JP2020168837A - Gas barrier laminate, packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having excellent gas barrier property and a small amount of solvent emitted during production, a method for producing the laminate, and a packaging material using the laminate. SOLUTION: A step of forming a printing layer on a base material using a water-based liquid ink, and a step of applying a solvent-free gas barrier adhesive on a sealant layer to form a solvent-free gas barrier adhesive layer. A method for producing a laminate, which comprises a step of laminating a base material and a sealant layer via a solvent-free gas barrier adhesive layer. [Selection diagram] None

Description

The present invention relates to a gas barrier laminate and a packaging material obtained by using the gas barrier laminate.

Packaging materials used for packaging foods and daily necessities are required to have functions such as strength, resistance to cracking, and gas barrier properties in order to protect the contents from impacts received during distribution and deterioration due to oxygen and moisture. When the contents are heat sterilized, retort resistance, heat resistance, etc. are required, and transparency may be required so that the contents can be confirmed. However, it is difficult to satisfy the required functions with one kind of material. For example, the non-stretched polyolefin film used when sealing by heat sealing is excellent in heat processability, but has insufficient oxygen barrier property. Nylon film, on the other hand, has excellent gas barrier properties, but is inferior in heat seal properties.

For this reason, a laminate obtained by laminating different types of polymer materials is widely used as a packaging material. In general, a laminate for packaging materials has a product protection function such as impact resistance and gas barrier property, and has a thermoplastic plastic film as an outer layer and a thermoplastic film having a sealant function as an inner layer. Is used. As a method for laminating these, a dry laminating method (Patent Document 1) and the like are known. In addition, the packaging material is provided with a printing layer for displaying information on decorations and contents. The print layer is often printed using a solvent-based gravure ink (Patent Document 2).

JP-A-2003-13032 JP-A-2018-76461

However, when the laminate is produced by such a method, it is necessary to volatilize the solvent from the gravure ink or the adhesive, and a treatment is required to prevent the volatilized organic solvent (VOC) from being released into the atmosphere. .. Incineration and cooling / recovery are performed, but all of them require considerable energy. Furthermore, the recovered organic solvent is a mixture of a plurality of types of organic solvents and is difficult to isolate, and its use is often limited even if it is to be reused. In order to reduce the burden on the environment, there is a demand for a laminate that emits less organic solvent during manufacturing.

The present invention has been made in view of such circumstances, and provides a laminate having excellent gas barrier properties and a small amount of solvent emitted during production, a method for producing the laminate, and a packaging material using the laminate. The purpose is.

According to the present invention, a base material, a sealant layer, a printing layer arranged between the base material and the sealant layer and formed by using a water-based liquid ink, and between the printing layer and the printing layer. The present invention relates to a laminate containing a gas barrier adhesive layer arranged and formed by using a solvent-free gas barrier adhesive, and a packaging material obtained by using the laminate.

According to the laminate of the present invention, it is possible to provide a laminate having excellent gas barrier properties and a small amount of solvent discharged during production, and a packaging material using the laminate.

<Laminated body>
The laminate of the present invention includes a base material, a printing layer, a gas barrier adhesive layer, and a sealant layer. Hereinafter, each layer will be described in detail.

(Base material)
As the base material, any film or sheet having excellent chemical and physical strength (unless otherwise specified below, film is also a general term for film and sheet) can be used without particular limitation. Further, the base material may be a single-layer film or a multilayer laminated film. It can be appropriately selected according to the contents and type of the packaging material, which will be described later, and the usage conditions such as the presence or absence of heat treatment after filling the contents.

Specific examples of the base material include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ionomer, and ethylene-. (Meta) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-propylene copolymer, methylpentene, polyacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, Polypropylene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), vinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), poly Examples include, but are not limited to, resin films such as butylene terephthalate and polyethylene naphthalate, K-coated stretched polypropylene films, K-coated stretched nylon films, and composite films in which two or more of these films are laminated.

Among them, uniaxial or biaxially stretched polyester film such as polyethylene terephthalate and polyethylene naphthalate, uniaxial or biaxially stretched polyamide film such as nylon 6, nylon 66 and MXD6 (polymethoxylylen adipamide), biaxially stretched polypropylene film. Etc. can be preferably used.

The film thickness of the film is not particularly limited, and may be appropriately selected in the range of 1 to 300 μm from the viewpoint of moldability and transparency. It is preferably in the range of 1 to 100 μm. If it is less than 1 μm, the strength is insufficient, and if it exceeds 300 μm, the rigidity becomes too high, which may make processing difficult.

The base film used was some surface treatment, such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, physical treatment such as glow discharge treatment, or chemicals. It may be subjected to chemical treatment such as oxidation treatment or other treatment.

As the base film, for example, one or more selected from the above-mentioned resins are used, and the film is manufactured by a conventionally known film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, and an inflation method. can do. Alternatively, it can be produced by a multi-layer coextrusion film forming method using two or more kinds of resins selected from the above-mentioned resins. From the viewpoint of film strength, dimensional stability, and heat resistance, the film may be stretched in the uniaxial or biaxial directions by using a tenter method, a tubular method, or the like.

The base film may contain additives, if necessary. Specifically, improve workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. For the purpose of modification, plastic compounding agents and additives such as lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents and pigments can be added. The amount of additive added should be adjusted within a range that does not affect other performance.

The substrate may include an inorganic vapor deposition layer on at least one surface of the film. The inorganic vapor deposition layer is a layer having a gas barrier property that prevents the permeation of oxygen gas and water vapor gas, and is a vapor deposition layer made of an inorganic substance or an inorganic oxide. Examples of the inorganic substance or inorganic oxide include aluminum, alumina, silica and the like, and these may be used alone or in combination of two or more. Two or more inorganic vapor deposition layers may be provided. When two or more inorganic vapor deposition layers are provided, they may have the same composition or different compositions.

The inorganic vapor deposition layer can be provided directly on the substrate or via a layer formed by using an adhesive, a primer coating agent, an undercoat agent, a vapor deposition anchor coating agent, or the like by a conventionally known method. Examples of the method for forming the inorganic vapor deposition layer include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, a plasma chemical vapor deposition method, and heat. Examples thereof include a chemical vapor deposition method (Chemical Vapor Deposition method (CVD method)) such as a chemical vapor deposition method and a photochemical vapor deposition method.

The thickness of the inorganic vapor deposition layer is preferably 1 to 200 nm. When the inorganic vapor-deposited layer is an aluminum-deposited layer, the film thickness is more preferably 1 to 100 nm, more preferably 15 to 60 nm, and even more preferably 10 to 40 nm. When the inorganic vapor deposition layer is a silica or alumina vapor deposition layer, the film thickness is preferably 1 to 100 nm, more preferably 10 to 50 nm, and even more preferably 20 to 30 nm.

When the base material has an inorganic vapor deposition layer, a barrier coat layer may be provided on the inorganic vapor deposition layer. The barrier coat layer protects the inorganic vapor deposition layer and can enhance the gas barrier property of oxygen, water vapor and the like. Such a gas barrier coat layer is obtained by polycondensing a mixture of, for example, a metal alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel method catalyst or a solvent such as water or an organic solvent to hydrolyze the metal alkoxide. It is formed from a resin composition such as a product or a hydropolycondensate of a metal alkoxide.

As the metal alkoxide, one kind or two or more kinds represented by the following general formula can be used.

（上記一般式中、Ｒ１、Ｒ２は炭素原子数１〜８の有機基を表し、Ｍは金属原子を表し、ｎは０以上の整数を表し、ｍは１以上の整数を表し、ｎ＋ｍはＭの原子価を表す。）

(In the above general formula, R1 and R2 represent organic groups having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents M. Represents the valence of.)

Examples of the metal atom M include silicon, zirconium, titanium, and aluminum. Specific examples of the organic group represented by R ¹ and R ² include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group. it can. Within the same molecule, these alkyl groups may be the same or different.

Specific examples of the metal alkoxide include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Examples thereof include silane coupling agents such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The metal alkoxide may be used alone or in combination of two or more.

Examples of the water-soluble polymer include polyvinyl alcohol-based resins and ethylene / vinyl alcohol copolymers. A commercially available product may be used as the water-soluble polymer, and as a commercially available product of the polyvinyl alcohol-based resin, RS-110 (manufactured by Kuraray Co., Ltd., RS polymer, degree of polymerization; 99%, degree of polymerization; 1,000), Kuraray Poval LM-20SO (manufactured by Kuraray Co., Ltd., degree of polymerization; 40%, degree of polymerization; 2,000), Gosenol NM-14 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., degree of polymerization; 99%, degree of polymerization; 1 , 400) and the like. Commercially available products of ethylene-vinyl alcohol-based copolymers include EVAL EP-F101 (manufactured by Kuraray Co., Ltd., ethylene content; 32 mol%) and Soanol D2908 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ethylene content; 29 mol%). And so on.

Examples of the sol-gel method catalyst include acid or amine compounds. As the amine compound, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is preferable. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. In particular, N, N-dimethylbenzylamine is preferable. As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid can be used.

As the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

In the gas barrier coat layer, a resin composition containing these compounds is applied once or multiple times by a roll coating such as a gravure roll coater, a spray coating, a spin coating, dipping, a brush, a bar code, an applicator, or the like. Formed by coating. More specifically, the resin composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel method catalyst, water, an organic solvent, and if necessary, other components. The polycondensation reaction gradually proceeds in the resin composition. Next, the resin composition is applied onto the inorganic thin-film deposition layer by a conventional method and dried. Upon drying, the polycondensation reaction between the metal alkoxide and the water-soluble polymer further proceeds, and a layer of the composite polymer is formed. It is also preferable to repeat this operation to form the gas barrier coat layer. Finally, the laminate coated with the resin composition is heated at 20 to 250 ° C., preferably 50 to 220 ° C. for 1 second to 10 minutes. Thereby, the gas barrier coat layer can be formed on the inorganic thin-film deposition layer.

The film thickness of the gas barrier coat layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm. If it is smaller than 0.01 μm, the gas barrier property is not sufficiently improved, and if it is larger than 100 μm, cracks are likely to occur.

A commercially available film including an inorganic thin-film deposition layer, an inorganic thin-film deposition layer, and a gas barrier coat layer may be used as a base material. Commercially available products including an inorganic vapor deposition layer, an inorganic vapor deposition layer and a gas barrier coat layer include "GL FILM" series manufactured by Toppan Printing Co., Ltd., "PRIME BARRIER" series, "Tech Barrier" series manufactured by Mitsubishi Chemical Corporation, and Toray Industries, Inc. Examples include the "Barrier Rocks" series manufactured by Film Processing Co., Ltd., the "Eco-Cial" series manufactured by Toyobo Co., Ltd., and the "IB Film" series manufactured by Dai Nippon Printing Co., Ltd.

