WO2005016782A1 - 包装容器 - Google Patents
包装容器 Download PDFInfo
- Publication number
- WO2005016782A1 WO2005016782A1 PCT/JP2004/009897 JP2004009897W WO2005016782A1 WO 2005016782 A1 WO2005016782 A1 WO 2005016782A1 JP 2004009897 W JP2004009897 W JP 2004009897W WO 2005016782 A1 WO2005016782 A1 WO 2005016782A1
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- WIPO (PCT)
- Prior art keywords
- component
- oxygen
- packaging container
- resin
- absorbing
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
- B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
Definitions
- the present invention relates to a packaging container having functions such as gas barrier property and oxygen absorption property, and more particularly, excellent gas barrier property and oxygen property that are continuously provided from the initial stage of filling a container with contents.
- the present invention relates to a packaging container that can exhibit absorbency. Background art
- Polyester resin represented by polyethylene terephthalate has excellent properties such as moldability, transparency, mechanical strength, and chemical resistance, and has relatively high gas barrier properties such as oxygen. It is used in various fields as a packaging material for bottles and the like.
- oxygen scavengers have been used for a long time, and as an example of applying them to the container wall, an oxygen scavenger composed mainly of a reducing substance such as iron powder is mixed with an oxygen-permeable resin.
- a multi-layer structure for packaging is known, in which a layer having the following properties and a layer having an oxygen gas barrier property are laminated (Japanese Patent Publication No. 63-184224).
- a functional resin layer having gas barrier properties such as an ethylene monoacetate vinyl acetate copolymer or polyamide, is provided as an intermediate layer between the inner and outer layers.
- Packaging materials are also known (Japanese Patent Application Laid-Open No. Sho 63-203340).
- a composition comprising a polymer having oxygen-scavenging properties or a packaging barrier comprising a layer of the composition, wherein the composition is formed by metal-catalyzed oxidation of an oxidizable organic component.
- a packaging barrier characterized by trapping oxygen has been proposed, and it is also known that polyamides, especially xylylene group-containing polyamides, can be used as the oxidizable organic component (Table 2). No. 50864 publication).
- an oxygen-absorbing resin composition containing a polyamide resin, an oxidizing organic component and a transition metal-based catalyst, and a packaging material and a multilayer packaging container obtained by molding the resin composition are also known.
- Japanese Unexamined Patent Publication No. 2002-22416 Japanese Unexamined Patent Publication No. 2002-22416. Disclosure of the invention
- oxygen-free water aqueous solution in which oxygen is not dissolved
- the oxygen-free water absorbs oxygen gas contained in the air and resin remaining in the space of the container, and the aqueous solution is removed.
- the oxygen concentration inside gradually increases.
- a multi-layer container with a gas barrier layer made of polyamide resin or the like as an intermediate layer with oxygen-free water has the effect of reducing the amount of gas permeating from the outside to the inside of the container.
- the oxygen gas contained in the air and the resin in the innermost layer remaining in the water is absorbed, and the oxygen concentration in the oxygen-free water also gradually increases.
- the filled oxygen-free water still remains in the container for several days.
- Oxygen concentration in water in the multilayer container may continue to increase due to absorption of oxygen remaining in the resin of the inner layer. This is because even if a transition metal or the like that promotes oxygen absorption is added to the gas barrier resin layer, the gas barrier resin diffuses oxygen gas remaining in the container and the innermost resin into the oxygen absorption layer. It seems to act as a shield.
- the resin constituting the middle layer (two middle layers located between the inner and outer layers and the center layer) of the five-layer container (internal An oxygen-absorbing functional resin composition comprising an oxidizing organic component and a transition metal-based catalyst [polymethyxylene adipamide: 94.75% by weight, polyene-based oxidizing organic component: 5% by weight, and a transition metal-based Catalyst: 0.25 wt% (350 ppm in metal conversion)] from 1.5 wt% to 3 wt% based on the container weight, even after 3 days of filled anoxic water Dissolved oxygen concentration and dissolved oxygen concentration after 14 days (both at 22 ° C, 6 (Stored at 0 RH) is almost the same at around 400 ppm and does not decrease.
- a transition metal-based catalyst polymethyxylene adipamide: 94.75% by weight, polyene-based oxidizing organic component: 5% by weight, and a transition metal-based Catalyst: 0.
- a resin having an oxygen absorbing function having a gas barrier property and an oxygen absorbing property forming an island portion is mixed with the base resin forming the sea portion. If the ratio of the surface area of the island portion to the inner volume of the vessel is below a certain value, the initial dissolved oxygen concentration of the oxygen-free water in the vessel will not increase and decrease.
- the present inventors have proposed a resin having an oxygen absorbing function of forming an island portion which is a dispersed phase in a base resin forming a sea portion which is a continuous phase as an intermediate layer of a packaging container, particularly a multilayer container.
- the dissolved oxygen concentration of the oxygen-free water filled in the container is increased by making the total surface area of the island portion a certain ratio or more with respect to the internal volume of the multilayer container.
- the present inventors have found that a low concentration can be maintained from the initial stage of filling, and have completed the present invention.
- an object of the present invention is to provide a packaging container having excellent gas barrier properties and oxygen absorption from the beginning of filling the container.
- Another object of the present invention is to provide a packaging container capable of continuously reducing the initial oxygen concentration of the contents from the beginning of filling the container.
- a packaging container having an oxygen-absorbing layer comprising a base resin component (component A) and an oxygen-absorbing functional component (component B), wherein the oxygen-absorbing layer is a base resin component (A) Has a sea-island structure in which a sea portion is a continuous phase and an island portion in which the oxygen-absorbing functional component (component B) is a dispersed phase, and comprises the oxygen-absorbing functional component (component B) in an oxygen-absorbing layer.
- a packaging container is provided, wherein the ratio (NZM) of (M em 3 ) is 20 (cm— 1 ) or more.
