Oxygen-scavenging resins and containers having minimal color

<u style="single">Background of the invention</u> Thermoplastics, such as polyethylene terephthalate (PET), are commonly used to make packaging materials. PET processed under appropriate conditions produces high-strength articles with excellent gas barrier properties. Foods, beverages and medicines can deteriorate or be impaired when exposed to oxygen. Therefore, in order to improve the shelf life and flavor retention of products such as foods, beverages and medicines, the blocking protection provided by PET is often supplemented by the addition of an additional layer of packaging material or an oxygen scavenger. Adding a gas blocking film layer is known as passive blocking packaging. Ethyl Vinyl Alcohol (EVOH), Polybini<u style="single">Ri</u>Dendichloride (PVDC) and nylon MXD6 are examples of films commonly used for this purpose due to their excellent oxygen blocking properties. However, it is not preferable to use separate layers of different substances. This is because it adds cost to the packaging manufacturing and does not reduce the oxygen levels already present in the packaging.

The addition of an oxygen scavenger to the PET resin is known as active blocking packaging. This approach of protecting oxygen-sensitive products has two sides; the packaging prevents oxygen from reaching the product from the outside and also allows some of the oxygen present in the container from there into the polymer matrix. Absorb. In some applications, a parcel or pouch containing an oxygen scavenger is added to the packaging and placed next to the food. Pouches are generally limited to solid foods, in which pouches can be easily removed from foodstuffs and are not accidentally ingested. The annoying nature of manufacturing sachets and introducing them into the packaging results in increased costs.

One way to overcome the shortcomings of sachets is to incorporate the remover directly into the wall of the food packaging. This can be done by placing the remover throughout the remover wall or by placing the remover in only one layer between the layers of the side wall of the container. It should be recognized that the sidewalls and walls also refer to the lid and bottom of the container. Currently, the incorporation of removers throughout the container wall is found in non-transparent trays or packaging films where the remover is invisible to the naked eye. Virtually any remover can be used in this application. Because no remover is found. However, containers that need to be transparent and colorless have traditionally been limited to organic species removers that maintain the transparency of the container when placed in an independent layer within the container wall. The use of organic scavengers in single-layer or single-layer structures is limited by the nature of the organic scavengers or the cost and regulation of removal reactions by by-products.

Part of the cost is the logical problem encountered with the use of organic species removers. In most embodiments, a transition metal catalyst is used to activate the oxidizing polymer. The drawback of this technique is that the polymer begins to react with oxygen as soon as the packaging is manufactured. As a result, the bottle must be filled immediately. Large amounts of remover are used to compensate for the loss of removal capacity between the time the bottle is manufactured and the time the bottle is filled.

In another technique, UV irradiation is used to activate the oxidizing polymer. However, UV activation techniques are relatively expensive and initiators are often not specified for use in food packaging. Packagings designed for beer and juice are specifically designed to prevent UV transmission, and therefore UV activation will not be practical for these containers that block UV.

An alternative to visually acceptable organics is to use removed particles dispersed in the side walls of the vessel, such as powders of reduced metal. Reduced iron powder is commonly used for oxygen removal in food packaging. Iron reacts with oxygen to form iron oxide. For most applications, salts and hygroscopic agents are also used as reaction enhancers to improve the potency of iron powder. Since the reaction usually requires water, the iron removal composition remains inert until it is filled in the packaging and the reaction is activated by the water in the packaging contents. It travels through the polymer and comes into contact with the removal composition.

The use of the removed powder in clear packaging was previously limited aesthetically, especially by haze or color. High loadings of iron powder, typically on the order of 500-5000 ppm, are required to obtain sufficient oxygen absorption. The usual knowledge and prior art teaches practitioners to use the maximum removed surface area possible to improve their efficiency and capacity and minimize the amount of iron added. In practice this means a large number of small particles. Unfortunately, previous attempts to produce resin compositions containing large amounts of small iron particles for use in transparent packaging have resulted in packaging with poor optical properties. This is especially true when the resin composition is stretched or stretched to some extent in forming the final product, eg polyester bottles. Typically, bottles made from such resin compositions are translucent. The haze value of these bottles is generally high, lacks transparency, and the bottles are very dark.

Therefore, there remains a demand for packaging materials containing oxygen-removing resin compositions that have an acceptable visual appearance and can be activated. The present invention relates to oxygen scavenging resin compositions useful in packaging and other applications. In particular, the present invention relates to film-forming, oxygen-removing polyester compositions with low haze and minimal darkness. The present invention also relates to a container having an effective oxygen scavenging function and a low haze. The present invention further relates to a method for incorporating large amounts of oxygen scavenging particles into a film-forming polyester resin composition with low haze and minimal darkness.

<u style="single">A brief overview of the invention</u> Generally, the present invention contains an effective amount of oxygen scavenging particles containing film-forming polyester and at least one oxygen scavenging element, in which particles with dimensions less than about 25 microns are represented by the formula: ppm = 512.3 × d [in the formula, ppm is the approximate concentration of mass ppm for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ] Provided is a resin composition in which the particles have a particle size distribution that does not exceed the concentration determined by.

The present invention also includes a film-forming polyester and an effective amount of oxygen-removing iron particles, in which the iron particles have a particle size distribution such that the particles having a size of less than about 25 microns do not exceed about 1250 mass ppm of the resin. Includes compositions. The present invention also comprises a film-forming polyester and a resin composition containing about 50 to about 2500 mass ppm of iron particles, wherein the concentration of iron particles having a size of less than about 25 microns does not exceed about 1250 mass ppm of the resin. Including.

The present invention is also a polyester resin composition containing iron particles of about 50 to about 2500 mass ppm of resin for use in forming a transparent product having a low haze, wherein the transparent product has a hunter haze value of about. Hunter L when compared to controls containing 10% or less and no oxygen scavenging particles^*Includes resin compositions with a change of less than about 0.4%. The present invention is also an article formed from a resin composition containing an effective amount of oxygen scavenging particles, wherein the hunter haze value of the article is about 10% or less, as compared to a control containing no oxygen scavenging particles. Hunter L^*Includes articles with a change of less than about 0.4%.

The present invention contains an effective amount of oxygen scavenging particles and has a high L^*Containers with the same color or darkness are also provided. In particular, the present invention has at least one wall, the wall comprising a population occupied region, the population occupied region comprising a particle population containing a film-forming polymer and an effective amount of oxygen deficient particles, the number of particles of which is polymer 1. Approximately (1 x 10) per cubic centimeter⁷Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ] Concentration does not exceed the permeation hunter L of the wall^*The variation includes vessels that are less than about 0.4 per mil of vessel wall when compared to controls that do not contain deoxygenated particles.

The present invention also includes a method of incorporating a large amount of oxygen-removing particles into a film-forming polyester resin composition with a low haze, in which the method prepares an effective amount of oxygen-removing particles containing at least one oxygen-removing element. In the formula, the particles with dimensions less than about 25 microns are: ppm = 512.3 × d [in the formula, ppm is the approximate concentration of the mass ppm of the particles with dimensions less than about 25 microns, and d is the dimensions about. An apparent density of cubic centimeters per gram of particles less than 25 microns. ] Steps in which the particles have a particle size distribution that does not exceed the concentration specified by; melt phase polymerization of polyester; after polymerization and before pelletization; solid phase polymerization of polyester; and during one or more process steps of extrusion Includes a step of adding the oxygen-removing particles to the polyester resin composition.

