Laminate, laminated laminate, and packaging material

Abstract

Provided is a laminate having excellent interlayer adhesion, exhibiting excellent laminate strength when formed into a laminate, and also having excellent clarity and blocking resistance. 【Solution means】A laminate comprising a plastic film, an ink layer located on one surface thereof, and a matte ink layer located on the other surface, wherein the ink composition forming the ink layer contains a polyhydroxy polyurethane resin (A1), a vinyl chloride-vinyl acetate copolymer (B1), and silica (C1) having a predetermined average particle diameter, the content of (C1) being 0.1 to 15% by mass based on the total solid content, and the matte ink composition forming the matte ink layer contains a polyhydroxy polyurethane resin (A2), a vinyl chloride-vinyl acetate copolymer (B2), silica (C2) having a predetermined average particle diameter, and an extender pigment (D) having a predetermined average particle diameter, and the total content of (C2) and (D) is 35 to 62% by mass based on the total solid content.

Description

Technical Field

[0001] The present invention relates to a laminate, a laminated laminate, and a packaging material.

Background Art

[0002] For packaging of foods, daily necessities, etc., a packaging material having a laminate structure in which a plastic film and a resin layer functioning as a sealant layer are laminated is used. Such a packaging material is usually provided with an ink layer for the purpose of decoration, information description, etc. The ink layer is formed, for example, by printing on a plastic film with gravure ink or the like. The ink layer is often located between the plastic film and the resin layer. In recent years, in order to further improve the design and functionality, in a packaging material having a laminate structure, a matte ink layer may be provided on a part or the whole of the surface of the plastic film on the side (visual recognition side) directly touched by the consumer. As an example of the configuration of such a packaging material, a configuration such as "matte ink layer / plastic film / ink layer / adhesive layer / resin layer" can be cited. In manufacturing a packaging material having such a configuration, a laminate having a configuration of "matte ink layer / plastic film / ink layer" may be manufactured in advance, and then this laminate and the resin layer may be laminated.

[0003] An important physical property required for the above ink layer is adhesion to the plastic film and the adhesive layer. If the adhesion of the ink layer to the plastic film or the adhesive layer is low, the laminate strength of the packaging material becomes weak. The laminate strength is important for suppressing laminate peeling and appearance defects. Important physical properties required for the above matte ink layer include matting property and transparency. The matting property is important for realizing a sufficient matte tone. Transparency is important for clearly visualizing the pattern of the ink layer.

[0004] On the one hand, in recent years, as a new environmentally friendly polyurethane resin following biomass polyurethane resin, a polyurethane resin using carbon dioxide directly has been reported. Specifically, a polyhydroxy polyurethane resin obtained by an addition reaction of a cyclic carbonate compound obtained by reacting an epoxy compound with carbon dioxide and an amine compound has been reported. This polyhydroxy polyurethane resin has a chemical structure with a hydroxyl group in its side chain, which is different from ordinary polyurethane resins due to the nature of its synthesis. Therefore, it has excellent adhesion to various plastic substrates and its use as a binder resin in printing inks is being studied.

[0005] Patent Document 1 discloses a printing ink containing a binder resin containing a polyhydroxy polyurethane resin, a crosslinking agent, and a colorant. Patent Document 2 discloses a printing ink composition containing a polyhydroxy polyurethane resin, a vinyl chloride-vinyl acetate copolymer, and a colorant.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] In a laminate having a structure of "mat ink layer / plastic film / ink layer", using a polyhydroxy polyurethane resin as the binder resin for both the ink layer and the mat ink layer is more CO 2It is very effective in improving the reduction effect. In addition, since the polyhydroxy polyurethane resin has excellent adhesion to a plastic film that has not been subjected to corona discharge treatment, it is also possible to use a plastic film that has not been subjected to corona discharge treatment on both sides, which is very useful from the viewpoints of workability and cost.

[0008] However, when the same binder resin is used for the ink layer and the matte ink layer in the laminate having the above configuration, the blocking resistance is significantly reduced. This is because when the printed laminate is wound up, the ink layer and the matte ink layer come into contact with each other, and if the same binder resin is used at that time, the compatibility is very good. The printing inks proposed in Patent Document 1 and Patent Document 2 are not assumed to have a configuration in which a matte ink layer is laminated, and effective means for solving the problems in this configuration have not yet been found.

[0009] As a method for improving the blocking resistance, a method of containing silica is widely known. However, it is known that when silica is contained in the ink layer, the surface unevenness occurs and the lamination strength is significantly reduced. In addition, it is known that when silica is additionally contained in the matte ink layer, the transparency is reduced and the sharpness of the pattern of the ink layer is greatly impaired. Therefore, when a polyhydroxy polyurethane resin is used for the binder resins of both the ink layer and the matte ink layer, effective means for improving the blocking resistance, the lamination strength, and the sharpness are required.

[0010] The present invention has been made in view of such circumstances, and the problem to be solved is to provide a laminate having excellent interlayer adhesion, excellent lamination strength when formed into a laminated laminate, and also excellent sharpness and blocking resistance, as well as a laminated laminate and a packaging material using this laminate.

Means for Solving the Problems

[0011] The present invention has the following aspects. [1] A plastic film, an ink layer formed from an ink composition and located on one surface of the plastic film, and a matte ink layer formed from a matte ink composition and located on the other surface of the plastic film. The ink composition contains a polyhydroxy polyurethane resin (A1), a vinyl chloride-vinyl acetate copolymer (B1), and silica (C1) having an average particle diameter of 2 to 8 μm. The content of the silica (C1) in terms of solid content is 0.1 to 15% by mass based on the total solid content of the ink composition. The matte ink composition contains a polyhydroxy polyurethane resin (A2), a vinyl chloride-vinyl acetate copolymer (B2), silica (C2) having an average particle diameter of 2 to 10 μm, and an extender pigment (D) having an average particle diameter of 0.02 to 0.5 μm. The total content of the silica (C2) and the extender pigment (D) in terms of solid content is 35 to 62% by mass based on the total solid content of the matte ink composition. A laminate. [2] The laminate according to [1], wherein the total content of the polyhydroxy polyurethane resin (A1) and the vinyl chloride-vinyl acetate copolymer (B1) in terms of solid content is 20 to 65% by mass based on the total solid content of the ink composition. [3] The laminate according to [1] or [2], wherein the total content of the polyhydroxy polyurethane resin (A2) and the vinyl chloride-vinyl acetate copolymer (B2) in terms of solid content is 25 to 50% by mass based on the total solid content of the matte ink composition. [4] The laminate according to any one of [1] to [3], wherein the mass ratio (C2) / (D) of the silica (C2) to the extender pigment (D) in terms of solid content is 0.08 to 0.4. [5] The laminate according to any one of [1] to [4], wherein the hydroxyl value of the polyhydroxy polyurethane resin (A1) and the hydroxyl value of the polyhydroxy polyurethane resin (A2) are each 40 to 85 mgKOH / g. [6] The mass ratio in terms of solid content of the vinyl chloride-vinyl acetate copolymer (B1) to the polyhydroxy polyurethane resin (A1), represented by (B1) / (A1), and the mass ratio in terms of solid content of the vinyl chloride-vinyl acetate copolymer (B2) to the polyhydroxy polyurethane resin (A2), represented by (B2) / (A2), are each 0.1 to 0.7, and the laminate according to any one of [1] to [5]. [7] The laminate according to any one of [1] to [6], wherein the mat ink composition further contains a curing agent. [8] The laminate according to any one of [1] to [7], wherein the ink layer and the mat ink layer are each a layer formed by gravure printing. [9] A laminate laminate in which an adhesive layer and a resin layer are laminated in this order on the surface on the ink layer side of the laminate according to any one of [1] to [8].

[10] A packaging material comprising the laminate laminate according to [9].

Effect of the Invention

[0012] According to the present invention, it is possible to provide a laminate excellent in interlayer adhesion, exhibiting excellent laminate strength when formed into a laminate laminate, and also excellent in clarity and blocking resistance, as well as a laminate laminate and a packaging material using this laminate.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the present invention will be described in detail with reference to embodiments. The following embodiments are merely examples for explaining the present invention, and it is not intended to limit the present invention only to these embodiments. The present invention can be implemented in various modes without departing from its gist. In this specification, the contents of the polyhydroxy polyurethane resin and the vinyl chloride-vinyl acetate copolymer are all in terms of solid content. "Solid content" means non-volatile content, that is, the components excluding volatile media such as organic solvents, and specifically, it is measured in accordance with JIS K 5601-1-2:2008. The solid content of the ink composition will ultimately form the ink layer. The solid content of the matte ink composition will ultimately form the matte ink layer. In this specification, when the average particle size of silica is 100 nm or more, it is the particle size at the integrated value 50% (D50) based on volume in the particle size distribution measured by the laser diffraction / scattering method, and when the average particle size is less than 100 nm, it is the particle size at the integrated value 50% (D50) based on number in the particle size distribution measured using a transmission electron microscope (TEM). Similarly, when the average particle size of the extender pigment is 100 nm or more, it is the particle size at the integrated value 50% (D50) based on volume in the particle size distribution measured by the laser diffraction / scattering method, and when the average particle size is less than 100 nm, it is the particle size at the integrated value 50% (D50) based on number in the particle size distribution measured using a transmission electron microscope (TEM). In this specification, "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value.

