Multilayered container, die for multilayered container, and method for producing multilayered container.
Abstract
Disclosed is a multilayered container that has excellent gas-barrier properties and resistance to inter-layer delamination and that can be produced even without using a molding method of which the steps are cumbersome or specialized devices of the sort that raise production costs. Specifically, disclosed is a multilayered containerâ¿¿which has a layered structure comprising at least three layers, and having at least a gas-barrier layer between an innermost layer and an outermost layerâ¿¿wherein, at the portion comprising the aforementioned layered structure, the aforementioned gas-barrier layer has a portion having a thickness that is 0.01 to 0.9 times the maximum thickness of said gas-barrier layer. Further disclosed are: a die suited for producing said multilayered container; and a method for producing the multilayered container using said die.

Term
4.6 yearsleft in the term
Expires 15 April 2031.
- Priority
- Filed
- Granted
- Today
- Expires
13 claims: 7 independent, 6 dependent
- 1REIVINDICACIONES Habiéndose descrito la invención como antecede, se reclama como propiedad lo contenido en las siguientes reivindicaciones:1. Un recipiente de múltiples capas, caracterizado porque comprende una estructura laminada de tres o más capas que tiene al menos una capa de barrera a gases entre una capa más interior y una capa más exterior, en donde la capa de barrera a gases en un sitio formado de la estructura laminada tiene una porción que tiene un espesor 0.01 a 0.9 veces tan grande como un espesor máximo de la capa de barrera a gases.
- 2El recipiente de múltiples capas de conformidad con la reivindicación 1, caracterizado porque una masa del sitio formado de la estructura laminada da cuenta de 3 0% en masa o más de un recipiente completo de múltiples capas.
- 3El recipiente de múltiples capas de conformidad con la reivindicación 1 o 2, caracterizado porque la estructura laminada comprende una estructura laminada de tres capas o cinco capas.
- 4El recipiente de múltiples capas de conformidad con cualquiera de las reivindicaciones 1 a 3, caracterizado porque la capa de barrera a gases se forma de al menos una clase de componente seleccionado de una resina de poliamida, una resina de copolímero de etileno-acetato de vinilo, una resina poliacrilonitrilo, una resina de cloruro de polivinilideno, y un ácido poliglicólico.
- 5El recipiente de múltiples capas de conformidad con la reivindicación 4, caracterizado porque la resina de poliamida comprende una resina de poliamida que contiene grupos m-xilileno.
- 6El recipiente de múltiples capas de conformidad con cualquiera de las reivindicaciones 1 a 5, caracterizado porque la estructura laminada comprende una capa más interior y una capa más exterior cada una formada de al menos una clase de componente seleccionado de una resina de poliéster termoplástico, una resina de poliéster de copolímero termoplástico, una resina basada en poliolefina, una resina de poliamida alifática, una resina de policarbonato, una resina de poliacrilonitrilo, una resina de cloruro de polivinilo, y una resina de poliestireno.
- 7El recipiente de múltiples capas de conformidad con cualquiera de las reivindicaciones 1 a 6, caracterizado porque el recipiente múltiples capas comprende un cuerpo de botella.
- 8Un molde para un recipiente de múltiples capas, caracterizado porque comprende:una porción (I) de mitad fría que incluye una cavidad;y una porción (II) de mitad caliente que incluye una primera ruta de flujo de resina para conectar un interior de un primer cilindro de inyección a la cavidad, una segunda ruta de flujo de resina para conectar un interior de un segundo cilindro de inyección a la cavidad, y una porción de unión de la primera ruta de flujo de resina y la segunda ruta de flujo de resina, en donde la porción de unión incluida en la porción (II) de mitad caliente se coloca corriente arriba de una porción de orificio de inyección abierta a la cavidad incluida en la porción (I) de mitad fría, y la segunda ruta de flujo de resina incluye un medio para inhibir parcialmente un flujo de resina.
- 9El molde para un recipiente de múltiples capas de conformidad con la reivindicación 8, caracterizado porque:el medio para inhibir parcialmente un flujo de resina comprende un medio para proporcionar una porción convexa en al menos una parte en la segunda ruta de flujo de resinas;y una porción más larga en una dirección al diámetro y una porción más larga en una dirección tangencial circunferencial de una sección transversal en una dirección vertical a una dirección de flujo de la segunda ruta de flujo de resina tiene una longitud de a mm y una longitud de b mm, respectivamente, a y b que satisfacen las siguientes relaciones: 0.01r a lr (Expresión 1);y 0.01r b lr (Expresión 2) donde r representa un radio (mm) de la segunda ruta de flujo de resinas.
- 10El molde para un recipiente de múltiples capas de conformidad con la reivindicación 8 o 9, caracterizado porque el medio para inhibir parcialmente un flujo de resina comprende un medio para proporcionar una porción convexa en al menos dos sitios en la segunda ruta de flujo de resina.
- 11El molde para un recipiente de múltiples capas de conformidad con cualquiera de las reivindicaciones 8 a 10, caracterizado porque la porción convexa se proporciona entre 0 cm a 5 cm corriente arriba de la porción de unión de la primera ruta de flujo de resina y la segunda ruta de flujo de resina.
- 12Un método de producción para un recipiente de múltiples capas que comprende una estructura laminada de tres o más capas que tiene al menos al menos una capa de barrera a gases entre una capa más interior y una capa más exterior, en la cual la capa de barrera a gases en un sitio formado de la estructura laminada tiene una porción que tiene un espesor 0.01 a 0.9 veces tan grande como un espesor máximo de la capa de barrera a gases, caracterizado porque comprende llevar a cabo el moldeo usando el molde de conformidad con cualquiera de las reivindicaciones 8 a 11.
- 13Un método de producción para un recipiente de múltiples capas que comprende una estructura laminada de tres o más capas que tiene al menos una capa de barrera a gases entre una capa más interior y una capa más exterior, en el cual la capa de barrera a gases en un sitio formado de la estructura laminada tiene una porción que tiene un espesor 0.01 a 0.9 veces tan grande como un espesor máximo de la capa de barrera a gases, caracterizado porque comprende:formar una preforma de múltiples capas usando el molde de conformidad con cualquiera de las reivindicaciones 8 a 11;y luego moldeo por soplado la preforma de múltiples capas.
Independent claims13
243 paragraphs in 3 sections, as filed
(54) Title: MULTIPLE LAYER CONTAINER, NOZZLE FOR MULTIPLE LAYER CONTAINER, AND METHOD TO PRODUCE MULTIPLE LAYER RECIPIENT.
(54) Title: MULTILAYERED CONTAINER, DIE FOR MULTILAYERED CONTAINER, AND METHOD FOR PRODUCING MULTILAYERED CONTAINER.
(57) Summary
A multi-layer container is provided with excellent delamination resistance and excellent gas barrier property, which can be produced without employing any molding method involving a special apparatus, increasing the production cost, and in no complicated steps . Specifically, the multi-layer container includes a three or more layer laminate structure having at least one gas barrier layer between an innermost layer and an outermost layer, in which the gas barrier layer in a The formed site of the laminate structure has a portion that is 0.01 to 0.9 times as thick as the maximum thickness of the gas barrier layer. Additionally, a suitable mold for producing the multi-layer container is provided, and a production method for a multi-layer container using the mold.
(57) Abstract
Disclosed is a multilayered container that has excellent gas-barrier properties and resistance to inter-layer delamination and that can be produced even without using a molding method of which the steps are cumbersome or specialized devices of the sort that raise production costs. Specifically, disclosed is a multilayered containerá¿¿which has a layered structure comprising at least three layers, and having at least a gas-barrier layer between an innermost layer and an outermost layerá¿¿wherein, at the portion comprising the aforementioned layered structure, the aforementioned gas-barrier layer has a portion having a thickness that is 0.01 to 0.9 times the maximum thickness of said gas-barrier layer. Further disclosed are: a die suited for producing said multilayered container; and a method for producing the multilayered container using said die.
MULTIPLE LAYER CONTAINER, NOZZLE FOR CONTAINER
MULTIPLE LAYERS, AND METHOD TO PRODUCE A CONTAINER OF
MULTIPLE LAYERS
Field of the Invention
The present invention relates to a multilayer container in which delamination is suppressed and which has an excellent gas barrier property, a suitable mold for making the multilayer container and a method for making a multilayer container , using the mold.
