JP2022112187A - Liquid printing ink, printed matter, and laminate - Google Patents

Abstract

To provide liquid printing ink that is excellent in gas barrier property, and is excellent especially in blocking resistance required as printability of the liquid printing ink.SOLUTION: There are provided: liquid printing ink that contains an amorphous polyester resin (1-1) or an amorphous polyester urethane resin (1-2) having an ester skeleton that is a polycondensate of a polyvalent carboxylic acid component containing at least one of an ortho-oriented aromatic dicarboxylic acid or its anhydride, and a polyhydric alcohol component containing at least one selected from the group consisting of ethylene glycol, propylene glycol. butylene glycol, neopentyl glycol and cyclohexane dimethanol, a coloring agent, an organic solvent, and silica or silicone resin fine particles, and contains 0.001-5.0 mass% of the silica or the silicone resin fine particles to an ink solid content; and a laminate.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a liquid printing ink that can be used as a laminate gravure ink or flexographic ink for flexible packaging, and more particularly to a liquid printing ink having gas barrier properties and printed matter.

Conventionally, the most common method for satisfying gas and water vapor barrier properties to protect the contents of packaging materials used for food and industrial materials is ethylene-vinyl alcohol copolymer, polyvinyl alcohol, etc. However, packaging materials made from these polymers have the problem that the oxygen barrier property is greatly reduced due to their hydrophilicity under high humidity conditions. There was a problem of poor resistance to
In order to exhibit a certain level of barrier properties even under these humidity conditions, adhesives used when laminating plastic films, which are base materials for packaging materials, vapor-deposited films obtained by vapor-depositing metals or metal oxides, or metal foils (see, for example, Patent Document 1), and a method of imparting a gas barrier function to the printing ink itself used for the purpose of displaying the contents of the package or decorating the package (see, for example, Patent Document 2). reference).

Of these inks, as described above, the main purpose of the printing ink is to display the contents of the package, to decorate the package, and the like, and various printability is required in addition to the gas barrier property. Gravure inks and flexo inks (gravure inks and flexo inks are collectively called liquid printing inks), which are widely used for packaging materials (soft packaging) in particular, have excellent printability, especially ink adhesion and resistance to printing substrates. Blocking properties (a phenomenon in which the ink film is transferred to the non-printed surface when the film printed with ink is stored in a wound state) are required, and the required properties are becoming stricter year by year.
However, the printing ink described in Patent Literature 2 sometimes has insufficient blocking resistance properties required for liquid printing inks.

JP 2012-57033 A WO2018116903

The problem to be solved by the present invention is to provide a liquid printing ink that is excellent in gas barrier properties, and in particular, is excellent in blocking resistance that is required as the printability of liquid printing inks.

The present inventors have solved the above problems by using a resin having gas barrier properties such as polyester resin or polyester urethane resin as a binder for printing ink, and by using silica and silicon beads together in a specific ratio. .

That is, the present invention provides a polyvalent carboxylic acid component containing at least one ortho-oriented aromatic dicarboxylic acid or anhydride thereof, and a polyvalent carboxylic acid component selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. an amorphous polyester resin (1-1) or an amorphous polyester urethane resin (1-2) having an ester skeleton that is a polycondensate with a polyhydric alcohol component containing at least one polyhydric alcohol component, a coloring agent, and an organic Provided is a liquid printing ink containing a solvent and silica or silicone resin fine particles, wherein the silica or silicone resin fine particles are contained in an amount of 0.001 to 5.0% by mass based on the solid content of the ink.

The present invention also provides a printed matter comprising a substrate and a printed layer printed on the substrate, wherein the printed layer is the ink composition described above.

The present invention also provides a laminate comprising, in this order, at least a first substrate, a printed layer printed on the first substrate, a gas barrier adhesive layer, and a second substrate, A laminate is provided wherein the printing layer is the liquid printing ink described above.

The liquid printing ink of the present invention satisfies the blocking properties required for the printability of liquid printing inks and has gas barrier properties. As a result, a packaging material having gas barrier properties can be provided.

(Definition of words)
In the present invention, liquid printing ink refers to liquid ink such as gravure printing ink or flexographic printing ink, which is applied to a printing method using a printing plate, preferably gravure printing ink or flexographic printing ink. Also, the liquid printing ink of the present invention does not contain an active energy curable component, i.e. it is a liquid printing ink non-reactive to active energy rays.
In the present invention, "ink" means "printing ink". Moreover, all "parts" indicate "parts by mass".

(resin with gas barrier properties)
A resin having gas barrier properties (sometimes referred to as a gas barrier resin) used in the present invention specifically includes a polyvalent carboxylic acid component containing at least one ortho-oriented aromatic dicarboxylic acid or its anhydride, An amorphous polyester having an ester skeleton (1) which is a polycondensate with a polyhydric alcohol component containing at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. Resin (1-1) or amorphous polyester urethane resin (1-2) is preferred.

(Amorphous polyester resin (1-1))
The amorphous polyester resin (1-1) used in the present invention is obtained by polycondensation of a polyhydric carboxylic acid component including an ortho-oriented aromatic polycarboxylic acid component and a polyhydric alcohol component.

(Ortho-oriented aromatic polycarboxylic acid component)
The ortho-oriented aromatic polycarboxylic acid component is specifically ortho-phthalic acid and its acid anhydrides. Orthophthalic acid and its anhydride have an asymmetric skeleton structure. Therefore, it is presumed that the rotation of the molecular chain of the obtained polyester is suppressed, and this is presumed to result in excellent gas barrier properties. In addition, it is presumed that due to this asymmetric structure, it exhibits non-crystallinity, provides sufficient adhesion to the substrate, and is excellent in adhesive strength and gas barrier properties. Furthermore, when used as a gravure ink, it has high solvent solubility, which is essential, and is characterized by excellent handleability.

(aromatic polycarboxylic acid)
The ortho-oriented aromatic polycarboxylic acid may preferably be used in combination with another aromatic polycarboxylic acid. Specific examples of aromatic polycarboxylic acids include terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Examples include naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, and anhydrides or ester-forming derivatives of these dicarboxylic acids. These can be used singly or as a mixture of two or more. Among them, terephthalic acid and isophthalic acid are preferred.

Specific examples of other polycarboxylic acids that can be used in combination with the aromatic polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, maleic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. carboxylic acids, and alicyclic polyvalent carboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. These can be used singly or as a mixture of two or more. Acid anhydrides of these can also be used. Among them, succinic acid, maleic acid, and 1,3-cyclopentanedicarboxylic acid are preferably used in combination.

(Polyhydric alcohol component)
Polyhydric alcohols used in the present invention specifically include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5 - as pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyhydric phenols, hydroquinone , resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, ethylene oxide extensions thereof, and hydrogenated alicyclics.

Among them, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol are preferred, since it is estimated that the smaller the number of carbon atoms between oxygen atoms, the less likely the molecular chain becomes excessively flexible, and ethylene glycol. is more preferred.

The polycondensation reaction between the polyhydric carboxylic acid component including the ortho-oriented aromatic polycarboxylic acid component and the polyhydric alcohol component can be carried out by a known method.

(Amorphous polyester urethane resin (1-2))
The amorphous polyester urethane resin (1-2) used in the present invention is a reaction product of the polyester polyol resin having a terminal hydroxyl group among the amorphous polyester resins (1-1) and an isocyanate compound. Examples of isocyanate compounds include polyisocyanates having an aromatic structure in the molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and xylylene diisocyanate, and NCOs of these polyisocyanates. Compounds partially modified with carbodiimide; Alphanate compounds derived from these polyisocyanates; Molecular structures such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,3-(isocyanatomethyl)cyclohexane, etc. Polyisocyanates having an alicyclic structure within; linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate, and alphanate compounds thereof; isocyanurate compounds of these polyisocyanates allophanate compounds derived from these polyisocyanates; biuret compounds derived from these polyisocyanates; trimethylolpropane-modified adducts; be done.