[0014] [Laminated body] The laminated body of this embodiment includes a plastic film, an ink layer located on one surface of the plastic film, and a matte ink layer located on the other surface of the plastic film. In other words, it is a laminated body in which the ink layer, the plastic film, and the matte ink layer are laminated in this order. Other layers may be provided between the layers.

[0015] (Plastic film) The plastic film functions as a base material for forming the ink layer and the matte ink layer. Hereinafter, the plastic film may be referred to as the base material. Examples of the plastic film include polyolefins (such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), polypropylene (PP), etc.), polyesters (such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc.), polystyrene (PS), polyamide (NY), polycarbonate, polyimide, polyvinyl chloride, etc.). The plastic film may be subjected to stretching processing. Examples of the stretching processing include biaxial stretching, uniaxial stretching, non-stretching, etc. A vapor deposition layer may be provided on at least one surface of the plastic film. Examples of the vapor deposition layer include a metal vapor deposition layer such as aluminum, and a transparent vapor deposition layer such as alumina and silica. A surface treatment may be performed on at least one surface of the plastic film. Examples of the surface treatment include corona discharge treatment, plasma treatment, flame treatment, solvent treatment, and coating treatment. Decoration such as printing using colored ink may be performed on at least one surface of the plastic film, separately from the ink layer described later. One type of plastic film may be used alone, or two or more types may be laminated and used. The thickness of the plastic film is, for example, 6 to 50 μm.

[0016] (Ink layer) The ink layer is a layer formed from an ink composition. The ink composition will be described in detail later. The ink layer may be provided over the entire surface on one surface of the plastic film or may be provided partially. The ink layer typically constitutes a pattern such as decoration and information. The thickness of the ink layer is, for example, 0.5 to 3 μm.

[0017] (Mat ink layer) The mat ink layer is a layer formed from a mat ink composition. The mat ink composition will be described in detail later. The matte ink layer may be provided over the entire surface or partially on the other surface of the plastic film. The thickness of the matte ink layer is, for example, 0.5 to 5 μm.

[0018] (Ink composition) The ink composition contains a polyhydroxy polyurethane resin (A1), a vinyl chloride-vinyl acetate copolymer (B1), and silica (C1). The ink composition may further contain a liquid medium. Examples of the liquid medium include an organic solvent (E1), water, and a mixed solvent thereof. The ink composition is preferably an oil-based ink composition containing an organic solvent (E1). In the oil-based ink composition, the content ratio of the organic solvent in the liquid medium is 95% by mass or more. The ink composition may further contain components other than those described above (optional components).

[0019] <Polyhydroxy polyurethane resin (A1)> The polyhydroxy polyurethane resin (A1) is a reaction product of a 5-membered cyclic carbonate compound formed by the reaction of an epoxy compound and carbon dioxide, and an amine compound.

[0020] The polyhydroxy polyurethane resin (A1) is obtained by reacting an epoxy compound and carbon dioxide in the presence of a catalyst, and then reacting the resulting 5-membered cyclic carbonate compound with an amine compound.

[0021] Examples of the epoxy compound used in the synthesis include the following compounds. These epoxy compounds may be used alone or in combination of two or more. When an epoxy compound and carbon dioxide are reacted, the epoxy ring of the epoxy compound becomes a 5-membered ring having a carbonate bond in the ring skeleton.

[0022]

Chemical formula

[0023] [Chemical]

[0024] Examples of the catalyst used in the synthesis include a base catalyst, a Lewis acid catalyst, and the like. Examples of the base catalyst include tertiary amines such as triethylamine, tributylamine, diazabicycloundecene, diazabicyclooctane, and pyridine; alkali metal salts such as lithium chloride, lithium bromide, lithium fluoride, and sodium chloride; alkaline earth metal salts such as calcium chloride; quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, and benzyltrimethylammonium chloride; carbonates such as potassium carbonate and sodium carbonate; metal acetates such as zinc acetate, lead acetate, copper acetate, and iron acetate; metal oxides such as calcium oxide, magnesium oxide, and zinc oxide; phosphonium salts such as tetrabutylphosphonium chloride, and the like. Examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin octoate, and the like. These catalysts may be used alone or in combination of two or more.

[0025] Examples of the amine compound used in the synthesis include methylenediamine, ethylenediamine, trimethylenediamine, 1,3-diaminopropane, hexamethylenediamine, octamethylenediamine, phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis(phenylamine), 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, metaxylylenediamine, paraxylylenediamine, 1,4-cyclohexanediamine, 4,4'-diaminocyclohexylmethane, 1,4'-diaminomethylcyclohexane, isophoronediamine, monoethanoldiamine, ethylaminoethanolamine, hydroxyethylaminopropylamine, and bis(aminopropyl)piperazine, and the like. These amine compounds may be used alone or in combination of two or more thereof.

[0026] The hydroxyl value of the polyhydroxy polyurethane resin (A1) is preferably 40 to 85 mgKOH / g, more preferably 45 to 75 mgKOH / g, and particularly preferably 50 to 70 mgKOH / g. When the hydroxyl value of the polyhydroxy polyurethane resin (A1) is at least the above lower limit value, the adhesion to the substrate, abrasion resistance, and heat resistance are more excellent. When the hydroxyl value of the polyhydroxy polyurethane resin (A1) is at most the above upper limit value, the blocking resistance, solubility in an organic solvent of the polyhydroxy polyurethane resin (A1), and ink stability are more excellent.

[0027] The weight average molecular weight (hereinafter also referred to as Mw) of the polyhydroxy polyurethane resin (A1) is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, and particularly preferably 30,000 to 60,000. When the weight average molecular weight of the polyhydroxy polyurethane resin (A1) is at least the above lower limit value, the blocking resistance, abrasion resistance, and heat resistance are more excellent. When the weight average molecular weight of the polyhydroxy polyurethane resin (A1) is at most the above upper limit value, the adhesion to the substrate is more excellent. In this specification, Mw takes a value in terms of standard polystyrene determined by gel permeation chromatography (GPC) method. Specifically, it is as described in the examples described later.

[0028] <Vinyl chloride-vinyl acetate copolymer (B1)> The vinyl chloride-vinyl acetate copolymer (B1) is a copolymerization reaction product of vinyl chloride and vinyl acetate, and contains vinyl chloride units and vinyl acetate units. The vinyl chloride-vinyl acetate copolymer (B1) may contain monomer units other than vinyl chloride units and vinyl acetate units (other monomers) as necessary. The other monomers are not particularly limited as long as they can copolymerize with vinyl chloride and vinyl acetate. Examples of the vinyl chloride-vinyl acetate copolymer (B1) include vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-vinyl alcohol copolymers, vinyl chloride-vinyl acetate-hydroxyalkyl (meth)acrylate copolymers, and vinyl chloride-vinyl acetate-dicarboxylic acid copolymers. One of them may be used alone, or two or more of them may be used in combination. As the vinyl chloride-vinyl acetate copolymer (B1), a vinyl chloride-vinyl acetate-vinyl alcohol copolymer is preferred.

[0029] The content of vinyl chloride units relative to the total mass of the vinyl chloride-vinyl acetate copolymer (B1) is preferably 50 to 98% by mass, more preferably 70 to 98% by mass, and particularly preferably 80 to 95% by mass. When the content of vinyl chloride units is at least the above lower limit, the blocking resistance is more excellent. When the content of vinyl chloride units is at most the above upper limit, the adhesion to the substrate and the anti-fogging property are more excellent.

[0030] The content of vinyl acetate units relative to the total mass of the vinyl chloride-vinyl acetate copolymer (B1) is preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass, and particularly preferably 0.5 to 5% by mass. When the content of vinyl acetate units is at least the above lower limit, the adhesion to the substrate and the anti-fogging property are more excellent. When the content of vinyl acetate units is at most the above upper limit, the blocking resistance is more excellent.

[0031] The glass transition temperature (hereinafter also referred to as Tg) of the vinyl chloride-vinyl acetate copolymer (B1) is preferably 40 to 110°C, more preferably 50 to 100°C, and particularly preferably 60 to 90°C. When the Tg of the vinyl chloride-vinyl acetate copolymer (B1) is at least the above lower limit, the blocking resistance, abrasion resistance, and heat resistance are more excellent. When the Tg of the vinyl chloride-vinyl acetate copolymer (B1) is at most the above upper limit, the adhesion to the substrate is more excellent. In this specification, Tg is determined from the intersection point of the baseline and the tangent line of the endothermic curve in the curve (DSC curve) obtained by heating 10 mg of the sample from -100°C to 160°C at a rate of 20°C / min using a differential scanning calorimeter in accordance with JIS K 7121.

[0032] The number average molecular weight (hereinafter also referred to as Mn) of the vinyl chloride-vinyl acetate copolymer (B1) is preferably from 10,000 to 100,000, more preferably from 15,000 to 80,000, and particularly preferably from 20,000 to 50,000. When the Mn of the vinyl chloride-vinyl acetate copolymer (B1) is at least the above lower limit value, the blocking resistance, abrasion resistance, and heat resistance are more excellent. When the Mn of the vinyl chloride-vinyl acetate copolymer (B1) is at most the above upper limit value, the adhesion to the substrate is more excellent. In this specification, Mn takes the value in terms of standard polystyrene determined by gel permeation chromatography (GPC) method.