Background of the Invention
Currently, a multi-layer container such as a plastic container produced primarily from polyester such as polyethylene terephthalate (PET) is widely used for tea, a fruit juice drink, a beverage
<td>carbonated</td><td>and the like.</td><td>The</td><td>percentage</td><td colspan="2">from a container</td>
<td>small of</td><td>plastic in</td><td>the</td><td>container</td><td>of plastic</td><td>I know</td>
<td>increases</td><td>year with year.</td><td>A</td><td>reduction</td><td>in size</td><td>of the</td>
Container increases surface area per unit volume. Therefore, as the plastic container becomes smaller in size, the shelf life of the contents tends to become shorter. Additionally, in recent years, the plastic container has been used for a beer container that is prone
Ref .: 231179 to be affected by oxygen and light, and a plastic bottle has also been used as a container for hot tea. In this way, the range of use of the plastic container is increasing. Accordingly, there is a need for a further improvement in the gas barrier property of the plastic container.
In order to address the aforementioned need, a multilayer container or mixing container using a thermoplastic polyester resin and a gas barrier resin, or a barrier coated container obtained by subjecting a single layer bottle produced from a thermoplastic polyester resin to carbon coating, vapor deposit, or barrier resin coating, It has been developed as a method of imparting the gas barrier property to a multi-layered container.
As an example of the multilayer container, a container obtained by using a thermoplastic polyester resin such as PET as a resin to each form an innermost and an outermost layer and by using a resin has been put to practical use. thermoplastic having the gas barrier property such as poly-m-xyleneadipamide (called polyamide MXD6) as a resin to form an inner layer, and injecting these resins simultaneously or successively to fill a mold cavity, and molding a preform structure (parison) having three or five layers, and additionally subjecting the resulting preform to biaxial stretch blow molding.
In addition, a resin having an oxygen scavenging function has been developed to remove oxygen in a container while oxygen is blocked from outside the container and has been applied to the multi-layer container has been developed, as a container Removal Oxygen, a multi-layer container that uses, in a gas barrier layer, a MXD6 polyamide resin composition (made by MITSUBISHI GAS CHEMICAL COMPANY, INC ..) mixed with a transition metal-based catalyst in view of transparency, oxygen absorption rate, strength, moldability and the like.
The multi-layer container, mentioned above, is used as a container for beer, tea, a carbonated drink or the like due to its satisfactory gas sweeping property. The multi-layer container is used for those applications to achieve quality control of the contents and improvement of shelf life. However, there is a problem in that delamination occurs between the different resins, for example, between each of an innermost layer and an outermost layer and a gas barrier layer, resulting in a decrease in commercial value.
Regarding a method of solving this problem, Patent Document 1 describes that delamination is improved, during the final injection of a resin to each form an innermost layer and an outermost layer in a mold cavity , by interposing a crude mixed resin between the layers using a backflow control apparatus capable of allowing a predetermined amount of resin to flow back to the side of the gas barrier layer, thus preparing a preform.
Additionally, Patent Document 2 describes a method that includes subjecting a preform to thermal shrinkage during secondary molding and then blowing the resulting under high pressure again.
Prior Art Documents
Patent Document
Patent Document 1: Japanese Patent Application Revealed No. 2000-254963
Patent Document 2: Japanese Patent Application Revealed No. 2001-206336
Brief Description of the Invention Problems to be Solved by the Invention
However, the method described in disclosed Japanese Patent Application No. 2000-254963 has a problem in that the production cost is increased because a special backflow control apparatus is used. Meanwhile, the molding method which includes subjecting a preform to thermal shrinkage and then blowing the resulting under high pressure, such as the method described in disclosed Japanese Patent Application No. 2001-206336, has a problem in that the formability is poor, in the inferior form of a molded article, and the method comprises a complicated step.
An object of the present invention is to provide a multilayer container that is excellent in delamination resistance and gas barrier property, which can be produced without employing any molding method comprising a special apparatus, which would increase the production cost, and a complicated step, a suitable mold to produce the multilayer container and a production method for a multilayer container using the mold.
Means To Solve Problems
The present invention relates to the following points [1] to [13].
[1] A multi-layer container, which includes a laminated structure of three or more layers having at least one gas barrier layer between an innermost layer and an outermost layer, in which the gas barrier layer in A formed site of the laminated structure has a portion that is 0.01 to 0.9 times as thick as a maximum thickness of the gas barrier layer.
[2] The multilayer container according to item [1] mentioned above, in which the mass of the formed site of the laminated structure accounts for 30% by mass or more of a complete multilayer container.
[3] The multi-layer container according to point [1] or [2] mentioned above, in which the laminated structure comprises a three-layer or five-layer laminated structure.
[4] The multi-layer container according to any of the points [1] to [3] mentioned above,
<td colspan="2">in which the</td><td colspan="4">gas barrier layer is formed of at least</td>
<td>one class</td><td>of</td><td colspan="2">selected components</td><td>of a resin</td><td>of</td>
<td>polyamide,</td><td>a</td><td>resin</td><td>polyamide that</td><td>contains groups</td><td>m-</td>
<td>xylylene,</td><td>a</td><td>resin</td><td>copolymer</td><td>ethylene-acetate</td><td>of</td>
vinyl, a polyacrylonitrile resin, a polyvinylidene chloride resin, and polyglycolic acid.
[5] The multi-layer container according to the above-mentioned point [4], in which the polyamide resin comprises a polyamide resin containing m-xylylene groups.
[6] The multi-layer container according to any of the points [1] to [5] mentioned above, in which the laminated structure comprises an innermost layer and an outermost layer each formed of at least one kind is Selected component of a thermoplastic polyester resin, a thermoplastic copolymer polyester resin, a polyolefin based resin, an aliphatic polyamide resin, a polycarbonate resin, a polyacrylonitrile resin, a polyvinyl chloride resin, and a polystyrene resin.
[7] The multi-layer container according to any of the points [1] to [6] mentioned above, in which the multi-layer container comprises a bottle body.
[8] A mold for a multi-layer container, including:
a portion (I) of cold half including a cavity; and a portion (II) of hot half including a first resin flow path to connect the interior of a first injection cylinder to the cavity, a second resin flow path to connect the interior of a second injection cylinder to the cavity, and a joint portion of the first resin flow path and the second resin flow path, wherein the bonding portion included in the hot half portion (II) is placed upstream of the open injection port to the cavity included in the cold half portion (I), and the second resin flow path includes a means to partially disable a flow of resin.
[9] The mold for a multi-layer container according to point [8] mentioned above, in which:
the means for partially inhibiting a resin flow comprises a means for providing a convex portion in at least one part in the second resin flow path; and a longer portion in a diameter direction and a longer portion in a circumferential tangential direction of a cross section in a vertical direction to a flow direction of the second resin flow path has a length of a mm and a length of b mm, respectively, a and b satisfying the following relationships:
0.01r <a <lr (Expression 1); and
0.01r <b <lr (Expression 2) where r represents a radius (mm) of the second resin flow path.
[10] The mold for a multilayer container according to point [8) or [9] mentioned above, in which the means to partially inhibit a flow of resin comprises a means to provide a convex portion in at least two places in the second resin flow path.
[11] The mold for a multilayer container according to any of the points [8] to [10] mentioned above, in which the convex portion is provided between 0 cm to 5 cm upstream of the union portion of the first resin flow path and the second resin flow path.
[12] A method of producing a multi-layer container that includes a three or more layer laminated structure having at least one gas barrier layer between an innermost layer and an outermost layer, in which the layer of gas barrier at a formed site of the laminated structure has a portion having a thickness 0.01 to 0.9 times as large as a maximum thickness of the gas barrier layer, the method includes carrying out the molding using the mold according to any of the points [8] to [11] mentioned above.
[13] Method of producing a multi-layer container including a three or more layer laminate structure having at least one gas barrier layer between an innermost layer and an outermost layer, in which the barrier layer is gases at a formed site of the laminated structure has a portion having a thickness 0.01 to 0.9 times as large as a maximum thickness of the gas barrier layer, the method includes forming a multi-layer preform using the mold according to any of the points [8] to [11] mentioned above; and then blow molding the multi-layer preform.
Effects of the Invention
The multilayer container of the present invention is of excellent delamination resistance and excellent gas barrier property. Furthermore, delamination can be circumscribed even when the multilayer container is not formed into a shape having small uneven and flex portions, allowing a degree of freedom in the shape of the container to be increased.
Additionally, a mold for a multilayer container according to the invention of the present application can be used to produce the multilayer container without using any molding method comprising a special apparatus, which would increase the cost of production and a complicated step.
