JP2022014242A - Oxygen-absorbing laminate to be used for paper container for liquid - Google Patents

Abstract

To provide an oxygen-absorbing laminate to be used for a paper container for liquid, 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 and a paper container for liquid produced using the laminate.SOLUTION: An oxygen-absorbing laminate 1 for a paper container for producing a paper container for liquid at least includes a layer constitution with a paper 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 a specific oxygen-absorbing adhesive composition. The oxygen-absorbing adhesive composition at least contains an oxygen-absorbing compound and an oxidation accelerator catalyst.SELECTED DRAWING: Figure 1

Description

INDUSTRIAL APPLICABILITY The present invention suppresses deterioration of the contents due to oxygen by absorbing oxygen in the contents accommodating space and barrier property against oxygen gas from the outside with less generated odor, and heat retention, content resistance, etc. The present invention relates to an oxygen-absorbing laminate used for a liquid paper container, which has an excellent balance with sealing properties and is suitable for filling and packaging, and an oxygen-absorbing packaging material and an oxygen-absorbing paper container made from the oxygen-absorbing laminate. ..

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. It has been replaced with gas by gas, and an oxygen scavenger containing reduced iron powder etc. has been included.
However, these have problems such as insufficient performance, increased packaging cost, increased waste waste, performance only in a moist environment, and accidental ingestion. be.
Further, Patent Document 1 describes a packaging material using a resin having oxygen absorption and less generated odor, but this resin is insoluble in a polar solvent and does not have an active hydrogen group. It is a cyclododecene and is not suitable as a raw material for an adhesive to a packaging material made of a laminate.
Further, Patent Document 2 describes 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.
Patent Document 3 describes oxygen in 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 rings. Although an absorbent 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.
As a gas-barrier packaging material containing a paper base material, a paper base material (hereinafter, also referred to as “base paper”) having a gas barrier layer composed of a water-soluble polymer and an inorganic layered compound (Patent Document 4, Patent Document 4,). Patent Document 5), those having a barrier layer made of a specific vinyl alcohol-based polymer on a coating layer (Patent Documents 5 and 6) and the like are disclosed, and synthetic as a water vapor barrier packaging material containing a paper substrate is disclosed. A wrapping paper (Patent Document 7) having a moisture-proof layer composed of a resin latex, a wax and inorganic fine particles is disclosed.
However, packaging materials made by laminating or laminating a resin having a gas barrier property and a resin having a water vapor barrier property on a paper base material (base paper) meet various required qualities because there are restrictions on the types of resins that can be laminated. There was a problem that it could not be done.
On the other hand, there are few restrictions on the types of resins that can be used for packaging materials that have gas barrier properties and water vapor barrier properties by coating a paper base material (base paper) with a resin having gas barrier properties and a resin having water vapor barrier properties. Therefore, it is possible to meet various required qualities. However, when the moisture-proof layer of Patent Document 7 is provided on the packaging material having both the gas barrier property and the water vapor barrier property, for example, the packaging material having the gas barrier property of Patent Document 4 or Patent Document 5, good water vapor is good. Although the barrier property can be obtained, there is a problem that the gas barrier property cannot be obtained. Further, even when the gas barrier layer of Patent Document 4 or Patent Document 5 is provided on the moisture-proof paper having the water vapor barrier layer of Patent Document 7, it is not possible to obtain both sufficient gas barrier property and water vapor barrier property. rice field.

Japanese Patent No. 5873770 Japanese Patent No. 5671816 Japanese Patent No. 6555699 Japanese Unexamined Patent Publication No. 2009-184138 Japanese Unexamined Patent Application Publication No. 2003-094574 Japanese Patent No. 5331265 Japanese Unexamined Patent Publication No. 2005-162213

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 laminate used for liquid paper containers, which has an excellent balance of odor, low oxygen concentration, fragrance retention, content resistance, and filling and packaging properties, and packaging materials and liquid paper containers manufactured using the laminate. Is to provide.