- the average particle size of the island portion in the oxygen absorbing layer is less than 3.5 m;
- the base resin component (component A) is a thermoplastic polyester resin
- thermoplastic polyester resin is polyethylene terephthalate;
- component B oxygen-absorbing functional component
- gas-barrier resin an oxygen-barrier resin, an oxidizing organic component and a transition metal catalyst;
- the oxidizable organic component comprises a polymer derived from polyene, particularly an acid-modified polyene polymer,
- the oxidizing organic component is contained in the oxygen-absorbing functional component (component B) at a rate of 0.01 to 10% by weight,
- the transition metal-based catalyst is contained in the oxygen-absorbing functional component (component B) at a ratio of 100 to 3000 ppm as transition metal atom,
- the transition metal catalyst is a carboxylic acid cobalt salt.
- oxidizing organic component in the (1 1) is a Jiamin component terminal amino group concentration mainly xylylenediamine under 40 e qZ 1 0 6 g and a dicarboxylic acid component by polycondensation reaction Being the obtained polyamide resin,
- the oxygen-absorbing layer has a multilayer structure in which another layer is laminated.
- the oxygen-absorbing layer contains an oxygen-absorbing functional component (component B) at a ratio of 10 to 60% by weight. is being done,
- FIG. 1 is a diagram showing an example of the cross-sectional structure of the packaging container of the present invention.
- FIG. 2 is a diagram showing the relationship between the composition of the oxygen-absorbing resin composition and the dissolved oxygen concentration in the packaging container.
- the packaging container of the present invention is a packaging container having an oxygen-absorbing layer comprising a base resin component (component A) and an oxygen-absorbing functional component (component B), wherein the oxygen-absorbing layer is a base resin component (component A) ) Forms a sea-island structure in which the sea portion and the oxygen-absorbing functional component (component B) are island portions, and the total surface area of the island portion in the oxygen-absorbing layer composed of the oxygen-absorbing functional component (component B)
- the ratio (NZM) of N cm 2 ) to the internal volume (M em 3 ) of the packaging container is 20 (cm) or more, particularly preferably 25 (cm 1 ) or more, and particularly preferably 28 (cm ′′ 1 ) or more.
- a packaging container having an oxygen-absorbing layer having a sea-island structure as described above.
- the ratio (NZM) of the total surface area (N cm 2 ) of the island portion composed of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer to the internal volume (Mem 3 ) of the packaging container is 20 ( If it is less than cm 1 ), the oxygen absorbing function is not sufficiently exhibited from the beginning of filling the container, and it is difficult to keep the oxygen concentration low from the beginning of filling the contents into the container.
- the total surface area (N cm 2 ) of the island portion can be obtained from an enlarged observation result of a cross section of the extruded film or sheet when it is not stretched, but the final form is a bottle or cup.
- the main part, especially the side wall part is thinned when it is subjected to a stretching process or the like, and it is difficult to observe an enlarged cross section. Therefore, the sea-island structure is fundamentally formed when preform sheets are formed, the weight of the oxygen-absorbing layer (sea portion and island portion) does not change before and after stretching, and the stretching ratio is the same.
- the cross-sectional enlargement of the unextended portion such as the lower part of the bottleneck ring or the vicinity of the wrench flange indicates The total surface area can be determined.
- the total surface area of the islands was determined by measuring the shortest and longest diameters of all the islands in an electron micrograph (SEM) as described in the examples below, and averaging the average particle diameter of the islands.
- the total particle size divided by the number of particles is taken as the average particle size r (cm)
- the total surface area of the island is N (cm 2 )
- the container weight is X (g)
- the oxygen absorption in the container Assuming that the layer is Y (% by weight), the ratio of the oxygen-absorbing functional component B in the oxygen-absorbing layer is Z (% by weight), and the specific gravity of the component B is d (g / cm 3 ), the weight of one island is Is 4 7 ⁇ r 3 dZ3, and the weight of component B in the oxygen-absorbing layer is (X YZ 100) (Z / 100), so the total surface area N (cm 2 ) of the island portion is
- N (X ⁇ 7. / ⁇ 0 4 ) Z (4 ⁇ r 3 d / 3) x (4 ⁇ r 2 )
- the ratio (NZM) between the total surface area (N cm 2 ) of the island portion composed of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer and the internal volume (M em 3 ) of the packaging container is 20 (
- the molding conditions necessary to obtain a sea-island structure of cm " 1 ) or more include the resin mixing ratio, the melt viscosity of the resin, the viscosity ratio, and the shearing conditions of the molten resin.
- melt viscosity of the oxygen-absorbing functional component (component B) constituting the island portion is lower than that of the base resin component (component A) constituting the sea portion, and (b) oxygen absorption in the multilayer container.
- the oxygen absorbing functional component (component B) in the layer be in the range of 10 to 60% by weight and the base resin component (component A) in the range of 40 to 90% by weight.
- the oxygen-absorbing functional resin component (component B) is 0.5 to 3% by weight
- the base resin component (component A) is 97 to 99.5% by weight.
- the average particle diameter r of the oxygen-absorbing functional component (component B) constituting the island portion of the oxygen-absorbing layer is desirably less than 3.5 jUm, and particularly desirably 3.0 ⁇ m or less.
- the average particle diameter is less than 3.5 m, the mechanical strength, the transparency, and the oxygen absorption performance due to the increase in the surface area are improved.
- an oxidizing organic component when contained as the oxygen-absorbing functional resin component (B), no oxidizing organic component is present in the sea portion composed of the base resin component (component A). Is particularly desirable to improve the transparency of the packaging container.
- the reason that the transparency of the container is affected by the state of the oxidizing organic component is that the scattering point of light increases because the oxidizing organic component used in the present invention exists not only in the island portion but also in the sea portion. It is believed that this oxidizing organic component and marine
- the poor compatibility with the base resin component (particularly polyester resin), which is a component of the polymer reduces the transparency even if the oxidizable organic component present in the sea area exists at a particle size that causes light scattering. It is thought that it is a factor to cause.
- the base resin component (component A) used in the present invention forms a sea portion, and specific examples thereof include a thermoplastic polyester resin, a polycarbonate resin, a polyacrylonitrile resin, a polyolefin resin, and a polyvinyl chloride resin. Of these, thermoplastic polyester resins are preferred. Further, among thermoplastic polyester resins, polyethylene terephthalate, a copolymer using isophthalic acid as a part of terephthalic acid in polyethylene terephthalate, and polyethylene naphthalate are particularly preferred.