(Print layer)
The printing layer is a layer in which characters, figures, symbols, and other desired patterns are printed using water-based liquid ink. In the present specification, water-based liquid ink is a general term for water-based inks used for gravure printing or flexographic printing. The water-based liquid ink contains a water-based resin, a pigment, and a water-based solvent as essential components. Additives may be used if necessary.

Examples of the water-based resin include water-soluble or water-dispersible urethane resin, polyester resin, acrylic resin, urethane acrylic resin, styrene acrylic resin, styrene maleic acid resin, and the like, and can be used alone or in combination of two or more. .. As a method for making these resins water-based, conventionally known methods can be used without particular limitation. For example, a method of neutralizing the acid groups contained in these resins with a neutralizing agent, or a method of containing an acid group in these resins. Examples thereof include a method of graft-polymerizing an ethylenically unsaturated monomer and then neutralizing it with a neutralizing agent, and a method of polymerizing an ethylenically unsaturated monomer in an aqueous solvent using an aqueous resin having an acid group as a polymer emulsifier. Not limited to this. When dissolving or dispersing the aqueous resin in the aqueous solvent, a homogenizer or the like may be used if necessary.

Examples of the neutralizing agent include amine compounds such as ammonia, triethylamine, N, N-dimethylethanolamine and monoethanolamine, non-volatile amine compounds such as triethylenediamine, diethanolamine, triethanolamine, diethylenetriamine and diazabicyclooctene, and hydroxide. Examples thereof include metal hydroxides such as lithium, potassium hydroxide and sodium hydroxide, metal chlorides such as potassium chloride and sodium chloride, and metal sulfides such as copper sulfate. From the viewpoint of reducing VOC, it is preferable to use a non-volatile compound such as a non-volatile amine compound, a metal hydroxide, a metal chloride, or a metal sulfide.

An emulsifier may be used in combination to disperse the aqueous resin in an aqueous solvent described later. Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer; oleic acid. Anionic systems such as fatty acid salts such as sodium, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkansulfonate sodium salts, and alkyldiphenyl ether sulfonic acid sodium salts. Emulsifiers: Cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzylammonium salts can be mentioned.

The acid value of the aqueous resin is preferably 10 mgKOH / g or more and 300 mgKOH / g or less. The glass transition temperature of the aqueous resin is not particularly limited, but is 60 to 130 ° C. as an example.

The content of the water-based resin is arbitrary, but as an example, it is preferably 20% by mass or more with respect to the total mass of the water-based liquid ink, and 70% by mass or less from the viewpoint of appropriate ink viscosity and work efficiency during ink production and printing. Further, the range of 40 to 60% by mass is preferable.

As the pigment, for example, an achromatic pigment such as carbon black, titanium oxide, or calcium carbonate or a chromatic organic pigment can be used. Organic pigments include insoluble azo pigments such as Truisin Red, Truisin Maroon, Hansa Yellow, Benzidine Yellow, and Pyrazolone Red, soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, Arizarin, Indantron, and Thioindigo Derivatives from building dyes such as Maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene curlet, isoindolinone yellow , Isoindolinone-based organic pigments such as Isoindrinone Orange, Pyranslon-based organic pigments such as Pyranthron Red and Pyranthron Orange, Thioindigo-based organic pigments, Condensed Azo-based organic pigments, Benzimidazolone-based organic pigments, Kinoftalone Yellow, etc. Examples of quinophthalone-based organic pigments and other pigments include flavanthron yellow, acylamide yellow, nickel azo yellow, copper azomethin yellow, perinone orange, anthron orange, dianthraquinonyl red, and dioxazine violet.

Organic pigments such as yellow, magenta, cyan, and black are preferably blended in a proportion of 5 to 30% by weight based on the total mass of the aqueous liquid ink. Further, in the case of white titanium oxide, it is preferable to mix it in a ratio of 10 to 60% by mass with respect to the total mass of the water-based liquid ink.

The water-based liquid ink may contain a pigment-dispersing resin for dispersing the pigment. As the pigment-dispersing resin, any water-soluble resin can be used as long as it maintains the stability of the ink and has a pigment-dispersing ability. Examples of such pigment-dispersed resins include polyvinyl alcohol, polyvinylpyrrolidone (commercially available products such as K-30, K-60, and K-90 manufactured by ISP), polyethylene glycol, poly (meth) acrylic acid, and the like. (Meta) acrylic acid- (meth) acrylic acid alkyl ester copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, styrene- (meth) acrylic acid copolymer, maleic acid- (Meta) acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid- (meth) acrylic acid alkyl ester copolymer, styrene-maleic acid half ester copolymer, vinyl naphthalene- (meth) ) Acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinylpyrrolidone- (meth) acrylic acid alkyl ester copolymer, vinylpyrrolidone-styrene copolymer, vinylpyrrolidone-vinyl acetate copolymer, vinyl acetate- Crotonic acid copolymer, vinyl acetate- (meth) acrylic acid copolymer, vinyl acetate-crotonic acid copolymer, polyvinyl sulfonic acid, sodium polyvinyl sulfonate, polystyrene sulfonic acid, sodium polystyrene sulfonate (Polynas manufactured by Toso Co., Ltd.) PS-1, Polynas PS-5, etc.), styrene sulfonic acid-maleic acid copolymer, polyitaconic acid, polyhydroxyethyl (meth) acrylate, poly (meth) acrylamide, (meth) acrylamide- (meth) acrylic acid copolymer A water-soluble vinyl-based copolymer such as a coalescence, polyvinyl methyl ether, methyl vinyl ester, or carboxyvinyl polymer; a urethane resin obtained by a double addition reaction of polyisocyanate and a polyol, and the entire resin is solubilized by the introduction of a hydrophilic group. Water-soluble polyurethane resin; a polyester resin obtained by a copolymerization reaction of a polyvalent carboxylic acid and a polyol, and a water-soluble polyester resin in which the entire resin is solubilized by the introduction of a hydrophilic group; methyl cellulose, ethyl cellulose, propyl cellulose, ethyl. Cellulous derivatives such as methyl cellulose, hydroxyalkyl cellulose, hydroxypropyl methyl cellulose, carboshikimethyls cellulose, alkali metal carboxymethyl cellulose, alkali metal cellulose sulfate, cellulose graft polymer; and polypeptides such as polyglutamic acid and polyaspartic acid; etc. Can be mentioned, alone or Can be used in combination of two or more.

Among them, from the viewpoint of excellent pigment adsorption ability and dispersion stability, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer , Styrene- (meth) acrylic acid copolymer, maleic acid- (meth) acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid- (meth) acrylic acid alkyl ester copolymer, It is preferably a styrene-maleic acid half ester copolymer. Further, these resins may be synthesized by solution polymerization or bulk polymerization with a radical initiator, or commercially available products may be used.

As commercially available products, for example, BASF Corp. JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60J, JONCRYL61J, JONCRYL62J, JONCRYL63D, JONCRYLHPD-96J, JONCRYL501J, JONCRYLPDX-6102, manufactured by BYK Chemie DYSPERBYK180, DYSPERBYK187, DYSPERBYK190 , DYSPERBYK191, DYSPERBYK194, DYSPERBYK2010, DYSPERBYK2015, DYSPERBYK2090, DYSPERBYK2091, DYSPERBYK2095, DYSPERBYK2155, DYSPERBYK2155, DYSPERBYK2155, DYSPERBYK2155, DYSPERBYK2155, DYSPERBYK2155, DYSPERBYK2155

The pigment-dispersed resin is preferably used in the range of 10 to 60 parts by mass in terms of solid content with respect to 100 parts by mass of the pigment. If the amount of the pigment-dispersed resin is less than 10 parts by mass with respect to 100 parts by mass of the pigment, the pigment dispersion stability may be lowered, and the dispersion stability and storage stability of the aqueous liquid ink may be deteriorated. On the other hand, if the pigment-dispersed resin exceeds 60 parts by mass with respect to 100 parts by mass of the pigment, the viscosity of the aqueous liquid ink increases remarkably, which may adversely affect the storage stability of the ink. In addition, the physical properties of the coating film (base material adhesion, water friction resistance, blocking resistance) may also decrease due to the occurrence of poor drying of the coating film and the increase in the components eluted in water.

Water is used as the aqueous solvent, but if necessary, monovalents such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol and the like are used. Alcohol solvent;
Ethylene glycol, 1,3-propanediol, propylene glycol, 1,2-butanediol, 1,4-butanediol, pentylene glycol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol , Glycol-based solvents such as tetraethylene glycol;

Ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl Ethylene, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol dimethyl ether, Glycol ether-based solvents such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether;

Lactam solvents such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, ε-caprolactam;
Hydrophilic solvents such as formamide, N-methylformamide, N, N-dimethylformamide, Idemitsu Equamid M-100, Equamid B-100 and other amide solvents may be used in combination. These hydrophilic solvents may be used alone or in combination of two or more.

By using these hydrophilic solvents together, it is possible to control the wettability to the base material and the dryness of the water-based liquid ink (poor drying of the ink coating film). From the viewpoint of VOC reduction, the content of the hydrophilic solvent is preferably 10% by mass or less, and more preferably 5% by mass or less of the total amount of the aqueous liquid ink.

In addition to these, the water-based liquid ink may contain a wax and a film-forming emulsion for imparting coating film resistance. Waxes include beeswax, lanolin wax, whale wax, candelilla wax, carnauba wax, rice wax, wood wax, animal and plant waxes such as jojoba oil, montan wax, ozogerite, selecin, paraffin wax, microcrystallin wax, petrolatum, etc. Minerals, petroleum wax, Fisher Tropsch wax, polyethylene wax, polyethylene oxide wax, synthetic hydrocarbon wax such as polypropylene oxide wax, monttan wax derivative, paraffin wax derivative, modified wax such as microcrystallin wax derivative, hardened castor oil, Hydrogenated wax such as a cured castor oil derivative, polytetrafluoroethylene wax and the like can be used. Polyethylene wax is preferable from the viewpoint of the balance between static friction and dynamic friction.

Examples of the film-forming emulsion include resin emulsions that form a film at a glass transition temperature of 10 ° C. or lower. Specific examples thereof include an acrylic resin emulsion, a water-soluble styrene-acrylic resin emulsion, a water-soluble styrene-maleic acid-based resin emulsion, and a water-soluble styrene-acrylic maleic acid-based resin emulsion. A material obtained by copolymerizing a styrene-based monomer, an alkyl ester of (meth) acrylic acid, or the like using a water-soluble acrylic resin as a polymer emulsifier can be preferably used.