Examples of chain extenders used in the amorphous polyester urethane resin include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, etc. 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyropyrethylenediamine , di-2-hydroxypyropyrethylenediamine, di-2-hydroxypropylethylenediamine, and other amine compounds having a hydroxyl group in the molecule can also be used. These chain extenders can be used alone or in combination of two or more.
A monovalent active hydrogen compound can also be used as a terminal blocker for the purpose of terminating the reaction. Examples of such compounds include dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator, especially when it is desired to introduce a carboxyl group into the polyurethane resin. These terminal blocking agents can be used alone or in combination of two or more.

The reaction between the polyester polyol resin, the isocyanate compound, and the amine compound can be carried out by a known method.

In the amorphous polyester resin (1-1) or the amorphous polyester urethane resin (1-2), the content of the ortho-oriented aromatic dicarboxylic acid or its anhydride relative to the total polyvalent carboxylic acid component is 50 to It is preferably 100% by mass. If it is this range, preferable gas-barrier property can be exhibited. Among them, 70 to 100% by mass is more preferable.

The amorphous polyester resin (1-1) preferably has a number average molecular weight of 450 to 5,000. Alternatively, the number average molecular weight of the amorphous polyester urethane resin (1-2) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
When the number average molecular weight of the amorphous polyester resin (1-1) or the amorphous polyester urethane resin (1-2) is less than 450, the blocking resistance of the resulting ink composition, the strength of the printed film, and the Oil resistance tends to be low, and when it exceeds 50000, the resulting liquid printing ink tends to have a high viscosity and the glossiness of the printed film tends to be low.

(Resin used together)
The amorphous polyester resin (1-1) or amorphous polyester urethane resin (1-2) is used as a binder in the liquid printing ink of the present invention. You may use resin together. For example, vinyl chloride vinyl acetate copolymer resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, ethylene vinyl alcohol resin, polyvinyl alcohol resin, vinyl acetate resin, polyvinylidene chloride resin, cellulose resin, polyamide resin, acrylic resin , polyester resins, alkyd resins, polyvinyl chloride resins, rosin-based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, chlorinated rubbers, butyral, and petroleum resins. The combined resin can be used alone or in combination of two or more. The content of the combined resin is preferably 1 to 25% by weight, more preferably 2 to 15% by weight, based on the total weight of the nonvolatile matter of the ink components. Furthermore, as binder resins that do not improve or deteriorate gas barrier properties, vinyl chloride vinyl acetate copolymer resins and polyvinylidene chloride resins are preferred for organic solvent-based liquid printing inks, and ethylene vinyl alcohol resins and polyvinyl alcohol resins are preferred for water-based liquid printing inks. preferable.
In particular, when the liquid printing ink of the present invention is applied as a printing ink for so-called flexible packaging materials such as plastic films, it is preferable to use a vinyl chloride-vinyl acetate copolymer resin having hydroxyl groups in combination.

(vinyl chloride vinyl acetate copolymer resin)
The vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group preferably has a hydroxyl value of 50 to 200 mgKOH/g and a vinyl chloride component content of 80 to 95% by weight in the copolymer resin.

The vinyl chloride-vinyl acetate copolymer resin having hydroxyl groups used in the present invention can be obtained by two methods. One is obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer and vinyl alcohol in appropriate proportions. The other is obtained by copolymerizing vinyl chloride and vinyl acetate and then partially saponifying vinyl acetate. The vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group determines the properties of the resin film and the dissolution behavior of the resin depending on the monomer ratio of vinyl chloride, vinyl acetate and vinyl alcohol. That is, vinyl chloride imparts toughness and hardness to the resin coating, vinyl acetate imparts adhesiveness and flexibility, and vinyl alcohol imparts good solubility in polar solvents.

When used as a printing ink for flexible packaging materials, performances such as adhesiveness, blocking resistance, and printability are required. The raw material vinyl chloride is preferably 80 to 95 parts by weight. Moreover, the hydroxyl value obtained from vinyl alcohol is preferably 50 to 200 mgKOH/g.

The content of the amorphous polyester resin (1-1) or amorphous polyester urethane resin (1-2) used in the liquid printing ink of the present invention in the ink is sufficient to ensure the adhesion of the ink to the substrate to be printed. 4% by weight or more based on the total weight of the non-volatile matter of the ink components from the viewpoint of reducing % range is preferred.

The content of the vinyl chloride-vinyl acetate copolymer resin used in the liquid printing ink of the present invention in the ink is preferably 0.1 to 30% by weight, more preferably 1 to 30% by weight, based on the total weight of the nonvolatile matter of the ink components. A range of 15% by weight is preferred.

Further, the ratio of the amorphous polyester resin (1-1) or the amorphous polyester urethane resin (1-2) used in the liquid printing ink of the present invention to the vinyl chloride vinyl acetate copolymer resin is Crystalline polyester resin (1-1) or amorphous polyester urethane resin (1-2): vinyl chloride vinyl acetate copolymer resin is preferably blended in the range of 100:2 to 100:30, A range of 100:5 to 100:20 is more preferred and a range of 100:6 to 100:15 is most preferred.

(coloring agent)
The coloring agent used in the present invention includes organic and inorganic pigments and dyes for coloring that are used in general inks, paints, recording agents, and the like.
Examples of organic pigments include soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthanthrone, dianthraquinonyl, anthrapyrimidine, perylene, perinone, quinacridone, Examples include thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, and carbon black pigments. Also, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance Ron blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigments, and the like. Both non-acid-treated pigments and acid-treated pigments can be used.

Inorganic pigments include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, litbon, antimony white, and gypsum. Among inorganic pigments, the use of titanium oxide is particularly preferred. Titanium oxide exhibits a white color and is preferable from the viewpoints of coloring power, hiding power, chemical resistance and weather resistance. From the viewpoint of printing performance, the titanium oxide is preferably treated with silica and/or alumina.

Examples of non-white inorganic pigments include aluminum particles, mica (mica), bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, Prussian blue, red iron oxide, yellow iron oxide, iron black, and zircon. Although the aluminum is in the form of powder or paste, it is preferable to use it in the form of paste from the viewpoints of handling and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and density.

The amount of the pigment is sufficient to ensure the density and coloring strength of the liquid printing ink, that is, 1 to 60% by mass of the total mass of the ink, and 10 to 90% by mass of the solid content in the ink. preferably included. Moreover, these pigments can be used individually or in combination of 2 or more types.

In order to stably disperse a colorant, especially a pigment, in an organic solvent, the resin alone can be dispersed, but a dispersant can also be used in combination to stably disperse the pigment. Anionic, nonionic, cationic, and amphoteric surfactants can be used as dispersants. For example, a comb-structure polymer compound obtained by adding polyester to polyethyleneimine, or an alkylamine derivative of an α-olefin maleic acid polymer may be used. Specific examples include Solspers series (ZENECA), Ajisper series (Ajinomoto), Homogenol series (Kao), and the like. BYK series (BYK-Chemie), EFKA series (EFKA) and the like can also be used as appropriate. From the viewpoint of storage stability of the ink, the dispersant is preferably contained in the ink in an amount of 0.05% by weight or more relative to the total weight of the nonvolatile matter of the ink components, and 5% by weight or less from the viewpoint of lamination suitability. Preferably, it ranges from 0.1 to 2% by weight.

(Organic solvent)
The organic solvent used in the present invention is not particularly limited, but for example aromatic hydrocarbon organic solvents such as toluene, xylene, Solvesso #100 and Solvesso #150, hexane, methylcyclohexane, heptane, octane, decane and the like. Various ester-based organic solvents such as aliphatic hydrocarbon-based organic solvents, methyl acetate, ethyl acetate, isopropyl acetate, normal-propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate can be used. Water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, butanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl. Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, Di)methyl ether, propylene glycol (mono, di)methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol (mono, di)methyl ether, and other glycol ether organic solvents can be used. These may be used alone or in combination of two or more.