Brief Description of the Figures
In the attached figures:
Figure 1 is a conceptual diagram of a mold used in Example 1 under a state in which injection molding is not carried out on the mold;
Figure 2 is a conceptual diagram of the mold used in Example 1 in a state just prior to molding a multi-layer container into the mold;
Figure 3 is a conceptual diagram of the vicinity of a cavity to illustrate a position in which a means is provided to partially inhibit a flow of resin in the mold used in Example 1;
Figure 4 is a conceptual diagram of the vicinity of a junction portion of the first resin flow path and a second resin flow path to illustrate a position in which the means is provided to partially inhibit resin flow in a mold of the present invention;
Figure 5 (a) is a schematic view of a cross section taken along the direction of arrow AA in Figure 4 of the means for partially inhibiting a flow of resin from the mold of the present invention, and Figure 5 (b) is a schematic cross-sectional view taken along the direction of arrow BB in Figure 4 of the means for partially inhibiting a flow of resin from the mold of the present invention;
Figures 6 (a) to 6 (d) are each a schematic cross-sectional view taken along the direction of arrow AA in Figure 4 of an aspect of the means for partially inhibiting a flow of resin from the mold of the present invention, and it should be noted that Figure 6 (d) is a schematic view of a mold in which a resin flow path 23A is also provided in the central portion of a resin flow path 23B, and a means for partially inhibiting a resin flow is also provided in the circumferential portion of the resin flow path 23A in the central portion of the resin flow path 23B;
Figures 7 (a) and 7 (b) are schematic cross-sectional views taken along the direction of arrow AA and the direction of arrow BB, respectively, of Figure 4 in a way to partially inhibit a resin flow from the mold in Example 1; and
Figure 8 is a schematic view of a second resin layer (gas barrier layer) in a cross section of the multilayer container molded using the mold of the present invention.
Detailed Description of the Multilayer Container Invention
A multi-layer container of the present invention is a multi-layer container, including a three or more layer laminate structure having at least one gas barrier layer between an innermost layer and an outermost layer, in which the gas barrier layer at a formed site of the laminated structure has a site (hereinafter, sometimes referred to as a concave portion of the gas barrier layer (having a thickness (ti) 0.01 to 0.9 times as large as the maximum thickness (t<sub>0</sub>) of the gas barrier layer.
The gas barrier layer has a concave portion that is 0.9 times or less thick (0.01 to 0.9 times as large as the gas barrier layer is continuous) as large as the maximum thickness (t<sub>0</sub>) of the gas barrier layer, and thus delamination of the multi-layer container is effectively suppressed. From this point of view, the gas barrier layer has a concave portion having a thickness of preferably 0.01 to 0.8 times, more preferably 0.02 to 0.7 times, even more preferably 0.03 to 0.6 times, particularly preferably 0.05 to 0.5 times as large as the maximum thickness of the gas barrier layer. The position of the concave portion of the gas barrier layer is not particularly limited. However, from the viewpoint of further improving the resistance to delamination, it is recommended that at least one, preferably two or more (approximately 2 to 15), more preferably 3 or more (approximately 3 to 10) even more preferably 4 or more (about 4 to 8) concave portions exist in a cross section in the case of horizontal cutting of the multilayer container in round cuts. When there is a plurality of concave portions in the cross section in the case of horizontally cutting the multi-layer container in round cut, the ratios ti / t<sub>0</sub> of the respective concave portions may be identical to or different from each other.
In the multi-layer container of the present invention, the laminated structure having a gas barrier layer is preferably three-layer or five-layer. The mass of the formed site of the laminated structure accounts for, from the point of view of satisfying the gas barrier property of the multilayer container, preferably 30% by mass or more, more preferably 4 0% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 8 0% by mass or more of the complete multi-layer container.
In the multi-layer container, the outermost layer, the innermost layer, and the respective layers excluding the gas barrier layer each have a thickness preferably of 0.01 to 2 mm, more preferably of 0.05 to 1.5 mm, and the gas barrier layer is bonded to a thickness preferably from 0.005 to 0.2 mm (from 5 to 200 pm), more preferably from 0.01 to 0.15 mm (10 to 150 pm). Additionally, the thickness of the multi-layer container is not necessarily constant across the entire bottle but generally falls within the range preferably of about 0.2 to 4 mm.
In the multilayer container of the present invention, the mass of the gas barrier layer is preferably 1 to 20 mass% relative to the total mass of the formed site of the laminate structure having a barrier layer to gases. When the mass falls within the aforementioned range, a satisfactory gas barrier property is obtained and molding of a multi-layer preform as a precursor in a multi-layer container is facilitated. From this point of view, the mass of the gas barrier layer is preferably 2 to 15% by mass, even more preferably 3 to 10% by mass with respect to the total mass of the formed site of the structure laminate having a gas barrier layer.
The multi-layer container of the present invention has excellent delamination resistance and excellent gas barrier property and is therefore useful for a container for a liquid beverage, liquid food, or the like. The shape is not particularly limited but is preferably a bottle body.
Layer Components Excluding Barrier Layer a
Gases
The components for forming the layers (including an outermost layer and an innermost layer) excluding the gas barrier layer contained in the multi-layer container of the present invention, are not particularly limited, and components which are They will use for a multi-layer container such as a beverage container. Examples of the components to form layers excluding the gas barrier layer include: thermoplastic polyester resins such as polyethylene terephthalate (PET), polylactic acid (PLA), or polyethylene-2,6-naphthalate (PEN); a thermoplastic copolymer polyester resin; a polyolefin based resin; an aliphatic polyamide resin; a polycarbonate resin; a polyacrylonitrile resin; a polyvinyl chloride resin; and a polystyrene resin. One class of these components can be used alone, or two or more classes of these can be used in combination. The combination of two or more classes is, for example, a mixture of PET and PEN. Of these, a polyester resin (hereinafter referred to as polyester (A)) is preferred. It should be noted that it is not denied that the outermost layer, the innermost layer, and any of the other layers each have a gas barrier property, all layers may have a gas barrier property, but generally a shape in which the gas barrier layer is sandwiched between the aforementioned components is adopted from the point of view of production cost or the like.
Polyethylene terephthalate (PET) and polylactic acid (PLA) are each suitably used as the polyester (A). Of these, polyethylene terephthalate is more preferred because it exhibits excellent characteristics in all of transparency, mechanical strength, injection molding capacity, and stretch blow molding capacity.
Here, the term polyethylene terephthalate generally means polyester in which terephthalic acid gives
<td colspan="2">80% mole count or</td><td>plus</td><td>, of</td>
<td>or more than one</td><td colspan="2">component</td><td>of</td>
<td>ethylene glycol gives</td><td>bill</td><td>of</td><td> 80</td>
<td>preferred 90%</td><td>in mol</td><td>or</td><td>plus</td>
in mole or more, so you can use, as the remaining acid component excluding terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid , adipic acid, cabasic acid, decane-1,10-dicarboxylic acid, and hexahydroterephthalic acid. Additionally, as the remaining diol component excluding ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, 2,2'-bis (4-hydroxyethoxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane. , and the like. Furthermore, an oxyacid such as p-oxybenzoic acid can also be used as a raw material monomer for the thermoplastic polyester resin.
Polyether (A) has an intrinsic viscosity preferably from 0.55 to 1.3, more preferably 0.65 to 1.2, even more preferably from 0.70 to 0.9. When the intrinsic viscosity is 0.55 or more, the multilayer preform can be obtained in a transparent amorphous form and the resulting multilayer container also has satisfactory mechanical strengths. When the intrinsic viscosity is 1.3 or less, the bottle is molded easily without impairing flowability during molding. It should be noted that the intrinsic viscosity (η) was measured using a phenol / tetrachloroethane mixed solvent = 6/4 (mass ratio). It should be noted that the intrinsic viscosity is determined, for example, by
ASTMD4603—03 or ASTM D1601.
It is preferred that the outermost layer or the innermost layer of the multi-layer container of the present invention be formed primarily of polyester (A). However, a product obtained by mixing polyester (A) with other thermoplastic resins and various can be used.
<td>additives in a</td><td>interval</td><td>such</td><td>than</td><td>not</td><td>I know</td><td>deteriorate</td><td>the</td>
<td>characteristic of</td><td colspan="2">the present</td><td colspan="2">invention.</td><td>In</td><td>that case,</td><td>I know</td>
<td>prefers that 90%</td><td>en masse or</td><td>plus</td><td>of the</td><td>cap</td><td>plus</td><td>outside or</td><td>the</td>
innermost layer is produced from polyester (A).