[0033] The hydroxyl value of the vinyl chloride-vinyl acetate copolymer (B1) is preferably from 60 to 180 mgKOH / g, more preferably from 80 to 170 mgKOH / g, and particularly preferably from 100 to 160 mgKOH / g. When the hydroxyl value of the vinyl chloride-vinyl acetate copolymer (B1) is at least the above lower limit value, the compatibility with the polyhydroxy polyurethane resin (A1) and the adhesion to the substrate are more excellent. When the hydroxyl value of the vinyl chloride-vinyl acetate copolymer (B1) is at most the above upper limit value, the ink stability is more excellent.

[0034] <Silica (C1)> Silica (C1) may be either a natural product or a synthetic product, and may be either crystalline or amorphous. As the synthesis method, either a dry method or a wet method may be used. As the dry method, a combustion method and an arc method are known. As the wet method, a precipitation method and a gel method are known. Silica (C1) may be either hydrophobic silica or hydrophilic silica. Hydrophobic silica is silica whose surface has been hydrophobized. The hydrophobization treatment of the silica surface can be carried out by a known method using a surface treatment agent. Examples of the surface treatment agent include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, silicone oil, and the like. The surface treatment agent may be used alone or in combination of two or more kinds. Silica (C1) may be used alone or in combination of two or more kinds.

[0035] The average particle diameter of silica (C1) is 2 to 8 μm, preferably 2.5 to 7.5 μm, and more preferably 3 to 7 μm. When the average particle diameter of silica (C1) is at least the above lower limit value, the antiblocking property is excellent. When the average particle diameter of silica (C1) is at most the above upper limit value, the adhesion to the substrate, the laminating strength, and the printability are excellent.

[0036] <Organic solvent (E1)> Examples of the organic solvent (E1) include ketone solvents, hydrocarbon solvents, ester solvents, ether solvents, glycol ether solvents, and alcohol solvents, etc., and one of them can be used alone or in combination of two or more kinds. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as n - hexane, n - heptane, and n - octane; and alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and cyclooctane, etc. Examples of ester solvents include methyl acetate, ethyl acetate, n - propyl acetate, n - butyl acetate, and isobutyl acetate, etc. Examples of ether solvents include tetrahydrofuran, dioxane, diethyl ether, and methyl ethyl ether, etc. Examples of glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether, etc. Examples of alcohol solvents include monohydric alcohols such as methanol, ethanol, n - propanol, isopropanol, and n - butanol; and polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, etc. As the organic solvent (E1), from the viewpoint of the safety of the working environment such as odor and safety, an organic solvent substantially free of aromatic hydrocarbon solvents such as toluene and xylene is preferred.

[0037] The organic solvent (E1) preferably contains at least one selected from the group consisting of ester solvents and alcohol solvents from the viewpoints of the solubility, storage stability, and drying property of the polyhydroxy polyurethane resin (A1) and the vinyl chloride - vinyl acetate copolymer (B1). The content ratio of the ester solvent in the organic solvent (E1) is preferably 30 - 90% by mass based on the whole of the organic solvent (E1). The content ratio of the alcohol solvent in the organic solvent (E1) is preferably 0 - 50% by mass based on the whole of the organic solvent (E1).

[0038] <Optional component> [Colorant] The ink composition can contain a colorant, if necessary. The colorant is not particularly limited, and for example, conventionally known inorganic color pigments and organic color pigments can be used.

[0039] Examples of the inorganic color pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, aluminum, and mica. The inorganic color pigment may be used alone or in combination of two or more.

[0040] Examples of the organic color pigment include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, and diketopyrrolopyrrole pigments. The organic color pigment may be used alone or in combination of two or more.

[0041] More specifically, examples of the colorant by Color Index name are as follows. C.I.Pigment Yellow 13, 14, 17, 83, 180; C.I.Pigment Orange 13, 16; C.I.Pigment Red 48:1, 48:2, 48:3, 49:1, 53:1, 57:1, 101, 122, 146, 185; C.I.Pigment Violet 23, 24; C.I.Pigment Blue 15:1, 15:3, 15:4, 17:1; C.I.Pigment Green 7; C.I.Pigment Black 7; C.I.Pigment White 4, 6, 18.

[0042] [Other optional components] The ink composition can contain other optional components other than the above, as long as the effects of the present invention are not impaired, as necessary. Examples of other optional components include pigments other than colorants, pigment derivatives, waxes, rosin derivatives, cellulose-based resins, chelating agents, fatty acid amides, surfactants, anti-settling agents, cross-linking agents, silane coupling agents, ultraviolet absorbers, antioxidants, antistatic agents, leveling agents, thickeners, defoamers, plasticizers, wetting agents, dispersants, stabilizers, and the like. These optional components may be used alone or in combination of two or more.

[0043] <Content ratio> The mass ratio (B1) / (A1) in terms of solid content of the vinyl chloride-vinyl acetate copolymer (B1) to the polyhydroxy polyurethane resin (A1) is preferably 0.1 to 0.7, more preferably 0.14 to 0.5, and particularly preferably 0.18 to 0.4. When (B1) / (A1) is at least the above lower limit, the blocking resistance, the abrasion resistance of the ink layer, and the heat resistance are more excellent. When (B1) / (A1) is at most the above upper limit, the adhesion to the substrate of the ink layer is more excellent.

[0044] <Content> The total content in terms of solid content of the polyhydroxy polyurethane resin (A1) and the vinyl chloride-vinyl acetate copolymer (B1) is preferably 20 to 65% by mass, more preferably 22 to 63% by mass, and still more preferably 25 to 60% by mass with respect to the total solid content of the ink composition. When the total content is at least the above lower limit, the adhesion to the substrate of the ink layer, the laminating strength, and the printability of the ink composition are more excellent. When the total content is at most the above upper limit, the blocking resistance is more excellent.

[0045] The content of silica (C1) in terms of solid content is 0.1 to 15% by mass, preferably 0.3 to 12% by mass, and more preferably 0.5 to 8% by mass with respect to the total solid content of the ink composition. When the content of silica (C1) is at least the above lower limit value, the blocking resistance is excellent. When the content of silica (C1) is at most the above upper limit value, the adhesion of the ink layer to the substrate, the laminating strength, and the printability of the ink composition are excellent. Also, the ink composition is less likely to exhibit thixotropy.

[0046] When the ink composition contains an organic solvent (E1), the content of the organic solvent (E1) can be appropriately set according to the method of forming the ink layer (printing method) so as to obtain a desired solid content concentration. When the ink layer is formed by gravure printing, the solid content concentration of the ink composition is preferably 10 to 50% by mass with respect to the total mass of the ink composition. The content of the organic solvent (E1) is preferably 50 to 90% by mass with respect to the total mass of the ink composition.

[0047] When the ink composition contains a colorant, the content of the colorant is preferably 10 to 80% by mass with respect to the total solid content of the ink composition from the viewpoints of concentration and coloring power.

[0048] In the ink composition, the content of hydrocarbon wax is preferably 2% by mass or less with respect to the total solid content of the ink composition from the viewpoint of laminating strength. Examples of the hydrocarbon wax include the same ones as those mentioned in the description of the matte ink composition described later.

[0049] In the ink composition, the content of rosin derivative is preferably 2% by mass or less with respect to the total solid content of the ink composition from the viewpoint of blocking resistance. Examples of the rosin derivative include rosin-modified maleic acid resin, rosin-modified fumaric acid resin, rosin-modified phenol resin, rosin ester, hydrogenated rosin, polymerized rosin, and terpene phenol resin. These rosin derivatives may be used alone or in combination of two or more.

[0050] <Method for producing ink composition> The ink composition is obtained by dissolving or dispersing, for example, a polyhydroxy polyurethane resin (A1), a vinyl chloride-vinyl acetate copolymer (B1), silica (C1), and, if necessary, optional components in an organic solvent (E1). The mixing method of each component is not particularly limited, and each component can be mixed by various methods. The method of dissolving or dispersing each component in the organic solvent (E1) is not particularly limited, and it can be carried out using a known disperser. Examples of the disperser include a paint shaker, a ball mill, an attritor, a sand mill, a bead mill, a dynomill, a roll mill, an ultrasonic mill, a high-pressure collision disperser, etc. At this time, one kind of disperser may be used for one or more dispersion treatments, or two or more kinds of dispersers may be used in combination for a plurality of dispersion treatments.

[0051] (Matte ink composition) The matte ink composition contains a polyhydroxy polyurethane resin (A2), a vinyl chloride-vinyl acetate copolymer (B2), silica (C2), and a extender pigment (D). The matte ink composition may further contain a liquid medium. Examples of the liquid medium include an organic solvent (E2), water, and a mixed solvent thereof. The matte ink composition is preferably an oil-based ink composition containing an organic solvent (E2). The matte ink composition may further contain components other than the above (optional components). Note that the matte ink composition is usually different from the above-described ink composition in that the content of the colorant is 1% by mass or less based on the total solid content.

[0052] <Polyhydroxy polyurethane resin (A2)> Examples of the polyhydroxy polyurethane resin (A2) include the same ones as the polyhydroxy polyurethane resin (A1), and the preferred embodiments are also the same. The polyhydroxy polyurethane resin (A2) may be the same as or different from the polyhydroxy polyurethane resin (A1).

