JP2022014240A - Oxygen-absorbing laminate for molding component to be used for blister packaging container - Google Patents

Abstract

To provide a laminate for a molding component of a blister packaging container with less odor generation, excellent in barrier properties against an oxygen gas, capable of absorbing oxygen to reduce an oxygen concentration in a content housing space and preventing a content from being deteriorated by oxygen, while excellent in a balance of heat sealability, low odor property, low oxygen concentration, aroma retention, content resistance, and filling packaging property, and also to provide a packaging material for a molding component, a molding component and a blister packaging container produced using the laminate for a molding component.SOLUTION: An oxygen-absorbing laminate for a molding component to be used for a molding component of a blister packaging container at least includes a layer constitution with a substrate layer 2, an oxygen barrier layer 3, an oxygen-absorbing adhesive layer 4 and a sealant layer 5 laminated in this order. The oxygen-absorbing adhesive layer is a layer composed of an oxygen-absorbing adhesive composition containing a specific oxygen-absorbing compound and an oxidation accelerator catalyst.SELECTED DRAWING: Figure 1

Description

INDUSTRIAL APPLICABILITY The present invention has less odor generated, has a barrier property against oxygen gas from the outside, suppresses deterioration of the contents due to oxygen by absorbing oxygen in the contents storage space, and has heat retention, content resistance, etc. For molded parts made from an oxygen-absorbing laminate for molded parts used for molded parts of blister packaging containers, which has an excellent balance with sealing properties and is suitable for filling and packaging, and an oxygen-absorbing laminate for molded parts. The present invention relates to an oxygen-absorbing packaging material, an oxygen-absorbing molded part, and an oxygen-absorbing packaging container manufactured by using the molded part. In the present invention, it is described as a blister packaging container including the PTP packaging container.

Conventionally, as a packaging method for suppressing deterioration of the quality of the contents of foods, medical care, chemical products, cosmetics, etc. due to oxygen, a packaging material having a high oxygen barrier property has been used, or an inert gas such as nitrogen gas has been used for the contents storage part. Depending on the gas, the oxygen scavenger containing reduced iron powder is included, but the performance is insufficient, the packaging cost increases, and the amount of waste as waste increases. , The problem that the performance is exhibited only in the environment with water and that it is accidentally swallowed is mentioned.
Further, in Patent Document 1, a packaging material using a resin having oxygen absorption and less generated odor has been developed, but this resin is insoluble in a polar solvent and does not have an active hydrogen group. It is a dodecene and is difficult to apply as a raw material for an adhesive to a packaging material made of a laminate.
Patent Document 2 proposes a laminating adhesive made of a resin using methyltetrahydrophthalic acid as a raw material having oxygen absorption, but has a drawback of low oxygen absorption and instability.
In Patent Document 3, oxygen absorption of a thermoplastic resin having a repeating unit consisting of a saturated five-membered ring having a substituent containing a carbon-carbon double bond and a -CH = CH- group connecting the saturated five-membered ring. Although a sex resin is described, it has drawbacks such as being difficult to use due to its poor solubility in a solvent and having a strong generated odor.

Japanese Patent No. 5873770 Japanese Patent No. 5671816 Japanese Patent No. 6555699

The problems of the present invention are that there is little generated odor, the barrier property against oxygen gas is excellent, the oxygen concentration in the content storage space is reduced, the deterioration due to oxygen of the content is suppressed, and the heat seal property is low. A laminated body for molded parts of a blister packaging container, which has an excellent balance of odor resistance, low oxygen concentration, fragrance retention, content resistance, and filling and packaging property, and a molded part manufactured by using the laminated body for molded parts. To provide packaging materials, molded parts, and blister packaging containers.

（式中、ａ～ｅは各々１以上の数であり、Ｒ^１、Ｒ^２、Ｒ^３の各々は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含み、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。）
９．前記酸素吸収性化合物が、下記式（５）で示される化合物を含有する、
上記１～５の何れかに記載の、成型部品用酸素吸収性積層体。

（式中、ｆは０以上の数であり、Ｒ^４とＲ^５の各々は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含む有機基であり、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。）
１０．前記酸化促進触媒が、過酸化物、または遷移金属からなるカチオンを含む化合物である、
上記１～９の何れかに記載の、成型部品用酸素吸収性積層体。
１１．前記の遷移金属からなるカチオンを含む化合物が、遷移金属からなるカチオンまたは錯体を放出可能な遷移金属化合物と、脂肪酸からなるアニオンまたは配位子とからなる金属石鹸である、
上記１～１０の何れかに記載の、成型部品用酸素吸収性積層体。
１２．前記酸素吸収性接着剤組成物が、変性剤をさらに含有し、
該変性剤は、イソシアネート系化合物、および／または水酸基含有化合物を含有する、上記１～１１の何れかに記載の、成型部品用酸素吸収性積層体。
１３．前記イソシアネート系化合物が、キシレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、およびこれらの誘導体からなる群から選ばれる１種または２種以
上である、
上記１２に記載の、成型部品用酸素吸収性積層体。
１４．前記水酸基含有化合物が、ポリエステルポリオール、ポリ（メタ）アクリル酸エステルポリオール、ポリアルキレンエーテルジオール、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上を含む、
上記１２または１３に記載の、成型部品用酸素吸収性積層体。
１５．上記１～１４の何れかに記載の成型部品用酸素吸収性積層体を用いて作製された、ブリスター包装容器の成型部品用酸素吸収性包装材料。
１６．上記１５に記載のブリスター包装容器の成型部品用酸素吸収性包装材料を用いて作製された、ブリスター包装容器の酸素吸収性成型部品。
１７．上記１６に記載のブリスター包装容器の酸素吸収性成型部品を用いて作製された酸素吸収性ブリスター包装容器であって、
前記酸素バリア層は、前記酸素吸収性接着剤層よりも外側に位置する層である、
酸素吸収性ブリスター包装容器。 Therefore, in order to solve the above problems, the present inventors have at least a base material layer, an oxygen barrier layer, an oxygen-absorbing adhesive layer formed from a specific oxygen-absorbing adhesive composition, and a sealant layer. It was found that a laminated body including a layer structure in which the layers are laminated in this order can solve the above-mentioned problems.
That is, the present invention is characterized by the following points.
1. 1. Oxygen absorbency for molded parts used in molded parts of blister packaging containers, including at least a layer structure in which a base material layer, an oxygen barrier layer, an oxygen absorbing adhesive layer, and a sealant layer are laminated in this order. It ’s a laminate,
The oxygen-absorbing adhesive layer is a layer formed from the oxygen-absorbing adhesive composition, and is a layer.
The oxygen-absorbing adhesive composition contains at least an oxygen-absorbing compound and an oxidation-promoting catalyst.
The oxygen-absorbing compound has one or more unsaturated five-membered rings and has one or more unsaturated five-membered rings.
Any bond between the five carbon atoms constituting the unsaturated five-membered ring is a carbon-carbon double bond.
A monovalent and / or divalent or higher electron donating organic group 1 is bonded to the unsaturated five-membered ring.
When the unsaturated five-membered ring is one, the five-membered ring or the organic group 1 is a functional group having active hydrogen, or the active hydrogen of the functional group having active hydrogen becomes a monovalent organic group 2. Has substituted groups and
When there are two or more unsaturated five-membered rings, the unsaturated five-membered rings have a divalent value or higher that replaces the active hydrogen of each of the five-membered rings or the active hydrogen group on the organic group 1. Bonded via organic group 2,
Oxygen-absorbing laminate for molded parts.
2. 2. The structure of the unsaturated five-membered ring or the structure consisting of the unsaturated five-membered ring and the organic group 1 is one or two selected from the group consisting of cyclopentadiene, dicyclopentadiene, norbornene, and derivatives thereof. It is derived from the above,
The oxygen-absorbing laminate for molded parts according to 1 above.
3. 3. The organic group 2 contains an isocyanate-based compound, or a structural portion derived from an isocyanate-based compound and a hydroxyl group-containing compound.
The oxygen-absorbing laminate for molded parts according to 1 or 2 above.
4. The isocyanate-based compound is one or more selected from the group consisting of xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and derivatives thereof.
The oxygen-absorbing laminate for molded parts according to 3 above.
5. The hydroxyl group-containing compound is selected from the group consisting of polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and urethane chain extension polyols thereof1. Seeds or more than one
The oxygen-absorbing laminate for molded parts according to 3 or 4 above.
6. The organic group 2 does not have a crosslinkable functional group.
The oxygen-absorbing laminate for molded parts according to any one of 1 to 5 above.
7. The organic group 2 has one or more crosslinkable functional groups.
The crosslinkable functional group is a hydroxyl group and / or an isocyanate group.
The oxygen-absorbing laminate for molded parts according to any one of 1 to 5 above.
8. The oxygen-absorbing compound contains one or more selected from the group consisting of the compounds represented by the following formulas (1) to (4).
The oxygen-absorbing laminate for molded parts according to any one of 1 to 5 above.

(In the formula, a to e are each a number of 1 or more, and each of R ¹ , R ² and R ³ is an organic group having 1 or more carbon atoms and contains at least an alkylene and / or a phenylene structure, and further. One or more selected from the group consisting of polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and urethane chain extension polyols thereof. It can include the structure from which it is derived.)
9. The oxygen-absorbing compound contains a compound represented by the following formula (5).
The oxygen-absorbing laminate for molded parts according to any one of 1 to 5 above.

(In the formula, f is a number of 0 or more, and each of ^R4 and R5 is an organic group having ¹ or more carbon atoms, which is an organic group containing at least an alkylene and / or a phenylene structure, and further has a polyvalent value. Derived from one or more selected from the group consisting of alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and urethane chain extension polyols thereof. Can include structure.)
10. The oxidation-promoting catalyst is a compound containing a cation consisting of a peroxide or a transition metal.
The oxygen-absorbing laminate for molded parts according to any one of 1 to 9 above.
11. The compound containing a cation composed of a transition metal is a metal soap composed of a transition metal compound capable of releasing a cation or complex composed of a transition metal and an anion or a ligand composed of a fatty acid.
The oxygen-absorbing laminate for molded parts according to any one of 1 to 10 above.
12. The oxygen-absorbing adhesive composition further contains a denaturing agent.
The oxygen-absorbing laminate for molded parts according to any one of 1 to 11 above, wherein the modifier contains an isocyanate-based compound and / or a hydroxyl group-containing compound.
13. The isocyanate-based compound is one or more selected from the group consisting of xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and derivatives thereof.
The oxygen-absorbing laminate for molded parts according to 12 above.
14. The hydroxyl group-containing compound comprises one or more selected from the group consisting of polyester polyols, poly (meth) acrylic acid ester polyols, polyalkylene ether diols, and urethane chain extension polyols thereof.
The oxygen-absorbing laminate for molded parts according to 12 or 13 above.
15. An oxygen-absorbing packaging material for molded parts of a blister packaging container, which is produced by using the oxygen-absorbing laminate for molded parts according to any one of 1 to 14 above.
16. An oxygen-absorbing molded part of a blister-packed container manufactured by using the oxygen-absorbing packaging material for a molded part of the blister-packed container according to 15 above.
17. An oxygen-absorbing blister-packed container manufactured by using the oxygen-absorbing molded parts of the blister-packed container according to 16 above.
The oxygen barrier layer is a layer located outside the oxygen-absorbing adhesive layer.
Oxygen-absorbing blister packaging container.

According to the present invention, there is little generated odor, the barrier property against oxygen gas is excellent, the oxygen concentration in the content storage space is absorbed to reduce the oxygen concentration, the deterioration of the content due to oxygen is suppressed, and the heat seal property is low. A laminated body for molded parts of a blister packaging container, which has an excellent balance of odor resistance, low oxygen concentration, fragrance retention, content resistance, and filling and packaging property, and a molded part manufactured by using the laminated body for molded parts. Packaging materials, molded parts, and blister packaging containers can be obtained.
The packaging material produced from the laminate of the present invention is particularly suitable for flexible packaging applications, shortens the packaging process, reduces costs, and reduces the weight of the packaging, and the packaging has been conventionally included. Since it is not necessary to bundle the oxygen scavenger, it is possible to eliminate the accidental ingestion of the oxygen scavenger and reduce the amount of dust composed of the oxygen scavenger.

It is sectional drawing which shows an example of the layer structure of the oxygen-absorbing laminated body for molded parts of this invention. It is sectional drawing which shows one example of another aspect of the layer structure of the oxygen-absorbing laminate for molded parts of this invention. It is sectional drawing which shows an example of the oxygen-absorbing blister package container using the oxygen-absorbing packaging material for molded parts of this invention.

The present invention described above will be described in more detail below. The description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not specified in these contents unless the gist thereof is exceeded.
In the present invention, the film and the sheet are synonymous with each other.

<Oxygen-absorbing laminate for molded parts>
The oxygen-absorbing laminate for molded parts of the present invention is a laminate used for molded parts of blister packaging containers, and at least includes a base material layer, an oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer. Includes a layered structure in which the above layers are laminated in this order.
Oxygen-absorbing packaging material for molded parts (hereinafter, also abbreviated as oxygen-absorbing packaging material) produced from the oxygen-absorbing laminate for molded parts (hereinafter, also abbreviated as oxygen-absorbing laminate). ) To produce oxygen-absorbing molded parts for blister packaging containers (hereinafter, also abbreviated as molded parts), heat-sealed with lid parts, and oxygen-absorbing blister packaging containers (hereinafter, also referred to as “molded parts”). When forming a blister packaging container or a packaging container, the sealant layer is heat-sealed, and the oxygen barrier layer is placed on the outside of the oxygen-absorbing blister packaging container rather than the oxygen-absorbing adhesive layer. To position.
By locating the oxygen barrier layer outside the oxygen-absorbing adhesive layer, oxygen passing through the molded part from the outside is reduced, and the oxygen-absorbing adhesive layer absorbs oxygen in the content storage space to oxygen. The efficiency of reducing the concentration can be increased.