The present invention also includes film-forming polyesters and granules, in which particles less than about 25 microns in size are of the formula: ppm = 512.3 × d [where ppm is the mass of particles less than about 25 microns in size. Approximate concentration of ppm, d is the apparent density of particles less than about 25 microns in size, in centimeters per gram. ] Includes resin compositions in which the granules have a particle size distribution that does not exceed the concentration determined by.

The present invention conveniently overcomes the problems associated with the prior art by providing a thermoplastic resin composition that contains an effective amount of iron or other oxygen scavenger and has acceptable color and haze properties. Iron or other oxygen scavengers are present in sufficient amounts to effectively remove oxygen and provide longer shelf life for oxygen sensitive substances. The particle size of the oxygen scavenger is optimized to provide effective scavenging activity, while reducing dark tinting and haze.

<u style="single">Detailed description of the invention</u> The present invention relates to a container containing a film-forming, oxygen-removing resin composition and a film-forming polymer. The wall contains a mass occupied area containing a film-forming polymer. Suitable thermoplastic polymers for use in the present invention include any thermoplastic homopolymer or copolymer. Examples of thermoplastic polymers are polyamides such as nylon 6, nylon 66 and nylon 612, linear polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polyethylene naphthalate, branched polyesters, polystyrene, polycarbonate, polyvinyl chloride. Vinyl, polyvinylidene dichloride, polyacrylamide, polyacrylonitrile, polyvinyl acetate, polyacrylic acid, polyvinyl methyl ether, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, polyethylene, polypropylene, ethylene propylene copolymer, poly (1-hexane), poly Includes (4-methyl-1-pentene), poly (1-butene), poly (3-methyl-1-butene), poly (3-phenyl-1-propene) and poly (vinylcyclohexane). Preferably, the thermoplastic polymer used in the present invention includes a polyester polymer or a copolymer.

A film-forming polymer will be understood to be a polymer that can be formed on a film or sheet. However, the present invention is not limited to films or sheets. The container of the present invention also includes the wall of the bottle, the tray, the bottom surface or the lid of the container. Containers, such as the walls of blow-molded bottles and thermoformed trays, can be thought of as films or sheets formed in the shape of the container, and are therefore also within the scope of the present invention. The bottom and lid of the container are also considered to be the walls of the container.

The polymer used in the present invention can be produced by a polymerization procedure well known in the art and customary. Polyester polymers and copolymers can be produced by melt phase polymerization, which involves the reaction of a diol with a dicarboxylic acid or its corresponding diester. Various copolymers resulting from the use of various diols and diacids can also be used. Polymers with only one repeating unit of chemical composition are homopolymers. Polymers that have two or more chemically different repeating units in the same polymer are called copolymers. The diversity of repeating units depends on the number of different monomer species present during the initiating polymerization reaction. In the case of polyesters, copolymers involve the reaction of one or more diols with a diacid or a variety of diacids and are sometimes referred to as terpolymers.

Suitable dicarboxylic acids include those having about 6 to about 40 carbon atoms. Specific dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, 1,3-phenylenedioxydiacetic acid, 1 , 2-Phenylenedioxydiacetic acid, 1,4-Phenylenedioxydiacetic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like, but not limited to these. Specific esters include, but are not limited to, phthalates and naphthalates diesters.

These acids or esters are aliphatic diols having about 2 to about 10 carbon atoms, alicyclic diols having about 7 to about 14 carbon atoms, and aromatics having about 6 to about 15 carbon atoms. It can react with group diols or glycol ethers with 4-10 carbon atoms. Suitable diols include, but are not limited to, 1,4-butanediol, trimethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, resorcinol and hydroquinone. Polyfunctional comonomer can also be typically used in an amount of about 0.1 to about 3 mol%. Suitable comonomer includes, but are not limited to, trimellitic anhydride, trimethylolpropane, pyromelitonic dianhydride (PMDA) and pentaerythritol. Polyester-forming polyacids or polyols can also be used.

One preferred polyester is polyethylene terephthalate (PET), which is formed from a stoichiometric reaction of terephthalic acid or an ester thereof with ethylene glycol at about 1: 1. Another preferred polyester is polyethylene naphthalate (PEN) formed from a stoichiometric reaction of naphthalenedicarboxylic acid or an ester thereof with ethylene glycol from about 1: 1 to 1: 1.6. Yet another preferred polyester is polybutylene terephthalate (PBT). PET copolymers, PEN copolymers and PBT copolymers are also preferred. Certain copolymers and terpolymers of interest are PET in combination with isophthalic acid or diesters thereof, 2,6-naphthalic acid or diesters thereof and / or cyclohexanedimethanol.

The esterification or polycondensation reaction of a carboxylic acid or ester with a glycol is typically carried out in the presence of a catalyst. Suitable catalysts include, but are not limited to, antimony oxide, antimony triacetate, antimony ethyleneglycolate, organic magnesium, tin oxide, titanium alkoxide, dibutyltin dilaurate and germanium oxide. These catalysts can be used in combination with zinc, manganese or magnesium acetate or benzoate. A catalyst containing antimony is preferred.

Another preferred polyester is polytrimethylene terephthalate (PTT). It can be produced, for example, by reacting 1,3-propanediol with at least one aromatic diacid or an alkyl ester thereof. Preferred diacids and alkyl esters include terephthalic acid (TPA) or dimethyl terephthalate (DMT). Therefore, PTT preferably contains at least about 80 mol% of either TPA or DMT. Other diols that can be copolymerized in such polyesters include, for example, ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. Aromatic and aliphatic acids that can be used simultaneously to make copolymers include, for example, isophthalic acid and sebacic acid.

Preferred catalysts for producing PTT include titanium and zirconium compounds. Suitable catalytic titanium compounds include, but are not limited to, titanium alkylates and derivatives thereof, titanium complex salts, titanium complexes with hydroxycarboxylic acids, titanium dioxide-silicon dioxide-co-deposits and hydrated alkali-containing titanium dioxide. .. Specific examples are tetra- (2-ethylhexyl) -titanate, tetrastearyl titanate, diisopropoxy-bis (acetylacetonato) -titanium, di-n-butoxy-bis (triethanolaminoto) -titanium, tributylmono. Includes acetyl titanates, triisopropyl monoacetyl titanates, tetrabenzoic acid titanates, alkaline titanium oxalates and malonates, potassium hexafluoro titanates, and titanium complexes with tartaric acid, citric acid or lactic acid. Preferred catalytic titanium compounds are titanium tetrabutyrate and titanium tetraisopropirate. Corresponding zirconium compounds can also be used. The polymers of the present invention may also contain small amounts of phosphorus compounds such as phosphates and catalysts such as cobalt compounds which tend to impart a blue hue.

Following the melt phase polymerization described above, a crystallization step followed by a solid phase polymerization (SSP) step can be performed to achieve the intrinsic viscosity required for bottle production. Crystallization and polymerization can be carried out in a tumble dryer reaction in a batch system. Instead, crystallization and polymerization can be accomplished in a continuous solid state method, whereby the polymer flows from one container to another after the scheduled treatment within each container.

Crystallization conditions preferably include temperatures of about 100 to about 150 ° C. Solid phase polymerization conditions preferably include temperatures from about 200 to about 232 ° C, more preferably from about 215 to about 232 ° C. Solid phase polymerization can be carried out for a time sufficient to increase the intrinsic viscosity to a desired level depending on the application. The preferred intrinsic viscosity for typical bottle applications is approximately 0.65 to approximately 1.0 deciliter / gram when measured by ASTM D-4603-86 in a mixture of phenol and tetrachloroethane with a mass of 60/40 at 30 ° C. Is. The time required to reach this viscosity can range from about 8 to about 21 hours. In one embodiment of the invention, the film-forming polymers of the invention may include regenerated polyesters or substances derived from regenerated polyesters such as polyester monomers, catalysts and oligomers.

