JP7195494B1 - Laminate with printed layer of water-based liquid ink - Google Patents

Abstract

The present invention provides a laminate having at least a first printed layer and a second printed layer in this order on a plastic film, wherein the first printed layer is a polyol (ia ) and a polyisocyanate (ib) is a reaction product of a water-based varnish or a water-based liquid ink printing layer containing at least a urethane resin, the second printing layer is a (meth)acrylic resin and an alcohol alkoxylate-based It is a laminate that is a printed layer of water-based varnish or water-based liquid ink containing a leveling agent.

Description

TECHNICAL FIELD The present invention relates to a laminate having a printed layer formed by water-based gravure printing or water-based flexographic printing on a plastic film.

Gravure inks and flexographic inks are widely used for the purpose of imparting decorativeness and functionality to printed materials of flexible packaging films. When a gravure or flexographic printed material is used as a flexible packaging material for food products or sanitary goods among other packaging materials, it is generally subjected to lamination. In this case, various printing materials and lamination processes are used depending on the type of contents and purpose of use. By laminating printed matter and various films with an adhesive, it is possible to maintain film surface strength, storage stability, boiling and retort suitability, etc., which cannot be obtained with printed matter alone.

When laminating printed matter, the printed matter itself is often intended to protect the contents. In this case, since the printed material consisting of the base plastic and the printing ink layer is laminated with the sealant film using an adhesive, the printing ink layer does not directly touch the contents, but lamination aptitude is required. . In order to maintain the suitability for lamination, it is common practice to provide an anchor coat layer under the printed ink layer to improve the adhesion between the plastic film as the substrate and the printed ink layer.

However, in response to the recent efforts to conserve resources and simplify packaging, there is a demand for using gravure and flexographic printing itself as packaging material in order to reduce the amount of petroleum-based film used and simplify post-processing. Accordingly, the printing ink layer itself is required to have high coating film properties such as film adhesion, abrasion resistance, water resistance, and blocking resistance.
In addition, the superiority or inferiority of the printed design of flexible packaging film packaging material has a great impact on the quality of the contents, and high image reproducibility that can correspond to advanced designs that are conscious of aesthetics is required. .

In recent years, there has been a shift away from petroleum resources, based on the perspective of sustainability against the backdrop of worsening air pollution caused by VOCs and global warming, as well as occupational health and safety, as well as flammability and explosiveness. Accordingly, it is expected to replace the organic solvent in ink with water-based ink. For example, Patent Document 1 discloses an invention of a printing ink laminate using a water-based liquid ink containing an acrylic resin or a polyurethane resin as the printing ink adjacent to a polyethylene terephthalate (PET) film.

JP 2016-155340 A

The laminate described in Patent Document 1 uses a polyethylene terephthalate (PET) film as the plastic film. However, when plastic films made of different materials are used, even if the same liquid ink is used for printing, required physical properties such as adhesion are inferior, and performance is not sufficient. Plastic films used for flexible packaging film packaging include film substrates used for beverage labels, such as biaxially oriented polypropylene (OPP) film, shrink PET, shrink biaxially oriented polystyrene (OPS), and shrink PET/OPS. There are hybrids, etc. In addition, there are a wide variety of film substrates from the viewpoint of recent diversification of packaging materials and recyclability. Conventionally, it has been done to design the optimum ink for these various film substrates, but there is a problem that it is time-consuming because it is necessary to switch the printing ink at the same time as the film substrate is switched. .

Therefore, the problem to be solved by the present invention is to provide a laminate having an aqueous liquid ink printed layer that has excellent adhesion to various plastic substrates and also has excellent water resistance and abrasion resistance. to provide.

The present inventors have made intensive studies to solve the above problems, using a specific urethane resin for the printing layer that directly contacts the plastic film, and further providing a printing layer using a specific (meth)acrylic resin. Thus, the inventors have found that the above problems can be solved.
That is, the present invention provides a laminate having at least a first printed layer and a second printed layer in this order on a plastic film,
The first printing layer is an aqueous varnish or aqueous liquid ink printing layer containing at least a urethane resin that is a reaction product of a polyol (ia) containing a polyether polyol (ia-1) and a polyisocyanate (ib). can be,
The laminate is such that the second printed layer is a printed layer of aqueous varnish or aqueous liquid ink containing a (meth)acrylic resin and an alcohol alkoxylate leveling agent.

ADVANTAGE OF THE INVENTION By this invention, the laminated body which has the adhesiveness with which the plastic base material and printing layer were excellent, and the printing layer was excellent in water resistance and abrasion resistance can be provided.

The present invention will be described in detail. In addition, "ink" used in the following description all means "aqueous liquid ink". All "parts" indicate "parts by mass", and all "%" indicate "% by mass".

The laminate of the present invention has at least a first printed layer and a second printed layer in this order on a plastic film, and the first printed layer is a polyol (ia) containing a polyether polyol (ia-1) and polyisocyanate (ib), and the second printed layer contains a (meth)acrylic resin and an alcohol alkoxylate leveling agent.

<First printed layer>
The first printing layer is printed with aqueous liquid ink or aqueous varnish containing at least urethane resin (I) which is a reaction product of polyol (ia) containing polyether polyol (ia-1) and polyisocyanate (ib). It is formed by The laminate of the present invention has improved adhesion by having the first printed layer as a layer in direct contact with the plastic film.

The water-based liquid ink or water-based varnish forming the first printed layer is a composition containing at least the urethane resin (I) (hereinafter referred to as "first composition").
(Urethane resin (I))
Polyol (ia) constituting urethane resin (I) contains at least polyether polyol (ia-1). As the polyether polyol (ia-1), for example, one or more compounds having two or more groups having active hydrogen atoms (—NH— or —OH) are used as an initiator, and an alkylene oxide is subjected to addition polymerization. Those that have been made

Examples of the initiator include hydroxyl groups such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and bisphenol A. and compounds having three hydroxyl groups such as glycerin, trimethylolethane, and trimethylolpropane.

Examples of the alkylene oxide include epoxide compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide and epichlorohydrin; Cyclic ethers having 4) carbon atoms and the like can be mentioned.

The number average molecular weight of the polyether polyol is preferably 500 or more, more preferably 1,000 or more, and preferably 4,000 or less, more preferably 3,000 or less, from the viewpoint of compatibility with pigments and the like. be.
In this specification, the number average molecular weight shall represent the value obtained by measuring by gel permeation chromatography (GPC) method.

Polyol (ia) preferably contains a polyol other than polyether polyol (ia-1). Other polyols preferably include a polyol (ia-2) having an acid group. The acid group of the acid group-containing polyol (ia-2) includes, for example, a carboxy group or a sulfonic acid group, and the acid group-containing polyol (ia-2) includes, for example, a carboxy group-containing polyol, Examples thereof include polyols having sulfonic acid groups.
As the polyol having a carboxyl group, one or two or more can be used, and examples thereof include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, hydroxy acid; polyester polyol having a carboxy group; The polyester polyol having the carboxy group can be obtained by reacting the hydroxy acid with various polycarboxylic acids.

As the polyol having a sulfonic acid group, one or more kinds can be used. A polyester polyol or the like, which is a reactant, may be mentioned. Examples of the dicarboxylic acid having a sulfonic acid group include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5-(4-sulfophenoxy)isophthalic acid and the like. Examples of the low-molecular-weight polyol include alkanediols having 1 to 10 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; carbon atoms such as diethylene glycol; Examples include polyether polyols having a number of 2 to 10.

The number average molecular weight of the acid group-containing polyol (ia-2) is preferably 100 or more, preferably 2000 or less, and more preferably 1000 or less.

In this specification, the number average molecular weight and the weight average molecular weight shall represent the polystyrene conversion value obtained by measuring by the gel permeation chromatography (GPC) method.

The polyol (ia) is preferably composed of a polyether polyol (ia-1) and a polyol (ia-2) having an acid group from the viewpoint of further improving adhesion, and the polyether polyol (ia-1) and a polyol (ia-2) having a carboxy group.

The total content of the polyether polyol (ia-1) and the polyol (ia-2) having an acid group is preferably 60% by mass or more, more preferably 75% by mass or more, more preferably 75% by mass or more in the polyol (ia). is 80% by mass or more, more preferably 90% by mass or more, and may be 95% by mass or less.

The polyol (ia) may further contain a polyol (ia-3) having an alicyclic structure. As the polyol (ia-3) having an alicyclic structure, one or two or more can be used. Saturated diols having an alicyclic structure such as diols, butylcyclohexanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, dicyclohexanediol, hydrogenated bisphenol A, 1,3-adamantanediol; 1,1′-bicyclohexane Unsaturated diols having an alicyclic structure such as silidenediol; saturated triols having an alicyclic structure such as cyclohexanetriol; The polyol (ia-3) having an alicyclic structure preferably has a number average molecular weight of 100 or more and 500 or less.