The oxygen-absorbing laminate for molded parts can optionally include other layers having various functions.
For example, it can have a base material layer or a printing layer, and has various conditions such as deformation resistance, drop impact resistance, pinhole resistance, heat resistance, sealing property, quality maintainability, workability, hygiene, and the like. Can include a reinforcing layer to satisfy.
In addition, it has a functional layer for enhancing the oxygen gas barrier property, imparting a barrier property against water vapor, etc., and providing a fragrance-retaining property for the contents to be filled and packaged, and preventing the contents from causing discoloration or offensive odor. You can also.
Furthermore, a general-purpose adhesive layer for improving the interlayer adhesiveness can be included in each of the above layers or in each layer.

[Contents]
In the above, examples of the contents include pharmaceuticals, medical devices including prefield syringes, health foods such as vitamins, metal members such as ham, bacon, cheese, raw meat, screws, and the like. ..

<About each layer constituting the oxygen-absorbing laminate for molded parts>
≪Oxygen barrier layer≫
The oxygen barrier layer is an oxygen-absorbing blister package made of an oxygen-absorbing molded part and a lid part, and allows oxygen to permeate through the molded part from the outside of the oxygen-absorbing blister package to the internal content container. It is a layer to suppress.
In the oxygen-absorbing blister packaging container, the oxygen barrier layer is located outside the oxygen-absorbing adhesive layer to suppress the permeation of oxygen from the outside of the oxygen-absorbing blister packaging container, thereby suppressing the permeation of oxygen from the outside of the oxygen-absorbing blister packaging container. Can enhance the effect of absorbing oxygen in the contents accommodating portion of the oxygen-absorbing blister packaging container to lower the oxygen concentration.
Various oxygen barrier materials can be used for the oxygen barrier layer. Further, it may be an oxygen barrier material having not only oxygen but also gas barrier property against water vapor and the like, light shielding property against sunlight and the like, and fragrance retaining property against the contents. Further, a barrier material having a gas barrier property against water vapor or the like, a light shielding property against sunlight or the like, and a fragrance retaining property against the contents may be used in combination.

Specific examples of the oxygen barrier material include one or two selected from the group consisting of, for example, a metal foil, a resin film with an inorganic vapor deposition layer, and a resin coating film or a resin film made of an oxygen barrier resin. The above can be used. Examples of the inorganic compound of the inorganic vapor deposition layer include metals, metal oxides, metal nitrides, and metal carbides.
Among the above, in particular, one of a resin film with a metal vapor deposition layer, a resin film with a metal oxide vapor deposition layer, a resin coating film made of a barrier resin, or a resin film is oxygen gas, water vapor, light-shielding property, and maintenance. It is preferable because it has excellent barrier properties such as fragrance and is environmentally friendly in terms of container disposal.

Specific examples of the metal foil include aluminum foil. The thickness of the aluminum foil is preferably 6 μm to 40 μm.
Specific examples of the metal elements constituting the above-mentioned inorganic compound include, for example, aluminum (Al), silicon (Si), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), and sodium (Na). ), Boron (B), Titanium (Ti), Lead (Pb), Zirconium (Zr), Yttrium (Y), Zinc (Zn), Vanadium (V), Barium (B)
a), chromium (Cr) and the like can be mentioned.

Specific examples of the inorganic compound include the above-mentioned metals composed of metal elements, metal oxides, metal nitrides, metal carbides and the like, and in addition to these, indium tin oxide (ITO), chemical vapor phase growth method and the like are used. Examples thereof include a composite inorganic compound such as a made SiO _{X CY} film.
Specific examples of the inorganic compound of the inorganic thin-film deposition layer include silicon nitride, silicon carbide and the like. Among these, silica and alumina are preferable.

The notation of the average composition of the inorganic compound is MO _x , MO _x Cy such as SiO _x , AlO _x , SiO _{x Cy} (however, in the formula, M represents a metal element, and the values of x and _y are expressed. Has a different range depending on the metal element.). In the case of metal oxides, the range of X values is 0 to 2 for silicon, 0 to 1.5 for aluminum, 0 to 1 for magnesium, 0 to 1 for calcium, and 0 to 0 for potassium. 5, tin is 0 to 2, sodium is 0 to 0.5, boron is 0 to 1, 5, titanium is 0 to 2, lead is 0 to 1, zirconium is 0 to 2, yttrium is It can take a value in the range of 0 to 1.5.
In the above MO _X , when x = 0, it is a metal and is not transparent, and the upper limit of the range of x is the value when it is completely oxidized.
In the present invention, silicon oxide and aluminum oxide are preferably used, and silicon oxide has a value in the range of 1.0 to 2.0 for x and aluminum oxide has a value in the range of 0.5 to 1.5 for x. be able to.
The oxygen barrier layer may be formed of one of these barrier materials, may be used in combination of two or more, or may be used in combination of two or more. Further, it may be composed of one layer, may be composed of multiple layers having the same or different composition, and may not be adjacent to each other in the case of multiple layers.

As the resin film that supports the above-mentioned inorganic thin-film deposition layer, since the inorganic-deposited layer is provided on the resin film, it has excellent mechanical, physical, chemical, and other properties, and is particularly strong and tough. A resin film having heat resistance can be used.

Specifically, in the present invention, examples of the resin film supporting the inorganic vapor deposition layer include polyester resin films such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and polyamide resins such as various nylons. Polyethylene films such as films, polyethylene resins, polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), polybuden resin films, etc. Polyvinyl chloride resin, polycarbonate resin, polyimide resin, polyamideimide resin, polyarylphthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, cellulose resin , Poly (meth) acrylic resin, polyvinylidene chloride film, acetal resin film, fluororesin, etc. can be used.
In the present invention, biaxially stretched polyethylene terephthalate, polyacrylonitrile, ethylene-vinyl alcohol copolymer, unstretched polypropylene (CPP), low density polyethylene, linear low, which can be bonded by heat seal or adhesive. It is preferably a resin film made of density polyethylene or the like.
Further, the resin film used for the vapor-filmed resin film may be a resin film constituting the base material layer.

As a method for forming the inorganic vapor deposition layer, a physical vapor deposition method, a PVD method, for example, a vacuum vapor deposition method, a sputtering method, an ion plating method, a cluster ion beam method, etc., using the above-mentioned inorganic compound as a raw material. ), Or an inorganic vapor deposition on a resin film using a chemical vapor deposition method (CVD method, CVD method) such as a plasma chemical vapor deposition method, a thermochemical vapor deposition method, or a photochemical vapor deposition method. Layers can be formed.

More specifically, in the above PVD method, for example, a take-up type vapor deposition machine is used, and the resin film taken out from the unwinding roll is put into the vapor deposition chamber in a vacuum chamber. An inorganic vapor deposition layer is formed via a mask on the cooled resin film on the coated drum while evaporating the vapor deposition source heated in the pot and, if necessary, ejecting oxygen or the like from the oxygen outlet. Then, by winding the resin film on which the inorganic thin-film deposition layer is formed on a take-up roll, the resin film with the inorganic thin-film deposition layer according to the present invention can be produced.

On the other hand, in the above CVD method, the resin film surface unwound from the unwinding roll arranged in the vapor deposition chamber is cooled in the vapor deposition chamber, and for example, a monomer is supplied from the vapor deposition raw material volatilization supply device on the peripheral surface of the electrode drum. It is possible to introduce a mixed gas composed of an organic silicon compound, an oxygen gas, an inert gas or the like as a gas, and produce a resin film in which a thin-film vapor oxide layer is formed by plasma.

In the above, the thickness of the inorganic thin-film deposition layer is preferably 30 Å to 3000 Å, more preferably 40 Å to 2500 Å, and even more preferably 50 Å to 2000 Å in order to obtain sufficient oxygen barrier properties.
More specifically, in the above PVD method, the thickness of the inorganic vapor-filmed layer made of aluminum oxide is preferably 30 Å to 1000 Å, more preferably 50 Å to 500 Å.
Further, in the above CVD method, the thickness of the inorganic vapor deposition layer made of silicon oxide is preferably 30 Å to 3000 Å, more preferably 100 Å to 300 Å.
In the above, in the case of an inorganic thin-film vapor deposition layer generally composed of a metal oxide or an inorganic substance, if the thickness of the inorganic thin-film deposition layer exceeds the above range, cracks or the like are likely to occur in the inorganic thin-film deposition layer, and the warp has a barrier property. It is not preferable because there is a risk that it will decrease and the material cost will increase. Further, if it is less than the above range, it tends to be difficult to exhibit the oxygen barrier property, which is not preferable.

An oxygen barrier resin coating film or an oxygen barrier resin film made of an oxygen barrier resin can also be used as an oxygen barrier material, and at the same time, it can exhibit gas barrier property to water vapor and the like and fragrance retention property.
Examples of the oxygen barrier resin include polyvinylidene chloride resin (PVDC), polyester resin, polyamide resin (particularly aromatic polyamide such as nylon MXD6), and ethylene-vinyl acetate copolymer (vinyl acetate is about 79 wt%). Ethylene-vinyl alcohol copolymer (EVOH) with an ethylene content of 25 mol% to 50 mol%, which is completely saponified (~ 92 wt%), a film of a resin having a rich gas barrier property such as polyvinyl alcohol, polyvinylidene chloride, etc., or A coating film can be used.
The thickness of the oxygen barrier resin coating film or the oxygen barrier resin film is arbitrary, but is preferably 0.5 μm to 300 μm, more preferably 1 μm to 100 μm.

Further, the resin film with an inorganic vapor deposition layer has a water vapor transmission rate of preferably 3.0 g / m ² · day or less measured in accordance with the JIS K7129 method in an environment of a temperature of 40 ° C. and a humidity of 100% RH. It is more preferably 2.0 g / m ² · day or less, and further preferably 1.5 g / m ² · day or less. If the water vapor transmission rate satisfies the above numerical range, it is possible to sufficiently suppress the invasion of water vapor from the outside of the package into the content accommodating portion inside the package.
Further, the resin film with an inorganic thin-film deposition layer has an acidity permeability measured in accordance with the JIS K7126 method under an environment of a temperature of 23 ° C. and a humidity of 90% RH, preferably 3.0 cc / m ² · a.
It is tm · day or less, more preferably 1.0 cc / m ² · atm · day or less, and even more preferably 0.5 cc / m ² · atm · day or less. If the oxygen permeability satisfies the above numerical range, it is possible to sufficiently suppress the intrusion of oxygen from the outside of the package into the content storage portion inside the package.

At the time of forming the above-mentioned inorganic thin-film deposition layer, the surface of the resin film to be vapor-deposited is cleaned by pretreatment such as SiO _x plasma, and polar groups, free radicals, etc. are generated on the surface of the resin film to generate the inorganic vapor-film deposition layer and the resin. It is possible to increase the tight adhesion with the film.
Further, when two or more inorganic vapor deposition layers are continuously laminated using a plasma chemical vapor deposition apparatus consisting of at least two or more film forming chambers, each layer is vapor-deposited so as to have a high gas barrier property. Therefore, a gas barrier property higher than that of a single layer can be obtained, and further, foreign matter, dust, etc. that cause cracks can be deposited between the inorganic vapor deposition layers by continuous vapor deposition without opening to the atmosphere. It can be prevented from being mixed with the plasma, and its gas barrier property is improved.
Furthermore, if the composition of each thin-film vapor deposition layer is different, the permeation of oxygen gas, water vapor, etc. can be suppressed more efficiently because the inorganic vapor-film deposition layers are discontinuous layers different from each other.

When the oxygen barrier layer is formed of a resin film with an inorganic thin-film deposition layer, the surface of the inorganic-deposited layer can be adhered and laminated so as to face the base material layer via a general-purpose adhesive layer.
Then, when laminating the resin film with the inorganic thin-film deposition layer, if necessary, in order to strengthen the adhesive strength with other layers, the surface of the resin film with the inorganic thin-film deposition layer is subjected to corona discharge treatment, ozone treatment, etc. It is also possible to form a surface treatment layer by preliminarily performing a physical surface treatment such as a plasma treatment, a glow discharge treatment, a sandblast treatment, or a chemical surface treatment such as an oxidation treatment using a chemical.

≪Oxygen absorbent adhesive layer≫
The oxygen-absorbing adhesive layer is a layer formed by using the oxygen-absorbing adhesive composition.

<< Oxygen Absorbent Adhesive Composition >>
The oxygen-absorbing adhesive composition of the present invention is an oxygen-absorbing adhesive composition containing at least an oxygen-absorbing compound and an oxidation-promoting catalyst.
The oxygen-absorbing adhesive composition can further contain a denaturing agent, a diluting solvent, various additives and the like, if necessary.

As the oxygen-absorbing adhesive composition, the oxygen-absorbing compound may be added to the existing adhesive composition, or the oxygen-absorbing adhesive composition may be prepared by using the oxygen-absorbing compound as a resin component.
Here, the existing oxygen-absorbing adhesive composition may be a one-component oxygen-absorbing adhesive composition or a two-component oxygen-absorbing adhesive composition.
The oxygen-absorbing adhesive composition can contain one or more oxygen-absorbing compounds.
The oxygen-absorbing adhesive composition and / or the existing adhesive composition described above may be curable or non-curable. In the case of curability, it may be any of thermosetting, photocurable, electron beam curable and the like.
The oxygen-absorbing compound may or may not react with the components contained in the existing adhesive composition. Further, the oxygen-absorbing compounds may react with each other.
Depending on the presence or absence of the above reaction and the type of reaction, the oxygen-absorbing compound may be a compound having no functional group, a compound having a (co) polymerizable functional group, or a functional group capable of reacting as a main agent or a curing agent. Although it has, one kind or two or more kinds can be selected and used.