Examples of the other thermoplastic resins include a thermoplastic polyester resin such as polyethylene-2,6-naphthalenedicarboxylate, a resin based on polyolefin, polycarbonate, polyacrylonitrile, polyvinyl chloride, and polystyrene.
Additionally, examples of additives include a UV absorber, an oxygen absorber, a colorant, and an infrared light absorber (reheat additive) to shorten the cycle time at the time of molding through acceleration of heating. of a preform.
Component of the Gas Barrier Layer
A component for forming the gas barrier layer contained in the multilayer container of the present invention is not particularly limited and a known resin having gas barrier property can be used. The component for forming the gas barrier layer is preferably one that satisfies the following oxygen transmission coefficient. Examples thereof include: a polyamide resin such as a polyamide resin containing m-xylylene groups (nylon resin
MX); an ethylene-vinyl acetate copolymer resin; a polyacrylonitrile resin; a polycididene chloride resin; and polyglycolic acid (PGA). One class of this can be used alone, or two or more of these classes can be used in combination. Of these, a polyamide resin is preferred and a myxylene group containing polyamide resin is more preferred from the viewpoints of the gas barrier property and the recycle property.
The phrase having gas barrier property as used herein means that a layer itself that forms a gas barrier layer has an oxygen transmission coefficient of 1.0 cc «mm / (m<sup>2</sup>* day * atm) or less under the condition of a temperature of 23 ° C and a relative humidity of 80% RH during the molding of a multilayer container. The oxygen transmission coefficient is preferably 0.8 cc »mm / (m<sup>2</sup>"Day" atm) or less, more preferably 0.20 cc * mm / (m<sup>2</sup>»Day« atm) or less, even more preferably 0.15 cc »mm / (m<sup>2</sup>* day * atm), particularly preferably 0.09 cc * mm / (m<sup>2</sup>"Day * atm) or less. When the resin that has the gas barrier property can be used as the gas barrier layer, the resulting multi-layer container has satisfactory gas barrier performance, which can contribute to the extension of the expiration to consume the contents that will be preserved.
The preferred myxylene group containing polyamide resin (MX nylon resin) as the component to form the gas barrier layer is preferably polyamide (hereinafter, referred to as polyamide (B)) obtained by subjecting a diamine component including 70 mol% or more of m-xylylenediamine and a dicarboxylic acid component including 50 mol% or more of an α, ω-linear aliphatic dicarboxylic acid It has 4 to 20 carbon atoms to polycondensation. Polyamide (B) has high barrier performance, exhibits excellent characteristics in injection molding capacity and stretch blow molding capacity with polyester (A), and has satisfactory molding capacity.
The diamine component in the polyamide (B) preferably contains 70 mol% or more, more preferably 75 mol% or more, more preferably 80 mol% or more of m-xylylene diamine. When the m-xylylene diamine content in the diamine component is 70 mol% or more, the polyamide (B) exhibits a satisfactory gas barrier property.
A diamine component that can be used for the diamine component excluding m-xylylene diamine in the polyamide (B) is exemplified by: aliphatic diamines such as tetramethylenediamine, pentamethylenediamine,
222 methylpentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4, trimethylhexamethylenediamine, and 2,2,4-trimethylhexamethylenediamine;
alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3, aminocyclohexane, 1,4, -diaminocyclohexane, bis, (4-aminocyclohexyl) methane, 2,2-bis ( 4-aminocyclohexyl) propane, bis (aminomethyl) decalin, and bis (aminomethyl) tricyclodecane; and diamines each having an aromatic ring, such as, but not limited to, bis, (4-aminophenyl) ether, p-phenylenediamine, p-xylylenediamine, and bis (aminomethyl) naphthalene.
The dicarboxylic acid component in polyamide (B) preferably contains 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more of an aliphatic dicarboxylic acid α , ω-linear having from 4 to 20 carbon atoms. When the content of the α, lineal-linear aliphatic dicarboxylic acid falls within the range mentioned above, the polyamide exhibits excellent gas sweeping property and excellent molding ability. Examples of the α, lineal-linear aliphatic dicarboxylic acid having from 4 to 20 carbon atoms and include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, pimeric acid, suberic acid, acelaic acid, adipic acid, sebaic acid, undecanedioic acid and dodecanedioic acid. Of these, adipic acid and sebasic acid are preferred.
Additionally, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are given, such as dicarboxylic acid excluding a, lineal-linear aliphatic dicarboxylic acid in polyamide (B).
A dicarboxylic acid component that includes 100 to 50 mol% of the aliphatic α, ωlinear dicarboxylic acid having 4 to 20 carbon atoms and 0 to 50 mol% of an aromatic dicarboxylic acid is preferably used as the component of dicarboxylic acid in the polyamide (B).
Polyamide (B) can be made by a melt condensation method. For example, polyamide is made by a method that includes heating a nylon salt formed of m-xylylene diamine and adipatic acid under pressure in the presence of water, and polymerizing the nylon salt in a molten state while removing added water. and condensation water. Additionally, the polyamide is also made by a method that includes directly adding m-xylylene diamine to adipic acid in a molten state and subjecting the mixture to polycondensation under normal pressure. In this case, in order to maintain a reaction system in a homogeneous liquid state, polycondensation to the additional m-xylylenediamine to adipic acid is carried out continuously as the temperature of a reaction system increases so that the temperature of Reaction does not drop below the melting point of each of the oligoamide and polyamide to be produced. It should be noted that a small amount of a monoamine or a monocarboxylic acid can be added as a molecular weight adjuster during a polycondensation reaction.
Additionally, polyamide (B) can be made by a melt polycondensation method and then subjected to polycondensation by solid phase polymerization. A production method for the polyamide is not particularly limited and the polyamide is produced by a conventionally known method under a conventionally known polymerization condition.
The aforementioned MX nylon resin has a generally adequate relative viscosity of 1.5 or more, preferably 2 to 4, more preferably 2.1 to 3.5. It should be noted that the relative viscosity is a viscosity in the case where a solution obtained by dissolving 1 g of a resin in 100 ml of 96% sulfuric acid is measured at 25 ° C using a viscometer
Cannon — Fenske or the like.
Polyamide (B) has a number average molecular weight preferably from 18,000 to 43,500, more preferably from 20,000 to 30,000. When the number average molecular weight falls within the range, molding into a multilayer molded article is performed satisfactorily, and a multilayer container to be obtained exhibits excellent resistance to delamination. It is noted that when polyamide (B) has a number average molecular weight of 18,000 to 43,500, polyamide (B) has a relative viscosity of about 2.3 to 4.2, and when it is 20,000 to 30,000, it is about 2.4 to
3.2.
A phosphorous compound can be added to the polyamide (B) to improve processing stability during melt molding or to prevent polyamide (B) from coloring. The phosphorus compound to be used preferably is a phosphorus compound that includes an alkali metal or an alkaline earth metal. Examples of this include alkali metal salts or alkaline earth metal salts, such as sodium, magnesium or calcium salts, of phosphoric acid, hypophosphorous acid and phosphoric acid. In particular, a phosphorous compound using an alkali metal salt or an alkaline earth metal salt of hypophosphorous acid is preferably used because it is particularly excellent in the coloration-preventing effect of polyamide. The concentration of the phosphorous compound in the polyamide (B) is preferably from 1 to 500 ppm, more preferably from 350 ppm or less, even more preferably from 200 ppm or less of the phosphorus atom. Even when the concentration of the phosphorous atom exceeds 500 ppm, the coloration-preventing effect reaches a plateau. Additionally, when the concentration of the phosphorous atoms is 500 ppm or less, there is no risk that a film obtained by using the polyamide (B) that has the phosphorus compound added to it, has an excessively high opacity value.
Another polyamide can be added to polyamide (B) for the purpose of improving delamination resistance. Examples of the other polyamide include: aliphatic polyamides such as homopolymers including poly (6-aminohexanoic acid) (PA-6) also known as poly (caprolactam), poly (hexamethylene-adipamide) (PA-6, 6), poly (7-aminoheptanoic acid) (PA —7), poly (10-aminodecanoic acid) (PA-10), poly (11-aminoundecanoic acid) (PA11), poly (12-aminododecanoic acid) (PA-12), poly (hexamethylensebacamide) (PA-6,10) , poly (hexamethylenezelamide) (PA-6.9), and poly (tetramethylene adipamide) (PA-4.6), a caprolactam / hexamethylene-adipamide hexamethylene-adipamide / caprolactam copolymer (PA-6 / 6,6); and amorphous semi-aromatic polyamides such as poly (hexamethylene isophthalamide) (PA-61), a copolymer of copolymer (PA-6,6 / 6)) and a hexamethylene-isophthalamide / hexamethylene-terephthalamide (PA-6I / 6T ), poly (m-xylylene-isophthalamide) (PA-MXDI), a caprolactam / m-xylylene-isophthalamide copolymer (PA6 / MXDI), and a caprolactam / hexamethylene isophthalamide copolymer (PA-6 / 6I), but not limited to this.
