Latex ink film

Abstract

The present invention addresses the problem of providing a film for a latex ink, the film having a latex-ink-receiving layer that is excellent in terms of both ink adhesion and abrasion resistance, and excellent in terms of water-resistant adhesion of ink. This problem is solved by configuring the film to have a layered structure in which a latex-ink-receiving layer (X) and a substrate (Y) are layered, the latex-ink-receiving layer (X) being formed from a resin composition (x1) that contains: an acrylic resin (A) having a crosslinkable functional group; a specific crosslinking agent (B); a UV-curable acrylate compound (C); a photopolymerization initiator (D); and a polymerizable tertiary amine (E).

Description

[Technical Field]

[0001] The present invention relates to a film for latex inks. [Background technology]

[0002] In recent years, printing methods using latex ink have been attracting attention (see, for example, Patent Document 1). Unlike solvent inks, which dissolve pigments in organic solvents, latex inks are water-based inks in which pigments are dispersed in water together with latex (a polymer). Therefore, unlike solvent inks, they do not emit volatile organic compounds (VOCs) that result from organic solvents, which is a problem when using solvent inks. Therefore, printed materials using latex inks have the advantage of being safe for use in a variety of locations, including restaurants, educational institutions, medical institutions, and commercial facilities.

[0003] Taking these advantages into consideration, the present applicant has proposed a film for latex ink in Patent Document 2. The film for latex ink described in Patent Document 2 comprises a substrate and a printing coating layer to which latex ink is applied. The printing coating layer contains a material having a structure in which a polymeric material whose constituent monomers are vinyl chloride, vinyl acetate, and a crosslinkable monomer is crosslinked by a crosslinking agent. This results in a film for latex ink having a printing coating layer that has excellent adhesion to both the area printed with latex ink and the substrate.

[0004] The "printing coating layer" in Patent Document 2 is referred to as the "latex ink-receiving layer" in this specification. That is, the "latex ink-receiving layer" refers to the layer to which latex ink is applied and has the function of fixing the printed portion of the applied latex ink. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-120719 [Patent Document 2] Japanese Patent Application Publication No. 2019-172877 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, printing methods using latex inks have been widely adopted, and various requirements have been increasing for the latex ink-receiving films used in such methods. Specifically, from the viewpoint of preventing scratches on the surface of the latex ink-receiving layer, the latex ink-receiving layer of the latex ink-receiving film may be required to have abrasion resistance.

[0007] However, in order to ensure adhesion of the latex ink-receiving layer to the area printed with latex ink (hereinafter simply referred to as "ink adhesion"), the latex ink-receiving layer needs to have a certain degree of softness. As a result, the surface of the latex ink-receiving layer is easily scratched and has poor abrasion resistance. For these reasons, the "printing coating layer" in Patent Document 2 also has poor abrasion resistance. Thus, there is a problem in that it is difficult to achieve both ink adhesion and abrasion resistance in a latex ink-receiving layer.

[0008] Furthermore, latex ink films are sometimes applied to glass surfaces in stores, showrooms, offices, etc. for advertising and decorative purposes. When applying a latex ink film to an adherend such as a glass surface, water or an aqueous solution containing a surfactant is sprayed onto the application surface (adhesive layer surface) of the latex ink film or the mating surface of the adherend to prevent air from getting between the latex ink film and the adherend, and after the two are brought into close contact and positioned, the water and air are scraped out from the latex ink film side using a squeegee to apply the film, a method known as water application. In this case, the aqueous solution may also be sprayed onto the latex ink-receiving layer side, which is the side opposite the adhesive layer, to improve the slipperiness of the squeegee. Therefore, the latex ink receiving layer of a film for latex ink that is to be applied with water must be able to maintain adhesion to the printed area of ​​the latex ink even when rubbed with a squeegee while in contact with water (hereinafter, this will also be referred to as "water-resistant adhesion of the ink"). However, a film for latex ink that not only has ink adhesion and abrasion resistance but also water-resistant ink adhesion has not yet been created.

[0009] The present invention has been made in consideration of such problems, and an object of the present invention is to provide a film for latex ink having a latex ink-receiving layer that is excellent in both ink adhesion and abrasion resistance, as well as in water-resistant ink adhesion.