The water-based liquid ink may contain a surface conditioner in order to adjust the leveling property to the substrate. Examples of the surface conditioner include Surfinol 104E, 104H, 104A, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, PSA-336, 61, 2502 manufactured by Nissin Chemical Co., Ltd. , Dynol 604, 607, BYK-381, 3441, 302, 307, 325, 331, 333, 342, 345, 346, 347, 348, 349, 378, 3455, and the like, but are not limited thereto.

Furthermore, the water-based liquid ink is an extender pigment such as calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, clay, and talc in order to improve the drying property, and inorganic fine particles and an adhesive resin (acrylic resin) in order to impart anti-slip properties. , Vinyl acetate resin), various additives such as a defoaming agent for imparting defoaming property, and a basic compound such as caustic soda for imparting resolubility.

The water-based liquid ink can be produced by a conventionally known method. After mixing the water-based resin, the pigment, the water-based solvent and the pigment dispersion resin added as needed, various meat kneading machines such as bead mill, pearl mill and sand mill are used. , Ball mill, attritor, roll mill, etc. are used to knead the meat, and the rest of the predetermined material and, if necessary, additives are mixed.

When the water-based liquid ink is used as a water-based flexo ink, its viscosity may be 7 to 25 seconds at 25 ° C. using Zahn Cup # 4 manufactured by Rigo Co., Ltd., more preferably 10 to 20 seconds. The surface tension of the obtained water-based flexographic printing ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as fill, but when the surface tension is less than 25 mN / m, the ink spreads and the halftone dots adjacent to each other are adjacent to each other. Tend to be easily connected, which tends to cause stains on the printed surface called dot bridge. On the other hand, when the surface tension exceeds 50 mN / m, the wettability of the ink to a base material such as a film is lowered, which tends to cause repelling.

On the other hand, when it is used as a water-based gravure ink, its viscosity may be 7 to 25 seconds at 25 ° C. using Zahn Cup # 3 manufactured by Rigo Co., Ltd., and more preferably 10 to 20 seconds. The surface tension of the obtained water-based gravure ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m, as with the water-based flexographic ink. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as fill, but when the surface tension is less than 25 mN / m, the ink spreads and the halftone dots adjacent to each other are adjacent to each other. Tend to be easily connected, which tends to cause stains on the printed surface called dot bridge. On the other hand, when the surface tension exceeds 50 mN / m, the wettability of the ink to a base material such as a film is lowered, which tends to cause repelling.

(Gas barrier adhesive layer)
The gas barrier adhesive layer is a cured coating film of the gas barrier adhesive. The gas barrier adhesive that can be used is not particularly limited as long as it is a solvent-free adhesive having a gas barrier property. In the present specification, the gas barrier adhesive is a coating film coated at 3 g / m ² (solid content) having an oxygen barrier property of 500 cc / m ² / day / atm or less at 23 ° C. and 0% RH, or water vapor. A barrier property of 120 g / m ² / day or less that satisfies at least one of the conditions.

In the present specification, the solvent-free adhesive is a method in which an adhesive is applied to a base material and then bonded to another base material without a step of heating in an oven or the like to volatilize an organic solvent, so-called non-solvent. A form used in the laminating method. Since there is no step to volatilize the organic solvent, the solvent-free adhesive dissolves the adhesive component such as resin, and the organic solvent for lowering the viscosity of the adhesive, specifically toluene, xylene, methylene chloride, tetrahydrofuran. , Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane and other organic solvents are substantially free. If the constituent components of the adhesive and the organic solvent used as the reaction medium in the production of the raw material cannot be completely removed and remain in the adhesive, it is understood that the organic solvent is not substantially contained.

Further, in the two-component reactive adhesive containing the polyol composition (A) and the polyisocyanate composition (B), even if the polyol composition (A) contains a low molecular weight alcohol, the low molecular weight alcohol is poly. Since it reacts with the isocyanate composition (B) and becomes a part of the coating film, it is not necessary to volatilize it after coating. Therefore, such a form is also treated as a solvent-free adhesive.

The gas barrier adhesive is not particularly limited as long as it has the above-mentioned gas barrier properties and is solvent-free, but for example, the polyol composition (A) containing at least one of the following polyester polyols (A1) to (A5). A two-component adhesive comprising a polyisocyanate composition (B) containing a compound having at least two isocyanate groups in one molecule (hereinafter, also simply referred to as an isocyanate compound).

(1) A polyester polyol (A1) obtained by reacting a polyester polyol having three or more hydroxyl groups with a carboxylic acid anhydride or a polycarboxylic acid.
(2) Polyester polyol (A2) having a polymerizable carbon-carbon double bond
(3) Polyester polyol having a glycerol skeleton (A3)
(4) Polyester polyol (A4) obtained by polycondensing an ortho-oriented polyvalent carboxylic acid and a polyhydric alcohol.
(5) Polyester polyol having an isocyanul ring (A5)

The polyester polyol (A1) is obtained by reacting a polyester polyol (a1) having three or more hydroxyl groups with a carboxylic acid anhydride or a polyvalent carboxylic acid, and has at least one carboxyl group and two or more hydroxyl groups. Have. The polyester polyol (a1) can be obtained by making a part of the polyvalent carboxylic acid or polyhydric alcohol trivalent or higher.

The polyvalent carboxylic acid used for preparing the polyester polyol (A1) preferably contains at least one of orthophthalic acid and orthophthalic anhydride. The polyester polyol obtained by using these compounds as a polyvalent carboxylic acid has excellent gas barrier properties and adhesiveness. It is presumed that the reason why the gas barrier property of the adhesive is excellent by using orthophthalic acid and orthophthalic anhydride is that the rotation of the polyester chain obtained by using orthophthalic acid and its acid anhydride is suppressed. It is presumed that the reason why the adhesiveness is excellent is that the polyester chain exhibits non-crystallinity due to the asymmetry and sufficient substrate adhesion is imparted.

Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride. In order to prevent gelation during synthesis, it is preferable to use a trivalent carboxylic acid as a trivalent or higher polyvalent carboxylic acid.

Other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanediocarboxylic acid; unsaturated bond-containing polyvalent carboxylic acids such as maleic anhydride, maleic acid, and fumaric acid; , 3-Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic polyvalent carboxylic acids; terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5 -Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and acid anhydrides or ester-forming derivatives of these dicarboxylic acids , P-Hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and aromatic polyvalent carboxylic acids such as ester-forming derivatives of these dihydroxycarboxylic acids, and one or more are used in combination. be able to. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid and acid anhydrides thereof are preferable.

The polyhydric alcohol used for preparing the polyester polyol (A1) preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It is presumed that the smaller the number of carbon atoms between oxygen atoms, the less flexible the molecular chain is and the more difficult it is for oxygen to permeate. Therefore, it is particularly preferable to use ethylene glycol.

Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol and the like. Be done. In order to prevent gelation during synthesis, it is preferable to use a trihydric alcohol as a trihydric or higher polyhydric alcohol.

Other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetra. Aliphatic diols such as ethylene glycol, dipropylene glycol and tripropylene glycol; hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, these ethylene oxide extensions and hydrolyzed fats. Examples thereof include aromatic polyhydric phenols such as ring group.

The polyester polyol (A1) reacts the polyvalent carboxylic acid or its acid anhydride with the polyester polyol (a1) having three or more hydroxyl groups, which is a reaction product of the above-mentioned polyvalent carboxylic acid and polyhydric alcohol. You can get it. The ratio of the hydroxyl group to be reacted with the polyvalent carboxylic acid is preferably 1/3 or less of the hydroxyl group contained in the polyester polyol (a1). The polyvalent carboxylic acid or its acid anhydride to be reacted with the polyester polyol (a1) is preferably divalent or trivalent. Succinic anhydride, maleic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, phthalic anhydride, 2, Examples thereof include, but are not limited to, 3-naphthalenedicarboxylic acid anhydride and trimellitic anhydride.

The polyester polyol (A2) having a polymerizable carbon-carbon double bond can be obtained by using a component having a polymerizable carbon-carbon double bond as the polyvalent carboxylic acid and the polyhydric alcohol.

Maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride, 3-methyl-4-cyclohexene-1, as polyvalent carboxylic acids having a polymerizable carbon-carbon double bond. , 2-Dicarboxylic acid and its acid anhydride and the like. Of these, maleic anhydride, maleic acid, and fumaric acid are preferable because it is presumed that the smaller the number of carbon atoms, the less flexible the molecular chain is and the more difficult it is for oxygen to permeate.

Other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid; alicyclic groups such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Polyvalent carboxylic acid; orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl Dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and acid anhydrides or ester-forming derivatives of these dicarboxylic acids, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid And aromatic polyvalent carboxylic acids such as ester-forming derivatives of these dihydroxycarboxylic acids can be mentioned, and one or more of them can be used in combination. Moreover, these acid anhydrides can also be used. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable, in order to obtain gas barrier property.

Examples of the polyhydric alcohol having a polymerizable carbon-carbon double bond include 2-butene-1,4-diol and the like.

Other polyhydric alcohols may be copolymerized as long as the effects of the present invention are not impaired. Specifically, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol. , Dimethylbutanediol, Butylethylpropanediol, Diethylene glycol, Triethylene glycol, Tetraethylene glycol, Dipropylene glycol, Tripropylene glycol and other aliphatic diols; Hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F , Tetramethylbiphenol, these ethylene oxide extenders, aromatic polyvalent phenols such as hydrogenated alicyclic group, and the like can be exemplified. Among them, it is presumed that the smaller the number of carbon atoms between oxygen atoms, the less flexible the molecular chain is and the more difficult it is for oxygen to permeate. Therefore, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedim Methanol is preferred, and ethylene glycol is more preferred.

The polyester polyol (A2) having a polymerizable carbon-carbon double bond is a reaction product of a polyester polyol (a2) having a hydroxyl group and a carboxylic acid having a polymerizable double bond or a carboxylic acid anhydride. You may. Examples of the carboxylic acid having a polymerizable double bond or its acid anhydride include a carboxylic acid having a polymerizable double bond such as maleic acid, maleic anhydride, or fumaric acid, and unsaturated fatty acids such as oleic acid and sorbic acid. Can be mentioned. The polyester polyol (a2) preferably has three or more hydroxyl groups. When the polyester polyol (a2) has two or less hydroxyl groups, the number of hydroxyl groups contained in the polyester polyol (A2) is 0 to 1, and molecular elongation is unlikely to occur during the reaction with the polyisocyanate composition (B) described later. As a result, the adhesive strength and the like may decrease.

