine, or substituted bisphenol cardo, such as substituted bis (hydroxyphenyl) fluorene, substituted phenolphthalein or substituted phenolphthalimidine, under sufficient conditions to cause the reaction of the nucleophilic moieties of the dinucleophilic monomer with epoxy moieties to form a polymer side chain containing side hydroxyl groups and ether, imine, amino, sulfonamide or ester linkages. These hydroxyphenoxy ether polymers are described in US Patent No. 5,184,373.

[0215] Poly (hydroxyaminoethers) ("PHAE" or polyether amines) represented by formula VIII are prepared by contacting one or more diglycidyl ether of a dihydric phenol with an amine having two amine hydrogens, under conditions sufficient to cause reaction of the amine moieties with epoxy moieties to form a side chain polymer containing amine bonds, ether bonds and hydroxyl side groups. These compounds are described in US Patent No. 5,275,853. For example, polyhydroxyaminoether copolymers can be made from resorcinol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl ether, or mixtures thereof.

[0216] Hydroxyphenoxy ether polymers are products of the condensation reaction of a dihydric polycyclic phenol, such as bisphenol A, and epihalohydrin, and have repeat units represented by formula IV in which Ar is an isopropylidene diphenylene moiety. The method of their preparation is described in US Patent No. 3,305,528, incorporated herein in its entirety by reference. One preferred, non-limiting hydroxyphenoxy ether polymers, PAPHEN 25068-38-6, is commercially available from Phenoxy Associates, Inc. Other preferred phenoxy resins are available from InChem® (Rock Hill, South Carolina), including materials such as the INCHEMREZ product lines^tm PKHH and PKHW, but not limited to them.

[0217] Generally, preferred phenoxy type materials form stable aqueous solutions or dispersions. Preferably, the properties of the solutions / dispersions are not impaired when in contact with water. Materials with a solids content in the range from about 10% to about 50%, including about 15%, 20%, 25%, 30%, 35%, 40% and 45%, and in ranges including such percentages are preferred. Preferably, the material used is dissolved or dispersed in polar solvents. These polar solvents include, but are not limited to, water, alcohols and glycol ethers. See, for example, US Patent Nos. 6,455,116, 6,180,715, and 5,834,078, which describe some preferred solutions and / or dispersions of phenoxy type materials.

[0218] One preferred phenoxy type material is a polyhydroxyaminoether (PHAE) copolymer represented by Formula VIII, dispersion or solution. The dispersion or solution, when applied to a container or preform, significantly reduces the permeation rate of various gases through the container walls in a predictable and well known manner. One of the dispersions or latex made from it contains 10-30 percent solids. The PHAE solution / dispersion can be prepared by mixing or otherwise stirring the PHAE in solution in water with an organic acid, preferably acetic or phosphoric acid, but also including lactic, malic, citric or glycolic acid and / or mixtures thereof. These PHAE solutions / dispersions also include organic acid salts formed by the reaction of polyhydroxyaminoethers with these acids.

[0219] In other preferred embodiments, phenoxy type thermoplastics are mixed or blended with other materials using methods known to those skilled in the art. In some embodiments, a compatibilizer may be added to the mix. When compatibilizers are used, preferably one or more properties of the blends are improved, and such properties include, but are not limited to, color, turbidity, and adhesion between the layer containing the blend and other layers. One preferred blend contains one or more phenoxy type thermoplastics and one or more polyolefin. The preferred polyolefin is polypropylene. In one embodiment, the polypropylene or other polyolefins may be grafted or modified with a polar molecule or monomer, including but not limited to maleic anhydride, glycidyl methacrylate, acrylic methacrylate and / or similar compounds for increased compatibility.

[0220] The following PHAE solutions or dispersions are examples of suitable solutions or dispersions of phenoxy type materials that can be used if one or more resin layers are applied as a liquid, such as by dipping, flow or spray coating, as described in WO 04 / 004929 and U.S. Patent No. 6,676,883. One suitable material is the BLOX® experimental barrier resin, for example XU-19061.00 made with phosphoric acid, manufactured by Dow Chemical Corporation. For this particular PHAE dispersion the following typical characteristics are given: 30% solids, specific density 1.30, pH 4, viscosity 24 centipoise (Brookfield, 60 rpm, LVI, 22 ° C), and particle size between 1,400 and 1,800 angstroms. Other suitable materials include BLOX® 588-29 resins based on resorcinol, also giving excellent results as barrier material. The following typical characteristics are given for this particular dispersion: 30% solids, specific density 1.2, pH 4.0, viscosity 20 centipoise (Brookfield, 60 rpm, LVI, 22 ° C), and particle size between 1500 and 2000 angstroms . Other variations within the polyhydroxyaminoether compounds, such as crystalline versions based on hydroquinone diglycidyl ethers, may be useful. Other suitable materials include polyhydroxyaminoether solutions / dispersions from Imperial Chemical Industries ("ICI," Ohio, USA) available under the name OXYBLOK. In one embodiment, PHAE solutions or dispersions can be cross-linked (semi-cross-linked), completely or exactly to the desired degree, depending on what is appropriate for the particular application, by adding the appropriate cross-linking material. Advantages of crosslinking include, but are not limited to: improved chemical resistance, improved abrasion resistance, low cloudiness, low surface tension. Examples of crosslinking materials include, but are not limited to, formaldehyde, acetaldehyde, or other members of the aldehyde material family. Appropriate crosslinking agents may also allow a change in T_g material, which may facilitate the formation of specific containers. Other suitable materials include BLOX® 5000 resin dispersion, BLOX® XUR 588-29, BLOX® 0000 and 4000 series resins. Solvents used to dissolve these materials include, but are not limited to, polar solvents such

Like alcohols, water, glycol ethers or mixtures thereof. Other suitable materials include, but are not limited to, BLOX®Rl.

[0221] In one embodiment, preferred phenoxy type thermoplastics are soluble in aqueous acid. The polymer solution / dispersion can be made by mixing or otherwise stirring the thermoplastic epoxy material in solution in water with an organic acid, preferably acetic or phosphoric acid, but also including lactic, malic, citric or glycolic acid and / or mixtures thereof. In a preferred embodiment, the acid concentration in the polymer solution is preferably in the range of about 5% -20%, including about 5% -10% by weight based on the total weight. In other preferred embodiments, the acid concentration may be below about 5% or above about 20%; and may vary depending on factors such as the type of polymer and its molecular weight. In other preferred embodiments, the acid concentration ranges from about 2.5 to about 5% by weight. The amount of dissolved polymer in a preferred embodiment ranges from about 0.1% to about 40%. A homogeneous and free flowing polymer solution is preferred. In one embodiment, a 10% polymer solution is prepared in a 10% acetic acid solution at 90 ° C. The still hot solution is then diluted with 20% distilled water to give an 8% polymer solution. At higher polymer concentrations, the polymer solution tends to be more viscous.

[0222] Examples of preferred copolyester materials and their method of preparation are described in US Patent No. 4,578,295 issued by Jabarin. They are generally produced by heating a mixture of at least one reagent selected from isophthalic acid, terephthalic acid and their C esters₁ to C.₄ alkyl with 1,3 bis (2-hydroxyethoxy) benzene and ethylene glycol. Optionally, the mixture may further contain one or more ester forming dihydroxy hydrocarbons and / or bis (4-hydroxyethoxyphenyl) sulfone. Particularly preferred copolyester materials are available from Mitsui Petrochemical Ind. Ltd. (Japan) as B-OlO, B-030 and others from this family.

[0223] Examples of preferred polyamide materials include MXD-6 from Mitsubishi Gas Chemical (Japan). Other preferred polyamide materials include Nylon 6 and Nylon 66. Other preferred polyamide materials are blends of polyamide and polyester, including those containing about 1-20% by weight polyester, more preferably about 110% by weight polyester, where the polyester is preferably PET or modified PET. In another embodiment, preferred polyamide materials are blends of polyamide and polyester, including those containing about 1-20% by weight polyamide, more preferably about 1-10% by weight polyamide, where the polyester is preferably PET or modified PET. The mixtures may be ordinary mixtures or they may be compatible with an antioxidant or other material. Examples of such materials include those described in US Patent Publication No. 2004/0013833, filed March 21, 2003, which is hereby incorporated in its entirety by reference. Other preferred polyesters include, but are not limited to, PEN and PET / PEN copolymers.

3. Preferred foam materials [0224] The term "foam material," as used herein, is a broad term and is used in its usual sense, and may include, without such limitation, a foaming agent, a mixture of a foaming agent and a binding material or carrier, expandable material cellular, and / or material having pores. The terms "foam material" and "expandable material" are used interchangeably herein. Preferred foam materials may exhibit one or more physical characteristics that improve the thermal and / or structural characteristics of the products (e.g. containers) and may enable preferred embodiments to be able to withstand the processing and physical loads that typically affect containers. In one embodiment, the foam material provides structural support for the container. In another embodiment, the foam material forms

A protective layer that reduces damage to the container during processing. For example, foam material may provide abrasion resistance of the container during transport. In one embodiment, the protective foam layer may increase the shock resistance or impact strength of the container, and thus prevent or reduce damage to the container. In addition, in another embodiment, the foam can provide a comfortable gripping surface and / or increase the aesthetics or attractiveness of the container.

[0225] In one embodiment, the foam material comprises a foaming or blowing agent and a carrier material. In one preferred embodiment, the foaming agent comprises expandable structures (e.g., microspheres) that can be expanded and interact with the carrier material to form foam. For example, the foaming agent may be thermoplastic microspheres, such as EXPANCEL® microspheres sold by Akzo Nobel. In one embodiment, the microspheres can be thermoplastic hollow spheres containing thermoplastic shells that surround a gas. Preferably, when the microspheres are heated, the thermoplastic shell softens and the gas pressure increases, causing the microspheres to expand from the initial position to the expanded position. The expanded microspheres and at least a portion of the carrier material may form a foam portion of the products described herein. The foam material can form a layer that contains a single material (e.g., a generally homogeneous mixture of a foaming agent and support material), a blend or blend of materials, a matrix formed of two or more materials, two or more layers, or multiple microlayers (lamellas), preferably containing at least two different materials. Alternatively, the microspheres may be any suitable material expandable in a controlled manner. For example, the microspheres can be structures containing materials that produce gas in or out of structures. In one embodiment, the microspheres are hollow structures containing chemicals that produce or contain gas, in which an increase in gas pressure causes the expansion and / or bursting of the structures. In another embodiment, the microspheres are structures made of and / or containing one or more materials that break down or react to form gas, thereby expanding and / or bursting the microspheres. Optionally, the microsphere may be a generally solid structure. Optionally, the microspheres may be shells filled with solids, liquids and / or gases. The microspheres can be of any configuration and shape suitable to form a foam. For example, microspheres can be generally spherical. Optionally, the microspheres can be elongated or oblique spheroids. Optionally, the microspheres may contain any gas or gas mixtures suitable for expanding the microspheres. In one embodiment, the gas may be an inert gas such as nitrogen. In one embodiment, the gas is generally non-flammable. However, in some embodiments, the microsphere shells may be filled with inert and / or combustible gas. In some embodiments, the foam material may contain foaming or blowing agents such as are known in the art. In addition, the foam material may be mainly or completely a foaming agent.

[0226] Although some preferred embodiments contain microspheres that do not break or break, other embodiments contain microspheres that break, break, break and / or the like. Optionally, some of the microspheres may break while the remainder of the microspheres may not break. In some embodiments, it breaks to about 0.5%, 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30%, 40%, 50%, 60% 70%, 80%, 90 % by weight of microspheres, and ranges including these amounts. In one embodiment, for example, a substantial portion of the microspheres may burst and / or break during expansion. Additionally, blends and blends of microspheres can be used to make foam material.

[0227] The microspheres can be formed from any material suitable for causing expansion. In one embodiment, the microspheres may have a shell containing a polymer, resin, thermoplastic, thermosetting material, or the like as described herein. The microsphere shell may contain a single material or

A mix of two or more different materials. For example, the microspheres may have an outer shell comprising ethylene-vinyl acetate copolymer ("EVA"), polyethylene terephthalate ("PET"), polyamides (e.g., Nylon 6 and Nylon 66), glycol modified polyethylene terephthalate (PETG), PEN, copolymers PET, and their combinations. In one embodiment, the PET copolymer contains a CHDM comonomer in an amount between what is usually called PETG and PET. In another embodiment, comonomers such as DEG and IPA are added to the shell of the microspheres. A suitable combination of material type, size and inert gas can be selected to achieve the desired expansion of the microspheres. In one embodiment, the microspheres are shells formed of high temperature material (e.g., PETG or similar material) which, when subjected to high temperatures, is able to expand, preferably without causing the microspheres to burst. If the microspheres have a shell made of a low-temperature material (e.g. EVA), the microspheres may break when subjected to high temperatures that are suitable for processing some carrier materials (e.g. PET or polypropylene having a high melting point). Under certain circumstances, for example, EXPANCEL® microspheres may break when processed at relatively high temperatures. Advantageously, medium-temperature or high-temperature microspheres can be used with a carrier material having a relatively high melting point, in a controlled manner to produce expandable foam material without breaking the microspheres. For example, the microspheres may contain medium temperature (e.g. PETG) or high temperature material (e.g. acrylonitrile) and may be suitable for relatively high temperature applications. Thus, the blowing agent for foaming polymers can be selected depending on the processing temperatures used.

[0228] The foam material may be a matrix containing a carrier material, preferably a material that can be mixed with a blowing agent (e.g., microspheres) to form an expandable material. The support material may be a thermoplastic, thermosetting material, or polymeric material such as ethylene / acrylic acid copolymer ("EAA"), ethylene / vinyl acetate copolymer ("EVA"), linear low density polyethylene ("LLDPE"), polyethylene polyethylene terephthalate glycol-modified ethylene (PETG), poly (hydroxyaminoethers) ("PHAE"), PET, polyethylene, polypropylene, polystyrene ("PS"), pulp (e.g. pulp of wood or paper, or pulp mixed with one or more polymers), mixtures thereof, and the like. However, other materials suitable as carriers for the foaming agent may be used to achieve one or more desired thermal, structural, optical and / or other foam characteristics. In some embodiments, the carrier material has properties (e.g. high alloying number) for easier and quick expansion of microspheres, which shortens the time cycle, which results in increased production.

[0229] In preferred embodiments, the formable material may contain two or more ingredients, including a plurality of ingredients, having each other processing window and / or physical properties. The ingredients can be combined so that the moldable material has one or more desirable characteristics. The proportions of the ingredients can be changed to obtain the desired processing window and / or physical properties. For example, the first material may have a processing window similar or different to the processing window of the second material. The processing window may be based, for example, on pressure, temperature, viscosity, or the like. Thus, the components of the formable material can be mixed to obtain the desired range, e.g., pressure or temperature, to shape the material.

[0230] In one embodiment, the combination of the first material and the second material may give a material having a processing window more desirable than a processing window of the second material. For example, the first material may be suitable for processing in a wide range of temperatures, and the second material may be suitable for processing in

Narrow temperature range. A material having a portion formed from the first material and another portion formed from the second material may be suitable for processing in a temperature range that is wider than the narrow processing range of the second material. In one embodiment, the multi-component material processing window is similar to the first material processing window. In one embodiment, the formable material is a multilayer sheet or tube, comprising a layer comprising PET and a layer comprising polypropylene. Material formed from PET and polypropylene can be processed (e.g. extruded) in a wide temperature range similar to the range of processing temperatures suitable for PET. The processing window may be a window for one or more parameters such as pressure, temperature, viscosity, and / or the like.