[0053] <Vinyl chloride-vinyl acetate copolymer (B2)> As the vinyl chloride-vinyl acetate copolymer (B2), the same ones as the vinyl chloride-vinyl acetate copolymer (B1) can be mentioned, and the preferred embodiments are also the same. The vinyl chloride-vinyl acetate copolymer (B2) may be the same as or different from the vinyl chloride-vinyl acetate copolymer (B1).

[0054] <Silica (C2)> Silica (C2) may be either a natural product or a synthetic product, and may be either crystalline or amorphous. As the synthesis method, either a dry method or a wet method may be used. As the dry method, a combustion method and an arc method are known. As the wet method, a precipitation method and a gel method are known. Silica (C2) may be either hydrophobic silica or hydrophilic silica. From the viewpoint of more excellent antiblocking property, hydrophobic silica is preferred. Hydrophobic silica is silica whose surface has been hydrophobized. The hydrophobization treatment of the silica surface can be carried out by a known method using a surface treatment agent. Examples of the surface treatment agent include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, silicone oil, etc. The surface treatment agent may be used alone or in combination of two or more. Silica (C2) may be used alone or in combination of two or more.

[0055] The average particle diameter of silica (C2) is 2 to 10 μm, preferably 2.3 to 8 μm, and more preferably 2.6 to 6 μm. When the average particle diameter of silica (C2) is at least the above lower limit value, the antiblocking property is excellent. When the average particle diameter of silica is at most the above upper limit value, the adhesion to the substrate, transparency, abrasion resistance, and printability are excellent.

[0056] <Extender pigment (D)> The extender pigment (D) is solid particles formed of an inorganic material. Examples of the extender pigment (D) include barium sulfate, calcium sulfate, calcium carbonate, calcium silicate, magnesium silicate, aluminum oxide, zirconium oxide, tin oxide, clay, kaolin, and the like. Among them, barium sulfate and calcium carbonate are preferable from the viewpoint of excellent transparency. The extender pigment (D) may be used alone or in combination of two or more.

[0057] The average particle diameter of the extender pigment (D) is 0.02 to 0.5 μm, preferably 0.03 to 0.45 μm, and more preferably 0.04 to 0.4 μm. When the average particle diameter of the extender pigment (D) is at least the above lower limit value, the blocking resistance and heat resistance are excellent. When the average particle diameter of the extender pigment (D) is at most the above upper limit value, the transparency is excellent.

[0058] <organic solvent (E2)> Examples of the organic solvent (E2) include the same ones as the organic solvent (E1). The organic solvent (E2) may be the same as or different from the organic solvent (E1). From the viewpoint of the safety of the working environment such as odor and safety, an organic solvent substantially free of aromatic hydrocarbon solvents such as toluene and xylene is preferable as the organic solvent (E2).

[0059] The organic solvent (E2) preferably contains at least one selected from the group consisting of an ester solvent and an alcohol solvent from the viewpoints of the solubility, storage stability, and drying property of the polyhydroxy polyurethane resin (A2) and the vinyl chloride-vinyl acetate copolymer (B2). The content ratio of the ester solvent in the organic solvent (E2) is preferably 20 to 90% by mass based on the whole of the organic solvent (E2). The content ratio of the alcohol solvent in the organic solvent (E2) is preferably 10 to 80% by mass based on the whole of the organic solvent (E2).

[0060] <optional component> [hydrocarbon wax] The matte ink composition can contain a hydrocarbon wax for the purpose of further improving the abrasion resistance. Examples of the hydrocarbon wax include polyethylene wax, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, polypropylene wax, etc. Among them, polyethylene wax and Fischer-Tropsch wax are preferable. Examples of the polyethylene wax can include high-density polyethylene, low-density polyethylene, oxidized polyethylene, acid-modified polyethylene, and special monomer-modified polyethylene. The Fischer-Tropsch wax is a wax produced by the Fischer-Tropsch method using carbon monoxide and hydrogen as raw materials, and has a substantially saturated and straight-chain molecular structure without branching. The hydrocarbon wax may be used alone or in combination of two or more.

[0061] The penetration (hardness) of the hydrocarbon wax at 25°C is preferably 30 or less, more preferably 25 or less, and particularly preferably 20 or less. When the penetration (hardness) of the hydrocarbon wax is below the above upper limit value, the abrasion resistance is more excellent. In this specification, the penetration (hardness) is a value measured in accordance with JIS K 2207.

[0062] The melting point of the hydrocarbon wax is preferably 50 to 160°C, more preferably 80 to 150°C, and particularly preferably 100 to 140°C. When the melting point of the hydrocarbon wax is at or above the above lower limit value, the heat resistance and blocking resistance are more excellent. When the melting point of the hydrocarbon wax is at or below the above upper limit value, the abrasion resistance is more excellent.

[0063] [Chlorinated polyolefin resin] The matte ink composition can contain a chlorinated polyolefin resin for the purpose of further improving the adhesion to the substrate. Chlorinated polyolefin resin is a polyolefin in which at least a part of hydrogen atoms is substituted with chlorine atoms. As the polyolefin constituting the chlorinated polyolefin resin, a homopolymer or copolymer of an α-olefin-based unsaturated hydrocarbon such as polypropylene, poly-1-butene, poly-4-methyl-1-pentene is preferable, and polypropylene is more preferable. Chlorinated polyolefin may be used alone or in combination of two or more.

[0064] The Mw of the chlorinated polyolefin resin is preferably 1,000 to 100,000, more preferably 2,000 to 80,000, and particularly preferably 3,000 to 50,000. When the Mw of the chlorinated polyolefin resin is at least the above lower limit value, the adhesion to the substrate is more excellent. When the Mw of the chlorinated polyolefin resin is at most the above upper limit value, the compatibility is more excellent.

[0065] The chlorine content of the chlorinated polyolefin resin is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and particularly preferably 20 to 50% by mass. When the chlorine content of the chlorinated polyolefin is at least the above lower limit value, the compatibility is more excellent. When the chlorine content of the chlorinated polyolefin is at most the above upper limit value, the adhesion to the substrate is more excellent. The chlorine content of the chlorinated polyolefin is the content ratio (% by mass) of chlorine atoms to the total mass of the chlorinated polyolefin.

[0066] [Resin beads] The matte ink composition can contain resin beads for the purpose of further improving the blocking resistance and the matting property. Examples of the resin beads include resin particles such as melamine resins, benzoguanamine resins, (meth)acrylic resins, polystyrene resins, urethane resins, silicone resins, polycarbonate resins, copolymers of (meth)acrylic monomers and styrene monomers, polyolefin resins, polyester resins, polyamide resins, polyimide resins, and polytetrafluoroethylene resins. Among them, from the viewpoint of excellent heat resistance, it is more preferable to use benzoguanamine resin beads. The resin beads may be either crosslinked or non-crosslinked. The resin beads may be used alone or in combination of two or more.

[0067] The average particle diameter of the resin beads is preferably 0.1 to 10 μm, more preferably 0.5 to 7 μm, and particularly preferably 1 to 5 μm. When the average particle diameter of the resin beads is at least the above lower limit value, the antiblocking property, matting property, and heat resistance are more excellent. When the average particle diameter of the resin beads is at most the above upper limit value, the abrasion resistance and printability are more excellent. In this specification, the average particle diameter of the resin beads is the particle diameter at the volume-based integrated value 50% (D50) in the particle size distribution measured by the laser diffraction / scattering method.

[0068] [Hardening agent] The matte ink composition may contain a hardening agent for the purpose of further improving the adhesion to the substrate, heat resistance, and abrasion resistance. As the curing agent, an isocyanate-based curing agent is preferred. The isocyanate-based curing agent is a compound having two or more isocyanate groups in one molecule. Examples of the isocyanate-based curing agent include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-MDI, 2,4'-MDI, 2,4-tolylene diisocyanate (TDI), 2,6-TDI, m-xylylene diisocyanate (XDI), and 1,4-phenylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate (IPDI), 1,3-bis(isocyanatomethyl)cyclohexane (hydrogenated XDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), and 1-methylcyclohexane-2,4-diisocyanate (hydrogenated TDI); aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and 2,4,4-trimethylhexamethylene diisocyanate; and isocyanate prepolymers such as adducts of various diisocyanates, isocyanurates of various diisocyanates, biuret of HDI, and allophanate of HDI; etc. The curing agent may be used alone or in combination of two or more.

[0069] [Other optional components] The matte ink composition can contain other optional components other than the above, as necessary, within a range not impairing the effects of the present invention. Examples of other optional components include pigments other than extender pigments (D), pigment derivatives, waxes other than hydrocarbon waxes, rosin derivatives, cellulose-based resins, chelating agents, fatty acid amides, surfactants, anti-settling agents, silane coupling agents, ultraviolet absorbers, antioxidants, antistatic agents, leveling agents, thickeners, defoamers, plasticizers, wetting agents, dispersants, stabilizers, etc. These optional components may be used alone or in combination of two or more.

[0070] [Content ratio] The mass ratio (B2) / (A2) representing the solid content conversion of the vinyl chloride-vinyl acetate copolymer (B2) to the polyhydroxy polyurethane resin (A2) is preferably from 0.1 to 0.7, more preferably from 0.14 to 0.5, and particularly preferably from 0.18 to 0.4. When (B2) / (A2) is at least the above lower limit, the blocking resistance, the abrasion resistance of the matte ink layer, and the heat resistance are more excellent. When (B2) / (A2) is at most the above upper limit, the adhesion to the substrate of the matte ink layer is more excellent.