The polyester polyol (A2) preferably has a double bond component ratio of 5 to 60% by mass. If it is less than 5% by mass, the number of cross-linking points between the polymerizable double bonds is reduced, and it becomes difficult to obtain gas barrier properties. If it exceeds 60% by mass, the number of cross-linking points increases, and the flexibility of the cured coating film may decrease, making it difficult to obtain adhesive strength. In this specification, the ratio of double bond components in the polyester polyol (A2) is calculated using the following formula (a). In the following formula, the monomer refers to a polyvalent carboxylic acid and a polyhydric alcohol used in the synthesis of polyester polyol (A2).

Further, as the polyester polyol (A2), a drying oil or a semi-drying oil can be mentioned. Examples of the drying oil or semi-drying oil include known and commonly used drying oils and semi-drying oils having a carbon-carbon double bond.

The polyester polyol (A3) having a glycerol skeleton has a glycerol skeleton represented by the following general formula (1).

（一般式（１）中、Ｒ_１〜Ｒ_３は各々独立に、水素原子、または下記一般式（２）である。但し、Ｒ_１〜Ｒ_３のうち少なくとも一つは、下記一般式（２）で表される基を表す。）

(In the general formula (1), R _{1 to} R ₃ are independently hydrogen atoms or the following general formula (2). However, at least one of R _{1 to} R ₃ is the following general formula (2). ) Represents a group represented by.)

（一般式（２）中、ｎは１〜５の整数を表し、Ｘは、置換基を有してもよい１，２−フェニレン基、１，２−ナフチレン基、２，３−ナフチレン基、２，３−アントラキノンジイル基、及び２，３−アントラセンジイル基から成る群から選ばれるアリーレン基を表し、Ｙは炭素原子数２〜６のアルキレン基を表す。）

(In the general formula (2), n represents an integer of 1 to 5, and X is a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group which may have a substituent. It represents an arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracendyl group, and Y represents an alkylene group having 2 to 6 carbon atoms.)

Polyester polyol (A3) is _a compound any one of R 1, _{R 2} and _{R 3} is a group represented by the general formula _(2), R 1, _{R 2} and one of _{R 3} 2 two generally formula A mixture of two or more compounds of the compound represented by (2) and the compound represented by the general formula (2) in which all of R ₁ , R ₂ and R ₃ are represented by the general formula (2). May be. It is more preferable that all of R _{1 to} R ₃ are groups represented by the general formula (2).

In the general formula (2), when X is substituted with a substituent, it may be substituted with one or more substituents, and the substituent is any carbon atom on X different from the free radical. Is bound to. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.

Specific examples of Y in the general formula (2) include an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, and a 1,6-hexylene group. It is an alkylene group having 2 to 6 carbon atoms, such as a methylpentylene group and a dimethylbutylene group. A propylene group and an ethylene group are preferable, and an ethylene group is more preferable.

The polyester polyol (A3) is obtained by reacting glycerol, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or an acid anhydride thereof, and a polyhydric alcohol as essential components.

Examples of the aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or an acid anhydride thereof include orthophthalic acid or an acid anhydride thereof, naphthalene 2,3-dicarboxylic acid or an acid anhydride thereof, naphthalene 1,2-dicarboxylic acid. Examples thereof include an acid or an acid anhydride thereof, anthraquinone 2,3-dicarboxylic acid or an acid anhydride thereof, and 2,3-anthracenecarboxylic acid or an acid anhydride thereof. These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.

As the polyvalent carboxylic acid, another polyvalent carboxylic acid may be copolymerized as long as the effect of the present invention is not impaired. Specifically, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanediocarboxylic acid; unsaturated bond-containing polyvalent carboxylic acids such as maleic anhydride, maleic acid, and fumaric acid; , 3-Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic polyvalent carboxylic acids; terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5 -Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, diphenic acid and its acid anhydride, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and these dicarboxylic acids Examples thereof include aromatic polyvalent carboxylic acids such as acid anhydrides or ester-forming derivatives, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids. Species or two or more species can be used together. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid, and diphenic acid are preferable.

Examples of the polyhydric alcohol include an alkylene diol having 2 to 6 carbon atoms. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, and dimethylbutanediol. Can be exemplified.

Further, a polyhydric alcohol other than glycerol and an alkylene diol having 2 to 6 carbon atoms may be copolymerized as long as the effect of the present invention is not impaired. Specifically, aliphatic polyhydric alcohols such as erythritol, pentaerythol, dipentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol and tripropylene glycol, cyclohexanedi. Aliphatic polyhydric alcohols such as methanol and tricyclodecanedimethanol, aromatic polyhydric phenols such as hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, or ethylene oxide thereof. Elongates and hydrolyzed aliphatic ring groups can be exemplified.

When the polyol composition (A) contains the polyester polyol (A3) as a main component, the content of the glycerol residue contained in the polyester polyol (A3) in the solid content of the gas barrier adhesive is 5% by mass or more. preferable. The glycerol residue refers to a residue (C ₃ H ₅ O ₃ = 89.07) excluding R _{1 to} R ₃ in the general formula (1), and is calculated using the following formula (b).

In the above formula (b), P refers to the polyester polyol (A3). The resin solid content mass of the gas barrier adhesive is determined from the total mass of the polyol composition (A) and the polyisocyanate composition (B) to be used, the diluting solvent (in the case of the dry lamination adhesive), and the polyisocyanate composition (B). It is the mass excluding the mass of the volatile component and the inorganic component contained in.

The polyester polyol (A4) obtained by polycondensing an ortho-oriented polyvalent carboxylic acid and a polyhydric alcohol is a polyvalent carboxylic acid containing at least one orthophthalic acid and its acid anhydride, ethylene glycol, and propylene. It consists of a polyhydric alcohol containing at least one selected from the group consisting of glycols, butylene glycols, neopentyl glycols, and cyclohexanedimethanol. In particular, a polyester polyol in which the usage rate of the orthophthalic acid and its acid anhydride with respect to the total amount of the polyvalent carboxylic acid is 70 to 100% by mass is preferable.

The polyvalent carboxylic acid requires either orthophthalic acid or an acid anhydride thereof, but other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, the aliphatic polyvalent carboxylic acid includes succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid and the like, and the unsaturated bond-containing polyvalent carboxylic acid includes maleic anhydride and maleic acid. Fumaric acid and the like, 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid as alicyclic polyvalent carboxylic acids, and terephthalic acid, isophthalic acid and pyromerit as aromatic polyvalent carboxylic acids. Acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p '-Dicarboxylic acids and acid anhydrides or ester-forming derivatives of these dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids. Can be used alone or in admixture of two or more. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.

The polyhydric alcohol includes at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, but other polyhydric alcohols can be used as long as the effects of the present invention are not impaired. It may be copolymerized. Specifically, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetra. Aliphatic diols such as ethylene glycol, dipropylene glycol and tripropylene glycol; hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol and their ethylene oxide extensions, hydrogenated Examples thereof include aromatic polyhydric phenols such as alicyclic compounds.

The polyester polyol (A5) having an isocyanul ring is represented by the following general formula (3).

（一般式（３）中、Ｒ_１〜Ｒ_３は各々独立して、−（ＣＨ_２）_ｎ１−ＯＨ（但し_ｎ１は２〜４の整数を表す）、又は下記一般式（４）で表される基を表す。但しＲ_１、Ｒ_２及びＲ_３の少なくとも１つは一般式（４）で表される基である。）

(In the general formula (3), R _{1 to} R ₃ are independently represented by − (CH ₂ ) _n1 −OH (where _n1 represents an integer of 2 to 4) or the following general formula (4). However, at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4).)

（一般式（４）中、ｎ２は２〜４の整数を表し、ｎ３は１〜５の整数を表し、Ｘは１，２−フェニレン基、１，２−ナフチレン基、２，３−ナフチレン基、２，３−アントラキノンジイル基、及び２，３−アントラセンジイル基から成る群から選ばれ、置換基を有していてもよいアリーレン基を表し、Ｙは炭素原子数２〜６のアルキレン基を表す。）

(In the general formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, and X is a 1,2-phenylene group, a 1,2-naphthylene group, and a 2,3-naphthylene group. , 2,3-anthraquinonediyl group, and 2,3-anthracendiyl group selected from the group and may have a substituent, Y represents an alkylene group having 2 to 6 carbon atoms. Represent.)

Polyester polyol (A5) _includes a compound any one of R 1, _{R 2} and _{R 3} is a group represented by the general formula _(4), R 1, _{R 2} and one of _{R 3} 2 two generally formula A mixture of two or more compounds of the compound represented by (4) and the compound represented by the general formula (4) in which all of R ₁ , R ₂ and R ₃ are represented by the general formula (4). May be. It is more preferable that all of R _{1 to} R ₃ are groups represented by the general formula (4).

In the general formula (3), the alkylene group represented by − (CH2) _n1 − may be linear or branched. Of these, n1 is preferably 2 or 3, and most preferably 2.

In the general formula (4), when X is substituted with a substituent, it may be substituted with one or more substituents, and the substituent is any carbon atom on X different from the free radical. Is bound to. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.

The substituent of X is preferably a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimide group, a carbamoyl group, an N-ethylcarbamoyl group or a phenyl group, preferably a hydroxyl group, a phenoxy group, a cyano group, a nitro group or a phthalimide group. A phenyl group is more preferred.

Specific examples of Y in the general formula (4) include an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, and a 1,6-hexylene group. It is an alkylene group having 2 to 6 carbon atoms, such as a methylpentylene group and a dimethylbutylene group. A propylene group and an ethylene group are preferable, and an ethylene group is more preferable.

The polyester polyol (A5) is obtained by reacting a triol having an isocyanul ring, an aromatic polyvalent carboxylic acid in which a carboxylic acid is substituted at the ortho position or an acid anhydride thereof, and a polyhydric alcohol as essential components.

Examples of the triol having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris (2-hydroxyethyl) isocyanuric acid and 1,3,5-tris (2-hydroxypropyl) isocyanuric acid. And so on.

Examples of the aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or its acid anhydride include orthophthalic acid or its acid anhydride, naphthalene 2,3-dicarboxylic acid or its acid anhydride, and naphthalene 1,2-dicarboxylic acid. Examples thereof include an acid or an acid anhydride thereof, anthraquinone 2,3-dicarboxylic acid or an acid anhydride thereof, and 2,3-anthracenecarboxylic acid or an acid anhydride thereof. These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.