The gas barrier layer is preferably formed primarily from polyamide (B), and from the point of view of gas barrier performance, polyamide (B) is included in an amount more preferably of 70% in mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more.
The gas barrier layer can be mixed with one or more kinds of other resins such as polyester, olefin, and phenoxy resins as long as the effect of the present invention is not noticeably impaired.
Additionally, additives such as: inorganic fillers such as fiberglass and carbon fiber can be added; plate-like inorganic fillers such as glass flakes, talc, kaolin, mica, montmorillonite, and an organic clay; impact resistance modifiers such as various elastomers; crystal nucleating agents; lubricants such as fatty acid amide based compounds, fatty acid metal salt based compounds, and a fatty acid amide based compound; antioxidants such as a copper compound, an organic or inorganic halogen based compound, a hindered phenol based compound, a hindered amide based compound, a hydrazine based compound, a sulfur based compound, and a phosphorous based compound; thermal stabilizers; anti-coloring agents;
UV absorbers such as a benzonitrile based UV absorber; mold release agents; plasticizers; colorants; flame retardants; and a cobalt metal containing compound that serves as a compound to impart oxygen scavenging capacity and an alkaline compound to prevent gel formation of the polyamide. Mold for Multi-Layer Container
In the multilayer container of the present invention, the multilayer container can be produced using the following mold without employing any molding method comprising a special apparatus, which would increase the production cost and would be a complicated step. Later in the present, the mold is described in detail.
A mold for a multilayer container according to the present invention (hereinafter referred to simply sometimes as a mold includes: a portion (I) of cold half including a cavity; and a portion (II) of half Hot includes a first resin flow path to connect the inside of a first injection cylinder to the cavity. A second resin flow path for connecting the interior of a second injection cylinder to the cavity, and a bonding portion of the first resin flow path and the second resin flow path, in which the bonding portion included in the hot half portion (II) is placed upstream of an injection port portion open to the cavity in the cold half portion (I), and the second resin flow path includes a means to partially inhibit a resin flow.
It should be noted that the term upstream used herein means the side of an injection cylinder, and the term downstream means the side of a cavity.
The mold of the present invention is a mold to be used for an apparatus for molding a multi-layer container and includes a portion (22) of hot half and a portion (21) of cold half as illustrated for example in Figure 1. The hot half portion (22) has a tube through which a molten and plasticized resin flows while maintaining its molten state by virtue of a screw of an injection molding apparatus. The hot half portion (22) has a first resin flow path (23A) for connecting the interior of a first injection cylinder (10A) to a cavity (25), a second resin flow path (23B) for connecting the interior of a second injection cylinder (10B) to the cavity (25), and a joint portion in which the first resin flow path (23A) and the second flow path (23B) are joined together resin. The second resin (eg, polyamide (B)) as the component to form the gas barrier layer of the multi-layer container flows through the second resin flow path (23B). The first resin (for example, the resin that excludes the component to form the gas barrier layer, such as polyester (A)) as the component to form the outermost layer and the innermost layer flows through the first resin flow path (23A). It should be noted that the first resin may have a gas barrier property.
The cold half portion (21) is a portion into which a molten, plasticized resin is injected, cooled, and molded into a multi-layer container. The cold half portion (21) has at least one or more cavities therein.
A general mold structure for a multi-layer molding apparatus is found in, for example, disclosed Japanese patent application No. Hei 11-165330, disclosed Japanese patent application No. Sho 63-99918, and Japanese Patent Translation No. 2001504763. The mold of the present invention has a means of partially inhibiting a flow of resin (28) in the second resin flow path (23B) of the hot half portion (22) of the mold (see Figures 1 to 3).
It is preferred that the tube shape of each of the flow path cross sections in the case of cutting the first resin flow path (23A) and the second resin flow path (23B) of the present mold Invention in a plane vertical to the direction of flow of resin is circular. However, the shape of the tube is not limited to this shape, and any shape such as a rectangular shape can be adopted.
In the mold of the present invention, a site whose layer thickness is reduced due to inhibition of a flow of resin, specifically, a site (concave portion) having a thickness 0.01 to 0.9 times as large as the maximum thickness of the second resin layer as described above can be produced in part from the second resin layer (gas barrier layer) of the resulting multi-layer container, by providing the means to partially inhibit a resin flow in the second resin flow path (23B). It should be noted that Figure 8 illustrates an aspect of the cross sectional shape of the second resin layer (gas barrier layer) in the multilayer container molded using the mold of the present invention.
As described above, delamination of the multilayer container is suppressed by allowing thickness to fluctuate in the circumferential direction of the second resin layer of the multilayer container. In general, a fluctuation in thickness leads to an increase in surface area, which seems to promote delamination. However, one way in which the first resin layer leads to a wedge in the second resin layer resulted in an opposite effect than expected. This is probably because this shape improved the impact tracking ability of the second resin layer to the first resin layer in the case where an effort such as impact is applied to the multi-layer container, which contributed to an improvement in the resistance to delamination of the multilayer container.
In the mold of the present invention, the means for partially inhibiting a resin flow provided in the second resin flow path (23B) is provided in the side wall of the second resin flow path (23B). The number of the medium to be provided is preferably 2 or more, more preferably 3 or more, more preferably 4 or more from the point of view of improving the ability to track the impact of the second layer of resin to the first layer of resin to improve resistance to delamination. The upper limit value of the number of the medium to be provided is not particularly limited, but is preferably 15 or less, more preferably 12 or less, even more preferably 10 or less, particularly preferably 8 or less from the point of view of improving the impact tracking ability of the second resin layer to the first resin layer to improve resistance to delamination. Therefore, from the same point of view, the number of the means to partially inhibit a flow of resin to be provided is preferably from 2 to 15, more preferably from 2 to 12, even more preferably from 3 to 12 , even more preferably 3 to 10, even more preferably 4 to 10, particularly preferably 4 to 8.
In the mold of the present invention, the means for partially inhibiting a resin flow is preferably provided in the second resin flow path (23B) between the junction portion of the first resin flow path (23A) and the second resin flow path (23B) and the second injection cylinder (10B). In this case, it is particularly preferred that the means for partially inhibiting a flow of resin is placed in the vicinity of the aforementioned bonding portion and is preferably provided from 0 to 5 cm, more preferably from 0 to 3 cm, even more preferably from 0 to 1 cm, particularly preferably from 0 to 0.5 cm upstream of the joint portion. When the means for partially inhibiting a flow of resin is provided in the range mentioned above, it is easy to allow the thickness to fluctuate in the circumferential direction of the second resin layer of the resulting multi-layer container.
Additionally, when two or more means are provided to partially inhibit a flow of resin, the means may be provided at an identical or different distance from each other from the joint portion at which the second flow path (23B) is joined together. resin and the first resin flow path (23A).
Figure 4 illustrates an aspect of the mold of the present invention. The shape of the medium to partially inhibit a flow of resin is described. Figure 5 (a) is a conceptual diagram illustrating the shape of a cross section in the vertical direction to the resin flow direction of the resin flow path of the medium to partially inhibit a resin flow (cross section taken at along direction AA of figure 4) (it should be noted that only in the figure a means to partially inhibit a flow of resin is illustrated).
When the longest portion in the direction of the diameter and the longest portion in the circumferential tangential direction of the cross section (vertical direction) of the means to partially inhibit a flow of resin has a length of a mm and a length of b mm, respectively, it is preferred that a and b of the medium to partially inhibit a flow of resin satisfy the following expressions, respectively, from the standpoint of resistance to delamination. It should be noted that the length a of the longest portion in the diameter direction has a perpendicular relationship with the length b of the longest portion in the circumferential tangential direction. It should be noted that r represents a radius of the second resin flow path and is preferably 0.5 to 5 mm, more preferably 0.5 to 4 mm, even more preferably 1 to 3 mm.
0.01r <a <lr
0.01r <b £ lr
The lower limit value of a is preferably 0.03r, more preferably 0.05r, even more preferably O.lr. The upper limit value of a is preferably 0.9r, more preferably 0.8r, even more preferably 0.7r.
Additionally, the lower limit value of b is preferably 0.03r, more preferably 0.05r, even more preferably O.lr. The upper limit value of b is preferably 0.9r, more preferably 0.8r, even more preferably 0.7r.