（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。）
１１．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１～７の何れかに記載の、紙容器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。）
１２．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１～１１の何れかに記載の、紙容器用酸素吸収性積層体。
１３．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１～１１の何れかに記載の、紙容器用酸素吸収性積層体。
１４．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１～１３の何れかに記載の、紙容器用酸素吸収性積層体。
１５．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１４に記載の、紙容器用酸素吸収性積層体。
１６．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１３または１４に記載の、紙容器用酸素吸収性積層体。
１７．上記１～１６の何れかに記載の紙容器用酸素吸収性積層体を用いて作製された、紙容器用酸素吸収性包装材料。
１８．上記１７に記載の紙容器用酸素吸収性包装材料を用いて作製された液体用酸素吸収性紙容器であって、
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、
液体用酸素吸収性紙容器。 In order to solve the above problems, the present inventors have at least a laminated body including a layer structure in which a paper substrate layer, an oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer are laminated in this order. , Found that the above problem can be solved.
That is, the present invention is characterized by the following points.
1. 1. Oxygen absorbency for a paper container for producing a liquid paper container, which comprises a layer structure in which at least a paper base material layer, an oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer are laminated in this order. It ’s a laminated body,
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 paper containers.
2. 2. A reinforcing layer is further provided between the oxygen-absorbing adhesive layer and the sealant layer.
The oxygen-absorbing laminate for paper containers according to 1 above.
3. 3. The paper substrate layer contains a coated resin layer on the surface thereof.
The oxygen-absorbing laminate for paper containers according to 1 or 2 above.
4. 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 a paper container according to any one of 1 to 3 above.
5. 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 a paper container according to any one of 1 to 4 above.
6. 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 paper containers according to 5 above.
7. 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 paper containers according to 5 or 6 above.
8. The organic group 2 does not have a crosslinkable functional group.
The oxygen-absorbing laminate for a paper container according to any one of 1 to 7 above.
9. 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 a paper container according to any one of 1 to 7 above.
10. 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 a paper container according to any one of 1 to 7 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.)
11. The oxygen-absorbing compound contains a compound represented by the following formula (5).
The oxygen-absorbing laminate for a paper container according to any one of 1 to 7 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.)
12. The oxidation-promoting catalyst is a compound containing a cation consisting of a peroxide or a transition metal.
The oxygen-absorbing laminate for a paper container according to any one of 1 to 11 above.
13. 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 a paper container according to any one of 1 to 11 above.
14. The oxygen-absorbing adhesive composition further contains a denaturing agent.
The oxygen-absorbing laminate for a paper container according to any one of 1 to 13 above, wherein the modifier contains an isocyanate-based compound and / or a hydroxyl group-containing compound.
15. 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 paper containers according to 14 above.
16. 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 a paper container according to 13 or 14 above.
17. An oxygen-absorbing packaging material for a paper container, which is produced by using the oxygen-absorbing laminate for a paper container according to any one of 1 to 16.
18. An oxygen-absorbing paper container for liquids produced by using the oxygen-absorbing packaging material for paper containers according to 17 above.
The oxygen barrier layer is a layer located outside the oxygen-absorbing adhesive layer.
Oxygen-absorbing paper container for liquids.

According to the present invention, there is little generated odor, the barrier property against oxygen gas is excellent, the oxygen concentration in the content accommodating space is absorbed to reduce the oxygen concentration, the deterioration due to oxygen of the content is suppressed, and the heat seal property is low. A laminate used for liquid paper containers, which has an excellent balance of odor, low oxygen concentration, fragrance retention, content resistance, and filling and packaging properties, and packaging materials and liquid paper containers manufactured using the laminate. 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 a paper container of this invention. It is sectional drawing which shows one example of another aspect of the layer structure of the oxygen-absorbing laminated body for a paper container of this invention. It is a perspective view which shows an example of the oxygen-absorbing paper container of this invention. It is a front view which shows the blank plate used for manufacturing the oxygen-absorbing paper container shown in FIG.