Polyhydric alcohols include alkylenediols having 2 to 6 carbon atoms, specifically ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Examples of diols such as 1,6-hexanediol, methylpentanediol, and dimethylbutanediol can be used.

Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as the triol compound having an isocyanul ring, and the carboxylic acid is in the ortho position. A polyester polyol (A5) having an isocyanul ring using orthophthalic anhydride as the aromatic polyvalent carboxylic acid or its acid anhydride substituted with, and ethylene glycol as the polyhydric alcohol has improved gas barrier properties and adhesiveness. Excellent and preferable.

The isocyanul ring is highly polar and does not form hydrogen bonds. Generally, as a method for improving adhesiveness, a method of blending highly polar functional groups such as a hydroxyl group, a urethane bond, a ureido bond, and an amide bond is known, but a resin having these bonds forms an intermolecular hydrogen bond. It is easy and may impair the solubility in solvents such as ethyl acetate and 2-butanone, which are often used for solvent-based adhesives, but polyester resins having an isocyanul ring do not impair the solubility, so that the solubility is easily impaired. It can be diluted.

Further, since the isocyanul ring is trifunctional, a polyester polyol compound having the isocyanul ring as the center of the resin skeleton and a polyester skeleton having a specific structure in the branched chain can obtain a high crosslink density. It is presumed that by increasing the crosslink density, the gap through which a gas such as oxygen passes can be reduced. As described above, it is presumed that the isocyanul ring has high polarity and high crosslink density without forming an intermolecular hydrogen bond, so that gas barrier properties and adhesiveness can be ensured.

From this point of view, when the polyol composition (A) contains the polyester polyol (A5) as a main component, the content of the isocyanul ring contained in the polyester polyol (A5) in the solid content of the gas barrier adhesive is 5% by mass. The above is preferable. The isocyanul ring refers to the residue (C ₃ N ₃ O ₃ = 126.05) excluding R _{1 to} R ₃ in the general formula (3), and is calculated using the following formula (b).

In the above formula (c), P refers to the polyester polyol (A5). The resin solid content mass of the gas barrier adhesive is determined from the total mass of the polyol composition (A) and the polyisocyanate composition (B) to be used, the diluting solvent (in the case of the dry lamination adhesive), and the polyisocyanate composition (B). It is the mass excluding the mass of the volatile component and the inorganic component contained in.

The hydroxyl value of the polyester polyol is preferably 20 mgKOH / g or more and 250 mgKOH / g or less. When the hydroxyl value is smaller than 20 mgKOH / g, the viscosity of the polyol composition (A) becomes high because the molecular weight is too large, and good coating suitability cannot be obtained. When the hydroxyl value exceeds 250 mgKOH / g, the molecular weight is too small and the crosslink density of the cured coating film becomes too high, so that good adhesive strength cannot be obtained.

When the polyester polyol has an acid group, the acid value is preferably 200 mgKOH / g or less. When the acid value exceeds 200 mgKOH / g, the reaction between the polyol composition (A) and the polyisocyanate composition (B) becomes too fast, and good coating suitability cannot be obtained. The lower limit of the acid value of the polyester polyol is not particularly limited, but as an example, it is 20 mgKOH / g or more. When the acid value is 20 mgKOH / g or more, good gas barrier properties and initial cohesive force can be obtained by intermolecular interaction. The hydroxyl value of the polyester polyol can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070.

When the number average molecular weight of the polyester polyol as described above is 300 to 5000, it is particularly preferable that a crosslink density having an excellent balance between adhesiveness and gas barrier property can be obtained. More preferably, the number average molecular weight is 350 to 3000. If the molecular weight is less than 300, the cohesive force of the adhesive at the time of coating becomes too small, and there is a possibility that the film may be displaced during laminating or the bonded film may be lifted. On the other hand, if the molecular weight is higher than 5000, the viscosity at the time of coating becomes too high and the coating cannot be performed, or the adhesiveness is low and the lamination cannot be performed. The number average molecular weight is calculated from the obtained hydroxyl value and the number of functional groups of the designed hydroxyl group.

The glass transition temperature of the polyester polyol is preferably −30 ° C. or higher and 80 ° C. or lower, more preferably 0 ° C. or higher and 60 ° C. or lower, and further preferably 25 ° C. or higher and 60 ° C. or lower. If the glass transition temperature exceeds 80 ° C., the flexibility of the polyester polyol at around room temperature is low, so that the adhesion to the substrate is poor and the adhesiveness may be lowered. On the other hand, if the temperature is lower than -30 ° C, the molecular motion of the polyester polyol at around room temperature is intense, so that sufficient gas barrier properties may not be obtained.

The polyester polyol may be a polyester polyurethane polyol having a number average molecular weight of 1000 to 15000 by urethane elongation of polyester polyols (A1) to (A5) by reaction with a diisocyanate compound. Since the urethane-extended polyester polyol has a molecular weight component of a certain level or more and a urethane bond, it has excellent gas barrier properties, excellent initial cohesive force, and is excellent as an adhesive for laminating.

The polyisocyanate composition (B), which is a component of a two-component adhesive having a gas barrier property, contains an isocyanate compound. As the isocyanate compound, conventionally known compounds can be used without particular limitation, and tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, xylylene diisocyanate, hydride xylylene diisocyanate, isophorone diisocyanate or Trimerics of these isocyanate compounds, and excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane. , Gglycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylene diamine and other low molecular weight active hydrogen compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, Examples thereof include adducts obtained by reacting with a high molecular weight active hydrogen compound of polyamides. Polyester polyisocyanate obtained by reacting polyester polyols (A1) to (A5) with a diisocyanate compound in an excess ratio of hydroxyl groups and isocyanate groups may be used. These can be used alone or in combination of two or more.

Further, blocked isocyanate may be used as the isocyanate compound. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, acetoxime, methylethylketooxime, cyclohexanone oxime, and methanol. Alcohols such as ethanol, propanol and butanol, ethylene chlorohydrin, 1,3-dichloro-2-
Examples thereof include halogen-substituted alcohols such as propanol, tertiary alcohols such as t-butanol and t-pentanol, and lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propyrrolactam. In addition, active methylene compounds such as aromatic amines, imides, acetylacetones, acetoacetate esters, and malonic acid ethyl esters, mercaptans, imines, ureas, diaryl compounds, sodium disulfide and the like can also be mentioned. The blocked isocyanate is obtained by subjecting the above-mentioned isocyanate compound and an isocyanate blocking agent to an addition reaction by a known and commonly used method.

Of these, xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate are preferable because good gas barrier properties can be obtained, and isocyanate compounds having a metaxylene skeleton such as metaxylylene diisocyanate and metahydrogenated xylylene diisocyanate are preferable. Is more preferable to use.

Examples of the isocyanate compound having a metaxylene skeleton include a trimer of xylene diisocyanate, a burette compound synthesized by a reaction with an amine, and an adduct compound formed by a reaction with an alcohol. When the adhesive is a solvent type, it is preferable to use an adduct body because the solubility in the organic solvent used for the solvent type adhesive is better than that of the trimer body and the burette body. As the adduct, an adduct formed by reacting with an alcohol appropriately selected from the above low molecular weight active hydrogen compounds can be used. Among them, ethylene oxide adducts of trimethylolpropane, glycerol, triethanolamine, and metaxylene diamine can be used. An adduct body with an object is preferable.

Further, when a composition containing a polyester polyol having a carboxylic acid group remaining like the polyester polyol (A1) is used as the polyol composition (A), the polyisocyanate composition (B) contains an epoxy compound. You may be. Examples of epoxy compounds include diglycidyl ether of bisphenol A and its oligomer, diglycidyl ether of bisphenol A and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid di. Glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butandiol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimeric acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl Examples thereof include propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, and triglycidyl ether as a glycerol alkylene oxide adduct.

When an epoxy compound is used, a widely known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing as long as the object of the present invention is not impaired.

When a composition containing a polyol having a polymerizable carbon-carbon double bond such as the polyester polyol (A2) is used as the polyol composition (A), in order to promote the polymerization of the carbon-carbon double bond, A known polymerization catalyst can be used in combination, and a transition metal complex is mentioned as an example. The transition metal complex is not particularly limited as long as it is a compound having an ability to oxidatively polymerize a polymerizable double bond. For example, metals such as cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, copper, octyl acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, linseed oil fatty acid, Salts with soybean oil fatty acids and the like can be used. The blending amount of the transition metal complex is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass with respect to the resin solid content contained in the polyol composition (A).

The polyol composition (A) and the polyisocyanate composition (B) have an equivalent ratio of the hydroxyl group contained in the polyol composition (A) to the isocyanate group contained in the polyisocyanate composition (B) of 1/0. It is preferably blended so as to be 5 to 1/10, and more preferably to be blended to be 1/1 to 1/5. When the isocyanate compound is excessive, the excess isocyanate compound remaining in the cured coating film of the adhesive may bleed out from the adhesive layer. On the other hand, if the reactive functional groups contained in the polyisocyanate composition (B) are insufficient, the adhesive strength may be insufficient.

Various additives may be added to the gas barrier adhesive as long as the adhesiveness and gas barrier properties are not impaired.

An inorganic filler may be used as such an additive. Examples of the inorganic filler include silica, alumina, aluminum flakes, glass flakes and the like. In particular, it is preferable to use a plate-shaped inorganic compound as the inorganic filler because the adhesive strength, gas barrier property, light-shielding property and the like are improved. Plate-like inorganic compounds include hydrous silicates (phyrosilicate minerals, etc.), kaolinite-serpentine clay minerals (haloisite, kaolinite, enderite, dicite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllium. Light-Tark (pyrophyllite, talc, kerolai, etc.), smectite clay minerals (montmorillonite, biderite, nontronite, saponite, hectrite, saconite, stivuncite, etc.), vermiculite clay minerals (vermiculite, etc.), mica or Mica clay minerals (white mica, gold mica, etc., margarite, tetracylic mica, teniolite, etc.), green mudstones (cookate, sudoite, clinochloa, chamosite, nimite, etc.), hydrotalcite, plate sulfate Examples include barium, boehmite, and aluminum polyphosphate. These minerals may be natural clay minerals or synthetic clay minerals. The plate-like inorganic compound may be used alone or in combination of two or more.

The plate-like inorganic compound may be an ionic compound having an electric charge between layers, or a nonionic compound having no electric charge. The presence or absence of electric charge between layers does not directly affect the gas barrier property of the adhesive layer. However, ionic plate-like inorganic compounds and inorganic compounds that have swelling properties with respect to water are inferior in dispersibility in solvent-based adhesives, and when the amount added is increased, they become thicker with the adhesives or become chysole. As a result, the coating suitability may decrease. Therefore, the plate-like inorganic compound is preferably nonionic without interlayer electrification.