When the polyol (ia-3) having the alicyclic structure is used, the content is preferably 0% by mass or more, more preferably 5% by mass, based on the total amount of polyol (ia) from the viewpoint of suppressing blocking of printed matter. or more, preferably 40% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
The total content of the polyether polyol (ia-1), the polyol (ia-2) having an acid group, and the polyol (ia-3) having an alicyclic structure is preferably 70 mass in the polyol (ia) % or more, more preferably 80 mass % or more, and still more preferably 90 mass % or more.

The polyol (ia) may further contain another polyol (ia-4). Examples of the other polyols include polyester polyols, low-molecular-weight polyols (for example, molecular weights of 50 to 300), polycarbonate polyols, and polyolefin polyols.
Examples of the polyester polyols include polyester polyols obtained by esterifying a low-molecular-weight polyol (e.g., a polyol having a molecular weight of 50 to 300) and a polycarboxylic acid; ring-opening polymerization of a cyclic ester compound such as ε-caprolactone; polyester polyols obtained by reaction; and copolymerized polyester polyols thereof.
Examples of the low molecular weight polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol and 1,4-butanediol. , 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol, etc. ) and the like.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; and anhydride- or ester-forming derivatives of polycarboxylic acids and aromatic polycarboxylic acids.
As the low-molecular-weight polyol, a polyol having a molecular weight of about 50 to 300 can be used. Examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. , 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol and other aliphatic polyols having 2 to 6 carbon atoms; 1,4-cyclohexanediol, cyclohexane alicyclic structure-containing polyols such as dimethanol; bisphenol compounds such as bisphenol A and bisphenol F; and aromatic structure-containing polyols such as alkylene oxide adducts thereof.

Examples of the polycarbonate polyols include reaction products of carbonic acid esters and polyols; reaction products of phosgene and bisphenol A and the like.

Examples of the carbonate include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.
Examples of the polyol that can react with the carbonate ester include, for example, the polyols exemplified as the low-molecular-weight polyols; high-molecular-weight polyols (weight average molecular weight of 500 or more and 5,000 or less).

Examples of the polyolefin polyol include polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, and hydrogenated (hydrogenated) polyisoprene polyol.

The content of the other polyol (ia-4) in the polyol (ia) is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 20% by mass. Below, particularly preferably, it is 10% by mass or less.
In particular, the polyester polyol content in the polyol (ia) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

As the polyisocyanate (ib), one or two or more can be used. Aromatic polyisocyanates such as tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane Examples include polyisocyanates having an alicyclic structure such as diisocyanates.
The polyisocyanate (ib) preferably contains a polyisocyanate having an alicyclic structure. The content of the polyisocyanate having an alicyclic structure is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass in the polyisocyanate (ib). % or less.

The equivalent ratio [isocyanate group/hydroxyl group] of the isocyanate group of the polyisocyanate (ib) to the hydroxyl group contained in the polyol (ia) is preferably 0.8 or more, more preferably 0.9 or more on a molar basis. , preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.5 or less.

A chain extender may be used as necessary when producing the urethane resin (I).

As the chain extender, one or more can be used, and examples thereof include polyamines, hydrazine compounds, and other compounds having active hydrogen atoms.

Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-ethylaminoethylamine, N-methylaminopropylamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N- diamines having a hydroxyl group such as hydroxypropylaminopropylamine; triamines such as diethylenetriamine and dipropylenetriamine; and tetramines such as triethylenetetramine. Among these, ethylenediamine is preferred.

Examples of the hydrazine compound include hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, and β-semicarbazide. propionic acid hydrazide, 3-semicarbazide propylcarbazate, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane and the like.

Examples of other compounds having active hydrogen include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose. , methylene glycol, glycerin, glycols such as sorbitol; etc.

For example, when polyamine is used as the chain extender, the equivalent ratio [amino group/isocyanate group] between the amino group and the isocyanate group in the polyamine is preferably 1.2 or less, and is preferably in the range of 0.3 to 1. more preferred.

The weight average molecular weight of the urethane resin (I) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and preferably 500,000, from the viewpoint of improving the durability of the printed matter. Below, more preferably 200,000 or less, still more preferably 100,000 or less. By increasing the weight average molecular weight, it is possible not only to improve the durability of the printed matter, but also to suppress blocking due to poor drying. etc. can be suppressed.

The acid value of the urethane resin (I) is preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 25 mgKOH/g or less. As used herein, the acid value means a theoretical value calculated based on the amount of the acid group-containing compound such as polyol (i) used in the production of the urethane resin (I).

The urethane resin (I) can be produced by reacting the polyol (ia) with the polyisocyanate (ib) and, if necessary, further reacting with a chain extender. An organic solvent may coexist when the polyol (ia) and the polyisocyanate (ib) are reacted. The reaction temperature for reacting the polyol (ia) and the polyisocyanate (ib) is preferably 50° C. or higher and 150° C. or lower.

As the organic solvent, one or two or more can be used. Examples include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butyl acetate; and nitriles such as acetonitrile. Solvent; amide solvents such as dimethylformamide and N-methylpyrrolidone.

Further, the organic solvent may be partially or wholly removed by, for example, distillation under reduced pressure during or after the production of the urethane resin (I) in order to reduce the load on the environment and safety.

The content of the urethane resin (I) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and particularly preferably 100% by mass, based on the total amount of the binder in the first composition. %.
The urethane resin (I) may be dispersed in advance in an aqueous medium to be described later. As a method for dispersing urethane resin (I) in an aqueous medium (aqueous method), urethane resin (I) is prepared (urethane resin (I) preparation step), the obtained urethane resin (I) and a base described later (neutralization step), and mixing the resulting mixture with the aqueous medium to prepare a dispersion (dispersion step).
When using a chain extender, the chain extender may be added in the urethane resin (I) preparation step, or may be added after the dispersion step.

The content of the urethane resin (I) is preferably 10% by mass or more in the dispersion, from the viewpoints of resolubility of the aqueous ink, inhibition of blocking of printed matter, improvement of printing density, and adhesion to the substrate. It is more preferably 20% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less.

In the aqueous method, an emulsifier may be used as necessary. In addition, when dissolving or dispersing in water, a machine such as a homogenizer may be used as necessary. Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene/polyoxypropylene copolymers. Fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, alkyldiphenyl ether sulfonate sodium salts, etc. cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzylammonium salts. Among them, anionic or nonionic emulsifiers are preferable from the viewpoint of storage stability.

The basic compound preferably contains a basic metal compound and an organic amine.
Examples of the basic metal compound include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and magnesium hydroxide; metal chlorides such as sodium chloride and potassium chloride; metals such as copper sulfate. Sulfate and the like can be mentioned.

Examples of the organic amines include ammonia; primary amines such as monoethanolamine; tertiary amines such as triethylamine and diethylethanolamine; and cyclic amines such as morpholine.

The basic metal compound and the organic amine may form a salt with the acid group of the urethane resin (I) in the first composition. Since the basic compound and the organic amine neutralize the acid group of the binder having the acid group, the water dispersibility can be easily improved.

The content of the basic compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the urethane resin (I). Yes, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 4 parts by mass or less.

(solvent)
Examples of solvents contained in the first composition include water; hydrophilic organic solvents; water and hydrophilic water; hydrophilic organic solvents; mixtures of water and hydrophilic organic solvents; from the viewpoint of water or a mixture of water and a hydrophilic organic solvent.

As the hydrophilic organic solvent, one or more kinds can be used, and it is preferable to use one that is miscible with water. For example, alcohol solvents such as methanol, ethanol, n-propanol and 2-propanol; acetone , methyl ethyl ketone and other ketone solvents; ethylene glycol, diethylene glycol, propylene glycol, polyalkylene glycol, glycerin and other polyhydric alcohol solvents; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethyl carbitol and ether solvents such as N-methyl-2-pyrrolidone; and amide solvents such as N-methyl-2-pyrrolidone.

When the aqueous medium water and the hydrophilic organic solvent are included, the content of water is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more in the entire solvent. % by mass or less, or even 95% by mass or less is allowed.

(pigment)
The first composition may be used as a water-based anchor coat varnish without containing a coloring material, or may contain a coloring material and may be used as so-called ink for white, black, or color printing.

Specific examples of the coloring material include inorganic pigments and organic pigments 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. Specific examples of preferred organic pigments are given below.

Examples of black pigments include C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7, C.I. I. Pigment Black 9, C.I. I. Pigment Black 20 and the like.

Examples of the indigo pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:5, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17:1, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 24:1, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 26, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 61, C.I. I. Pigment Blue 62, C.I. I. Pigment Blue 63, C.I. I. Pigment Blue 64, C.I. I. Pigment Blue 75, C.I. I. Pigment Blue 79, C.I. I. Pigment Blue 80 and the like.

