JP2006111795A - Composition having oxygen-absorbing power, laminated material containing layer of the composition and packaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new composition having oxygen absorbing power, a laminated material containing a layer of the composition and a packaging material produced by using the laminated material, especially an oxygen-absorbing packaging material having excellent safety and transparency, having high oxygen-absorbing power to quickly eliminate oxygen in a packaged material and keeping the film properties of the packaging material. <P>SOLUTION: The composition having oxygen-absorbing power contains (A) a thermoplastic resin having carbon-carbon double bond, (B) a thermoplastic resin other than the resin A, (C) an unsaturated fatty acid or a glycerol unsaturated fatty acid ester carotenoid, and (D) tocopherol. The invention further provides a laminated material and a packaging material containing a layer of the composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composition having a novel oxygen-absorbing ability, a laminate comprising the composition layer, and a package, and the package has a high oxygen-absorbing capacity and quickly removes oxygen from the package, and further packaging. It is used in a wide field as a package having an oxygen-absorbing ability with excellent transparency without deteriorating physical film properties.

In the field of packaging business for packaging various contents, “package” or “packaging” includes the following three elements.
(1) “Display effects” such as giving consumers purchase awareness and presenting dangers.
(2) “Content resistance” so that the package itself is not affected by the filled content itself.
(3) “Protection of contents” against external stimuli.

  Of these, the protection of the contents from oxygen is particularly attracting attention in terms of “protecting the contents”. In particular, in recent years, importance has been placed on the protection of contents against oxygen in the fields of food, industrial products, medicine and pharmaceuticals. In most cases, oxygen is dissolved in the contents of the package filled with the contents of the container and sealed, and the headspace gas is present in the upper part of the container. Recently, since oxygen remaining in the headspace also deteriorates the contents, attempts have been made to remove oxygen in the headspace by replacing the inert gas. The situation remains.

Patent documents are described below.
Japanese Patent No. 2991437 Japanese Patent No. 3064420 Japanese Patent No. 3390555.

Thus, in order to remove a small amount of oxygen inside the package, development of an oxygen absorbing resin has been performed. Examples of these typical types include the following (1) and (2). As a general method for using tocopherol, the method (3) can be mentioned.
(1) Type using oxidation of thermoplastic resin with transition metal (Patent Document 1)
(2) Type using oxidative decomposition or oxygen addition reaction of thermoplastic resin having carbon-carbon double bond (Patent Document 2)
(3) A type in which tocopherol is used as a hindered phenol antioxidant (Patent Document 3).

  However, the type (1) uses a polymer oxidation mechanism utilizing auto-oxidation with a transition metal, but there are problems such as low oxygen absorption capacity or slow start-up speed.

The type using the oxidation or oxygen addition reaction of the thermoplastic resin having a carbon-carbon double bond of (2) is superior in oxygen absorption capacity to the type of (1), but is easily oxidizable. The capacity rise speed is insufficient for the material. Therefore, in order to improve the rising speed, a photosensitizer such as benzophenone is added to improve the speed by ultraviolet irradiation, but there is a problem in the safety of the photosensitizer.

  Further, for both types (1) and (2), an oxidation reaction of a resin using an oxidation catalyst made of a transition metal is used. However, oxidation catalysts such as cobalt, which have the most accelerating effect, are problematic in terms of safety.

  For the type (3), tocopherol is used for the effect opposite to that of the present invention, which is used in place of the hindered phenol antioxidant.

  The present invention has been made in consideration of the above technical background, and provides a composition having a novel oxygen-absorbing ability, a laminate comprising the composition layer, and a package using the laminate. For the purpose. In particular, the present invention provides a package having a high oxygen-absorbing capacity, quickly removing oxygen in the package, and further having an oxygen-absorbing capacity that is excellent in safety and transparency without deteriorating the film physical properties of the package. is there.

To achieve the above objectives, ie
The invention according to claim 1 includes a thermoplastic resin (A) having a carbon-carbon double bond, a thermoplastic resin (B) other than the thermoplastic resin (A), an unsaturated fatty acid or an unsaturated fatty acid ester of glycerol, and a carotenoid. It is a composition having oxygen-absorbing ability characterized by containing (C) and tocopherol (D).