The present invention 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 paper containers>
The oxygen-absorbing laminate for a paper container of the present invention is a laminate used for a liquid paper container, and has at least a paper substrate layer, an oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer. It includes a layer structure laminated in this order. Further, it is preferable to have a reinforcing layer between the oxygen-absorbing adhesive layer and the sealant layer.
Oxygen-absorbing packaging material for paper containers made from an oxygen-absorbing laminate for paper containers (hereinafter, may be abbreviated as oxygen-absorbing laminate) (hereinafter, abbreviated as oxygen-absorbing packaging material). When forming an oxygen-absorbing paper container for liquid (hereinafter, may be abbreviated as a liquid paper container or an oxygen-absorbing paper container) using the above, the sealant layer is heat-sealed. The oxygen barrier layer is located outside the oxygen-absorbing paper container for liquids rather than the oxygen-absorbing adhesive layer.
By locating the oxygen barrier layer outside the oxygen-absorbing adhesive layer, oxygen passing through the oxygen-absorbing paper container for liquid from the outside is reduced, and the oxygen-absorbing adhesive layer is oxygen in the content storage space. Can be absorbed to increase the efficiency of reducing the oxygen concentration.

The oxygen-absorbing laminate for paper containers can optionally include other layers having various functions.
For example, it can have another base material layer or a printing layer, and has various features such as deformation resistance, drop impact resistance, pinhole resistance, heat resistance, sealing property, quality maintainability, workability, hygiene, etc. A reinforcing layer for satisfying the above conditions can be included.
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.
Further, an adhesive resin layer for improving the interlayer adhesiveness can be included in each of the above layers or in each layer.

[Contents]
In the above, the content is a liquid, and examples thereof include beverages, alcoholic beverages such as alcoholic beverages and wine, soups, seasonings, shampoos, cosmetics, and the like.

<About each layer constituting the oxygen-absorbing laminate for paper containers>
≪Oxygen barrier layer≫
The oxygen barrier layer is an oxygen-absorbing paper container for liquids made from an oxygen-absorbing laminate for paper containers. It is a layer that suppresses the permeation of oxygen.
In the oxygen-absorbing paper container for liquids, 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 paper container for liquids, thereby causing oxygen-absorbing adhesion. The effect that the agent layer absorbs oxygen in the content accommodating portion of the oxygen-absorbing paper container for liquid and lowers the oxygen concentration can be enhanced.
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 4 μm to 40 μm, more preferably 6 μm or more and 12 μm or less, still more preferably 7 μm or more and 9 μm or less.
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), Ittrium (Y), Zinc (Zn), Vanadium (V), Barium (Ba), Chromium (Cr) and the like. ..

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 obtained 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. A mixed gas composed of an organic silicon compound as a gas, an oxygen gas, an inert gas, or the like can be introduced to 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 30 Å to 3
000 Å is preferable, and 100 Å to 300 Å is more preferable.
In the above, in the case of an inorganic thin-film deposition layer made of a metal oxide or an inorganic substance as a whole, 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, thereby improving the 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 vapor-deposited 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 1.0 cc / m ² · atm · day or less. Yes, more preferably 0.5 cc / m ² · atm · day or less, still more preferably 0.1 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 the adhesive resin 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, 1, 8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3- Examples thereof include diols such as pentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecandiol, and 2,2'-oxydiethanol, and glycerin, mannitol, and sorbitol.
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 A poly (meth) acrylic acid ester polyol is a (meth) acrylic acid ester (co) polymer having two or more hydroxyl groups.
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（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 (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. 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. Can include structures derived from.)

（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（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 1 or more (in the formula, each of b and c is 1 or more, R ² is an organic group having 1 or more carbon atoms, and has at least an alkylene and / or phenylene structure. One 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. Or it can include structures derived from two or more species.)

（式中、ｄとｅの各々は１以（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 (in the formula, each of d and e is 1 or more, R ³ is an organic group having 1 or more carbon atoms, and has at least an alkylene and / or phenylene structure. One 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. Or it can include structures derived from two or more species.)

[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 a layer for heat-sealing the oxygen-absorbing laminates when forming the oxygen-absorbing paper container for liquid, it is preferable to contain a resin having a heat-sealing property.

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 25 μm or more and 150 μm or less, and more preferably 40 μm or more and 70 μm or less.