Examples of green pigments include C.I. I. Pigment Green 1, C.I. I. Pigment Green 4, C.I. I. Pigment Green 7, C.I. I. Pigment Green 8, C.I. I. Pigment Green 10, C.I. I. Pigment Green 36 and the like.

Examples of red pigments include C.I. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 10, C.I. I. Pigment Red 11, C.I. I. Pigment Red 12, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 18, C.I. I. Pigment Red 19, C.I. I. Pigment Red 20, C.I. I. Pigment Red 21, C.I. I. Pigment Red 22, C.I. I. Pigment Red 23, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 38, C.I. I. Pigment Red 41, C.I. I. Pigment Red 43, C.I. I. Pigment Red 46, C.I. I. Pigment Red 48, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C.I. I. Pigment Red 48:3, C.I. I. Pigment Red 48:4, C.I. I. Pigment Red 48:5, C.I. I. Pigment Red 48:6, C.I. I. Pigment Red 49, C.I. I. Pigment Red 49:1, C.I. I. Pigment Red 49:2, C.I. I. Pigment Red 49:3, C.I. I. Pigment Red 52, C.I. I. Pigment Red 52:1, C.I. I. Pigment Red 52:2, C.I. I. Pigment Red 53, C.I. I. Pigment Red 53:1, C.I. I. Pigment Red 53:2, C.I. I. Pigment Red 53:3, C.I. I. Pigment Red 54, C.I. I. Pigment Red 57, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 58, C.I. I. Pigment Red 58:1, C.I. I. Pigment Red 58:2, C.I. I. Pigment Red 58:3, C.I. I. Pigment Red 58:4, C.I. I. Pigment Red 60:1, C.I. I. Pigment Red 63, C.I. I. Pigment Red 63:1, C.I. I. Pigment Red 63:2, C.I. I. Pigment Red 63:3, C.I. I. Pigment Red 64:1, C.I. I. Pigment Red 68, C.I. I. Pigment Red 68, C.I. I. Pigment Red 81:1, C.I. I. Pigment Red 83, C.I. I. Pigment Red 88, C.I. I. Pigment Red 89, C.I. I. Pigment Red 95, C.I. I. Pigment Red 112, C.I. I. Pigment Red 114, C.I. I. Pigment Red 119, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 136, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150, C.I. I. Pigment Red 164, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 169, C.I. I. Pigment Red 170, C.I. I. Pigment Red 171, C.I. I. Pigment Red 172, C.I. I. Pigment Red 175, C.I. I. Pigment Red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 180, C.I. I. Pigment Red 181, C.I. I. Pigment Red 182, C.I. I. Pigment Red 183, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 188, C.I. I. Pigment Red 190, C.I. I. Pigment Red 192, C.I. I. Pigment Red 193, C.I. I. Pigment Red 194, C.I. I. Pigment Red 200, C.I. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 207, C.I. I. Pigment Red 208, C.I. I. Pigment Red 209, C.I. I. Pigment Red 210, C.I. I. Pigment Red 211, C.I. I. Pigment Red 213, C.I. I. Pigment Red 214, C.I. I. Pigment Red 216, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 237, C.I. I. Pigment Red 238, C.I. I. Pigment Red 239, C.I. I. Pigment Red 240, C.I. I. Pigment Red 242, C.I. I. Pigment Red 245, C.I. I. Pigment Red 247, C.I. I. Pigment Red 248, C.I. I. Pigment Red 251, C.I. I. Pigment Red 253, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 256, C.I. I. Pigment Red 257, C.I. I. Pigment Red 258, C.I. I. Pigment Red 260, C.I. I. Pigment Red 262, C.I. I. Pigment Red 263, C.I. I. Pigment Red 264, C.I. I. Pigment Red 266, C.I. I. Pigment Red 268, C.I. I. Pigment Red 269, C.I. I. Pigment Red 270, C.I. I. Pigment Red 271, C.I. I. Pigment Red 272, C.I. I. Pigment Red 279, and the like.
Examples of purple pigments include C.I. I. Pigment Violet 1, C.I. I. Pigment Violet 2, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 3:1, C.I. I. Pigment Violet 3:3, C.I. I. Pigment Violet 5:1, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 19 (γ type, β type), C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 27, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 31, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 38, C.I. I. Pigment Violet 42, C.I. I. Pigment Violet 50, and the like.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, Pigment Yellow 17, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 120, Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 137, C.I. I. Pigment, Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 213 and the like.

Examples of orange pigments include C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 37, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Range 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, or C.I. I. Pigment Orange 74 and the like.

Examples of brown pigments include C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, or C.I. I. Pigment Brown 26 and the like.

Among them, as a preferable pigment, C.I. I. Pigment Black 7, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Green 7, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C.I. I. Pigment Red 48:3, C.I. I. Pigment Red 146, C.I. I. Pigment Red 242, C.I. I. Pigment Red 185, C.I. I. Pigment Red 122, C.I. I. Pigment Red 178, C.I. I. Pigment Red 149, C.I. I. Pigment Red 144, C.I. I. Pigment Red 166, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 37, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 139, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 64, etc., and it is preferable to use at least one or two or more selected from these groups.

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 average particle size of the pigment is preferably in the range of 1 to 300 nm, more preferably about 50 to 150 nm. The amount of the pigment is sufficient to ensure the concentration and coloring strength of the aqueous liquid printing ink, that is, 1 to 60% by weight relative to the total weight of the ink composition, and the solid content weight ratio in the ink composition is 10 to 10%. It is preferably contained in a proportion of 90% by weight. Moreover, these pigments can be used individually or in combination of 2 or more types.

(other ingredients)
The first composition may further contain general-purpose resins and auxiliaries other than the urethane resin (I), if necessary. Examples of the auxiliary agent include waxes such as paraffin waxes, polyethylene waxes, and carnauba waxes for imparting abrasion resistance and slipperiness; fatty acid amide compounds such as oleic acid amide, stearic acid amide, and erucic acid amide; printing; A silicone-based or non-silicon-based antifoaming agent, dispersant, extender, or the like can be used as appropriate to suppress foaming at the time.
As the dispersant, a nonionic dispersant is preferable. The acid value of the dispersant is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, still more preferably 20 mgKOH/g or less, and may be, for example, 1 mgKOH/g or more, or even 3 mgKOH/g or more. .

The acid value of the dispersant is preferably smaller than the acid value of the urethane resin (I). The difference between the acid value of the urethane resin (I) and the dispersant is, for example, 1 mgKOH/g or more, more preferably 3 mgKOH/g or more, preferably 30 mgKOH/g or less, more preferably 20 mgKOH/g. It is below.

The content of the dispersant is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and preferably 100 parts by mass or less, with respect to 100 parts by mass of the coloring agent. It is more preferably 80 parts by mass or less, still more preferably 75 parts by mass or less.

The content of the dispersant is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 100 parts by mass with respect to 100 parts by mass of the urethane resin (I). parts or less, more preferably 80 parts by mass or less, and even more preferably 60 parts by mass or less.

<Second printed layer>
The second printed layer is formed by printing a water-based liquid ink or water-based varnish containing at least (meth)acrylic resin (II) and an alcohol alkoxylate leveling agent. The laminate of the present invention has improved water resistance by having the second printed layer. In addition, the second printed layer is excellent in coating film strength, particularly abrasion resistance and scratch resistance, and is therefore suitable for a configuration in which the printed layer is the outermost layer. In the surface-printed matter and the reverse-printed matter, a laminate having the second printed layer of the present invention on the outermost layer during distribution is preferable because the effect of the present invention can be maximized.

The water-based liquid ink or water-based varnish that forms the second printed layer is a composition containing at least a (meth)acrylic resin (II) and an alcohol alkoxylate-based leveling agent (hereinafter referred to as a "second composition"). ).
((Meth) acrylic resin (II))
A (meth)acrylic resin can be a (meth)acrylate homopolymer or copolymer. These polymers are not particularly limited, but for example, polymers or copolymers of one or two or more (meth)acrylate monomers, one or two or more (meth)acrylate monomers and vinyl monomers It is preferable to use a copolymer with Further, it is preferably a copolymer having an acid value for the purpose of imparting water dispersibility and water solubility.

The "(meth)acrylate" refers to either or both of acrylate and methacrylate, and the "(meth)acryl" refers to either or both of acrylic and methacrylic.