Specifically, for example, a two-component urethane-based adhesive composition containing an isocyanate-based compound and a hydroxyl group-containing compound has an oxygen-absorbing compound having no functional group and / or an oxygen-absorbing property having a functional group. Compounds can be added. In this case, the functional group is preferably an isocyanate group and / or a hydroxyl group.
Further, for example, the combination of the main agent and the curing agent of the oxygen-absorbing adhesive composition may be a combination of an isocyanate-based compound and an oxygen-absorbing compound having a hydroxyl group, or a hydroxyl group-containing compound and an oxygen-absorbing compound having an isocyanate group. The oxygen-absorbing adhesive composition can be prepared by combining the above or a combination of an oxygen-absorbing compound having a hydroxyl group and an oxygen-absorbing compound having an isocyanate group.
The oxygen-absorbing adhesive composition is preferably a urethane-based oxygen-absorbing adhesive composition.

The content of the solid content in the oxygen-absorbing adhesive composition is not particularly limited, but is preferably 20% by mass or more and 100% by mass or less.

The content of the oxygen-absorbing compound in the solid content excluding the oxidation-promoting catalyst in the oxygen-absorbing adhesive composition is preferably 40% by mass or more and 100% by mass or less. If it is less than the above range, oxygen absorption may be insufficient. The case of 100% by mass is a case where the oxygen-absorbing compound can be used as a resin component of the adhesive composition, and has sufficient adhesiveness by itself or has a functional group which can be cured by itself. In this case, an oxygen-absorbing compound having a functional group as a main agent and an oxygen-absorbing compound having a functional group as a curing agent are mixed and used.

The content of the oxidation-promoting catalyst in the oxygen-absorbing adhesive composition is preferably 10 ppm or more and 6000 ppm or less with respect to the oxygen-absorbing compound.
If the content is less than the above range, oxygen absorption may be insufficient, and if the content is more than the above range, oxygen absorption tends to be unstable, and oxygen is introduced before the package is prepared. Absorbency is consumed, and there is a risk that the effect of suppressing deterioration due to oxygen after manufacturing the contents of the package is impaired.

[Oxygen-absorbing compound]
The oxygen-absorbing compound of the present invention has oxygen-absorbing property, has little generated odor, can be used alone, or can be mixed with a resin or a resin composition.
The oxygen-absorbing compound of the present invention is an unsaturated five-membered ring-containing compound having one or two or more unsaturated five-membered rings, among the five carbon atoms constituting the unsaturated five-membered ring. One of the bonds is a carbon-carbon double bond, and the unsaturated five-membered ring has a monovalent and / or a divalent or higher electron-donating organic group 1 bonded to the unsaturated five-membered ring.
When the unsaturated five-membered ring is one, the five-membered ring or the organic group 1 is a functional group having active hydrogen, or the active hydrogen of the functional group having active hydrogen becomes a monovalent organic group 2. When it has a substituted group and the number of the unsaturated five-membered rings is two or more, the unsaturated five-membered rings substitute the active hydrogen of the active hydrogen group on each of the organic groups 1. It is bonded via an organic group 2 having a valence or higher.
When there are two or more unsaturated five-membered rings in one molecule, the unsaturated five-membered rings have active hydrogen of a functional group having active hydrogen on each of the five-membered rings or the organic group 1. It is bonded via a structure substituted with a divalent or higher organic group 2.
Each of the unsaturated five-membered ring, the organic group 1, and the organic group 2 present in one molecule may be one kind or two or more kinds, and the number may be one or two or more. Further, the number of organic groups 1 bonded to one unsaturated five-membered ring may be one or two or more. Furthermore, the oxygen-absorbing compound is a mixture of two or more types of molecules having different types and numbers of unsaturated five-membered rings, organic groups 1 and organic groups 2 existing in one molecule as described above. May be.

When the organic group 1 donates electrons to the unsaturated five-membered ring, the electron density of the carbon-carbon double bond portion of the unsaturated five-membered ring is increased, the reactivity with oxygen is enhanced, and the oxygen absorbability is increased. Will increase.
It is preferable that no electron-withdrawing group is attached to the unsaturated five-membered ring. Due to the binding of the electron-withdrawing group, the electron density of the carbon-carbon double bond portion of the unsaturated five-membered ring is lowered, the reactivity with oxygen is lowered, and the oxygen absorption is lowered.
The specific molecular structure of the oxygen-absorbing compound is, for example, one in which one unsaturated five-membered ring and one monovalent or divalent organic group 1 are bonded, and one unsaturated five-membered ring. A monovalent or divalent organic group 1 and a monovalent organic group 2 bonded in this order, two unsaturated five-membered rings are interposed via a divalent organic group 1 and a divalent organic group 2. Examples thereof include those in which the three unsaturated five-membered rings are bonded via a divalent organic group 1 and a trivalent organic group 2.

Further, the oxygen-absorbing compound does not have to have a crosslinkable functional group, but may have one.
The crosslinkable functional group may be a functional group possessed by the compound from which the organic group 2 is derived, or may be a functional group added by chemical modification.
Since the oxygen-absorbing compound has a crosslinkable functional group, when the oxygen-absorbing compound is mixed with the resin or the resin composition, the oxygen-absorbing compound has compatibility with the resin or the resin composition. The resin or the resin composition becomes difficult to bleed from the resin or the resin composition or the cured product of the resin composition by increasing or becoming a part of the crosslinked structure of the resin or the resin composition. The content of the oxygen-absorbing compound in the substance can be increased.
Specific examples of the crosslinkable functional group include an aliphatic hydroxyl group, an aromatic hydroxyl group, an isocyanate group, an amino group, an epoxy group, a (meth) acrylic group and the like. Among these, isocyanate groups and aliphatic hydroxyl groups are preferable.
When having a crosslinkable functional group, the number of the crosslinkable functional groups of the oxygen-absorbing compound is preferably one or two or more in one molecule. Further, the crosslinkable functional group contained in one molecule may be one kind or two or more kinds.
The functional group equivalent of the crosslinkable functional group is not particularly limited, but is preferably 500 to 20000, more preferably 1000 to 15000, and even more preferably 1500 to 10000.

The number average molecular weight of the oxygen-absorbing compound is preferably 100 to 10000, more preferably 200 to 5000, and even more preferably 300 to 2500. When the number average molecular weight is smaller than the above range, it tends to precipitate when mixed with a resin or a resin composition. When the number average molecular weight is larger than the above range, when mixed with a resin or a resin composition, the viscosity of the mixture becomes high, so that it is easy to need to contain a large amount of a diluting solvent, and it is difficult to obtain a thick film or layer. Coating suitability tends to deteriorate.

Further, the oxygen absorbing action of the oxygen absorbing compound of the present invention can be promoted by heating or adding a catalyst.

(Unsaturated five-membered ring)
The unsaturated five-membered ring of the oxygen-absorbing compound has a carbon-carbon double bond in the unsaturated five-membered ring. Here, the carbon-carbon double bond is any bond between the five carbon atoms constituting the unsaturated five-membered ring, and may be one in one unsaturated five-membered ring. It may be two.
The carbon-carbon double bond reacts with oxygen molecules in the air to take up oxygen molecules, so that the oxygen-absorbing compound exhibits oxygen-absorbing property.
Examples of the compound from which the unsaturated five-membered ring or the unsaturated five-membered ring to which the electron-donating organic group 1 is bonded as described above include cyclopentadiene, dicyclopentadiene, norbornene, and derivatives thereof. Can be mentioned. The oxygen-absorbing compound can have an unsaturated five-membered ring derived from one or more selected from the group consisting of these.
The unsaturated five-membered ring concentration in the oxygen-absorbing compound is not particularly limited, but is preferably 1% by mass or more and 70% by mass or less, and more preferably 5% by mass or more and 60% by mass or less. If it is lower than the above range, oxygen absorption tends to be insufficient, it is difficult to obtain an oxygen-absorbing compound higher than the above range, and the balance with various physical properties tends to be poor.

(Electron-donating organic group 1)
Specific examples of the organic group 1 include an alkyl group, an alkylene group, a cyclic alkylene group and the like. Among these, cyclic alkylene groups are preferable, and those constituting an aliphatic bicyclic alkylene group together with the unsaturated five-membered ring are more preferable.
Specific examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group and the like. Of these, the cyclopentylene group is more preferred.

(Electronic withdrawing organic group)
Specific examples of the electron-withdrawing group include a phenyl group, a phenylene group, a carbonyl group, a halogen and the like.
Inden and Kumaron in which only these electron-withdrawing groups are bonded to an unsaturated five-membered ring have a low electron density in the carbon-carbon double bond portion of the unsaturated five-membered ring, and the reactivity with oxygen is reduced. However, the oxygen absorption is low.

(Functional group with active hydrogen)
Functional groups with active hydrogen are chemically reactively active.
Specific examples of the functional group having active hydrogen include a primary amino group, a secondary amino group, an aliphatic hydroxyl group, an aromatic hydroxyl group, an imino group, a carboxyl group, a urethane group, a urea group and the like, and among them, a primary amino group. Amino groups, secondary amino groups, aliphatic hydroxyl groups and aromatic hydroxyl groups are preferable, and aliphatic hydroxyl groups are more preferable.

(Organic group 2)
The organic group 2 replaces the active hydrogen of the functional group having active hydrogen on the five-membered ring or the organic group 1 and is bonded to the five-membered ring or the organic group 1 in a monovalent and / or divalent or higher value. Is the basis of.
When there are two or more unsaturated five-membered rings in one molecule, the unsaturated five-membered rings have a structure in which the active hydrogen of the functional group having active hydrogen is replaced with the organic group 2 having a valence of 2 or more. It is connected through.
As a specific example, for example, the functional group having active hydrogen on the organic group 1 reacts with the isocyanate group of the isocyanate-based compound having the structural part from which the organic group 2 is derived, and the active hydrogen becomes the organic group 2. It can be substituted and bonded by a urethane group.
Due to the binding of the organic group 2, the oxygen-absorbing compound can have two or more of the unsaturated five-membered rings in one molecule, and is further mixed with a resin or a resin composition to prepare a mixture. The compatibility, dispersibility, and reactivity can be enhanced. Furthermore, the mixture and the cured product of the mixture can be softly adjusted.

The organic group 2 may be an aliphatic group, an aromatic group, or may have both an aliphatic group and an aromatic group.
The organic group 2 present in one molecule of the oxygen-absorbing compound may be one kind or two or more kinds.
The organic group 2 is preferably a group containing a structural portion derived from an isocyanate-based compound and / or a hydroxyl group-containing compound. Here, the structural portion derived from the isocyanate-based compound and / or the hydroxyl group-containing compound also includes the structural portion derived from the reaction product of the isocyanate-based compound and the hydroxyl group-containing compound.

(Isocyanate compound)
Examples of the isocyanate-based compound from which the organic group 2 is derived include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornan diisocyanate, xylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylenedi isocyanate, diphenyl ether diisocyanate, and water. Examples thereof include diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, their trimethylolpropane adducts, burettes, allophanates, isocyanurates (trimers), and various derivatives thereof. Among these, toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate are preferably burettes.
In the present invention, one or more selected from the group consisting of these isocyanate compounds can be used as the origin of the structural part of the above monovalent and / or divalent or higher hydrocarbon group. When two or more kinds are used, two kinds may be used in the same molecule of an oxygen-absorbing compound, or the molecule of an oxygen-absorbing compound having a different kind may be mixed.

The number average molecular weight of the isocyanate compound is preferably 100 to 10000, more preferably 160 to 5000. When the number average molecular weight is smaller than the above range, it tends to precipitate when mixed with a resin or a resin composition. When the number average molecular weight is larger than the above range, when mixed with a resin or a resin composition, the viscosity of the mixture becomes high, so that it is easy to need to contain a large amount of a diluting solvent, and it is difficult to obtain a thick film or layer. Coating suitability tends to deteriorate.

(Hydroxy group-containing compound)
The hydroxyl group-containing compound is a compound from which the above-mentioned organic group 2 is derived, and has two or more hydroxyl groups.
Examples of the hydroxyl group-containing compound include polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and urethane chain extension polyols thereof. Among these, polyether polyols and polyolefin polyols are preferable.
The hydroxyl group-containing compound preferably has no double bond in the aliphatic chain of the main skeleton or has two hydroxyl groups in order to prevent the generation of odor. It is preferable that the one having a hydroxyl group at the end is easily available, but it is not necessary to have it at the end.
In the present invention, one or more selected from the group consisting of these can be used as the hydroxyl group-containing compound from which the above-mentioned organic group 2 is derived. When two or more kinds are used, two kinds may be used in the same molecule of an oxygen-absorbing compound, or a molecule of an oxygen-absorbing compound having a different kind may be mixed.
The number average molecular weight of the hydroxyl group-containing compound is preferably 500 to 10000, more preferably 750 to 5000, and even more preferably 1000 to 3000. When the number average molecular weight is smaller than the above range, it tends to precipitate when mixed with a resin or a resin composition. When the number average molecular weight is larger than the above range, when mixed with a resin or a resin composition, the viscosity of the mixture becomes high, so that it is easy to need to contain a large amount of a diluting solvent, and it is difficult to obtain a thick film or layer. Coating suitability tends to deteriorate.