At least one wall of the container of the present invention comprises a mass occupied area. There is a technique that can localize deoxidized particles to one area of the vessel wall. For example, if the contact surface of the film or wall is a surface adjacent to the material to be packaged, the oxygen scavenger can be advantageously localized on the contact surface in one area. Examples of these techniques include, but are not limited to, stacking, simultaneous extrusion, simultaneous injection, and the like. Examples of techniques capable of localizing the population are further disclosed in U.S. Pat. Nos. 5,153,038, 6,413,600, 4,525,134, 4,439,493 and 4,436,778, which are referred to herein. Completely incorporate by doing. Large amounts of particles can be incorporated into the film or wall produced by using these techniques. The localized region in which the particle population is substantially arranged is referred to as a population occupied region in the present specification.

The population-occupied region includes a particle population containing oxygen-removing particles. The thickness of the mass occupied area is measured cross-sectionally through the container wall, measured from the content side of the packaging wall to the outer edge of the wall, starting with the first particle and ending when 95% of the deoxygenated particles are accounted for. The thickness of the mass occupied area in one layer of film or container is the thickness of the film or container wall. In the non-layered container wall, the thickness of the mass occupied area is somewhat thinner than the wall thickness. The thickness of the mass occupied area of the laminated wall is the thickness of the wall layer containing at least 95 percent of the particle population. In multilayer films or walls where the layers fuse at the interface, such as those formed by co-extrusion, the thickness of the population occupied area is the cross-sectional thickness of the layer containing at least about 95 percent of the particle population.

For two or more separate group occupied areas, the thickness of the group occupied area is reduced by the thickness of one or more unoccupied areas between the inner and outermost group occupied areas. This is the case of the A / B / A structure in which A contains a population. The thickness of the mass occupied area is the thickness of A + B + AB. In the case of A / B / A / B, the thickness is still A + B + AB. Using the same principle, B / A / B / A / B has a thickness of A + B + AB. A / B / A / B / A has a population thickness of 3 × A-2 × B. The particle population includes deoxygenated particles and any other container component as discussed herein, which are present in the form of dispersed particles.

Suitable oxygen scavenging particles contain at least one substance capable of reacting with molecular oxygen. Desirably, select a substance that reacts with oxygen too quickly and does not make the handling of the substance infeasible. Therefore, stable oxygen scavengers that do not easily explode or burn in contact with molecular oxygen are preferred. Low toxicity substances are preferred from a food safety standpoint, but are not limited by appropriate precautions. Particles should not adversely affect the sensory acceptability of the final product. Preferably the oxygen scavenging particles are calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium and these. Contains oxygen scavenging elements selected from the combination of. More preferably, the oxygen scavenging particles contain an oxygen scavenging element selected from calcium, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc or tin. More preferably, the oxygen-removing particles contain iron. It will be appreciated that these oxygen scavenging elements can be present as a mixture in compounds such as oxides and salts, or can be combined with other elements. However, the condition is that the oxygen scavenging element can react with molecular oxygen. Alloys containing at least one oxygen scavenging element are also suitable. Oxygen-removing particles may contain impurities that do not affect the practice of the present invention.

In the art, it is known that certain substances enhance the oxygen scavenging reaction. In a preferred embodiment of the present invention, the oxygen-removing particles are pretreated with one or more reaction enhancers that promote the oxygen removal reaction. Any reaction enhancer known in the art can be used. In one embodiment of the invention, the oxygen scavenging particles include iron particles. Iron reacts with oxygen as an oxygen scavenger in its function. Iron metals or alloys or mixtures containing iron metals can be used. Furthermore, it should be understood that iron metals may contain impurities that do not affect the practice of the present invention.

At least three types of iron metal powders: electrolytic iron, sponge iron and carbonyl iron are available. Electrolytic iron is produced by electrolysis of iron oxide and is available, for example, from OM Group, Inc. in annealed and unannealed forms. Sponge iron is available, for example, from North American Hoeganaes, Inc. There are at least two types of sponge iron: hydrogen-reduced sponge iron and carbon monoxide-reduced sponge iron. Carbonyl iron powder can be obtained, for example, from Reade Advanced Materials. It is manufactured using the carbonyl degradation method.

Depending on the type of iron selected, the particles can vary widely in purity, surface area and particle shape. The following non-limiting examples of typical features contained herein illustrate variants that may be encountered. Electrolytic iron is known for its high purity and high surface area. The particles are tree-like. The carbonyl iron particles are substantially uniform spheres and can have a purity of up to about 99.5 percent. Carbon monoxide reduced sponge iron is typically about 95 square meters per kilogram (m)²It has a surface area of (/ kg), while hydrogen-reduced sponge iron typically has a surface area of about 200 m.²It has a surface area of / kg. Iron sponge may contain small amounts of other elements such as carbon, sulfur, phosphorus, silicon, magnesium, aluminum, titanium, vanadium, manganese, calcium, zinc, nickel, cobalt, chromium and copper. Carbon monoxide reduced sponge iron is preferable.

Oxygen-removing particles are present in an effective amount for sufficient oxygen-removing capacity. If too few oxygen-removing particles are present, a large amount of oxygen can pass through the vessel wall without being removed. The amounts required for sufficient oxygen scavenging capacity include the application, the type of polymer used, the desired amount of gas blocking protection, the type of scavenging particles, the particle size of the scavenging particles and the moisture content of the packaged material. It depends on the factors. Preferably, the oxygen scavenger of the present invention contains at least about 50 mass ppm of oxygen scavenging particles of the resin. More preferably, the container of the present invention contains at least about 100 mass ppm of oxygen-removing particles of the resin. More preferably, the container of the present invention contains at least about 500 mass ppm of oxygen-removing particles of the resin. More preferably, the container of the present invention contains at least about 1000 mass ppm of oxygen-removing particles of the resin.

We have found that containers containing oxygen-removing particles up to 12,000 mass ppm (1.2 mass percent) of resin, such as films or bottles, can have acceptable color properties. It will be appreciated that the amount of deoxygenated particles or other particles can be quite large for applications where color is not an important issue. Further features of the particle population required for the practice of the present invention are given below.

Preferably, the number of deoxidized particles in the mass occupied area is 1 x 10 per cubic centimeter of polymer.⁷Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ] Concentration does not exceed. More preferably, the number of particles in the mass occupied area is 0.8 × 10 per cubic centimeter of polymer.⁷Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ] Concentration does not exceed. More preferably, the number of particles in the mass occupied area is per cubic centimeter of polymer (0.6 × 10).⁷Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ] Concentration does not exceed.

"Approximately 1 x 10" within the description and claims⁷The statement "does not exceed" is intended to include smaller amounts of particles, depending on the preferred amount. Desirably a large amount of particles are added to the resin, L^*The effect on is minimized. This can be achieved by selecting the particle size distribution of the particle population and controlling the total number of particles per unit volume of the polymer to be kept below a certain maximum. This maximum value is related to the thickness of the mass occupied area.

The compositions of the present invention, optionally, may further comprise one or more reaction enhancers known in the art to facilitate the oxygen scavenging reaction. Examples of known reaction enhancers are discussed in US Pat. Nos. 5,744,056 and 5,885,481, which are fully incorporated by reference herein. Suitable agents are variously described as hydroscopic substances, electrolyte acidifying agents, non-electrolyte acidifying agents, metal halides, metal sulfates, metal hydrogen sulfates and salts. Reaction enhancers can be added to the polymer melt or during extrusion.