In terms of work hygiene during printing and the toxicity of packaging materials, use ethyl acetate, propyl acetate, isopropanol, normal propanol, etc., and do not use aromatic solvents such as toluene or ketone solvents such as methyl ethyl ketone. is more preferred.
For drying adjustment, glycol ethers can be added as long as they are less than 10 mass % of the total amount of the ink.

(silica or silicone resin fine particles)
The present invention is characterized by containing silica or silicone resin fine particles in an amount of 0.001 to 5.0% by mass based on the solid content of the ink.

(silica)
Silica is not particularly limited, and includes naturally occurring, synthetic, crystalline, non-crystalline, hydrophobic, and hydrophilic silicas. Silica is classified into a dry method and a wet method according to the synthetic method. Known dry methods include a combustion method and an arc method, and wet methods include a sedimentation method and a gel method. In the present invention, it may be synthesized by any method. Silica may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with an alkylsilane or the like to make it hydrophobic.

The silica used in the present invention preferably has an average particle size of 1 to 30 μm, in order to form irregularities on the surface of the ink layer. The average particle size of silica particles means the particle size at an integrated value of 50% (D50) in the particle size distribution, and can be obtained by the Coulter counter method. Further, the silica particles preferably have a specific surface area of 50 to 600 m2/g by the BET method. More preferably 100m2/g to 450m2/g. The silica particles (C) used in the gravure ink for laminate of the present invention can be used in combination with those having different average particle sizes or BET specific surface areas.
Silica is preferably contained in an amount of 0.001 to 1.0% by mass, more preferably 0.01 to 0.02% by mass, based on the solid content of the ink.

(silicone resin fine particles)
Polymethylsilsesquioxane is particularly preferred as the silicone resin fine particles.
The polymethylsilsesquioxane has a basic structure represented by the following formula (1).

_{CH3SiO3 /2} (1)

That is, a methyl group is bonded to one of the four bonds possessed by a silicon atom, and the other three bonds are, in principle, three-dimensionally crosslinked with other silicon atoms via oxygen atoms to form a network structure. is a spherical polymethylsilsesquioxane that forms a It is essential that the spherical polymethylsilsesquioxane have an average particle size in the range of 1.0 to 10.0 μm. More preferably, the average particle size is in the range of 2.0 to 6.0 μm. If the average particle size is 1.0 μm or more, the adhesiveness to the substrate, lamination strength, scratch resistance, abrasion resistance, blocking resistance, etc. tend to be maintained comprehensively. This tends to maintain the adhesion to the substrate and the laminate strength.
Among others, the content of silicone resin fine particles is preferably 0.002 to 2.0% by mass, more preferably 0.3 to 1.0% by mass, based on the solid content of the ink.

The particles of polymethylsilsesquioxane used in the liquid printing inks of the invention are spherical in shape. There is no problem with the degree of spherical shape, as long as it can be recognized as a substantially spherical shape by observation with an electron microscope.
In the liquid printing ink of the present invention, it is preferable to use silicone resin fine particles having an average particle size of 1.0 to 10.0 μm.

It is also preferable to use the silica and the silicone resin fine particles in combination. When used in combination, it is preferable that the mass ratio of the silica to the silicone resin fine particles is in the range of 0.1:0.1 to 5:1. Within this range, the ink can have excellent anti-blocking properties while maintaining gas barrier properties. Among them, the mass ratio is preferably in the range of 0.1:0.1 to 3.0:1.0, most preferably in the range of 0.5:0.3 to 1.0:0.6. .

(polyisocyanate)
In the present invention, polyisocyanate may be used as a curing agent. The polyisocyanate reacts with the hydroxyl groups of the amorphous polyester resin (1-1) or amorphous polyester urethane resin (1-2) used in the liquid printing ink of the present invention to give a three-dimensional crosslinked structure. Among the polyisocyanates, a divalent or higher polyisocyanate compound (5-1) having an aromatic ring in the molecule is preferred.

(Divalent or higher polyisocyanate compound (5-1) having an aromatic ring in the molecule)
The bivalent or higher polyisocyanate compound (5-1) having an aromatic ring in the molecule is not particularly limited, and known compounds can be used. For example, at least one diisocyanate selected from xylylene diisocyanate, meta-xylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and methylphenylethane diisocyanate, a reaction product of the diisocyanate with a monohydric alcohol, and an alcohol having two hydroxyl groups. Reaction products, carbodiimide-modified products, and the like can be mentioned.
As the polyisocyanate compound having a valence of 3 or more, an excess amount of the diisocyanate is added to a polyfunctional alcohol, such as trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, diethanolamine, triethanolamine, or other low-molecular-weight active hydrogen. Compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, adducts which are reaction products with polymeric active hydrogen compounds of polyamides, and the like. In addition, a nurate, which is a polymer of the above diisocyanate, can also be preferably used.

Among them, meta-xylylene diisocyanate, xylylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate are preferred, and meta-xylylene diisocyanate is most preferred. In addition, the reaction products, modified products, and polymers of these isocyanate compounds may also be used.

(Polyisocyanate compound having no aromatic ring in the molecule)
In the present invention, it is more preferable to use the divalent or higher polyisocyanate compound (5-1) having an aromatic ring in the molecule and the polyisocyanate compound having no aromatic ring in the molecule as a curing agent. With conventional polyisocyanates having aromatic rings, the cured coating film becomes hard and it is difficult to obtain good adhesive strength. By using diisocyanate in combination, flexibility is imparted to the coating film while maintaining barrier properties, and adhesion to metal-based substrates such as aluminum foil, aluminum vapor-deposited film, and transparent vapor-deposited film is improved, and barrier properties are also improved. improves.

The polyisocyanate compound having no aromatic ring in the molecule used in the present invention includes hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, metaxylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated methylphenylethane diisocyanate, hydrogenated naphthalene- Examples thereof include at least one diisocyanate selected from 1,5-diisocyanates, a reaction product of the diisocyanate with a monohydric alcohol, a reaction product with an alcohol having two hydroxyl groups, a carbodiimide-modified product, and the like.
As the polyisocyanate compound having a valence of 3 or more, an excess amount of the diisocyanate is added to a polyfunctional alcohol, such as trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, diethanolamine, triethanolamine, or other low-molecular-weight active hydrogen. Compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, adducts which are reaction products with polymeric active hydrogen compounds of polyamides, and the like. In addition, a nurate, which is a polymer of the above diisocyanate, can also be preferably used.

Among them, a polyisocyanate compound (5-2) having a cyclic skeleton and no aromatic ring in the molecule is preferred. The cyclic skeleton includes an alicyclic skeleton, a nurate skeleton, and the like.
As the polyisocyanate having an alicyclic skeleton, isophorone diisocyanate, norbornane diisocyanate, hydrogenated metaxylene diisocyanate, hydrogenated toluenediisocyanate, hydrogenated methylphenylethane diisocyanate, and hydrogenated naphthalene-1,5-diisocyanate are preferred. Further, the reaction products, modified products and polymers of these isocyanate compounds may also be used.

(Mixing ratio of divalent or higher polyisocyanate compound (5-1) having an aromatic ring in the molecule and polyisocyanate compound (5-2) having a cyclic skeleton and not having an aromatic ring in the molecule)
The mixing ratio of the divalent or higher polyisocyanate compound (5-1) having an aromatic ring in the molecule and the polyisocyanate compound (5-2) having a cyclic skeleton and not having an aromatic ring in the molecule is It cannot be generalized because it depends on the molecular weight or valence of each compound to be used. Therefore, the mixing ratio of the divalent or higher polyisocyanate compound (5-1) having an aromatic ring in the molecule and the polyisocyanate compound (5-2) having no aromatic ring in the molecule is converted to isocyanate content. , preferably in the range of 1:5 to 10:1, more preferably in the range of 1:3 to 5:1.