The (meth)acrylate monomer is not particularly limited, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2 - ethylhexyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, di cyclopentanyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-pentafluoropropyl (meth)acrylate, Perfluorocyclohexyl (meth)acrylate, glycidyl (meth)acrylate, allyl glycidyl ether, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, (meth)acrylamide, N -monoalkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N-methylol (meth)acrylamide, N-isopropoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide, 2-aziridinylethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, acrolein, diacetone (meth)acrylamide, acetoacetoxyethyl (meth)acrylate, and other (meth)acrylic monomers can be done. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the vinyl monomer include vinyl acetate, vinyl propionate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, (meth)acrylonitrile, styrene, α-methylstyrene, divinylstyrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like. Among them, styrene-based monomers such as styrene, α-methylstyrene and divinylstyrene are preferably used. Each of these may be used alone, or two or more of them may be used in combination.

(Meth)acrylic acid, crotonic acid, itaconic acid, It can be obtained by copolymerizing a (meth)acrylic monomer having a carboxyl group such as maleic acid, fumaric acid, β-(meth)acryloyloxyethyl hydrogen succinate, β-(meth)acryloyloxyethyl hydrogen phthalate.
When an acidic group is introduced, it is preferable to appropriately adjust the amount of the monomer so that the acid value is within the desired range, which will be described later in detail.

Among them, the (meth)acrylic resin (II) is a copolymer of two or more (meth)acrylate monomers, or a copolymer of one or more (meth)acrylate monomers and a vinyl monomer. preferable. For example, (1) a copolymer of two or more (meth)acrylate monomers having no carboxyl group and (meth)acrylate monomers having a carboxyl group such as (meth)acrylic acid, having an acid value (meth ) Acrylic copolymer (2) A copolymer of two or more (meth)acrylate monomers having no carboxyl group, a styrenic monomer, and a (meth)acrylate monomer having a carboxyl group such as (meth)acrylic acid, Styrene (meth)acrylic copolymers with acid numbers are preferred.
More preferably, the (meth)acrylic monomer having no carboxyl group used in (1) or (2) is methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl Aliphatic chain (meth)acrylates such as (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and hexyl (meth)acrylate are preferred.

The (meth)acrylic resin (II) can be produced, for example, by polymerizing various monomers in the presence of a polymerization initiator in a temperature range of 50°C to 180°C. A region is more preferable. Polymerization methods include, for example, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Moreover, the polymerization mode includes, for example, random copolymers, block copolymers, graft copolymers, and the like.

The (meth)acrylic resin (II) used in the present invention may be an emulsion forming a core-shell type. In the present invention, the core-shell emulsion refers to a state in which the polymer (a2) is dispersed by the polymer (a1) in an aqueous medium. portion, and part or all of the polymer (a2) often forms the core portion. Hereinafter, in the present invention, the resin forming the shell portion is referred to as polymer (a1), and the resin forming the core portion is referred to as polymer (a2).

[Polymer (iia) Constituting Shell Portion]
The core-shell type emulsion used in the present invention has one or more hydrophilic groups selected from the group consisting of carboxyl groups and carboxylate groups formed by neutralizing carboxyl groups for the polymer (iia) constituting the shell portion. It is preferably composed of an acrylic copolymer having At that time, the acid value of the shell portion is preferably in the range of 40 mgKOH/g or more and 250 mgKOH/g or less, more preferably 120 mgKOH/g or less.

The carboxyl group of the polymer (iia) constituting the shell portion is preferably neutralized with a basic compound to form a carboxylate group.

Examples of the basic compound that can be used for neutralization include ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine, etc. Use of ammonia and triethylamine improves the hot water resistance of the coating film. , is preferable for further improving corrosion resistance and chemical resistance.
The basic compound is used in an amount of [basic compound/carboxyl group] relative to the total amount of carboxyl groups possessed by the polymer (iia) in order to further improve the aqueous dispersion stability of the obtained core-shell emulsion. = 0.2 to 2 (molar ratio).

Among the monomers having a polymerizable unsaturated double bond, those obtained by polymerizing a (meth)acrylic monomer containing a (meth)acrylic monomer having a carboxyl group are preferably used. In particular, as the polymer (iia), methyl (meth)acrylate, butyl (meth)acrylate, It is more preferable to use one obtained by combining and polymerizing (meth)acrylic acid, etc., in order to form a coating film having excellent film-forming properties, hot water resistance, corrosion resistance and chemical resistance.

[Polymer (iib) constituting core portion]
As the polymer (iib) constituting the core portion, a copolymer such as an acrylic monomer similar to the acrylic resin described above can be used. At this time, the weight average molecular weight of the core portion is preferably in the range of 200,000 to 3,000,000, more preferably 800,000 or more. Tg is preferably in the range of -30°C to 30°C.

The polymer (iib) constituting the core portion may be a copolymer of acrylic monomers similar to those of the acrylic resin described above, but is preferably produced using an aqueous medium. Specifically, it can be produced by supplying the above-mentioned monomers, a polymerization initiator, etc. to a reaction vessel containing an aqueous medium all at once or successively for polymerization. At that time, a pre-emulsion is produced by mixing the monomer, an aqueous medium, and, if necessary, a reactive surfactant or the like in advance, and the polymerization initiator or the like is supplied to a reaction vessel containing the aqueous medium. may be polymerized.

Examples of polymerization initiators that can be used in producing the polymer (iib) include radical polymerization initiators such as persulfates, organic peroxides and hydrogen peroxide, 4,4′-azobis(4-cyano valeric acid), 2,2'-azobis(2-amidinopropane) dihydrochloride and the like can be used. Moreover, the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent to be described later.

Examples of the persulfate include potassium persulfate, sodium persulfate, and ammonium persulfate. Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxylaurate, and t-butyl peroxybenzoate. , cumene hydroperoxide, paramenthane hydroperoxide, t-butyl hydroperoxide and the like can be used.

Examples of the reducing agent include ascorbic acid and its salts, erythorbic acid and its salts (sodium salts, etc.), tartaric acid and its salts, citric acid and its salts, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, Sodium bisulfite, ferric chloride and the like can be used.

The amount of the polymerization initiator to be used should be an amount that allows the polymerization to proceed smoothly. It is preferably 0.01% by mass to 0.5% by mass with respect to the total amount of monomers used. Moreover, when the polymerization initiator is used in combination with the reducing agent, the total amount used is preferably within the above range.

Further, when producing the pre-emulsion, reactive surfactants, anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, etc. are used. good too.

The acid value of the (meth)acrylic resin (I) is preferably 20 mgKOH/g or more and 120 mgKOH/g or less, more preferably 25 mgKOH or more.
If the acid value is 20 mgKOH/g or more, the abrasion resistance, water abrasion resistance, and scratch resistance of the laminate can be improved when the curing agent is added.
The term "acid value" as used herein refers to the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of resin.

The (meth)acrylic resin (I) preferably has a weight average molecular weight in the range of 5,000 to 100,000. When the weight-average molecular weight is 5,000 or more, the heat resistance of the resin film does not deteriorate, and the laminate tends to retain its abrasion resistance and water abrasion resistance. If it is 100,000 or less, there is a tendency that the laminate can have both adhesion to the substrate and scratch resistance.
The glass transition temperature (sometimes referred to as Tg) of the (meth)acrylic resin (I) is preferably in the range of 0°C to 55°C. When the Tg of the copolymer (A) is 0° C. or higher, the film strength is maintained and the water abrasion resistance of the laminate does not decrease. There is a tendency that the abrasion resistance, water abrasion resistance, and scratch resistance of the laminate can be maintained satisfactorily without deterioration.

The glass transition temperature (Tg) refers to a so-called calculated glass transition temperature, which is a value calculated by the following method.
(Formula 1) 1/Tg(K)=(W1/T1)+(W2/T2)+...(Wn/Tn)
(Formula 2) Tg (°C) = Tg (K) - 273
W1, W2, . It represents the glass transition temperature (K). The values of T1, T2, . . . Tn are those described in Polymer Handbook (Fourth Edition, J. Brandrup, EH Immergut, EA Grulke).

In addition, although the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature was measured using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument Co., Ltd.) in accordance with JIS K7121. It was measured by the method. Specifically, the polymer, from which the solvent has been completely removed by vacuum suction, is measured for changes in calorific value in the range of −100° C. to +200° C. at a heating rate of 20° C./min. The point at which a straight line equidistant from the vertical axis and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.

The (meth)acrylic resin (I) is preferably contained in the water-based liquid ink of the present invention in an amount of 5 to 50% by mass in terms of solid content. When the content of the (meth)acrylic resin (I) is 5% by mass or more, the strength of the ink coating film does not decrease, and the adhesiveness to the substrate and the resistance to water rubbing are well maintained. Conversely, when the amount is 50% by mass or less, it is possible to suppress a decrease in coloring power, avoid high viscosity, and prevent a decrease in workability.

(leveling agent)
The second composition contains an alcohol alkoxylate leveling agent as a leveling agent. Specific examples of alcohol alkoxylate-based surfactants include alcohol ethoxylates and alcohol polyethoxylates. The alcohol alkoxylate leveling agents may be used alone or in combination of two or more. Moreover, other leveling agents than the alcohol alkoxylate-based leveling agent may be used in combination.