The compositions of the present invention, if desired, include toughening agents, mold release agents, denesting agents, stabilizers, crystallization aids, antioxidants, UV absorbers, catalyst activators, colorants, nuclei. It may further comprise one or more components selected from the group consisting of agents, acetaldehyde reducing agents, reheat reducing agents, fillers, branching agents, foaming agents, accelerators and the like. If any of the above components retain distinct properties in the resin, it will be understood that they are part of a particle population as defined herein.

Increased darkness (this is L^*Corresponds to the decrease in. ) Can be minimized while incorporating a large number of particles into the polyester resin composition. The particles can be mixed with thermoplastic polymers, polymer melts or molded powders or pellets during or after polymerization, from which injection molded articles are formed or films or sheets are cast. Thus, the particles can be added during any process step, eg, during melt phase polymerization, after melt phase polymerization (after polymerization), before pelletization, during solid phase polymerization and during extrusion. Alternatively, a masterbatch of oxygen scavenging resin can be made and then mixed or blended with additional resin. Preferably the masterbatch contains a relatively large amount of particles and the desired particle concentration in the product polymer is achieved by mixing or blending the masterbatch with an additional amount of resin.

The container of the present invention advantageously comprises both an effective oxygen scavenging function and acceptable optical properties. The optical properties of a polymer are related to both the degree of crystallinity and the actual polymer structure. Transparency is defined as a state in which an object can be recognized by passing through a sample. Transmission is transmitted light. Transparency is measured as the amount of unbiased light. In other words, transparency is the original intensity of the incident light minus all the light lost by absorption, scattering or any other method. While many polymers are transparent, polymers that are transparent to visible light can become opaque as a result of the presence of additives such as fillers, stabilizers, flame retardants, moisture and gas. The opacity is due to the light scattering process that occurs in the material. Light scattering reduces the contrast between the light and dark areas of the object seen through the material, and between other colored areas, resulting in emulsion or haze in the transmitted image. Haze is a measure of the amount of light that deflects at least 2.5 degrees from the direction of light transmission.

The color and lightness of the polyester product can be visually observed and can be quantitatively measured with the HunterLab ColorQuest Spectrometer. This device is a color and lightness 1976 CIE a^*, B^*And L^*Use symbols. a^*The coordinates define the axis of color, in which positive values are on the red side of the color spectrum and negative values are on the green side. b^*The coordinates define the second axis of color, in which positive values are on the yellow side of the spectrum and negative values are on the blue side. High L^*The value indicates the enhanced brightness of the substance. Generally, the acceptable color of an article, such as a bottle or film, is visually defined. However, the HunterLab ColorQuest Spectrometer is an article or resin L^*Can be shown quantitatively. This quantitative measurement is referred to herein as Permeation Hunter L.^*Or just L^*Is called.

In this technique, stretched films often have a lower L than the unstretched counterpart.^*It is known that it will have or will be darker. Therefore L^*Measurements were obtained on stretched and unstretched container walls, as well as through the bottle itself. The container wall of the present invention may include an unstretched film or sheet. The production of films and sheets is known in the art, and any of many suitable techniques can be used to produce the film.

The container of the present invention may also include a bottle developed from a premolded article. A premold is a molded structure that is developed to form a bottle in a mold. Alternatively, the container may include a film, pouch or other packaging material. Generally, polyester bottles are manufactured by a blow molding method, in which the premold is heated above the glass transition temperature of the polyester, the heated premold is placed in a mold of the desired bottle form and into the premold. This is done by injecting air, pressing the premolded part into the shape of the mold, and pushing the molded bottle out of the mold onto the conveyor belt.

Stretching material L^*Accurately measure L^*Two factors to consider when comparing values are the thickness of the article being measured and the blow window. The optimum blow window is determined based on the haze. A blow window graph is constructed to establish an appropriate temperature and processing time to obtain the lowest haze value by the polyester resin crystallization method alone. Blow window graphs show haze as a function of heat exposure time of the premold. The graph is usually constructed by creating isotherms and heating each premold at the same temperature for different lengths of time. The heated premold is then stretched and haze measurements are taken at the stretched portion. Several different temperatures are selected. Generally, the resin has the best temperature that produces the lowest haze value, which temperature is used to perform the rest of the evaluation. In the work described here, one temperature is selected and the time parameter is changed to determine the optimum blow window.<u style="single">To</u>I let you.

Granular additives reduce transparency when polyester has excellent optical properties even when crystallized by strain curing (stretching).^*Can be reduced. The number and particle size of the particles affect the color of both stretched and unstretched films and articles. Those skilled in the art will recognize that the thermoplastic resins disclosed herein vary considerably in density. In addition, the density of oxygen-removing particles can vary. Therefore, the preferred concentration of oxygen-removing particles in the resin is expressed as the number of particles per resin volume.

It will be understood that not all particles in every particle population have the same size and include a particle size range. In addition, the particles in the population may or may not have a uniform and well-shaped shape. A particle population or any part of the population can be described with an average particle size as measured by any standard technique known in the art. These techniques include measurement of the equilibrium rate at which particles settle in the liquid under the influence of gravity, resistance pulse counters, optical blockage counters, image analysis, laser diffraction spectroscopy and photon correlation spectroscopy. Statistical values commonly used to describe the particle size of a particle population are (1) the geometric mean dimension (which is the average particle size calculated on the log basis) and (2) the arithmetic mean (which is the linear basis). Includes (3) median dimension (which is the 50th percentile of the distribution), and (4) mode dimension (which is the most predominant particle size of the distribution).

In addition, the sample may be described by a particle size range or below a predetermined particle size. These can be defined by sieving techniques known in the art or other techniques. Therefore, any given particle population will have a particle size distribution that is a description of the particle size range and the amount of particles in each dimension. Techniques for particle size measurement are further described by Paul Webb and Clyde Orr in Analytical Methods in Fine Particle Technology, Micromeritics Instrument Corp. (1997), and James PM Syvitski in Principles, Methods, and Applications of Particle Size Analysis, Cambridge University. Discussed within the Publishing and Publishing Office (1991), both of which are fully incorporated by reference here.

We have found that various parameters are desirable for particle size within the particle population. It will be recognized that significant amounts of such large particles should be avoided, for example particles larger than the thickness of the vessel wall can create a rough surface. The particle size is generally preferably in the range of about 1 to about 70 microns, more preferably about 10 to about 70 microns, even more preferably about 15 to about 70 microns. More preferably, the particle size is in the range of about 20 to about 70 microns. These preferred ranges are given only as a general guide, and a few particles may be outside these ranges that do not affect the essential characteristics of the resin, and therefore they are of the present invention. It will be understood that it is within the range. Large amounts of particles can be added to the polymer as described above, and the effect on color is minimized by selecting the particle size distribution of the particle population and controlling the total number of particles to remain below a certain maximum. To. This maximum value is related to the thickness of the mass occupied resin, which is described above.