  The invention according to claim 2 is characterized in that the tocopherol (D) is blended in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin (B). It is a composition which has this.

  According to a third aspect of the present invention, the thermoplastic resin (A) having a carbon-carbon double bond is a butadiene rubber, isoprene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, dicyclopentadiene. The composition having oxygen-absorbing ability according to claim 1, wherein the composition is an alicyclic unsaturated hydrocarbon such as norbornene or cyclohexene, or a derivative thereof alone or a mixture of one or more thereof.

  The invention according to claim 4 is characterized in that the thermoplastic resin (B) is polyethylene, an ethylene-α-olefin copolymer, an α-polyolefin comprising at least one α-olefin, an ethylene-α-olefin copolymer, Typical examples include polyolefin resins such as ethylene-cyclic olefin copolymers, ethylene-α, β-unsaturated carboxylic acids or esterified products thereof, ionic cross-linked products thereof, ethylene-vinyl acetate copolymers or partially saponified products or completely saponified products thereof. The ethylene-based copolymer, or graft-modified polyolefin resin such as acid anhydride, polystyrene, polyacrylonitrile or the like alone or a mixture of one or more thereof. The composition having an oxygen absorbing ability described in 1.

  The invention according to claim 5 is characterized in that the tocopherol (D) is any tocopherol selected from α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol. The composition having oxygen absorbing ability according to any one of the above.

  An invention according to claim 6 is a laminate including at least the composition layer having oxygen absorption capacity according to any one of claims 1 to 5.

  The invention according to claim 7 has a three-layer structure in which the composition layer having oxygen absorbing ability is used as an intermediate layer, and outer layers on both sides thereof are thermoplastic resin (B) layers. It is a laminated body.

  The invention according to claim 8 is characterized in that 1 to 30 parts by weight of tocopherol is blended in the intermediate layer and / or outer layers on both sides with respect to 100 parts by weight of the thermoplastic resin (B). Or it is a laminated body of 7.

Invention, the at least either side of the stack of three-layer, 25μm / m ² /24hr/1.0×10 oxygen permeability 50 cm ³ or less of the ⁵ Pa barrier performance according to claim 9 The laminate according to any one of claims 6 to 8, wherein at least one layer selected from a thermoplastic resin layer having an organic compound and an inorganic compound vapor-deposited thermoplastic resin layer is provided.

  The invention according to claim 10 is characterized in that the thermoplastic resin layer is made of polyester, polyamide, polyacrylonitrile, polyvinyl acetate part or complete saponified product, ethylene-vinyl acetate copolymer part or complete saponified product, or polyvinylidene chloride. It consists of at least 1 or more types of thermoplastic resins selected, The laminated body of Claim 9 characterized by the above-mentioned.

  The invention according to an eleventh aspect is the laminate according to the ninth aspect, wherein the inorganic compound vapor deposition of the inorganic compound vapor deposition thermoplastic resin layer comprises silica vapor deposition or alumina vapor deposition.

  The invention which concerns on Claim 12 consists of a laminated body of any one of Claims 8-11, It is a package body characterized by the above-mentioned.

<Action>
In the composition having oxygen absorbing ability in the present invention, a tocopherol added in a specific amount has an oxidation promoting effect, generates free radicals upon receiving energy such as heat or light, and the generated free radicals include oleic acid and the like Attacks unsaturated fatty acids of glycerol, unsaturated fatty acid esters of glycerol, and carotenoids to produce R. ROO · produced by adding oxygen to it has excellent oxygen absorption capacity by extracting adjacent hydrogen or hydrogen of the thermoplastic resin (A) having a carbon-carbon double bond to produce ROOH and R ·. Estimated.

  According to the present invention, it is possible to provide a composition having a novel oxygen absorbing ability, a laminate including the composition layer, and a package using the laminate. In particular, it is possible to provide a package having a high oxygen absorption capacity and capable of quickly removing oxygen in the package, and further having an oxygen absorption capacity excellent in safety and transparency without deteriorating the film physical properties of the package. it can.

  The package of the present invention is widely used in various fields such as the food field, the industrial product field, and the medical / pharmaceutical field, in which protection of contents against oxygen is regarded as important.