(Blending ratio of amorphous polyester resin (1-1) or amorphous polyester urethane resin (1-2) and polyisocyanate (5))
The amorphous polyester resin (1-1) or the amorphous polyester urethane resin (1-2) and the polyisocyanate (5) are the amorphous polyester resin (1-1) or the amorphous polyester urethane. The ratio of the resin (1-2) and the polyisocyanate (5) is such that the hydroxyl groups of the amorphous polyester resin (1-1) or the amorphous polyester urethane resin (1-2) and the polyisocyanate (5 ) is preferably 1/0.01 to 1/10 (equivalent ratio), more preferably 1/0.1 to 1/5. Addition of the polyisocyanate (5) improves the adhesion of the ink to the substrate and the heat resistance during boiling and retorting. If the amount of the polyisocyanate (B) exceeds this range, the excess polyisocyanate (5) may remain and may bleed out from the adhesive layer after adhesion.

(Plate-like inorganic compound)
The liquid printing ink of the present invention may contain a plate-like inorganic compound for the purpose of imparting a higher gas barrier function. When a plate-like inorganic compound is used in combination, the lamination strength and barrier properties are improved due to the plate-like shape. Examples of plate-like inorganic compounds used in the present invention include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, endellite, dickite, nacrite, etc., antigorite, , chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or mica group clay minerals (mica such as muscovite, phlogopite, etc., margarite, tetrasilylic mica, teniolite, etc.), chlorite group (cookieite, pseudoite, clinochlore, chamosite, nimite, etc.), hydrotalcite, plate-like barium sulfate, boehmite, aluminum polyphosphate, and the like. These minerals may be natural clay minerals or synthetic clay minerals.

The charge between the layers does not directly affect the barrier property, but when the solvent is an organic solvent, the dispersibility in the resin is significantly inferior with the ionic inorganic compound, and if the amount added is increased, printability becomes an issue (thixotropic becomes). On the other hand, in the case of the non-chargeable material, printability can be ensured even if the added amount is increased. As for the particle size, barrier properties are likely to be exhibited when the particle size is larger than about 1 μm, and good barrier properties cannot be obtained at the nanometer level. If the particle size is too large, the plate-like inorganic compound does not enter the gravure plate in the case of gravure printing and the like, so printability cannot be obtained. The particle size is preferably 0.1-100 μm. More preferably, it is 1 to 40 μm. The average particle size in the present invention means the particle size with the highest appearance frequency when the particle size distribution of a certain plate-like inorganic compound is measured with a light scattering type measuring device.

The aspect ratio of the plate-like inorganic compound used in the present invention is preferably high in order to improve the barrier performance due to the labyrinthine effect of the gas component molecules. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more. Although the content of the plate-like inorganic compound is arbitrary, it is preferably 50% by mass or less. If it exceeds 50% by mass, printability and appearance may become insufficient.

Since the liquid printing ink of the present invention is characterized by the fact that the resin has a barrier property, it can also be used as a substantially transparent medium or extender for adjusting color density without using a coloring agent. For the purpose of higher blocking prevention, it is preferable to use an inorganic pigment, and from the viewpoint of not coloring, barium sulfate, calcium carbonate, silica, and mica (mica) are preferable. Further, from the viewpoint of improving the barrier property, the plate-like inorganic compound such as mica is more preferable.
In the case of a printed matter with many plain colors, by printing the above-mentioned medium and extender over the entire surface of the base material, barrier properties can be imparted to the packaging material.

(other ingredients)
The liquid printing ink of the present invention may contain various additives as long as the effects of the present invention are not impaired. Additives include extender pigments, leveling agents, defoaming agents, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, antioxidants, heat stabilizers, fragrances, flame retardants, antistatic agents, lubricants, and antiblocking agents. agents, coupling agents, and the like.

(Ink manufacturing method)
The liquid printing inks of the present invention can be produced by dissolving and/or dispersing resins, colorants, etc. in organic solvents. Specifically, a pigment dispersion is produced by dispersing a pigment or the like in an organic solvent using an amorphous polyester resin (1-1) or an amorphous polyester urethane resin (1-2), and the obtained pigment dispersion is Ink can be produced by blending other compounds, etc., with the above as required.

The particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the ejection speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the dispersing machine, commonly used roller mills, ball mills, pebble mills, attritors, sand mills and the like can be used.
If air bubbles or unexpected coarse particles are contained in the ink, it is preferable to remove them by filtration or the like, as they reduce the quality of printed matter. A conventionally known filter can be used.

The viscosity of the ink produced by the above method is preferably in the range of 10 mPa·s or more from the viewpoint of preventing sedimentation of the pigment and appropriately dispersing the pigment, and in the range of 1000 mPa·s or less from the viewpoint of work efficiency during ink production and printing. preferable. The above viscosity is measured at 25° C. with a B-type viscometer manufactured by Tokimec.
The viscosity of the ink can be adjusted by appropriately selecting the types and amounts of raw materials used, such as polyurethane resins, colorants, organic solvents, and the like. Also, the viscosity of the ink can be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.

As for the hue of the ink of the present invention, there are five basic process colors, yellow, red, indigo, black, and white, depending on the type of coloring agent used, and red (orange) and grass (grass) as process gamut external colors. There are three colors: green) and purple. Further, transparent yellow, peony, vermillion, brown, gold, silver, pearl, almost transparent medium for adjusting color density (including extender pigment if necessary), etc. are prepared as base colors. The ink for boiling retort is appropriately selected in consideration of the migration property and heat resistance of the pigment. The base ink of each hue is diluted with a diluting solvent to a viscosity and density suitable for gravure printing, and supplied to each printing unit singly or in combination.

(printed matter)
The printed matter of the present invention is a printed matter comprising a substrate and a printed layer of the liquid printing ink of the present invention on the substrate. The base material will now be described in detail in the description of the laminate.

As a printing method, known printing methods such as gravure printing and flexographic printing can be used, but printing by the gravure printing method is particularly preferable. A well-known cylinder such as an engraving type or an etching type is used for gravure printing.

A printed matter can be obtained by applying the composition to a base material using the above-mentioned printing method, drying it in an oven, or curing and fixing it. The base material may be subjected to vapor deposition coating treatment with a metal oxide or the like and/or coating treatment such as polyvinyl alcohol on the surface, and further may be subjected to surface treatment such as corona treatment.

The liquid printing ink of the present invention can be preferably used as ink for surface printing, ink for reverse printing, or ink for lamination. When used as an ink for surface printing, an overprint varnish layer can be provided separately. On the other hand, when it is used as an ink for reverse printing, an anchor coat varnish layer can be separately provided. In addition, films laminated with plastic films such as ethylene-vinyl alcohol copolymer and polyvinyl alcohol with gas barrier properties, vapor-deposited films vapor-deposited with metals and metal oxides, films using metal foils, etc., and adhesion of films It is preferable to print on a film having gas barrier properties, such as a film laminated with an adhesive agent having gas barrier properties, because a synergistic effect of gas barrier properties can be expected.

Since the liquid printing ink of the present invention has good oxygen barrier properties in gravure printing or flexographic printing, it can be used as a packaging liquid printing ink for food packaging, sanitary, cosmetics, electronic materials, construction materials, and industrial materials. It can be suitably used in applications where oxygen barrier properties are desired.

(Laminate)
The laminate of the present invention is a laminate comprising at least a first substrate, a printed layer printed on the first substrate, a gas barrier adhesive layer, and a second substrate in this order. and the printing layer is the liquid printing ink of the present invention.