- a multi-layer container formed of at least an inner and outer layer and an intermediate layer as a packaging container is provided with an oxygen-absorbing layer comprising a base resin component (component A) and an oxygen-absorbing functional component (component B) as an intermediate layer.
- a base resin component (component A) a resin having adhesiveness to a resin constituting a layer in contact with the intermediate layer can be used.
- those conventionally used as an adhesive resin for forming an adhesive layer for example, carboxylic acids such as maleic acid, itaconic acid and fumaric acid, or anhydrides, amides and esters of these carboxylic acids
- a graft-modified olefin resin modified by grafting can be used as the base resin component (component A).
- the resin to be graft-modified is preferably polyethylene, polypropylene, an ethylene-olefin copolymer, or the like.
- graft-modified resin for example, ethylene-acrylic acid copolymer, ion-crosslinked resin-based copolymer, ethylene-vinyl acetate copolymer, copolymerized polyester, copolymerized polyamide
- a carbonyl group is added to the main chain or side chain by 1 to 100 milliequivalents.
- Examples of the oxygen-absorbing functional component (component B) used in the present invention include: (ii) a component comprising a gas barrier resin, an oxidizing organic component, and a transition metal catalyst; or (ii) an oxidizing organic component and a transition metal catalyst.
- a component consisting of: (i) a component comprising the above-mentioned (i) a gas barrier-compatible resin, an oxidizing organic component, and a transition metal-based catalyst is more preferable.
- the term “oxygen-absorbing functional component (component B)” is a term used to indicate that it is different from the resin component relating to the base resin component (component A).
- the oxygen-absorbing functional component (component B) composed of the gas barrier resin, the oxidizing organic component and the transition metal catalyst of the present invention forms an island portion in the oxygen-absorbing layer.
- the content of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer is preferably 10 to 60% by weight, more preferably 10 to 40% by weight. It is.
- the content is preferably 0.5 to 3% by weight, more preferably 0.5 to 2% by weight.
- both the oxygen-absorbing function and the gas-barrier function can be effectively exerted from the initial stage of filling the contents into the packaging container.
- the gas barrier resin referred to here has a gas shielding property against various gases, and examples thereof include an ethylene-vinyl alcohol copolymer, a polyamide resin, and the like generally used in the field of packaging materials. It is possible to use other gas barrier resins.
- the ethylene-vinyl alcohol copolymer examples include, for example, an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol 0 / o, particularly 25 to 50 mol 0 / o, 9 6 0/0 or more, are preferred copolymer saponification product obtained by saponifying such particularly from 9 9 mol% or more.
- the ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer) has a molecular weight sufficient to form a film.
- the weight ratio of [phenolic water] should be at least 0.01 dLZg, especially 0.05 dLZg, measured at 30 ° C in a mixed solvent of 85 to 15%. It is desirable to have the above intrinsic viscosity.
- gas barrier resins other than the ethylene-vinyl alcohol copolymer include the following polyamide resins.
- polyamide resin examples include (a) an aliphatic, alicyclic or semi-aromatic polyamide derived from a dicarboxylic acid component and a diamine component, (b) a polyamide derived from an aminocarboxylic acid or its lactam, Or (c) these copolyamides or their blends.
- dicarboxylic acid component examples include succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, pendecanedicarboxylic acid, dodecanedicarboxylic acid, etc., aliphatic dicarboxylic acids having 4 to 15 carbon atoms, terephthalic acid, disophthalic acid, etc. Aromatic dicarboxylic acid.
- the diamine components include 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, etc., having 4 to 25 carbon atoms, particularly 6 to 18 carbon atoms.
- Linear or branched alkylenediamine bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 4,4,1-diamino-3,3'-dimethyldicyclo Xylmethane, especially alicyclic diamines such as bis (4-aminocyclohexyl) methane, 1,3-bis (aminocyclohexyl) methane, 1,3-bis (aminomethyl) cyclohexane, and m-xylylenediamine And araliphatic diamines such as p- or x-xylylenediamine.
- aminocarboxylic acid component examples include aliphatic aminocarboxylic acids such as ⁇ , ⁇ -aminocaproic acid, ⁇ -aminooctanoic acid, ⁇ -aminoundecanoic acid, ⁇ -aminododecanoic acid, and, for example, para-aminomethylbenzoic acid, paraaminophenyl.
- aliphatic aminocarboxylic acids such as ⁇ , ⁇ -aminocaproic acid, ⁇ -aminooctanoic acid, ⁇ -aminoundecanoic acid, ⁇ -aminododecanoic acid, and, for example, para-aminomethylbenzoic acid, paraaminophenyl.
- araliphatic aminocarboxylic acids such as acetic acid.
- xylylene group-containing polyamides are preferred, and specifically, polymethaxylylene adipamide, polymethaxylylene sebacamide, polymetaxylylene veramide, polyparaxylamide Lempimerami Homopolymers such as polymethylxylylene azeramide, and metaxylylene novaxylylene adipamide copolymers, metaxylylene Z-paraxylylene pimelamide copolymers, and metaxylylene novaxylylene sebacamide Copolymer, meta-xylylene
- Copolymers such as Z-paraxylylene zeramide copolymer, or components of these homopolymers or copolymers and aliphatic diamines such as hexamethylene diamine and alicyclic diamines such as piperazine
- Aromatic diamines such as parabis (2-aminoethyl) benzene, aromatic dicarboxylic acids such as terephthalic acid, lactams such as ⁇ -caprolactam, ⁇ -aminocarboxylic acids such as 7-aminoheptanoic acid, and paraffinic methylbenzoic acid Copolymers obtained by copolymerizing an aromatic amino carboxylic acid and the like may be mentioned.
- Examples thereof include a diamine component having m-xylylenediamine and / or p-xylylenediamine as a main component, and an aliphatic dicarboxylic acid and / or an aromatic dicarboxylic acid.
- the polyamide obtained from the above can be particularly preferably used.
- xylylene group-containing polyamides have excellent oxygen barrier properties as compared with other polyamide resins, and are preferred for the purpose of the present invention.