Hereinafter, a preferred embodiment of the present invention will be described. The composition having oxygen-absorbing ability of the present invention comprises a thermoplastic resin (A) having a carbon-carbon double bond, a thermoplastic resin (B) other than the thermoplastic resin (A), an unsaturated fatty acid or an unsaturated glycerol. It contains a fatty acid ester, carotenoid (C) and tocopherol (D).

  Examples of the thermoplastic resin (A) having a carbon-carbon double bond used in the present invention include butadiene rubber, isoprene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, dicyclopentadiene. , Alicyclic unsaturated hydrocarbons such as norbornene, cyclohexene, etc., or simple substances of these derivatives or mixtures of one or more of these.

  The thermoplastic resin (B) used in the present invention is, for example, polyethylene, ethylene-α-olefin copolymer, α-polyolefin comprising at least one α-olefin, ethylene-α-olefin copolymer, Typical examples include polyolefin resins such as ethylene-cyclic olefin copolymers, ethylene-α, β-unsaturated carboxylic acids or esterified products thereof, ionic cross-linked products thereof, ethylene-vinyl acetate copolymers or partially saponified products or completely saponified products thereof. An ethylene copolymer, a graft-modified polyolefin resin such as an acid anhydride, a simple substance such as polystyrene or polyacrylonitrile, or a mixture of one or more of these.

  Examples of the unsaturated fatty acid used in the present invention include oleic acid, linoleic acid, ricinoleic acid, unsaturated fatty acid esters of glycerol represented by various oils, carotenoids, and the like.

  Examples of the tocopherol (D) used in the present invention include α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol. As the acceleration rate, α-tocopherol is preferable. As an addition amount, it is desirable that 1 to 30% by weight is added to the thermoplastic resin. When the addition amount is less than 1% by weight, an antioxidant function is exhibited, and when it exceeds 30% by weight, the content may be transferred.

  A laminate including at least a composition layer having oxygen absorbing ability can be obtained using the composition having oxygen absorbing ability of the present invention having the above-described configuration. As an example, FIG. 2 shows a laminate 20 having a three-layer structure in which a composition layer having oxygen absorption ability is used as an intermediate layer 13 and outer layers 14 on both sides thereof are made of a thermoplastic resin (B) layer. As another example, a composition layer having oxygen absorbing ability is used as an intermediate layer 13, and an outer layer 15 on both sides thereof is a laminate having a three-layer structure composed of a thermoplastic resin (B) layer. FIG. 3 shows a laminate 30 in which 1 to 30 parts by weight of tocopherol is added to 100 parts by weight of the thermoplastic resin (B).

Furthermore, the composition layer having an oxygen absorption capacity of the as an intermediate layer, on at least either side of the three-layer structure on both sides thereof to the thermoplastic resin (B) ^{layer, 25μm / m 2 / 24hr /} 1. This is a laminated body provided with at least one layer selected from a thermoplastic resin layer having a barrier performance with an oxygen permeability of 50 cm ³ or less at 0 × 10 ⁵ Pa and an inorganic compound vapor-deposited thermoplastic resin layer.

  The thermoplastic resin of the thermoplastic resin layer constituting the above laminate may be polyester, polyamide, polyacrylonitrile, polyvinyl acetate part or complete saponified product, ethylene-vinyl acetate copolymer part or complete saponified product, Examples thereof include at least one thermoplastic resin selected from vinylidene chloride.

  Moreover, as inorganic compound vapor deposition of the inorganic compound vapor deposition thermoplastic resin layer which has transparency which comprises a laminated body, silica vapor deposition or alumina vapor deposition etc. are mentioned.

As an example of the laminated body having the above-described configuration, it is shown in FIGS. As shown in FIG. 4, the laminate 40 of the present invention has the composition layer having oxygen absorbing ability shown in FIG. 2 as the intermediate layer 13, and the outer layers 14 on both sides thereof are made of a thermoplastic resin (B) layer. This is a laminate 40 in which a barrier layer made of, for example, an alumina-deposited polyester film 11 is formed on one surface of a laminate 20 having a three-layer structure with an adhesive layer 12 interposed therebetween. Moreover, as shown in FIG. 5, the laminated body 50 of this invention mix | blends 1-30 weight part of tocopherol with the outer layer 15 of both sides shown in FIG. 3 with respect to 100 weight part of thermoplastic resins (B). For example, the laminated body 50 is formed by forming a barrier layer made of, for example, an alumina-deposited polyester film 11 on one surface of the laminated body 30 with an adhesive layer 12 interposed therebetween.