[0231] Optionally, the amount of each material component can be varied to obtain the desired processing window. Optionally, the materials can be combined to produce formable material suitable for processing in a desired wide range of pressure, temperature, viscosity and / or the like. For example, the proportion of material having a more desirable processing window may be increased, and the proportion of material having a less desirable processing window may be reduced so as to obtain material having a processing window that is very similar to the processing window of the first material or substantially the same. Of course, if a more desirable processing window is located between the first processing window of the first material and the second processing window of the second material, the proportion of the first and second materials may be selected to obtain the desired processing window of the formable material.

[0232] Optionally, a plurality of materials may be combined, each having a similar or different processing window, to obtain the desired processing window for the material so obtained.

[0233] In one embodiment, the rheological features of the formable material can be changed by changing one or more of its components having different rheological features. For example, the substrate (e.g. PP) may have a high alloying number and is extrudable. PP can be combined with other material, such as PET, which has a low alloying number, which makes it difficult to extrude, creating a material suitable for extrusion processes. For example, a layer of PP or other strong material may form the substrate for the PET layer during co-extrusion (e.g., horizontal or vertical co-extrusion). Thus, moldable material formed of PET and polypropylene can be processed, e.g. extruded, in a temperature range generally suitable for PP and generally not suitable for PET.

[0234] In some embodiments, the composition of the formable material may be selected to affect one or more properties of the articles. For example, using the formable materials described herein, thermal properties, structural properties, barrier properties, optical properties, rheological properties, favorable aromatic properties, and / or other properties or characteristics disclosed herein may be obtained.

4. Additives for materials that improve their properties [0235] The advantage of the preferred methods disclosed herein is their flexibility, allowing the use of many functional additives. Additives known to those skilled in the art for their ability to provide a CO barrier may be used₂, barriers for Fr.₂, UV protection, scratch resistance, turbidity resistance, impact strength and / or chemical resistance.

[0236] Preferred additives may be prepared by methods known to those skilled in the art. For example, additives can be mixed directly with a specific material, they can be dissolved / dispersed separately and then added to the specific material,

Or they may be combined with specific material to be added to the solvent that forms the solution / dispersion of the material. In addition, in some embodiments, the preferred additives can be used alone as a single layer.

[0237] In preferred embodiments, the barrier properties of the layer can be increased by the addition of various additives. The additives are preferably present in an amount of up to about 40% of the material, also including up to about 30%, 20%, 10%, 5%, 2% and 1% by weight of the material. In other embodiments, the additives are preferably present in an amount less than or equal to 1% by weight, preferred ranges of materials include, but are not limited to, about 0.01% to about 1%, about 0.01% to about 0.1%, and about 0.1% to about 1% by weight. In addition, in some embodiments, the additives are preferably stable under water conditions. For example, resorcinol (m-dihydroxybenzene) derivatives can be used in combination with various preferred materials as blends or as additives or monomers for the production of the material. The higher the resorcinol content, the greater the barrier properties of the material. For example, resorcinol diglycidyl ether can be used in PHAE, and resorcinol hydroxyethyl ether can be used in PET and other polyester and copolyester barrier materials.

[0238] Another additive that can be used are "nanoparticles" or "nanoparticle material". For convenience, the term nanoparticles will be used herein to refer to both nanoparticles and nanoparticle material. These nanoparticles are tiny particles of materials with a micron or submicron size (diameter) that increase the barrier properties of the material by creating a more tortuous path for migrating gas particles, e.g. oxygen or carbon dioxide that they must pass as they pass through the material. In preferred embodiments, the nanoparticle material is present in amounts ranging from 0.05 to 1% by weight, including 0.1%, 0.5% by weight, and ranges including these amounts.

[0239] One preferred type of nanoparticle material is a microparticle clay based product, available from Southern Clay Products. One of the preferred product lines available from Southern Clay are Cloisite® nanoparticles. In one embodiment, preferred nanoparticles are montmorillonite modified with a quaternary ammonium salt. In another embodiment, the nanoparticles are montmorillonite modified with a tertiary ammonium salt. In other embodiments, the nanoparticles are natural montmorillonite. In further embodiments, the nanoparticles are organic clays as described in US Patent No. 5,780,376, the disclosure of which is herein incorporated by reference and forms part of the present application. Other suitable organic and inorganic products based on micronized clay may also be used. Artificial and natural products are also suitable.

[0240] Another type of preferred nanoparticle material is metal composite material. For example, one of the relevant composites is an aqueous dispersion of alumina in nanosized form available from BYK Chemie (Germany). It is believed that this type of nanoparticle material provides one or more of the following advantages: increased abrasion resistance, increased scratch resistance, increased Tg, and thermal stability.

[0241] Another type of preferred nanoparticle material is a polysilicate composite. In preferred embodiments, the silicate is montmorillonite. Suitable polymer-silicate nanoparticle materials are available from Nanocor and RTP Company.

[0242] In preferred embodiments, the UV protective properties of the material may be increased before the addition of various additives. In a preferred embodiment, the UV protective material used provides UV protection up to about 350 nm or less, preferably about 370 nm or less, more preferably about 400 nm or less. UV protection material can be used as an additive with additional layers

Functionality or applied separately as a single layer. Preferably, additives that provide increased UV protection are present in the material in an amount of from about 0.05 to 20% by weight, but also including about 0.1%, 0.5%, 1%, 2%, 3%, 5%, 10%, and 15% by weight, and ranges covering these amounts. Preferably, the UV protective material is added in a form that is compatible with other materials. For example, the preferred UV protection material is UV390A ClearShield® from Milliken. UV390A is an oily liquid whose mixing is assisted by first mixing this liquid with water, preferably approximately equal parts by volume. This mix is ​​then added to a material solution, for example BLOX® 599-29, and mixed. The resulting solution contains about 10% UV390A and when applied to a PET preform, it provides UV protection up to 390 nm. As described previously, in another embodiment, the UV390A solution is applied as an independent layer. In other embodiments, the preferred UV protective material is a polymer grafted or modified with a UV absorber, which is added as a concentrate. Other preferred UV protection materials are, but are not limited to, benzotriazoles, phenothiazines and azafenothiazines. UV protection materials may be added during the melt phase of the process prior to use, e.g. before injection molding or extrusion, or added directly to the coating material that is in the form of a solution or dispersion. Suitable UV protection materials are available from Milliken, Ciba and Clariant.

[0243] In preferred embodiments, the materials can be given Co capture properties₂. In one preferred embodiment, such properties are obtained by incorporating an active amine that will react with CO₂, forming a salt with high gas barrier. This salt will then act as a passive barrier to CO₂. The active amine may be an additive or may be one or more moieties of thermoplastic resin material forming one or more layers.

[0244] In preferred embodiments, preferred materials may be given O-scavenging properties₂, by introducing capture substances₂such as anthraquinone and others known in the art. In another embodiment, one of the appropriate scavengers O₂ is AMOSORB®, available from BP Amoco Corporation and ColorMatrix Corporation, which is disclosed in US Patent No. 6,083,585 Cahill et al., the disclosure of which is hereby incorporated in its entirety by reference. In one embodiment, the capture properties of O₂ are imparted to preferred phenoxy type materials or other materials by incorporating O-scavengers into the phenoxy type material₂ with different activation mechanisms. Preferred capture substances₂ they can act spontaneously, gradually or have delayed action up to initiation by a specific trigger. In some embodiments, the capture substances O₂ are activated by exposure to UV or water (e.g. present in the contents of the container), or by a combination of both. Capture substance O₂ is preferably present in an amount of from about 0.1 to about 20 weight percent, more preferably in an amount of from about 0.5 to about 10 weight percent, and most preferably, in an amount of about 1 to about 5 weight percent, based on total weight of the coating layer.

[0245] In another preferred embodiment, a coating or top layer is applied to impart chemical resistance to stronger chemical substances compared to the protection provided by the outer layer. In some embodiments, preferably these coatings or top layers form aqueous or non-aqueous acrylic polyesters or polymers that are optionally partially or completely cross-linked. The preferred water-based polyester is polyethylene terephthalate, however other polyesters may also be used. In some embodiments, the topcoat application process is the process disclosed in US Patent Publication No. 2004/0071885, entitled Dip, Spray, And Flow Coating Process For Forming Coated Articles, the disclosure of which is herein incorporated by reference in its entirety.

[0246] A preferred aqueous based polyester resin is described in U.S. Patent No. 4,977,191 (Salsman), herein incorporated by reference. More specifically, US Patent No. 4,977,191 describes an aqueous based polyester resin containing a reaction product of 20-50% by weight of waste terephthalate polymer, 10-40% by weight of at least one glycol and 5-25% by weight of at least one alkoxylated polyol.

[0247] Another preferred aqueous based polymer is an aqueous based sulfonated polyester resin composition that is described in US Patent No. 5,281,630 (Salsman), herein incorporated by reference. More specifically, US Patent No. 5,281,630 describes an aqueous suspension of a water-soluble or water-dispersible sulfonated polyester resin that is a reaction product of 20-50% by weight of terephthalate polymer, 10-40% by weight of at least one glycol and 5-25% by weight of at least one alkoxylated polyol to form a prepolymer resin having hydroxyalkyl functional groups, which prepolymer resin is further reacted with about 0.10 moles to about 0.50 moles of alpha, beta-ethylenically unsaturated dicarboxylic acid per 100 g of prepolymer resin, and the resin thus prepared, with terminal residues of alpha, beta-ethylenically unsaturated acid dicarboxylic acid is reacted with about 0.5 moles to about 1.5 moles of sulfite per mole of alpha, beta-ethylenically unsaturated dicarboxylic acid residues to form a resin with sulfonated terminal groups.

[0248] Still another preferred aqueous based polymer is the coating described in US Patent No. 5,726,277 (Salsman), hereby incorporated by reference. More specifically, US Patent No. 5,726,277 describes coating compositions comprising a reaction product of at least 50% by weight of waste terephthalate polymer and a glycol mixture containing an oxyalkylated polyol in the presence of a glycolysis catalyst, which reaction product is further reacted with a bifunctional organic acid, and in which a weight ratio acid to glycols ranges from 6: 1 to 1: 2.

[0249] Although the above examples are shown as preferred aqueous based polymer coating compositions, there are other aqueous based polymers suitable for use in the products and methods described herein. By way of example only and without limitation, further suitable aqueous based compositions are described in U.S. Patent No. 4,104,222 (Date, et al.), Herein incorporated by reference. U.S. Patent No. 4,104,222 describes a dispersion of a linear polyester resin obtained by mixing a linear polyester resin with a higher alcohol and ethylene oxide adduct surfactant, melting the mixture, and dispersing the resulting alloy by pouring it into an alkaline aqueous solution under stirring. More specifically, this dispersion is obtained by mixing a linear polyester resin with a higher alcohol and ethylene oxide adduct surfactant, melting the mixture and dispersing the resulting alloy by pouring it into an aqueous alkanolamine solution under stirring at 70-95 ° C. what said alkanolamine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monomethylethanolamine, monoethylethanolamine, diethylethanolamine, propanolamine, butanolamine, pentanolamine, N-phenylethanolamine, and glycerol alkanolamine, and said alkanolamine is present in an aqueous solution in an amount of 0.2 to 5 percent by weight, said surfactant of the higher alcohol and ethylene oxide adduct type is an addition product ethylene oxide for a higher alcohol having an alkyl group with at least 8 carbon atoms, alkyl substituted phenol or phenol monoacylate and the surfactant has an HLB value of at least 12.

[0250] Similarly, for example, US Patent No. 4,528,321 (Allen) discloses a dispersion of water-soluble or water-swellable polymer particles in a non-liquid liquid.

Water miscible which has been produced by reverse phase polymerization in a water-immiscible liquid and which contains a nonionic compound selected from C glycol monoethers_4-12 alkylene, their C_1-4 alkanates, C6- glycol monoethers₁₂ polyalkylene and their C_1-4 alkanoates.

[0251] Materials of some embodiments may be crosslinked to improve thermal stability for various applications, for example, hot fill applications. In one embodiment, the inner layers may contain weakly crosslinked materials, and the outer layers may contain highly crosslinked materials or other suitable combinations. For example, non-crosslinked or lightly crosslinked material, such as BLOX® 588-29, can be used in the inner coating on PET surface, and another material, such as EXP 12468-4B from ICI, capable of crosslinking can be used in the outer coating to provide maximum crosslinking adhesion to PET. Appropriate cross-linkable additives may be added to one or more layers. Suitable crosslinkers may be selected depending on the chemical structure and functionality of the resins or material to which they are added. For example, amine crosslinkers may be useful for crosslinking resins containing epoxy groups. Preferably, crosslinkers, if present, are present in an amount of from about 1% to 10% by weight of the coating solution / dispersion, preferably from about 1% to 5%, more preferably from about 0.01% to 0.1% by weight, also including 2%, 3%, 4%, 6%, 7%, 8%, and 9% by weight. Optionally, thermoplastic epoxy material (TPE) used with one or more crosslinkers may be used. In some embodiments, the means (e.g. carbon black) can also be coated on TPE material or introduced into it. TPE material may form part of the products disclosed herein. It is contemplated that carbon black or other additives may be used in other polymers to improve material properties.

[0252] Materials of some embodiments may optionally contain a crosslinker. The term "crosslinking agent" as used herein is a broad term and is used in its usual sense and includes, without such limitation, a chemical crosslinking catalyst, thermal amplifier, and the like. The term "thermal amplifier," as used herein, is a broad term and is used in its usual sense, and includes, without such limitation, transition metals, transition metal compounds, radiation absorbing additives (e.g., carbon black). Suitable transition metals include, but not limited to cobalt, rhodium and copper Suitable transition metal compounds include, but are not limited to, metal carboxylates. Preferred metal carboxylates include, but are not limited to, neodecanoate, octoate and acetate. Thermal amplifiers can be used alone or in combination with one or more other thermal amplifiers.

[0253] A thermal amplifier may be added to the material and may significantly increase the material temperature during the crosslinking process compared to material without a thermal amplifier. For example, in some embodiments, a heat enhancer (e.g., carbon black) may be added to the polymer such that the temperature of the polymer undergoing crosslinking (e.g. by IR irradiation) was much higher than the temperature of the polymer without a thermal amplifier subjected to the same or similar crosslinking process. The increased polymer temperature, caused by the thermal amplifier, can increase the crosslinking speed and therefore increase the production speed. In some embodiments, the thermal amplifier generally has a higher temperature than at least one of the product layers when the thermal amplifier and the article are heated by means of a heating device (e.g., an infrared heating device).

[0254] In some embodiments, the thermal enhancer is present in an amount of about 5 to 800 ppm, preferably about 20 to about 150 ppm, preferably about 50 to 125 ppm,

Preferably about 75 to 100 ppm, also including about 10, 20, 30, 40, 50, 75, 100, 125, 150, 175, 200, 300, 400, 500, 600, and 700 ppm and ranges covering these quantities. The amount of thermal amplifier can be calculated relative to the weight of the layer that contains the thermal amplifier or the total weight of all the layers that make up the product.

[0255] In some embodiments, the preferred thermal enhancer is carbon black. In one embodiment, carbon black may be used as an ingredient in the coating material to increase crosslinking of the coating material. Carbon black, when used as a component of a coating material, is added to one or more coating materials before, during, and / or after the coating material (e.g., impregnation, coating, etc.) has been applied to the product. Preferably, carbon black is added to the coating material and mixed to ensure thorough mixing. The thermal amplifier may contain additional materials to achieve the desired properties of the product material.