It should be noted that the shape of a cross section taken along the vertical direction to the resin flow direction of the resin flow path of the medium to partially inhibit a resin flow is not particularly limited, and by For example, the shape of a portion that excludes a surface in contact with the flow path is a circle, a semicircle, or a polygon or a rectangle such as a triangle, a square, or a trapezoid (see Figures 6 (a) - 6 (d)).
So, Figure 5 (b) is a conceptual diagram illustrating the shape of a cross section taken along the direction parallel to the resin flow direction of the resin flow path of the medium to partially inhibit a flow of resin (taken along the direction BB of figure 4) (it should be noted that the figure only illustrates a means to partially inhibit a flow of resin).
When the longest portion in the diameter direction and the longest cross-sectional (parallel direction) portion of the medium for partially inhibiting resin flow have a length of a mm and a length of y mm, respectively, it is preferred that a and e of the medium for partially inhibiting a flow of resin satisfy the following expressions, respectively, from the standpoint of resistance to delamination. It should be noted that the length a of the longest portion in the direction of diameter has a perpendicular relationship to length and of the longest portion in the direction parallel to the resin flow path. It should be noted that r has the same definition as described above, and the preferred range for r is also the same.
0.01r <a <lr
0.01r <and <2r
The lower limit value of a is preferably 0.03r, more preferably 0.05r, even more preferably O.lr. The upper limit value of a is preferably 0.9r, more preferably 0.8r, even more preferably 0.7r. Any combination of the respective lower limit value and the upper limit value can be selected.
The lower limit value of y is preferably 0.03r, more preferably 0.05r, even more preferably O.lr. The upper limit value of y is preferably 1.8r, more preferably 1.5r. Any combination of the respective lower limit value and the upper limit value can be selected.
It should be noted that the shape of a cross section taken along the direction parallel to the resin flow direction of the resin flow path of the medium to partially inhibit a resin flow is not particularly limited, and by For example, the shape of a portion that excludes a surface in contact with the flow path is a circle, a semicircle, or a polygon or a rectangle such as a triangle, a square, or a trapezoid.
In the medium to partially inhibit a flow of resin, when a, b, and y fall within the above-mentioned range, there is a trend for the impact tracking ability of the second resin layer to be improved to the first resin layer to improve additionally the resistance to delamination.
The complete form of the medium for partially inhibiting a resin flow from the mold of the present invention may be, for example, linear, acicular, rod-like, plate-type, columnar, semicolumnar, or globular, or may be triangular, pyramidal, rectangular, cubic, conical or trapezoidal. Additionally, the form is not limited to these forms.
Additionally, a material for forming the means to partially inhibit a flow of resin is not particularly limited, and for example, it may be the same metallic material as that for a mold, it may be a metal such as iron, aluminum, copper or zinc, or it can be a thermosetting resin that has property of adhesion to metal.
Production method for multi-layer container
The present invention also provides the following production method for a multi-layer container:
a production method for a multi-layer container including a three or more layer laminate structure having at least one gas barrier layer between an innermost layer and an outermost layer, in which the gas barrier layer at a formed site the laminated structure has a site having a thickness (ti) 0.01 to 0.9 times as great as the maximum thickness (t<sub>0</sub>) of the gas barrier layer, the method including carrying out molding using the mold for a multi-layer container; and a production method for a multi-layer container including a three or more layer laminate structure having at least one gas barrier layer between an innermost layer and an outermost layer, in which the barrier layer is gases at a formed site of the laminated structure has a site that has a thickness (ti) 0.01 to 0.9 times as great as the maximum thickness (t<sub>0</sub>) in the gas barrier layer, the method including: forming a multi-layer preform using the mold for a multi-layer container; and then blow molding the multi-layer preform.
As described above, the multilayer container of the present invention can be produced using the mold for a multilayer container according to the present invention. Specifically, The multilayer container can be produced by injecting the polyester (A) from an injection cylinder at the site of the first resin flow path (23A) and by injecting a resin that has the gas barrier property (resin of gas barrier) from an injection cylinder on the side of the second resin flow path (23B) through the hot half portion (22) into the cavity (25) of the cold half portion (21) using an injection molding machine that has two injection cylinders.
In the multilayer container of the present invention, a molded multilayer container can be used using the mold of the present invention without any treatment, or a multilayer container (for example, a multilayer container can also be used partially having a three-layer or five-layer laminated structure) obtained by molding a multi-layer preform (for example, a preform partially having a three layer or five layer laminate structure) using the mold of the present invention and then carrying out heat treatment and blow molding. In particular, a multilayer container obtained by blow molding a multilayer preform is preferred. Examples of the multi-layer container include a multi-layer bottle and a multi-layer cup.
A production method for a multi-layer preform having a three-layer or five-layer laminate structure is not particularly limited and a known method is used. For example, a multi-layer preform can be produced from a three-layer structure (first resin layer / second resin layer / second resin layer), in the step of injecting a resin to each form an innermost and an outermost layer from an injection cylinder on the side of the first resin flow path (23A) and injecting a resin to form a layer of gas barrier from an injection cylinder on the side of the second resin flow path (23B), continuously injecting the first resin and simultaneously injecting a required amount of the second resin, and then stop the injection of the first resin. Additionally, a multi-layer preform of a three-layer structure (first resin layer / second resin layer / first resin layer) can be produced with the use of a mold in which the first resin layer flows into the center of the second resin layer (see figure 6 (d)), by continuously injecting the first resin and simultaneously injecting a required amount of the second resin, and then by stopping the injection of the first resin.
Additionally, a multi-layer preform of a five-layer structure can be produced (first layer of resin / second layer of resin / first layer of resin / second layer of resin / first layer of resin), in the step of injecting a first resin to each form an innermost and outermost layer from an injection cylinder at the site of the first resin flow path (23A) and by injecting a second resin from a cylinder injection on the side of the second resin flow path (23B), by first injecting the first resin, then by injecting the second resin alone, and finally by injecting the first resin to fill the cavity (25).
It should be noted that the production method for a multi-layer preform is not limited to just the method mentioned above.
The multilayer preform obtained by molding using the mold of the present invention can be further subjected to biaxial stretch blow molding and molded in a multilayer container. For example, it is preferred that the surface of the multilayer preform is heated to 90 to 110 ° C and subjected to blow molding during biaxial stretch blowing. The heating temperature is more preferably from 95 ° C to 108 ° C. When the heating temperature falls within the range, a satisfactory blow molding capacity is obtained, a first resin layer (polyester layer (A)) that each forms an outermost layer and an innermost layer does not undergo bleaching Due to the cold section, a second resin layer (gas barrier layer) does not undergo whitening due to crystallization, and additionally satisfactory resistance to delamination is obtained. It should be noted that the surface temperature can be measured using an infrared radiation thermometer. The measurement can be carried out in general by adjusting the emissivity to 0.95. Thus, in the case of heating the surface of the multilayer preform, in general, the heating is preferably carried out with several or more heaters, and the output balance of the heater is also important. An appropriate heater outlet balance and an appropriate heating time that is adjusted as appropriate with the use of an outside air temperature or a surface heating temperature of the multilayer preform are preferred.
The multilayer container molded using the mold of the present invention is of satisfactory molding capacity and hardly undergoes delamination due to drop and impact. Additionally, delamination occurs hardly even in a shape that includes uneven and bent portions, and therefore the shape of the multilayer container is not limited to a shape that has few uneven and bent portions, leading to an increase in the degree of design freedom. The multi-layer container of the present invention is suitable for storage and preservation of various items such as: liquid drinks including carbonated drinks, juice, water, milk, beer, wine, sake, whiskey, shochu, coffee, tea, gelatin drinks , and healthy drinks, seasonings including liquid seasonings, sauces, soy sauce, dressings, and concentrated broths, liquid food items, including liquid soups; liquid pharmaceuticals; skin lotions; milky lotions; Articles of hairdressing; hair dyes; and shampoos.
Examples
Hereinafter, the present invention is described in more detail based on examples with reference to the figures. However, the present invention is by no means limited to these examples. It should be noted that each multi-layer container produced in each example or comparative example was evaluated according to the following methods.
(1) Evaluation method for resistance to delamination
The delamination height of a container was determined by a drop test based on ASTM D2463-95 Procedure B and was used as an indicator of delamination resistance. First, a multi-layer container was filled with water and covered. After that, the multi-layer container was dropped from any height and the presence or absence of delamination was visually assessed. In this case, the multi-layer container was dropped in the vertical direction so that the bottom of the multi-layer container contacted the floor. An interval for a drop height was set to 15 cm and the total number of test vessels was set to 30.