  As described above, the laminates obtained in various configurations can be directly developed into packaging bodies for various uses. These examples are not limited to the contents described above, and can be developed into various packaging forms. Moreover, it becomes possible to form the package body which absorbs oxygen by combining these packaging forms. As an example of the package of the present invention, an example of a pouch package is shown in FIG. As shown to (a), after laminating | stacking the laminated body 10 containing the composition layer which has the oxygen absorptivity which comprises a pouch in two, it is the three-way seal | sticker 1a. (B) is a XY direction cross-section schematic diagram of the pouch packaging body shown to (a). (C) is an enlarged schematic cross-sectional view showing a part (A region) of the laminate, in which an intermediate layer 13 is a composition layer having oxygen absorption ability, and outer layers 14 on both sides thereof are thermoplastic resins. The example of the laminated body 10 which formed the barrier layer which consists of the alumina vapor deposition polyester film 11 in the laminated body of the 3 layer structure which consists of (B) layer through the contact bonding layer 12 is shown.

  The package of the present invention may be exposed to oxygen by irradiating light from the barrier layer side or the sealant side. For example, a low pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp is used. However, the present invention is not limited to this.

  In addition, various additives other than the above, for example, various additives such as a flame retardant, a slip agent, an antiblocking agent, and a UV absorber may be blended in each layer as necessary in terms of a package.

  As a manufacturing method of the packaging body having these oxygen absorbing ability, various predetermined blending amounts of materials set according to the final product forming method and the required oxygen absorbing ability are used using a ribbon mixer, a tumbler mixer, a Henschel mixer, etc. Dry blended or blended in a predetermined amount using each feeder pre-installed in a kneader, using a kneader such as a single screw extruder, twin screw extruder, or a Banbury mixer The base thermoplastic resin is kneaded at a melting point of not lower than 260 ° C., preferably not higher than 240 ° C., more preferably not higher than 220 ° C.

  Various methods can be used to laminate the barrier layer and the oxygen-absorbing layer. The most typical example is a method of laminating by a dry lamination method using a urethane-based adhesive. Using a urethane adhesive on the barrier substrate, the laminate containing the oxygen-absorbing resin formed in-line is laminated in the barrier layer in-line by the extrusion lamination method or neram method, or the sand lamination method. A method of sandwiching a laminate containing an oxygen-absorbing resin on a provided urethane-based adhesive with a polyolefin-based resin formed by extrusion lamination and the like. There is a method of laminating cast or blown films.

The packaging body having oxygen absorbing ability of the present invention is a single film or laminated body having oxygen absorbing ability using various molding methods such as extrusion lamination molding, extrusion casting, inflation molding, injection molding, direct blow molding and the like. Is possible. In addition, it is possible to obtain a laminate by dry lamination, wet lamination, or non-solvent lamination for the film (inflation etc.) obtained by the molding method described above, and stretch the preform obtained by injection molding. Although it is possible to form a multilayer stretch blow bottle by blow molding, it is not limited to these molding methods.

  Hereinafter, specific examples of the present invention will be described. The present invention is not limited to these examples.

First, a material used for a composition having oxygen absorbing ability, a blending ratio of the materials, and a method for manufacturing a laminate including a composition layer having oxygen absorbing ability are described below.
[Materials used for composition having oxygen absorbing ability]
. Thermoplastic resin having carbon-carbon double bond (A)
C1: Styrene-butadiene copolymer C2: Polybutadiene / thermoplastic resin (B)
A1: Low density polyethylene / unsaturated fatty acid O1: oleic acid / tocopherol T1: α-tocopherol T2: β-tocopherol / antioxidant D1: Irganox 1076.