-Multihydric alcohols Polyhydric alcohols are monomers having two or more hydroxyl groups.
Specific examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, cyclohexanedimethanol, and 1, 8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2
-Methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, 2,2'- Examples thereof include diols such as oxydiethanol, glycerin, mannitol, sorbitol and the like.
Among the above, ethylene glycol is preferable from the viewpoint of oxygen absorption.

-Polyolefin polyol A polyolefin polyol is a polyolefin resin having two or more hydroxyl groups.
As a specific example of the polyolefin polyol, the main skeleton is polyethylene, polypropylene, polybutylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer. Examples thereof include polyolefins such as a coalescence, an ethylene- (meth) acrylic acid copolymer, and an ethylene-propylene copolymer, which have a hydroxyl group.
Among these, those having an ethylene-vinyl acetate copolymer and hydrogenated polyisoprene as the main skeleton are particularly preferable.

-Polyether polyol The polyether polyol is a polyether resin having two or more hydroxyl groups.
The polyether polyol is obtained, for example, by dehydrating and condensing the above-mentioned polyhydric alcohols and polyolefin polyols, and has a polyether structure in the main skeleton and has a hydroxyl group.
Specific examples of the polyether polyol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene ether diol, polypropylene ether diol, polybutylene ether diol, and glycerin-modified polyether polyols. Among these, polypropylene ether diol is particularly preferable.

-Polyester polyol A polyester polyol is a polyester resin having two or more hydroxyl groups.
The polyester polyol is obtained by, for example, an esterification reaction of various polyvalent carboxylic acids or derivatives thereof with the above-mentioned polyhydric alcohols, polyolefin polyols, polyether polyols, etc., has a polyester structure in the main skeleton, and has a hydroxyl group. Has.
Specific examples of polyvalent carboxylic acids include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelli acid, azelaic acid, sebacic acid, suberic acid, and glutal. Examples thereof include acids, 1,4-cyclohexanedicarboxylic acid, trimellitic acid and the like, and examples of the derivatives of these polyvalent carboxylic acids include esterified products, acid anhydrides and acylated products.
Among the above, in order to reduce the crystallinity, a polyester polyol in which two or more kinds of polyhydric alcohols and two or more kinds of polyvalent carboxylic acids are used in combination is preferable.

-Polycarbonate polyol A polycarbonate polyol is a polycarbonate-based resin having two or more hydroxyl groups.
Polycarbonate has a polyol-derived portion in the main skeleton, and the polyol-derived portion may be derived from the above-mentioned polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols and the like.
Among these, a polycarbonate polyol in which two or more kinds of polyhydric alcohols are used in combination is preferable in order to lower the crystallinity.

Poly (meth) acrylic acid ester polyol Poly (meth) acrylic acid ester polyol has two or more hydroxyl groups, (meth)
It is an acrylic acid ester (co) polymer.
The poly (meth) acrylic acid ester polyol is, for example, 2-hydroxyethyl methacrylate, a (meth) acrylic acid ester having a hydroxyl group synthesized from one (meth) acrylic acid or a derivative thereof and one diol, and the like. It can be obtained by polymerizing the hydroxyl group-containing monomers with each other or copolymerizing with a (meth) acrylic acid ester having no hydroxyl group by using the hydroxyl group-containing monomer of.
As the diol for synthesizing the (meth) acrylic acid ester having a hydroxyl group, the above-mentioned diols, polyolefin polyols, polyether polyols and the like can be used.
Among these, a poly (meth) acrylic acid ester copolymer using 2-hydroxyethyl methacrylate is preferable.

-Phenoxy resin Phenoxy resin is a resin obtained by reacting a polyhydric phenol compound with a polyvalent epoxy compound, and has a structure in which an aliphatic hydroxyl group is generated at a bonding portion where an aromatic hydroxyl group and an epoxy group have reacted. is doing.
As the phenoxy resin, a resin obtained by reacting bisphenols with diglycidyl etherified bisphenols is easily available and is generally used.
Examples of the polyvalent phenol compound include bisphenol A and bisphenol F, and examples of the polyvalent epoxy compound include bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.
Among these, a phenoxy resin using bisphenol A is preferable.
The terminal of the phenoxy resin may be an aromatic hydroxyl group or an epoxy group.

-Urethane chain extension polyol The urethane chain extension polyol is a polyol having two or more hydroxyl groups obtained by extending the above hydroxyl group-containing compound with a urethane chain.
The urethane chain-extended polyol can be obtained, for example, by polymerizing the above-mentioned various hydroxyl group-containing compounds with the above-mentioned isocyanate-based compound to extend the urethane chain. Further, if necessary, diamines and amino alcohols may be used in combination for polymerization.
Among the above, urethane chain-extended polyols obtained by reacting the various hydroxyl group-containing compounds having hydroxyl groups at both ends with diisocyanate compounds are preferable.

(Specific example of oxygen-absorbing compound)
Specific examples of oxygen-absorbing compounds are shown below.
3a, 4,5,6,7,7a-hexahydro-4,7-methano-1H-indenol represented by the formula (1) and 3a, 4,5,6 represented by the formula (1-b). 7,7a-Hexahydro-4,7-methano-1H-indenamine and 3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-inden represented by the formula (1-c). -1-ol is an example of an oxygen-absorbing compound having one unsaturated five-membered ring, one organic group 1, and one organic group 1 having a hydroxyl group or an amino group as a functional group having active hydrogen. Is.

（式中、ａは１以上の数であり、Ｒ¹は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含み、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） The oxygen-absorbing compound represented by the formula (2) is derived from, for example, a hydroxyl group which is a functional group having an active hydrogen on the organic group 1 of the oxygen-absorbing compound represented by the formula (1), and the organic group 2. The isocyanate group of R ¹ (NCO) _a , which is an isocyanate compound, reacts with the active hydrogen of the hydroxyl group, and a unsaturated five-membered ring and the organic group 1 are bonded via R ¹ . It is an oxygen-absorbing compound that can be obtained.

(In the formula, a is a number of 1 or more, R ¹ is an organic group having 1 or more carbon atoms, contains at least an alkylene and / or a phenylene structure, and further contains polyhydric alcohols, polyolefin polyols, and polyether polyols. , Polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and structures derived from one or more selected from the group consisting of these urethane chain extended polyols.)

（式中、ｆは０以上の数であり、Ｒ⁴とＲ⁵の各々は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含む有機基であり、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） The oxygen-absorbing compound represented by the formula (5) has a = 2 in the formula (2), and R ¹ is, for example, the isocyanate-based compound OCN-R ⁴ -NCO and the hydroxyl group-containing compound HO-R. It is an oxygen-absorbing compound when it is a group containing a structural part derived from ⁵ -OH and produced by the reaction of both.

(In the formula, f is a number of 0 or more, and each of R ⁴ and R ⁵ is an organic group having 1 or more carbon atoms, which is an organic group containing at least an alkylene and / or a phenylene structure, and further has a polyvalent value. Derived from one or more selected from the group consisting of alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and urethane chain extension polyols thereof. Can include structure.)

（式中、ｂとｃの各々は１以上の数であり、Ｒ²は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含み、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） In the formula (2), the oxygen-absorbing compound represented by the formula (3) contains, for example, a structural portion in which R ¹ is derived from an isocyanate-based compound and a hydroxyl group-containing compound, and both are reacted to form a structural portion. It is an oxygen-absorbing compound when the excess hydroxyl group contains a hydroxyl group due to residual or chemical modification.

(In the formula, each of b and c is a number of 1 or more, R ² is an organic group having 1 or more carbon atoms, contains at least an alkylene and / or a phenylene structure, and further, polyhydric alcohols and polyolefin polyols. , Polyester polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and structures derived from one or more selected from the group consisting of these urethane chain extended polyols. can.)

（式中、ｄとｅの各々は１以上の数であり、Ｒ³は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含み、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） In the formula (2), the oxygen-absorbing compound represented by the formula (4) contains, for example, a structural portion in which R ¹ is derived from an isocyanate-based compound and a hydroxyl group-containing compound, and both are reacted to form a structural portion. It is an oxygen-absorbing compound when the excess isocyanate group contains an isocyanate group due to residual or chemical modification.

(In the formula, each of d and e is 1 or more, R ³ is an organic group having 1 or more carbon atoms, contains at least an alkylene and / or phenylene structure, and further, polyhydric alcohols and polyolefin polyols. , Polyester polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and structures derived from one or more selected from the group consisting of these urethane chain extended polyols. can.)

[Oxidation-promoting catalyst]
The oxidation-promoting catalyst is a compound that promotes the action of an oxygen-absorbing compound by absorbing oxygen molecules to be oxidized.
Examples of the oxidation-promoting catalyst include peroxides and compounds containing cations composed of transition metals.
Specific examples of the peroxide include hydrogen peroxide and the like.
As the compound containing a cation composed of a transition metal, a metal soap composed of a transition metal-containing compound capable of releasing a cation or a complex of a transition metal atom and an anion or a ligand composed of a fatty acid is preferable.
The transition metal is preferably cobalt, manganese, iron, nickel, copper, or the like, and the anion or ligand is preferably an anion or ligand composed of stearic acid, naphthenic acid, octylic acid, acetylacetonato, or the like.
The oxidation-promoting catalyst includes one or more cations selected from the group consisting of the above transition metals and one or more selected from the group consisting of the above long-chain fatty acids. A metal soap formed in combination with an anion composed of a fatty acid can be used. Specific examples of the compound include cobalt octylate, cobalt acetylacetone (II), cobalt acetylacetone (III), manganese acetylacetone (III), iron (III) acetylacetone and the like.

[Denaturant]
The modifier is a compound having a functional group that reacts with the oxygen-absorbing compound when the oxygen-absorbing compound has a functional group, and various reactive monomers and resins can be used.
By including the modifier in the oxygen-absorbing adhesive composition, the oxygen-absorbing compound can be bound to other components in the oxygen-absorbing adhesive composition, or oxygen-absorbing in the oxygen-absorbing adhesive composition. The content of the compound can be adjusted, and the hardness of the cured product of the oxygen-absorbing adhesive composition can be adjusted.

For example, when the oxygen-absorbing compound has a hydroxyl group or an isocyanate group, a modifier composed of an isocyanate-based compound and / or a hydroxyl group-containing compound can be used.
When the oxygen-absorbing adhesive composition is urethane-based, the equivalent ratio NCO / OH of the oxygen-absorbing adhesive composition is preferably 0.5 or more and 8 or less. If it is smaller than the above range, the curing of the oxygen-absorbing adhesive composition may be insufficient and sufficient laminating strength (adhesive strength) may not be obtained. If it is larger than the above range, oxygen-absorbing adhesion may be obtained. The pot life of the agent composition may be too short.

(Isocyanate compound for denaturing agent)
As the isocyanate-based compound for the modifier, the isocyanate-based compound used in the synthesis of the oxygen-absorbing compound can be used, and any of aromatic isocyanate, aliphatic isocyanate, and urethane chain-extended isocyanates thereof can be used. .. Further, in order to cure the oxygen-absorbing adhesive composition, those having two or more isocyanate groups in one molecule are preferable. However, an isocyanate-based compound having one isocyanate group in one molecule can also be used in combination as long as the sufficient effect of the oxygen-absorbing adhesive composition is not impaired.
As the isocyanate-based compound having two or more isocyanate groups in one molecule, a burette of hexamethylene diisocyanate is particularly preferable.

Specific isocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornan diisocyanate, xylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, phenylenedi isocyanate, diphenyl ether diisocyanate, and polymethylene polyphenyl. Examples thereof include polyisocyanates, their trimethylol propanadducts, burettes, allophanates, isocyanurates (trimers), and various derivatives thereof. Among these, toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate are preferably burettes.

(Hydroxy group-containing compound for denaturant)
As the hydroxyl group-containing compound for the modifier, the hydroxyl group-containing compound used in the synthesis of the oxygen-absorbing compound can be used, and any of the aromatic hydroxyl group-containing compound, the aliphatic hydroxyl group-containing compound, and these urethane chain extension polyols can be used. Can be used. Further, in order to cure the oxygen-absorbing adhesive composition, one having two or more hydroxyl groups in one molecule is preferable. However, a hydroxyl group-containing compound having one hydroxyl group in one molecule can also be used in combination as long as the sufficient effect of the oxygen-absorbing adhesive composition is not impaired.
As the hydroxyl group-containing compound having two or more hydroxyl groups in one molecule, either an aromatic hydroxyl group-containing compound or an aliphatic hydroxyl group-containing compound system can be used, and it may be alcohol-based or phenol-based.
As the isocyanate-based compound having two or more isocyanate groups in one molecule, a polyalkylene ether diol and a urethane chain-extended polyol of a polyalkylene ether diol are particularly preferable.

[Diluting solvent]
The diluting solvent is not particularly limited as long as it uniformly dissolves or disperses the oxygen-absorbing compound and the oxidation-promoting catalyst, makes the oxygen-absorbing adhesive composition uniform, and is suitable for the dry lamination step, for example, ester-based dilution. A solvent, a ketone-based diluted solvent, a hydrocarbon-based diluted solvent, or the like can be used.
Specific examples of the ester-based diluted solvent include ethyl acetate, butyl acetate and the like, specific examples of the ketone-based diluted solvent include methyl ethyl ketone and the like, and specific examples of the hydrocarbon-based diluted solvent include toluene and the like. .. Among these, ethyl acetate is preferable because it is easy to use.