The total amount of the alcohol alkoxylate-based leveling agent added is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, more preferably 0.1 to 1% by mass, of the total amount of the ink. is most preferred. When the total amount of the alcohol alkoxylate leveling agent added is 0.1 mass % or more of the total amount of the ink, the wettability with the substrate is improved and the adhesion with the substrate can be maintained. If the total amount of the alcohol alkoxylate-based leveling agent added is 5% by mass or less of the total amount of the ink, abrasion resistance, water abrasion resistance and scratch resistance do not deteriorate.

Further, if necessary, other leveling agents such as acetylene-based leveling agents, acrylic polymer-based leveling agents (eg Polyflow WS-314 manufactured by Kyoeisha Chemical Co., Ltd.) and modified silicone-based leveling agents (eg Polyflow KL-401 Kyoeisha) (manufactured by Kagaku Co., Ltd.) may also be used. The total amount of the leveling agent used is preferably 0.1 to 5 mass % of the total amount of the ink for the reasons described above.

(wax)
The second composition preferably contains wax. A hydrocarbon wax is preferable as the wax. Specific examples include liquid paraffin, natural paraffin, synthetic paraffin, microcrystalline wax, polyethylene wax, fluorocarbon wax, ethylene-propylene copolymer wax, tetrafluoroethylene resin wax, and Fischer-Tropsch wax. Among them, polyethylene wax is preferred.

These waxes may be used alone or in combination of two or more, and the total amount of these waxes added is preferably 0.5 to 5% by mass of the total amount of the ink. If the total amount of wax added is 0.5% by mass or more based on the total amount of the ink, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained. If the total amount of wax added is 5% by mass or less of the total amount of the ink, adhesion to the substrate, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained.

(curing agent)
In the present invention, a curing agent capable of reacting with acid may be used in combination. The curing agent that can react with an acid is not particularly limited, and known curing agents that can be used in an aqueous medium can be used. Examples thereof include epoxy-based curing agents, carbodiimide-based curing agents, and oxazoline-based curing agents. In the present invention, even in a system in which a curing agent is further added to the liquid ink, it is possible to achieve excellent viscosity stability, substrate adhesion of the cured coating film, and various coating film strengths.

The epoxy-based curing agent is not particularly limited as long as it is a compound having at least one epoxy group. Examples of epoxy-based curing agents include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether. [0042] The carbodiimide-based curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (-N=C=N-). As the carbodiimide curing agent, a polycarbodiimide compound having at least two carbodiimide groups is preferred.

The oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of oxazoline-based curing agents include Epocross series manufactured by Nippon Shokubai Co., Ltd., and the like.

Examples of the epoxy compound include diglycidyl ether of bisphenol A and its oligomers, diglycidyl ether of hydrogenated bisphenol A and its oligomers, diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, and p-oxybenzoic acid. diglycidyl ester, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, Examples include diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and triglycidyl ether of glycerol alkylene oxide adducts.

The addition amount of the curing agent used in the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 9.0% by mass in terms of solid content of the total amount of the composition. If the amount added is 0.1% by mass or more, the effect as a curing agent is obtained, while if it is 10.0% by mass or less, substrate adhesion, abrasion resistance, and water abrasion resistance tend to be maintained. Become.

(solvent)
As the solvent used for the second composition, the same solvent as the liquid ink for forming the first printing layer can be used.

(pigment)
The second composition may be used as a water-based varnish without containing a coloring material, or may be used as a so-called ink for white, black, or color printing with a coloring material. If it does not contain a coloring material, it becomes a transparent film after printing and is a colorless transparent ink (in this technical field, it is used for the purpose of solid printing on the outermost layer of the color printing layer and protecting the color printing layer, so it is commonly called overcoat varnish, OP In the present invention, it may be referred to as OP varnish). Of course, they can also be used as inks for so-called white, black and color printing containing coloring materials.

As the coloring material, the same liquid ink as used for forming the first printing layer can be used.

(other ingredients)
The second composition may optionally contain a general-purpose resin other than the acrylic resin (I), an extender pigment, a pigment dispersant, a leveling agent, an antifoaming agent, a plasticizer, an infrared absorber, and an ultraviolet absorber. , fragrances, flame retardants, and the like. Among them, fatty acid amides such as oleic acid amide, stearic acid amide, and erucic acid amide for imparting friction resistance, slipperiness, etc., silicon-based and non-silicon-based defoaming agents for suppressing foaming during printing, Various pigment dispersants and the like are often contained to improve the wettability of the pigment.

(Method for producing liquid ink)
The first composition or the second composition is obtained by dispersing a pigment, water alone, or a mixture containing water and an organic solvent that is miscible with water, a pigment dispersant, an antifoaming agent, etc., using a dispersing machine, to obtain a pigment dispersion. get A resin, water, or an organic solvent miscible with water, and if necessary, additives such as a leveling agent are added to the obtained pigment dispersion, and mixed with stirring to form the first composition or the second composition. can get. As a dispersing machine, a bead mill, eiger mill, sand mill, gamma mill, attritor, etc., which are generally used for the production of gravure and flexographic printing inks, are used.

When the first composition or the second composition is used as a flexo ink, the viscosity is preferably 7 to 25 seconds at 25° C. using Zahn Cup #4 manufactured by Rigosha, more preferably 10 to 25 seconds. 20 seconds. The surface tension of the obtained flexographic ink at 25° C. is preferably 25-50 mN/m, more preferably 33-43 mN/m. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as a film. tends to be easily connected, and tends to cause stains on the printing surface called dot bridges. On the other hand, if the surface tension exceeds 50 mN/m, the wettability of the ink to the base material such as a film is lowered, which tends to cause repelling.

On the other hand, when the first composition or the second composition is used as a gravure ink, the viscosity is preferably 7 to 25 seconds at 25° C. using Zahn Cup #3 manufactured by Rigosha. 10-20 seconds. The surface tension of the obtained gravure ink at 25° C. is preferably 25 to 50 mN/m, more preferably 33 to 43 mN/m, like the flexo ink. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as a film. tends to be easily connected, and tends to cause stains on the printing surface called dot bridges. On the other hand, if the surface tension exceeds 50 mN/m, the wettability of the ink to the base material such as a film is lowered, which tends to cause repelling.

(Method for forming printed layer)
The first printed layer or the second printed layer is obtained by printing the first composition or the second composition on the substrate to provide the printed layer. Usually, a printing layer is obtained by applying ink to a base material using a printing method such as gravure or flexography, drying the ink in an oven, and fixing the ink. The drying temperature is usually about 40-60°C.
In the present invention, it is preferable to print liquid printing ink using a flexographic printing method from the viewpoint of high-speed printing suitability, printing reproducibility, and the like. Flexographic printing is a type of letterpress printing, and mainly uses a rubber plate as a printing plate (letterpress), and uses a fine-mesh engraving roll called an anilox roll for the part that supplies ink to the printing plate. The anilox roll receives ink from the chamber-type doctor and applies ink to the printing plate, and there is an advantage that the ink can be uniformly transferred to the printing plate through the anilox roll.

Specifically, ink is applied to the surface of an anilox roll having partition walls and many openings surrounded by the partition walls, and a doctor is pressed against the surface of the anilox roll to scrape off the ink present on the top surface of the partition walls of the anilox roll. , to fill the recesses, which are openings, with ink. Subsequently, the flexographic plate is pressed against the anilox roll to transfer the ink present in the concave portions of the anilox roll to the convex portions (patterned portions) of the printing plate, and then the plate is brought into contact with the base material to transfer the ink present in the patterned portions of the plate. The ink is transferred to the substrate to obtain a print.

Moreover, you may combine a rotary printing method. For example, in a method for producing a thermoplastic resin film rotary print, rotary printing is performed on the surface of a wound thermoplastic resin film using an aqueous liquid ink. After printing, processes such as lamination, slitting (cutting unnecessary width portions), and bag making (cutting and heat-sealing to form bags) can be performed. High-speed printing is possible by rolling the liquid printing ink onto a thermoplastic resin film, and productivity is excellent. Rotary printing includes gravure rotary printing and flexographic rotary printing, and either method may be used. Rotary printing will be described in detail. In this specification, rotary printing means rotary gravure printing and flexographic rotary printing, and does not include other printing methods such as ink jet printing and silk screen printing.

In flexographic rotary printing, ink is supplied directly from a container for storing liquid printing ink or via an ink supply pump or the like to an anilox roller having an uneven surface. It is transferred to the plate surface by contact with the projections, and finally transferred to the thermoplastic resin film by contact between the plate surface and the thermoplastic resin film to form a pattern and/or characters.