(Base material)
The first base material and the second base material are not particularly limited, and film-like base materials can be used according to the desired application. For example, when the laminate of the present invention is used as a packaging material, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: Polyolefin films such as high-density polyethylene film) and polypropylene films (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol films, ethylene-vinyl alcohol copolymer films, and the like can be used. These films may be stretched. As a stretching treatment method, it is common to melt-extrude a resin into a sheet by an extrusion film-forming method or the like, and then subject the sheet to simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then laterally stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and lateral stretching using a tenter is often used.

Of course, a barrier film containing a vapor-deposited layer of a metal such as aluminum, a metal oxide such as silica or alumina, or a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used in combination. good too. By using such a film, it is possible to obtain a laminate having a high barrier property against water vapor, oxygen, alcohol, inert gas, volatile organic matter (fragrance), and the like.

As a more specific structure of the laminate,
(1) Base film 1/printed layer/adhesive layer 1/sealant film (2) Base film 1/printed layer/adhesive layer 1/metal deposition unstretched film (3) Base film 1/printed layer/adhesive layer 1/metal vapor deposition stretched film (4) transparent vapor deposition stretched film/printing layer/adhesive layer 1/sealant film (5) base film 1/printing layer/adhesive layer 1/base film 2/adhesive layer 2/sealant film ( 6) Base film 1/printed layer/adhesive layer 1/metal vapor deposition stretched film/adhesive layer 2/sealant film (7) Base film 1/printed layer/adhesive layer 1/transparent vapor deposited stretched film/adhesive layer 2/sealant Film (8) Base film 1/printed layer/adhesive layer 1/metal layer/adhesive layer 2/sealant film (9) Base film 1/printed layer/adhesive layer 1/base film 2/adhesive layer 2/metal Layer/adhesive layer 3/sealant film (10) base film 1/printing layer/adhesive layer 1/metal layer/adhesive layer 2/base film 2/adhesive layer 3/sealant film and the like, but not limited thereto . In addition, a "printing layer" is a printing layer of the liquid printing ink of this invention here.

Examples of the base film 1 used in the configuration (1) include OPP film, PET film, nylon film (hereinafter also referred to as Ny film), and the like. Further, as the base film 1, a film coated for the purpose of improving gas barrier properties, ink receptivity when providing a printing layer described later, and the like may be used. Commercial products of the coated base film 1 include K-OPP film and K-PET film. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of sealant films include CPP films and LLDPE films. A printed layer may be provided on the surface of the substrate film 1 on the adhesive layer 1 side (when a coated substrate film 1 is used, the surface of the coating layer on the adhesive layer 1 side). The printed layer is formed by a general printing method conventionally used for printing on polymer films using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.

Examples of the base film 1 used in the configurations (2) and (3) include an OPP film and a PET film. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. A VM-CPP film obtained by vapor-depositing a metal such as aluminum on a CPP film may be used as the unstretched metal vapor-deposited film, and a VM-OPP film obtained by vapor-depositing a metal such as aluminum on an OPP film may be used as the stretched metal-deposited film. can be done. A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

Examples of the transparent vapor-deposited stretched film used in the configuration (4) include films obtained by vapor-depositing silica or alumina on OPP film, PET film, nylon film, or the like. For the purpose of protecting the inorganic deposition layer of silica or alumina, etc., a film obtained by coating the deposition layer may be used. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the transparent vapor deposited stretched film (when using a film having a coated inorganic vapor deposited layer, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as that of configuration (1).

Examples of the base film 1 used in the configuration (5) include a PET film and the like. Examples of the base film 2 include a nylon film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

Examples of the base film 1 of the configuration (6) include those similar to those of the configurations (2) and (3). Examples of the metal-deposited oriented film include VM-OPP film and VM-PET film obtained by subjecting an OPP film or PET film to metal deposition such as aluminum. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

Examples of the base film 1 of configuration (7) include a PET film and the like. Examples of the transparent vapor-deposited stretched film include those similar to those of the configuration (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

Examples of the base film 1 of configuration (8) include a PET film and the like. Aluminum foil etc. are mentioned as a metal layer. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

Examples of the base film 1 of configurations (9) and (10) include PET films. Examples of the base film 2 include a nylon film. Aluminum foil etc. are mentioned as a metal layer. At least one of the adhesive layers 1, 2 and 3 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

(adhesion layer)
As the adhesive used for the adhesive layer, a known adhesive for film lamination can be appropriately used, but if an adhesive having gas barrier properties is used as the adhesive, a laminate having particularly excellent barrier properties can be obtained. can.
Especially preferable as an adhesive with excellent gas barrier properties is that the cured coating film of the adhesive applied at 3 g/m ² (solid content) has an oxygen barrier property of 300 cc/m ² /day/atm or less, or a water vapor barrier property of 120 g/m 2 /day/atm or less. It means that it satisfies at least one condition of m ² /day or less. Examples of commercially available products include "PASLIM" series such as PASLIM VM001 and PASLIM J350X manufactured by DIC Corporation, and "Maxieve" manufactured by Mitsubishi Gas Chemical Company.

Alternatively, a polyol composition (A) containing at least one polyester polyol of the following (A1) to (A5) and a compound having at least two isocyanate groups in one molecule (hereinafter simply referred to as an isocyanate compound) Poly A two-component adhesive consisting of the isocyanate composition (B) can also be preferably used.

(1) Polyester polyol (A1) obtained by reacting a polyester polyol having 3 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 polycondensation of ortho-oriented polyhydric carboxylic acid and polyhydric alcohol
(5) Polyester polyol (A5) having an isocyanuric ring

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

The polycarboxylic acid used for preparing the polyester polyol (A1) preferably contains at least one of orthophthalic acid and orthophthalic anhydride. Polyester polyols obtained by using these compounds as polycarboxylic acids are excellent in gas barrier properties and adhesiveness. Trivalent or higher polyvalent carboxylic acids include trimellitic acid and its acid anhydrides, pyromellitic acid and its acid anhydrides, and the like.

Other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid; unsaturated bond-containing polycarboxylic acids such as maleic anhydride, maleic acid and fumaric acid; ,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic polycarboxylic 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. be able to. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid and their acid anhydrides are preferred.

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. Among them, 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, and dipentaerythritol. be done.

Other polyhydric alcohols 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, ethylene oxide extensions thereof, and hydrogenated fats Aromatic polyhydric phenols such as cyclic aromatic polyhydric phenols can be exemplified.

The polyester polyol (A1) is obtained by reacting the polyester polyol (a1) having 3 or more hydroxyl groups, which is a reaction product of the above-described polycarboxylic acid and polyhydric alcohol, with a polycarboxylic acid or an acid anhydride thereof. obtained by The ratio of hydroxyl groups to be reacted with the polycarboxylic acid is preferably 1/3 or less of the hydroxyl groups of 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 anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, 2, 3-naphthalenedicarboxylic anhydride, trimellitic anhydride, etc., but not limited thereto.

A polyester polyol (A2) having a polymerizable carbon-carbon double bond is obtained by using a component having a polymerizable carbon-carbon double bond as a polyhydric carboxylic acid or a polyhydric alcohol.

Maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydrides, 3-methyl-4-cyclohexene-1 as polyvalent carboxylic acids having polymerizable carbon-carbon double bonds , 2-dicarboxylic acids and their acid anhydrides. Among them, maleic anhydride, maleic acid and fumaric acid are preferred.

Other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic 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 acids, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acids 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. Acid anhydrides of these can also be used. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydrides of orthophthalic acid, and isophthalic acid are preferred for obtaining gas barrier properties, and orthophthalic acid and acid anhydrides thereof are more preferred.

Examples of polyhydric alcohols having a polymerizable carbon-carbon double bond include 2-butene-1,4-diol.

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 . Among them, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol are preferred, and ethylene glycol is more preferred.