In some applications, it may be desirable to further control the particle size distribution of the particle population. Such desirability may depend on factors including container type, processing conditions and draw ratio. Manufactured by using an iron-containing thermoplastic resin composition when the oxygen-removing particles contain iron and the particles with an iron particle size distribution of about 25 microns or less do not exceed about 1250 mass ppm of the resin. Bottles and other packaging materials have been advantageously found to have acceptable color and haze properties. Preferably, iron particles less than about 20 microns do not exceed about 800 mass ppm of the resin. More preferably, particles smaller than about 20 microns do not exceed about 500 mass ppm of resin. More preferably, particles less than about 20 microns do not exceed about 100 mass ppm of resin. Desirably, iron particles smaller than about 10 microns do not exceed about 800 mass ppm of resin. More preferably, iron particles smaller than about 10 microns do not exceed about 500 mass ppm of resin. More preferably, iron particles smaller than about 10 microns do not exceed about 100 mass ppm of resin. Preferably, iron particles of about 5 microns or less do not exceed about 500 mass ppm of the resin. More preferably, iron particles of about 5 microns or less do not exceed about 100 mass ppm of the resin.

Therefore, it is understood that the statement "less than about 25 microns" in the specification and claims includes smaller iron particle sizes of 20 microns, 10 microns, 5 microns and less than 5 microns, depending on the preferred dimensions. It should be. Similarly, the statement "does not exceed about 1250 ppm" includes lesser amounts of 800 ppm, 500 ppm and 100 ppm, depending on the preferred amount. Particles larger than the thickness of bottles and other packaging materials produced by using the polyiron thermoplastic resin composition can create a rough surface, so significant amounts of such large particles should be avoided. That will be recognized.

More generally, the favorable particle size distribution of deoxygenated particles is defined as a function of the apparent density of the particles. The density of metal powder particles is not necessarily the same as the density of the material from which they are made, due to the internal pore space of the particles. Apparent density refers to the mass of a unit volume of loose particles, usually cubic centimeters per gram (g / g /<u style="single">c</u>m³). The characteristics of the powder that determine its apparent density are discussed in Peter K. Johnson, Powder Metallurgy, Kirk Othmer Encyclopedia of Chemical Technology, §§4.1, 4.2 (1995). The apparent density values typical of iron particles reported by Johnson range from about 0.97 to about 3.4 grams per cubic centimeter. When using particles containing iron or other substances, the advantageous particle size distribution of the particles is determined by the following formula.

Preferably, the particle size distribution of the deoxidized particles is such that particles of about 25 microns or less have the formula: ppm = 512.3 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 25 microns, d. Is the apparent density of cubic centimeters per gram of particles less than about 25 microns in size. ] Does not exceed the concentration specified by. The constant 512.3 in the above equation was derived from a calculation based on a particle size distribution such that particles of about 25 microns or less do not exceed a concentration of 1250 mass ppm, in which the particles have an apparent density of about 2.44 grams per cubic centimeter.

More preferably, the particle size distribution of the oxygen-removing particles is such that particles of about 20 microns or less have the formula: ppm = 327.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 20 microns. d is the apparent density of cubic centimeters per gram of particles less than about 20 microns in size. ] Does not exceed the concentration specified by. The constant 327.9 was determined by the same method as the above equation, as in each of the following equations. More preferably, the particle size distribution of the oxygen-removing particles is such that particles of about 20 microns or less have the formula: ppm = 204.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 20 microns. d is the apparent density of cubic centimeters per gram of particles less than about 20 microns in size. ] Does not exceed the concentration specified by. It is preferable that the particle size distribution of the oxygen-removing particles is about 20 microns or less. ppm = 41.0 × d [In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 20 microns in size, and d is the apparent density of particles less than about 20 microns per gram per cubic centimeter. ] Does not exceed the concentration specified by.

Desirably, the particle size distribution of the oxygen-removed particles is such that particles of about 10 microns or less have the formula: ppm = 327.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 10 microns, d. Is the apparent density of cubic centimeters per gram of particles less than about 10 microns in size. ] Does not exceed the concentration specified by. More preferably, the particle size distribution of oxygen-removing particles is such that particles of about 10 microns or less have the formula: ppm = 204.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 10 microns. d is the apparent density of cubic centimeters per gram of particles less than about 10 microns in size. ] Does not exceed the concentration specified by. More preferably, the particle size distribution of the oxygen-removing particles is such that particles of about 10 microns or less have the formula: ppm = 41.0 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 10 microns. d is the apparent density of cubic centimeters per gram of particles less than about 10 microns in size. ] Does not exceed the concentration specified by.

Preferably, the particle size distribution of the oxygen-removed particles is such that particles of about 5 microns or less have the formula: ppm = 204.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 5 microns, d. Is the apparent density of cubic centimeters per gram of particles less than about 5 microns in size. ] Does not exceed the concentration specified by. More preferably, the particle size distribution of the oxygen-removing particles is such that particles of about 5 microns or less have the formula: ppm = 41.0 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 5 microns. d is the apparent density of cubic centimeters per gram of particles less than about 5 microns in size. ] Does not exceed the concentration specified by.

The present invention also includes film-forming polyesters and granules, in which particles less than about 25 microns in size are of the formula: ppm = 512.3 × d [where ppm is the mass of particles less than about 25 microns in size. Approximate concentration of ppm, d is the apparent density of particles less than about 25 microns in size, in centimeters per gram. ] Provided a resin composition in which the granules have a particle size distribution that does not exceed the concentration determined by. The granules may or may not contain an oxygen scavenging element. Suitable granules include, but are not limited to, ceramics, plastics and metal granules, molecular sieves and the like.

Prepare the particle population, select the particle size distribution of the population to include the appropriate number of particles within the preferred dimensional range, melt phase polymerization of the polymer, after polymerization and before pelletization, solid phase polymerization of the polymer and During one or more extrusion process steps, this oxygen scavenging particle population is added to the polymer to form a mixture of polymer and particles, using the mixture of polymer and particles to have at least one wall. By including the step of forming the container, a large amount of oxygen-removing particles can be incorporated into the container wall with the minimum color shift. As described above, the oxygen-removing particles can be localized in one or more mass-occupied regions of the vessel wall by various techniques. In this embodiment, the mass-occupied region comprises a mixture of polymers and particles, and the method of assembling the mixture further combines the mixture with additional polymer to form a wall having the mass-occupied region and at least one other region. Including the process of The additional polymer can be a different polymer or the same polymer in the absence of a remover.

High L of the present invention^*The container with can contain an unstretched film or sheet of any thickness typically used in polymer film technology. In a preferred embodiment, the film has a thickness of at least about 0.5 mil and a transmission hunter L of at least about 80, more preferably at least 85, even more preferably at least about 90.^*Have a number. L of polyester sample without oxygen scavenging particles or other particles^*Lower than the number, but these L^*The values are well within the acceptable range for many commercial uses.

L^*The absolute number of L is due to the incorporation of oxygen-removing particles^*Not as important as the shift of. L^*The shift is caused by the addition of oxygen-removing particles L^*It's a change. L by adding oxygen scavenging particles^*It is desirable to minimize the shift. Thus the results of container walls or films and / or sheets containing oxygen-removing particles are compared to control walls, films or sheets of similar thickness and stretch, made from the same resin but not containing oxygen-removing particles. did. L^*The shift is the control L^*It can be defined as the difference between the value and the value of the Sample.

Preferably, the wall transparent hunter L of the present invention^*The change is less than about 0.4 per mil of wall when compared to a control containing no deoxygenated particles. More preferably, the wall transparent hunter L of the present invention^*The change is less than about 0.3 per mil of wall when compared to a control containing no deoxygenated particles. More preferably, the wall transparent hunter L of the present invention^*The change is less than about 0.25 per mil of wall when compared to a control containing no deoxygenated particles.