- polyamides should also have a molecular weight sufficient to form a film, for example, having a relative viscosity of at least 1.1 measured at 30 ° C in concentrated sulfuric acid (concentration 1.0 g / dL), especially It is desirable that it be 1.5 or more.
- the Jiamin component terminal amino group concentration is mainly of 4 0 eq / 1 0 6 g or more xylylenediamine and dicarboxylic acid component by polycondensation reaction to give Polyamide resin is preferred because it does not undergo oxidative degradation during oxygen absorption.
- the oxidizable organic component examples include an ethylenically unsaturated group-containing polymer. This polymer has a carbon-carbon double bond, and the methylene adjacent to the double bond and especially the double bond is easily oxidized by oxygen, thereby trapping oxygen.
- Such an ethylenically unsaturated group-containing polymer is derived, for example, using polyene as a monomer.
- polyene include, but are not limited to, conjugated gens such as butadiene and isoprene; 1,4-hexadiene, 3-methyl- 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene Chain non-conjugated gens: methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-1-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-1-norpolenene, 6-chloromethyl-1-isopro Cyclic non-conjugated gens such as dinyl-1-norbornene and dicyclopentad
- a homopolymer of the above polyene, or a random copolymer or a block copolymer obtained by combining two or more of the above polyenes or combining with other monomers can be used as the oxidizable polymer.
- monomers to be copolymerized with the polyene include monoolefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 4-methyl-11-pentene, 1-hexene, 1-hexene, —Heptene, 1—Octene, 1—Nonene, 1—Decene, 1-Pendene, 1—Dodecene, 1 —Tridecene, 1-Tetradecene, 1—Pentadecene, 1—Hexadecene, 1—Heptadecene, 1—Nonadecene, 1—1 Examples include eicosene, 9-methyl-1-decene, 11-methyl-11-dodecene, and 12-ethyl-1-tetradecene.
- styrene vinyltriene, acrylonitrile, methacrylonitrile, and the like.
- Ril vinyl acetate, methyl methacrylate, ethyl acrylate, and the like can also be used.
- polystyrene-butadiene rubber examples include polystyrene (PS), polystyrene (IR), natural rubber, nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), Chloroprene rubber, ethylene-propylene-gen rubber (EPDM) and the like are suitable, but are not limited thereto.
- BR polybutadiene
- IR polyisoprene
- natural rubber nitrile-butadiene rubber
- NBR nitrile-butadiene rubber
- SBR styrene-butadiene rubber
- EPDM ethylene-propylene-gen rubber
- a polymer which is easily oxidized itself for example, a polypropylene, an ethylene-propylene copolymer, or the like can be used as the oxidizing organic component.
- the viscosity at 40 ° C. of the above-mentioned oxidizable polymer or its copolymer is in the range of 1 to 200 Pas. .
- These polyene-based polymers are preferably acid-modified polyene polymers into which carboxylic acid groups, carboxylic acid anhydride groups, and hydroxyl groups have been introduced. Examples of monomers used for introducing these functional groups include ethylenically unsaturated monomers having a functional group.
- an unsaturated carboxylic acid or a derivative thereof is desirably used as the ethylenically unsaturated monomer having the functional group.
- acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citracone Acid, tetrahydrophthalic acid, etc. unsaturated monocarboxylic acid, unsaturated carboxylic acid such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid, maleic anhydride, anhydride A, —Unsaturated carboxylic acid anhydrides such as itaconic acid, anhydrous citraconic acid, and tetrahydrophthalic anhydride; bicyclo [2,2,1] hept-1-ene-5,6-dicarboxylic anhydride And anhydrides of unsaturated carboxylic acids.
- the acid modification of the polyene polymer is carried out by using a resin having a carbon-carbon double bond as a base polymer and graft copolymerizing an unsaturated carboxylic acid or a derivative thereof with the base polymer by a known method.
- a resin having a carbon-carbon double bond as a base polymer
- graft copolymerizing an unsaturated carboxylic acid or a derivative thereof with the base polymer by a known method.
- it can also be produced by random copolymerization of the aforementioned polyene with an unsaturated carboxylic acid or a derivative thereof.
- the acid-modified polyene polymer particularly suitable for the purpose of the present invention preferably contains an unsaturated carboxylic acid or a derivative thereof in an amount of 0.01 to 10 mol%.
- the acid-modified polyene polymer can be well dispersed in the polyamide resin, and the oxygen can be absorbed smoothly.
- a hydroxyl group-modified polyene polymer having a hydroxyl group at a terminal can also be used favorably.
- oxidizing organic component it is also possible terminal amino group concentration to use poly meta xylylene azide Pami de less than 4 0 eq Z 1 0 6 g .
- the viscosity at 40 ° C. of the above-mentioned oxidizable polymer and its copolymer is in the range of 1 to 200 Pas. is there.
- the oxidizing organic component comprising the oxidizing polymer or the copolymer thereof is contained in the oxygen-absorbing functional component (component B) at a rate of 0.01 to 10% by weight, and particularly preferably 1 to 10% by weight. It is preferable to mix them in a proportion of 8% by weight.
- metals belonging to Group VIII of the periodic table such as iron, cobalt and nickel are suitable, but other metals belonging to Group I such as copper and silver and Group IV metals such as tin, titanium and zirconium are also suitable. It may be a metal, a Group V metal such as vanadium, a Group VI metal such as chromium, a Group VII metal such as manganese, or the like. Among them, cobalt particularly promotes oxygen absorption (oxidation of oxidizing organic components) remarkably, and is particularly suitable for the purpose of the present invention.
- the transition metal catalyst is generally used in the form of a low-valent inorganic, organic or complex salt of the transition metal.
- the inorganic salts include halides such as chlorides, potassium oxysalts such as sulfates, nitrogen oxysalts such as nitrates, phosphates such as phosphates, and silicates.
- Examples of the organic salt include carboxylate, sulfonate, phosphonate and the like, and carboxylate is suitable for the purpose of the present invention.