The average particle size of the plate-shaped inorganic compound is not particularly limited, but as an example, it is preferably 0.1 μm or more, and more preferably 1 μm or more. If it is smaller than 0.1 μm, the detour route of oxygen molecules will not be long, and improvement of gas barrier property cannot be expected sufficiently. The upper limit of the average particle size is not particularly limited, but if the particle size is too large, defects such as streaks may occur on the coated surface depending on the coating method. Therefore, as an example, the average particle size is preferably 100 μm or less, and preferably 20 μm or less. In the present specification, the average particle size of the plate-shaped inorganic compound means the particle size that appears most frequently when the particle size distribution of the plate-shaped inorganic compound is measured by a light scattering type measuring device.

The aspect ratio of the plate-like inorganic compound is preferably high in order to improve the gas barrier property due to the maze effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

The blending amount of the plate-shaped inorganic compound is arbitrary, but as an example, when the total solid content of the polyol composition (A), the polyisocyanate composition (B), and the plate-shaped inorganic compound is 100 mass, the plate-shaped inorganic compound is formed. The blending amount of the inorganic compound is 5 to 50 parts by mass.

The gas barrier adhesive may contain an adhesion promoter. Examples of the adhesion accelerator include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate-based coupling agents, aluminum-based coupling agents, and epoxy resins. Silane coupling agents and titanate-based coupling agents can be expected to have the effect of improving the adhesiveness to various film materials.

When the gas barrier adhesive layer needs to be acid resistant, the gas barrier adhesive may contain a known acid anhydride. Examples of the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, and tetrapromphthalic acid. Anhydride, tetrachlorphthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic acid anhydride, 2,3,6,7-naphthalintetracarboxylic acid dianhydride, 5- (2) , 5-Oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, maleic anhydride copolymer, and the like.

If necessary, a compound having an oxygen trapping function or the like may be further added. Examples of the compound having an oxygen trapping function include low molecular weight organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, cobalt, manganese, nickel, iron, and the like. Examples thereof include transition metal compounds such as copper.

If necessary, a tackifier such as xylene resin, terpene resin, phenol resin, or rosin resin may be added in order to improve the adhesiveness to various film materials immediately after application. When these are added, the blending amount thereof is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the polyol composition (A) and the polyisocyanate composition (B).

When the polyol composition (A) contains a polyester polyol (A2), active energy rays can also be used as a method for reacting the polymerizable carbon-carbon double bond. A known technique can be used as the active energy ray, and it can be cured by irradiating it with ionizing radiation such as an electron beam, ultraviolet rays, or γ rays. When curing with ultraviolet rays, a known ultraviolet irradiation device equipped with a high-pressure mercury lamp, an excimer lamp, a metal halide lamp, or the like can be used.

When curing by irradiating with ultraviolet rays, if necessary, add 0.1 to 20 parts by mass of a light (polymerization) initiator that generates radicals or the like by irradiation with ultraviolet rays with respect to 100 parts by mass of polyester polyol (A2). It is preferable to add to some extent.

Radical-generating photo (polymerization) initiators include hydrogen abstraction types such as benzyl, benzophenone, Michler's ketone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone, and benzoin ethyl ether, diethoxyacetophenone, benzylmethylketal, and hydroxy. Examples thereof include photocleavable types such as cyclohexylphenyl ketone and 2-hydroxy-2-methylphenyl ketone. Among these, one or a plurality of them can be used alone or in combination.

In addition, the gas barrier adhesive may contain stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, blocking inhibitors, colorants, crystal nucleating agents, and the like. .. These various additives may be added to either or both of the polyol composition (A) and the polyisocyanate composition (B) in advance, or the polyol composition (A) and the polyisocyanate composition ( It may be added when mixing with B).

(Sealant layer)
The sealant layer is a layer containing a heat-sealing resin (sealant film) that can be melted by heat and fused to each other. Suitable resins for the sealant film include polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- ( Acrylic acid, methacrylic acid, maleic anhydride, and other olefinic resins such as meta) acrylate copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene. Fumaric acid and other modified olefin resins modified with unsaturated carboxylic acid, ternary copolymer of ethylene- (meth) acrylic acid ester-unsaturated carboxylic acid, cyclic polyolefin, cyclic olefin copolymer, polyethylene terephthalate (PET), polyacrylonitrile (PAN) and the like. A resin film, sheet, or other coating film made of one or more of these resins can be used as a sealant film.

As the sealant film, any unstretched, uniaxially stretched, or biaxially stretched film can be used.

The stretched film stretched in the biaxial direction is vertically stretched 2 to 4 times by, for example, a roll stretching machine at 50 to 100 ° C., and further laterally stretched 3 to 5 times by a tenter stretching machine in an atmosphere of 90 to 150 ° C. Subsequently, it is obtained by heat treatment with a tenter stretching machine in an atmosphere of 100 to 240 ° C. Alternatively, simultaneous biaxial stretching and sequential biaxial stretching may be used.

An easily peelable sealant film (easy peel film) may be used for the sealant layer. As the easily peelable sealant film, any of the interfacial peeling type, the coagulation peeling type, and the delamination type can be applied, and can be appropriately selected according to the type of the packaging material and the required characteristics described later. The index of easy peelability is appropriately set according to the type of packaging material and required characteristics, and as an example, the seal strength is 2 to 20 N / 15 mm. For example, easy peelability can be exhibited by a phase-separated polymer blend in which polypropylene is combined with high-density polyethylene, low-density polyethylene, an ethylene-vinyl acetate copolymer, or the like.

The film thickness of the sealant film can be arbitrarily selected, but is selected in the range of 5 to 500 μm, for example, when applied to a packaging material described later. It is more preferably 10 to 250 μm, further preferably 15 to 100 μm. If it is less than 5 μm, sufficient laminating strength as a packaging material cannot be obtained, and there is a risk that piercing resistance and the like will be lowered. If it exceeds 250 μm, the cost will increase and the film will become hard, resulting in reduced workability.

The sealant layer may include an inorganic vapor deposition layer on at least one surface of the sealant film. Such an inorganic vapor deposition layer can be formed by the same material and method as the inorganic vapor deposition layer provided on the base material. Similar to the base material layer, a barrier coat layer may be further provided on the inorganic vapor deposition layer provided on the sealant film.

(Laminate and other layers)
The laminate of the present invention may have other layers, if necessary. For example, a film may be arranged between the gas barrier adhesive layer and the sealant layer. As the film, the same film as that exemplified as the base material can be used. Uniaxial or biaxially stretched polyester film such as polyethylene terephthalate and polyethylene naphthalate, uniaxial or biaxially stretched polyamide film such as nylon 6, nylon 66 and MXD6 (polymethoxylylen adipamide), biaxially stretched polypropylene film and the like. It can be preferably used.

When the film is arranged between the gas barrier adhesive layer and the sealant layer, the film and the sealant layer may be bonded to each other via an adhesive. The adhesive used at this time may or may not be the gas barrier adhesive described above. The film may be bonded to a base material (printing layer) via a gas barrier adhesive layer, or another layer may be further arranged between the film and the gas barrier adhesive layer. ..

(Manufacturing method of laminated body)
The laminate of the present invention is obtained by laminating a base material provided with a printing layer and a sealant layer by a non-solvent laminating method using a gas barrier adhesive. In the obtained laminate, a printing layer is arranged between the base material and the sealant layer, and a gas barrier adhesive layer is arranged between the printing layer and the sealant layer. When the substrate is provided with an inorganic vapor deposition layer, the inorganic vapor deposition layer is arranged between the substrate and the printing layer. In other words, the printing layer is printed directly on the inorganic vapor deposition layer of the substrate or via a gas barrier coat layer. When the sealant layer is provided with the inorganic vapor deposition layer, it is preferable that the sealant layer is arranged so that the inorganic vapor deposition layer and the gas barrier adhesive layer are in contact with each other.

If the laminate has a separate layer in addition to these layers, for example if it has an additional film between the gas barrier adhesive layer and the sealant layer, the laminate of the invention will be with the sealant layer. It is obtained by laminating a film with a non-solvent laminating layer using a solvent-free adhesive, and then laminating the laminate and a base material by a non-solvent laminating method using a gas barrier adhesive. Alternatively, a laminate obtained by laminating a base material and a film by a non-solvent laminating method using a gas barrier adhesive is bonded to a sealant layer by a non-solvent laminating method using a solvent-free adhesive. When a film provided with an inorganic vapor deposition layer is used, it is preferable that the film is arranged so that the inorganic vapor deposition layer and the gas barrier adhesive layer are in contact with each other.

The printing layer is provided by printing the water-based liquid ink by a gravure printing method or a flexographic printing method and then drying it in an oven. The film thickness of the printed layer is arbitrary, the character to be printed varies depending on the pattern or the like, is 0.3g ^{/ m 2} ~10g ^/ m 2 as an example.

The gas barrier adhesive layer is preliminarily set to about 40 ° C. to 100 ° C. on either the base material (on the printed surface of the base material) or the sealant layer (on the inorganic vapor-deposited layer when the inorganic-deposited layer is provided). After applying the heated gas barrier adhesive using a roll such as a gravure roll, the other is immediately bonded to obtain the laminate of the present invention. It is preferable to perform an aging treatment after laminating. The aging temperature is preferably room temperature to 70 ° C., and the aging time is preferably 6 to 240 hours. The amount of the gas barrier adhesive applied is appropriately adjusted, but as an example, it is 1 g / m ² or more and 10 g / m ² or less, preferably 1 g / m ² or more and 5 g / m ² or less.

<Packaging material>
The laminate of the present invention can be used as a multi-layer packaging material for the purpose of protecting foods, pharmaceuticals and the like. When used as a multi-layer packaging material, its layer structure may change depending on the contents, usage environment, and usage pattern.