The container of the present invention can contain bottles, wherein the side walls of each bottle have a thickness of about 9 to about 35 mils, preferably about 11 to about 25 mils, more preferably about 14 to about 21 mils. Have. In a preferred embodiment, the sidewalls of each bottle have a thickness of about 14 to about 21 mils, and the bottle is at least about 78, more preferably at least about 80, even more preferably at least about 83 Hunter L.^*The number has the optimum blow window conditions. L of polyester sample without iron or other particles in the oxygen scavenging composition^*Lower than the number, but these L^*The values are well within the acceptable range for many commercial uses.

The maximum preferred particle concentration described above was defined for unstretched films with a crystallinity of less than about 1 percent. Generally, as the crystallinity of the polymer resin increases, L^*Decreases. Therefore, it will be appreciated that the highest preferred particle concentration will be lower in polymer compositions with higher crystallinity. To illustrate the practice of the present invention, the following examples were prepared and tested as described in the General Experiments section disclosed below. However, the examples should not be considered as limiting the scope of the invention. The claims play a role in defining the present invention.

<u style="single">General experiment (GENERAL EXPERIMENTATION)</u><u style="single">Preparation of Examples Nos. 1-26</u> PET copolymer resins were prepared according to the teachings of US Pat. No. 5,612,423, which is fully incorporated by reference herein. Iron particle samples with various particle sizes were obtained. Hydrogen-reduced sponge iron from Pyron was used for Examples 1-10. Carbonyl iron powder obtained from ISP Technologies was used for Examples 11-26. The iron particles used in Example 3 had a particle size range of about 25 to about 38 microns. It will be appreciated that such samples can be prepared using, for example, a sieve. Iron particles were added to the polyester resin by using a metered feeder with a twin-screw screw extruder to form a resin masterbatch containing 2.5% by weight of the iron-containing resin composition. This masterbatch was blended with the base resin to give the desired concentration. The base resin / iron mixture was dried under reduced pressure at 325 ° F (163 ° C) for 18 hours. Dry resin, Novotec of Nissei ASB 50T Injection Blow-Molding machine Transferred to a dry hopper. The hopper was heated to 325 ° F (163 ° C) and set for a dew point of -40 ° F (-40 ° C).

In a two-step process, bottle premolds were produced and blown into bottles. First, the premold was manufactured on a Mini-jector or Nissei machine. The bottle was then blown from the premolded article on a Cincinnati Milacron Reheat Blow Lab (RHB-L) injection molding machine. Premolds were manufactured in a Mini-jector with a cycle time of 45 seconds and an injection time of 15 seconds at a rear heater temperature of 270 ° C, a front heater temperature of 275 ° C and a nozzle heating of 275 ° C. The injection pressure was between about 1000-1500 psig. The oven temperature at Milacron RHB-L ranged from about 163 to about 177 ° C. The exposure time was about 31 to about 52 seconds.

Transparent Hunter L^*Measurements were made through the side wall of the bottle, which is the thinned stretched portion. Since these measurements were made for the entire bottle, the thickness effectively has two sidewalls. We used the HunterLab ColorQUEST Sphere Spectrophotometer System with an IBM PS / 2 model 50Z computer, an IBM Proprinter II dot matrix printer, a categorized specimen holder, green, gray and white calibration tiles, and an optical trap. The HunterLab Spectrocolorimeter integrating sphere sensor is a color and appearance measuring instrument. Light from the lamp was diffused by an integrating sphere and traveled from the subject to the lens through either (transmission) or reflection (reflectance). The lens collects the light and directs it to the grating, which disperses it to its component wavelengths. The dispersed light is reflected by the silicon diode array. The signal from the diode travels through the amplifier to the converter and is processed to produce data. L^*The data is provided by the software. Samples made for either transmittance or reflectance must be clean and free of surface scratches or wear. The sample size must match the geometry of the spherical opening, and in the case of transmittance, the sample size is limited to the size of the compartment. Each sample is tested at four different locations, such as the side wall of the bottle or a typical film area.

A Panametrics Magna-Mike 8000 Hall Effect Thickness Gauge was used to measure the thickness of the side wall of the bottle. Place a small steel ball on one surface of the test material and place the magnetic probe down. The distance between the sphere and the probe is measured by a Hall effect sensor. In particular, we used the Magna-Mike 8000 with a DPU-411 thermal printer (Type II), remote footswitch, target ball kit and Standard 801PR Probe. The measurements were taken twice and averaged. Tables 1 and 2 summarize the iron particle concentration, the average grain size of iron, and the optical properties under constant sample thickness of about 11 to about 13 mils and optimum blow window conditions. Comparative Examples 1, 6 and 11 did not contain iron particles. The particle size of the iron particles reported in Table 1 was provided by the supplier. The particle size of the iron particles in Table 2 was measured as a geometric mean based on volume. Haze and L * in Tables 1 and 2 were measured for the entire bottle. The average mill of 22 mils on both sides is L per mil.^*Used to measure changes.

<tables num="1"><img file="JP4166152B2_D0001.tif" /></tables>

<tables num="2"><img file="JP4166152B2_D0002.tif" /></tables>

<u style="single">Creation of Examples 27 to 32</u> Examples 28 to 33 are stretched film samples produced as described above. Example 27 is a control and does not contain oxygen scavenging particles. The results are shown in Table 3. The type of iron used for Examples 28, 29 was hydrogen-reduced sponge iron with a geometric mean particle size of about 11.96 microns based on volume. The iron used for Examples 30-11 was unannealed electrolytic iron with a volume-based geometric mean particle size of approximately 17.41 microns. The iron used for Examples 32 and 33 was carbon monoxide reduced sponge iron with a geometric mean particle size of about 18.61 microns based on volume. The number of parts of iron per cubic centimeter of polymer can be compared, but the number of particles per cubic centimeter of polymer increases as the particle size decreases, and the permeation hunter L from the control per mil of film thickness.^*Shifts will also increase. For Examples 27-33, L^*It should be noted that the measurements were made through all bottles. The superior performance of carbon monoxide reduced sponge iron is demonstrated by comparing Examples 32 and 33, with a shift of about 50% less than other types of iron with the same particle number.

<tables num="3"><img file="JP4166152B2_D0003.tif" /></tables>

<u style="single">Creation of Examples 34 to 48</u> Films were made using a Haake mixer to determine the optimum concentration of particles of various sizes in the unstretched resin. 2500.0 grams of HiPERTUF 89010 copolyester resin was weighed into each of several 1 gallon cans and dried overnight at approximately 100 ° C under full decompression in a vacuum oven. The decompression was returned to atmospheric pressure with nitrogen. An appropriate amount of carbonyl iron powder (manufactured by ISP Technologies) was weighed under nitrogen in vials at different desired concentrations. The nominal particle size range of iron provided by the supplier was about 7 to about 9 microns. The geometric mean particle size based on the volume of this iron powder was about 7.891 microns. Iron was added to the resin just before removing the thermoplastic from the oven, the vials were sealed and the mixture was blended on a roller mill for about 5 minutes.

The blended mixture was added to the feed hopper of the Haake Polylab extrusion system for film production. The resin was melted in an extruder and extruded from the die in the form of a flat sheet. A thin, uncoated, substantially amorphous film was fed through a temperature controlled three-roll polishing stack and quenched to minimize crystallinity to give a final polished surface. The cooling film was wound around the core. Measured film thickness (mill), permeation hunter L for a typical film sample with a constant iron concentration^*And L per mil^*The shifts are shown in Table 4. The iron concentration in Examples 37 and 38 was about 0.9659 × 10 particles per cubic centimeter of polymer.⁶In Examples 39 to 41, the number of particles is about 2.8978 × 10 per cubic centimeter of polymer.⁶It is an individual. L as the film thickness increases^*Decreases, but L per 1 mil film thickness^*It turns out that the changes are substantially the same. In Examples 42-48, the film thickness was kept constant at about 11 mils and the number of particles per cubic centimeter of polymer was varied. When the particle concentration increases, L^*Decreased, L from control per mil thickness^*It can be seen that the shift increases.