(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.
Among the above resins, it is preferable to use a polyolefin resin from the viewpoint of adhesion, manufacturing cost and the like, and among the polyolefin resins, low density polyethylene, linear low density polyethylene and the like are particularly preferable.

It is preferable to use a plant-derived polyolefin resin as the raw material polyolefin resin for the heat-sealing polyolefin resin and the acid-modified polyolefin resin. However, it may contain a polyolefin resin derived from fossil fuel.
By using a plant-derived polyolefin resin, the environmental load can be reduced.
As the plant-derived resin, one having an appropriate density or MFR can be selected according to the physical characteristics of the fossil fuel-derived resin to be used in combination and the usage conditions of the laminate.
The content of the plant-derived polyolefin resin in the sealant layer is preferably 40% by mass or more and 100% by mass or less. If it is smaller than the above range, the effect of reducing the environmental load will be low.
When the sealant layer has a multi-layer structure, the sealant layer may include 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, which is the outermost surface of the laminate, does not contain a plant-derived polyolefin resin. Furthermore, when the sealant layer has a multilayer structure of three or more layers, it is preferable that the layers on both surfaces of the sealant layer do not contain the plant-derived polyolefin resin and the inner layer contains the plant-derived polyolefin resin. ..

(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, polyethylene-based resin is also referred to 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.

The polyolefin-based resin is classified into a fossil fuel-derived polyolefin resin and a plant-derived polyolefin resin according to the origin of the raw material monomer.
(Polyolefin resin derived from fossil fuel)
In the present invention, the fossil fuel-derived polyolefin resin is a polyolefin resin using a raw material monomer obtained by thermally decomposing naphtha obtained from fossil fuel as before, without using a plant-derived raw material monomer.
(Plant-derived polyolefin resin)
In the present invention, "plant-derived" means that carbon derived from a plant raw material is contained, and for example, it means that it is produced using a compound obtained from a plant as a raw material.
As a method for producing a plant-derived polyolefin resin, for example, first, according to a conventional method, sugar solution or starch obtained from plants such as sugar cane, corn, and sweet potato is fermented with microorganisms such as yeast to produce bioethanol. Then, this is heated in the presence of a catalyst to obtain ethylene and α-olefin (1-butene, 1-hexene, etc.) by an intramolecular dehydration reaction or the like.
Then, by using these as raw material monomers for polymerization and polymerizing in the presence of a conventional catalyst in the same manner as in the production of fossil fuel-derived polyolefin-based resins, plant-derived polyolefin-based resins can be produced. The catalyst and polymerization method at the time of polymerization are the same as those of the fossil fuel-derived polyolefin resin.
If necessary, fossil fuel-derived monomers can be used in combination with a part of the raw material monomer for polymerization or the copolymerized monomer.

(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.

≪Paper substrate layer≫
As a material for the paper base layer, for example, as a basic material constituting the paper base layer of a liquid paper container, it has excellent mechanical, physical, chemical, and other properties, and is particularly supportive. A general publicly known and public paper substrate having can be used.
The paper substrate 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 paper base material layer may further include a resin layer. The resin layer may be formed by applying a resin or a resin composition or by extrusion lamination, or may be formed by laminating a resin film.
For example, a coated resin layer having a size of 2 μm or more and 50 μm or less can be provided on the surface of the paper base material layer to improve the water resistance of the paper base material layer.

Specific resins include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins such as nylon, polyaramid resins, and polycarbonate resins. Examples thereof include tough thermoplastic resins such as polyacetal-based resins, fluororesins, and others.
When the coated resin layer is extruded, it is preferable to use a polyethylene resin, and it is particularly preferable to use LDPE.
The resin film made from the above resin can be either an unstretched film or a stretched film stretched in the uniaxial or biaxial direction.
Among the above, biaxially stretched PET film and biaxially stretched polypropylene film are preferably used.
Further, in order to improve moisture resistance and adhesion to other layers, a multilayer resin film obtained by laminating polyvinylidene chloride (PVDC) on the above resin film by coating, or polyethylene, polypropylene, cyclic olefin copolymer, fluorine. A multilayer resin film laminated with a resin or the like can also be used.
In addition, in order to improve the adhesiveness with the adjacent layer, the surface of the resin layer may be subjected to physical surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, sandblast treatment, etc., as necessary. Chemical surface treatment such as chemical treatment using chemicals and oxidation treatment may be performed.