When water-based flexographic printing inks are used, the drying properties of the inks are slightly inferior to solvent-based flexographic printing inks, so the thickness of the ink is preferably as thin as possible. From this point of view, it is preferable that the amount of ink supplied to the Aronix roller is as small as possible. On the other hand, since the print density tends to decrease as the film thickness decreases, the pigment density of the water-based flexographic printing ink to be used may be appropriately controlled. Specifically, when the pigment concentration of the water-based flexographic printing ink is 1 to 5% by weight higher than the concentration of the solvent-based flexographic printing ink, a suitable printing density can be obtained.

Rolled thermoplastic resin film is a roll of thermoplastic resin film with a specified width, and is different from sheet paper in which each sheet is cut in advance, and is used for rotary printing. is. The width of the film is appropriately selected based on the plate width of the rotary printing press to be used and the width of the image (pattern) portion of the gravure plate.
In addition, when colors are superimposed using rotary printing inks of a plurality of colors, the order of printing is not particularly limited.

When surface printing is performed, it is common to first print with white ink and then print with color inks, if necessary. When a plurality of color inks are used, for example, they can be printed in order of yellow, magenta, cyan, and black, but are not particularly limited. In the case of surface printing, abrasion resistance, water resistance, etc. can be improved by applying an overcoat agent to the printing surface of the rotary printed material as necessary.

When the substrate is white, that is, in the case of, for example, a paper substrate and a thermoplastic resin film into which a white pigment is kneaded, printing with only color inks is possible as required.
In the case of reverse printing, it is common to first print color ink and then white ink on the wound thermoplastic resin film. When multiple colors of ink are used, for example, printing can be performed in the order of black, cyan, magenta, and yellow, but there is no particular limitation. In large-sized printing presses, special colors and the like can be used in addition to the basic colors. That is, a large-sized printing press has a plurality of printing units corresponding to 5 to 10 colors, one printing unit is provided with ink of one color, and 5 to 10 colors of overprinting can be performed at one time.

The printed matter obtained by reverse printing may be used as it is, or the printed surface of the rotary printed matter obtained by the above method may be coated with an anchor coating agent, an adhesive, etc., dried as necessary, and then coated with a film, etc. It can also be laminated to form a laminate.
(Laminate)
The laminate of the present invention may be a laminate having at least a laminate structure in which a first printed layer and a second printed layer are laminated in this order on a plastic film by a printing method using a plate.

Although the plastic film is not particularly limited, for example, a thermoplastic resin film is preferable. The thermoplastic resin film is not particularly limited, and examples thereof include polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene phthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, and polybutylene. Biodegradable resins typified by polyester resins such as terephthalate and polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, and aliphatic polyester resins such as poly(ethylene succinate) and poly(butylene succinate), Polyolefin resins such as polypropylene (PP) and polyethylene, films made of thermoplastic resins such as polyimide resins, polyarylate resins, or mixtures thereof, and laminates thereof include polyester, polyamide, polyethylene, and polypropylene. A film can be preferably used.

These films may be either unstretched films or stretched films, and the manufacturing method thereof is not limited. Also, the thickness of the base film is not particularly limited, but it is usually in the range of 1 to 500 μm.
In addition, if the printed surface of the film is subjected to corona discharge treatment, the adhesiveness to the substrate can be further improved, which is preferable. In addition, silica, alumina, or the like may be vapor-deposited, and a gas barrier coating layer such as an oxygen gas barrier layer may be laminated.

Moreover, the base material which laminated|stacked the other base material on the surface different from the 1st printed layer of a plastic film may be used. Examples of other substrates include paper, synthetic paper, thermoplastic resin films, steel plates, aluminum foil, wood, woven fabrics, knitted fabrics, non-woven fabrics, gypsum boards, wood boards, and the like. It is possible to use a base material in which a plurality of types of base materials are combined. Specifically, for example, a base material in which paper and a plastic film are laminated, a base material in which a plastic film and an aluminum foil are laminated, and the like can be mentioned. The lamination method is also not particularly limited, and a general-purpose one-liquid adhesive, two-liquid adhesive, etc. may be used for adhesion, or if a plurality of thermoplastic resin films are laminated together by extrusion molding. may be

The substrate is provided with the first printed layer and the second printed layer of the present invention. In the laminate of the present invention, the number of printed layers is not particularly limited, and the laminate may have a third printed layer. The third printed layer may be provided between the first printed layer and the second printed layer, or may be provided on the second printed layer. The third printed layer can be formed of a printed layer formed with a general-purpose ink. For example, liquid ink containing at least the same acrylic resin as the second printed layer, or It is preferably composed of an ink containing at least a urethane resin similar to the above.

In addition, the laminate of the present invention may further have one or more other printed layers in addition to the first printed layer, the second printed layer, and the third printed layer. . The structure of the other layers is not particularly limited, and a known ink layer or overcoat varnish layer can be provided. For example, there is a configuration in which a printed layer containing a known urethane resin is provided on the first printed layer, or a printed layer containing a known urethane resin is provided between the third printed layer and the second printed layer. preferable.

A more specific configuration of the laminate will be described below. Of course, the present invention is not limited to this configuration, and it is possible to obtain a printed matter and a laminate expressed by a plurality of printed layers according to a desired design. As abbreviations, the overcoat varnish is expressed as "OP", the anchor coat varnish as "AC", and the layer printed with a general-purpose water-based liquid ink as a "general-purpose printed layer". Note that "/" means adjacent, for example, in the case of "substrate/first printing layer (color)/second printing layer OP", the first printing ink is adjacent to the substrate. A layer is provided and adjacent to the printed ink layer an overcoat varnish with a second printed layer is provided. It means.
Film/first printed layer (color)/second printed layer OP
Film/first printed layer (color)/second printed layer (color)
Film/first printed layer (color)/third printed layer (color)/second printed layer OP
Film/first printed layer (color)/third printed layer (color)/second printed layer (color)
Film/first printed layer (color)/third printed layer (color)/other general-purpose printed layer (color)/second printed layer OP
Film/first printed layer (color)/third printed layer (color)/other general-purpose printed layer (color)/second printed layer (color)
Film/First printed layer (color)/Third printed layer (color)/Other general-purpose printed layer (color)/Second printed layer (color)/General-purpose printed layer OP
Film/first printed layer AC/second printed layer OP
Film/first printed layer AC/second printed layer (color)
Film/first printed layer AC/third printed layer (color)/second printed layer OP
Film/first printed layer AC/third printed layer (color)/second printed layer (color)
Film/first printed layer AC/third printed layer (color)/other general-purpose printed layer (color)/second printed layer OP
Film/first printed layer AC/third printed layer (color)/other general-purpose printed layer (color)/second printed layer (color)
Film/First printed layer AC/Third printed layer (color)/Other general-purpose printed layer (color)/Second printed layer (color)/General-purpose printed layer OP
The first printed layer of the present invention can improve the adhesion of the laminate by being in direct contact with the film. In addition, since the second printed layer of the present invention is excellent in coating film strength, particularly abrasion resistance and scratch resistance, the outermost layer of the laminate, that is, the uppermost layer farthest from the thermoplastic resin film that is the base material By providing this printed layer, the strength of the laminate becomes more sufficient, and the basic coating film strength such as substrate adhesion, abrasion resistance, water abrasion resistance, and scratch resistance is better maintained. There is a tendency. Depending on the desired design, the printed layer at this time may be applied as a colored ink containing a suitable coloring material or as an overcoat varnish containing no coloring material. A white ink containing a white pigment is most often applied as a color ink containing a coloring material. In addition, since a stronger printed layer surface can be obtained by printing the second printed layer and stacking multiple printed layers, the second printed layer can be printed in the same color (for example, white ink again on top of white ink). It may be made into a layered printing layer. In addition, a printing layer may be formed by stacking a plurality of overcoat varnishes containing no colorant on color ink (for example, white ink).

The laminate of the present invention has excellent adhesion regardless of the type of plastic film substrate, and the second printed layer has excellent coating strength, especially abrasion resistance and scratch resistance. , is suitable for a form in which the printed layer is the outermost layer. Among the surface-printed matter and the reverse-printed matter, a printed matter having a printed layer of the water-based liquid ink (A) according to the present invention on the outermost surface during distribution is preferable because the effect of the present invention can be maximized. It can be used in a variety of applications, such as plastic labels for beverage and food bottles (such as shrink labels and body wrap labels), integrated packages, and exterior packages.

"Parts" in the following examples represent "parts by mass" and "%" represents "% by mass".

The measurement of the weight average molecular weight (in terms of polystyrene) by GPC (gel permeation chromatography) in the present invention was carried out under the following conditions using an HLC8220 system manufactured by Tosoh Corporation. Separation column: 4 TSKgelGMHHR-N manufactured by Tosoh Corporation are used. Column temperature: 40°C. Moving bed: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml/min. Sample concentration: 1.0% by mass. Sample injection volume: 100 microliters. Detector: differential refractometer.