[0256] In another embodiment, when carbon black is used in the injection molding process, carbon black may be added to the molten polymer blend.

[0257] In some embodiments, the polymer contains about 5 to 800 ppm, preferably about 20 to about 150 ppm, preferably about 50 to 125 ppm, preferably about 75 to 100 ppm, also including about 10, 20, 30, 40, 50 , 75, 100, 125, 150, 175, 200, 300, 400, 500, 600, and 700 ppm thermal amplifier and ranges covering these amounts. In a further embodiment, the coating material is crosslinked using radiation, such as infrared (IR) heating. In preferred embodiments, IR heating provides a more effective coating than crosslinking using other methods. Other heat enhancers and crosslinking and methods of use are disclosed in U.S. Patent Application No. 10 / 983,150, filed November 5, 2004, entitled "Catalyzed Process for Forming Coated Articles," the disclosure of which is hereby incorporated by reference.

[0258] In some embodiments, it is desirable to add anti-foam / anti-bubble agents. In some embodiments that use solutions or dispersions, these solutions or dispersions form foam and / or bubbles that interfere with preferred processes. One way to avoid this interference is to add anti-foaming / anti-bubble agents to the solution / dispersion. Suitable anti-foaming agents include, but are not limited to, nonionic surfactants, ethylene oxide based materials, siloxane based materials, and ionic surfactants. Preferably, anti-foaming agents, if present, are present in an amount of from about 0.01% to about 0.3% solution / dispersion, preferably about 0.01% to about 0.2%, but also including about 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.25%, and ranges covering these amounts .

[0259] In another embodiment, anti-foaming agents may be added to the coating materials to foam the coating layer. In a further embodiment, a foaming agent reaction product is used. Useful foaming agents include, but are not limited to, azobisformamide, azobisisobutyronitrile, diazoaminobenzene, N, N-dimethyl-N, N-dinitrosoterephthalamide, N, N-dinitrosopentamethylene tetraamine, benzenesulfonylhydrazide, benzene-1,3-disulfonylsulfonylsulfonyl disulfonyl hydrazide, 4,4'-oxybisbenzenesulfonyl hydrazide, p-toluenesulfonylsemicarbazide, barium azodicarboxylate, butylaminonitrile, nitroureas, trihydrazinitrazine, phenylmethylurethane, p-sulfonylhydrazide, peroxides, ammonium bicarbonate, and sodium bicarbonate. As currently considered, commercially available foaming agents include, but are not limited to, EXPANCEL®, CELOGEN®, HYDROCEROL®, MIKROFINE®, CEL-SPAN®, and PLASTRON® FOAM.

[0260] The foaming agent is preferably present in the coating material in an amount of from about 1 to about 20 weight percent, more preferably from about 1 to about 10 weight percent, and most preferably from about 1 to about 5 weight percent, in relation to the weight of the coating layer. Instead of the conventional foaming agents mentioned above, newer technologies known to those skilled in the art using compressed gas may be used as an alternative foam generating agent.

[0261] The tie layer is preferably a polymer having functional groups such as anhydrides and epoxides that react with carboxyl and / or hydroxyl groups on PET polymer chains. Useful materials for the tie layer include, but are not limited to, BYNEL® from DuPont, ADMER® from Mitsui, EPOLINE from Eastman, LOTADER from Arkema and EVELOY® from ExxonMobil.

D. Methods and systems for producing lamellar material [0262] The multi-component layer or article may also be made of a lamellar melt stream, which preferably contains at least two components. The term "lamellar melt stream" as used herein includes, but is not limited to, an melt stream comprising at least two layers in which the layers in the melt stream are generally parallel. Although the lamellar melt stream may contain only two layers, the lamellar melt stream may contain, and preferably contain, a plurality of thin layers. When the lamellar melt stream is made of two materials, the melt stream preferably generally has successive thin layers of two materials. The materials used to form the lamellar melt stream are preferably polymers such as thermoplastic polymers, including polyester, polyolefin, phenoxy and other materials as described herein. Layer materials may also contain mixtures of two or more materials. Layer materials may also contain additives such as nanoparticles, free radical scavengers, UV absorbents, compatibilizers, and the like. In one embodiment, the lamellar melt stream comprises recycled polyester, such as recycled PET, and barrier material.

[0263] One method of forming a lamellar melt stream uses a system similar to that disclosed in many US patents granted to Schrenka, numbers 5,202,074, 5,540,878, and 5,628,950, the disclosures of which are incorporated herein in their entirety by reference, although currently considering the use of this method as well as other methods of producing lamellar melt flux. With reference to FIGURE 27, an embodiment of the system 482 for generating the lamellar melt stream is schematically shown. The arrangement in FIGURE 27 illustrates one embodiment of the arrangement for two materials, but it will be understood that the arrangement for three or more materials will function in a similar manner. The two materials to form the layers are placed in separate hoppers or inlets 484 and 485, which feed two separate extruders 486 and 487, respectively. In a preferred embodiment, extruders 486 and 487 are screw extruders in which a combination of heat and pressure can be used to convert raw materials into an alloy. The materials are extruded at such speeds and thicknesses to obtain the desired relative amounts of each material and the melt streams from the extruders are combined to form a double-layer 488 melt stream consisting of layers from each cylinder, preferably arranged so that one layer lies on top of the second layer.

[0264] Next, the two-layer melt stream 488 coming out of the connected cylinders is preferably fed to a 490 layer multiplication system. In the illustrated 490 layer multiplication system, the two-layer alloy 488 stream is multiplied to a multi-layer 492 alloy stream that has 10 layers in the illustrated embodiment, shown in FIGURE 27A. The drawing of FIGURE 27A is schematic and somewhat idealistic in that in that although the layers of lamellar material are on average preferably generally parallel to each other, the lamellar material may contain layers,

Which are not parallel to each other and / or layers may generally be parallel at some points and non-parallel at others.

[0265] The multiplication of the layers can be carried out by any of a number of methods. In one embodiment, the alloy stream section is first divided into two pieces perpendicular to the contact surface of the two layers. The two pieces are then flattened so that each of the two pieces is approximately as long as the exit section before it is divided in half in the first stage, but only has half the thickness of the exit section. Then the two pieces are reassembled into one, having similar dimensions as the exit section, but having four layers, by stacking one piece on top of another piece in such a way that the sublayers of the two materials are parallel to each other (i.e. stacking in perpendicular to the alloy flow layer). In order to create thinner layers, these splitting, flattening and recombining steps of the alloy stream can be carried out several times. The melt stream can be multiplied by repeatedly splitting, flattening, and recombining to produce a single melt stream consisting of multiple sub-layers of constituent materials. In this two-material version, the composition of the layers will alternate from one material to another. Other methods for producing layers include performing steps similar to those outlined above, but flattening the melt stream before or after recombining it. Alternatively, instead of dividing the alloy stream into sections, you can wrap it up on each other instead of dividing it. A combination of dividing and wrapping can also be used, but it should be noted that slightly different results are achieved by wrapping and dividing because wrapping will double one layer back on itself. The output from the layer multiplication system passes through an orifice 494, such as a nozzle or valve, and is used to form the article or multi-component layer in the article, such as by injecting or introducing a lamellar melt stream into the mold.

[0266] In the illustrated bimaterial embodiment, the composition of the layer generally alternates from one material to another. However, in other embodiments, any number of materials can be combined into a complex melt stream and then delivered to a 490 layer multiplication system that can produce a lamellar melt stream with any desired number and / or size of repeating blocks or stacks of materials. For example, in one embodiment, the 482 system includes three extruders that simultaneously supply material to the 490 layer multiplication system. The 490 layer multiplication system can form a stack of layers formed from three materials.

[0267] When the lamellar melt stream contains one or more materials that provide gas barrier properties, it is preferred that the lamellar melt stream is used in a manner that orientates it so that the melt stream layers are generally parallel to one or more wide surfaces product. For example, in the preform or container, the layers are preferably generally parallel to the length of the wall section or body portion. Although parallel orientation is preferred, other orientations may be used and are within the scope of the present disclosure. For example, one or more portions of the container wall may have layers that are parallel to each other and to the wall surface, while one or more other portions have layers that are not parallel to each other. The desired winding path through the container wall is determined by the orientation and shape of the layers forming the container. For example, layers that are parallel to each other and to the wall surface can significantly increase the path length through the wall to pass through the gas molecule. Alternatively, layers that are parallel to each other and transverse to the wall result in a shorter or reduced winding fluid path through the wall and would therefore have weaker barrier properties than the same parallel oriented alloy flow.

[0268] Products, such as the containers and preforms disclosed herein, can be formed using a lamellar melt stream coming out of a system such as the one illustrated. In some embodiments, the lamellar alloy contains materials that have generally similar melt temperatures, T_m, for convenient processing and forming. However, the lamellar alloy may contain materials that have substantially different T_m. For example, lamellar material may contain materials that have T_m in the range of about 500 ° F (about 260 ° C). Materials of lamellar material can be selected based on thermal properties, structural properties, barrier properties, rheological properties, processing properties and / or other material properties. Preferably, the lamellar alloy can be formed and cooled before one or more of the components is significantly degraded. The skilled person can select materials forming the lamellar material so as to obtain the desired material stability, appropriate for the processing characteristics and selected end use.

E. Methods and devices for making preferred products [0269] Monolayer and multilayer products (including packaging, such as closures, preforms, containers, bottles) can be produced by a molding process (e.g. injection, including co-injection). One method of making multilayered products is generally referred to as overmolding here, and sometimes as "inject-over-inject" ("IOI"). The name refers to a procedure in which injection is used to inject one or more layers of material onto an existing layer, which has preferably been produced by injection alone. Here, the terms "overmolding" and "overmolding" are used to describe the coating process of injecting a layer of material onto an existing layer or preform.

[0270] One overmolding method for making preforms involves using an injection molding machine in combination with a mold comprising a mandrel or core and a die. The first preform layer is formed between the core and the first matrix of the mold by injection of a molten polymer (i.e. a polymer alloy) into the cavity of the mold. The first layer remains on the core while the mandrel is pulled out of the matrix, transferred and introduced into the second mold matrix. Then a second material layer is injected onto the existing first preform layer. The mandrel and associated preform are then removed from the second matrix and the preform removed from the mandrel.

[0271] In some embodiments, the overmoulding process is performed while the underlying layer has not yet been completely cooled. The underlying layer may have retained internal heat from the injection process in which the underlying layer was produced. In some embodiments, the underlying layer may be at room temperature or at any other temperature suitable for overmolding. For example, products at room temperature can be overmolded with one or more layers of material. These products may be stored for a longer period of time before overmolding.

[0272] Spraying can be used to place one or more layers of material (s), such as those containing PP, expandable / foam material, PET (including recycled PET, unused PET), lamellar material, barrier materials, their combinations, and / or other materials described herein on the surface of the substrate (i.e., the underlying layer). In some non-limiting embodiments, the substrate is in the form of a preform, preferably having an inner surface for contacting food products. In some embodiments, the substrate preform comprises PET (such as unused PET), phenoxy type thermoplastic, combinations thereof, and / or the like.

[0273] The articles may comprise one or more layers or parts having one or more of the following preferred features: insulating layer, barrier layer, layer

EP 1 742 785 B1 in contact with the food product, aroma protection layer, high strength layer, compatibility layer, binding layer, gas scavenging layer, layer or part suitable for application with hot filling, layer having adequate melt strength for extrusion. In some embodiments, the monolayer or multilayer material includes one or more of the following materials: PET (including recycled PET and / or PET unused), PETG, foam, polypropylene, phenoxy type thermoplastics, polyolefins, blends of phenoxy type thermoplastic with polyolefins, blends thermoplastic material, and / or combinations thereof. For convenience, the products are mainly described with reference to preforms, containers, and closures.

[0274] In some embodiments, the articles may include foam material. Foam material can be made by combining a foaming agent and a carrier material. In one embodiment, the carrier material and the foaming agent are co-extruded into a preferably generally homogeneous mixture of foam material. The amount of carrier material and foaming agent may vary depending on the desired amount of one or more of the following: expansion properties, structural properties, thermal properties, supply pressure, and the like. In some non-limiting embodiments, the expandable / foam material contains less than about 10% by weight, also including less than about 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% by weight , foaming agent. In some non-limiting embodiments, the expandable / foam material contains about 1-6% by weight of the foaming agent. In another non-limiting embodiment, the expandable / foam material contains about 3-6% by weight of the foaming agent. In another non-limiting embodiment, the expandable / foam material contains about 2-8% by weight of the foaming agent. It is contemplated that the expandable / foam material may contain any amount of foaming agent, including those above and below the specific percentages indicated above, depending on the desired properties of the foam material.

[0275] In some embodiments, a hopper material (e.g., polypropylene pellets) and a foaming agent in the form of microspheres, preferably EXPANCEL® microspheres or similar material are provided in the hopper. The support material and microspheres are heated to melt the support material for effective mixing of the materials. When heating the mixture, the microspheres can expand or expand. Preferably, the temperature of the blend is in a temperature range such that it does not cause complete expansion or bursting of a substantial part of the microspheres. For example, if the temperature of the mix reaches a sufficiently high temperature, the gas inside the microspheres may expand so that the microspheres will burst or collapse. The melted foam material may be coextruded, and is preferably rapidly cooled to limit the amount of expansion of the microspheres.

[0276] When the foam material is heated for processing (e.g., extrusion, injection, etc.), the microspheres according to one embodiment may partially expand from their initially generally non-expanded position. When such microspheres are partially expanded, they maintain the ability to undergo further expansion to increase the size of the microspheres. Preferably, the pressure and temperature are such that the microspheres are not completely expanded during extrusion to allow further expansion of the microspheres, e.g. during blow molding. In addition, the pressure of the foam material may be increased to reduce or substantially prevent the expansion of the microspheres. Thus, the pressure and temperature of the foam material can be varied to obtain the desired level of expansion of the microspheres. Partially expanded microspheres may expand further when they are reheated (e.g., during a blow molding cycle) as described herein.

[0277] It is contemplated that the articles described herein may be manufactured or modified by any suitable method, including, but not limited to, (1) dip or flow coating, (2) coating by spraying, (3) flame spraying, (4) immersion in a fluidized bed, (5) electrostatic powder coating, (6) overmolding (e.g. inject-over-inject), and / or (7) injection (including co-injection). For example, preferred methods and apparatus for carrying out these methods are disclosed in US Patent No. 6,352,426 and US Publication No. 20040071885, which are incorporated by reference and form part of the disclosure of this application. It is also contemplated that these methods and apparatus may be used to form other products described herein. The preforms disclosed herein may be blow molded using the methods and apparatus disclosed in the references (e.g. U.S. Patent No. 6,352,426), incorporated herein by reference.

1. Methods and apparatus for making a foam-containing article [0278] An article, such as preform 30, can be injection-molded using an injection mold. FIGURE 28 illustrates a mold 501 that has a mold cavity 500 defined by a core 499 and a mold matrix section 504. Mold 501 can mold an article that includes expandable / foam material. In some embodiments, including the illustrated embodiment, the foam material is passed through line 509 and passes through injection port 508 and into the forming cavity 500. The foam material can fill the forming cavity 500, forming the preform 30. The foam material inside the forming cavity 500 can be rapidly cooled or hardened to limit the expansion of the foaming agent and you can reduce the number of cycles by increasing production. The mold may have an injection opening or needle valve 511 to prevent backflow of expanding foam.