(Paper base material)
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, milk base paper, barrier coated paper, etc. can be used.
The basis weight of the paper substrate is preferably 100 g / m ² or more and 500 g / m ² or less, and more preferably 120 g / m ² or more and 400 g / m ² or less. By setting the basis weight of the paper base material within the above numerical range, it is possible to improve the strength of the paper container manufactured by using the laminated body while maintaining the processability of the laminated body.
The paper base material layer may be a laminate of a plurality of these paper layers.

In addition, in order to improve the adhesiveness with the adjacent layer, the surface of the paper substrate may be subjected to physical surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, sandblast treatment, etc., if necessary. , Chemical surface treatment such as chemical treatment using chemicals and oxidation treatment may be performed.
Specific chemicals used in chemical treatment include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agents, water resistant agents, water retention agents, thickeners, lubricants and the like. These can be used alone or in combination of two or more.
Pigments can be mixed and used with the above-mentioned various agents.
Pigments include kaolin, clay, engineered kaolin, delaminated clay,
Inorganic pigments such as heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin white, and solid, hollow, or core shell. Organic pigments such as molds can be used alone or in admixture of two or more.
The method of surface treatment of the paper substrate is not particularly limited, but a known coating device such as a rod metering size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, and a curtain coater should be used. Can be done.
The method of producing (papermaking) the base paper is not particularly limited, and papermaking is performed by an acidic papermaking method, a neutral papermaking method, or an alkaline papermaking method using a known long net former, on-top hybrid former, gap former machine, or the like. Paper substrate can be manufactured.

The base paper is made from pulp and may contain a filler, various auxiliaries and the like.
The pulp includes broad-leaved bleached kraft pulp (LBKP), broad-leaved unbleached kraft pulp (LUKP), coniferous bleached kraft pulp (NBKP), coniferous unbleached kraft pulp (NUKP), chemical pulp such as sulphite pulp, stone grind pulp, and thermostat. Mechanical pulp such as mechanical pulp, wood fiber such as deinked pulp and used paper pulp, non-wood fiber obtained from kenaf, bamboo, hemp, etc. can be used, and even if one type is used alone, two or more types can be used. May be appropriately mixed and used.
Among these, it is preferable to use chemical pulp or mechanical pulp of wood fiber, and it is more preferable to use chemical pulp because of less foreign matter contamination, less discoloration with time, high whiteness, and good surface feeling at the time of printing. preferable.
As the filler, a known filler can be used. Specific examples include white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, zeolite, synthetic resin filler and the like.
As various additives, aluminum sulfate bands and various anionic, cationic, nonionic or amphoteric yield improvers, drainage improvers, paper strength enhancers, internal sizing agents and other internal additives for papermaking are used. It can be used as needed. Further, a dye, a fluorescent whitening agent, a pH adjusting agent, a defoaming agent, a pitch control agent, a slime control agent and the like can be added as needed.

The paper base material and resin used for the paper base material layer may have workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, and flame retardancy, if necessary. , Antifungal properties, electrical properties, strength, etc. for the purpose of improving and modifying lubricants, cross-linking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. A plastic compounding agent, an additive, or the like can be added, and the amount thereof can be arbitrarily added as long as it does not adversely affect other performance.

≪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 can be provided on the surface of the paper base material layer on the outside of the liquid paper container by using a conventionally known printing ink. The printing method is not particularly limited, and conventionally known methods such as gravure printing, flexographic printing, and screen printing can be used. 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.
When forming the liquid paper container, it is preferable that the print layer is the outermost layer or the layer outside the print layer is transparent so that the print layer can be visually recognized.