- Specific examples include acetic acid, propionic acid, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3 , 5,5-Trimethylhexanoic acid, decanoic acid, neodecanoic acid, pendecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachic acid, lindelic acid, odzic acid, petroselinic acid, oleic acid , Linoleic acid, linolenic acid, arachidonic acid, formic acid,
- Transition metal salts such as minic acid and naphthenic acid can be mentioned.
- Examples of the complex of a transition metal include a complex with: 8-diketone or -keto acid ester.
- diketones and; 8-keto acid esters include, for example, acetylacetone, ethyl acetate, 1,3-cyclohexadione, methylenebis-1,3-cyclohexadione, 2-benzyl-1,1,3-cyclohexadione Acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexyl Sanone, 2-acetyl-1,3-cyclohexadione, benzoyl p-chlorobenzoylmethane, bis (4-methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diace
- the transition metal catalyst has a concentration of 100 to 300 ppm in the oxygen-absorbing functional component (component B) as a transition metal atom concentration (based on weight concentration; the same applies hereinafter). In the range of 1000 to 2000 ppm for cobalt, 150 to 1500 ppm for iron, and 200 to 2000 ppm for manganese. Is preferred.
- the oxygen absorbing functional component (component B) comprising the oxidizing organic component and the transition metal catalyst of the present invention forms an island portion in the oxygen absorbing layer.
- the content of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer is preferably 10 to 60% by weight, more preferably 20 to 60% by weight when the packaging container has a multilayer structure. It is. When the packaging container has a single-layer structure, the content is preferably 0.5 to 3% by weight, more preferably 1 to 3% by weight.
- both the oxygen-absorbing function and the gas-barrier function can be effectively exerted from the initial stage of filling the contents into the packaging container.
- the type and blending ratio of the transition metal catalyst to be used are the same as those in the above (i).
- both blended products can be easily prepared.
- the transition metal catalyst is in a smaller amount than the gas barrier resin and the oxidizing organic component, the transition metal catalyst is generally dissolved in an organic solvent, and the solution is mixed with the powder or granules to homogenize the blend.
- the gas barrier resin and the oxidizing organic component are mixed, and if necessary, the mixture is dried under an inert atmosphere.
- Solvents for dissolving the transition metal catalyst include alcohol solvents such as methanol, ethanol and butanol, dimethyl ether, dimethyl ether, methyl ethyl ether, ether solvents such as tetrahydrofuran and dioxane, methyl ethyl ketone and cyclohexanone. And a hydrocarbon solvent such as n-hexane, cyclohexane and the like, and it is generally preferable to use a concentration such that the concentration of the transition metal catalyst becomes 5 to 90% by weight.
- an oxygen-absorbing functional component comprising an oxidizing organic component and a transition metal catalyst (component
- the mixing of B) and the subsequent storage should be performed in a non-oxidizing atmosphere to prevent oxidation in the previous stage.
- mixing or drying under reduced pressure or in a nitrogen stream is preferred.
- This mixing and drying can be performed at a stage prior to the molding step using an extruder or an injection machine equipped with a vent type or a dryer.
- a masterbatch of a gas barrier resin and / or an oxidizing organic component containing a relatively high concentration of a transition metal catalyst was prepared, and this masterbatch was not blended. Dry blending with the gas barrier resin of the present invention, the oxygen absorbing functional component of the present invention (component
- the oxygen-absorbing functional component (component B) of the present invention is not generally required, but may be incorporated with an activator known per se, if desired.
- Suitable examples of the activator include, but are not limited to, polyethylene glycol, polypropylene glycol, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, and hydroxyl- and carboxyl-containing polymers such as various ionomers. It is.
- hydroxyl and / or carboxyl group-containing polymers can be blended in an amount of 30 parts by weight or less, particularly 0.01 to 10 parts by weight, based on 100 parts by weight of the gas barrier resin.
- the oxygen absorbing functional component (component B) used in the present invention includes a filler, a coloring agent, a heat stabilizer, a weather stabilizer, an antioxidant, an antioxidant, a light stabilizer, an ultraviolet absorber, an antistatic agent.
- a known resin compounding agent such as an agent, a lubricant such as metal soap or wax, a modifying resin or rubber, or the like can be blended according to a formulation known per se.
- Lubricants include metal oxides such as magnesium stearate and calcium stearate, fluids, hydrocarbons such as natural or synthetic paraffin, microwax, polyethylene wax, chlorinated polyethylene wax, and fatty acids such as stearic acid and lauric acid.
- Fatty acid monoamides or bisamides such as stearic acid amide, balmitic acid amide, oleic acid amide, erlic acid amide, methylene bisstear amide, ethylenebisstear amide
- ester-based compounds such as butyl stearate, hydrogenated castor oil, and ethylene glycol monostearate
- alcohol-based compounds such as cetyl alcohol and stearyl alcohol, and a mixture thereof are generally used.
- the amount of the lubricant to be added is determined based on ( ⁇ ) the gas-barrier resin, the oxygen-absorbing functional component composed of an oxidizable organic component and a transition metal catalyst (component ⁇ ), based on the gas-barrier resin, or (ii) the oxidizing agent.
- Oxygen absorbing functional component consisting of organic component and transition metal catalyst
- the method of blending the base resin component (component A) and the oxygen-absorbing functional component (component B) includes the gas-barrier resin of the oxygen-absorbing functional component (component B), the oxidizable organic component, and the transition metal catalyst (oxidizing).
- a catalyst) by dry or melt blending directly with the base resin component (component A) to form an oxygen-absorbing layer, or by combining the oxygen-absorbing functional component (component B) with the base resin component (component A) in advance.
- the base resin component (component A) The gas barrier resin, the oxidizable organic component, and the transition metal catalyst are dispersed in the sea portion, and in the latter case, the oxidizable organic component and / or the transition metal catalyst are contained in the sea portion composed of the base resin component (component A).
- the above-mentioned gas barrier resin, the oxidizing organic component, and the transition metal catalyst must be biaxial.
- the strand-shaped resin composition After degassing using an extruder, the strand-shaped resin composition is formed into a pellet, and then the strand-shaped resin composition is pelletized, and then dry-blended with a base resin component (component A) to form an extruder for an oxygen absorbing layer. It is desirable to supply the hopper with an oxygen absorbing layer.