[Various additives]
The oxygen-absorbing adhesive composition can contain various additives, if necessary.
For example, to suppress a decrease in oxygen absorption during storage and use of a curing accelerator, a curing adjusting agent for prolonging the pot life, and an oxygen-absorbing adhesive composition and before the contents are contained in the package. Antioxidants, adhesive aids, tackifiers, leveling agents, UV absorbers, defoaming agents, coloring pigments, and extender pigments can also be added.

(Curing accelerator)
As the curing accelerator, any one that promotes the curing reaction of the oxygen-absorbing adhesive composition can be used without particular limitation.
Specific curing accelerators include metal-containing compounds such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dibutyltin dimalate, tetrabutyl titanate, and tetraisopropyl titanate, and 1,8-diaza-bicyclo (5,4). , 0) Undecene-7, 1,5-diazabicyclo (4,3,0) nonen-5, tertiary amines such as triethanolamine, etc., and one or more selected from the group consisting of these. Can be used.

(Hardening conditioner)
When the pot life of the oxygen-absorbing adhesive composition is shortened by the oxidation-promoting catalyst contained therein, the pot life can be lengthened by using a curing modifier in combination.
Specific curing modifiers are preferably phosphoric acids, and examples thereof include orthophosphoric acid, metaphosphoric acid, polyphosphoric acid and ester derivatives thereof, and one or more selected from the group consisting of these is used. be able to.
The amount of the reaction modifier added is preferably 200 ppm or more and 400 ppm or less with respect to the resin component of the oxygen-absorbing adhesive composition. If it is less than the above range, it is difficult to obtain the effect of prolonging the pot life, and if it is more than the above range, the curing of the oxygen-absorbing adhesive composition may be hindered.

(Antioxidant)
Suppresses deterioration of oxygen absorption during storage and use of the oxygen absorbing adhesive composition, and in the process before the package produced by using the oxygen absorbing adhesive composition contains the contents. In order to maintain high oxygen absorption after containing the contents, the oxygen absorbing adhesive composition may contain an antioxidant.
Specific examples of antioxidants include phenol-based, lactone-based, thioether-based, gallic acid-based, ascorbic acid, erythorbic acid, catechin, dibutylhydroxytoluene, tocopherol, citric acid, butylhydroxyanisole, phosphite ester, and hindered amine. Examples include aromatic amines, and one or more selected from the group consisting of these can be used.
In addition, when it is assumed that heat or light is used as a trigger for the development of oxygen absorption, it is preferable to use an antioxidant having low heat resistance and light resistance such as ascorbic acid and tocopherol, and high heat resistance such as phenol. , It is not preferable to use a highly light-resistant antioxidant.
The amount of the antioxidant added is preferably 10 ppm or more and 10,000 ppm or less with respect to the oxygen-absorbing compound. If it is less than the above range, the antioxidant effect tends to be insufficient, and if it is more than the above range, oxygen absorption may be lowered.

(Adhesive aid)
As the adhesive aid for assisting the adhesive force, a silane coupling agent is preferable.
Examples of the silane coupling agent include γ-glycidoxypropyltrialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-glycidoxypropylmethyldialkoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrialkoxy. Silane, γ-aminopropyltrialkoxysilane, γ-aminopropylmethyldialkoxysilane, N- (β-aminoethyl) -γ-aminopropyltrialkoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyl Examples thereof include dialkoxysilane, N-butyl-3-amino-2-methylpropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, and γ-mercaptopropylmethyldialkoxysilane, and examples of the alkoxy group include a methoxy group or an ethoxy group. Preferably, one or more selected from the group consisting of these can be used.

(Adhesive)
Examples of the tackifier include paraffin wax, polyethylene wax, rosin, rosing lyserine ester, terpene, alkylphenol and the like, and one or more selected from the group consisting of these can be used.

(Leveling agent)
Examples of the leveling agent include an acrylic polymer type, a modified silicone type, an acetylenediol type, and the like, and one kind or two or more kinds selected from the group consisting of these can be used.

(UV absorber)
Examples of the ultraviolet absorber include benzotriazole-based, hydroxyphenyltriazine-based, and hindered amine-based agents, and one or more selected from the group consisting of these can be used.

(Defoamer)
Examples of the defoaming agent include a surfactant, a polyether-modified silicone oil, and the like, and one or more selected from the group consisting of these can be used.

(Coloring pigment)
Coloring pigments include organic pigments such as anthraquinone, diketopyrrolopyrrole, perylene maroon, carbon black, dioxazine, perylene, benzimidazolone, isoindoline, isoindoline, phthalocyanine, and indanslen, and yellow iron oxide. , Red iron oxide, isomethine copper complex, titanium oxide, silicon oxide and other inorganic pigments, and one or more selected from the group consisting of these can be used.

(Constitution pigment)
The extender pigment is a white or colorless pigment that is used as a bulking agent or as an adjusting agent for coloring power, gloss, strength, usability, and the like.
Specific examples include barium sulfate, barium carbonate, calcium carbonate, magnesium oxide, magnesium carbonate, magnesium hydroxide, barium titanate, calcium hydroxide, calcium sulfite, calcium sulfate, calcium oxide, calcium silicate, titanium oxide, silica, and the like. Examples thereof include inorganic pigments such as zeolite and talc, and one or more selected from the group consisting of these can be used.

<< Preparation method of oxygen-absorbing adhesive composition >>
The oxygen-absorbing adhesive composition can be produced by mixing all the constituents such as an oxygen-absorbing compound, an oxidation-promoting catalyst, and, if necessary, a modifier, a diluting solvent, and various additives. Alternatively, it can be produced by mixing an oxygen-absorbing compound, an oxidation-promoting catalyst, and, if necessary, a denaturing agent, a diluting solvent, various additives, and the like with an existing adhesive composition.
The method for performing the above mixing and the order for mixing each component are not particularly limited, and a general method for preparing an adhesive composition and a mixing order can be applied.
Specific examples of the mixing method include a method of dissolving in a solvent and mixing, and a method of melt-kneading. At this time, it is preferable to adjust the heating temperature in order to improve the solubility and dispersibility.

<< How to use the oxygen-absorbing adhesive composition >>
The method of using the oxygen-absorbing adhesive composition is not particularly limited, and a general method of use as an adhesive can be applied.
For example, a non-solvent type lamination method used by heating to an appropriate viscosity, a dry lamination method used by adding a diluting solvent or another compound adhesive to adjust the coating viscosity, and the like can be mentioned.
When the adhesive layer is formed using the oxygen-absorbing adhesive composition, the coating amount is preferably 2 to 5 g / m ² and more preferably 3 to 5 g / m ² . If it is less than the above range, sufficient oxygen absorption may not be obtained, and if it is more than the above range, the oxygen absorption does not change so much, which leads to cost demerit, which is not preferable.

The laminate obtained by forming and adhering an adhesive layer using an oxygen-absorbing adhesive composition is usually aged at 20 ° C. or higher and 50 ° C. or lower for 2 days or more and 5 days or less. Is preferable.
When aging, it is preferable to perform aging at a low temperature as much as possible or in an atmosphere of an inert gas so as not to reduce the oxygen absorption of the laminated body.
Even when the produced laminate is stored, it is preferable to store it at 10 ° C. or lower or in an inert gas atmosphere so as not to reduce the oxygen absorption of the laminate.

<< About objects that can be adhered >>
The object to which the oxygen-absorbing adhesive composition can be adhered is not particularly limited, and is, for example, on a resin molded product, a resin film, paper, a metal, a metal foil, an inorganic vapor-deposited film surface, or an inorganic oxide vapor-deposited film surface. Adhesion is possible.

Specific examples of the resin of the resin film include polyester resin such as polyethylene terephthalate (PET), polyamide resin such as various nylons, polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, and acrylonitrile-styrene. Polymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyolefin resin such as polybutene resin, polyvinyl chloride resin, polycarbonate resin, polyimide resin, polyamideimide resin, diallyl phthalate Resin-based resin, silicone-based resin, polysulfone-based resin, polyphenylene sulfide-based resin, polyether sulfone-based resin, polyurethane-based resin, cellulose-based resin, poly (meth) acrylic-based resin, polyvinylidene chloride-based resin, acetal-based resin, fluorine-based Examples include resin.

Specific examples of the paper include, for example, a bleached or unbleached paper base material for a paper layer having a strong size property, or a paper base material such as pure white roll paper, kraft paper, paperboard, coated paper, processed paper, and milk base paper. , Others, etc.
Specific examples of the metal foil include aluminum foil, copper foil, stainless steel foil and the like.
Specific examples of the metal of the inorganic thin-film deposition layer include aluminum.
Specific examples of the inorganic oxide of the inorganic vapor deposition layer include silica, alumina, tin oxide, zinc oxide, tin oxide, titanium oxide, zirconium oxide, vanadium oxide, barium oxide, chromium oxide, silicon nitride, silicon carbide and the like. Can be mentioned. Among these, silica and alumina are preferable.

≪Sealant layer≫
The sealant layer may be composed of one layer, or may be a multi-layer structure having two or more layers having the same or different composition.
Since the sealant layer is heat-sealed with the lid material forming the blister packaging container, it is preferable that the sealant layer contains a resin having a heat-sealing property with the lid material and has a heat-sealing property. Moreover, it can also have easy-opening property (easy peeling property).
In order to have easy opening property, it is preferable that the sealant layer has an easy peel layer as the outermost layer of the sealant layer, and further has a support layer for supporting the easy peel layer.
The easy peel layer can provide easy opening by, for example, coagulation fracture of the easy peel layer having a sea-island structure, peeling of the sea-island interface, and having an appropriate adhesive strength.
In the case of an easy peel layer having a sea-island structure, the easy peel layer is a layer made of a blended polymer containing two or more kinds of resins that are incompatible with each other. In order to have a heat-sealing property, it is preferable that the sea structure portion contains a resin having a heat-sealing property.
Here, the blended polymers are not positively reacted with each other. And since they are incompatible with each other, they form a sea-island structure. Since it is incompatible and the bond at the sea-island interface is weak, peeling is likely to occur at the sea-island interface at the time of peeling, and it is possible to bring about easy peeling property of the easy peel layer as a whole.
In the case of an easy peel layer having an appropriate adhesive strength, the easy peel layer is preferably a heat-sealing resin having an appropriate adhesive strength, or a blend of a resin having a strong adhesive strength and a heat-sealing resin having a weak adhesive strength. Furthermore, the adhesive strength can be adjusted by containing an adhesive resin or a filler.
Further, the type of resin to be blended and the blending ratio thereof can be adjusted according to the composition of the resin on the surface of the molded part to be heat-sealed.
The support layer for supporting the easy peel layer preferably contains a heat-sealing resin because it has heat-sealing properties.
The sealant layer having such easy peelability can be formed by laminating a publicly known and publicly available easy peel film.

Further, the sealant layer may contain any additive as long as it does not significantly impair the effects of the present invention. As additives, various resin additives generally used for preparing the molding processability and productivity of resin films and various physical properties, such as antiblocking agents, slip agents, antioxidants, pigments, and flow control. Examples include materials, flame retardants, fillers, ultraviolet absorbers, surfactants and the like.
The thickness of the sealant layer is preferably 10 μm to 200 μm, more preferably 30 μm to 100 μm.

(Resin with heat sealability)
As the resin having heat-sealing property, a polyolefin-based resin or an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, or itaconic acid or an anhydride thereof is used as the polyolefin-based resin. , Acid-modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, and other resins that have been acid-modified by graft polymerization or copolymerization can be used. These resins can be used alone or in combination of two or more.

(Polyolefin resin)
Specific examples of the polyolefin-based resin include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, and both ethylene-α and olefins polymerized using a metallocene catalyst. Polymers, polypropylene, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ionomer resins, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene -Cyclic of methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene (co) polymer, butene (co) polymer, ethylene-acrylic acid copolymer, ethylene-methacrylate copolymer, polynorbonene, etc. Examples thereof include olefin (co) polymers. The copolymer may be a random or block copolymer.
The polyolefin-based resin is classified into, for example, a polyethylene-based resin or a polypropylene-based resin according to the skeleton of the monomer used in the synthesis of the polyolefin, and may be a copolymer. In the present invention, "based resin" is added as a generic term for various types, and for example, it is also referred to as polyethylene-based resin as a generic term for various types of polyethylene.
The polyolefins produced by polymerizing using α-olefins such as ethylene, propene, 1-butene, 1,3-butadiene, and 1-hexene as raw materials are polyethylene-based resins, polypropylene-based resins, and polybutylene-based resins, respectively. It is called a resin, a polybutadiene resin, a polyhexene resin, or the like.
As the polymerization method, for example, a high pressure method is used for low density polyethylene, and a low pressure polymerization method (a gas phase polymerization method using a Ziegler-Natta catalyst or a liquid phase weight using a metallocene catalyst) is used for linear low density polyethylene. (Legal), slurry method, solution method, gas phase polymerization method and other polymerization methods are common.

(Method of forming the sealant layer)
The method for forming the sealant layer is not particularly limited, and a conventionally known method for laminating a sealant layer can be applied.
A sealant film composed of one layer or two or more layers for the sealant layer may be prepared in advance, and the sealant film may be adhered to another layer constituting the laminate via an adhesive or the like and laminated. As a method for producing a sealant film, one or more kinds of resin compositions are melt-extruded and formed into a film by an inflation method, or melt-extruded and narrowed on a roll by an extrusion method using T-die molding or the like. It may be made into a film.
Here, it is preferable that one side of the produced sealant film is corona-treated, and the corona-treated surface is opposed to the side to be laminated and adhered to be laminated.
Alternatively, the resin composition for forming the sealant layer was melted, melted (co) extruded, flowed onto the layer to be laminated, and T-die molding using a feed block method or a multi-manifold method was used. A sealant layer composed of one layer or multiple layers may be laminated on another layer constituting the laminated body by an extrusion method.
In either method, a multilayer sealant film can be produced by co-melt extrusion using resin compositions having the same or different compositions.