<tables num="4"><img file="JP4166152B2_D0004.tif" /></tables>

<tables num="5"><img file="JP4166152B2_D0005.tif" /></tables>

As shown in Table 2, if the iron particle size is less than about 8 microns, then at least about 80% L^*Obtained at iron levels up to about 800 ppm, L per mil^*The change is less than 0.4. Furthermore, if the grain size of iron is about 5 microns or less, at least about 80% L^*Values are obtained at iron levels up to about 500 ppm.

As shown in Table 3, when the particle population is a constant number of parts per cubic centimeter of polymer, the number of particles per cubic centimeter of polymer decreases as the particle size increases. As the number of particles per cubic centimeter of polymer increases, L^*Decreased, L per mil^*Change increases. As shown in Table 4, as the sample thickness increases, the total transmission hunter L^*Decreased, L per mil^*Change increases. L per mil, as shown in Table 5^*The change is at least about (1 x 10) per cubic centimeter of polymer⁷Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ], The particle concentration is less than about 0.4% per 1 mil of the container wall.

As will be appreciated, the present invention overcomes the problems associated with the prior art by providing a thermoplastic resin composition containing an effective amount of oxygen-removing particles and having acceptable color and haze properties. The resulting resin can be used to form clear bottles, films and other container and packaging materials. These materials contain oxygen-removing particles in sufficient amounts to effectively remove oxygen, providing a longer shelf life for oxygen-sensitive materials. In addition, these materials have acceptable haze properties.