- the packaging container of the present invention may be a packaging container comprising an oxygen-absorbing layer alone comprising a base resin component (component A) and an oxygen-absorbing functional component (component B), but is preferably an oxygen-absorbing layer. It is desirable that the container has a multilayer structure including at least one layer of at least one layer, especially for the purpose of preventing exposure to the outer surface of the container and avoiding direct contact with the contents. It is desirable to use an oxygen absorbing layer as the layer.
- Fig. 1 shows an example of the cross-sectional structure of the packaging container of the present invention, which shows an unstretched portion that has not been stretched, and includes two types of five layers: an inner layer 1a, an outer layer 1b, an intermediate layer 2, and an oxygen absorbing layer 3.
- An oxygen absorbing layer 3 is provided between the inner layer 1 a and the intermediate layer 2 and between the outer layer 1 b and the intermediate layer 2.
- thermoplastic resin of the other layer combined with the oxygen absorbing layer includes a thermoplastic polyester resin, a polycarbonate resin, a polyacrylonitrile resin, a polyolefin resin, or a polyvinyl chloride resin, and a gas-barrier resin. Is mentioned.
- thermoplastic polyester resin examples include the resins described above as those used for the base resin component (A).
- Polyolefin resins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (L LDPE), and linear ultra-low-density polyethylene (Polethylene (PE) such as LV LD PE), polypropylene (PP), ethylene-propylene copolymer, polybutene-1, ethylene-butene-11 copolymer, propylene-butene-11 copolymer, ethylene-propylene Examples include a butene-11 copolymer, an ethylene-vinyl acetate copolymer, an ion-crosslinked olefin copolymer (Ionoma-1), and a blend thereof.
- LDPE low-density polyethylene
- MDPE medium-density polyethylene
- HDPE high-density polyethylene
- L LDPE linear low-density polyethylene
- Polyethylene (PE) such as LV LD PE
- Echirenbi alkenyl alcohol copolymer for example, ethylene-containing organic weight 20 to 60 mole 0/0, especially 25 to 50 mole 0
- EVOH Echirenbi alkenyl alcohol copolymer
- the saponified ethylene-vinyl alcohol copolymer should have a molecular weight sufficient to form a film, and generally has a concentration of 30% by weight in a 85:15 mixed solvent of phenol: water by weight.
- a cyclic olefin copolymer (COC) in particular, a copolymer of ethylene and a cyclic olefin can also be used.
- the polycarbonate resin, polyacrylonitrile resin, or polyvinyl chloride resin is not particularly limited, and those commercially available for films and sheets can be widely used.
- an adhesive resin may be interposed between the resin layers as necessary.
- an adhesive resin include a carboxylic acid, a carboxylic acid anhydride, a carboxylic acid salt, a carboxylic acid amide, and a carboxylic acid ester based carbonyl (1-CO—) group in a main chain or a side chain;
- a thermoplastic resin contained in a concentration of 100 meq Z 100 g resin, particularly 10 to 500 meq / 100 g resin can be used.
- Suitable examples of the adhesive resin include ethylene-monoacrylate copolymer, ion-crosslinked olefin copolymer, maleic anhydride graft polyethylene, maleic anhydride graft polypropylene, acrylic acid graft polyolefin, and ethylene-vinyl acetate copolymer.
- One or a combination of two or more such as coalescing, copolymerized polyester, copolymerized polyamide and the like.
- These resins are useful for co-extrusion or lamination by sandwich lamination, etc.
- an isocyanate-based or epoxy-based resin is used for adhesion lamination of a preformed gas barrier resin film and a moisture-resistant resin film.
- Thermosetting adhesive resin is also used.
- the thickness of the oxygen-absorbing layer is not particularly limited, but in the case of a packaging container composed of a single layer of the oxygen-absorbing layer, it is generally 10 to 1 OOO jt m, and particularly preferably 100 to 500. It is preferably in the range of im, also when used as a multilayered container is generally 1 to 3 0 0 ⁇ M, especially c that is preferably in the range of 3 to 5 0 ⁇ m, the thickness of the oxygen absorbing layer If it is thinner than a certain range, barrier properties or oxygen absorption performance is poor, and if it is thicker than a certain range, there is no particular advantage in terms of oxygen absorption, and economical points such as an increase in resin amount. This is because it is disadvantageous in terms of container characteristics such as reduced flexibility and flexibility of the material.
- a T-die, a Seki Yura-dai Primary molding of films, sheets, etc. is performed through a ring die
- secondary molding is performed to form packaging containers in the form of bottles, cups, trays, tube containers, and the like.
- containers and preforms for manufacturing containers are manufactured by injecting molten resin into an injection mold. Furthermore, when the compression molding method is adopted, a certain amount of molten resin is extruded by an extruder, and this is subjected to compression molding with a mold to produce containers and preforms for producing containers.
- the packaging container of the present invention is useful as a container capable of preventing a decrease in flavor of contents caused by oxygen.
- Contents that can be filled include tea, coffee, beer, wine, fruit drinks, carbonated soft drinks, etc. for beverages, fruits, nuts, vegetables, meat products, infant food, coffee, jam, mayonnaise, ketchup, cooking oil for foods , Dressings, sauces, boiled tsukudani, dairy products, etc., and pharmaceuticals, cosmetics, gasoline, etc., and other contents that deteriorate in the presence of oxygen, but are not limited to these examples.
- the evaluation method in the present example is as follows.
- oxygen-free water was produced using an oxygen-free water production device (LOW DISSOLVED OXYGEN: manufactured by Miura Kogyo Co., Ltd.). Fully filled with oxygen-free water and sealed with an aluminum cap. Oxygen indicater: orb i sphere The dissolved oxygen concentration in the multi-layer bottle when stored in a constant temperature and humidity room at 22 ° C and 60% for 14 days.
- an oxygen-free water production device LOW DISSOLVED OXYGEN: manufactured by Miura Kogyo Co., Ltd.