[0071] The mass ratio (C2) / (D) representing the solid content conversion of the silica (C2) to the extender pigment (D) is preferably from 0.08 to 0.4, more preferably from 0.1 to 0.35, and particularly preferably from 0.12 to 0.3. When (C2) / (D) is at least the above lower limit, the blocking resistance and the heat resistance of the matte ink layer are more excellent. When (C2) / (D) is at most the above upper limit, the adhesion to the substrate of the matte ink layer, the abrasion resistance, and the printability of the matte ink composition are more excellent.

[0072] <Content> The total content in terms of solid content of the polyhydroxy polyurethane resin (A2) and the vinyl chloride-vinyl acetate copolymer (B2) is preferably 25 to 50% by mass, more preferably 27 to 45% by mass, and still more preferably 30 to 40% by mass with respect to the total solid content of the matte ink composition. When the total content is at least the above lower limit, the adhesion to the substrate of the matte ink layer, the abrasion resistance, and the printability of the matte ink composition are more excellent. When the total content is at most the above upper limit, the blocking resistance and the heat resistance of the matte ink layer are more excellent.

[0073] The total content in terms of solid content of the silica (C2) and the extender pigment (D) is 35 to 62% by mass with respect to the total solid content of the matte ink composition, preferably 40 to 60% by mass, and more preferably 45 to 58% by mass. When the total content is at least the above lower limit, the blocking resistance and the matting property are excellent. When the total content is at most the above upper limit, the adhesion to the substrate of the matte ink layer, the transparency, the abrasion resistance, and the printability of the matte ink composition are excellent.

[0074] When the matte ink composition contains an organic solvent (E2), the content of the organic solvent (E2) can be appropriately set according to the method for forming the matte ink layer (printing method) so as to achieve a desired solid content concentration. When forming the matte ink layer by gravure printing, the solid content concentration of the matte ink composition is preferably 10 to 50% by mass based on the total mass of the matte ink composition. The content of the organic solvent (E2) is preferably 50 to 90% by mass based on the total mass of the matte ink composition.

[0075] When the matte ink composition contains a hydrocarbon wax, the content of the hydrocarbon wax in terms of solid content is preferably 0.1 to 5% by mass, more preferably 0.5 to 3.5% by mass, and still more preferably 1 to 2% by mass based on the total mass of the matte ink composition. When the matte ink composition contains a hydrocarbon wax, the content of the hydrocarbon wax in terms of solid content is preferably 2 to 8% by mass, more preferably 2.5 to 6.5% by mass, and still more preferably 3 to 5% by mass based on the total solid content of the matte ink composition. When the content of the hydrocarbon wax is at least the above lower limit value, the abrasion resistance is more excellent. When the content of the hydrocarbon wax is at most the above upper limit value, the heat resistance and transparency are more excellent.

[0076] When the matte ink composition contains a chlorinated polyolefin resin, the content of the chlorinated polyolefin resin in terms of solid content is preferably 0.1 to 3% by mass, more preferably 0.1 to 2% by mass, and still more preferably 0.2 to 1% by mass based on the total mass of the matte ink composition. When the matte ink composition contains a chlorinated polyolefin resin, the content of the chlorinated polyolefin resin in terms of solid content is preferably 0.1 to 4% by mass, more preferably 0.2 to 3% by mass, and still more preferably 0.4 to 2% by mass based on the total solid content of the matte ink composition. When the content of the chlorinated polyolefin resin is at least the above lower limit value, the adhesion to the substrate is more excellent. When the content of the chlorinated polyolefin resin is at most the above upper limit value, the heat resistance is more excellent.

[0077] When the matte ink composition contains resin beads, the content of the resin beads in terms of solid content is preferably 0.1 to 4% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.2 to 2% by mass based on the total mass of the matte ink composition. When the matte ink composition contains resin beads, the content of the resin beads in terms of solid content is preferably 0.1 to 5% by mass, more preferably 1 to 4.5% by mass, and still more preferably 2 to 4% by mass based on the total solid content of the matte ink composition. When the content of the resin beads is at least the above lower limit value, the blocking resistance, matting property, and heat resistance are more excellent. When the content of the resin beads is at most the above upper limit value, the adhesion to the substrate, transparency, abrasion resistance, and printing suitability are more excellent.

[0078] When the matte ink composition contains a curing agent, the content of the curing agent in terms of solid content is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, and still more preferably 1 to 3% by mass based on the total mass of the matte ink composition. When the matte ink composition contains a curing agent, the content of the curing agent in terms of solid content is preferably 0.1 to 8% by mass, more preferably 2 to 7.5% by mass, and still more preferably 4 to 7% by mass based on the total solid content of the matte ink composition. When the content of the curing agent is at least the above lower limit value, the adhesion to the substrate, heat resistance, and abrasion resistance are more excellent. When the content of the curing agent is at most the above upper limit value, the blocking resistance is more excellent.

[0079] <Method for producing matte ink composition> The matte ink composition can be obtained, for example, by dissolving or dispersing a polyhydroxy polyurethane resin (A2), a vinyl chloride-vinyl acetate copolymer (B2), silica (C2), an extender pigment (D), and, if necessary, optional components in an organic solvent (E2). The mixing method of each component is not particularly limited, and each component can be mixed by various methods. The method of dissolving or dispersing each component in the organic solvent (E2) is not particularly limited and can be carried out using a known disperser. Examples of the disperser include a paint shaker, a ball mill, an attritor, a sand mill, a bead mill, a dyno mill, a roll mill, an ultrasonic mill, a high-pressure collision disperser, and the like. At this time, the dispersion treatment may be carried out once or a plurality of times using one type of disperser, or the dispersion treatment may be carried out a plurality of times using two or more types of dispersers in combination.

[0080] (Method for manufacturing a laminate) The laminate of the present embodiment can be obtained, for example, by coating an ink composition on one surface of a plastic film to form an ink layer and coating a mat ink composition on the other surface of the plastic film to form a mat ink layer. The method of coating each of the ink composition and the mat ink composition is not particularly limited, and various known coating methods can be used. For example, gravure printing, flexographic printing, brush coating, gravure coater method, die coater method, bar coater method, spray coating method, flow coating method, dip coating method, spin coating method, and curtain coating method can be mentioned. Among these, gravure printing and flexographic printing are preferable because they are excellent in drying property and can cope with high-speed printing. In particular, gravure printing is preferable because an appropriate coating amount can be ensured and the color harmony reproducibility is also excellent. Therefore, the ink layer and the mat ink layer are preferably layers formed by gravure printing, respectively. After coating the ink composition or the mat ink composition, drying is carried out as necessary. As the drying method, it is only necessary to be able to remove the organic solvent in the ink composition or the mat ink composition, and examples thereof include heat drying and natural drying. When heat drying is carried out, the drying temperature is preferably 30 to 60°C, and more preferably 35 to 55°C.

[0081] <Function and effect> The laminate of the present embodiment described above has an ink layer formed from the above-described ink composition and a matte ink layer formed from the above-described matte ink composition. Therefore, each of the ink layer and the matte ink layer has excellent adhesion to the substrate, excellent interlayer adhesion, and also excellent laminating strength when a resin layer is laminated on the laminate to form a laminated laminate. Further, the matte ink layer has excellent transparency, and the ink layer can be clearly visually recognized from the matte ink layer side. Further, it has excellent blocking resistance, and blocking is less likely to occur when a long laminate is wound into a roll or a plurality of sheet-like laminates are stacked.

[0082] [Laminated Laminate] The laminated laminate of the present embodiment is one in which an adhesive layer and a resin layer are laminated in this order on the surface of the above-described laminate on the ink layer side. In other words, it is a laminate in which a resin layer, an adhesive layer, an ink layer, a plastic film, and a matte ink layer are laminated in this order. Other layers may be provided between the layers.

[0083] (Resin Layer) The resin layer typically functions as a sealant layer. Examples of the resin constituting the resin layer include heat-sealable resins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and polypropylene (PP). The resin constituting the resin layer may be one type or two or more types. The resin layer may be a single layer or a multilayer. The thickness of the resin layer is, for example, 2 to 100 μm.

[0084] (Adhesive Layer) As the adhesive for forming the adhesive layer, a known adhesive can be used according to the method of laminating the laminate and the resin layer. Examples of the adhesive used in the dry lamination method include two-component adhesives composed of a mixture of a polyol and an isocyanate curing agent. Examples of the polyol include polyester polyols and polyether polyols. Specifically, products such as "Seika Bond E-263 / C-75N" and "Seika Bond A-159 / C89(F)" manufactured by Dainichi Seika Chemicals Co., Ltd. can be mentioned. Examples of the adhesive used in the extrusion lamination method include two-component adhesives composed of a mixture of a polyol and an isocyanate curing agent. Specifically, products such as "Seika Dyn 2710A / Seika Dyn 2710C" manufactured by Dainichi Seika Chemicals Co., Ltd. can be mentioned. The thickness of the adhesive layer is, for example, 0.01 to 5 g / m when converted to the mass of the adhesive layer per unit area (dry coating amount of the adhesive). 2 That is.