≪Adhesive resin layer≫
An adhesive resin layer or an anchor coat layer can be included between the layers constituting the oxygen-absorbing laminate.
The adhesive resin layer may be, for example, a layer (extruded resin layer) formed by a (co) extrusion lamination method for melt-extruding an adhesive resin composition, a T-die (co) extrusion method, or the like, and is a dry laminate. It may be a layer (dry laminate layer) formed by dry lamination using an adhesive.
Among the above, the extruded resin layer is preferable in the present invention. Then, if necessary, the surface of the laminated adhesive resin layer is subjected to physical surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, sandblast treatment, etc., and oxidation using chemicals. Chemical surface treatment such as treatment may be applied.
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 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, polyethylene-based resin is also referred to 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.

The adhesive resin layer contains additives such as antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, antiblocking agents, flame retardant agents, cross-linking agents, and colorants as long as the characteristics of the present invention are not impaired. Can include.
The thickness of the adhesive resin layer is not particularly limited, but is preferably 5 μm or more and 60 μm or less in the case of an extruded resin, and 0.1 g / m ² in the case of a dry laminate adhesive. As mentioned above, it is preferably 20 g / m ² or less. By setting the thickness of the adhesive resin layer within the above numerical range, stable adhesive strength can be obtained.
Specific examples of the dry laminating adhesive constituting the adhesive resin layer formed by the dry laminating include a two-component curable urethane adhesive, a polyester urethane adhesive, a polyether urethane adhesive, and an acrylic. Adhesives such as polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, epoxy adhesives, rubber adhesives, and the like 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 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.
In the present invention, it is preferable to use a polyester resin for the reinforcing layer.
Examples of the polyester resin include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polytetramethylene terephthalate, polycyclohexanedimethylene terephthalate (PCT) and the like. Can be mentioned.
Further, the resin film may be unstretched or stretched in a uniaxial or biaxial direction.
The reinforcing layer may be provided with a vapor-deposited film for the purpose of improving the barrier property, and is an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, and an anti-layer as long as the characteristics of the present invention are not impaired. Additives such as blocking agents, flame retardants, cross-linking agents and colorants can be included.
The thickness of the reinforcing layer is not particularly limited, but is preferably 5 μm or more and 500 μm or less, and more preferably 10 μm or more and 200 μm or less.

<How to make an oxygen-absorbing laminate for paper containers>
A method for producing an oxygen-absorbing laminate for a paper container 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 for paper containers is performed by the laminating method used when manufacturing ordinary packaging materials, for example, wet lamination method, dry lamination method, solvent-free dry lamination method, and extrusion lamination. It can be carried out by any method such as a method, a T-die co-extrusion molding method, a co-extrusion lamination method, an inflation method, and the like.
The oxygen-absorbing laminate for paper containers 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, biocompatibility, etc. It is also possible to perform secondary processing for the purpose of imparting surface function and the like.
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 paper substrate 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 a paper container having a layer structure of a paper substrate 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 paper substrate 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 paper containers can be obtained.

<Oxygen-absorbing packaging material for paper containers>
The oxygen-absorbing packaging material for paper containers is a packaging material made from an oxygen-absorbing laminate for paper containers and used for producing liquid paper containers.
The oxygen-absorbing packaging material for paper containers may further contain layers having various functions, if necessary.

<Oxygen-absorbing paper container for liquids>
The oxygen-absorbing paper container for liquids of the present invention is a paper container for liquids produced by using the oxygen-absorbing packaging material for paper containers of the present invention. In addition, various shape designs and print decorations can add value.
In one embodiment, the liquid oxygen-absorbing paper container of the present invention has a shape as shown in FIG. 3, and the paper container 20 of the present invention has a body portion 21 and an opening end portion above the body portion 20. A roof-shaped top 22 having an inclined upper surface and a bottom 23 formed at an open end below the body 21 are provided. Further, the paper container 20 can be manufactured from, for example, the blank plate 24 shown in FIG.
In the oxygen-absorbing paper container for liquids, the oxygen barrier layer is located outside the oxygen-absorbing adhesive layer.