- r ⁇ r, ⁇ / n... (1)
- n the number of islands
- N 3 XYZ / (r d x 1 0 "... (2)
- X is the container weight (g)
- Y is the proportion of the oxygen-absorbing layer in the bottle (% by weight)
- Z is the proportion of the oxygen-absorbing functional component B in the oxygen-absorbing layer (% by weight)
- d is the component B Specific gravity (gZcm 3 )
- T one 600: Toyobo Co., Ltd.] used as the substrate 5% by weight of liquid maleic anhydride-modified polybutadiene [M-2000-20: Nippon Petrochemical Co., Ltd.] as the oxidizing organic component, and cobalt neodecanoate as the transition metal catalyst [DI CNAT E 5000: Dainippon Ink and Chemicals, Ltd.]
- Manufactured by Kogyo Co., Ltd.] was kneaded with an oxygen-absorbing functional resin composition containing 350 ppm in terms of metal to prepare an oxygen-absorbing functional resin composition pellet.
- a dry blend consisting of (Component A) and the oxygen-absorbing functional component (Component B) in a composition ratio of 50:50 is supplied, and the inner and outer layers and the intermediate layer are PET layers, and the oxygen-absorbing intermediate layer is between them.
- (Oxygen absorbing layer) A multilayer preform of two types and five layers (aZcZbZcZa) was sequentially injection-molded.
- the preform weighed 26.5 g, of which the proportion occupied by the oxygen-absorbing intermediate layer was 3% by weight.
- the obtained preform is biaxially stretch blow-molded to create a two-layer, five-layered multi-layer bottle with an inner volume of 327 ml, filled with oxygen-free water, stored at 22 ° C and 60% for 14 days, and then placed in a container. Of dissolved oxygen in water was measured.
- the cross section of the multilayer pottle preform was observed with an electron microscope, and the average particle diameter and the ratio (NZM) of the total surface area of the islands to the content of the multilayer container were determined.
- Example 1 was repeated except that polyethylene terephthalate (NES 2040: manufactured by Unitika Ltd.) having a lower melt viscosity than that of Example 1 was used as the base resin component (Component A) in the injection machine (c).
- polyethylene terephthalate NES 2040: manufactured by Unitika Ltd.
- Component A base resin component
- two-layer, five-layer multilayer bottles were prepared, the dissolved oxygen concentration in water was measured, and the phase structure was analyzed by electron microscopy.
- Example 4 Injection machine (c) was used as a gas-barrier resin of the oxygen-absorbing functional component (component B), polymethaxylylene adipamide resin having a higher melt viscosity than that of Example 1 [T-660: manufactured by Toyobo Co., Ltd.]
- Example 2 was repeated except that the above was used.
- Two-layer, five-layer bottles were prepared in the same manner as in Example 1, the dissolved oxygen concentration in water was measured, and the phase structure was analyzed by electron microscopy. (Example 4)
- Example 2 In the same manner as in Example 1 except that a dry blend comprising a base resin component (component A) and an oxygen-absorbing functional component (component B) in a composition ratio of 60:40 was supplied to the injection machine (c). A five-layer seed multi-layer bottle was prepared, the dissolved oxygen concentration in water was measured, and the phase structure was analyzed by electron microscopy.
- component A base resin component
- component B oxygen-absorbing functional component
- Example 5 A dry blend consisting of a base resin component (component A) and an oxygen-absorbing functional component (component B) having a composition ratio of 70:30 is supplied to the injection machine (c), and a pot with an internal volume of 31 Om I is supplied.
- a two-layer, five-layer multilayer bottle was prepared in the same manner as in Example 1 except that the water content was measured, the dissolved oxygen concentration in water was measured, and the phase structure was analyzed by observation with an electron microscope.
- a two-layer, five-layer multilayer bottle was prepared in the same manner as in Example 5, except that the two-layer, five-layer multilayer preform was successively injection-molded, and the proportion occupied by the oxygen-absorbing intermediate layer was 8% by weight. The dissolved oxygen concentration was measured and the phase structure was analyzed by electron microscopy.
- a two-layer, five-layer multilayer bottle was prepared in the same manner as in Example 7 except that the two-layer, five-layer multilayer preform was successively injection-molded and the ratio of the oxygen absorbing layer was 8% by weight. Measurement and phase structure analysis by electron microscope observation were performed.
- the moisture-proof packaging opened after the terminal amino group concentration of 24 e 1 0 6 g and a poly-m-xylylene azide Pami de resin Perez preparative [60 07: manufactured by Mitsubishi Gas Chemical Co.]
- Neodecanoic acid cobalt [DI CANAT E 500 00: manufactured by Dainippon Ink and Chemicals, Inc.] was applied at 400 ppm in terms of cobalt, melt-kneaded with a twin-screw extruder, and oxygen-absorbing functional resin composition pellets were added.
- a two-layer, five-layer bottle was prepared in the same manner as in Example 6 except that the oxygen-absorbing functional component (component B) of the oxygen-absorbing layer was changed to 10% by weight. Measurements and phase structure analysis by electron microscope observation were performed.
- a dry blend comprising a base resin component (component A) and an oxygen-absorbing component (component B) in a composition ratio of 98: 2 is supplied to the injection machines (a), (b) and (c).
- the oxygen concentration in water was measured and the phase structure was analyzed by electron microscopy in the same manner as in Example 5, except that a single-layer bottle was prepared by injection molding the ohm.
- polyethylene terephthalate (N ES 2040: manufactured by Unitika Ltd.] having a lower melt viscosity than that of Example 1 was used, and the oxygen absorbing functional component (component B) was used.
- a polymetaxylylene adipamide resin [T-660: manufactured by Toyobo Co., Ltd.] having a higher melt viscosity than that of Example 1 was used as the gas barrier resin of Example 5.
- a multilayer bottle was prepared, the dissolved oxygen concentration in water was measured, and the phase structure was analyzed by electron microscopy.
- a polyethylene terephthalate (TR455OBH: manufactured by Teijin Limited) having a lower melt viscosity than that of Example 1 was used as the base resin component (component A) in the injection machine (c).
- a two-layer, five-layer bottle was prepared in the same manner as in Example 9 except that the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer was changed to 5% by weight, and the dissolved oxygen concentration in water was measured. Structural analysis was performed.