[0085] (Method for manufacturing a laminate) The laminate of this embodiment can be manufactured by a known method. Specifically, a dry lamination method in which an adhesive is applied to the surface of the laminate on the ink layer side or the surface of the resin film on which the resin layer is formed, dried, and then pressure-bonded; a known lamination method such as an extrusion lamination method in which, if necessary, an adhesive called an anchor coat agent is applied to the surface of the laminate on the ink layer side, and then a molten resin for forming the resin layer is extruded can be used.

[0086] (Applications) The laminate of this embodiment is suitable as a packaging material, particularly a flexible packaging material. Here, the "flexible packaging material" refers to a packaging material composed of a flexible material, that is, a flexible package, and is used for packaging foods, daily necessities, and the like.

Examples

[0087] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[0088] (Raw materials used) <Polyhydroxy polyurethane resins (A1), (A2), and their comparative products> · A-1: A polyhydroxy polyurethane resin obtained in Synthesis Example 1 described below, with a hydroxyl value of 64 mg KOH / g and an Mw of 43000. · A-2: A polyhydroxy polyurethane resin obtained in Synthesis Example 2 described below, with a hydroxyl value of 41.8 mg KOH / g and an Mw of 49000 · A-3: A polyhydroxy polyurethane resin obtained in Synthesis Example 3 described below, with a hydroxyl value of 82 mg KOH / g and an Mw of 42000. · A-4: A polyhydroxy polyurethane resin obtained in Synthesis Example 4 described below, with a hydroxyl value of 35 mg KOH / g and an Mw of 44000. · A-5: A polyhydroxy polyurethane resin obtained in Synthesis Example 5 described below, with a hydroxyl value of 90 mg KOH / g and an Mw of 45000. · A-6: A polyurethane resin with a hydroxyl value of 4.2 mg KOH / g and an Mw of 33000. Note that A-6 does not correspond to the polyhydroxy polyurethane resin (A) in that it is not a reaction product of a 5-membered cyclic carbonate compound formed by the reaction of an epoxy compound and carbon dioxide with an amine compound.

[0089] [Production Example 1: Production of carbonate compound (Compound I)] Into a reaction vessel equipped with a stirrer, thermometer, gas inlet tube, and reflux condenser, 100 parts of neopentyl glycol diglycidyl ether (trade name: "Denacol EX-211", manufactured by Nagase ChemteX Corporation) with an epoxy equivalent of 138 g / eq, 100 parts of N-methyl-2-pyrrolidone (NMP), and 20 parts of sodium iodide (manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved uniformly. While stirring, carbon dioxide gas (CO 2 gas) was introduced at a rate of 0.5 L / min, and the reaction was carried out at 100 °C for 10 hours.

[0090] After the reaction was completed, 400 parts of ethyl acetate and 800 parts of water were added, and the mixture was stirred for 1 hour. Then, the ethyl acetate phase was recovered, and the solvent was removed using an evaporator to obtain a viscous liquid compound. Using an infrared spectrophotometer (trade name: "FT-720", manufactured by Horiba, Ltd., hereinafter referred to as FT-IR), the obtained viscous liquid was subjected to IR analysis. As a result, the absorption peak derived from the epoxy group in the raw material near 910 cm -1 disappeared, and it was found that a new absorption peak derived from the carbonate group (carbonyl group) appeared near 1800 cm -1 . The obtained compound (reactant) was confirmed to be a compound (Compound I) represented by the following formula, which has a carbonate group with a cyclic structure formed by the reaction of an epoxy group and carbon dioxide. The carbon dioxide content of Compound I obtained above is 24.1% by calculation.

[0091] [Chemical formula]

[0092] [Synthesis Example 1: Synthesis of A-1] Into a reaction vessel equipped with a stirrer, a reflux condenser with an air opening, and a nitrogen inlet tube, 100 parts of Compound I obtained in Production Example 1, 18.8 parts of hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 87.3 parts of a dimer diamine having a C6 ring structure and 36 carbon atoms (manufactured by Croda Japan Co., Ltd., trade name "Priamine 1074", dimer structure ratio: 95% or more, amine value: 210 mgKOH / g), and 58.9 parts of ethyl acetate were added, and the reaction was carried out for 5 hours under reflux conditions at about 80 °C. After the reaction, the obtained reaction solution was analyzed by FT-IR. As a result, the absorption derived from the carbonyl group of Compound I observed near 1800 cm -1 completely disappeared, and a new absorption derived from the carbonyl group of the urethane bond was observed near 1760 cm -1 . It was confirmed that a prepolymer of a polyhydroxypolyurethane resin with a terminal NH 2 was synthesized.

[0093] Next, without cooling the above reaction solution, 21.8 parts of hexamethyldisilazane (product name: SZ-31, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 30 minutes. After 30 minutes had elapsed since the total amount was added dropwise, the N-Si-derived 933 cm -1After confirming that the nearby peak had disappeared, the reaction was terminated. To the solution after the reaction was completed, 378.9 parts of ethyl acetate was added as a diluting solvent, and the mixture was cooled to room temperature. Next, while stirring the cooled solution, 12.0 parts of isophorone diisocyanate (manufactured by Evonik Japan Co., Ltd.; the same product was used in other examples) was slowly added dropwise. After the addition, it was confirmed by FT-IR that the peak near 2260 cm -1 After confirming that the peak near had disappeared, the reaction was terminated. As a result, a polyhydroxy polyurethane resin solution that was pale yellow and transparent and had a resin content (solid content) of 35% was obtained.

[0094] Regarding the obtained polyhydroxy polyurethane resin, GPC measurement was performed using DMF (N,N-dimethylformamide) as a mobile phase. As a result, Mw was 43000. The GPC measurement was carried out using GPC-8820 (trade name, manufactured by Tosoh Corporation) as the measuring device and the following four columns. Specifically, four columns of SuperAW2500, AW3000, AW4000, and AW5000 (trade names, all manufactured by Tosoh Corporation) were used. Also, the hydroxyl value measured according to JIS-K1557-1 was 64 mgKOH / g as a solid content conversion value. In each of the following examples, Mw and the hydroxyl value were measured in the same manner as above.

[0095] [Synthesis Example 2: Synthesis of A-2] Into a reaction vessel equipped with a stirrer, a reflux condenser with an air opening, and a nitrogen inlet tube, 100 parts of Compound I obtained in Production Example 1, 20.4 parts of hexamethylenediamine, 94.6 parts of Priamine 1074, and 65 parts of ethyl acetate were added, and the reaction was carried out under reflux conditions at about 80 °C for 5 hours. After the reaction, when the obtained reaction solution was analyzed by FT-IR, the absorption derived from the carbonyl group of Compound I observed near 1800 cm -1 completely disappeared, and newly, the absorption derived from the carbonyl group of the urethane bond was observed near 1760 cm -1 , confirming that a prepolymer of a polyhydroxy polyurethane resin with a terminal of NH 2 was synthesized.

[0096] Next, without cooling the above reaction solution, 30.5 parts of hexamethyldisilazane (product name: SZ-31) was added dropwise over 30 minutes. After 30 minutes had elapsed since the addition of the entire amount, it was confirmed by FT-IR that the peak around 933 cm -1 derived from N-Si had disappeared, and the reaction was terminated. To the solution after the reaction was completed, 315.4 parts of ethyl acetate as a diluting solvent was added, and the mixture was cooled to room temperature. Next, while stirring the cooled solution, 18.0 parts of isophorone diisocyanate was slowly added dropwise. After the addition, it was confirmed by FT-IR that the peak around 2260 cm -1 derived from the isocyanate group had disappeared, and the reaction was terminated. As a result, a polyhydroxy polyurethane resin solution that was pale yellow and transparent and had a resin content (solid content) of 35% was obtained. The Mw of the obtained polyhydroxy polyurethane resin was 49,000. Also, the hydroxyl value was 41.8 mgKOH / g in terms of the solid content conversion value.

[0097] [Synthesis Example 3: Synthesis of A-3] Into a reaction vessel equipped with a stirrer, a refluxer with an air release port, and a nitrogen inlet tube, 100 parts of Compound I obtained in Production Example 1, 18.8 parts of hexamethylenediamine, 87.3 parts of Priamine 1074, and 58.0 parts of ethyl acetate were added, and a reaction was carried out under reflux conditions at about 80°C for 5 hours. After the reaction, when the obtained reaction solution was analyzed by FT-IR, the absorption derived from the carbonyl group of Compound I observed around 1800 cm -1 completely disappeared, and newly, an absorption derived from the carbonyl group of the urethane bond was observed around 1760 cm -1 , confirming that a prepolymer of a polyhydroxy polyurethane resin with a terminal NH 2 had been synthesized.

[0098] Next, without cooling the above reaction solution, 17.4 parts of hexamethyldisilazane (product name: SZ-31) was added dropwise over 30 minutes. After 30 minutes had elapsed since the addition of the entire amount, by FT-IR, the 933 cm -1After confirming that the nearby peak had disappeared, the reaction was terminated. To the solution after the reaction was completed, 372.6 parts of ethyl acetate as a diluting solvent were added, and the mixture was cooled to room temperature. Next, while stirring the cooled solution, 12.0 parts of isophorone diisocyanate were slowly added dropwise. After the addition, it was confirmed by FT-IR that the peak near 2260 cm -1 derived from the isocyanate group had disappeared, and the reaction was terminated. As a result, a polyhydroxy polyurethane resin solution that was pale yellow and transparent and had a resin content (solid content) of 35% was obtained. The Mw of the obtained polyhydroxy polyurethane resin was 42,000. The hydroxyl value was 82 mgKOH / g in terms of the solid content conversion value.