In addition, the acid value indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin.・Calculated from potentiometric titration with ethanol solution.
Moreover, the glass transition temperature (Tg) refers to a so-called calculated glass transition temperature, and refers to a value calculated by the following method.
(Formula 1) 1/Tg(K)=(W1/T1)+(W2/T2)+...(Wn/Tn)
(Formula 2) Tg (°C) = Tg (K) - 273
W1, W2, . It represents the glass transition temperature (K). The values of T1, T2, . . . Tn are those described in Polymer Handbook (Fourth Edition, J. Brandrup, EH Immergut, EA Grulke).

In addition, although the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature was measured using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument Co., Ltd.) in accordance with JIS K7121. It was measured by the method. Specifically, the polymer, from which the solvent has been completely removed by vacuum suction, is measured for changes in calorific value in the range of −100° C. to +200° C. at a heating rate of 20° C./min. The point at which a straight line equidistant from the vertical axis and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.

<Production of liquid ink forming the first printing ink layer>
(Synthesis Example 1: Preparation of polyurethane resin U1)
296 parts by mass of polyoxytetramethylene glycol (molecular weight: 2000), 82 parts by mass of isophorone diisocyanate, and 17 parts by mass of 2,2-dimethylolpropionic acid in a nitrogen-purged vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. and 3.6 parts by mass of neopentyl glycol in 205 parts by mass of methyl ethyl ketone to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.

Then, 1.4 parts by mass of a 50% by mass aqueous potassium hydroxide solution and 7.6 parts by mass of a 25% by mass aqueous ammonia solution are added to neutralize part or all of the carboxyl groups of the urethane prepolymer. Parts by mass and 3.4 parts by mass of an 80% aqueous hydrazine solution are added and sufficiently stirred to obtain an aqueous dispersion of urethane resin, followed by aging and removal of the solvent to obtain polyurethane resin U1 having a non-volatile content of 40% by mass. rice field.

This polyurethane resin U1 had a glass transition point Tg of 25° C. and an acid value of 17 mgKOH/g.

(Synthesis Example 2: Preparation of polyurethane resin U2)
296 parts by mass of polyoxytetramethylene glycol (molecular weight: 2000), 82 parts by mass of isophorone diisocyanate, and 17 parts by mass of 2,2-dimethylolpropionic acid in a nitrogen-purged vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. and 3.6 parts by mass of neopentyl glycol in 205 parts by mass of methyl ethyl ketone to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.

Then, 1.4 parts by mass of a 50% by mass aqueous potassium hydroxide solution and 7.6 parts by mass of a 25% by mass aqueous ammonia solution are added to neutralize part or all of the carboxyl groups of the urethane prepolymer. Parts by mass and 3.4 parts by mass of an 80% aqueous hydrazine solution are added and sufficiently stirred to obtain an aqueous dispersion of urethane resin, followed by aging and solvent removal to obtain polyurethane resin U2 having a non-volatile content of 40% by mass. rice field.

This polyurethane resin U2 had a glass transition point Tg of −50° C. and an acid value of 40 mgKOH/g.

(Comparative Synthesis Example 1: Preparation of polyurethane resin U3)
186.9 parts of PLACCEL 212 (manufactured by Daicel Chemical Industries, Ltd., polycaprolactone diol, hydroxyl value 90 mgKOH/g) and 100.0 parts of isophorodiisocyanate (abbreviated as IPDI) were charged. This was heated to 110° C. while stirring. After 1 hour, cool to 80°C, add 20.1 parts of dimethylolpropionic acid (abbreviated as DMPA), 0.3 parts of dibutyltin dilaurate and 76.8 parts of ethyl acetate, and react at 80°C for 2 hours. let me 18.1 parts of Barnock DN-980S (manufactured by DIC, hexamethylene diisocyanate-based polyisocyanate, NCO content: 20%) and 408 parts of methyl ethyl ketone (abbreviated as MEK) were added thereto. The NCO group content at this time was 4.9% in terms of solid content.

This was cooled to 30° C. or lower, 15.2 parts of triethylamine was added, and then 1293 parts of deionized water was added to obtain an oil-in-water (O/W) emulsion. Subsequently, 234 parts of a 5% aqueous solution of diethylenetriamine was gradually added, and after the addition was completed, the temperature was raised to 60° C. and stirring was continued for 30 minutes. Distillation was then carried out under reduced pressure to remove the solvent and part of the water to obtain an aqueous solution of polyurethane resin U3.

This product was a slightly opalescent translucent liquid, and when a small amount was taken in a test tube and tetrahydrofuran (abbreviated as THF) was added, it became cloudy, indicating that it was crosslinked and insoluble. It had a non-volatile content of 39.6%, a viscosity of 160 cps, a pH of 7.7 and an average particle size of 28.5 nm.

(Comparative Synthesis Example 2: Preparation of acrylic urethane resin U4)
A reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel and a reflux tube, and charged with 80.0 parts of n-propyl acetate. The temperature was raised to 90° C. while stirring in a nitrogen atmosphere. On the other hand, 32.0 parts of styrene, 20.0 parts of 2-hydroxyethyl methacrylate, 40.0 parts of 2-ethylhexyl acrylate, 8.0 parts of acrylic acid, and 3.0 parts of azobisisobutyronitrile were added to n-propyl acetate. It was dissolved in 40.0 parts and added dropwise over 4 hours using a dropping funnel. After completion of dropping, 1.6 parts of Barnock DN-980S (manufactured by DIC, hexamethylene diisocyanate-based polyisocyanate, NCO content: 20%) was gradually added, and the reaction was further continued for 6 hours. After completion of the reaction, the acrylic resin solution was cooled and neutralized by adding 4.0 parts of 30% aqueous ammonia. Further, deionized water was added and the solvent was replaced while heating to obtain an aqueous solution of acrylic urethane resin U4 having a solid content of 25%. The acid value was 62 mgKOH/g, the Tg was 30°C, and the weight average molecular weight was 600,000.

(Production of liquid ink or varnish composition)
After stirring and mixing the materials blended as shown in Tables 1 and 2, the mixture was kneaded in a bead mill to prepare compositions of Preparation Examples 1 to 4 and 100 to 103. It was confirmed that the resulting composition had a viscosity of 16 seconds (25° C.) with a Zahn cup #4 (manufactured by Rigosha).

Abbreviations in the table represent the following.
・ Indigo pigment: FASTOGEN BLUE LA5380 (manufactured by DIC Corporation)
- Polyurethane (U1): Polyurethane resin U1 prepared in Synthesis Example 1
- Polyurethane resin (U2): Polyurethane resin U2 prepared in Synthesis Example 1
・Polyurethane resin (U3): ester-based urethane resin prepared in Comparative Synthesis Example 1 ・Polyurethane resin (U4): acrylic-based urethane resin prepared in Comparative Synthesis Example 2 ・Pigment dispersion resin: styrene/maleic acid pigment dispersion resin < Production of Liquid Ink Forming Second Printing Ink Layer>
(Synthesis Example 3: Preparation of shell portion styrene-acrylic resin)
A reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel and a reflux tube, and charged with 65.0 parts of n-propyl acetate. The temperature was raised to 90° C. while stirring in a nitrogen atmosphere. On the other hand, 36.0 parts of styrene, 12.0 parts of ethyl methacrylate, 20.0 parts of 2-ethylhexyl acrylate, 32.0 parts of acrylic acid, 1.6 parts of azobisisobutyronitrile and 35.0 parts of n-propyl acetate and added dropwise over 4 hours using a dropping funnel. After the dropwise addition was completed, the reaction was further continued for 6 hours. After completion of the reaction, the acrylic resin solution was cooled and neutralized by adding 20.0 parts of 30% aqueous ammonia. Further, deionized water was added and the solvent was replaced while heating to obtain an aqueous acrylic resin solution having a solid content of 30%. The acid value was 250 mgKOH/g, the Tg was 61°C, and the weight average molecular weight was 10,200.

(Synthesis Example 4: Preparation of core-shell type styrene acrylic emulsion (A3) having a copolymer) Acid value 100
Equipped with a stirrer, a thermometer, a dropping funnel and a reflux pipe, a reaction vessel charged with 222.2 parts of the styrene acrylic resin aqueous solution prepared in Synthesis Example 3 is charged with 119.6 parts of ion-exchanged water. The temperature was raised to 75° C. while stirring in a nitrogen atmosphere. Subsequently, using a dropping funnel, 32.0 parts of methyl methacrylate, 46.0 parts of butyl acrylate, 10.0 parts of ethyl methacrylate, 18.0 parts of isobutyl methacrylate, and 3.5 parts of 30% ammonium persulfate were added dropwise over 4 hours. . After the dropping was completed, the reaction was further carried out for 6 hours to obtain a core-shell type styrene-acrylic emulsion (A1) having a solid content of 38.5%. The acid value was 100 mgKOH/g, the Tg was 42°C, and the weight average molecular weight was 1,200,000.