- Substrate resin Acidity absorbing functional component
- Component B component Nonoshima Multi-layer container 22 ° C 14
- PET MXD6MA- Pbd / Co 3 50 1. 59 11591 327 35. 4 377.
- MA-Pbd Liquid maleic anhydride-modified polyptadiene
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- Chemical & Material Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Food Science & Technology (AREA)
- Packages (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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AU2004265166A AU2004265166B2 (en) | 2003-08-14 | 2004-07-06 | Packaging container |
KR1020067002972A KR101136676B1 (ko) | 2003-08-14 | 2004-07-06 | 포장 용기 |
CA002535183A CA2535183C (en) | 2003-08-14 | 2004-07-06 | Packing container |
US10/567,360 US20070087145A1 (en) | 2003-08-14 | 2004-07-06 | Packing container |
EP04747365.7A EP1655238B1 (en) | 2003-08-14 | 2004-07-06 | Packaging container |
Applications Claiming Priority (6)
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JP2003-207590 | 2003-08-14 | ||
JP2003207590A JP3685187B2 (ja) | 2003-08-14 | 2003-08-14 | プラスチック包装体 |
JP2003-325486 | 2003-09-18 | ||
JP2003325486 | 2003-09-18 | ||
JP2004-125041 | 2004-04-21 | ||
JP2004125041A JP3903997B2 (ja) | 2003-09-18 | 2004-04-21 | 包装容器 |
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WO2005016782A1 true WO2005016782A1 (ja) | 2005-02-24 |
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PCT/JP2004/009897 WO2005016782A1 (ja) | 2003-08-14 | 2004-07-06 | 包装容器 |
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US (1) | US20070087145A1 (ja) |
EP (1) | EP1655238B1 (ja) |
KR (1) | KR101136676B1 (ja) |
AU (1) | AU2004265166B2 (ja) |
CA (1) | CA2535183C (ja) |
TW (1) | TWI377131B (ja) |
WO (1) | WO2005016782A1 (ja) |
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BRPI0518849A2 (pt) | 2004-12-06 | 2008-12-09 | Eastman Chem Co | concentrado sàlido, processos para a produÇço de uma prÉ-forma, e para a secagem de partÍculas, e, concentrado de polÍmero de poliÉster |
US7375154B2 (en) | 2004-12-06 | 2008-05-20 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
MX2007009868A (es) | 2005-02-15 | 2007-11-06 | Constar Int Inc | "composiciones depuradoras de ox??geno y envase que comprende dichas composiciones". |
JP4968329B2 (ja) * | 2007-03-28 | 2012-07-04 | 東洋製罐株式会社 | 二軸延伸ブロー成形容器及びその製造方法 |
WO2010119938A1 (ja) * | 2009-04-17 | 2010-10-21 | 東洋製罐株式会社 | 包装体 |
US20110045222A1 (en) * | 2009-08-19 | 2011-02-24 | Eastman Chemical Company | Oxygen-scavenging polymer blends suitable for use in packaging |
EP2402396B1 (en) * | 2010-06-30 | 2015-02-25 | Clariant Masterbatches (Italia) S.p.A. | Oxygen scavenging plastic material |
FR2987985B1 (fr) * | 2012-03-15 | 2014-06-06 | Albea Services | Tube flexible avec bouchon applicateur |
AU2013256532B2 (en) | 2012-04-30 | 2016-11-03 | Plastipak Packaging Inc. | Oxygen scavenging compositions |
US9710894B2 (en) * | 2013-06-04 | 2017-07-18 | Nvidia Corporation | System and method for enhanced multi-sample anti-aliasing |
KR102386406B1 (ko) * | 2014-08-22 | 2022-04-14 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 다층 플라스틱 용기 |
US11338983B2 (en) | 2014-08-22 | 2022-05-24 | Plastipak Packaging, Inc. | Oxygen scavenging compositions, articles containing same, and methods of their use |
US10351692B2 (en) | 2014-10-17 | 2019-07-16 | Plastipak Packaging, Inc. | Oxygen scavengers, compositions comprising the scavengers, and articles made from the compositions |
EP3221366B1 (en) | 2014-11-18 | 2023-06-07 | Plastipak Packaging, Inc. | Polyaminomethylbenzyloxalamides and compositions and methods related thereto |
WO2017156384A1 (en) * | 2016-03-11 | 2017-09-14 | Ring Container Technologies | Method of manufacture of a container |
KR102307435B1 (ko) * | 2021-02-15 | 2021-09-30 | 삼화화학공업주식회사 | 변형방지 특성을 가지는 산소흡수수지 조성물 |
CN114806165B (zh) * | 2022-05-30 | 2023-06-23 | 南京京锦元科技实业有限公司 | 一种食品包装用吸氧母粒及其制备装置和方法 |
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- 2004-07-06 CA CA002535183A patent/CA2535183C/en not_active Expired - Fee Related
- 2004-07-06 EP EP04747365.7A patent/EP1655238B1/en not_active Expired - Lifetime
- 2004-07-06 WO PCT/JP2004/009897 patent/WO2005016782A1/ja active Application Filing
- 2004-07-06 AU AU2004265166A patent/AU2004265166B2/en not_active Ceased
- 2004-07-06 KR KR1020067002972A patent/KR101136676B1/ko active IP Right Grant
- 2004-07-06 US US10/567,360 patent/US20070087145A1/en not_active Abandoned
- 2004-08-11 TW TW093124006A patent/TWI377131B/zh not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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EP1655238A1 (en) | 2006-05-10 |
US20070087145A1 (en) | 2007-04-19 |
CA2535183C (en) | 2008-12-16 |
TW200510174A (en) | 2005-03-16 |
EP1655238A4 (en) | 2010-11-03 |
EP1655238B1 (en) | 2013-12-11 |
KR20060065679A (ko) | 2006-06-14 |
AU2004265166B2 (en) | 2009-12-17 |
AU2004265166A1 (en) | 2005-02-24 |
KR101136676B1 (ko) | 2012-04-18 |
CA2535183A1 (en) | 2005-02-24 |
TWI377131B (en) | 2012-11-21 |
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