[Material constituting a support layer in a laminate including a three-layer structure in which a composition layer having oxygen absorbing ability is an intermediate layer and outer layers on both sides thereof are thermoplastic resin (B) layers (support layers)]
B1: Low density polyethylene [Method for producing a laminate including a composition layer having oxygen absorbing ability]
Using a three-kind three-layer coextrusion laminating machine, a two-kind three-layer coextruded multilayer film in which an intermediate layer was provided with a composition layer having oxygen absorption ability was formed. The layer structure is 15 μm / 40 μm / 15 μm from the outside. The material used for the intermediate layer and the outer layers (support layers) on both sides was a drive blended material. Low density polyethylene (PE) was used for the outer layer. Further, at least one of the multilayer films was subjected to corona treatment.

[Material mixing ratio of each layer constituting the laminate]
Oxygen absorbing layer A: A1-75 parts, C1-25 parts, O1-0.25 parts (relative to A1), T1-2.0 parts (relative to A1)
Support layer A: B1-100 parts Oxygen absorption layer B: A1-75 parts, C1-25 parts, O1-0.25 parts (relative to A1)
Support layer B: B1-100 parts, T1-2 parts, oxygen absorbing layer C: A1-75 parts, C1-25 parts, O1-0.25 parts (relative to A1), T2-2.0 parts (A1 Against)
Support layer C: B1-100 parts Oxygen absorption layer D: A1-75 parts, C1-25 parts, O1-0.25 parts (relative to C1), T1-5.0 parts (relative to A1)
-Support layer D: B1-100 parts-Oxygen absorption layer E: A1-75 parts, C1-25 parts, O1-0.25 parts (relative to C1), T1-2.0 parts (relative to A1)
Support layer E: B1-100 parts, D1-0.3 parts (relative to B1)
Oxygen absorbing layer F: A1-75 parts, C2-25 parts, O1-0.25 parts (relative to C1), T1-2.0 parts (relative to A1)
-Support layer F: B1-100 parts-Oxygen absorption layer G: A1-75 parts, C1-25 parts, O1-0.25 parts (relative to C1), T1-0.1 parts (relative to A1)
-Support layer G: B1-100 parts-Oxygen absorption layer H: A1-75 parts, C1-25 parts, T1-2.0 parts (relative to A1)
Support layer H: B1-100 parts Oxygen absorption layer I: A1-75 parts, C1-25 parts, O1-0.25 parts (relative to A1)
-Support layer I: B1-100 parts-Oxygen absorption layer J: A1-75 parts, C1-25 parts, O1-0.25 parts (relative to A1)
Support layer J: B1-100 parts, D1-0.3 parts (relative to B1).

<Example 1>
The laminate of the present invention having an “barrier substrate / adhesive layer / (support layer A / oxygen absorption layer A / support layer A)” structure from the outer layer is used as a dry laminate machine using an alumina-deposited polyester film as the barrier substrate. Obtained using For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The obtained sample was cut into a size of 180 × 220 mm, further folded in two, and then sealed with a heat sealer having a seal width of 10 mm to produce a 160 × 100 mm size pouch with an effective area of 32000 mm 2. 100 ml of air (O2 21% / N2 79%) was injected into the pouch, hermetically sealed, and stored at 60 ° C. The oxygen remaining amount after 1, 3, 7, 14 days in this pouch was evaluated using an oxygen concentration meter. The results are shown in Table 1. Further, the obtained sample was cut into a size of 220 × 220 mm, further folded in two, and then sealed with a heat sealer having a seal width of 10 mm to produce a 220 × 110 mm size pouch with an effective area of 40000 mm 2.

<Example 2>
Using an alumina-deposited polyester film as the barrier substrate, the laminate of the present invention having a configuration of “barrier substrate / adhesive layer / (support layer B / oxygen absorbing capacity layer B / support layer B)” from the outer layer is dry-laminated. Obtained using For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 1.

<Example 3>
An alumina-deposited polyethylene naphthalate film is used as the barrier substrate, and the laminate of the present invention having the configuration of “barrier substrate / adhesive layer / (support layer C / oxygen absorption layer C / support layer C)” is dried from the outer layer. Obtained using a laminating machine. For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 1.

<Example 4>
A laminate of the present invention having a configuration of “barrier substrate / adhesive layer / (support layer D / oxygen absorption layer D / support layer D)” from the outer layer is used as a dry laminate machine using an alumina-deposited polyester film as the barrier substrate. Obtained using For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 1.