≪Base material layer≫
As a material for the base material layer, for example, as a basic material constituting a molded part of a blister packaging container, it has excellent mechanical, physical, chemical, and other properties, and is particularly strong and tough. A general publicly known and publicly available resin film having heat resistance can be used. Furthermore, various paper base materials can be used, and the resin film and the paper base material can be used in combination.
The base material layer may be composed of one layer, or may be composed of two or more layers laminated by any laminating means having the same or different composition.
The thickness of the base material layer can be appropriately set by those skilled in the art, but is preferably 5 to 500 μm, for example, depending on the rigidity of the resin film used, for the purpose of imparting appropriate strength and waist to the laminated body.
For example, in the case of a biaxially stretched PET film, 5 to 100 μm is preferable, and in the case of a PPVC / PVDC composite film, 150 to 350 μm is preferable.

Specific examples of the resin contained in the resin film include polyethylene terephthalate (PET), polyester such as polyethylene naphthalate, polyolefin such as polypropylene, polyvinyl chloride (PVC), and the like.
The resin film can be either an unstretched film or a stretched film stretched in a uniaxial or biaxial direction.
Among the above, biaxially stretched PET film and PVC / PVDC composite film are preferably used.
Further, in order to improve oxygen barrier property, moisture resistance, adhesion to the lid sheet, etc., a multilayer resin film in which polyvinylidene chloride (PVDC) is laminated by coating on the above resin film, or polyethylene, polypropylene, etc. A multilayer resin film laminated with a cyclic olefin copolymer, a fluororesin, or the like can also be used.

The paper base material can impart moldability, bending resistance, rigidity, etc., and is, for example, a strong size bleached or unbleached paper base material for a paper layer, or pure white roll paper, kraft paper, etc. Paper base materials such as paperboard, coated paper, processed paper, and milk base paper, and others can be used.
As the paper substrate, a paper substrate having a basis weight of about 30 g / m ² to 600 g / m ² is preferable, and a paper substrate having a basis weight of about 50 g / m ² to 450 g / m ² is more preferable.

The resin film used for the base material may have workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy, and antifungal properties, if necessary. , Plastic compounding agents such as lubricants, cross-linking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. for the purpose of improving and modifying electrical properties, strength, etc. Additives and the like can be added, and the amount thereof can be arbitrarily added according to the purpose within a range that does not adversely affect other performance.
The base material layer can be laminated with another layer via the adhesive layer. Further, if necessary, in order to strengthen the adhesive strength between the base material layer and the adhesive layer, the surface of the base material layer on the side in contact with the adhesive is subjected to corona discharge treatment, ozone treatment, plasma treatment, and glow discharge. It is also possible to perform physical surface treatment such as treatment and sandblasting treatment, and chemical surface treatment such as oxidation treatment using chemicals in advance.

≪Print layer≫
The print layer is, for example, letters, numbers, figures, symbols, patterns, patterns for decoration, display of contents, display of expiration date, display of manufacturers, sellers, etc., and for giving a sense of beauty. Etc. are visually shown, and a desired design pattern can be formed.
The printing layer is preferably formed on one side or both sides of the base material layer by a printing method such as a gravure printing method or a flexographic printing method. The print layer may be provided on the entire surface of the surface to be printed, or may be provided on a part of the surface to be printed.
If the print layer is formed inside the oxygen-absorbing laminate, the adhesion of the print layer can be improved, and ink rubbing or peeling of the print layer due to external impact or friction can be suppressed.
When the oxygen-absorbing packaging material for molded parts has a printed layer, it is preferable that the layer outside the printed layer at the time of container formation is transparent so that the printed layer can be visually recognized.

≪General-purpose adhesive layer≫
A general-purpose adhesive layer or anchor coat layer can be included between the layers constituting the oxygen-absorbing laminate.
The general-purpose adhesive layer may be, for example, a layer (extruded resin layer) formed by a (co) extrusion laminating method, a T-die (co) extrusion method, or the like in which an adhesive resin composition is melt-extruded. It may be a layer (dry laminate layer) formed by dry lamination using a dry laminate adhesive.
Examples of the resin contained in the adhesive resin composition include a polyolefin resin and an unsaturated carboxylic resin such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Acid-modified polyolefin-based resins, polyvinyl acetate-based resins, poly (meth) acrylic-based resins, polyvinyl chloride-based resins, and other resins that have been acid-modified by graft polymerization or copolymerization using acids or their anhydrides. Can be used. These resins can be used alone or in combination of two or more.

Specific examples of the polyolefin-based resin include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, and both ethylene-α and olefins polymerized using a metallocene catalyst. Polymers, polypropylene, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ionomer resins, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene -Methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene (co) polymer, butene (co) polymer, polyisoprene, ethylene-acrylic acid copolymer, ethylene-methacrylate copolymer, polynorbonene Cyclic olefin (co) polymer and the like can be mentioned. The copolymer may be a random or block copolymer.

The above-mentioned polyolefin-based resin can contain a resin derived from fossil fuel and / or a resin synthesized by using a raw material derived from a plant. By containing a plant-derived polyolefin resin synthesized using a plant-derived raw material, the environmental load can be reduced.
As the plant-derived polyolefin resin, one having an appropriate density and MFR can be selected according to the physical properties of the fossil fuel-derived polyolefin resin to be used in combination and the use of the sealant layer.
The content of the plant-derived polyolefin resin in the sealant layer A or B is preferably 40% by mass or more and 100% by mass or less. If it is smaller than the above range, the degree of biomass of the sealant layer A or B or the laminate will be low, and the effect of reducing the environmental load will be low.
The biomass degree of the oxygen-absorbing laminate of the present invention is preferably 10% or more and 50% or less. If it is smaller than the above range, the reduction in environmental load is small, and if it is larger than the above range, the hand-cutting property and drop impact resistance of the laminated body are likely to decrease.
Further, the biomass degree of the sealant layer A or B is preferably 10% or more and 20% or less. If it is smaller than the above range, the reduction in environmental load is small, and if it is larger than the above range, the hand-cutting property and drop impact resistance of the laminated body are likely to decrease.
When the sealant layer A or B has a multi-layer structure, the sealant layer A or B may have a layer containing a plant-derived polyolefin resin and a layer not containing a plant-derived polyolefin resin. For example, it is preferable that the outer surface layer of the sealant layer A or B, which is the outermost surface of the laminate, does not contain a plant-derived polyolefin resin. Furthermore, when the sealant layer A or B has a multi-layer structure of three or more layers, the outer surface layer which is the outermost surface of the laminate and the inner surface layer in contact with the other layer contain a plant-derived polyolefin resin. However, it is preferable that the inner layer contains a plant-derived polyolefin resin.

The polyolefin-based resin is classified into, for example, a polyethylene-based resin or a polypropylene-based resin according to the skeleton of the monomer used in the synthesis of the polyolefin, and may be a copolymer. In the present invention, "based resin" is added as a generic term for various types, and for example, it is also referred to as polyethylene-based resin as a generic term for various types of polyethylene.
The polyolefins produced by polymerization using α-olefins such as ethylene, propene, 1-butene, 1,3-butadiene, and 1-hexene as raw materials are polyethylene-based resins, polypropylene-based resins, and polybutylene-based resins, respectively. It is called a resin, a polybutadiene resin, a polyhexene resin, or the like.

In the general-purpose adhesive layer, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, antiblocking agents, flame retardant agents, cross-linking agents, colorants and the like are added as long as the characteristics of the present invention are not impaired. Can include agents.
The thickness of the general-purpose adhesive layer is not particularly limited, but is preferably 1 g / m ² or more, 20 g / m ² or less, or 1 μm or more and 20 μm or less. By setting the thickness of the extruded resin layer within the above numerical range, stable adhesive strength can be obtained.
Specific examples of the dry laminating adhesive constituting the general-purpose adhesive layer formed by the dry laminating include a two-component curable urethane-based adhesive, a polyester urethane-based adhesive, and a polyether urethane-based adhesive. , Acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, epoxy adhesives, rubber adhesives, etc. can be used.

The anchor coat layer is a layer formed by applying an anchor coat agent and drying it, and can improve the adhesion between adjacent layers.
Examples of the anchor coating agent include any resin having a heat resistant temperature of 135 ° C. or higher, for example, an anchor coating agent made of a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, polyethyleneimine, or the like.
Among the above, in particular, a curable anchor coating agent containing a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups in one molecule as a main agent and an isocyanate compound as a curing agent. Is preferable.
Further, a silane coupling agent may be used in combination, or nitrocellulose may be used in combination to enhance heat resistance.
The thickness of the anchor coat layer is not particularly limited, but is preferably 0.05 μm or more and 1 μm or less, for example.

≪Functional layer≫
As the functional layer, it has a barrier property against oxygen gas, water vapor, etc., and / or has little adsorption of fragrance components and the like contained in the contents to be filled and packaged, and is rich in fragrance retention, etc., and further causes discoloration, offensive odor, etc. Examples thereof include a layer made of a resin having no property and capable of extruding, and a layer made of a light-shielding material (light-shielding layer).

Specific examples of the above resin include polyacrylic resin, polymethacrylic resin, polyacrylonitrile resin, polymethacrylic nitrile resin, polystyrene resin, polycarbonate resin, polyethylene terephthalate resin, and ethylene thereof. Resins in which a part of the component and / or the terephthalate component is copolymerized or modified with another di or higher polyhydric alcohol component or dicarboxylic acid component, polyester resin such as polyethylene naphthalate resin, polyamide resin, ethylene- Resins such as a saponified product of a vinyl acetate copolymer, a polyvinyl alcohol-based resin, a polyvinyl chloride-based resin, a polyvinylidene chloride-based resin, and the like can be used.
Among the above resins, it is preferable to use a resin having a fragrance-retaining property and a barrier property against oxygen gas, water vapor, etc., and specifically, for example, a saponified product of an ethylene-vinyl acetate copolymer or a polyamide-based resin. It is preferable to use a resin, a polyacrylonitrile-based resin, a polyester-based resin, or the like, which is rich in fragrance-retaining properties and barrier properties.

The above resin can contain a resin derived from fossil fuel and / or a resin synthesized by using a raw material derived from a plant. By containing a plant-derived resin synthesized using a plant-derived raw material, the environmental load can be reduced.
As the plant-derived resin, one having a suitable density and MFR can be selected according to the physical characteristics of the fossil fuel-derived resin to be used in combination and the use of the functional layer.
The content of the plant-derived resin in the functional layer is preferably 40% by mass or more and 100% by mass or less. If it is smaller than the above range, the biomass level of the functional layer or the laminate will be low, and the effect of reducing the environmental load will be low.
When the functional layer has a multi-layer structure, the functional layer may have a layer containing a plant-derived resin and a layer not containing a plant-derived resin. For example, the outer surface layer, which is the outermost surface of the laminate, preferably does not contain a plant-derived resin. Furthermore, when the reinforcing layer has a multi-layer structure of three or more layers, it is preferable that the layers on both surfaces of the functional layer do not contain the plant-derived resin and the inner layer contains the plant-derived resin.

The light-shielding layer is a layer provided to prevent ultraviolet rays and / or visible light from reaching the contents.
The light-shielding layer is a white ink whose main component is titanium oxide, a black ink whose main component is carbon black, a gray ink whose main component is aluminum paste, and a colorant-colored resin which is light-shielded by adding pigments and dyes. It can be formed by using a film, a metal foil, a metal vapor deposition film, or the like.
As described above, when a metal foil such as an aluminum foil is used as the barrier layer, the barrier layer can also serve as a light-shielding layer.
These light-shielding materials can be used alone or in combination of two or more.
When white ink, black ink, or gray ink is used, the thickness of the light-shielding layer is preferably 4 μm or more and 12 μm or less, and more preferably 5 μm or more and 9 μm or less.
In the case of aluminum foil, it is preferably 5 μm to 30 μm, in the case of a metal vapor deposition film, it is preferably 50 Å to 3000 Å, more preferably 100 Å to 1000 Å, and in the case of a colorant colored resin film, it is preferably 5 μm to 300 μm, and 10 μm to 10 μm. 100 μm is more preferable.

≪Reinforcement layer≫
The reinforcing layer is a layer that imparts mechanical strength, deformation resistance, drop impact resistance, pinhole resistance, heat resistance, sealing property, quality maintainability, workability, hygiene, etc. to the laminated body. ..
The reinforcing layer may be formed of any of an extruded or inflation-formed resin film, a resin-coated film, synthetic paper, or the like.

Specific examples of the resin contained in the reinforcing layer include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer weight. Combined, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin , Vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylic nitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butagen-styrene copolymer (ABS) (Resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, kneaded product of ethylene-vinyl acetate copolymer, fluororesin, diene resin, polyacetal resin, polyurethane resin, cellulose, Known resins such as nitrocellulose and others can be used.