It should be noted that a higher delamination height indicates a more satisfactory resistance to delamination.
(2) Oxygen transmission rate (QTR) measurement method
The oxygen transmission rate (OTR) of a multilayer container was determined in accordance with ASTM D3985 and was used as an indicator of gas barrier property. Specifically, an oxygen transmission rate [cc / (bottle »day * 0.21 atm)] under the conditions of 23 ° C and 100% RH inside a bottle and 50% RH outside the bottle was measured using an oxygen transmission rate measurement device (produced by Modern Controls, Inc., type: OX-TRAN 2/61).
It should be noted that a lower numerical value indicates a lower amount of oxygen transmission and a higher gas barrier property.
(3) Measurement method for maximum thickness (t<sub>0</sub>) of the gas barrier layer and thickness (ti) of the concave portion of the multi-layer container
A multi-layer container was cut into round cuts each having a thickness of 1 cm from the bottom site. Then, iodine tincture was applied to each cross section. A gas barrier layer was stained with iodine tincture and reddish brown or black was observed to color. The cross section was observed with a digital microscope produced by KEYENCE CORPORATION and measured for its thickness to determine t<sub>0</sub> and you.
Example 1
The previously mentioned mold (20) illustrated in Figure 1 was used. As illustrated in Figure 7 (a), four columnar (diameter: 0.2mm <j)), length: 3mm) means that it partially inhibits a flow of resin (component; the same metal as the mold) having the same shape were provided on the side wall of the second resin flow path (23B) 0.1 cm upstream of the joint portion of the first resin flow path (23A) and the second resin flow path (23B) of the mold (20) so that the media was arranged on the side wall of the resin flow path at regular intervals.
A form of the medium to partially inhibit a flow of resin; columnar, r = l.5 mm
A cross section taken along the <sup>5</sup> vertical direction to a resin flow path: a = 0.2 mm, b = 0.2 mm
A cross section taken along the direction parallel to a resin flow path: a = 0.2 mm, y = 3.0 mm <sup>10</sup> Polyethylene terephthalate (RT543C produced by Japan Unipet Co., Ltd., intrinsic viscosity: 0.75 dl / g) was used as a first resin for an outermost and innermost layer. Additionally, polyamide MXD6 (N-MXD6, MX nylon S6007 produced by MITSUBISHI GAS CHEMICAL was used.<sup>15</sup> COMPANY, INC, relative viscosity: 2.70, oxygen transmission rate: 0.1 cc * mm / m<sup>2</sup>* day * atm) as a second resin for a gas barrier layer.
With the use of the mold (20) mentioned above and an injection molding machine (type: M200, <sup>20</sup> four shots) produced by Meiki Co., Ltd., under the following conditions, a three-layer preform which was formed of a first resin layer / second resin layer / first resin layer and a total length of 95mm, a 22mm outer diameter, 4.2mm wall thickness, <sup>25</sup> and a weight of 27 g was injection molded by continuously injecting a first resin and simultaneously injecting a second resin, and then by stopping injection of the first resin, followed by cooling.
The resulting three-layer preform was then subjected to biaxial stretch blow molding under the following conditions to give a multi-layer container, having a total length of 223 mm, an outer diameter of 65 mm, an internal volume of 500 my, and a petaloid-type bottom shape. The conditions for blow molding are described below.
Table 1 shows the results of the evaluation of the resulting multi-layer container.
Injection molding conditions for the three layer preform
Injection cylinder temperature on the side of the first resin flow path: 270 ° C
Injection cylinder temperature on the side of the second resin flow path: 260 ° C
Resin flow path temperature in mold:
270 ° C
Cooling water temperature for mold:
15 ° C
Second resin ratio in multi-layer preform: 5% by mass
Biaxial stretch blow molding conditions
Blow Molding Machine: Model EFB1000ET (produced by Frontier, Inc.)
Preform heating temperature: 101 ° C
Stretch rod pressure: 0.5 MPa
Primary blowing pressure: 0.7 MPa
Secondary blowing pressure: 2.5 MPa
Primary Blow Delay Time: 0.34 sec
Primary blowing time: 0.30 sec
Secondary blow time: 2.0 sec
Blowout escape time: 0.6 sec
Mold temperature: 30 ° C
Example 2
A multi-layer container was obtained in the same manner as in Example 1 except that the means for partially inhibiting a flow of resin in the mold was changed to one having a shape described in Table 1. Table 1 shows the results. of evaluation of the resulting multilayer container.
Production example 1
Synthesis of poly-m-xylylene-sebacamide (N-MXD10)
Sebacic acid (produced by Itoh Oil Chemicals Co., Ltd., grade TA) was melted with heating to 170 ° C in a reaction pot. After that, while the content is stirred and gradually added dropwise to this m-xylylenediamine (produced by MITSUBISHI GAS CHEMICAL COMPANY, INC) so that the molar ratio of myxylenediamine and sebacic acid was 1: 1, the temperature was increased to 240 ° C by heating. After the completion of the dropwise addition, the temperature was increased to 260 ° C by further heating.
After the completion of the reaction, the content was collected as a strand and granulated with a granulator. The resulting granule was loaded into a drum and subjected to solid phase polymerization under reduced pressure to give poly-m-xylylene-sebacamide (hereinafter, referred to as N-MXD10) having an adjusted molecular weight. The N-MXD10 has a melting point of 191 ° C, a glass transition point of 60 ° C, a number average molecular weight of 23,000, and an oxygen transmission coefficient of 0.8 cc * mm / m<sup>2</sup>»Day» atm.
Comparative Example 1
A multi-layer container was obtained in the same manner as in Example 1 except that the means to partially inhibit a flow of resin in the mold was not provided in resin flow path 2. Table 1 shows the evaluation results of the resulting multi-layer container.
Example 3
A multi-layer container was obtained in the same manner as in Example 1, except that: the medium to partially inhibit a flow of resin in the mold was changed to one having a shape described in Table 1; Polylactic acid (PLA, produced by UNITIKA,. LTD, TERRAMAC grade TP-4 000) was used as the first resin, and the poly-m-xylylene-sebacamide (N-MXD10) obtained in the example was used as the second resin. 1 production. Table 1 shows the evaluation results of the resulting multi-layer container.
Comparative Example 2
A multi-layer container was obtained in the same manner as in Example 3 except that the means to partially inhibit a flow of resin in the mold was not provided in the resin flow path 2. Table 1 shows the evaluation results of the resulting multi-layer container.
Example 4
A multi-layer container was obtained in the same manner as in Example 1 except that the means for partially inhibiting a flow of resin in the mold was changed to one having a shape described in Table 1 (changed to one with a = 0.63 mm). Table 1 shows the evaluation results of the resulting multi-layer container.