<Manufacturing method of oxygen-absorbing paper container for liquid>
The paper container 20 can be formed, for example, by the following method. The examples given below are merely examples of the method for producing the oxygen-absorbing paper container for liquids of the present invention, and the present invention is not limited thereto.
First, the laminate shown in FIG. 2 is punched out to form a blank plate 24 as shown in FIG.
Next, the paper container 20 can be manufactured by attaching a spout component paired with the cap, bending the sealant layer so as to be inside, heat-sealing, and attaching the cap.
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 2500.
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.

[Adhesive resin layer, coating resin layer, anchor coating agent]
-DL Adhesive 1: A two-component curable polyester urethane adhesive manufactured by Rock Paint Co., Ltd. -LDPE1: LDPE manufactured by Japan Polyethylene Corporation, Novatec LC520. Density 0.923 g / cm ³ , MFR 3.6 g / 10 minutes.

AC agent 1: Urethane-based anchor coating agent.
[Paper substrate layer, reinforcing layer, barrier layer film]
-PET film 1: Biaxially stretched PET film manufactured by Toyobo Co., Ltd., E5200, 12 μm thick.
-Transparent vapor-deposited PET film 1: IB-PET manufactured by Dai Nippon Printing Co., Ltd. Single-sided transparent alumina vapor-deposited PET film. 12 μm thick.
-Paper base material 1: Uncoated base paper manufactured by Clearwater Paper Corporation with a basis weight of 400 g / m ² .
-Aluminum foil 1: Aluminum foil with a thickness of 7 μm.

[Ink for print layer]
-Gravure ink 1: SNP manufactured by Showa Ink Industry Co., Ltd.

[Film for sealant layer]
-LLDPE film 1: SK-L manufactured by Dai Nippon Printing Co., Ltd. Unstretched LLDPE film. 40 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 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]
After drying, the oxygen-absorbing adhesive A1 is applied and dried on one side of the PET film 1 as a reinforcing layer so that the coating amount is 3.0 g / m ² , and then the aluminum foil 1 for the oxygen barrier layer and the dry laminating method are applied. It was pasted together by.
Then, the AC agent 1 was applied to the surface of the bonded aluminum foil 1 so that the film thickness after drying was 0.5 μm, and dried to form an anchor coat layer.
Next, the anchor coat layer surface and the paper substrate were bonded by extrusion laminating via an adhesive resin layer made of melted LDPE1 at 330 ° C. extruded from an extrusion molding machine. The thickness of the adhesive resin layer was adjusted to 25 μm.
Then, the surface of the laminated paper base material 1 was extruded and coated with the melted LDPE1 at 330 ° C. extruded from the extrusion molding machine to form a coated resin layer having a thickness of 25 μm.
Next, the AC agent 1 was applied to the surface of the laminated PET film 1 so that the film thickness after drying was 0.5 μm, and dried to form an anchor coat layer.
Then, the anchor coat layer surface and the LLDPE film 1 for the sealant layer were bonded by extrusion laminating via an adhesive resin layer made of melted LDPE 1 at 330 ° C. extruded from a molding machine. The thickness of the adhesive resin layer was adjusted to 25 μm.
Next, the surface of the coated resin layer formed above was subjected to corona treatment to form a printing layer using gravure ink 1, and an oxygen-absorbing laminate for a paper container was obtained. Then, various evaluations were carried out.
Layer structure: Print layer / Coat resin layer (25 μm) / Paper base material layer (365 g / m ² ) / Adhesive resin layer (25 μm) / Anchor coat layer (0.5 μm) / Oxygen barrier layer (Aluminum foil 1: 7 μm) / Oxygen-absorbing adhesive layer (3 g / m ² ) / Reinforcing layer (12 μm) / Anchor coat layer (0.5 μm) / Adhesive resin layer (25 μm) / Sealant layer (40 μm)

[Examples 2 to 9, Comparative Examples 1 to 3]
Examples 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 Table 7. By operating in the same manner as in No. 1, an oxygen-absorbing laminate for a paper container was obtained and evaluated in the same manner.