Further, the polyester polyol (A2) having a polymerizable carbon-carbon double bond is a reaction product of the polyester polyol (a2) having a hydroxyl group and a carboxylic acid having a polymerizable double bond or a carboxylic acid anhydride. may Carboxylic acids having a polymerizable double bond or acid anhydrides thereof include carboxylic acids 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. is mentioned. The polyester polyol (a2) preferably has 3 or more hydroxyl groups.
Further examples of polyester polyols (A2) include drying oils and semi-drying oils. Drying oils or semi-drying oils include known and commonly used drying oils and semi-drying oils having carbon-carbon double bonds.

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 each independently a hydrogen atom or the following general formula (2), provided that at least one of R ₁ to R ₃ is represented by 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; X is a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, which may have a substituent; represents an arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms.)

The polyester polyol (A3) is a compound in which any one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (2), and any two of R ₁ , R ₂ and R ₃ are represented by the general formula A mixture of two or more of a compound represented by the group represented by (2) and a 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 More preferably, all of R ₁ to R ₃ are groups represented by general formula (2).

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

Specific examples of Y in 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, 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 preferred, and an ethylene group is more preferred.

The polyester polyol (A3) is obtained by reacting glycerol, 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 aromatic polyvalent carboxylic acids or acid anhydrides thereof in which a carboxylic acid is substituted at the ortho position include orthophthalic acid or acid anhydrides thereof, naphthalene 2,3-dicarboxylic acids or acid anhydrides thereof, naphthalene 1,2-dicarboxylic acids Examples include acids or acid anhydrides thereof, anthraquinone 2,3-dicarboxylic acid or acid anhydrides thereof, and 2,3-anthracenecarboxylic acid or acid anhydrides thereof. These compounds may have a substituent at any carbon atom of the aromatic ring. The substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.

As the polycarboxylic acid, other polycarboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid; unsaturated bond-containing polycarboxylic acids such as maleic anhydride, maleic acid and fumaric acid; ,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic polycarboxylic 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 anhydrides, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and dicarboxylic acids of these aromatic polycarboxylic 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; A species or two or more species can be used in combination. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid and diphenic acid are preferred.

Polyhydric alcohols include alkylene diols having 2 to 6 carbon atoms. 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.

Polyhydric alcohols other than glycerol and alkylenediol having 2 to 6 carbon atoms may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polyhydric alcohols such as erythritol, pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, and tripropylene glycol; Alicyclic polyhydric alcohols such as methanol and tricyclodecanedimethanol, aromatic polyhydric phenols such as hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, or ethylene oxides thereof Extensions and hydrogenated alicyclics can be exemplified.

A polyester polyol (A4) obtained by polycondensation of an ortho-oriented polyhydric carboxylic acid and a polyhydric alcohol is a polyhydric carboxylic acid containing at least one or more of orthophthalic acid and its acid anhydride, ethylene glycol, and propylene. A polyhydric alcohol containing at least one selected from the group consisting of glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. Particularly preferred is a polyester polyol containing 70 to 100% by mass of the orthophthalic acid and its acid anhydride relative to the total amount of the polyvalent carboxylic acid.

The polyvalent carboxylic acid is essentially either orthophthalic acid or its acid anhydride, but other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polycarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc., and unsaturated bond-containing polycarboxylic acids include maleic anhydride, maleic acid, Fumaric acid and the like, 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid as alicyclic polycarboxylic acids, and terephthalic acid, isophthalic acid, furandicarboxylic acid as aromatic polycarboxylic acids 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 acids and acid anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, etc. can be used singly or in a mixture of two or more. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid and isophthalic acid are preferred.

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 may 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 and hydrogenation Aromatic polyhydric phenols such as alicyclics can be exemplified.

The isocyanuric ring-containing polyester polyol (A5) 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 general formula (3), R ₁ to R ₃ are each independently —(CH ₂ ) _n1 —OH (where _n1 represents an integer of 2 to 4), or are represented by the following general formula (4) However, at least one of R ₁ , R ₂ and R ₃ is a group represented by 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 general formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, and X represents a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, , 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group, represents an arylene group which may have a substituent, and Y is an alkylene group having 2 to 6 carbon atoms. show.)

The polyester polyol (A5) is a compound in which any one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4), and any two of R ₁ , R ₂ and R ₃ are represented by the general formula A mixture of two or more of a compound represented by the group represented by (4) and a 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 More preferably, all of R ₁ to R ₃ are groups represented by general formula (4).

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

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

The substituent of X is preferably a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimido group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, a hydroxyl group, a phenoxy group, a cyano group, a nitro group, a phthalimido 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, 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 preferred, and an ethylene group is more preferred.

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

Examples of triols 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. etc.

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

Examples of 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, Diols such as 1,6-hexanediol, methylpentanediol and dimethylbutanediol can be exemplified.

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

The hydroxyl value of the polyester polyol is preferably 20 mgKOH/g or more and 250 mgKOH/g or less. Moreover, when the polyester polyol has an acid group, the acid value is preferably 200 mgKOH/g or less. Although the lower limit of the acid value of the polyester polyol is not particularly limited, one example is 20 mgKOH/g or more. 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.

It is particularly preferable that the polyester polyol has a number average molecular weight of 300 to 5000, since a crosslink density that is excellent in the balance between adhesion and gas barrier properties can be obtained. More preferably, the number average molecular weight is 350-3000. The number average molecular weight is obtained by calculation from the obtained hydroxyl value and the designed number of hydroxyl functional groups. 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.

The polyester polyols may be polyester polyurethane polyols obtained by subjecting the polyester polyols (A1) to (A5) to urethane elongation through reaction with a diisocyanate compound to have a number average molecular weight of 1,000 to 15,000. Since the urethane-extended polyester polyol has a certain molecular weight component or more and urethane bonds, it has excellent gas barrier properties, excellent initial cohesive strength, and is excellent as an adhesive for lamination.

The polyisocyanate composition (B), which is one component of the two-component adhesive having gas barrier properties, contains an isocyanate compound. As the isocyanate compound, conventionally known ones can be used without particular limitation, and tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or Dimers and trimers 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, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylenediamine and other low-molecular-weight active hydrogen compounds and their alkylene oxide adducts, various polyester resins, poly Examples thereof include adducts obtained by reacting with high-molecular active hydrogen compounds such as ether polyols and polyamides. A polyester polyisocyanate obtained by reacting the polyester polyols (A1) to (A5) with a diisocyanate compound in such a manner that the ratio of hydroxyl groups to isocyanate groups is in excess of isocyanate may be used. These can be used alone or in combination of two or more.

Moreover, you may use blocked isocyanate as an isocyanate compound. Examples of isocyanate blocking agents include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol and chlorophenol; oximes thereof such as acetoxime, methylethylketoxime and cyclohexanone oxime; Alcohols such as ethanol, propanol, butanol, ethylene chlorohydrin, 1,3-dichloro-2-
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-propyrolactam. In addition, aromatic amines, imides, active methylene compounds such as acetylacetone, acetoacetate and ethyl malonate, mercaptans, imines, ureas, diaryl compounds, sodium bisulfite, and the like can also be used. The blocked isocyanate can be obtained by addition reaction of the above isocyanate compound and an isocyanate blocking agent by a known and commonly used appropriate method.

Among them, xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate are preferred because they provide good gas barrier properties, and isocyanate compounds having a meta-xylylene skeleton such as meta-xylylene diisocyanate and meta-hydrogenated xylylene diisocyanate. is more preferred.

Examples of isocyanate compounds having a meta-xylene skeleton include trimers of xylylene diisocyanate, biuret compounds synthesized by reaction with amines, and adduct compounds formed by reaction with alcohols. When the adhesive is a solvent type, it is preferable to use the adduct because it has better solubility in the organic solvent used for the solvent-based adhesive than the trimer and the burette. As the adduct, an adduct obtained by reacting with an alcohol appropriately selected from the above low-molecular-weight active hydrogen compounds can be used. Adducts with substances are preferred.