[0279] The back pressure of the melt may not be high enough to cause the foaming agent to break in the form of microspheres. However, back pressure should prevent excessive expansion of the microspheres to allow blow molding of the preform to the desired shape and / or allow further expansion of the microspheres. The melt temperature may vary depending on the melt back pressure. For example, at high temperatures it can cause expansion of microspheres. To inhibit or prevent the expansion of microspheres, the back pressure may be increased to account for the increased pressure within each microsphere. However, if the melt pressure is too high, the microspheres may burst or collapse. Thus, the melt pressure is preferably kept in a range such that a substantial portion of the microspheres do not expand or break completely. However, in other embodiments, some of the balls or all of the balls may burst after complete expansion to form foam (e.g., open-cell foam).

[0280] In some embodiments, the alloy may expand at least partially before injection into the forming cavity 500. For example, after injection of the alloy into the forming cavity 500, the extruder screw may be retracted to collect the alloy for the next injection. After returning to normal, the screw may be decompressed to reduce melt pressure to achieve controlled expansion of the microspheres in the melt. In one embodiment, the alloy is not under pressure, so that the microspheres can expand freely. However, pressure can be applied to the melt to selectively control the expansion of the microspheres. Accordingly, the microspheres in the melt can be expanded partially or completely before the melt is injected into the forming cavity 500. Preferably, the microspheres are in an expansion state, such that the microspheres can expand further during, e.g., a blow molding heating process. The microsphere alloy can be injected into the forming cavity 500 to form a preform having expanded microspheres. The preform having expanded microspheres can then be formed into a container having generally evenly distributed microspheres.

[0281] The forming cavity 500 can be heated to achieve generally uniform distribution of the preform microspheres. Heat can generally cause a homogeneous expansion of the foam material. In some embodiments, the alloy may contain polypropylene and microspheres and is injected into a mold cavity 500, which may have a temperature from about 100 ° F (37.8 ° C) to about 250 ° F (121.1 ° C). The heated forming cavity 500 can ensure that the microspheres are generally evenly distributed throughout the preform. In another embodiment, the forming cavity 500 can be maintained at a temperature from about 150 ° F (65.6 ° C) to about 225 ° F (107.2 ° C). In yet another embodiment, the forming cavity 500 can be maintained at less than about 200 ° F (93.3 ° C). The forming cavity 500 can be cooled at any suitable time to achieve the desired distribution of the microspheres. In another embodiment, the alloy contains polyethylene and microspheres. The forming cavity 500 may have a temperature from about 75 ° F (23.9 ° C) to about 125 ° F (51.7 ° C) to form the preform, preferably with generally uniform distribution of microspheres. The preform may have evenly distributed microspheres, then it may subsequently be formed into a container that has evenly distributed microspheres. The temperatures listed above depend on the specific materials used. Regarding the present disclosure, one skilled in the art can choose material (s), processing parameters, and mold design for making various types of products.

[0282] The rate of passage of the alloy through the conduit 509 and the forming cavity 500 can cause frictional heat and thus, in addition to the melt heat, cause expansion of the microspheres. The illustrated mold of FIGURE 28 has a material 507 with a high heat transfer coefficient that can rapidly cool the alloy passing through the forming cavity 500, delaying the expansion of the microspheres. Material 507 with a high heat transfer coefficient may form part or all of the forming cavity section 504. Thus, operating parameters (e.g., flow rate, pressure, temperature, mix ratios, viscosity, and the like) may vary depending on the shape, size and other features of the mold.

[0283] In some embodiments, the preform in the forming cavity 500 can be rapidly cooled or quenched to delay or even stop the expansion of the microspheres. This allows the microspheres, which can be partially expanded, to form a tight structure that can be expanded during blow molding. After sufficient cooling of the preform, it can be conveniently manipulated without further expansion of the microspheres. In one embodiment, the forming cavity 500 is maintained at a temperature suitable to control the rate of expansion of the microspheres during the molding process. In one non-limiting embodiment, the forming cavity 500 is maintained at a temperature from about 400 ° F (4.4 ° C) to about 180 ° F (82.2 ° C) to reduce or stop the expansion of the microspheres. The temperature of the forming cavity 500 can be selected depending on e.g. molded materials, the size and shape of the preform, the size of the space filled by the foam material, and / or the processing parameters. The material processing temperature can be selected or determined by the skilled person for a given foam composition (carrier material, foaming agent, microspheres), the desired degree of expansion, and / or other parameters.

a. Manufacture of articles by blow molding process [0284] Articles in the form of molds can be manufactured by blow molding processes. The preform 30 product can be stretch blow molded to form a container, such as container 37 (FIGURE 4), and preferably causing expansion of the microspheres. The preform 30 may be subjected to a stretch blow molding process in the mold illustrated in FIGURE 3. The preform 30 containing the expandable material is placed in a mold 28 having a forming cavity corresponding to the desired shape of the container. Then the preform 30 is heated and expanded

By stretching the preform 30 to fill the mold cavity inside the mold 28, thereby forming a container. The stretching can be carried out, e.g., by forced air flow into the inner part of the preform 30. The blow molding operation is usually limited to the body part 34.

[0285] Before stretching the preform 30, the preform 30 is preferably preheated to a blow temperature range for the blow molding process. If the temperature of the preform 30 reaches the expansion temperature range, the microspheres of the preform 30 may expand. The expansion temperature range can be achieved before, during or after stretching the preform 30. Preferably, the microspheres of the preform 30 are heated to their expansion temperature range, causing at least partial expansion of the microspheres prior to blow molding the preform 30.

[0286] After raising the temperature of the preform 30 to the blow temperature range, air is passed into the inner portion of the preform 30, causing the preform to expand into the desired container shape 37. Preferably, the expansion temperature range is generally similar to the blow temperature range, so that microspheres can expand during heating or reheating for blow molding. The expandable material is expanded while the air forces the preform to stretch and form to the desired shape. In another embodiment, the preform 30 can be blow molded into the desired shape, and then the temperature of the container 37 can reach an expansion temperature range to cause expansion of the foam material of the container 37. To increase the expansion rate of the microspheres, the temperature during the blow molding cycle may be increased and / or the blow pressure may be reduced. To reduce the expansion rate of the microspheres, the temperature during the blow molding cycle may be reduced and / or the blow pressure may be increased. Thus, the preform can be heated / cooled and the pressure can be adjusted as needed.

[0287] With reference to FIGURE 3, the temperature of the walls 33 of the mold 28 can be controlled to achieve the desired expansion of the foam material of the preform 30 / container 37. In one embodiment, the mold 28 has a temperature control system for controlling the temperature of the walls 33. The temperature control system can have heating / cooling channels or any other suitable system for effectively controlling wall temperature 33.

[0288] In some embodiments, for example, the walls 33 are heated to cause expansion of the container microspheres 37. After blow-molding the preform 30 for forming the container 37, the heated walls 33 continue to expand the microspheres in the container wall 37, thereby reducing the wall density. In this way, the microspheres in the walls of the container 37 can be expanded or enlarged to obtain an effective thermal barrier due to the highly expanded microspheres.

[0289] The walls 33 of the mold 28 can be cooled to delay or prevent the expansion or further expansion of the microspheres. Walls 33 may be heated during one or more parts and cooled during one or more parts of the production cycle. Walls 33 may be heated during the heating cycle to induce expansion of the microspheres as discussed above. After the microspheres expand in the desired manner, the walls of the mold 33 are preferably cooled to reduce, or preferably stop, the further expansion of the microspheres. Thus, the walls 33 can be heated during the first part and cooled during the second part of the blow molding process. However, the walls 33 can be heated and / or cooled at any suitable time during the blow molding process. For example, in another embodiment, the walls 33 of the mold 28 are cooled while stretching the preform 30 from its initial position to the desired container shape. Preform 30

EP 1 742 785 B1 can be heated, blown and stretched until the wall of the preform contacts the cooled walls 33. Preferably, the expandable material forming the preform 30 undergoes localized expansion during stretching of the preform. When the preform 30 thermally communicates with the walls 33, heat is transferred from the stretched preform 30 to the mold 28, which causes the wall 84 of the shaped preform to cool. As the preform 30 cools, the expansion of the microspheres can be reduced or stopped. The pressure inside the mold 28 can be increased to reduce the rate of expansion of the microspheres. The pressure inside the mold 28 can be reduced to increase the rate of expansion of the microspheres.

[0290] The walls 33 of the mold 28 may have a surface treatment or structure to achieve the desired foaming reaction during the blow molding process, whereby the surface of the container 37 is textured. For example, the surface of the walls 33 may be rough or sand-textured, such that when the inner surface of the container 37 contacts the wall 33 during blow molding, the inner surface of the container 37 will have a textured foam surface. The textured surface of the wall 33 may cause further expansion of the microspheres upon contacting at least part of the container with the wall 33 of the mold 28. However, the surface of the wall 33 may have any treatment that will provide a suitable outer surface of the container 82. In another embodiment, for example, the wall 33 of the mold 28 may have a friction reducing finish, such as an abrasive jet finish, for easy removal of the container 37 from the mold 28. The friction reducing finish may be a substantially smooth surface to facilitate removal of the container. Mold 28 can be used to produce multi-layer containers, such as container 82 of FIGURE 6.

2. Preferred methods and apparatus for making preforms [0291] Monolayer or multilayer articles can be formed by injection molding processes such as co-injection, overmolding, and the like. It is contemplated that injection joints can be carried out to produce various product configurations.

a. Preferred methods and apparatus for co-injection [0292] FIGURE 28 illustrates a mold 501 that can be used for injection or co-injection to form monolayer or multilayer articles, respectively. Multilayer preforms can be formed by a co-injection procedure in which a plurality of materials are co-injected into the forming cavity 500. In some embodiments, the first material and the second material are co-injected into the forming cavity 500, forming a multilayer preform. In the embodiment illustrated in FIGURE 11, the first material that forms the inner layer 164 and the second material that forms the outer layer 162 can be co-injected through injection port 508. To complete the inner layer 164 along the inner surface of the preform 160, the flow of the first material forming the inner layer 164 can be stopped before the melt stream containing the first material passes through the entire forming cavity 500. Thus, one can be delivered through injection opening 508 to produce the desired product. or more materials at different flow rates, simultaneously or at different times, in different amounts, and the like.

[0293] The preform 160 may have an inner layer 164 thin relative to the outer layer 162. This is especially advantageous if the material forming the inner layer 164 is much more expensive than the material forming the outer layer 162. For example, some types of phenoxy type thermoplastic may be more expensive than readily available materials such as PET, so thermoplastic type

Phenoxy can be used in minimal amounts to reduce the cost of the preform material 160.

[0294] The preform 180 of FIGURE 12 can also be formed in a co-injection process using mold 501. The skilled person will readily recognize that the preform layers 160, 180 can be changed to obtain the desired properties of the preform. FIGURES 12A and 12B illustrate alternative embodiments of multilayer preforms. FIGURE 12B illustrates a preform 180B that includes an inner layer 184B and / or an outer layer 182B, which may have different thicknesses. The illustrated layers 182B, 184B include a thickened portion in the body portion of the preform. The inner layer 184B has a slightly thickened body portion relative to the neck finish. The thickness of the outer layer 182B is generally greater than the thickness of the inner layer 184B. Although not illustrated, the preform 190 of FIGURE 13 may also have an inner layer 194 and an outer layer 199 of different thicknesses.

[0295] It is contemplated that the preforms of Figures 11-14 may be sprayed with a material (e.g., barrier material), preferably with the formation of a layer that extends beyond the support ring along the body portion of the preform. He is incorporated in its entirety by reference US Patent No. 6,312,641, which describes methods, systems and products formed by one or more molding processes. In light of the present disclosure, various system combinations can be used to produce a wide range of products through co-injection processes.

b. First preferred overmolding method and device [0296] Products having multiple layers can be formed by an injection process, such as an overmolding process. FIGURE 29 illustrates an example of a form 520 for overmolding. Mold 520 has a core half 522 and a die half 524, illustrated in a closed position prior to overmoulding. The matrix half 524 includes a forming cavity in which the uncoated article (e.g., preform 528) is placed as a substrate. The overmolding process can be used to deposit one or more layers on a substrate.

[0297] The preform 528 may be a mono- or multi-layer preform. The illustrated preform is a monolayer preform that may contain one or more of the following: PET (e.g., unused PET and / or recycled PET), polyester, PP, phenoxy type thermoplastics, thermoplastics and / or the like. Preform 528 may also be similar to the preforms disclosed in the applications or patents incorporated into this application by reference.

[0298] The support ring 538 of the preform 528 can rest on the projection 536 and is held in place by a spinal half 522 that exerts pressure on the support ring 538, thereby forming a seal of the neck portion from the body portion of the preform as a substrate. The core half 522 includes the core 540. The core 540 selectively heats / cools the inside of the preform 528, while the channels 544 can heat / cool the matrix half 524. For example, cooling is accomplished by circulating fluid through channels 546 in half of core 522 of mold 520.

[0299] While the preform 528 is embedded in the mold matrix, the body part of the preform is substantially centered inside the forming cavity and is preferably completely surrounded by a hollow space or forming cavity 550. The preform thus positioned acts as an inner punch mandrel in a subsequent injection procedure. Then, a melt of the caking material is introduced into the mold cavity 550 from the injection molding machine through an injection port 554 which flows around the preform 528, preferably surrounding at least the body portion of the preform 528. After overmoulding, the layer applied in this way will take approximately the size and shape of the mold cavity 550.

[0300] The coating material may be heated to form an alloy with a viscosity compatible with the use of the injection molding machine. The temperature for this purpose, i.e. the injection temperature, will be different for different materials, because the melting ranges of polymers and melt viscosities can vary depending on the history, chemical nature, molecular weight, branching degree and other material characteristics.

[0301] Form 520 may be used to make the coated preforms disclosed herein, such as preform 50. The preform 50 of FIGURE 5 may have one of layers 52, 54 consisting essentially of PET, phenoxy type thermoplastics (including phenoxy materials and polyolefin blends with phenoxy), polypropylene, lamellar material, and / or other thermoplastics. In some embodiments, the second of layers 52, 54 of the preform 50 may include another material, such as foam. The expandable / foam material may contain a carrier material (e.g. PP, PET, and / or ethylene / acrylic acid copolymer) which is mixed with a foaming agent (e.g. microspheres, such as EXPANCEL® microspheres) to produce foam material. For example, the inner layer 54 may contain PET and the outer layer 52 may contain expandable / foam material. The underlying preform may contain PET. Foam material can be supplied through conduit 552 and injection port 554 to mold cavity 550. The injected expandable / foam material is then cooled for later removal. In light of the present disclosure, the skilled person will be able to choose the material (s) depending on the properties of the material (s) and the desired products to be made of it.

i. Preparation of multilayer articles by blow molding [0302] Multilayer articles can be blow molded in a similar manner to monolayer articles, except as described in further detail below. For convenience, blow molding of multilayer products will be described with reference to the preform 50. Of course, other multilayer preforms, in particular multilayer preforms containing foam material, can be blow molded in a similar manner.

[0303] The preform 50 is placed in a mold (e.g., mold 28 of FIGURE 3) having a die seat corresponding to the desired shape of the container. The preform 50 is then heated and expanded by introducing air pressure into the preform to stretch the preform so that it fills the mold cavity, thereby forming a multi-layer container. Optionally, the preform 50 can be stretched with a stretch rod or other means to stretch the preform.