[0099] [Synthesis Example 4: Synthesis of A-4] Into a reaction vessel equipped with a stirrer, a reflux condenser with an air opening, and a nitrogen inlet tube, 100 parts of Compound I obtained in Production Example 1, 20.2 parts of hexamethylenediamine, 99.1 parts of Priamine 1074, and 68.6 parts of ethyl acetate were added, and the reaction was carried out for 5 hours under reflux conditions at about 80 °C. After the reaction, when the obtained reaction solution was analyzed by FT-IR, the absorption derived from the carbonyl group of Compound I observed near 1800 cm -1 had completely disappeared, and newly, an absorption derived from the carbonyl group of the urethane bond was observed near 1760 cm -1 , confirming that a prepolymer of a polyhydroxy polyurethane resin with a terminal of NH 2 had been synthesized.

[0100] Next, without cooling the above reaction solution, 36.5 parts of hexamethyldisilazane (product name: SZ-31) were added dropwise over 30 minutes. After 30 minutes had elapsed since the total amount had been added dropwise, it was confirmed by FT-IR that the peak near 933 cm -1 derived from N-Si had disappeared, and the reaction was terminated. To the solution after the reaction was completed, 434.9 parts of ethyl acetate as a diluting solvent were added, and the mixture was cooled to room temperature. Next, while stirring the cooled solution, 19.0 parts of isophorone diisocyanate were slowly added dropwise. After the addition, it was confirmed by FT-IR that the peak near 2260 cm -1After confirming that the nearby peak had disappeared, the reaction was terminated. As a result, a polyhydroxy polyurethane resin solution that was pale yellow and transparent and had a resin content (solid content) of 35% was obtained. The Mw of the obtained polyhydroxy polyurethane resin was 44,000. Also, the hydroxyl value was 35 mgKOH / g in terms of the solid content conversion value.

[0101] [Synthesis Example 5: Synthesis of A-5] Into a reaction vessel equipped with a stirrer, a reflux condenser with an air opening, and a nitrogen inlet tube, 100 parts of Compound I obtained in Production Example 1, 20.2 parts of hexamethylenediamine, 99.1 parts of Priamine 1074, and 63.6 parts of ethyl acetate were added, and the mixture was reacted for 5 hours under reflux conditions at about 80 °C. After the reaction, when the obtained reaction solution was analyzed by FT-IR, the absorption derived from the carbonyl group of Compound I observed near 1800 cm -1 completely disappeared, and newly, an absorption derived from the carbonyl group of the urethane bond was observed near 1760 cm -1 , confirming that a prepolymer of a polyhydroxy polyurethane resin with NH 2 at the terminal had been synthesized.

[0102] Next, without cooling the above reaction solution, 14.0 parts of hexamethyldisilazane (product name: SZ-31) was added dropwise over 30 minutes. After 30 minutes had elapsed since the total amount had been added dropwise, it was confirmed by FT-IR that the peak near 933 cm -1 derived from N-Si had disappeared, and the reaction was terminated. To the solution after the reaction was completed, 402.5 parts of ethyl acetate was added as a diluting solvent, and the mixture was cooled to room temperature. Next, while stirring the cooled solution, 19.0 parts of isophorone diisocyanate was slowly added dropwise. After the addition dropwise, it was confirmed by FT-IR that the peak near 2260 cm -1 derived from the isocyanate group had disappeared, and the reaction was terminated. As a result, a polyhydroxy polyurethane resin solution that was pale yellow and transparent and had a resin content (solid content) of 35% was obtained. The Mw of the obtained polyhydroxy polyurethane resin was 45,000. Also, the hydroxyl value was 90 mgKOH / g in terms of the solid content conversion value.

[0103] <Vinyl chloride-vinyl acetate copolymer (B1), (B2)> · B-1: Copolymer with vinyl chloride unit / vinyl acetate unit / vinyl alcohol unit = 87.5 / 1 / 11.5 (mass ratio), Tg 75°C, Mn 29000.

[0104] <Silica (C1)> · C1-1: Nip seal E-220A (manufactured by Tosoh Silica Corporation, average particle size 4.2 μm). · C1-2: Silicia 300 (manufactured by Fuji Silysia Chemical Ltd., average particle size 1.7 μm). · C1-3: Silicia 882 (manufactured by Fuji Silysia Chemical Ltd., average particle size 10 μm).

[0105] <Silica (C2)> · C2-1: Silohobic 200 (manufactured by Fuji Silysia Chemical Ltd., average particle size 3.9 μm, hydrophobic silica). · C2-2: Silohobic 4004 (manufactured by Fuji Silysia Chemical Ltd., average particle size 8 μm, hydrophobic silica). · C2-3: Silicia 300 (manufactured by Fuji Silysia Chemical Ltd., average particle size 1.7 μm, hydrophobic silica).

[0106] <Extender pigment (D)> · D-1: Varifine BF10 (manufactured by Sakai Chemical Industry Co., Ltd., precipitated barium sulfate, average particle size 0.06 μm). · D-2: Variess B-34 (manufactured by Sakai Chemical Industry Co., Ltd., precipitated barium sulfate, average particle size 0.3 μm). · D-3: Byakuenka DD (manufactured by Shiraishi Calcium Co., Ltd., calcium carbonate, average particle size 0.1 μm). · D-4: Varifine BF40 (manufactured by Sakai Chemical Industry Co., Ltd., precipitated barium sulfate, average particle size 0.01 μm). · D-5: Shimbari 100 (manufactured by Sakai Chemical Industry Co., Ltd., precipitated barium sulfate, average particle size 0.6 μm).

[0107] <Organic solvent (E1), (E2)> ·E-1: A mixed solvent of ethyl acetate / isopropanol / propylene glycol monomethyl ether = 7 / 2 / 1 (by mass). ·E-2: A mixed solvent of n-propyl acetate / isopropanol = 2 / 1 (by mass).

[0108] <Colorant> ·CB: Carbon black (manufactured by Mitsubishi Chemical Corporation, trade name "Mitsubishi Carbon Black #95"). · Titanium oxide: Manufactured by Teika Corporation, trade name "JR-809". ·FB: Phthalocyanine blue (manufactured by DIC Corporation, trade name "FASTOGEN BLUE FA5375").

[0109] <Other optional components> ·220P: Hydrocarbon wax (manufactured by Mitsui Chemicals, Inc., trade name "Hiwax 220P", melting point 110 °C, penetration 13). ·814HS: Chlorinated polyolefin resin (manufactured by Nippon Paper Industries Co., Ltd., trade name "Super Kron 814HS", chlorine content 41%). ·MS: Resin beads (manufactured by Nippon Shokubai Co., Ltd., trade name "Epaster MS", benzoguanamine-formaldehyde condensate, average particle size 2 μm). · Hardener: Hexamethylene diisocyanate (HDI) adduct.

[0110] <Plastic film> ·PET: A polyethylene terephthalate film that has not been corona discharge treated on both sides (manufactured by Futamura Chemical Co., Ltd., trade name "FE2000", thickness: 12 μm). ·NY: A nylon film that has been corona discharge treated on one side (manufactured by Toyobo Co., Ltd., trade name "Harden N1102", thickness: 15 μm). In each example described later, when NY is used, an ink layer is formed on the treated surface and a matte ink layer is formed on the untreated surface. ·OPP: A biaxially oriented polypropylene film that has been corona discharge treated on both sides (manufactured by Futamura Chemical Co., Ltd., trade name "FOR-BT", thickness: 25 μm).

[0111] (Examples 1 to 31, Comparative Examples 1 to 17) (Preparation of Ink Composition) A polyhydroxy polyurethane resin (A1) or its comparative product, a vinyl chloride-vinyl acetate copolymer (B1), silica (C1), an organic solvent (E1), and a colorant were mixed according to the compositions shown in Tables 1 to 2, and the resulting mixture was kneaded with a paint shaker to obtain an ink composition. In Tables 1 to 2, "HPU" indicates "polyhydroxy polyurethane resin", "Vinyl Acetate" indicates "vinyl chloride-vinyl acetate copolymer", "NV" indicates the solid content, and "%" indicates mass%. The same applies to Tables 3 to 5 described later.

[0112] [Table 1]

[0113] [Table 2]

[0114] (Preparation of Matt Ink Composition) A polyhydroxy polyurethane (A2) or its comparative product, a vinyl chloride-vinyl acetate copolymer (B2), silica (C2), an extender pigment (D), an organic solvent (E2), and other optional components were mixed according to the compositions shown in Tables 3 to 5, and the resulting mixture was kneaded with a paint shaker to obtain a matt ink composition. In the table, the content of each component is the amount in terms of solid content.