(Synthesis Example 5: Preparation of Shell Part Acrylic Resin (Polymer a1))
A reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel and a reflux tube, and charged with 60.0 parts of n-propyl acetate. The temperature was raised to 90° C. while stirring in a nitrogen atmosphere. On the other hand, 36.0 parts of methyl methacrylate, 10.0 parts of ethyl methacrylate, 20.0 parts of n-butyl methacrylate, 10.0 parts of isobutyl methacrylate, 10.0 parts of 2-ethylhexyl acrylate, 14.0 parts of acrylic acid, azobis 1.0 parts of isobutyronitrile was dissolved in 40.0 parts of n-propyl acetate and added dropwise over 4 hours using a dropping funnel. After the dropwise addition was completed, the reaction was further continued for 6 hours. After completion of the reaction, the acrylic resin solution was cooled and neutralized by adding 8.0 parts of 30% aqueous ammonia. Further, ion-exchanged water was added and the solvent was replaced while heating to obtain an aqueous acrylic resin solution having a solid content of 55%.

The acid value was 105 mgKOH/g, the Tg was 65°C, and the weight average molecular weight was 16,000.

(Synthesis Example 6: Preparation of core-shell type acrylic emulsion (A2) having a copolymer) Acid value 42
A reaction vessel charged with 121.2 parts of the acrylic resin aqueous solution prepared in Synthesis Example 5 is equipped with a stirrer, a thermometer, a dropping funnel and a reflux tube, and 195.5 parts of ion-exchanged water is added. The temperature was raised to 75° C. while stirring in a nitrogen atmosphere. Subsequently, using a dropping funnel, 30.0 parts of methyl methacrylate, 20.0 parts of ethyl methacrylate, 25.0 parts of n-butyl acrylate, 25.0 parts of 2-ethylhexyl acrylate, and 3.3 parts of 30% ammonium persulfate were added for 4 hours. dripped over. After completion of the dropwise addition, the reaction was further carried out for 6 hours to obtain a core-shell type acrylic emulsion (A2) having a solid content of 40%. The acid value was 42 mgKOH/g, the Tg was 10°C, and the weight average molecular weight was 1,200,000.

(Manufacture of liquid ink)
After stirring and mixing the materials blended as shown in Tables 3 to 6, the mixture was kneaded in a bead mill to prepare compositions of Preparation Examples 21 to 27 and 200 to 204. It was confirmed that the resulting composition had a viscosity of 16 seconds (25° C.) with a Zahn cup #4 (manufactured by Rigosha).

<Viscosity stability>
The viscosity of the prepared acrylic resin ink/varnish of the present invention was evaluated using a Zahn cup #4 (manufactured by Rigosha Co., Ltd.) after 6 hours at 25° C. with a standard time of 15 seconds.
◎: The ink did not thicken at all (less than +1 second)
○: Slightly thickened ink (less than +3 seconds)
○△: Slightly thickened ink (less than +5 seconds)
△: Thickened ink (less than +10 seconds)
×: Remarkably thickened ink (+10 seconds or more)

Abbreviations in the table represent the following.
・ Titanium (IV) oxide: JR-800 (manufactured by Tayka)
Copolymer (A1): Core-shell styrene-acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 4
Copolymer (A2): Core-shell acrylic emulsion (A2) having the copolymer prepared in Synthesis Example 6
Copolymer (A3): Water-based self-crosslinking acrylic copolymer emulsion (Neocryl (registered trademark) A1125: manufactured by Kusumoto Kasei Co., Ltd.)
Polymer (A4): Polyurethane resin U3 prepared in Comparative Synthesis Example 1
・ Epoxy curing agent: Denacol EX-612 (manufactured by sorbitol polyglycidyl ether Nagase ChemteX Co., Ltd.)
<Preparation of printing ink laminate>
(Examples 1 to 27, Comparative Examples 1 to 13)
A solid pattern of 240 mm long × 80 mm wide is printed on a PET, OPP or OPS film substrate described in the table using a Flexoproof 100 test printer (Testing Machines, Inc., anilox 200 lines / inch), an anilox roll and Various liquid inks were printed with a resin plate at a printing speed of 100 m/min, and the resulting prints were aged at 40° C. for 20 hours to obtain printing ink laminates having the configurations shown in Tables 7 to 14. rice field.

The OP varnish or water-based liquid ink was printed according to Tables 7 to 14 in the order of the first printed layer, the second printed layer, the third printed layer, the fourth printed layer, and the fifth printed layer. The first printed layer described in Tables 7 to 14 corresponds to the "first printed layer", and the outermost layer of the second printed layer to the fifth printed layer is the "second It corresponds to the "printing layer".

Using the prepared laminate, the adhesiveness to the substrate, abrasion resistance, water abrasion resistance, and scratch resistance were evaluated as follows, and the viscosity stability of the prepared acrylic resin ink and varnish was also evaluated. went.

<Substrate adhesion>
A cellophane tape (12 mm width, manufactured by Nichiban Co., Ltd.) was applied to the ink-coated surface of the resulting printed ink laminate, and then rapidly peeled off to visually determine the degree of ink peeling.
The practical level is ◯△ or higher.
A: No ink peeled off at all O: Slightly peeled ink from film (less than 10%)
○△: Ink peeled from film (10% or more, less than 30%)
△: Ink peeled from the film (30% or more, less than 75%)
x: Ink is remarkably peeled from the film (75% or more)
<Abrasion resistance>
The printed ink laminate thus obtained was rubbed with high-quality paper using a Gakushin rub resistance tester, and the degree of peeling of the ink layer was visually determined. (500 reciprocations at a load of 500g)
The practical level is Δ or higher.
A: No ink peeled off at all ○: Slightly peeled ink from film (less than 10%)
○△: Ink peeled from film (10% or more, less than 30%)
△: Ink peeled from the film (30% or more, less than 75%)
×: Ink is remarkably peeled from the film (75% or more)
<Water friction resistance>
The obtained printing ink laminate was rubbed with a water-containing black cotton cloth using a Gakushin rub resistance tester, and the degree of peeling of the ink layer was visually determined. (500 round trips with a load of 200 g)
The practical level is Δ or higher.
A: No ink peeled off at all ○: Slightly peeled ink from film (less than 10%)
○△: Ink peeled from film (10% or more, less than 30%)
△: Ink peeled from the film (30% or more, less than 75%)
×: Ink is remarkably peeled from the film (75% or more)
<Scratch resistance>
The ink-coated surface of the resulting printed ink laminate was scratched with a nail, and the scratch resistance was visually evaluated from the degree of scratching of the coating film.
The practical level is ◯△ or higher.
◎: No scratches ○: Slight scratches ○△: Medium scratches between ○ and △ △: Scratches ×: Severe scratches peel off)

Abbreviations in the table represent the following.
・ PET: Corona-treated PET film (E5100, thickness 12 μm, manufactured by Toyobo Co., Ltd.)
・ OPP: Corona-treated polypropylene biaxially stretched film (Pylen P2161 manufactured by Toyobo Co., Ltd., thickness 20 μm)
・OPS: Corona-treated polystyrene biaxially stretched film (thickness 50 μm)

Claims (6)

A laminate having at least a first printed layer and a second printed layer in this order on a plastic film,
The first printing layer is an aqueous varnish or aqueous liquid ink printing layer containing at least a urethane resin that is a reaction product of a polyol (ia) containing a polyether polyol (ia-1) and a polyisocyanate (ib). can be,
A laminate, wherein the second printed layer is a printed layer of aqueous varnish or aqueous liquid ink containing a (meth)acrylic resin and an alcohol alkoxylate leveling agent. 2. The laminate according to claim 1, wherein the polyol (ia) further contains a polyol (ia-2) having an acid group. The laminate according to claim 1 or 2, wherein the (meth)acrylic resin is a copolymer formed from a (meth)acrylate monomer and having an acid value with a glass transition temperature of 0°C to 55°C. The leveling agent for the second printing layer further contains an alcohol alkoxylate leveling agent in an amount of 0.1 to 5% by mass and a wax in an amount of 0.5 to 5% by mass based on the total amount of the ink. 4. The laminate according to any one of 1 to 3. The laminate is a laminate further having a third printed layer,
5. The laminate according to any one of claims 1 to 4, wherein the third printed layer is a printed layer of aqueous varnish or aqueous liquid ink containing a (meth)acrylic resin. The laminate according to any one of claims 1 to 5, wherein the plastic film is a polyester resin film, a polyolefin resin film or a polystyrene film.