[0304] In some embodiments, the preform 50 comprises material having similar or different processing windows. The preform may include an inner layer 54 containing PET and an outer layer 52 containing other material, such as PP (including foamed and non-foamed PP). The outer layer 52 can be made mainly or entirely of PP. Advantageously, the inner layer 54 and the outer layer 52 can be blow molded with a processing window that is very visibly wider than the processing window of the preforms made entirely of PP. Preferably, the processing window can be widened regardless of the thickness of the inner layer 54 and the outer layer 52. Optionally, a layer 85 can be used to increase the adhesion between the inner layer 54 and the outer layer 52. In one embodiment, the coupling or joining agent (e.g., adhesive) forms a layer 85 and provides adhesion between the inner layer 54 and the outer layer 52.

[0305] In some embodiments, the layer 52 may be expandable material formed by overmolding using injection molding to inject at least one layer of expandable material onto an existing preform (e.g., a PET-containing preform, phenoxy type thermoplastics, etc.). Layer

Inner 54 and foam carrier material 52 may have similar T_gso that both layers 52, 54 can be processed within their preferred blowing temperature ranges. As discussed above, the expansion temperature range may be the temperature range that causes the microspheres to expand. The expansion temperature range can be changed by varying the pressure applied to the expandable material. Preferably, the expansion temperature range is similar or within the blowing temperature range of layers 52, 54. During the blow molding process, the temperature of the preform may be within the expansion temperature range, so as to cause at least partial expansion of the microspheres. Thus, the foaming agent of the foam layer 52 may expand (1) during heating of the blow molding preform, (2) during stretching of the preform to the shape of the container, (3) generally after the container has been formed, and / or (4) during the combination (1) , (2), and / or (3).

[0306] In some embodiments, the multilayer preform can be blow molded into a container that has an inner layer suitable for contact with the liquid in the container. For example, the preform or container may have an inner layer or coating (e.g., a plasma layer of silicon oxide, certain types of phenoxy materials, and the like) that is suitable for use in contact with drinking liquids, food products, or the like. This layer can be applied to the container (e.g. container 37 or container 83) at any appropriate time during the manufacture of the containers. For example, the plasma layer can be applied to a preform or to a shaped container.

c. Second preferred overmolding method and device [0307] The methods and devices described herein can be modified to produce other preforms disclosed herein. For example, FIGURE 30 illustrates a mold that can be used to form the underlying layer of the preform substrate before injection of the material. The preform may or may not have a neck finish. For example, the preform may be a neckless preform. Form 560 for the core section 561 and the matrix section 566 having the surface of the matrix section 568. The form 560 includes a molding seat 570 defined by the core 562 of the core section 561 and the matrix section 566. The line 572 can deliver the alloy through injection hole 574 and into the forming socket 570.

[0308] The forming cavity 570 has a shape corresponding to the desired shape of a part of the preform. In the illustrated embodiment, the forming cavity 570 is shaped and sized to form the inner layer 164 of the preform 160 of FIGURE 11. However, the forming cavity 570 can be shaped and sized to form any desired article. For example, the forming cavity 570 may have a shape that matches the shape of the inner layer, such as the inner layers of any of the preforms described above. The alloy may be injected into the forming cavity 570 in the manner described above to form the molded article. The molded article may be removed from the matrix section 566 and then introduced into another matrix section (e.g., matrix section 580 of FIGURE 31) for the overmolding process.

[0309] Overmolding is carried out using an injection molding process using equipment similar to that used for forming the inner layer 164. As shown in FIGURE 31, after the layer 164 is formed in the mold 560 of FIGURE 30, the core 562 can be inserted into the mold cavity section 580 Layer 164 and matrix section 580 may define a cavity or forming cavity 582 corresponding to the shape of outer layer 162 of preform 160 of FIGURE 11. Generally, the alloy is passed through line 584 and passes through injection hole 586 and into molding cavity 582. The alloy can fill molding cavity 582, forming outer layer 162. After sufficiently cooling the preform 160, it can be removed from molding cavity 582. After overmoulding, deformed outer layer

EP 1 742 785 B1

162 will assume approximately the size and shape of forming cavity 582.

[0310] To perform the overmolding procedure, it is preferred to heat the starting layer 164 to be sprayed, preferably to a temperature above its T_g. In the case of PET, the temperature is preferably about 100 to 200 ° C, more preferably from about 18 ° C to about 225 ° C. If a PET crystallization temperature of about 120 ° C or higher is used, care should be taken when cooling PET in the preform. Cooling should be sufficient to minimize the crystallization of PET in the preform, especially the body part, so that PET is in the preferred amorphous and / or semicrystalline state. Alternatively, the initial inner layer 164 may be injection molded just before and not completely cooled to be at elevated temperature, as is sometimes preferred for the overmolding process.

[0311] The material used for overmolding is heated to produce an alloy with a viscosity compatible with the use of the injection molding machine. For some materials, such as foam and PP, the injection temperature is preferably in the range of about 375 ° F to 550 ° F.

[0312] After the overmolding process, the multilayer preform is preferably cooled at least to the point where it can be removed from the mold or transferred without damage, and removed from the mold to a place where further cooling may occur. If the body part of the preform has been heated to a temperature near or above the crystallization temperature for the material forming the body part, the cooling should be fairly quick and sufficient to ensure that when the preform is completely cooled, the material is primarily in a semi crystalline state . As a result of this process, a strong and effective bond takes place between the initial layer 164 and the subsequently applied outer layer 162 of the material. The neck finish may have a greater proportion of crystalline material for increased dimensional stability, especially during subsequent processes (e.g., blow molding, hot filling, and the like). In light of the present disclosure, one of ordinary skill in the art will be able to choose the type and design of molds for making the mono and multilayer products described herein. Forms and processes for other embodiments of preforms, including those above, in light of the present disclosure. Additional details of molding processes (e.g., inject-over-inject molding process) can be found in U.S. Patent No. 6,352,426, incorporated herein by reference.

3. Methods and devices for making the closure [0313] The closure, such as the closures illustrated in FIGURES 18-21E, can be molded using an injection mold. The molds of FIGURES 31 and 32 are generally similar to the forms illustrated in FIGURES 28 to 31, with the exception of the further details described below.

[0314] FIGURE 31 illustrates a mold 700 that is shaped to form at least part of the closure. The mold 700 is defined by a core section 702 having a core 704 and a matrix section 706. In one embodiment, the material (e.g. PET, including unused and / or recycled PET, PP, phenoxy type thermoplastic, expandable / foam material, PP, and / or other suitable material (s) is passed through line 709 and passes through injection hole 708 and into forming socket 710, which is defined by core 704 and matrix section 706. The material can fill the forming cavity 710, forming at least part of the closure. The illustrated forming cavity 710 has the size and shape of the inner layer of the closure body. However, the forming cavity 710 may be shaped to form the entire closure. The forming cavity 710 optionally also includes a portion 711 for forming the strip and fasteners between the body and the closure strip.

[0315] The above-described closures having multiple layers can be formed by overmolding. FIGURE 33 illustrates overmolding form 730. Lying down

Layer or substrate 732 formed with mold 700 (FIGURE 32) may be placed in mold 730 (FIGURE 33). Mold 730 has a core section 734 and a matrix section 736, illustrated in a closed position prior to overmoulding. The split ring 740 can hold the body portion 742 and substrate strip 744 732. The matrix section 736 includes a forming seat 738 into which the uncoated substrate 732 is placed.

[0316] The illustrated substrate 732 is a monolayer part of the closure; however, substrate 732 may be multi-layered. In some non-limiting embodiments, substrate 732 may comprise one or more of the following: PET (e.g., unused PET and / or recycled PET), polyester, PP, phenoxy plastic, thermoplastics (including phenoxy type thermoplastics, layered materials, their combinations, and / or similar. Substrate 732 can also be a standard closure used for closing bottles. The skilled artisan knows how to choose the size and shape of the substrate 732 based on the desired end use of the closure.

[0317] When the substrate 732 is embedded in the mold matrix, the substrate body 742 732 is preferably centered inside the forming cavity and is completely surrounded by a cavity 750. The substrate 732 thus positioned acts as an internal punch in a subsequent injection procedure. Then, an alloy of overmolding material is introduced into the forming cavity from the injector through injection port 752 and flows around substrate 732, preferably surrounding at least the body portion of substrate 732. After overmoulding, the deformed layer will assume the approximate size and shape of the empty space 750.

[0318] Form 730 can be used to form the coated or multilayer closures disclosed herein. In some non-limiting embodiments, the closures of FIGURES 18-21E and 24 may have one or more layers comprising substantially PET, phenoxy type thermoplastics, polypropylene, foam material, and / or other thermoplastics. Optionally, at least one of the closure layers may comprise expandable / foam material. In some embodiments, closure 302 (FIGURE 19) may have a first material layer 314 (e.g., PET) and an outer layer of PP (e.g., foamed or non-foamed PP).

[0319] The methods and devices disclosed in the references incorporated by reference to the present application may be modified to produce closures. For example, molding machines, devices and methods disclosed in US Patent No. 6,352,426 (see e.g. FIGURES 10-15, 17-24) can be modified to produce closures. For example, the molds may contain high heat transfer coefficient material, cooling channels, tie layer systems, gas introduction systems, and / or the like.

F. Methods and devices for depositing material on a substrate [0320] Systems for producing articles may have one or more devices or systems for depositing multiple materials. The molds described above may have one or more delivery systems for depositing material on a substrate, such as a preform, closure, and the like. The deposited material may form at least part of a tie layer or other layer (e.g., barrier layer). For convenience, the delivery systems described herein are discussed primarily with respect to forming devices, such as injection molding devices for making preforms. However, delivery systems can be used to deliver other materials (e.g., barrier materials, plastics, including thermoplastics, foam material, and the like) to substrates in the form of closures, containers (e.g. bottles), sheets, pipes, etc.

[0321] Referring to FIGURE 34, a delivery system 1004 from a forming system

EP 1 742 785 B1

1008 it can be used in various types of molding systems, such as for example injection molding system or compression molding system. The molding devices may have a delivery system 1004 to strengthen adhesion between materials and / or assist in the release of the molded article.

[0322] FIGURE 33 illustrates a forming system 1000 for producing mono and / or multilayer preforms. The molding system 1000 has a feed system 1004 and a mold 1002 that is similar to the mold 501 illustrated in FIGURE 28, except for the further details given below.

[0323] Form 1002 of FIGURES 34 and 35 is adapted for an overmolding process. The illustrated mold 1002 is shaped to overmold many preforms and includes a core section 1052 and a matrix section 1054 that cooperate to define matrix seat 1008 when the mold 1002 is in the closed position of FIGURE 35.

[0324] With reference to FIGURES 34 and 35, the mold 1002 includes a fluid supply system 1004 for introducing material, preferably binding material, into the forming cavity 1008. Fluid delivery system 1004 has a supply line 1010 that receives fluid, preferably fluid under pressure, from fluid sources. Exhaust system 1012 includes an exhaust line 1016 that is connected to mold matrix 1008 and vent 1020 (FIGURE 33). Fluid delivery system 1004 injects fluid, preferably a tie fluid, through feed line 1010 and into forming seat 1008, coating at least a portion of substrate 1022 (FIGURE 35). The illustrated substrate 1022 is in the form of a preform. The preform is then sprayed with a layer of material. The tie fluid preferably forms a tie layer that binds the overmolding layer to the underlying preform 1022.

[0325] Fluid can be removed from forming seat 1008 by passing fluid through outlet line 1016 and out of vent 1020 (FIGURE 34). In some embodiments, at some point along the outlet conduit 1016, a pressure generating device (e.g., a pump) may be positioned to create pressure or a vacuum (i.e., suction) to facilitate the flow of binding fluid. Suction can be applied with or without pressurized binding fluid. Binding fluid under pressure supplied through supply line 1010 and vacuum may result in selectively controlling the flow rate inside forming cavity 1008. In some embodiments, the binding fluid is supplied to forming cavity 1008, and then vacuum is drawn to remove unused binding fluid. However, exhaust system 1012 may not have a device for creating a vacuum. For example, exhaust system 1012 may be vented directly to the atmosphere or through a scrubber to remove any potentially ecologically harmful materials such as VOCs.

[0326] Delivery system 1004 may be used to deliver material, preferably coating material, to mold 1002. In some embodiments, the material is a non-binding coating material. The term "coating material," as used herein, is a broad term used in its usual sense and may include, without such limitation, a fluid or binder material, a polymer alloy, adhesives and the like that form a layer on all or part of the surface product or layer in the mold. The coating material can give the substrate the desired properties. In some preferred embodiments, the coating material is adapted to form a structural layer (e.g., tie layer, polymer layer, barrier layer) on the surface.

[0327] The term "binding fluid", as used herein, is a broad term used in its ordinary sense and may include, without such limitation

In this case, a fluid that can be deposited on the preform to form a bonding, adhesive or bonding layer, or may contribute to adhesion between materials. For example, the tie fluid can be a chemical that can contribute to adhesion between thermoplastic polymers, foams, plastics, other materials described herein, and combinations thereof. The binding fluid may contain one or more polymers of anhydrides (e.g. maleic anhydride), polymers containing acrylate groups, polymers containing epoxy groups, acids, bases, organic solvents, etching agents, adhesives, crosslinking agents, and / or other adhesives, phenoxy plastics and / or phenoxy plastic / polyolefin mixtures. The binding fluid may be one or more of the following: fog, gas, plasma, particles, liquid, and / or combinations thereof. The binding fluid can be selected depending on the materials in contact with the binding fluid. In some embodiments, the tie fluid forms a tie layer, adapted or shaped to bond the foam layer to the PET layer. In some embodiments, the tie fluid forms a tie layer that causes the PP layer to adhere more strongly to the PET layer. Additives (e.g. chemicals, microparticles, binders, or the like) to increase the adhesive properties of the binding fluid. Thus, the tie fluid may form a tie layer, such as the tie layer of the container 83 of FIGURE 6. In some embodiments, the tie fluid comprises one or more of the tie materials described above. In some cases, the terms "binding fluid" and "binding material" are used interchangeably herein.

[0328] As shown in FIGURES 35 and 37, delivery system 1004 may be formed at the joint 1024 between the mold matrix surface elements 1018. Outlet or outlet 1028 is positioned along surface 1018 of the die mold and preferably spaced from injection port 1040. Injection port 1040 may be shaped to inject material (e.g., alloy, molten polymer and the like) into forming cavity 1008. The illustrated outlet 1028 is circumferentially formed around at least part of the forming cavity 1008. The outlet 1028 is sufficiently small so that molten material will not substantially pass during melt injection. Alternatively, outlet 1028 may include one or more individual holes or slots. Optionally, feed line 1010 has a valve assembly 1030 (FIGURE 34) to selectively regulate fluid flow through feed line 1010. Valve system 1030, if present, may be located at any point along supply line 1010. In some embodiments, including the illustrated embodiment of FIGURE 34, valve system 1030 is positioned upstream of multiple mold seats 1008. The valves selectively allow or inhibit flow through the 1010 power cord to the mold sockets. The valve system 1030 is preferably built into the material forming the matrix section 1054. Although not illustrated, valve assembly 1030 may be located near the outlet (e.g., outlet 1028) of feed line 1010.