<Example 5>
A laminate of the present invention having a configuration of “barrier substrate / adhesive layer / (support layer E / oxygen absorbing capacity layer E / support layer E)” from the outer layer is used as a dry laminate machine using an alumina-deposited polyester film as the barrier substrate. Obtained using For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 1.

<Example 6>
An alumina-deposited polyethylene naphthalate film is used as the barrier substrate, and the laminate of the present invention having the configuration of “barrier substrate / adhesive layer / (support layer F / oxygen absorption layer F / support layer F)” is dried from the outer layer. Obtained using a laminating machine. For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 1.

<Example 7>
As a comparative example for comparing the oxygen absorption capacity and performance of a pouch produced using the laminate of the present invention,
An alumina-deposited polyester film is used as the barrier substrate, and a laminate of “barrier substrate / adhesive layer / (support layer G / oxygen absorbing layer G / support layer G)” is formed from the outer layer using a dry laminator. Obtained. For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 2.

<Example 8>
As a comparative example for comparing the oxygen absorption capacity and performance of a pouch produced using the laminate of the present invention,
An alumina-deposited polyester film is used as the barrier substrate, and a laminate of “barrier substrate / adhesive layer / (support layer H / oxygen absorbing layer H / support layer H)” is formed from the outer layer using a dry laminator. Obtained. For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 2.

<Example 9>
As a comparative example for comparing the oxygen absorption capacity and performance of a pouch produced using the laminate of the present invention,
An alumina-deposited polyester film is used as the barrier substrate, and a laminate of “barrier substrate / adhesive layer / (support layer I / oxygen absorption capacity layer I / support layer I)” is formed from the outer layer using a dry laminating machine. Obtained. For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 2.

<Example 10>
As a comparative example for comparing the oxygen absorption capacity and performance of a pouch produced using the laminate of the present invention,
Using an alumina-deposited polyester film as the barrier substrate, a laminate of “barrier substrate / adhesive layer / (support layer J / oxygen absorbing capacity layer J / support layer J)” from the outer layer is dried using a dry laminator. Obtained. For the adhesive layer, a polyester polyol composed of terephthalic acid, isophthalic acid, adipic acid and 1,4-butanediol was used as the main agent, and a tolylene diisocyanate adduct of trimethylolpropane was used as the curing agent. The same evaluation as in Example 1 was performed. The results are shown in Table 2.

表１、２より、実施例１〜６で得られた本発明の包装体としてのパウチは、実施例７〜１０で得られた比較例としてのパウチの酸素吸収能に比較して、酸素吸収能が高く、かつ包装体中の酸素をすばやく除去できる。さらに、本発明の包装体としてのパウチは、包装体の膜物性を低下させることなく、安全性、透明性に優れることが確認できた。このことは、炭素−炭素二重結合を有する熱可塑性樹脂（Ａ）、熱可塑性樹脂（Ａ）以外の熱可塑性樹脂（Ｂ）、不飽和脂肪酸またはグリセロールの不飽和脂肪酸エステル、カロテノイド（Ｃ）およびトコフェロール（Ｄ）を含有する酸素吸収能を有する組成物層を含む積層体を用いた構成の包装体であることによるものである。

From Tables 1 and 2, the pouch as the packaging body of the present invention obtained in Examples 1 to 6 was compared with the oxygen absorption capacity of the pouch as a comparative example obtained in Examples 7 to 10, and oxygen absorption. High performance and can quickly remove oxygen in the package. Furthermore, it was confirmed that the pouch as the package of the present invention was excellent in safety and transparency without deteriorating the film physical properties of the package. This means that a thermoplastic resin having a carbon-carbon double bond (A), a thermoplastic resin (B) other than the thermoplastic resin (A), an unsaturated fatty acid or an unsaturated fatty acid ester of glycerol, a carotenoid (C) and It is because it is a package of the structure using the laminated body containing the composition layer which has oxygen absorption ability containing tocopherol (D).