The packaging material of the present invention is obtained by using the laminate of the present invention, laminating the surfaces of the sealant films of the laminate so as to face each other, and then heat-sealing the peripheral end portions thereof. As a bag-making method, the laminate of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type. There are three-way seal type, four-way seal type, envelope-attached seal type, gassho-attached seal type, fold-attached seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-seal methods. Be done. The packaging material of the present invention can take various forms depending on the contents, the usage environment, and the usage mode. Free-standing packaging materials (standing pouches), etc. are also possible. As a heat sealing method, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to produce a product using the packaging material of the present invention. The contents to be filled include rice confectionery, bean confectionery, nuts, biscuits / cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles, dried noodles, pasta. , Sterile packaged rice, elephant, porridge, packaged rice, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, licked mushrooms, konnyaku, processed wild vegetables, jams, peanut cream, salads, frozen Processed agricultural products such as vegetables and processed potatoes, hams, bacon, sausages, processed chicken products, processed livestock products such as corned beef, fish meat hams and sausages, marine products, kamaboko, glue, boiled vegetables, sardines, salted spicy, Processed marine products such as smoked salmon and spicy cod roe, peaches, tangerines, pineapples, apples, pears, cherries and other fruit meats, corn, asparagus, mushrooms, onions, carrots, radishes, potatoes and other vegetables, hamburgers, meats Prepared foods such as balls, fried fishery products, gyoza, croquette and other frozen side dishes, chilled side dishes, butter, margarine, cheese, cream, instant creamy powder, dairy products such as prepared milk powder for childcare, liquid seasonings, retort Examples include foods such as curry and pet food. In addition, the packaging material of the present invention can also be used as a packaging material for pharmaceuticals such as tobacco, disposable body warmers, infusion packs, cosmetics, and vacuum heat insulating materials.

Alternatively, the packaging material of the present invention may be a lid material using the laminate of the present invention.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The composition and other values are based on mass unless otherwise specified.

<Adjustment of solvent-free gas barrier adhesive>
(Adjustment of polyol composition)
In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., phthalic anhydride 1316.8 parts, ethylene glycol 573.9 parts, glycerin 409.3 parts and titanium tetraisopropoxide were placed. An amount corresponding to 100 ppm was charged with respect to the total amount of the polyvalent carboxylic acid and the polyhydric alcohol, and the temperature of the upper part of the rectification tube was gradually heated so as not to exceed 100 ° C. to maintain the internal temperature at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a hydroxyl value of 339.9 mgKOH / g. Next, the temperature was lowered to 120 ° C., and 421.8 parts of maleic anhydride was charged therein to maintain 120 ° C. The esterification reaction was terminated when the acid value was approximately half of the acid value calculated from the amount of maleic anhydride charged, and the number average molecular weight was about 520, the hydroxyl value was 216.6 mgKOH / g, and the acid value was 96.2 mgKOH / g. A polyester polyol was obtained. The number of design functional groups per molecule of polyester polyol is: 2 hydroxyl groups and 1 carboxy group.

(Adjustment of isocyanate composition)
Prepare an isocyanate composition by mixing 49.5 parts of Sumika Bayer Urethane "Death Module N3200" (biuret of hexamethylene diisocyanate) and 28.9 parts of Mitsui Chemicals "Takenate 500" (methoxylylene diisocyanate). did.

(Adjustment of solvent-free gas barrier adhesive)
100 parts of the polyester polyol prepared above and 78.4 parts of the isocyanate composition were mixed at 80 ° C. to obtain a two-component curing type solvent-free gas barrier adhesive.

<Adjustment of solvent-type gas barrier adhesive>
(Adjustment of polyol composition)
In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., phthalic anhydride 1223.3 parts, ethylene glycol 255.3 parts, glycerin 253.2 parts and titanium tetraisopropoxide were placed. An amount corresponding to 100 ppm was charged with respect to the total amount of the polyvalent carboxylic acid and the polyhydric alcohol, and the temperature of the upper part of the rectification tube was gradually heated so as not to exceed 100 ° C. to maintain the internal temperature at 220 ° C. The esterification reaction was terminated when the acid value became 1 mgKOH / g or less to obtain a polyester polyol having a number average molecular weight of about 650, a hydroxyl value of 261.2 mgKOH / g, and an acid value of 0.8 mgKOH / g. The number of design functional groups per molecule of polyester polyol is 3 hydroxyl groups and 0 carboxy groups.

(Preparation of isocyanate composition)
An isocyanate composition was prepared by mixing 143 parts of "Takenate D110N (NB)" manufactured by Mitsui Chemicals and 24.5 parts of "Takenate 500" manufactured by Mitsui Chemicals.

(Preparation of solvent-based gas barrier adhesive)
70 parts of the polyester polyol prepared above, 167.5 parts of the isocyanate composition, and 123 parts of ethyl acetate were mixed at 40 ° C. to obtain a two-component curable solvent-type gas barrier adhesive.

<Preparation of solvent-type non-gas barrier adhesive>
(Preparation of polyol composition)
442.3 parts of adipine, 105.45 parts of ethylene glycol, 178.67 parts of neopentyl glycol and titanium tetraisopropoxide in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. Was charged in an amount corresponding to 100 ppm with respect to the total amount of the polyvalent carboxylic acid and the polyhydric alcohol, and gradually heated so that the temperature of the upper part of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. .. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a hydroxyl value of 56.1 mgKOH / g. Further, while heating at 60 ° C., 664 parts of ethyl acetate was added as a diluting solvent and stirred for 1 hour to obtain a polyol composition.

(Adjustment of solvent type non-gas barrier adhesive)
A two-component curable solvent in which 100 parts of the polyol composition prepared above and 15.6 parts of a trimethylolpropane adduct of tolylene diisocyanate (Death Module L75 manufactured by Sumitomo Covestro Urethane Co., Ltd.) are mixed. A mold non-gas barrier adhesive was obtained.

<Adjustment of solvent-free non-gas barrier adhesive>
(Adjustment of polyol composition)
403.1 parts of adipic acid, 119.9 parts of ethylene glycol, 203.3 parts of neopentyl glycol and titanium tetraisopropoxide in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. Was charged in an amount corresponding to 100 ppm with respect to the total amount of the polyvalent carboxylic acid and the polyhydric alcohol, and gradually heated so that the temperature of the upper part of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. .. The esterification reaction was terminated when the acid value became 1 mgKOH / g or less to obtain a polyester polyol having a number average molecular weight of 600.

(Adjustment of isocyanate composition)
In a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, Snyder tube, and condenser, 92.00 parts of ethylene glycol, 118.50 parts of neopentyl glycol, 29.23 parts of adipic acid, and 0.01 part of titanium tetraisopropoxide. Was charged and gradually heated so that the temperature of the upper part of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester intermediate having a number average molecular weight of 800.

Put 119.05 parts of luplanate MI (mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) in a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, a cooling condenser, and a dropping funnel. The mixture was stirred while heating at 70 ° C., 81.63 parts of the polyester intermediate was added dropwise using a dropping funnel over 2 hours, and the mixture was further stirred for 4 hours to obtain a polyisocyanate composition.

(Adjustment of solvent-free non-gas barrier adhesive)
100 parts of the polyol composition prepared above and 107.2 parts of the polyisocyanate composition were mixed at 60 ° C. to obtain a two-component curing type solvent-free non-gas barrier adhesive.

<Adjustment of water-based liquid ink>
(Adjustment of resin for water-based ink)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 191 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 141 parts by mass of isophorone diisocyanate, and 26 parts by mass of 2,2-dimethylolpropionic acid. By reacting in a mixed solvent of 28 parts by mass, 1,4-cyclohexanedimethanol and 200 parts by mass of methyl ethyl ketone, an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal was obtained.

Next, 20 parts by mass of a 50% potassium hydroxide aqueous solution was added to neutralize a part or all of the carboxyl groups of the urethane prepolymer, and 700 parts by mass of water and 9.0 parts by mass of an 80% hydrazine aqueous solution were added sufficiently. An aqueous dispersion of a urethane resin was obtained by stirring the mixture, and then aging and solvent removal were performed to obtain a resin for an aqueous liquid ink having a non-volatile content of 40% by mass.

(Adjustment of water-based liquid ink)
Using the obtained resin for water-based liquid ink, the mixture was stirred and mixed with the following composition, and then kneaded with a bead mill to prepare a kneaded meat base.
[Meat base combination]
FASTPGEN BLUE LA5380 Indigo pigment (manufactured by DIC) 15 parts Resin for water-based liquid ink 40 parts Nonionic pigment dispersant (manufactured by BYK) 10 parts Isopropyl alcohol 3 parts Water 8 parts Silicone defoamer (manufactured by BYK) 0. Part 2

After adding 10 parts of resin for water-based liquid ink and 4 parts of water to the obtained kneaded meat base, the viscosity of the water-based liquid ink becomes 16 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha). Water was added in the same manner to obtain a water-based liquid ink. The amount of water used for adjusting the viscosity was 5 parts, the non-volatile content of the water-based liquid ink was 58%, and the surface tension at 25 ° C. was 35 mN / m. The surface tension was measured using an automatic surface tension meter DY-300 manufactured by Kyowa Interface Science Co., Ltd. based on the Whyhelmy method. The composition of the obtained water-based liquid ink is as follows.
[Combining water-based liquid ink]
FASTPGEN BLUE LA5380 Indigo pigment (manufactured by DIC) 15 parts Resin for water-based liquid ink 50 parts Nonionic pigment dispersant (manufactured by BYK) 10 parts Isopropyl alcohol 3 parts Water 17 parts Silicone defoamer (manufactured by BYK) 0. Part 2

<Adjustment of solvent type gravure ink>
(Adjustment of urethane resin solution)
80 parts of neopentyl glycol adipatediol (hydroxyl value: 56.6 mgKOH / g) and 20 parts of polyethylene glycol (hydroxyl value: 278 mgKOH / g) in a four-necked flask equipped with a stirrer, thermometer, reflux cooler and nitrogen gas introduction tube. g) and 29.68 parts of isophorone diisocyanate were charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.84% by mass, and then 69.8 parts of ethyl acetate. Was added to prepare a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 7.97 parts of isophorone diamine, 0.11 part of di-n-butylamine, 139.1 parts of ethyl acetate and 112.5 parts of isopropyl alcohol, and 5 at 45 ° C. The mixture was stirred for a time to obtain a polyurethane resin solution. The obtained polyurethane resin solution had a resin solid content concentration of 30.4%, a resin solid content Mw of 54,000, and a urethane bond concentration of 1.31 mmol / g.

(Adjustment of solvent type gravure ink)
A mixture of 30 parts of the obtained urethane resin solution, 30 parts of a vinyl chloride vinyl acetate resin solution having a hydroxyl group (15% solution), 10 parts of a phthalocyanine blue pigment (FASTGEN Blue LA5380 manufactured by DIC Co., Ltd.), and 30 parts of ethyl acetate. Was kneaded to prepare a base ink.
The viscosity of the obtained base ink was adjusted with ethyl acetate in Zahn Cup # 3 (manufactured by Rigosha) for 16 seconds (25 ° C.) to obtain a solvent-type gravure ink. The non-volatile content of the obtained gravure ink was 25%.