[0329] Valve system 1030 may be set in motion in response to pressure, such as positive or negative pressures, and may include one or more valves, such as a lift check valve. In one embodiment, the lift check valve is a ball check valve in a ball and seat arrangement. Pressure inside feed line 1010 may cause the ball to lift from the seat, but pressure in the opposite direction will press the ball into the seat and prevent flow in the opposite direction. Typically, there is also a spring that presses the ball into contact with the seat. When the pressure inside the feed line 1010 overcomes the spring pressure, the ball can be displaced from the seat, allowing flow to the forming seat 1008 (FIGURE 35). In some embodiments, negative pressure may cause fluid to flow through valve system 1030. For example, if the pressure in forming seat 1008 is negative, it may cause fluid to flow through valve system 1030. Alternatively, the valve system

EP 1 742 785 B1

1030 can be adjusted mechanically, regardless of pressure. For example, valve arrangement 1030 may include one or more valves (e.g., flap valves, disk valves, and the like). The system of valves 130 may be propelled to deliver a predetermined amount of binding fluid to forming seat 1008.

[0330] Outlet 1028 of FIGURE 35 can be located at any point along the mold matrix surface 1018. The outlet location 1028 may be determined at the desired fluid flow around the preform. For example, the illustrated mold 1002 of FIGURE 35 has an outlet 1028 located near or on a portion of the mold matrix 1008 corresponding to the bottom of the preform. The fluid supplied through the supply line 1010 may flow around the bottom of the preform and pass higher along the forming seat 1008 to the outlet line 1016, thereby depositing the material on at least part of the preform. The illustrated mold 1002 is shaped to deposit binding fluid on the body portion of the preform. As shown in FIGURE 37, outlet 1028 is preferably formed by a step 1036 with a depth between about 0.05 mm (0.002 inches) and about 0.127 mm (0.005 inches), and most preferably about 0.076 mm (0.003 inches). Because of its small size, outlet 1028 will generally not fill with alloy during injection, but will allow fluid (binder fluid, air, and / or other fluids) to be delivered outside outlet 1028. In some embodiments, fluid (e.g. air, binding fluid, etc.) may pass through outlet 1028 to wash any material from inside the outlet 1028. Although not illustrated, outlet 1028 may be located elsewhere along surface 1018. For example, outlet 1028 may be located along surface 1018 at a location corresponding to the body, neck, and / or prefroma support ring. For example, outlet 1028 may be located near the mold bottom region, below the preform support ring, at the neck of the preform, or at the body portion of the preform. In addition, multiple outlets 1028 may be located along surface 1018. The skilled artisan will be able to choose the size, shape, and position of outlet 1028 so as to achieve the desired material deposition on the substrate. The outlets 1028 may be located on the same or opposite portion of the preform as the inlet shaped to receive unused binding fluid. For example, outlet 1028 may be on the opposite side of the diameter from the inlet. In the illustrated embodiment, inlet 1029 and outlet 1028 are located on the same side of the preform.

[0331] With reference to FIGURES 34 and 35, exhaust duct 1016 is shaped to draw fluid from forming cavity 1008 (FIGURE 35). Next, exhaust line 1016 provides binding fluid for vent 1020, or recirculation system, so that fluid can be re-passed through forming seat 1008. Exhaust line 1016 may have a valve arrangement 1038, which may be similar to valve arrangement 1030, and will therefore not be described in further details.

[0332] During operation, after placing the preform in mold 1002, the arrangement of valves 1030 allows fluid to flow through the feed line 1010 and into the forming cavity 1008. As shown in FIGURES 36 and 37, the binding fluid TF can flow through the forming cavity 1008 and coat every at least part of the outer surface of the preform. Preferably, the TF binding fluid coats the body of the preform to form an inner surface defining the forming cavity 1008. In some embodiments, including the embodiment illustrated, the TF binding fluid forms a thin layer of material on most of the body parts of the preform, or a generally uniform continuous or discontinuous coating. However, the TF binding fluid can coat any portion of the preform exposed to the fluid. For example, the tie fluid may be the threaded end and the body portion coated, if the forming seat 1008 is defined by both the threaded end and the body portion of the preform.

[0333] To improve coating of the preform, the mold 1002 can selectively control

EP 1 742 785 B1. In one embodiment, the core 1040 of FIGURE 35 heats or cools the preform to improve coating of the preform. The skilled person will be able to choose the desired preform temperature depending on the properties of the binding fluid that coats the preform. Alternatively, the preforms may be electrostatically charged to improve coating of the preform. In other embodiments, the preform can be physically or chemically roughened or textured to improve coating of the preform. Optionally, the mold die surfaces 1018 may be thermally controlled to improve coating of the preform. For example, the surface of the mold matrix 1018 may be cooled to ensure that the gases in the forming cavity 1008 generally remain in the gas phase.

[0334] Optionally, the temperature of the binder material can be selectively controlled. For example, the binding material may include a binding fluid that is heated to reduce the viscosity of the binding fluid to facilitate the distribution of the binding fluid. Heating and / or cooling devices may be used to control the temperature of the binding material.

[0335] When the delivery system 1004 supplies the binding fluid to the forming cavity 1008, the binding fluid coats the preform and can flow from the forming cavity 1008 and into the outlet system 1012. After coating the preform or after a specified period of time, the delivery system 1004 may reduce, or preferably stop the flow of fluid into forming seat 1008. The coating on the preform may form a tie layer to bond the preform 1022 as a substrate to the material, which is then injected through injection port 1040 into forming cavity 1008. If the binding material is solvent / solute system, the flow may be reduced or stopped and the forming cavity 1008 may be vented. Supply line 1010 can supply gas or steam (e.g. air, inert gases such as nitrogen, or other gases) to blow the forming cavity 1008. The exhaust system 1012 may optionally provide negative pressure to remove gas or steam from the forming cavity 1008. In this way, one or more solvents may be removed to achieve the desired properties of the tie layer and / or deformed material.

[0336] During alloy injection, the valve system 1030 is preferably closed. The alloy injected through injection port 1040 passes further and fills the forming cavity 1008. In some embodiments, excess binding fluid is forced out of the mold forming cavity 1008 by means of the injected melt stream. Thus, the melt stream may cause the binding fluid to be removed from the forming cavity 1008. For example, if the binding fluid is gas, the gas may be forced out of forming seat 1008 by an advancing melt stream. The binding coating formed on the preform can be spread on the preform by a melt stream. When the melt stream propagates along forming cavity 1008, the melt stream can push and spread the bonding material around the surface of the preform, which ensures that at least a portion of the body portion, preferably most or all of the body portion, is coated with the bonding material. The skilled person will be able to determine the appropriate location of outlet 1028 based on the properties of the tie layer and the melt stream so as to achieve the desired tie layer in a container made of the preform.

[0337] Referring to FIGURE 35, during melt stream injection, valve system 1038 may be open to allow binding fluid to exit from forming seat 1008. Valve system 1038 may be closed after injecting a predetermined amount of melt stream to prevent or inhibit alloy entry into the conduit outlet 1016. In addition, the inlet 1029 of the outlet conduit 1016 may be small in size so that the alloy does not substantially enter it, but that it is possible to supply fluid (the binding fluid, air, and / or other fluids) to the outlet conduit 1016.

[0338] Optionally, after completing the injection, an outlet under pressure 1028, preferably air, is supplied to the outlet to destroy the vacuum that can be created between the preform and the wall of the forming cavity. Air is supplied to outlet 1028 at a pressure between about 75 psi (about 0.52 MPa) and 150 psi (about 1.03 MPa) and most preferably about 100 psi (about 0.69 MPa). In other embodiments, the preform is removed from the forming cavity 1018 without the help of pressure fluid from the supply line 1010. In addition, similar delivery systems can be used in other parts of the mold, such as, for example, a threaded surface, but without such limitation.

[0339] Optionally, core section 1052 and matrix section 1054 may cooperate to form a seal to inhibit or prevent the binding fluid from escaping from the environment surrounding the mold 1002 illustrated in FIGURE 35. Thus, if the binding fluid has volatile organic compounds (VOC) or other substances undesirable for inhalation or the environment, the binding fluid may be contained within mold 1002. Mold 1002 can circulate and reuse the binding fluid to also reduce waste. The tie fluid can be vented through outlet system 1012 or by other means. If the binding fluid is suitable for release into the atmosphere, the binding fluid may be vented to the atmosphere. For example, the binding fluid may escape between the preform and the edge 1056 and then may pass between the core section 1052 and the matrix section 1054 and out into the atmosphere.

[0340] The preform may be coated with a binding material before the mold 1002 is in the fully closed position. The binding material may be deposited on the substrate preform when the preform is introduced and moved forward to the matrix section 1054. Thus, the preform is coated with the binding material when the preform is near or at least partially within the matrix section 1054. In some embodiments, delivery system 1004 provides fluid when the mold 1002 is in a partially or fully open position. In one embodiment, the delivery system 1004 injects the binding fluid into the forming cavity 1008 when the mold 1002 is moved from the open position to the illustrated closed position of FIGURE 35. When the preform is moved forward into the die section 1054, the binding fluid flows upstream through the cavity 1008 and coats at least part of the preform. Before the form 1002 is in the closed position, the binding fluid can escape into the atmosphere. Thus, mold 1002 may or may not have an outlet system 1012. For example, if the tie material is deposited before the mold 1002 is in the closed position, the mold 1002 preferably has no outlet system 1012. If the binding material is deposited after the mold 1002 is in the closed position, the mold 1002 preferably has an outlet system 1012, especially when the binding fluid is not suitable for discharge directly into the atmosphere.

[0341] FIGURE 38 illustrates another embodiment of the delivery system 1004. The delivery system 1004 has a plurality of inlets 1060 for injecting or delivering fluid (e.g., binding fluid, air, etc.) to the forming cavity 1008. The fluid may be delivered in response to positive pressure in feed line 1010, or pulled into forming seat 1008 under negative pressure. In the illustrated embodiment, mold 1002 has a power cord 1010 connected to each inlet. Delivery system 1004 having a plurality of inlets 1060 may contribute to more uniform coating of the preform 1022.

[0342] The delivery system 1004 of FIGURE 39 has an inlet 1061 defined by the bottom region. Inlet position 1061 provides a generally uniform unidirectional flow through forming cavity 1008. In some embodiments, feed line 1010 provides the binding fluid in the form of a liquid that envelops the bottom of the preform. After providing a certain amount of binding fluid, the melt can be fed to forming seat 1008

EP 1 742 785 B1 through injection hole 1040. The alloy spreads the binding material on the surface of the preform.

[0343] Other devices disclosed herein may be used to deposit the binding material on the articles. For example, the molds of FIGURES 28, 30, 31 can be modified to deposit the bonding material on the inner layer or underlying substrate.

[0344] Optionally, delivery system 1004 may be connected to a conduit that delivers the alloy to the forming cavity. For example, feed line 1010 may deliver tie fluid to the line through an injection opening to coat the substrate. After coating the substrate, an alloy may be injected through the same conduit and injection port to form an outer layer.

[0345] In addition, the mold introduction system (e.g., the mold illustrated in FIGURE 26) from US Patent No. 6,352,426 and other incorporated applications and patents may inject a binding fluid to both coat the preforms and facilitate removal of the preform. The coated preform can then be overmolded as a substrate. The delivery system (or delivery systems) can be used to deliver other materials (e.g., one or more materials disclosed herein) for articles. For simplicity, the devices have been described as providing a binding fluid. However, in many cases it is understood that other materials may be provided with the devices described above. For example, the binder material or fluid may be replaced with a dye, chemical, alloy, polymer, powder, coating material, barrier material and / or any other material suitable for coating at least a portion of the substrate.

G. Preferred Articles [0346] Generally, preferred articles described herein include articles containing one or more materials. The material (s) may form one or more layers of articles. The product layers may advantageously provide some functionality and may be applied as multiple layers each having one or more functional properties, or as a single layer comprising one or more functional components. The articles may be in the form of packaging such as preforms, closures, containers, etc. The materials, methods, ranges and embodiments disclosed herein are given by way of example only and are not intended to limit this disclosure in any way. The articles disclosed herein may be formed from any suitable material disclosed herein. However, some products and materials are discussed below. In light of the present disclosure, embodiments and materials may be modified by one skilled in the art to produce other alternative embodiments and / or applications, and their obvious modifications and equivalents.

1. General description of preferred materials for forming products

a. Non-limiting articles containing foam material [0347] The articles may contain foam material. In some non-limiting embodiments, the foam material may form part of the product, such as the body or cervical end of the preform. In some non-limiting embodiments, the foam material comprises less than about 90% by weight, also including less than about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% by weight of the product (such as a preform , closure, container, sheet, etc.). In some non-limiting embodiments, the foam material comprises about 5-30% by weight of the product. In some non-limiting embodiments, the foam material comprises about 20% -60% by weight of the product. In some non-limiting embodiments, the foam material comprises about 10-30% by weight of the product. In some embodiments, the foam material comprises more than about 90% by weight

EP 1 742 785 B1. Foam material can form most or all of the product. Foam material can provide a reduced weight of products compared to conventional products and can therefore desirably reduce the cost of transporting the products. In addition, the foam material can reduce the amount of material that is used to form the articles because the foam material can have a significant number of bubbles.

[0348] The foam material may be made of expandable material. For example, at least a portion of the article may include expandable material that has a first density that decreases when the expandable material is expanded. In some non-limiting embodiments, the first material, preferably expandable material, has a first density, and the second material, preferably foam material made from the first material, has a second density. The second density is less than about 95%, 90%, 80%, 70%, 50%, 30%, 20%, 10%, 5%, 2%, 1% of the first density, and ranges including such percentages. In some non-limiting embodiments, the second density is in the range of about 30% to 60% of the first density. Thus, low density foam material relative to the expandable material may be produced. It is contemplated that the articles may contain any suitable amount of foaming agent, including those above and below the specific percentages listed above, depending on the desired use of the articles.

b. Non-limiting articles containing phenoxy type thermoplastic [0349] The articles may contain phenoxy type thermoplastics, such as phenoxy plastic and blends (e.g., polyolefin-phenoxy plastic blend), PET-phenoxy plastic blend, and combinations thereof. In some non-limiting embodiments, a phenoxy type thermoplastic can form part of an article, such as at least a portion of the interior surface of a preform, closure, container, etc. In some non-limiting embodiments, a phenoxy type thermoplastic comprises less than about 30% by weight of the article, including less than about 1%, 2%, 5%, 7.5%, 10%, 12%, 15%, 20%, 25%, 50% by weight. In another non-limiting embodiment, the phenoxy type thermoplastic makes up about 1-4% by weight of the product, In another non-limiting embodiment, the phenoxy type thermoplastic makes up about 1-15% by weight of the product. In another non-limiting embodiment, the phenoxy type thermoplastic makes up about 7-25% by weight of the article. In another non-limiting embodiment, the phenoxy type thermoplastic makes up about 5-30% by weight of the article. In some embodiments, the phenoxy type thermoplastic forms a separate layer or layer mixed with another material. In some embodiments, the separate layer comprises a phenoxy type thermoplastic that forms about 0.1% to 1% by weight of the product. In some embodiments, the separate layer comprises a phenoxy type thermoplastic that forms about 0.1% to 1% by weight of the product. In some embodiments, the phenoxy type thermoplastic is mixed with the polymer material (e.g., PET, polyolefin, their combinations) and may constitute more than about 0.5%, 1%, 2%, 5%, 7.5%, 10% , 12%, 15%, 20%, 25%, 50%, 70% by weight of the product. It is contemplated that in some embodiments, these percentages may be given by volume. By using a phenoxy type thermoplastic, articles having one or more of the following properties can be obtained: desirable aroma absorption, dye absorption, oxygen barrier, recyclability, and / or other properties particularly well suited to food contact. These percentages can effectively provide the desired properties, while minimizing the amount of phenoxy type thermoplastic used, thereby providing a cheap product.