Further, as the polyol composition (A), when using a composition containing a polyester polyol in which carboxylic acid groups remain, such as the polyester polyol (A1), the polyisocyanate composition (B) is a known epoxy compound. may contain Further, when using a composition containing a polyol having a polymerizable carbon-carbon double bond such as the polyester polyol (A2), a known polymerization catalyst is used in combination to promote the polymerization of the carbon-carbon double bond. For example, a known transition metal complex or photopolymerization initiator may be used in combination.

The polyol composition (A) and the polyisocyanate composition (B) are such that the equivalent ratio of the hydroxyl groups contained in the polyol composition (A) and the isocyanate groups contained in the polyisocyanate composition (B) is 1/0. It is preferable to mix 5 to 1/10, more preferably 1/1 to 1/5. If the amount of the isocyanate compound is excessive, the excessive 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. For example, inorganic fillers may be used. Inorganic fillers include silica, alumina, aluminum flakes, glass flakes and the like. In particular, it is preferable to use a plate-like inorganic compound as the inorganic filler, since it improves adhesive strength, gas barrier properties, light shielding properties, and the like. Plate-like inorganic compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, endellite, dickite, nacrite, etc., antigorite, chrysotile, etc.), pyrophyllite Light-talc group (pyrophyllite, talc, kerorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or Mica group clay minerals (mica such as muscovite and phlogopite, margarite, tetrasilylic mica, teniolite, etc.), chlorite group (cookieite, sudoite, clinochlore, chamosite, nimite, etc.), hydrotalcite, platy sulfuric acid barium, boehmite, aluminum polyphosphate, and the like. These minerals may be natural clay minerals or synthetic clay minerals. Plate-like inorganic compounds can be used singly or in combination of two or more.

In addition, adhesion promoters, acid anhydrides, compounds with oxygen scavenging functions, tackifiers, gas barrier adhesives, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, A lubricant, an antiblocking agent, a coloring agent, a crystal nucleating agent, etc. may be contained. These various additives may be added in advance to either one or both of the polyol composition (A) and the polyisocyanate composition (B), or may be added to the polyol composition (A) and the polyisocyanate composition ( B) may be added when mixing.

The gas-barrier adhesive to be used may be either solvent type or non-solvent type. Organic solvents used in the solvent type include 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 the like.

When the gas barrier adhesive to be used is solvent type, the adhesive of the present invention is applied onto the printed layer surface printed on the first substrate using a roll such as a gravure roll, and heated in an oven or the like. After evaporating the organic solvent, the other substrate is attached to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 80° C., and the aging time is preferably 12 to 240 hours.

When the gas barrier adhesive to be used is a non-solvent type, the adhesive of the present invention preheated to about 40° C. to 100° C. is applied onto the surface of the printed layer printed on the first substrate by a gravure roll or the like. After the application using the roll of No. 2, the other substrate is immediately laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.

When the gas barrier adhesive to be used is used as an adhesion aid, the adhesion aid of the present invention is applied onto the surface of the printed layer printed on the first base material using a roll such as a gravure roll, and then dried in an oven or the like. After volatilizing the organic solvent by heating, the laminate of the present invention is obtained by laminating the polymer material melted by an extruder.

The coating amount of the gas barrier adhesive to be used is appropriately adjusted. In the case of a solvent-based adhesive, for example, the solid content is adjusted to 1 g/m ² or more and 10 g/m ² or less, preferably 2 g/m ² or more and 5 g/m ² or less. In the case of a solventless adhesive, the coating amount of the adhesive is, for example, 1 g/m ² or more and 5 g/m ² or less, preferably 1 g/m ² or more and 3 g/m ² or less.

When the adhesive of the present invention is used as an adhesion aid, the coating amount is, for example, 0.1 g/m ² or more and 2 g/m ² or less (solid content).

(Laminate other layer)
The laminate of the present invention may further contain other films and substrates in addition to the above-described structures (1) to (10). As other substrates, in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather, which will be described later, can also be used. The adhesive used when bonding other substrates may or may not be the adhesive of the present invention.

As the paper, a known paper base material can be used without any particular limitation. Specifically, it is produced by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as Manila hemp pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps. The types of pulp that can be used include chemical pulp, ground pulp, chemi-grand pulp, thermomechanical pulp, and the like prepared by sulfate cooking, acid/neutral/alkaline sulfite cooking, soda salt cooking, and the like.

Moreover, various types of commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, paperboard, etc. can also be used. A printed layer may be provided on the outer surface or the inner surface of the paper layer, if necessary.

The "other layer" may contain known additives and stabilizers such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants and antioxidants. In addition, the "other layers" are pre-treated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. in order to improve adhesion when laminated with other materials. may

The laminate of the present invention can be used in various applications, such as packaging materials for foods, pharmaceuticals, and daily necessities, lids, paper straws, paper napkins, paper spoons, paper plates, paper tableware such as paper cups, barrier materials, and roofs. materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive components, signboards, outdoor industrial applications such as stickers, decorative sheets used for injection molding simultaneous decoration methods, etc. It can be suitably used as packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples. "Parts" and "%" are based on mass unless otherwise noted.

(Production Example 1) Production method of polyester polyol resin (PE1)
148.1 parts of phthalic anhydride, 84.2 parts of ethylene glycol and 0.03 parts of titanium tetraisopropoxide are charged into a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a rectifying tube, a water separator, etc., The inside temperature was maintained at 205°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (PE1) having a number average molecular weight of 900, a hydroxyl value of 126.2 mgKOH/g and an acid value of 0.36 mgKOH/g. Further, the mixture was diluted with ethyl acetate to obtain a polyester polyol resin (PE1) solution having a non-volatile content of 70%.

(Production Example 2) Production method of polyester polyol resin (PE2)
92.09 parts of glycerol, 888.72 parts of phthalic anhydride, 372 parts of ethylene glycol, and 0 of titanium tetraisopropoxide were added to a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, rectifying tube, water separator, etc. .13 parts were charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. The esterification reaction was terminated when the acid value became 1 mgKOH/g or less, and a polyester resin (PE2 ). Further, the mixture was diluted with ethyl acetate to obtain a polyester polyol resin (PE2) solution having a non-volatile content of 70%.

(Production Example 3) Production method of polyester urethane polyol resin (PEU31)
98.1 parts of phthalic anhydride, 78.5 parts of ethylene glycol and 0.01 part of titanium tetraisopropoxide are charged into a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a rectifying tube, a moisture separator, etc. The inside temperature was maintained at 205°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (PE3) having a number average molecular weight of 600. It was diluted with methyl ethyl ketone to obtain a polyester polyol resin solution (PE3) having a non-volatile content of 70%.
12.0 parts of m-xylylene diisocyanate was added to 100 parts of the polyester polyol resin solution (PE1) and heated to 80° C. to carry out the urethanization reaction until free isocyanato groups (hereinafter abbreviated as NCO groups) substantially disappeared. Further diluted with methyl ethyl ketone to obtain a polyester urethane polyol resin (PEU31) solution having a number average molecular weight of 1500 and a non-volatile content of 70%.

(Production Example 4) Production method of polyester urethane polyol resin (PEU32)
148.1 parts of phthalic anhydride, 84.2 parts of ethylene glycol and 0.03 parts of titanium tetraisopropoxide are charged into a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a rectifying tube, a water separator, etc., The inside temperature was maintained at 205°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (PE1) having a number average molecular weight of 900, a hydroxyl value of 126.2 mgKOH/g and an acid value of 0.36 mgKOH/g. Further, the mixture was diluted with ethyl acetate to obtain a polyester polyol resin (PE1) solution having a non-volatile content of 70%.
Add 16.5 parts of isophorone diisocyanate to 100 parts of the polyester polyol resin solution (PE1), heat to 80° C. to carry out a urethanization reaction until free NCO groups are substantially eliminated, and further dilute with methyl ethyl ketone, A polyester urethane polyol resin (PEU32) solution having a number average molecular weight of 5,000 and a non-volatile content of 70% was obtained.