[Example 10]
Oxygen absorbency for paper containers is operated in the same manner as in Example 1 except that the aluminum foil 1 for the oxygen barrier layer is changed to the transparent vapor-deposited PET film 1 and the vapor-deposited surface is used on the oxygen-absorbing adhesive 1 side. A laminate was obtained and evaluated in the same manner.
Layer structure: Print layer / Coat resin layer (25 μm) / Paper base material layer (365 g / m ² ) / Adhesive resin layer (25 μm) / Anchor coat layer (0.5 μm) / Oxygen barrier layer (PET film: 12 μm / Vapor deposition) Layer) / Oxygen-absorbing adhesive layer (3 g / m ² ) / Reinforcing layer (12 μm) / Anchor coat layer (0.5 μm) / Adhesive resin layer (25 μm) / Sealant layer (40 μm)

[Comparative Example 4]
A laminate was obtained by the same operation as in Example 10 except that the oxygen-absorbing adhesive 1 was changed to the DL adhesive 1, and evaluated in the same manner.

<Summary of results>
The oxygen-absorbing laminate for paper containers and the oxygen-absorbing paper container for liquids of all the examples showed an excellent balance between laminating strength, oxygen absorption amount and low odor.
On the other hand, the laminated body and the liquid paper container of the comparative example showed inferior results in any of the laminated strength, the oxygen absorption amount and the low odor property.

<Evaluation method>

[Oxygen absorption]
Using the obtained oxygen-absorbing laminate for paper containers, a box was manufactured so that the sealant layer was on the inside, and a paper container having a capacity of 200 mL was manufactured. The contents container of the obtained container was replaced with nitrogen and then sealed. Inject 1400 cc / m ² of air into the inside of the container with a syringe for the inner area of the bag, repair the injection part with adhesive tape, and store it in a constant temperature bath at 25 ° C for 14 days. Was sampled with a syringe, the oxygen concentration was measured, and the amount of oxygen absorbed 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 for paper containers, and the laminate strength between the layers via the oxygen-absorbing adhesive layer was measured using a tensile tester at a tensile speed of 50 mm / min. The laminate strength was measured at.

<Odor>
The odor in the pouch 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 paper containers 2: Paper substrate layer 3: Oxygen barrier layer 4: Oxygen-absorbing adhesive layer 5: Sealant layer 6: Printing layer 7: Coat resin layer 8: Adhesive resin layer 9: Anchor Coat layer 10: Reinforcing layer 20: Oxygen-absorbing paper container for liquid 21: Body 22: Top 23: Bottom 24: Blank plate

Claims (18)

Oxygen absorbency for a paper container for producing a liquid paper container, which comprises a layer structure in which at least a paper base material layer, an oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer are laminated in this order. It ’s a laminated body,
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 paper containers. A reinforcing layer is further provided between the oxygen-absorbing adhesive layer and the sealant layer.
The oxygen-absorbing laminate for a paper container according to claim 1. The paper substrate layer contains a coated resin layer on the surface thereof.
The oxygen-absorbing laminate for a paper container according to claim 1 or 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 a paper container according to any one of claims 1 to 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 a paper container according to any one of claims 1 to 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 a paper container according to claim 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 a paper container according to claim 5 or 6. The organic group 2 does not have a crosslinkable functional group.
The oxygen-absorbing laminate for a paper container according to any one of claims 1 to 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 a paper container according to any one of claims 1 to 7. 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 a paper container according to any one of claims 1 to 7.

(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 a paper container according to any one of claims 1 to 7.

(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 a paper container according to any one of claims 1 to 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 a paper container according to any one of claims 1 to 11. The oxygen-absorbing adhesive composition further contains a denaturing agent.
The oxygen-absorbing laminate for a paper container according to any one of claims 1 to 13, 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 a paper container according to claim 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 a paper container according to claim 13 or 14. An oxygen-absorbing packaging material for a paper container, which is produced by using the oxygen-absorbing laminate for a paper container according to any one of claims 1 to 16. An oxygen-absorbing paper container for liquids produced by using the oxygen-absorbing packaging material for paper containers according to claim 17.
The oxygen barrier layer is a layer located outside the oxygen-absorbing adhesive layer.
Oxygen-absorbing paper container for liquids.

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