[0350] Various combinations of phenoxy type thermoplastic with polyethylene, polypropylene, foam material, and the like can be used to make preforms, containers, and other packaging of relatively larger sizes and having desirable properties, especially when thermoplastic phenoxy type creates a packaging surface that comes into contact with food products. Phenoxy type thermoplastics can provide the desired adhesive between the PET containing layer and the PP containing layer.

[0351] It is contemplated that the articles may contain any suitable amount of phenoxy type thermoplastics, including those above and below the specific percentages indicated above, depending on the desired use of the articles.

2. Products in the form of preforms / containers [0352] Foam material may form one or more parts of the layers of articles (such as packaging, including preforms and containers). The preform 30 of FIGURE 1 may comprise foam material. In some embodiments, the preform 30 mainly comprises foam material. In some embodiments, the preform 30 may comprise a phenoxy type thermoplastic formed by a molding process. For example, the preform 30 may contain mainly a phenoxy type thermoplastic. In some embodiments, the preform 30 may be formed by a co-injection process in which the inner and outer parts of the preform 30 comprise different materials. The material produced by co-injection can be pressed into the desired shape. For example, the preform 30 may have an inner portion that includes one or more of the following materials: phenoxy type thermoplastic, PET, PETG, expandable / foam materials, or the like. The outer portion of the preform 30 may contain one or more of the following materials: polyethylene, polypropylene (including clarified polypropylene), PET, combinations thereof, and the like. Optionally, part of the preform 30 may comprise foam material.

[0353] In some embodiments, the preform 30 can be coated with a layer to improve its barrier properties. For example, the preform 30 may be coated with barrier material. For example, as in US Patent Application No. 10 / 614.731 (Publication No. 2004-0071885), which is incorporated in its entirety and which describes preform coating systems and methods. This system and other systems disclosed or incorporated herein may be used to form the barrier layers described herein. The coated preform can then be overmolded with another material forming the outer layer.

[0354] With reference to FIGURE 5, the preform 50 may include an uncoated preform 39, coated with a foam layer 52. Preferably, the uncoated preform 39 comprises a polymeric material, such as polypropylene, polyester, PET, PETG, phenoxy type thermoplastic, and / or other thermoplastic materials. In one embodiment, for example, the uncoated preform 39 primarily comprises polypropylene. In another embodiment, the uncoated preform 39 primarily comprises polyester.

[0355] The foam layer 52 may comprise either a single material or several materials (such as several microlayers of at least two materials). In some non-limiting embodiments, the foam layer 52 may be about 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, preforms, and ranges including such values rates. In some embodiments, the foam layer 52 comprises about 2% to about 90% of the preform. In some non-limiting embodiments, the foam layer 52 may comprise from about 5% to about 50% of the preform. In some embodiments, the foam layer 52 comprises from about 10% to about 30% of the preform. In some non-limiting embodiments, the foam layer 52 may comprise from about 5% to

About 25% preform. In some non-limiting embodiments, the foam layer 52 may comprise less than about 20% of the preform. It is contemplated that in various embodiments these percentages may be by weight or by volume. The foam layer 52 may include foam material that is not expanded. The outer layer 52 of the preform 50 may have a thickness, preferably an average wall thickness, from about 0.2 mm (0.008 inches) to about 0.5 mm (0.02 inches). In another non-limiting embodiment, the outer layer 52 has a thickness of about 0.3 mm (0.012 inches). In some embodiments, the average wall thickness is taken only along the body portion of the preform 50. In some non-limiting embodiments, the outer layer 52 is less than about 90% of the average wall thickness of the preform 50, also including less than about 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 9%, 8%, 7%, 6%, 5% of the average wall thickness of the preform 50.

[0356] The foam layer 52 may include microspheres that are, for example, either non-expanded or partially expanded. In addition, the foam layer 52 may be generally homogeneous or generally heterogeneous. Although not illustrated, the foam layer 52 may form other parts of the preform 50. For example, the foam layer 52 may form at least part of the inner surface of the preform 50 or neck portion 32.

[0357] In some embodiments, the inner layer 54 may comprise one or more of the following: polyethylene, PET, polypropylene (e.g., foamed polypropylene, non-foamed polypropylene, clarified polypropylene), combinations thereof, and the like. For example, the preform 50 may include an outer layer 52 of polypropylene (preferably foamed) and an inner layer 54 containing PET. Optionally, the tie layer may be applied between layers 52, 54 and may include phenoxy type thermoplastic.

[0358] In some embodiments, a barrier layer may be applied between layers 52, 54. The barrier layer may inhibit or prevent the entry and / or exit of one or more gases, UV rays, and the like through the walls of the container made of the preform 50.

[0359] In some embodiments, the second layer 54 comprises polypropylene. Polypropylene may be grafted or modified with maleic anhydride, glycidyl methacrylate, acrylic methacrylate and / or similar compounds to improve adhesion. In one embodiment, the polypropylene additionally contains nanoparticles. In a further embodiment, the polypropylene contains nanoparticles and is grafted or modified with maleic anhydride, glycidyl methacrylate, acrylic methacrylate and / or similar compounds.

[0360] With reference to FIGURE 6, the container 83 can be used as a carbonated beverage container, thickness 44, preferably the average wall thickness, outer layer 52 of the container 83 is about 0.76 mm (0.030 inches), 1.52 mm (0.060 inches), 2.54 mm (0.10 inches), 3.81 mm (0.15 inches), 5.08 mm (0.2 inches), 6.35 mm (0.25 inches), and ranges covering such thicknesses. In some embodiments, the outer layer is preferably less than about 7.62 mm (0.3 inches), more preferably about 1.27 mm (0.05 inches) to 5.08 mm (0.2 inches). The outer layer 52 may comprise foam material having a thickness of more than about 3.81 mm (0.15 inches). In some non-limiting embodiments, the outer layer 52 has a thickness in the range of about 0.127 mm (0.005 inches) to about 0.635 mm (0.025 inches).

[0361] In some non-limiting embodiments, the thickness 46 of the inner layer 54, preferably the average thickness of the inner layer 54 is preferably about 0.127 mm (0.005 inches), 0.635 mm (0.025 inches), 1.07 mm (0.040 inches), 1.52 mm (0.060 inches), 2.03 mm (0.080 inches), 2.54 mm (0.100 inches), 3.05 mm (0.120 inches), 3.56 mm (0.140 inches), 4.07 mm (0.160 inches), and ranges covering such thicknesses. In some embodiments,

The inner layer 54 of container 83 has a thickness of less than about 2.54 mm (0.1 inches) to provide a cheap food barrier. In some non-limiting embodiments, the inner layer 54 has a thickness ranging from about 0.127 mm (0.005 inches) to about 0.635 mm (0.025 inches). The overall wall thickness 48 of the container can be selected to achieve the desired properties of the container 83.

[0362] To increase the barrier properties of the container 83, the container 83 may have a barrier layer. One or more barrier layers may be formed on the inner surface of the inner layer 54, between the layers 52, 54, outside the outer layer 52, and the like. For example, the outer layer 52 of the container (or preform from which the container 83 is made) can be coated with barrier material using the methods disclosed herein. For example, the barrier layer may be formed using the devices, methods and systems disclosed in US Patent Application No. 10 / 614.731 (Publication No. 2004-0071885), which is incorporated in its entirety. In addition, in some embodiments, the container 82 includes foam with substantially closed cells that can inhibit fluid migration through the foam. For example, the foam can be a barrier that inhibits, preferably prevents, migration of CO₂ through the wall 84 of the container 83 formed of the preform.

[0363] The preform 60 of FIGURE 11 has an inner layer 164 that comprises a first material and an outer layer 162, preferably comprising another material. In some non-limiting embodiments, the layer 162 may be about 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, preforms, and ranges including such percentages . In some embodiments, the foam layer 162 is less than about 97%. In some embodiments, the layer 162 comprises from about 5% to about 99% of the preform. In some non-limiting embodiments, the layer 162 can be less than about 90% of the preform. In some non-limiting embodiments, the layer 162 can be from about 40% to 80% of the preform. In some non-limiting embodiments, the layer 162 can comprise about 60% to 90% of the preform. In some non-limiting embodiments, the layer 162 may comprise more than about 60% of the preform. It is contemplated that in various embodiments these percentages may be by weight or by volume. In some embodiments, the outer layer 162 may contain foam material and the inner layer 164 may contain polymeric material such as PET (e.g., unused or post consumer / recycled PET). The foam layer 162 may include foam material that is not expanded. For example, the foam layer 162 may include microspheres that, for example, are neither expanded nor partially expanded. The foam layer 162 can provide the desired insulating layer when the preform 160 is formed into a container.

[0364] Preferably, a substantial portion of the outer layer 162 comprises foam material and a substantial portion of the inner layer 164 comprises PET or other material for contacting food products. In one non-limiting embodiment, the foam material comprises PP and expandable microspheres. In yet another embodiment, the outer layer 162 comprises PP, and the inner layer 164 may comprise PET. Preferably, a substantial portion of the outer layer 162 comprises PP and a substantial portion of the inner layer 164 comprises PET. In one non-limiting embodiment, the outer layer 162 generally comprises completely PP. In yet another embodiment, significant portions of the inner layer 164 and outer layer 162 may comprise foam material. Preforms 76, 132 may similarly contain foam material and material suitable for contact with food products.

[0365] In some embodiments, the inner layer 164 may include one or more of the following: PET, phenoxy type thermoplastic (including blends), foam material (e.g., foamed PET), and / or coatings / layers suitable for contacting the products food. The outer layer 162 may include

One or more of the following: foam material (including foamed PP, foamed PET, etc.), non-foamed material (e.g., phenoxy, PET, PP thermoplastic), or other material suitable for forming the outer part of the preform, In some embodiments, the preform 160 comprises a phenoxy type thermoplastic. In some non-limiting embodiments, a phenoxy type thermoplastic may be less than about 1%, 2.5%, 5%, 10%, 20%, 30%, 50%, 60%, 70%, 80%, 90%, and ranges covering such thicknesses. In some embodiments, the phenoxy type thermoplastic material comprises about 10% to 30% by weight of the preform. In some embodiments, the phenoxy type thermoplastic material makes up most or all of the preform. The weight is the weight of a phenoxy type thermoplastic in separate or mixed form. It is contemplated that in various embodiments these percentages may be by weight or by volume. For example, in some embodiments, the layer 164 comprises a phenoxy type thermoplastic that forms less than 10% of the preform. Layer 164 may have a thickness suitable for forming a food contact layer. To create a low cost food contact layer, the thickness 174 of the inner layer 164 is preferably less than about 3.81 mm (0.150 inches). The thickness of inner layer 164 may be less than about 0.01 mm (0.0004 inches), 0.02 mm (0.0007 inches), 0.05 mm (0.002 inches), 0.10 mm (0.004 inches), 0.15 mm (0.006 inches), 0.20 mm (0.008 inches), 0.30 mm (0.01 inches), 0.5 mm (0.019 inches), and ranges including such thicknesses. In some non-limiting embodiments, the inner layer 174 comprising a phenoxy type thermoplastic has a thickness in the range of about 0.01 mm (0.0004 inches) to about 0.05 mm (0.002 inches). In some embodiments, the preform 160 can be made by a molding process, wherein the inner and outer parts of the preform comprise different materials.

[0366] In some embodiments, the outer layer 162 comprises a first material and the inner layer 164 preferably comprises a different material. For example, outer layer 162 may contain polypropylene, and inner layer 64 may contain PEtG. In another embodiment, the polypropylene may be grafted or modified with maleic anhydride, glycidyl methacrylate, acrylic methacrylate, and similar compounds to improve adhesion. In one embodiment, the polypropylene additionally contains nanoparticles. In a further embodiment, the polypropylene contains nanoparticles and is grafted or modified with maleic anhydride, glycidyl methacrylate, acrylic methacrylate and / or similar compounds.

[0367] The preform 180 (FIGURE 12) may have an inner layer 184 that is similar or identical to the inner layer 164 and an outer layer 182 that is similar or identical to the outer layer 162. The preform 190 (FIGURE 13) may have an inner layer 194 which is similar or identical to the inner layer 164 and the outer layer 199 that is similar or identical to the outer layer 162. The materials forming the inner layer 194 and the outer layer 199 can be selected to achieve the desired interaction with the blocking structure 197. The preform 202 (FIGURE 14) may have layers formed of similar or the same materials as the preform 160.

[0368] The preforms and the containers obtained therefrom may be particularly well suited for thermal applications such as hot-filling processes. The container 211 of FIGURE 14A can generally maintain its shape during hot-fill processes. After blow molding or hot filling, the final dimensions of the neck portion 132 of the container 211 are substantially identical to the initial dimensions of the preform. In addition, this results in reduced variability in thread dimensions at the neck finish. For example, the inner layer 283 may be formed of a material for contact with food products, such as PET. The outer layer 203 may contain moldable materials (e.g. mainly or entirely of PP,

EP 1 742 785 B1

PP and foaming agent, crystalline PET, lamellar material, homopolymers, copolymers, and other materials described herein) suitable for hot filling. The outer layer 203 provides dimensional stability to the neck finish 132, even during and after hot filling. The width of the outer layer 203 can be increased or decreased to increase or decrease, respectively, the dimensional stability of the neck finish 132. Preferably, one of the layers forming the neck finish 132 comprises a material having high thermal stability; however, neck finish 132 may also be made of materials having low temperature stability, especially for applications other than hot filling.

[0369] In addition, the dimensional stability of the outer layer 203 ensures that the closure 213 remains attached to the container 211 of FIGURE 14A. For example, the outer layer 203 of PP may maintain its shape, thereby preventing the closure 213 inadvertently detaching from the container 211.

[0370] The preforms described above can be modified by adding one or more layers to obtain the desired properties. For example, a barrier layer may be formed on the body parts of the preforms.

3. Articles in the form of closures [0371] Closures may comprise foam material. In some non-limiting embodiments, the foam material contains less than about 95% by weight of the closure, also including less than about 5%, 15%, 25%, 35%, 45%, 55%, 65%, 75%, 85%, and ranges including such percentages. It is contemplated that in various embodiments these percentages may be by weight or by volume. In some embodiments, the foam material has ranges covering these values ​​in percent by weight of the closure. In one non-limiting embodiment, the foam material comprises about 45-60% by weight of the closure. In another non-limiting embodiment, the foam material comprises about 15-70% by weight of the closure. In some embodiments, the closure comprises mainly or entirely foam material. For example, the closure may be a monolayer closure made of foam material.

[0372] With reference to FIGURE 19, at least a portion of the closure 302 includes foam material. Layer 314 and / or outer portion 311 may comprise foam material (e.g., foamed PET, foamed PP, etc.). In one embodiment, the outer portion 311 comprises foam material and the layer 314 contains non-foamed material (such as PP, PET, etc.).

[0373] In addition, the inner portion of the closure may comprise foam material. In some embodiments, the outer parts of the closure may or may not include foam material. The closures of FIGURES 21A to 21E may have similar or different inner and outer layers (or outer parts).

[0374] FIGURE 21C illustrates a closure 360 ​​that may have an intermediate layer 364 formed of materials that have the desired structural, thermal, optical, and / or barrier properties, and / or. For example, layer 364 may be formed of PET, PP, PET, PETG, and / or the like.

[0375] In one embodiment, an additional advantage is provided when the outer portion of the closure is formed of foam material to provide a comfortable gripping surface so that the user can conveniently remove the closure from the container. The outer portion 311 of FIGURE 19 may be foam to increase the space occupied by the outer portion 311 and may provide the user with a greater leverage for easier opening and closing of the closing device.