(A) is a plane schematic diagram which shows an example of the laminated body containing the composition layer which has the oxygen absorption ability of this invention, and a pouch packaging body. (B) is a XY direction cross-section schematic diagram of the pouch packaging body shown to (a). (C) is a cross-sectional enlarged schematic view showing a part (A region) of a laminate as an example constituting the package of the present invention. It is a cross-sectional schematic diagram which shows the laminated body containing the composition layer which has an oxygen absorptivity as one Example in this invention. It is a cross-sectional schematic diagram which shows the laminated body containing the composition layer which has an oxygen absorptivity as one Example in this invention. It is a cross-sectional schematic diagram which shows the laminated body containing the composition layer which has an oxygen absorptivity as one Example in this invention. It is a cross-sectional schematic diagram which shows the laminated body containing the composition layer which has an oxygen absorptivity as one Example in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Pouch packaging body 10, 20, 30, 40, 50 ... Laminated body 11 having oxygen absorbing ability ... Barrier layer 12 ... Adhesive layer 13 ... Composition having oxygen absorbing ability Layer 14 ... thermoplastic resin (b) layer 15 ... thermoplastic resin (b) layer 1a containing tocopherol ... seal part

Claims (12)

  Thermoplastic resin having carbon-carbon double bond (A), thermoplastic resin (B) other than thermoplastic resin (A), unsaturated fatty acid or unsaturated fatty acid ester of glycerol, carotenoid (C) and tocopherol (D) The composition which has oxygen absorption ability characterized by containing.   The said tocopherol (D) is mix | blended 1-30 weight part with respect to 100 weight part of said thermoplastic resins (B), The composition which has oxygen absorption ability of Claim 1 characterized by the above-mentioned.   The thermoplastic resin (A) having a carbon-carbon double bond is an alicyclic ring such as butadiene rubber, isoprene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, dicyclopentadiene, norbornene, or cyclohexene. 3. The oxygen-absorbing composition according to claim 1, wherein the composition is a simple substance of a formula unsaturated hydrocarbon or a derivative thereof, or a mixture of one or more thereof.   The thermoplastic resin (B) is polyethylene, ethylene-α-olefin copolymer, α-polyolefin comprising at least one α-olefin, ethylene-α-olefin copolymer, ethylene-cyclic olefin copolymer, etc. Polyolefin resins, ethylene-α, β-unsaturated carboxylic acids or esterified products thereof, or ionic cross-linked products thereof, ethylene-vinyl acetate copolymers or partially saponified or completely saponified ethylene-based copolymers, Alternatively, the oxygen-absorbing ability according to any one of claims 1 to 3, which is a graft-modified polyolefin resin such as an acid anhydride, a simple substance such as polystyrene or polyacrylonitrile, or a mixture of one or more thereof. Composition.   The said tocopherol (D) is any tocopherol selected from (alpha) -tocopherol, (beta) -tocopherol, (gamma) -tocopherol, and (delta) -tocopherol, The any one of Claims 1-4 characterized by the above-mentioned. A composition having oxygen absorbing ability.   A laminate comprising at least the composition layer having oxygen absorption capacity according to any one of claims 1 to 5.   The laminate according to claim 6, comprising a three-layer structure in which the composition layer having oxygen absorbing ability is an intermediate layer, and outer layers on both sides thereof are thermoplastic resin (B) layers.   The laminated body according to claim 6 or 7, wherein 1 to 30 parts by weight of tocopherol is blended in the intermediate layer and / or outer layers on both sides with respect to 100 parts by weight of the thermoplastic resin (B). At least either side of the stack of the three-layer, thermoplastic resin layer having an oxygen permeability at 25μm / m ² /24hr/1.0×10 ⁵ Pa has a 50 cm ³ or less of barrier performance, inorganic The laminate according to any one of claims 6 to 8, wherein at least one layer selected from a compound vapor deposition thermoplastic resin layer is provided.   The thermoplastic resin layer is at least one selected from polyester, polyamide, polyacrylonitrile, polyvinyl acetate partially or fully saponified, ethylene-vinyl acetate copolymer partially or completely saponified, and polyvinylidene chloride. The laminate according to claim 9, comprising a thermoplastic resin. The laminate according to claim 9, wherein the inorganic compound deposition of the inorganic compound deposition thermoplastic resin layer comprises silica deposition or alumina deposition.   A package comprising the laminate according to any one of claims 8 to 11.

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