<td colspan="3">Table 1</td><td>Example 1</td><td>Example two</td><td>Example comparative 1</td><td>Example 3</td><td>Example comparative 2</td><td>Example 4</td>
<td colspan="3">Radius r of the second resin flow path (mm)</td><td> 1.5</td><td> 1.5</td><td> 1.5</td><td> 1. 5</td><td> 1.5</td><td> 1.5</td>
<td colspan="2" rowspan="3"></td><td>Number of means that going to provide</td><td> 4</td><td> 5</td><td> 0</td><td> 3</td><td> 0</td><td> 4</td>
<td>Position in which one provides the medium (cm)<sup>11</sup></td><td> 0.1</td><td> 0.5</td><td> -</td><td> 1.1</td><td> -</td><td> 0.1</td>
<td>Shape</td><td>Columnar</td><td>Semi- columnar</td><td> -</td><td>Right- Gular</td><td> -</td><td>Colum- Nar</td>
<td rowspan="10">Means for inhibit • partially the resin flow</td><td rowspan="5">Section cross in direction vertical<sup>2</sup>*</td><td>Way in section cross</td><td>Circle</td><td>Semi circle</td><td> -</td><td>Rectangle- Gulo</td><td> -</td><td>Circle</td>
<td>a (mm)</td><td> 0.2</td><td> 0.05</td><td> -</td><td> 0.5</td><td> -</td><td> 0.2</td>
<td>b (mm)</td><td> 0.2</td><td> 0.03</td><td> -</td><td> 0.1</td><td> -</td><td> 0.2</td>
<td>a / r value</td><td> 0.13</td><td> 0.03</td><td> -</td><td> 0.33</td><td> -</td><td> 0.13</td>
<td>b / r value</td><td> 0.13</td><td> 0.02</td><td> -</td><td> 0.07</td><td> -</td><td> 0.13</td>
<td rowspan="5">Section cross in direction parallel<sup>31</sup></td><td>Way in section cross</td><td>Rectangle- gulo</td><td>Rectangle- gulo</td><td> -</td><td>Rectangle- gulo</td><td> -</td><td>Rectangle- gulo</td>
<td>a (mm)</td><td> 0.2</td><td> 0.05</td><td> -</td><td> 0.5</td><td> -</td><td> 0.63</td>
<td>b (mm)</td><td> 3</td><td> 1</td><td> -</td><td> 0.1</td><td> -</td><td> 3</td>
<td>a / r value</td><td> 0.13</td><td> 0.03</td><td> -</td><td> 0.33</td><td> -</td><td> 0.42</td>
<td>b / r value</td><td> 2.00</td><td> 0.67</td><td> -</td><td> 0.07</td><td> -</td><td> 2.00</td>
<td rowspan="2">results of measurement and</td><td colspan="2">First column</td><td>PET</td><td>PET</td><td>PET</td><td>PLA</td><td>PLA</td><td>PET</td>
<td colspan="2">Second column</td><td>N-MXD6</td><td>N-MXD6</td><td>N-MXDG</td><td>N-MXD10</td><td>N-MXD10</td><td>N-MXD6</td>
<td rowspan="5">results of evaluation</td><td>Maximum layer thickness of gas barrier t<sub>0</sub>/ p</td><td> 34</td><td> 36</td><td> 35</td><td> 30</td><td> 34</td><td> 34</td>
<td>Concave portion thickness of gas barrier layer ti / pm</td><td> 24</td><td> 32</td><td> -</td><td> 10</td><td> 4</td><td> 4</td>
<td>you / 1<sub>0</sub></td><td> 0.71</td><td> 0.89</td><td> 1</td><td> 0.33</td><td> 0.12</td><td> 0.12</td>
<td>Transmission speed oxygen [cc / (bottle.day.0.21 atm)]</td><td> 0.01</td><td> 0.009</td><td> 0.009</td><td> 0.12</td><td> 0.01</td><td> 0.01</td>
<td>Delamination height (cm)</td><td> 310</td><td> 300</td><td> 180</td><td> 295</td><td> 170</td><td> 320</td>
at üú (1) a distance from a joining portion of a first resin flow path and a second resin flow path (2) a cross section taken along the vertical direction to a resin flow direction of a resin flow path (3) a cross section taken along the direction parallel to the resin flow direction of a resin flow path
Table 1 revealed that the multilayer container molded using a mold including means for partially inhibiting a flow of resin according to the present invention exhibited very excellent resistance to delamination, while the multilayer container molded using a mold which does not include a means to partially inhibit a flow of resin was poor in resistance to delamination.
Industrial applicability
The multilayer container of the present invention is satisfactory in molding capacity and hardly undergoes delamination due to drop and impact. Additionally, delamination occurs with difficulty, even in a shape that includes uneven and bent portions, and therefore the shape of the multilayer container is not limited to a shape that has small uneven and bent portions, leading to an increase in degree of design freedom. The multi-layer container of the present invention is suitable for storing and preserving various items such as: liquid drinks including carbonated drinks, juice, water, milk, beer, wine, sake, whiskey, shochu, coffee, tea, jelly drinks , and healthy drinks; seasonings including liquid seasonings, sauces, soy sauce, dressings, and concentrated broths; liquid food items, including liquid soups, liquid pharmaceuticals; skin lotions; milky lotions; Hairdressing products; hair dyes; and shampoos.
Explanation of codes
twenty. - mold
twenty-one. - Portion of cold half
22. - Portion of hot half
23A, 23B.- Resin path flow
24. - Injection port portion
25. - cavity
26. - Injection hole cutting pin
27. - Air cylinder
28. - Medium to partially inhibit the flow of resin
40A, 40B-. Molten resin a The longest portion in the direction of the cross section diameter (AA direction) of the medium to partially inhibit a flow of resin b The longest portion in the circumferential tangential direction of the cross section (AA direction) of the medium to partially inhibit a flow of resin and the longest portion of the cross section (parallel direction) of the medium to partially inhibit a flow of resin
It is noted that in relation to this date, the best method known by the applicant to put the aforementioned invention into practice is the one that is clear from the present description of the invention.
Contents3
3 sheets
Sheet 1 Sheet 2 Sheet 3
20 members in 10 offices
Priority claims8
| Document | Office | Kind | Date |
|---|---|---|---|
| 2010099679 | Japan | A | |
| 2010099679 | Japan | A | |
| 2011059443 | Japan | W | |
| 2011059443 | Japan | W | |
| 2010099679 | – | – | – |
| JP1159443 | – | – | – |
| JP20100099679 | – | – | – |
| WO2011JP59443 | – | – | – |
Members20
| Document | Office | Kind | |
|---|---|---|---|
| WO2011132622A1 | World Intellectual Property Organization (WIPO) | A1 | |
| TW201202021A | Taiwan Province of China | A | |
| MX2012012151AThis record | Mexico | A | |
| CN102869489A | China | A | |
| EP2561970A1 | European Patent Office (EPO) | A1 | |
| US2013095265A1 | United States of America | A1 | |
| KR20130077817A | Republic of Korea | A | |
| JPWO2011132622A1 | Japan | A1 | |
| RU2012149956A | Russian Federation | A | |
| US2014220167A1 | United States of America | A1 | |
| EP2561970A4 | European Patent Office (EPO) | A4 | |
| US8815359B2 | United States of America | B2 | |
| JP5783169B2 | Japan | B2 | |
| RU2570053C2 | Russian Federation | C2 | |
| CN102869489B | China | B | |
| BR112012027108A2 | Brazil | A2 | |
| TWI545007B | Taiwan Province of China | B | |
| US9701076B2 | United States of America | B2 | |
| KR101863897B1 | Republic of Korea | B1 | |
| EP2561970B1 | European Patent Office (EPO) | B1 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 2012012151
- Publication, DOCDB
- 2012012151
- Publication, EPODOC
- MX2012012151
- Application
- 2012012151
- Application, DOCDB
- 2012012151
- Application, EPODOC
- MX20120012151
Titles2
- English
- MULTILAYERED CONTAINER, DIE FOR MULTILAYERED CONTAINER, AND METHOD FOR PRODUCING MULTILAYERED CONTAINER.
- Spanish
- RECIPIENTE DE MULTIPLES CAPAS, BOQUILLA PARA RECIPIENTE DE MULTIPLES CAPAS, Y METODO PARA PRODUCIR RECIPINTE DE MULTIPLES CAPAS.
Classification
- CPC, 67
- B29C45/1603
- B65D1/0215
- B29D22/003
- B29B11/08
- B29B11/14
- B29C49/0005
- B29C49/06
- B29K2025/00
- B29K2027/06
- B29K2067/043
- B29K2069/00
- B29K2077/00
- B29K2105/0026
- B29K2105/0032
- B29K2105/0038
- B29K2105/0044
- B29K2105/005
- B29K2105/16
- B29K2105/258
- B29K2995/0067
- B29L2009/00
- B29L2031/7158
- B32B27/08
- B32B27/304
- B32B27/306
- B32B27/34
- B32B27/36
- B32B3/02
- B32B2250/03
- B32B2250/05
- B32B2250/24
- B32B2250/244
- B32B2250/40
- B32B2307/518
- B32B2307/7242
- B32B2307/7244
- B32B2439/00
- B32B2439/60
- B32B2439/70
- Y10T428/1383
- Y10T428/1393
- Y10T428/1379
- B29C2949/3008
- B29C2949/3012
- B29C2949/302
- B29C2949/3016
- B29C2949/3028
- B29C2949/303
- B29C2949/3036
- B29C2949/3038
- B29C2949/0811
- B29C2949/0819
- B29C2949/082
- B29C2949/0829
- B29C2949/0872
- B29C2949/3032
- B29C49/071
- B29C2949/0715
- B29C2049/023
- B29C2049/7832
- B29C2049/7862
- B32B1/00
- B65D1/40
- B65D81/24
- B29C45/0046
- B29C45/13
- B29C45/1646
- IPC, 14
- B29C45 16
- B29C45 20
- B29C45 30
- B29K23 00
- B29K25 00
- B29K27 06
- B29K55 02
- B29K67 00
- B29K69 00
- B29K77 00
- B29L9 00
- B32B1 00
- B65D1 00
- B65D1 02