[0115] [Table 3]

[0116] [Table 4]

[0117] [Table 5]

[0118] <Fabrication of the laminate> The prepared ink composition was diluted with an organic solvent (E1) so that the viscosity at 20 °C measured using a Zahn cup #3 was 15 seconds, and printing ink was prepared. Using a gravure printing machine (manufactured by Matsuo Sangyo Co., Ltd., trade name "K Printing Proof Press") equipped with a heliogravure engraving plate of 175 lines / inch, the prepared printing ink was applied to one side of the plastic films shown in Tables 6 to 11 and dried to form an ink layer. Next, the prepared matte ink composition was diluted with an organic solvent (E2) so that the viscosity at 20 °C measured using a Zahn cup #3 was 17 seconds, and printing matte ink was prepared. Using a gravure printing machine (manufactured by Matsuo Sangyo Co., Ltd., trade name "K Printing Proof Press") equipped with a heliogravure engraving plate of 175 lines / inch, the prepared printing matte ink was applied to the other side of the plastic film on which the ink layer had been formed and dried to form a matte ink layer. Thereafter, aging was carried out at 40 °C for 48 hours to obtain a laminate.

[0119] <Evaluation> The following evaluations were performed. The results are shown in Tables 6 to 11.

[0120] [Evaluation of blocking resistance] Two test pieces of 5 cm × 5 cm were cut out from the laminate before aging. The ink layer of one test piece and the matte ink layer of the other test piece were overlapped, and a load of 4 kg / cm 2 was applied, and they were stored in a thermostat at 40 °C for 48 hours. Thereafter, the overlapped test pieces were peeled off, and the total area (ink taken) of the ink layer peeled off from one test piece and adhering to the matte ink layer of the other test piece and the matte ink layer peeled off from the other test piece and adhering to the ink layer of one test piece was measured, and the blocking resistance was evaluated according to the criteria shown below. A score of 3 to 5 is considered a pass. 5: The ink taken is less than 5% of the total area of the ink layer and the matte ink layer (5 cm × 5 cm × 2). 4: The ink take-up is 5% or more and less than 10% with respect to the total area of the ink layer and the matte ink layer. 3: The ink take-up is 10% or more and less than 20% with respect to the total area of the ink layer and the matte ink layer. 2: The ink take-up is 20% or more and less than 50% with respect to the total area of the ink layer and the matte ink layer. 1: The ink take-up is 50% or more with respect to the total area of the ink layer and the matte ink layer.

[0121] [Evaluation of Adhesion of Ink Layer] After sticking cellophane tape (manufactured by Nichiban Co., Ltd.) on the surface of the obtained laminate on the ink layer side, this cellophane tape was quickly peeled off, and the state of the ink layer remaining on the plastic film was visually confirmed. According to the evaluation criteria shown below, the adhesion of the ink layer to the plastic film was evaluated. A score of 3 to 5 is considered passing. 5: The ratio of the area of the peeled ink layer is 0% with respect to the total area of the ink layer. 4: The ratio of the area of the peeled ink layer exceeds 0% and is 20% or less with respect to the total area of the ink layer. 3: The ratio of the area of the peeled ink layer exceeds 20% and is 50% or less with respect to the total area of the ink layer. 2: The ratio of the area of the peeled ink layer exceeds 50% and is 80% or less with respect to the total area of the ink layer. 1: The ratio of the area of the peeled ink layer exceeds 80% with respect to the total area of the ink layer.

[0122] [Evaluation of Adhesion of Matte Ink Layer] After sticking cellophane tape (manufactured by Nichiban Co., Ltd.) on the surface of the obtained laminate on the matte ink layer side, this cellophane tape was quickly peeled off, and the state of the matte ink layer remaining on the plastic film was visually confirmed. According to the evaluation criteria shown below, the adhesion of the matte ink layer to the plastic film was evaluated. A score of 3 to 5 is considered passing. 5: The ratio of the area of the peeled matte ink layer is 0% with respect to the total area of the matte ink layer. 4: The ratio of the area of the peeled matte ink layer to the total area of the matte ink layer is more than 0% and 20% or less. 3: The ratio of the area of the peeled matte ink layer to the total area of the matte ink layer is more than 20% and 50% or less. 2: The ratio of the area of the peeled matte ink layer to the total area of the matte ink layer is more than 50% and 80% or less. 1: The ratio of the area of the peeled matte ink layer to the total area of the matte ink layer is more than 80%.

[0123] [Evaluation of Lamination Strength] Two 5 cm × 5 cm test pieces were cut out from the laminate before aging. The ink layer of one test piece and the matte ink layer of the other test piece were overlapped, and a load of 1 kg / cm 2 was applied and stored in a constant temperature machine at 40°C for 48 hours. Next, the overlapped test pieces were peeled off, and a dry laminating adhesive (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name "Seikabond E263 / C-75N") was applied onto the surface of the ink layer side (the overlapped side) of one test piece at a dry coating amount of 3 g / m 2 using a gravure printing machine (manufactured by Matsuo Sangyo Co., Ltd., trade name "K Printing Proofer"), dried with a dryer for 10 seconds, and heat-pressed with an LLDPE film (manufactured by Mitsui Chemicals Toagosei Co., Ltd., trade name "TUX-HC", thickness 60 μm). Then, aging was carried out at 40°C for 48 hours to obtain a laminated laminate. The obtained laminated laminate was cut into strips with a width of 15 mm, and a T-peel strength was measured by performing a T-peel test using a tensile testing machine (manufactured by A&D Company, Ltd., trade name "Tensilon RTG-1225") under the condition of a tensile speed of 300 mm / min, and the lamination strength was evaluated according to the criteria shown below. A pass is considered to be 3 to 5. 5: The T-peel strength is 2.0 N or more. 4: The T-peel strength is 1.5 N or more and less than 2.0 N. 3: The T-peel strength is 1.0 N or more and less than 1.5 N. 2: The T-peel strength is 0.5 N or more and less than 1.0 N. 1: The T-peel strength is less than 0.5 N.

[0124] [Measurement of 60° gloss value] The obtained laminate was placed on the black surface of the concealer test paper (manufactured by TP Giken Co., Ltd.) so that the matte ink layer was on the upper side (measurement side), and the 60° gloss value was measured using a gloss meter (manufactured by BYK Gardner, product name "micro-TRI-gloss"). The lower the 60° gloss value, the better the matte effect.

[0125] [Evaluation of clarity] After aging, the laminate was placed on the black surface of the concealer test paper (manufactured by TP Giken Co., Ltd.) so that the matte ink layer was on the upper side (measurement side), and the L * value was measured using a colorimeter (manufactured by x-rite, product name "exact"). L * A value of 30 or less is considered qualified. The lower the L * value, the less whitish the matte ink layer and the better its transparency, and the more clearly the color tone of the ink layer can be visually recognized from the matte ink layer side.

[0126]

Table 6

[0127]

Table 7

[0128]

Table 8

[0129]

Table 9

[0130]

Table 10

[0131]

Table 11

Industrial Applicability

[0132] The laminate of the present invention is excellent in interlayer adhesion, exhibits excellent laminate strength when formed into a laminate, and is also excellent in clarity and blocking resistance. Therefore, it is useful as a packaging material, particularly for flexible packaging materials.

Claims

1. A printing method for printing a printing medium comprising: a plastic film; an ink layer formed from an ink composition on one side of the plastic film; and a matte ink layer formed from a matte ink composition on the other side of the plastic film, the ink composition comprises a polyhydroxy polyurethane resin (A1), a vinyl chloride-vinyl acetate copolymer (B1), and silica (C1) having an average particle size of 2 to 8 μm, the content of the silica (C1) in terms of solid content being 0.1 to 15 mass% based on the total solid content of the ink composition; The matte ink composition contains a polyhydroxy polyurethane resin (A2), a vinyl chloride-vinyl acetate copolymer (B2), silica (C2) having an average particle size of 2 to 10 μm, and a body pigment (D) having an average particle size of 0.02 to 0.5 μm, and the total content of the silica (C2) and the body pigment (D) in terms of solid content is 35 to 62 mass % based on the total solid content of the matte ink composition.

2. The laminate according to claim 1, wherein a total content of the polyhydroxy polyurethane resin (A1) and the vinyl chloride-vinyl acetate copolymer (B1) in terms of solid content is 20 to 65 mass% based on the total solid content of the ink composition.

3. The laminate according to claim 1, wherein the total content of the polyhydroxy polyurethane resin (A2) and the vinyl chloride-vinyl acetate copolymer (B2) in terms of solid content is 25 to 50 mass% based on the total solid content of the matte ink composition.

4. 2. The laminate according to claim 1, wherein (C2) / (D), which represents a mass ratio of said silica (C2) to said body pigment (D) in terms of solid content, is 0.08 to 0.

4.

5. 2. The laminate according to claim 1, wherein the hydroxyl value of the polyhydroxy polyurethane resin (A1) and the hydroxyl value of the polyhydroxy polyurethane resin (A2) are each 40 to 85 mgKOH / g.

6. The laminate according to claim 1, wherein (B1) / (A1), which represents a mass ratio of the vinyl chloride-vinyl acetate copolymer (B1) to the polyhydroxy polyurethane resin (A1) in terms of solid content, and (B2) / (A2), which represents a mass ratio of the vinyl chloride-vinyl acetate copolymer (B2) to the polyhydroxy polyurethane resin (A2) in terms of solid content, are each 0.1 to 0.

7.

7. The laminate according to claim 1 , wherein the matte ink composition further comprises a curing agent.

8. 8. The laminate according to claim 1, wherein the ink layer and the matte ink layer are each formed by gravure printing.

9. A laminate comprising the laminate according to claim 8 , and an adhesive layer and a resin layer laminated in this order on the surface of the laminate on the ink layer side.

10. A packaging material comprising the laminate according to claim 9.

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