(Production Example 5) Production method of polyester urethane polyol resin (PEU41)
148.1 parts of phthalic anhydride, 153.4 parts of neopentyl glycol and 0.03 parts of titanium tetraisopropoxide are charged into a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, rectifying tube, water separator, etc. The inside temperature was maintained at 205°C by gradually heating so that the temperature at the top of the rectification tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (PE4) having a number average molecular weight of 600. It was diluted with methyl ethyl ketone to obtain a polyester polyol resin solution (PE4) having a non-volatile content of 70%.
18.9 parts of meta-xylylene diisocyanate was added to 100 parts of the polyester polyol resin solution (PE4), heated to 80° C. to carry out a urethanization reaction until free NCO groups were substantially eliminated, and further diluted with methyl ethyl ketone. Thus, a polyester urethane polyol resin (PEU41) solution having a number average molecular weight of 5,000 and a non-volatile content of 70% was obtained.

(Example and comparative example of liquid printing ink)
(Method for producing liquid printing ink)
The mixtures mixed at the blending ratios shown in the table were kneaded using a Dyno Mill (manufactured by Willie & Bacchofen) to prepare the inks described in Examples 1 to 14 and Comparative Example 1.

(Printing method)
The liquid printing ink obtained by the above manufacturing method was diluted with the mixed organic solvent of the same ratio as that used for ink preparation, and diluted with Zahn Cup No. 3 manufactured by Rigo Co., Ltd. so as to be 16 seconds. A biaxially oriented polyester film (PET, Toyobo Co., Ltd. E- 5100, thickness 12 μm) and a biaxially oriented polypropylene film (OPP, manufactured by Toyobo Co., Ltd. P2161, thickness 20 μm). Prints using the curing agent were aged at 40° C. for one day.

(Evaluation method for liquid printing ink prints)
(Oxygen barrier property)
Oxygen barrier properties in an atmosphere of 23° C. were measured for printed matter after printing and aging. The unit is cc/m ² ·day·atm. Note that RH represents humidity.

Oxygen barrier property (OTR) measurement at 23°C/0% RH: MOCON OX-TRAN 2/21 isobaric method (according to JIS K 7126)

(Blocking resistance)
The films are superimposed so that the printed surface and the non-printed surface of the printed matter obtained by the method for producing printed matter are in contact, a load of 10 kgf/cm ² is applied, and the film is aged in an environment of 40° C. for 12 hours. The state of ink transfer to the surface was visually evaluated in the following five grades.
(Evaluation criteria)
5: Transfer of ink to non-printed surface is 0% and no transfer is observed. 4: Transfer of less than 5% is observed.
3: More than 5% and less than 10% metastasis is observed.
2: 10% or more and less than 20% metastasis is observed.
1: A transfer amount of 20% or more is transferred.

Tables 1 and 2 show liquid printing ink compositions and liquid printing ink evaluation results.

The raw materials in the table are as follows.
・ R-780: Titanium oxide pigment manufactured by Ishihara Sangyo Co., Ltd. Average particle size 0.24 μm, oil absorption 33
- Fastogen Blue 5380: C.I. I. Pig. No. 15:3
Solbin A: vinyl chloride vinyl acetate copolymer resin manufactured by Nissin Chemical Industry Co., Ltd., resin composition "vinyl chloride/vinyl acetate/vinyl alcohol = 92/3/5 (weight ratio)" number average molecular weight 30,000 , glass transition point 76 ° C., K value = 48
・HM6025: HENGHAO mica (KAL ₂ (ALSi ₃ O ₁₀ ) (OH) ₂ ), non-swelling, plate-like, average particle diameter 10 μm, aspect ratio 100 or more ・IPA: isopropyl alcohol Takenate D110N: Mitsui Chemicals XDI-based polyisocyanate (having an aromatic ring) manufactured by Co., Ltd., non-volatile content/75%

As a result, the inks of the present invention had good oxygen barrier properties and good blocking resistance of 4 or more. On the other hand, the ink of Comparative Example 1, which does not contain silica, was inferior in blocking properties.

(Examples and comparative examples of laminates)
(Method for producing gas barrier adhesive (A))
A gas barrier adhesive "PASLIM VM001/VM108CP" manufactured by DIC Corporation was used.

(Laminate manufacturing method)
The liquid printing ink obtained in Example 1 was used on an OPP film (Toyobo P2161) with a thickness of 30 μm, and the gravure printing machine equipped with a laser gravure plate having a plate depth of 25 μm was used for printing. got Next, the adhesive 1 was applied onto the printed layer using a bar coater so that the coating amount was 2.0 g/m ² (solid content), and dried by volatilizing the diluent solvent with a dryer set at a temperature of 70°C. to form an adhesive layer. After bonding an OPP film and a 25 μm-thick aluminum-deposited CPP film (Toray Film Processing 2203) with an adhesive layer interposed therebetween, aging was performed at 40° C. for 2 days to obtain a laminate.

(Evaluation method for laminate)

(Oxygen barrier property)
The layered product after aging was measured for oxygen barrier properties in an atmosphere at 23°C. The unit is cc/m ² ·day·atm. Note that RH represents humidity.
Oxygen barrier property (OTR) measurement at 23°C/0% RH: MOCON OX-TRAN 2/21 isobaric method (according to JIS K 7126)

(Laminate strength (180 degree peeling, T-type peeling))
The laminate after aging is cut into a width of 15 mm perpendicular to the coating direction, and the space between the base film and the sealant film is measured using a Tensilon universal tester manufactured by Orientec Co., Ltd. at an ambient temperature of 25 ° C. The peeling speed was set to 300 mm/min, and the tensile strength when peeled by the 180 degree peeling method and the T-type peeling method was taken as the adhesive strength.

Table 4 shows the evaluation results of the laminate.

From the above results, it is clear that the laminate using the ink of the present invention has excellent oxygen barrier properties.

Claims (8)

Polyvalent carboxylic acid component containing at least one ortho-oriented aromatic dicarboxylic acid or anhydride thereof, and at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol Amorphous polyester resin (1-1) or amorphous polyester urethane resin (1-2) having an ester skeleton that is a polycondensate with a polyhydric alcohol component containing, a coloring agent, an organic solvent, silica or containing silicone resin fine particles,
A liquid printing ink characterized by containing 0.001 to 5.0% by mass of said silica or said silicone resin fine particles relative to the solid content of said ink. The liquid printing ink according to claim 1, which contains the silica and the silicone resin fine particles and satisfies the following relationship.
(1) Contains 0.001 to 5.0% by mass of silica based on the solid content of the ink.
(2) The ink contains 0.001 to 1.0% by mass of the silicone resin fine particles based on the solid content of the ink.
(3) The silica:silicone resin fine particle mass ratio is in the range of 0.1:0.1 to 5:1. The content of the ortho-oriented aromatic dicarboxylic acid or its anhydride in the amorphous polyester resin (1-1) or the amorphous polyester urethane resin (1-2) is 50 to 100 with respect to the total polycarboxylic acid component. %. A liquid printing ink according to any one of claims 1 to 3, wherein said silicone beads are methylsilsesquioxane beads. The liquid printing ink according to any one of claims 1 to 4, wherein the silica or silicone resin fine particles have an average particle size in the range of 2.0 to 11.0 µm. Liquid printing ink according to any one of claims 1 to 5, comprising a polyisocyanate (5). A printed matter comprising a substrate and a printed layer printed on the substrate, wherein the printed layer is the ink composition according to any one of claims 1 to 6. A laminate having, in this order, at least a first substrate, a printed layer printed on the first substrate, a gas barrier adhesive layer, and a second substrate, wherein the printed layer is the A laminate characterized by being the liquid printing ink according to any one of Items 1 to 6.