Although the best modes and preferred embodiments of the present invention have been shown in accordance with the Patent Statutes, the scope of the invention is not limited thereto, but rather is defined by the appended claims. The scope of the present invention therefore includes any modifications and modifications within the scope of the claims.<u style="single">The present invention includes the following embodiments.</u><u style="single">[1] Film-forming polyester and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">There are particles in it that are less than about 25 microns in size, but that is the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition in which particles have a particle size distribution that does not exceed the concentration determined by.</u><u style="single">[2] The resin composition according to the above [1], wherein the polyester contains a linear polyester or a branched polyester.</u><u style="single">[3] The above-mentioned [1], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. Resin composition.</u><u style="single">[4] Oxygen-removing elements include calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium or The resin composition according to the above [1], which comprises a combination thereof.</u><u style="single">[5] The resin composition according to the above [1], wherein the oxygen removing element contains iron.</u><u style="single">[6] The resin composition according to the above [1], wherein the effective amount of oxygen-removing particles is about 50 to about 2500 mass ppm of the resin.</u><u style="single">[7] The resin composition according to the above [1], wherein the oxygen-removing particles have a particle size range of about 20 to about 70 microns.</u><u style="single">[8] The resin composition according to the above [1], wherein particles having a size of less than about 25 microns have an apparent density of about 0.97 to about 3.4 grams per cubic centimeter.</u><u style="single">[9] The resin composition according to the above [1], wherein particles having a size of less than about 20 microns have an apparent density of about 0.97 to about 3.4 g / cubic centimeter and do not exceed a concentration of about 800 mass ppm of the resin.</u><u style="single">[10] The resin composition according to the above [1], wherein the oxygen scavenging particles are pretreated with one or more reaction enhancers.</u><u style="single">[11] Hunter L when the bottle made from the resin is compared to a control having a Hunter haze value of about 10% or less and no oxygen scavenging particles.</u>^{<u style="single">*</u>}<u style="single">The resin composition according to the above [1], which has a change of about 0.4% or less.</u><u style="single">[12] Film-forming polyester and</u><u style="single"> Effective amount of oxygen-removing iron particles</u><u style="single">A resin composition in which iron particles have a particle size distribution such that particles having a size of less than about 25 microns are present therein, but the particle size distribution does not exceed about 1250 mass ppm of the resin.</u><u style="single">[13] The resin composition according to the above [12], wherein the polyester contains a linear polyester or a branched polyester.</u><u style="single">[14] The above-mentioned [12], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. Resin composition.</u><u style="single">[15] The resin composition according to the above [12], wherein the effective amount of iron particles is about 50 to about 2500 mass ppm of the resin.</u><u style="single">[16] The resin composition according to the above [12], wherein the iron particles have a particle size range of about 20 to about 70 microns.</u><u style="single">[17] The resin composition according to the above [12], wherein particles having a size of less than about 20 microns do not exceed about 800 mass ppm of the resin.</u><u style="single">[18] The resin composition according to the above [12], wherein the oxygen scavenging particles are pretreated with one or more reaction enhancers.</u><u style="single">[19] Hunter L when a bottle made from the resin is compared to a control having a Hunter haze value of about 10% or less and no oxygen scavenging particles.</u>^{<u style="single">*</u>}<u style="single">The resin composition according to the above [12], which has a change of about 0.4% or less.</u><u style="single">[20] A resin composition containing about 50 to about 2500 mass ppm of oxygen-depleted iron particles of film-forming polyester and resin, in which the concentration of iron particles having a size of less than about 25 microns does not exceed about 1250 mass ppm of resin. ..</u><u style="single">[21] The resin composition according to the above [20], wherein the polyester comprises a linear polyester or a branched polyester.</u><u style="single">[22] The above-mentioned [20], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. Resin composition.</u><u style="single">[23] The resin composition according to the above [20], wherein the iron particles have a particle size range of about 20 to about 70 microns.</u><u style="single">[24] The resin composition according to the above [20], wherein particles having a size of less than about 20 microns do not exceed about 500 mass ppm of the resin.</u><u style="single">[25] The resin composition according to the above [20], wherein the oxygen scavenging particles are pretreated with one or more reaction enhancers.</u><u style="single">[26] When a bottle made from the resin is stretched to a thickness of about 11 to about 16 mils, when compared to a control having a hunter haze value of about 10% or less and no oxygen scavenging particles. Hunter L</u>^{<u style="single">*</u>}<u style="single">The resin composition according to the above [20], which has a change of about 0.4% or less.</u><u style="single">[27] A polyester resin composition containing iron particles of about 50 to about 2500 mass ppm of resin for use in forming a transparent product having a low haze, wherein the transparent product has a hunter haze value of about 10%. Hunter L when compared to or less, and controls that do not contain oxygen scavenging particles</u>^{<u style="single">*</u>}<u style="single">A resin composition having a change of about 0.4% or less.</u><u style="single">[28] The above-mentioned [27], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. Resin composition.</u><u style="single">[29] Particles with dimensions less than about 25 microns have the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">The resin composition according to the above [27], wherein the iron particles have a particle size distribution that does not exceed the concentration determined by.</u><u style="single">[30] When compared with a control product formed from a resin composition containing an effective amount of oxygen-removing particles and having a hunter haze value of about 10% or less and not containing oxygen-removing particles. Hunter L</u>^{<u style="single">*</u>}<u style="single">Goods with a change of about 0.4% or less.</u><u style="single">[31] The article according to [30] above, which is a bottle.</u><u style="single">[32] In the above [30], the resin composition comprises polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. The article described.</u><u style="single">[33] Hunter L when the hunter haze value of the article is about 8% or less and compared to a control that does not contain oxygen-removing particles.</u>^{<u style="single">*</u>}<u style="single">The article according to [30] above, wherein the change is about 0.4% or less.</u><u style="single">[34] In the process of preparing an effective amount of oxygen-removing particles containing at least one oxygen-removing element capable of reacting with molecular oxygen, there are particles having a size of less than about 25 microns. formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A process in which the particles have a particle size distribution that does not exceed the concentration determined by; </u><u style="single"> Molten phase polymerization of polyester;</u><u style="single"> After polymerization and before pelletization;</u><u style="single"> Solid-phase polymerization of polyester; and</u><u style="single"> Extrusion</u><u style="single">The step of adding the oxygen-removing particles to the polyester resin composition during one or more of the process steps of</u><u style="single">A method for producing a film-forming polyester resin composition, which incorporates a large amount of oxygen-removing particles in a low haze.</u><u style="single">[35] The method according to [34] above, wherein the step of adding the oxygen-removing particles to the polyester resin composition further comprises a step of producing a masterbatch of the oxygen-removing resin and adding the masterbatch to the additional resin.</u><u style="single">[36] The above [34], wherein the polyester resin contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. the method of.</u><u style="single">[37] Oxygen-removing particles are in oxidizable forms of calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, tin, aluminum, antimony, germanium, silicon, lead. , Cadmium, rhodium or a combination thereof, according to the method according to [34] above.</u><u style="single">[38] The method according to the above [34] or [35], wherein the oxygen scavenging element contains iron.</u><u style="single">[39] The method according to [34] above, wherein the effective amount of oxygen-removing particles is about 50 to about 2500 mass ppm of the resin.</u><u style="single">[40] The method according to [34] above, wherein particles less than about 25 microns in size have an apparent density of about 0.96 to about 3.4 grams per cubic centimeter.</u><u style="single">[41] The method according to [34] above, wherein particles having a size of less than about 20 microns have an apparent density of about 0.96 to about 3.4 grams per cubic centimeter and do not exceed a concentration of about 800 mass ppm of resin.</u><u style="single">[42] The method according to [34] above, wherein the oxygen-removing particles are pretreated with one or more reaction enhancers.</u><u style="single">[43] Hunter L when a bottle made from the resin is compared to a control having a Hunter haze value of about 10% or less and no oxygen scavenging particles.</u>^{<u style="single">*</u>}<u style="single">The method according to [34] above, which has a change of about 0.4% or less.</u><u style="single">[44] Film-forming polyester and</u><u style="single"> Granules containing oxygen-removing particles that can react with molecular oxygen</u><u style="single">There are particles in it that are less than about 25 microns in size, but that is the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition in which the granules have a particle size distribution that does not exceed the concentration determined by.</u><u style="single">[45] It has at least one wall, the wall contains a group occupied area, and the group occupied area is</u><u style="single"> Membrane-forming polymer, and</u><u style="single"> Particle population containing an effective amount of oxygen-removing particles</u><u style="single">The number of oxygen-removing particles, including</u><u style="single"> Approximately (1 x 10) per cubic centimeter of polymer</u>^{<u style="single">7</u>}<u style="single">Particles ÷ T)</u><u style="single">[In the formula, T is the thickness of the mill in the mass occupied area. ]</u><u style="single">Permeation hunter L on the wall without exceeding the concentration of</u>^{<u style="single">*</u>}<u style="single">The change is less than about 0.4 per mil of vessel wall when compared to controls that do not contain oxygen-removing particles.</u><u style="single">[46] The container according to [45] above, wherein the polymer contains polyester.</u><u style="single">[47] The container according to the above [46], wherein the polyester contains a linear polyester.</u><u style="single">[48] The above-mentioned [47], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. container.</u><u style="single">[49] The container according to [45] above, wherein the polyester is made from one or more polyfunctional comonomer.</u><u style="single">[50] The container according to [49] above, wherein the polyfunctional comonomer is selected from the group consisting of pyromelitoic dianhydride and pentaerythritol.</u><u style="single">[51] The container according to [45] above, wherein the effective amount of oxygen-removing particles is at least about 50 mass ppm of the polymer.</u><u style="single">[52] Oxygen-removing particles include calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium or The container according to any one of [45] to [48] above, which comprises a combination thereof.</u><u style="single">[53] The container according to any one of the above [45] to [48], wherein the oxygen-removing particles contain iron.</u><u style="single">[54] The container according to [45] above, wherein the oxygen-removing particles contain iron and the oxygen-removing particles are present in an amount of about 50 to about 12,000 mass ppm of the resin.</u><u style="single">[55] Polymers are strengthening agents, mold release agents, denesting agents, stabilizers, crystallization aids, antioxidants, UV absorbers, catalyst activators, colorants, nucleating agents, acetaldehyde reduction. The container according to [45] above, further comprising one or more components selected from the group consisting of agents, reheat reducing agents, fillers, branching agents, foaming agents and accelerators.</u><u style="single">[56] The container according to [45] above, wherein the particle population further comprises reaction-enhancing particles.</u><u style="single">[57] The above-mentioned [56], wherein the reaction-enhancing particles include a hydroscopic substance, an electrolyte acidifying agent, a non-electrolyte acidifying agent, a metal halide, a metal sulfate, a metal hydrogen sulfate, or a mixture thereof. container.</u><u style="single">[58] The container according to [45] above, wherein the oxygen scavenging particles are pretreated with at least one reaction enhancer.</u><u style="single">[59] Permeation hunter L from the control side wall with a side wall thickness of about 11 to about 25 mils and less than about 0.25 units per mil of container wall.</u>^{<u style="single">*</u>}<u style="single">The container according to any one of [45] to [48] above, which is a stretched bottle having a shift.</u><u style="single">[60] The container according to the above [45], wherein the collective occupied area constitutes a stack of container walls.</u><u style="single">[61] The container according to the above [45], wherein the mass occupied area constitutes a simultaneous extrusion layer of the container wall.</u><u style="single">[62] The container according to the above [45], wherein the thickness of the collective occupied area is equal to the thickness of the container wall.</u><u style="single">[63] The container according to the above [45], wherein the thickness of the collective occupied area is thinner than the thickness of the container wall.</u><u style="single">[64] The container according to [45] above, which is a tray.</u><u style="single">[65] The container according to any one of [45] to [48] above, wherein the oxygen-removing particles contain carbon monoxide-reduced sponge iron.</u><u style="single">[66] Film-forming polyester and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">The particles have a particle size distribution such that particles in the dimensional range of about 25 to about 38 microns and particles in the dimensional range of about 38 to about 45 microns are present, and Particles with dimensions less than about 25 microns, the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition that does not exceed the concentration determined by.</u><u style="single">[67] Film-forming polyester, and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">The particles have a particle size distribution such that particles in the dimensional range of about 38 to about 45 microns and particles in the dimensional range of about 45 to about 75 microns are present. Particles with dimensions less than about 25 microns, the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition that does not exceed the concentration determined by.</u><u style="single">[68] Film-forming polyester, and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">The particles have a particle size distribution such that particles in the dimensional range of about 25 to about 38 microns and particles in the dimensional range of about 38 to about 75 microns are present, and Particles with dimensions less than about 25 microns, the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition that does not exceed the concentration determined by.</u><u style="single">[69] Film-forming polyester and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">The particles have a particle size distribution such that particles in the dimensional range of about 25 to about 45 microns and particles in the dimensional range of about 45 to about 75 microns are present. Particles with dimensions less than about 25 microns, the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition that does not exceed the concentration determined by.</u>