[0376] The closures may have a threaded surface inside that is shaped 70

EP 1 742 785 B1 to fit the threaded surface of the container. The enlarged inner portion 311 of FIGURE 19 can provide a greater leverage so that the user can easily screw and unscrew the container closure 302. Preferably, a similar or the same amount of material that forms a conventional capsule can be used to produce a larger diameter closing device. Thus, the cost of materials for making closure 302 can be reduced.

[0377] The closures may comprise phenoxy type thermoplastic materials. In some non-limiting embodiments, the phenoxy type thermoplastic material comprises less than about 25% by weight of the closure, also including less than about 1%, 2%, 4%, 5%, 10%, 15%, 20% by weight. In some embodiments, the phenoxy type thermoplastic material ranges ranges within these percentages by weight of the closure. The weight is the weight of a phenoxy type thermoplastic in separate or mixed form. In one non-limiting embodiment, the phenoxy type thermoplastic material comprises about 0.5 to 5% by weight of the closure. In another non-limiting embodiment, the phenoxy type thermoplastic material comprises about 1 to 6% by weight of the closure.

[0378] Phenoxy type thermoplastic can form at least part of the inner surface of the closure. For example, a phenoxy type thermoplastic layer may be deposited on the inner surface 309 of layer 314 (FIGURE 19). Optionally, layer 314 can be made of phenoxy type thermoplastic. For example, phenoxy type thermoplastic may form at least part of closure layer 344 340 (FIGURE 21 A), closure layer 356 350 (FIGURE 21B), layer 366 and / or closure layer 364 360 (FIGURE 21C), closure layer 374 370 (FIGURE 21D), closure layers 383 380 (FIGURE 21E). Of course, these layers may contain material (e.g. lamellar material, PET, PP, and / or the like) which is coated with a phenoxy type thermoplastic, such as a phenoxy type thermoplastic or a polyolefin-phenoxy type thermoplastic blend.

[0379] The closures described above may have one or more barrier layers to increase their barrier properties. For example, the inner layer, one or more intermediate layers and / or outer barrier layers may be formed using the systems and methods disclosed in US Patent Application No. 10/614731 (Publication No. 2004-0071885), which is incorporated in its entirety and describes the systems and methods for creating barrier layers. In some embodiments, the closure materials can be modified to increase barrier properties. For example, the foam material may have additives (e.g., microparticles) that improve the barrier properties of the foam material. The skilled person will be able to choose the closure design to achieve the desired barrier properties.

4. Products with tie layers [0380] Examples of products may be multi-layer products. A tie layer may be arranged between one or more than one of the parts or layers of the articles. For example, the articles may have a tie layer applied between the layers of materials. The articles may have a plurality of tie layers, preferably one of the tie layers is sandwiched between a pair of adjacent layers. In some embodiments, there are many pairs of adjacent layers, each having one of the tie layers applied between them.

[0381] The container 83 of FIGURE 6 may have a tie layer 85 (FIGURE 7) between the layer 52 and the layer 54. In some non-limiting embodiments, the layer 52 comprises one or more of the following: foam material (including foamed PP,

(Foamed PET, etc.), non-foamed material (e.g., phenoxy, PET, PP thermoplastics), combinations thereof, or other material suitable for forming the outer part of the preform. Layer 54 contains one or more of the following materials: PET, phenoxy plastic, polyolefin-phenoxy plastic mixture, combinations thereof, or other suitable materials suitable for forming part of the container wall. In some embodiments, the outer layer 52 comprises PP (foamed or non-foamed) and the inner layer 54 comprises PET. The tie layer 85 may contain adhesives, phenoxy type thermoplastics, polyolefins, or combinations thereof (e.g., a polyolefin-phenoxy plastic blend). The tie layer 85 may preferably adhere to both layers 52, 54. The phenoxy material can provide the desired adhesion, for example between the inner layer 54 containing PET and the outer layer 52 containing PP.

[0382] The multilayer articles illustrated in FIGURES 8-14B and 18-21E may have one or more tie layers, preferably one of the tie layers is located between at least two of the tie layers. For example, the tie layer may be sandwiched between layers 52, 54 of preform 76 (FIGURE 9). The tie layer may be sandwiched between layers 134, 136 and / or between the preform 30 and layer 134 of FIGURE 10. The preform 160 (FIGURE 11) may have a tie layer sandwiched between layer 164 and layer 162. The preform 180 (FIGURE 12) may have a tie layer sandwiched between layer 184 and layer 183. The preform 190 (FIGURE 13) may have the tie layer sandwiched between layer 194 and layer 199. The preform 202 (FIGURE 14) may have a tie layer sandwiched between layer 203 and layer 283.

[0383] With reference to FIGURE 19, the closure 302 may have a tie layer between the layer 314 and the outer portion 311. In some non-limiting embodiments, the outer portion 311 comprises one or more of the following: foam material (including foamed PP, foamed PET, etc. ), non-foamed material (e.g., phenoxy, PET, PP thermoplastics), combinations thereof, or other materials suitable for forming the outer part of the closure. Layer 314 includes one or more of the following: PET, a phenoxy type thermoplastic, a polyolefin-phenoxy type thermoplastic blend, combinations thereof, or other materials suitable for forming part of the closure. The tie layer may contain adhesives, phenoxy type thermoplastics, polyolefins, their combinations (e.g., polyolefin-phenoxy type thermoplastic blend). Similarly, the closures illustrated in FIGURES 21A-21E may also have one or more tie layers, preferably at least one tie layer, between a pair of adjacent layers.

[0384] A further advantage is obtained when the tie layer comprises a phenoxy type thermoplastic, such as a phenoxy blend, which can help the compatibility of some degree of pure phenoxy layer and another layer. Phenoxy plastics are effective compatibilizers for polypropylene, polyethylene, and the like.

[0385] In light of the present disclosure, one of ordinary skill in the art may choose different material (s) and tie layer (s) to obtain desired product properties.

5. Articles containing lamellar material [0386] The lamellar material may form one or more parts of the layers of articles (such as packaging, including preforms, closures, and containers). With reference to FIGURE 2, the preform 30 may comprise lamellar material. FIGURE 40 is an enlarged cross-sectional view of the wall section 43 of the preform 30. In the illustrated embodiment, the wall section 43 comprises lamellar material that includes one or more layers.

EP 1 742 785 B1

Preferably, the lamellar material is made of a plurality of microlayers. However, the layers of lamellar material can be of any suitable size, depending on the desired properties and characteristics of the preform and the resulting container formed from the preform. The layers of the wall section 43 may contain materials generally similar or different. One or more of the layers forming the wall section 43 may be made of materials disclosed herein or other materials known in the art.

[0387] In the illustrated embodiment, the wall section 43 has an inner layer 47, an outer layer 45, and one or more intermediate layers 41 therebetween. In some embodiments, the inner layer 47 is suitable for contacting food products, such as unused polyethylene terephthalate ("PET"), or other suitable material that can form the inner chamber of a bottle made of preform 30.

[0388] Optionally, the wall section 43 may have at least one layer of material with good gas barrier properties. In some embodiments, the wall section 43 of the preform 30 has a plurality of layers having good gas barrier characteristics. Preferably, one or more layers of the wall section 43, which includes a barrier material, can inhibit or prevent fluid entry and / or exit through the wall of the container made of the preform 30. However, wall section 43 may include a plurality of layers that do not have good barrier properties.

[0389] The wall section 43 of the preform 30 may have at least one layer formed from recycled or post-consumer PET ("RPET"). For example, In one embodiment, the wall section 43 may have multiple layers formed from RPET. In some embodiments, the inner layer 47 may be formed of unused PET and the other layers of the wall section 43 may be formed of unused PET or RPET. Thus, the preform 30 may include alternating thin layers of PET, RPET, barrier material, and combinations thereof. In addition, other materials may be used to obtain the desired characteristics and physical properties of the preform 30, or the resulting container made of the preform 30.

[0390] Each of the layers of the wall section 43 may generally have the same thickness. Alternatively, the layers of the wall section 43 may have thicknesses generally different. The skilled person will be able to determine the desired number of layers, the thickness of each layer, and the composition of each of the layers of the wall section 43. In one non-limiting embodiment, the preform 30 may have a wall section 43 comprising more than two layers. In some embodiments, the wall section 43 has more than three layers.

[0391] As shown in FIGURE 40, the layers of lamellar material forming the wall section 43 may be generally parallel to one of the inner surface 49 and the inner surface 51 of the preform 30. Parts of the lamellar material forming the body portion 34 may include layers that are generally parallel to the axis longitudinal preform 30.

[0392] The distance and / or orientation of the layers of the wall section 45 may vary or remain generally constant along the wall section 43. In addition, the thickness of one or more layers of the wall section 43 may also vary, or they may be substantially constant along the preform 30. Brane it is contemplated that one or more of the layers may have holes, holes, or penetrate into the adjacent layer.

[0393] The lamellar material can also form other monolayer and multilayer products. With reference to, for example, Figure 5, the preform 50 may include an outer layer 52 and an inner layer 54 defining the inner surface of the preform 50. The outer layer 52 preferably does not extend to the neck portion 32, nor is it present on the inner surface of the preform 50 of at least one outer layer 52, and inner layer 54 may comprise lamellar material. In the illustrated work

On the other hand, the outer layer 52 contains lamellar material, and the inner layer 54 contains other material. Preferably, the inner layer 54 comprises PET, preferably unused PET, such that the inner surface of the preform 50 is suitable for contact with food products. In another embodiment, which is not illustrated, the inner layer 54 comprises lamellar material and the outer layer 52 comprises another material. Preferably, the inner layer 54 comprises PET, which forms the inner surface. However, the inner layer 54 may contain other materials described herein (e.g., foam, PET, including unused PET, and RPET, PP, etc.). Alternatively, both the inner layer 54 and the outer layer 52 may comprise lamellar material. Thus, various combinations of materials may be used to form the preforms disclosed herein.

[0394] The articles illustrated in FIGURES 6-17 may include a plurality of layers. One or more layers of these products may contain lamellar material. For example, the preform 60 illustrated in FIGURE 8A includes an outer layer 52 formed of lamellar material. The outer layer 52 covers the bottom surface of the support ring 38 and extends along the body portion 34.

[0395] With reference to Figure 10, one or more of layers 134 and 136 may comprise lamellar material. For example, in one embodiment, substantially all of the preform 132 is formed of different lamellar layers 134 and 136 that abut against each other. In some embodiments, at least one of layers 134 and 136 comprises lamellar material, foam material, phenoxy type thermoplastics, PET, PP (including foamed and non-foamed), and the like. Optionally, only one of layers 134 and 136 may be formed of lamellar material.

[0396] Closures may also contain lamellar material. The lamellar material may form an essential part of the closure or only a part thereof. In some non-limiting embodiments, the lamellar material constitutes less than about 95% by weight of the closure, also including less than about 5%, 15%, 25%, 35%, 45%, 55%, 65%, 75%, 85% by weight. In some embodiments, the lamellar material is in ranges including these values, the weight percentage of closure.

[0397] As shown in FIGURE 19, at least part of the closure 302 includes lamellar material. Layer 314 and / or outer portion 311 may comprise lamellar material. In one embodiment, the outer portion 311 comprises lamellar material and layer 314 comprises lamellar material (such as PP, PET, etc.). In addition, the inner part of the closures may contain lamellar material. In some embodiments, the outer parts of the closure may or may not contain lamellar material. The closures of FIGURES 21A to 21E may have similar or different inner and outer layers (or outer parts).

[0398] FIGURE 21 C illustrates a closure 360 ​​having an intermediate layer 364 that is formed of materials having the desired structural, thermal, optical, barrier, and / or features. For example, layer 364 may be formed of lamellar material.

[0399] The lamellar material may, for example, form at least part of the closure layer 344 340 (FIGURE 21A), the closure layer 356 350 (FiGuRA 21B), the layer 366 and / or the closure layer 364 360 (FIGURE 21C), the closure layer 374 370 (FIGURE 21D), closure layers 383 380 (FIGURE 21E). Other parts of the closure may be formed of similar material or different material. In some embodiments, most or all of the closures comprise lamellar material.

6. Products Containing a Heat Resistant Layer [0400] The products described herein may contain one or more heat resistant materials. The term "heat resistant materials" as used herein is a term

EP 1 742 785 B1 broadly and is used in its usual sense and includes, without such limitation, materials that may be suitable for applications with hot or hot filling. For example, the heat resistant material may include high heat resistance material that has dimensional stability during the hot fill process. The heat resistant material may include medium heat resistant material that has dimensional stability during the heat fill process. Heat resistant materials may include, without such limitation, polypropylene, crystalline material, polyester, and the like. In some embodiments, the heat resistant material has greater thermal stability than amorphous PET. Heat-resistant material can form part of the products (e.g. one or more layers of preform, container, closure, sheet, and other articles described herein.) [0401] In some embodiments, the container includes an inner layer containing a thermoplastic polyester, an outer layer containing a thermoplastic material (e.g. polymeric material (heat-resistant)) having a heat resistance greater than that of the thermoplastic polyester from the inner layer, and an intermediate bonding layer providing adhesion between the inner layer and the outer layer in which the layers are coextruded prior to blow molding. Preferably, the thermoplastic polyester of the inner layer is PET, and may further comprise at least one of an oxygen scavenger and a passive barrier material mixed with the thermoplastic polyester. Preferably, the passive barrier material is a polyamide such as MXD 6.

[0402] In light of the present disclosure, one skilled in the art is able to select different types of lamellar materials to obtain the desired properties of the article made thereof. The articles disclosed herein can be created by any suitable means. For example, the articles may be formed by injection, blow molding, injection blow molding, extrusion, co-extrusion, and injection stretch blow molding, and by other methods disclosed herein. The various methods and techniques described above provide many ways to implement the invention. Of course, it should be understood that not necessarily all of the objects or advantages described herein can be obtained in accordance with each particular embodiment described herein. Thus, for example, those skilled in the art will know that methods can be carried out in a manner that achieves or optimizes one advantage or group of advantages referred to herein, but not necessarily another advantage or group of advantages that can be mentioned or suggested here .

[0403] In addition, one of ordinary skill in the art will recognize the interchangeability of the various features of the various embodiments disclosed herein. Similarly, the various features and steps discussed above and other known equivalents for each of these features or stages may be mixed and adjusted by one of skill in the art to implement methods in accordance with the principles described herein. In addition, the methods that are described and illustrated herein are not limited to the exact sequence of operations described, and one of skill in the art can select various types of lamellar material (s) to achieve the desired properties of the article produced therefrom. The articles disclosed herein can be formed by any suitable means. For example, articles can be molded by injection molding, blow molding, blow molding, extrusion, coextrusion, and stretch blow molding, and other methods disclosed herein. The various methods and techniques described above provide many ways to implement the invention. Of course, it should be understood that not necessarily all of the objects or advantages described herein can be obtained in accordance with each particular embodiment described herein. Thus, for example, those skilled in the art will know that methods can be carried out in a manner that achieves or optimizes one advantage or group of advantages referred to herein, but not necessarily another advantage or group of advantages that can be mentioned or suggested here .

[0404] Although the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specific disclosed embodiments to other alternative embodiments and / or uses and their obvious modifications and equivalents. Accordingly, it is not intended to limit the invention by the specific embodiments disclosed herein. On the contrary, it is the applicant's intention that the scope of the invention be limited only by the appended claims and that variations of the methods and materials disclosed herein which will be apparent to those skilled in the art will fall within the scope of the applicant's invention.