The above resin can contain a resin derived from fossil fuel and / or a resin synthesized by using a raw material derived from a plant. By containing a plant-derived resin synthesized using a plant-derived raw material, the environmental load can be reduced.
As the plant-derived resin, one having a suitable density and MFR can be selected according to the physical characteristics of the fossil fuel-derived resin to be used in combination and the use of the reinforcing layer.
The content of the plant-derived resin in the reinforcing layer is preferably 40% by mass or more and 100% by mass or less. If it is smaller than the above range, the biomass level of the reinforcing layer or the laminate will be low, and the effect of reducing the environmental load will be low.
When the reinforcing layer has a multi-layer structure, the reinforcing layer may have a layer containing a plant-derived resin and a layer not containing a plant-derived resin. For example, the outer surface layer, which is the outermost surface of the laminate, preferably does not contain a plant-derived resin. Furthermore, when the reinforcing layer has a multi-layer structure of three or more layers, it is preferable that the layers on both surfaces of the reinforcing layer do not contain the plant-derived resin and the inner layer contains the plant-derived resin.

Further, the resin film may be unstretched or stretched in a uniaxial or biaxial direction.
The thickness of the reinforcing layer is not particularly limited, but can be selected and used from the range of several μm to 300 μm.

<How to make an oxygen-absorbing laminate>
A method for producing an oxygen-absorbing laminate using the above-mentioned materials will be described. The production method shown below is an example and does not limit the present invention.
Lamination of each layer constituting the oxygen-absorbing laminate is a laminating method used when manufacturing ordinary packaging materials, for example, wet lamination method, dry lamination method, solvent-free dry lamination method, extrusion lamination method, T. It can be carried out by any method such as a die co-extrusion molding method, a co-extrusion lamination method, an inflation method, and the like.
The oxygen-absorbing laminate of the present invention has a chemical function, an electrical function, a magnetic function, a mechanical function, a friction / wear / lubrication function, an optical function, a thermal function, a surface function such as biocompatibility, etc. It is also possible to perform secondary processing for the purpose of imparting.
Examples of secondary processing include embossing, painting, bonding, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, etc.) Coating, etc.) and the like. Further, the laminated body of the present invention can be subjected to laminating processing (dry laminating or extruded laminating), bag making processing, and other post-treatment processing.

Then, when performing the above lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the surface of each layer. Further, for example, an anchor coating agent such as isocyanate-based (urethane-based), polyethyleneimine-based, polybutagen-based, organic titanium-based, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinylacetate-based, cellulose-based, etc. Anchor coating agents such as adhesives for laminating such as, etc. can be arbitrarily used.

As long as the base material layer, the oxygen barrier layer, the oxygen-absorbing adhesive layer, and the sealant layer are laminated in this order, the order of formation and lamination of each layer may be arbitrary.
For example, a case of producing an oxygen-absorbing laminate for molded parts having a layer structure of a base material layer / oxygen barrier layer / oxygen-absorbing adhesive layer / sealant layer will be described.
For example, first, an oxygen barrier layer is formed on the corona-treated surface of the base material layer.
Next, the oxygen-absorbing adhesive composition is applied to the laminated oxygen barrier layer and dried if necessary to form the oxygen-absorbing adhesive layer.
Then, a sealant film for the sealant layer is adhered on the oxygen-absorbing adhesive layer to form the sealant layer.
Then, an aging process is performed as necessary.
In this way, an oxygen-absorbing laminate for molded parts can be obtained.

<< Oxygen-absorbing packaging material for blister packaging >>
The oxygen-absorbing packaging material is a packaging material for oxygen-absorbing molded parts made from an oxygen-absorbing laminate for molded parts.
The oxygen-absorbing packaging material may further contain layers having various functions, if necessary.

<Oxygen-absorbing molded parts for blister packaging containers>
The oxygen-absorbing molded part of the present invention is a molded part for a blister packaging container made from the oxygen-absorbing packaging material for a molded part of the present invention. In addition, various shape designs and print decorations can add value.
The oxygen-absorbing molded part may be, for example, a squeezed portion constituting a top portion in a blister container or a bottom component in a PTP packaging container which is a form of a blister container, and is used for accommodating the contents. It has a recess and a flange portion for heat-sealing the lid component, and has a tray-like shape, for example.

<Method of manufacturing oxygen-absorbing molded parts for blister packaging containers>
The oxygen-absorbing molded part is produced by molding the oxygen-absorbing packaging material for a molded part of the present invention into a shape and size according to the contents to be accommodated. Specific examples of the molding method include a sheet molding method and the like.

<Oxygen-absorbing blister packaging container>
The oxygen-absorbing blister packaging container of the present invention is a blister packaging container manufactured by using the oxygen-absorbing molded parts of the present invention. For example, as shown in FIG. 3, it is a packaging container manufactured in combination with a lid part or the like, and may be a packaging container of various forms. Specific examples thereof include a molded container and a squeezed container for ham. Be done. In addition, various shape designs and print decorations can add value.
As one form of the blister packaging container, there is a PTP (Press Through Package) packaging container, which is often used for storing tablet-type pharmaceutical products, for example, and pressure is applied from the molded part side to push the lid part together with the tablet to make the tablet simple. Can be taken out. The oxygen-absorbing blister packaging container of the present invention may be in the form of a PTP packaging container.
In the oxygen-absorbing blister packaging container, in the oxygen-absorbing molded part, the sealant layer is heat-sealed to the lid part, and the oxygen barrier layer is located outside the container than the sealant layer.
The lid component is not particularly limited, but it is preferable to have a heat seal layer for heat sealing with the molded component. The shape of the lid component is, for example, a film shape, and exhibits a shape that matches the outer periphery of the flange portion of the molded component, a shape that is one size larger than the outer periphery, or a shape that partially protrudes from the outer periphery. The layer structure of the lid component is not particularly limited, but it is preferable to have a heat-sealing layer for heat-sealing with the molded component, for example, a layer such as PET / polyamide / easy peel PP sealant layer. It can be formed from a packaging material that includes a composition.
The recesses in the oxygen-absorbing blister packaging can contain the contents, which are done before the lid part and the molded part are heat-sealed, and after the contents are housed, the flange of the molded part. The part and the film-shaped lid component can be bonded by heat sealing or adhesive, and the contents can be protected by airtight sealing. Then, the contained contents can be taken out by peeling off the lid parts.

<Method of manufacturing oxygen-absorbing blister packaging container>
The oxygen-absorbing blister packaging container can be produced, for example, by the following production method. The examples given below are merely examples of the method for producing the oxygen-absorbing blister packaging container of the present invention, and the present invention is not limited thereto.
In order to prepare the oxygen-absorbing blister packaging container shown in FIG. 3, first, the film-shaped lid component shown in FIG. 3 is prepared, and the tray shown in FIG. 3 is used using the oxygen-absorbing packaging material. The shaped molded part is molded, the lid part is placed so that the sealant layer of the lid part and the sealant layer of the molded part face each other, and the lid part and the molded part are heat-sealed at the flange portion of the molded part.
Here, in the above, when the lid part is placed on the molded part, one lid part may be placed on one molded part and heat-sealed, and one lid part may be placed on two or more molded parts. It may be placed and heat-sealed. Further, the two or more molded parts may be individually cut or may be connected.

Then, the lid part is cut into a shape that matches the outer circumference of the flange portion of the molded part, a shape that is one size larger than the outer circumference in an annular shape, or a shape that partially protrudes.
As another manufacturing method, in the above, the lid part is previously cut into a shape that matches the outer circumference of the flange portion of the molded part, a shape that is one size larger than the outer circumference in an annular shape, or a shape that partially protrudes. , May be heat-sealed by placing it on a molded part.
In the case of manufacturing an oxygen-absorbing blister packaging container filling containing and packaging the contents, the contents are stored in the recesses of the molded parts before the heat sealing, and then the sheet seal is applied. It is preferable to do it.
In the above, as the heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, and a flame seal can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Raw materials>
The main raw materials used in the examples are as follows.
[Raw material for oxygen-absorbing compounds]
-Polypropylene ether diol 1: SANNIX PP-1000 manufactured by Sanyo Chemical Industries, Ltd. Number average molecular weight 1000.
-Polypropylene ether diol 2: SANNIX PK-400 manufactured by Sanyo Chemical Industries, Ltd. Number average molecular weight 400.
-Hydroxy group terminal polyisoprene 1: Polyip manufactured by Idemitsu Kosan Co., Ltd. Number average molecular weight 2
500.
Hydroxyl-terminated polybutadiene 1: Poly bd R15HT manufactured by Idemitsu Kosan Co., Ltd. Number average molecular weight 1200. Hydroxyl-terminated 1,2-addition polymer of 1,3-butadiene.
-Toluene diisocyanate 1: Coronate T-65 manufactured by Tosoh Corporation.
-Oxygen-absorbing compounds 1: 3a, 4,5,6,7,7a-hexahydro-4,7-methano-1H-inden-6-ol.
-Oxidation-promoting catalyst solution 1: Octop AE manufactured by Hope Pharmaceutical Co., Ltd. A 4% ethyl acetate solution of cobalt octylate, which is an oxidation-promoting catalyst.
-Oxidation-promoting catalyst solution 2: Acetop Mn (III) manufactured by Hope Pharmaceutical Co., Ltd. A 10% ethyl acetate solution of acetylacetone manganese (III), which is an oxidation-promoting catalyst.

[General-purpose adhesive]
-DL Adhesive 1: A two-component curable polyester urethane adhesive manufactured by Rock Paint Co., Ltd. [Film for base material layer and barrier layer]
-PET film 1: Biaxially stretched PET film manufactured by Toyobo Co., Ltd., E5200, 12 μm thick.
-PVC / PVDC composite film 1: F-9459 manufactured by Mitsubishi Plastics Co., Ltd. 240 μm thickness. Both surfaces are PVC layers, and the intermediate layer contains a PVDC layer.
-Aluminum foil 1: 30 μm thick aluminum foil.

[Ink for print layer]
-Gravure Ink 1: Finale manufactured by DIC Graphics Co., Ltd.

[Film for sealant layer]
-LLDPE film 1: N-165 manufactured by Aicello Corporation. Unstretched LLDPE film. 50 μm thick.

<Preparation of raw material solution>
(Synthesis of polyol 1 and preparation of polyol solution 1)
The following raw materials were added to a flask equipped with a nitrogen introduction tube, a stirrer, a rectification column, and a condenser, and dehydration condensation was carried out at an internal temperature of 180 to 200 ° C. while stirring.
Ethylene glycol 53.8 parts by mass Neopentyl glycol 180.3 parts by mass 1,6-hexanediol 204.6 parts by mass Isophthalic acid 287.8 parts by mass Adipic acid 273.5 parts by mass Reaction solution Solid acid value is 15 mgKOH / When it reached g, the dehydration reaction was further promoted at 200 to 240 ° C. while blowing nitrogen.
When the acid value of the solid content of the reaction solution became 10 mgKOH / g or less, the internal pressure was reduced to 30 Torr and the reaction was continued.
When the acid value of the solid content of the reaction solution became 3 mgKOH / g or less, the reaction was terminated and the mixture was cooled to room temperature to obtain polyol 1.
The number average molecular weight of the obtained polyester polyol, polyol 1, was 2000.
Then, the polyol 1 was dissolved in ethyl acetate to prepare a solid content of 60% by mass to obtain a polyol solution 1.

(Synthesis of polyol 2 and preparation of polyol solution 2)
The following raw materials were placed in a flask equipped with a nitrogen introduction tube, a stirrer, and a condenser, heated while stirring, and a reflux reaction was carried out for 6 hours.
Polypropylene ether diol 1 300.0 parts by mass Polypropylene ether diol 2 250.0 parts by mass Toluene diisocyanate 1 104.0 parts by mass Ethyl acetate 163.5 parts by mass The absorption of isocyanate groups is completely eliminated in the infrared absorption spectrum. Was confirmed, the synthesis was terminated, and the mixture was cooled to obtain polyol 2.
The number average molecular weight of the obtained polyol 2 which is an extended urethane chain polyol was 2000.
Then, the polyol 2 was dissolved in ethyl acetate to prepare a solid content of 60% by mass to obtain a polyol solution 2.

(Preparation of polyisocyanate solution 1)
The following raw materials were added to a flask equipped with a nitrogen introduction tube, a stirrer, and a condenser and stirred to obtain a polyisocyanate solution 1 having a solid content of 60% by mass.
Hexamethylene diisocyanate burette 100.0 parts by mass Ethyl acetate 66.7 parts by mass

<Synthesis of oxygen-absorbing compounds and preparation of oxygen-absorbing compound solutions>
[Oxygen Absorbent Compound 2]
First, the following raw materials were added to a flask equipped with a nitrogen introduction tube, a stirrer, and a condenser, and the reaction was carried out at an internal temperature of 80 to 90 ° C. for 8 hours while stirring.
Oxygen-absorbing compound 1 100.0 parts by mass Isophorone diisocyanate 74.0 parts by mass After confirming that the absorption of isocyanate groups has completely disappeared in the infrared absorption spectrum, the synthesis is terminated, and the mixture is cooled to absorb oxygen. Compound 2 was obtained.
Then, the oxygen-absorbing compound 2 was dissolved in ethyl acetate to prepare an oxygen-absorbing compound solution 2 having a solid content of 80% by mass.

[Oxygen absorbent compound 3]
First, the following raw materials were added to a flask equipped with a nitrogen introduction tube, a stirrer, and a condenser, and the reaction was carried out at an internal temperature of 80 to 90 ° C. for 8 hours while stirring.
Oxygen-absorbing compound 1 100.0 parts by mass Polyisocyanate solution 1 212.5 parts by mass Synthesized after confirming that the content of NCO groups in the solid content of the reaction solution by the amine equivalent method was approximately 0.64% by mass. Was terminated, and the mixture was cooled to remove the solvent to obtain an oxygen-absorbing compound 3.
Then, the oxygen-absorbing compound 3 was dissolved in ethyl acetate to prepare an oxygen-absorbing compound solution 3 having a solid content of 60% by mass.