<Manufacturing of laminate>
(Example 1)
Aqueous liquid ink is printed on a substrate using a Flexoproof100 test printing machine (Testing Machines, Inc., Anilox 200 lines / inch) with a solid pattern of 240 mm in length and 80 mm in width, and then dried with a dryer to obtain a printed matter. It was. The coating amount of the printing layer (solid content of the coated water-based liquid ink) was 1.0 g / m ² . An alumina-deposited PET film (“GL-ARH” manufactured by Toppan Co., Ltd.) was used as the base material, and a printing layer was provided on the alumina-deposited surface (on the coat layer) of the base material.

Next, the solvent-free gas barrier adhesive was heated to 80 ° C. and applied onto the printing layer using a solvent-free test coater (manufactured by Polytype) so as to have a coating amount of 2.0 g / m ² . Next, as a sealant layer, it was laminated with a corona-treated surface of a CPP film (“P1128” manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm to prepare a laminate having a layer structure of PET film / printing layer / adhesive layer / CPP film. This laminate was aged at 40 ° C. for 3 days to obtain the laminate of Example 1.

(Example 2)
A laminate of Example 2 was obtained in the same manner as in Example 1 except that the base material was changed to a silica-deposited PET film (manufactured by Mitsubishi Chemical Holdings, "Tech Barrier LS)).
(Example 3)
A laminate of Example 3 was obtained in the same manner as in Example 1 except that the base material was changed to a silica-deposited PET film (manufactured by Mitsubishi Chemical Holdings, "Tech Barrier L)).
(Example 4)
A laminate of Example 4 was obtained in the same manner as in Example 1 except that the base material was changed to an alumina-deposited PET film (manufactured by Toray Film Processing Co., Ltd., "Barrierlocks 1011HG".
(Example 5)
A laminate of Example 5 was obtained in the same manner as in Example 1 except that the base material was changed to a dual vapor deposition film of silica and alumina (“Eco-Cial VE100” manufactured by Toyobo Co., Ltd.).

(Example 6)
Aqueous liquid ink is printed on a substrate using a Flexoproof100 test printing machine (Testing Machines, Inc., Anilox 200 lines / inch) with a solid pattern of 240 mm in length and 80 mm in width, and then dried with a dryer to obtain a printed matter. It was. The coating amount of the printing layer (solid content of the coated water-based liquid ink) was 1.0 g / m ² . A PET film having a thickness of 12 μm (“E-5102” manufactured by Toyobo Co., Ltd.) was used as the base material, and a printing layer was provided on the corona-treated surface of the base material.

Next, the solvent-free gas barrier adhesive was heated to 80 ° C. and applied onto the printing layer using a solvent-free test coater (manufactured by Polytype) so as to have a coating amount of 2.0 g / m ² . The inorganic vapor deposition layer of the transparent vapor deposition nylon film (Tech Barrier MX, manufactured by Mitsubishi Chemical Holdings) was laminated so as to be in contact with the adhesive layer. Furthermore, a solvent-free gas barrier adhesive is applied onto Tech Barrier MX so that the coating amount is 2.0 g / m ^2, and a polyethylene film ("TUX-HC" manufactured by Mitsui Kagaku Tohcello Co., Ltd.) is laminated as a sealant layer. Then, a laminate having a layer structure of PET film / printing layer / adhesive layer / transparent vapor-deposited nylon film / adhesive layer / PE film was prepared. This laminate was aged at 40 ° C. for 3 days, and the laminate of Example 6 was prepared. A laminate was obtained.

(Example 7)
A laminate of Example 7 was obtained in the same manner as in Example 6 except that Barrier Rocks 1011HG was used instead of Tech Barrier MX.
(Example 8)
A laminate of Example 8 was obtained in the same manner as in Example 6 except that an OPP film (manufactured by Toyobo Co., Ltd., “P-2171”) was used as a base material.

(Example 9)
Examples except that an OPP film (manufactured by Toyobo Co., Ltd., "P-2171") was used as a base material and an aluminum-deposited CPP film (manufactured by Toray Film Processing Co., Ltd., "2703") was used as a sealant layer. The laminate of Example 9 was obtained in the same manner as in 1.
(Example 10)
Example 1 except that a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) was used as a base material and an aluminum-deposited CPP film (“2703” manufactured by Toray Film Processing Co., Ltd.) was used as a sealant layer. In the same manner as above, the laminate of Example 10 was obtained.

(Example 11)
Example 1 except that an OPP film (manufactured by Toyobo Co., Ltd., "P-2171") was used as a base material and an aluminum-deposited OPP film (manufactured by Jindal Films, "Metallyte films SUPM 40") was used as a sealant layer. In the same manner as above, the laminate of Example 11 was obtained.
(Example 12)
Example 1 and Example 1 except that a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) was used as a base material and an aluminum-deposited OPP film (“Metallyte films SUPM 40” manufactured by Jindal Films) was used as a sealant layer. In the same manner, a laminate of Example 12 was obtained.

(Comparative Example 1)
A printed matter was obtained in the same manner as in Example 1 except that a solvent-type gravure ink was used instead of the water-based liquid ink and a printed layer was formed by a gravure printing machine equipped with a laser gravure plate having a plate depth of 35 μm. The coating amount of the printing layer (solid content of the applied solvent-type gravure ink) was 1.0 g / m ² . Next, a solvent-type gas barrier adhesive (nonvolatile content 50%) was applied onto the printed layer of the obtained printed matter using a bar coater so as to have a coating amount of 3.0 g / m ² (solid content). Then, the diluting solvent was volatilized with a dryer set at a temperature of 70 ° C.

Next, as a sealant layer, a CPP film having a thickness of 25 μm (“P1128” manufactured by Toyobo Co., Ltd.) is laminated so as to be in contact with the corona-treated surface, and has a layer structure of PET film / printing layer / adhesive layer / CPP film. A laminate was created. This laminate was aged at 40 ° C. for 2 days to obtain the laminate of Comparative Example 1.

(Comparative Example 2)
A laminate of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that the base material was changed to an alumina-deposited PET film (“Barrierlocks 1011HG” manufactured by Toray Film Processing Co., Ltd.).
(Comparative Example 3)
A laminate of Comparative Example 3 was obtained in the same manner as in Comparative Example 2 except that a general-purpose solvent-type adhesive (nonvolatile content 33.3%) was used as the adhesive.
(Comparative Example 4)
A laminate of Comparative Example 4 was obtained in the same manner as in Comparative Example 2 except that a solvent-free gas barrier adhesive was used as the adhesive.
(Comparative Example 5)
A laminate of Comparative Example 5 was obtained in the same manner as in Example 9 except that a solvent-type gravure ink was used instead of the water-based liquid ink. The print layer was formed in the same manner as in Comparative Example 1.
(Comparative Example 6)
A laminate of Comparative Example 6 was obtained in the same manner as in Example 9 except that a general-purpose solvent-free adhesive was used as the adhesive.

<Evaluation>
(Theoretical environmental solvent emission per 1 m ² )
The amount of solvent (theoretical value) per 1 m ² discharged when the laminate was manufactured was calculated. The unit is g / m ² . The results are summarized in Tables 1-3.

(Oxygen permeability)
The aging-finished laminate is adjusted to a size of 10 cm x 10 cm, and OX-TRAN2 / 21 (manufactured by Mocon: oxygen permeability measuring device) is used, and according to JIS-K7126 (isopressure method), 23 ° C. 90% RH. Oxygen permeability was measured in the atmosphere of. Note that RH represents humidity. The results are summarized in Tables 1-3.

(Oxygen permeability after bending test)
The aging-finished laminate was adjusted to a size of 30 cm x 20 cm, and a bending test was conducted with a Gelboflex tester (BE-1006 Gelboflex tester with constant temperature bath, Tester Sangyo Co., Ltd.) according to ASTM F392. .. The bending test was carried out at 440 ° / 90 mm, linear motion 65 mm, and 23 ° C. under the conditions of 5 times of bending, and the oxygen permeability after the gelboflex treatment was measured. The unit is cc / m ² / day / atm. The results are summarized in Tables 1-3.

(Water vapor permeability)
The aging-completed laminate was measured by an isobaric method using a water vapor transmittance measuring device 7002 manufactured by Systec Illinois in an atmosphere of 40 ° C. and 90% RH. Note that RH represents humidity. The results are summarized in Tables 1-3.

(Water vapor permeability after bending test)
The laminated film after aging was adjusted to a size of 30 cm × 20 cm, and a bending test was conducted with a gelboflex tester (BE-1006 gelboflex tester with a constant temperature bath, Tester Sangyo Co., Ltd.). The number of bendings was 5 times. A multilayer film composed of Examples and Comparative Examples shown in Table 1 was prepared, and the water vapor transmittance after the Gelboflex treatment was measured. The results are summarized in Tables 1-3.

As is clear from Examples and Comparative Examples, the laminate of the present invention has excellent gas barrier properties and a small amount of solvent discharged during production. On the other hand, although the laminates of Comparative Examples 1, 2, 4, and 5 have excellent gas barrier properties, a large amount of solvent is discharged during production. The laminate of Comparative Example 3 does not have sufficient gas barrier properties, and a large amount of solvent is discharged during production. Although the laminate of Comparative Example 6 emits a small amount of solvent during production, it does not have sufficient gas barrier properties.

Claims (6)

With the base material
With the sealant layer
A printing layer arranged between the base material and the sealant layer and formed using a water-based liquid ink,
A laminate including a gas barrier adhesive layer arranged between the printing layer and the sealant layer and formed by using a solvent-free gas barrier adhesive. The laminate according to claim 1, wherein the printing layer is printed by a flexographic printing method. The process of forming a printing layer on the substrate using water-based liquid ink,
The process of applying a solvent-free gas barrier adhesive on the sealant layer to form a solvent-free gas barrier adhesive layer, and
A method for producing a laminate, which comprises a step of laminating the base material and the sealant layer via the solvent-free gas barrier adhesive layer. The process of forming a printing layer on the substrate using water-based liquid ink,
A step of applying a solvent-free gas barrier adhesive on the printing layer to form a solvent-free gas barrier adhesive layer, and
A method for producing a laminate, which comprises a step of laminating the base material and the sealant layer via the solvent-free gas barrier adhesive layer. The method for producing a laminate according to any one of claims 3 or 4, wherein the printing layer is provided by a flexographic printing method. A packaging material obtained by using the laminate according to any one of claims 1 or 2 or the laminate obtained by the production method according to claims 3 to 5.