[Oxygen Absorbent Compound 4]
First, the following raw materials were added to a flask equipped with a nitrogen introduction tube, a stirrer, and a condenser, and the reaction was carried out at an internal temperature of 80 to 90 ° C. for 8 hours while stirring.
Oxygen-absorbing compound 1 100.0 parts by mass Polyol solution 1 682.3 parts by mass Polyisocyanate solution 1 265.6 parts by mass Confirm that the absorption of isocyanate groups has completely disappeared in the infrared absorption spectrum before synthesizing. It was terminated and cooled to remove the solvent to give the oxygen-absorbing compound 4.
Then, the oxygen-absorbing compound 4 was dissolved in ethyl acetate to prepare an oxygen-absorbing compound solution 4 having a solid content of 60% by mass.

[Oxygen Absorbent Compound 5]
An oxygen-absorbing compound 5 was obtained by operating in the same manner as in the above oxygen-absorbing compound 4 except that the polyol solution 2 was used instead of the polyol solution 1.
Then, the oxygen-absorbing compound 5 was dissolved in ethyl acetate to prepare an oxygen-absorbing compound solution 5 having a solid content of 60% by mass.

[Oxygen Absorbent Compound 6]
The following raw materials were placed in a flask equipped with a nitrogen introduction tube, a stirrer, and a condenser, and the reaction was carried out at an internal temperature of 80 to 90 ° C. for 6 hours while stirring.
Polyisoprene at the hydroxyl group 1 100.0 parts by mass Isophorone diisocyanate 4.7 parts by mass After confirming that the absorption of isocyanate groups has completely disappeared in the infrared absorption spectrum, the synthesis is terminated, and the mixture is cooled to form a urethane polyol. An oxygen-absorbing compound 6 was obtained.
The number average molecular weight of the obtained oxygen-absorbing compound 6 was 7000.
Then, the oxygen-absorbing compound 6 was dissolved in ethyl acetate to prepare an oxygen-absorbing compound solution 6 having a solid content of 60% by mass.

Table 2 summarizes the preparation composition of the reaction solution when the oxygen-absorbing compounds 2 to 6 were synthesized.
In addition, the preparation compositions of the oxygen-absorbing compound solutions 2 to 6 are summarized in Table 3.

<Preparation of oxygen-absorbing adhesive composition>
(Preparation of Oxygen Absorbent Adhesive Composition A1)
The following raw materials were mixed and homogenized at room temperature to obtain an oxygen-absorbing adhesive composition A1 and various evaluations were carried out.
Oxygen-absorbing compound solution 2 100 parts by mass Polyol solution 1 100 parts by mass Polyisocyanate solution 1 10 parts by mass Oxidation-promoting catalyst solution 1 1 part by mass Ethyl acetate 140 parts by mass

(Preparation of Oxygen Absorbent Adhesive Compositions A2 to A9 and B1 to B2)
According to the formulations shown in Tables 4 and 5, the oxygen-absorbing adhesive compositions A1 and the oxygen-absorbing adhesive compositions A2 to A9 and B1 to B2 were obtained in the same manner as in the oxygen-absorbing adhesive composition A1.

[Example 1]
(Manufacturing and evaluation of oxygen-absorbing laminate for molded parts)
The oxygen-absorbing adhesive composition A1 is applied to the PVC / PVDC composite film 1 as the base material layer so that the dry coating amount is 3 g / m ² , dried, and then bonded to the LLDPE film 1 for the sealant layer. After aging treatment at 40 ° C. for 3 days, an oxygen-absorbing laminate for molded parts having the following layer structure was prepared and various evaluations were carried out.
Layer structure: PPVC / PVDC composite film 1 (240 μm) / oxygen-absorbing adhesive composition A1 (3 g / m ² ) / LLDPE film 1 (50 μm)

(Preparation and evaluation of oxygen-absorbing blister packaging container)
First, a heat adhesive containing a vinyl chloride-vinyl acetate-maleic acid copolymer resin as a main component is applied to the matte surface of an aluminum foil having a thickness of 17 μm by a gravure coat so that the dry coating amount is 5.5 g / m ² . Then, the coating film was dried at a surface temperature of about 150 ° C. and a drying time of about 4 seconds to form a heat-adhesive layer to prepare a packaging material for a lid.
On the other hand, using a blister pack molding machine (manufactured by CKD Corporation), from the oxygen-absorbing laminate for molded parts obtained above, the recess and the fringe portion are formed so that the sealant layer is in contact with the contents at the recess. An oxygen-absorbing molded part having was produced.
Then, the sealant layers of the packaging material for the lid obtained above were overlapped with each other so as to face each other, and the fringe portion was heat-sealed to obtain an oxygen-absorbing blister packaging container, and various evaluations were carried out.

[Examples 2 to 9, Comparative Examples 1 to 3]
Except that the oxygen-absorbing adhesive composition A1 of Example 1 was changed to any of the oxygen-absorbing adhesive compositions A2 to A9, B1, B2, and DL adhesive 1 according to the description in Tables 7 and 8. By operating in the same manner as in Example 1, an oxygen-absorbing laminate for molded parts, an oxygen-absorbing molded part, and an oxygen-absorbing blister packaging container were obtained and evaluated in the same manner.

[Example 10]
(Manufacturing and evaluation of oxygen-absorbing laminate for molded parts)
First, the DL adhesive 1 was applied and dried on the corona-treated surface of the PET film 1 so that the dry coating amount was 3 g / m ² , and then the aluminum foil 1 and the dry laminate were bonded together.
Then, the oxygen-absorbing adhesive composition A1 is applied and dried on the surface of the laminated aluminum foil so that the dry coating amount is 3 g / m2, and then bonded to the LLDPE film 1 and cured at 40 ° C. for 3 days. Then, an oxygen-absorbing packaging material for molded parts was prepared and various evaluations were carried out.
Layer structure: PET film 1 (12 μm) / DL adhesive 1 (3 g / m ² ) / Aluminum foil 1 (30 μm) / Oxygen scavenger composition A1 (3 g / m ² ) / LLDPE film 1 (50 μm)

(Preparation and evaluation of oxygen-absorbing blister packaging container)
An oxygen-absorbing laminate for molded parts, an oxygen-absorbing molded part, and an oxygen-absorbing blister package container were obtained by operating in the same manner as in Example 1, and evaluated in the same manner.

[Comparative Example 4]
Oxygen-absorbing laminate for molded parts, oxygen-absorbing molded parts, oxygen-absorbing blister packaging container are operated in the same manner as in Example 9 except that the oxygen-absorbing adhesive composition A1 is changed to DL adhesive 1. Was obtained and evaluated in the same manner.

<Summary of results>
The oxygen-absorbing laminates or oxygen-absorbing blister packs for molded parts of all examples showed an excellent balance between laminate strength, oxygen absorption and low odor.
On the other hand, the laminate or the blister packaging container of the comparative example showed inferior results in any of the laminate strength, the oxygen absorption amount, and the low odor property.

<Evaluation method>

[Oxygen absorption]
The obtained lid component and the flange portion of the tray-shaped molded component having a recess were replaced with nitrogen and heat-sealed to seal.
Then, inside the container, 1400 cc / m ² of air is used for the inner area of the container with a syringe, and the injection part is repaired with adhesive tape. The oxygen concentration was measured by sampling with, and the oxygen absorption amount was calculated. The oxygen concentration was measured using a zirconia-type oxygen concentration meter (manufactured by Toray Industries, Inc.).

[Laminate strength]
A strip-shaped test piece having a width of 15 mm was prepared from the obtained oxygen-absorbing laminate, and the laminate strength between the layers via the oxygen-absorbing adhesive layer was measured at a tensile speed of 50 mm / min using a tensile tester. The laminate strength was measured.

[Odor sensory evaluation]
The odor in the blister packaging container after measuring the oxygen absorption amount was sniffed, and the odor was judged according to the following criteria. The odor derived from the sealant layer was excluded from the determination.
Evaluation criteria:
0: Odorless 1: Faint odor 2: Weak odor 3: Medium odor 4: Strong odor

1 Oxygen-absorbing laminate for molded parts, oxygen-absorbing packaging material for molded parts 2 Base material layer 3 Oxygen barrier layer 4 Oxygen-absorbing adhesive layer 5 Sealant layer 7 General-purpose adhesive layer 8 Reinforcing layer 10 Oxygen-absorbing blister Packaging container 11 Oxygen scavenging molded parts 12 Contents storage recess 13 Flange part 14 Lid parts

Claims (17)

Oxygen absorbency for molded parts used in molded parts of blister packaging containers, including at least a layer structure in which a base material layer, an oxygen barrier layer, an oxygen absorbing adhesive layer, and a sealant layer are laminated in this order. It ’s a laminate,
The oxygen-absorbing adhesive layer is a layer formed from the oxygen-absorbing adhesive composition, and is a layer.
The oxygen-absorbing adhesive composition contains at least an oxygen-absorbing compound and an oxidation-promoting catalyst.
The oxygen-absorbing compound has one or more unsaturated five-membered rings and has one or more unsaturated five-membered rings.
Any bond between the five carbon atoms constituting the unsaturated five-membered ring is a carbon-carbon double bond.
A monovalent and / or divalent or higher electron donating organic group 1 is bonded to the unsaturated five-membered ring.
When the unsaturated five-membered ring is one, the five-membered ring or the organic group 1 is a functional group having active hydrogen, or the active hydrogen of the functional group having active hydrogen becomes a monovalent organic group 2. Has substituted groups and
When there are two or more unsaturated five-membered rings, the unsaturated five-membered rings have a divalent value or higher that replaces the active hydrogen of each of the five-membered rings or the active hydrogen group on the organic group 1. Bonded via organic group 2,
Oxygen-absorbing laminate for molded parts. The structure of the unsaturated five-membered ring or the structure consisting of the unsaturated five-membered ring and the organic group 1 is one or two selected from the group consisting of cyclopentadiene, dicyclopentadiene, norbornene, and derivatives thereof. It is derived from the above,
The oxygen-absorbing laminate for molded parts according to claim 1. The organic group 2 contains an isocyanate-based compound, or a structural portion derived from an isocyanate-based compound and a hydroxyl group-containing compound.
The oxygen-absorbing laminate for molded parts according to claim 1 or 2. The isocyanate-based compound is one or more selected from the group consisting of xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and derivatives thereof.
The oxygen-absorbing laminate for molded parts according to claim 3. The hydroxyl group-containing compound is selected from the group consisting of polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and urethane chain extension polyols thereof1. Seeds or more than one
The oxygen-absorbing laminate for molded parts according to claim 3 or 4. The organic group 2 does not have a crosslinkable functional group.
The oxygen-absorbing laminate for molded parts according to any one of claims 1 to 5. The organic group 2 has one or more crosslinkable functional groups.
The crosslinkable functional group is a hydroxyl group and / or an isocyanate group.
The oxygen-absorbing laminate for molded parts according to any one of claims 1 to 5. The oxygen-absorbing compound contains one or more selected from the group consisting of the compounds represented by the following formulas (1) to (4).
The oxygen-absorbing laminate for molded parts according to any one of claims 1 to 5.

(In the formula, a to e are each a number of 1 or more, and each of R ¹ , R ² and R ³ is an organic group having 1 or more carbon atoms and contains at least an alkylene and / or a phenylene structure, and further. One or more selected from the group consisting of polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and urethane chain extension polyols thereof. It can include the structure from which it is derived.) The oxygen-absorbing compound contains a compound represented by the following formula (5).
The oxygen-absorbing laminate for molded parts according to any one of claims 1 to 5.

(In the formula, f is a number of 0 or more, and each of ^R4 and R5 is an organic group having ¹ or more carbon atoms, which is an organic group containing at least an alkylene and / or a phenylene structure, and further has a polyvalent value. Derived from one or more selected from the group consisting of alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylic acid ester polyols, phenoxy resins, and urethane chain extension polyols thereof. Can include structure.) The oxidation-promoting catalyst is a compound containing a cation consisting of a peroxide or a transition metal.
The oxygen-absorbing laminate for molded parts according to any one of claims 1 to 9. The compound containing a cation composed of a transition metal is a metal soap composed of a transition metal compound capable of releasing a cation or complex composed of a transition metal and an anion or a ligand composed of a fatty acid.
The oxygen-absorbing laminate for molded parts according to any one of claims 1 to 10. The oxygen-absorbing adhesive composition further contains a denaturing agent.
The oxygen-absorbing laminate for molded parts according to any one of claims 1 to 11, wherein the modifier contains an isocyanate-based compound and / or a hydroxyl group-containing compound. The isocyanate-based compound is one or more selected from the group consisting of xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and derivatives thereof.
The oxygen-absorbing laminate for molded parts according to claim 12. The hydroxyl group-containing compound comprises one or more selected from the group consisting of polyester polyols, poly (meth) acrylic acid ester polyols, polyalkylene ether diols, and urethane chain extension polyols thereof.
The oxygen-absorbing laminate for molded parts according to claim 12 or 13. An oxygen-absorbing packaging material for molded parts of a blister packaging container, which is produced by using the oxygen-absorbing laminate for molded parts according to any one of claims 1 to 14. An oxygen-absorbing molded part of a blister-packed container manufactured by using the oxygen-absorbing packaging material for a molded part of the blister-packed container according to claim 15. An oxygen-absorbing blister-packed container manufactured by using the oxygen-absorbing molded part of the blister-packed container according to claim 16.
The oxygen barrier layer is a layer located outside the oxygen-absorbing adhesive layer.
Oxygen-absorbing blister packaging container.

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