[0010] In this specification, the term "ink adhesion" refers to the adhesion between a latex ink-receiving layer and a printed portion formed on the latex ink-receiving layer with latex ink when the printed portion is not in contact with liquid water. The quality of the adhesion can be evaluated, for example, by an ink adhesion test in the examples described later. In addition, in this specification, the term "water-resistant adhesion of ink" refers to the adhesion between a latex ink-receiving layer and a printed portion formed with latex ink when the printed portion is in contact with liquid water. The quality of the adhesion can be evaluated, for example, by a water-resistant adhesion test of ink in the examples described later. [Means for solving the problem]

[0011] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have discovered that the above-mentioned problems can be solved by a latex ink-receiving layer formed from a resin composition containing an acrylic resin having a crosslinkable functional group, a specific crosslinking agent, an ultraviolet-curable acrylate compound, a photopolymerization initiator, and a polymerizable tertiary amine. Based on this discovery, the present inventors have conducted further research and have completed the present invention. That is, the present invention relates to the following [1] to [8]. [1] A laminated structure in which a latex ink receiving layer (X) and a substrate (Y) are laminated, the latex ink-receiving layer (X) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group, a crosslinking agent (B), an ultraviolet-curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary amine (E); the crosslinking agent (B) contains an isocyanurate compound (B1), The isocyanurate compound (B1) includes an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2), The isocyanurate compound (B1-1) is a trimer of 1,6-hexamethylene diisocyanate, The modified isocyanurate compound (B1-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups. [2] The film for latex ink according to [1] above, wherein the substrate (Y) contains a polyester resin. [3] The latex ink-receiving layer (X) is laminated on one surface of the substrate (Y), The film for latex ink according to the above [1] or [2], wherein a pressure-sensitive adhesive layer (Z) is provided on the other surface of the substrate (Y). [4] The film for latex ink according to the above [3], wherein the adhesive surface of the adhesive layer (Z) is covered with a release liner. [5] The film for latex ink according to any one of [1] to [4] above, which is used for printing using latex ink containing an acrylic resin. [6] A method of using the film for latex ink according to any one of [1] to [5] above, to form a printed portion on the latex ink-receiving layer of the film for latex ink using latex ink. [7] A method for producing a printed matter, comprising the step of forming a printed portion using latex ink on the latex ink-receiving layer of the film for latex ink according to any one of [1] to [5] above. [8] A printed matter having a printed area printed with latex ink on the latex ink-receiving layer of the film for latex ink according to any one of [1] to [5] above. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a film for latex ink having a latex ink-receiving layer that is excellent in both ink adhesion and abrasion resistance, as well as in water-resistant ink adhesion. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a cross-sectional view showing one embodiment of a film for latex ink of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0014] In this specification, the term "active ingredient" refers to the components contained in the target composition, excluding diluent solvents such as water and organic solvents. In this specification, the term "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid," and the term "(meth)acryloyl group" refers to both "acryloyl group" and "methacryloyl group." Furthermore, in this specification, for preferred numerical ranges (e.g., ranges of content, etc.), the lower and upper limits described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." In this specification, the numerical values ​​in the examples are numerical values ​​that can be used as upper or lower limit values.

[0015] [Embodiments of the film for latex ink of the present invention] The film for latex ink of the present invention has a laminated structure in which a latex ink-receiving layer (X) and a substrate (Y) are laminated together. The latex ink receiving layer (X) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group, a crosslinking agent (B), an ultraviolet-curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary amine (E). The crosslinking agent (B) contains an isocyanurate compound (B1). The isocyanurate compound (B1) includes an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2). The isocyanurate compound (B1-1) is a trimer of 1,6-hexamethylene diisocyanate, and the modified isocyanurate compound (B1-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups.

[0016] As a result of extensive research, the present inventors have found that a latex ink-receiving layer formed from a resin composition (x1) containing "an acrylic resin (A) having a crosslinkable functional group," "a crosslinking agent (B) containing an isocyanurate compound (B1)," "an ultraviolet-curable acrylate compound (C)," "a photopolymerization initiator (D)," and "a polymerizable tertiary amine (E)" has excellent ink adhesion and abrasion resistance, as well as excellent water-resistant ink adhesion. After further extensive research, the present inventors have completed the present invention.

[0017] The latex ink film of the present invention will be described in detail below with respect to its configuration, the components constituting the latex ink film (substrate, latex ink-receiving layer, adhesive layer, and release liner), the method for producing the latex ink film, and uses of the latex ink film.

[0018] [Latex ink film composition] The film for latex ink of the present invention has a laminated structure in which a latex ink-receiving layer (X) and a substrate (Y) are laminated together.

[0019] A cross-sectional schematic diagram of one embodiment of the film for latex ink of the present invention is shown in Figure 1. The film for latex ink 1 shown in Figure 1 has a laminated structure in which a latex ink-receiving layer (X) is laminated on one surface (Ya) of a substrate (Y). 1, the film for latex ink according to one embodiment of the present invention preferably has a pressure-sensitive adhesive layer (Z) provided on the other surface (Yb) of the substrate (Y), which allows the film for latex ink to be suitably used as a pressure-sensitive adhesive film.

[0020] Although not shown, the adhesive surface of the pressure-sensitive adhesive layer (Z) may be covered with a release liner, which may be peeled off when the adhesive is attached to an adherend, to expose the adhesive surface of the pressure-sensitive adhesive layer (Z). Although not shown in the figure, a latex ink receiving layer (X) may be provided on both the one surface (Ya) and the other surface (Yb) of the substrate (Y) without providing the adhesive layer (Z). Although not shown, another layer may be provided between the latex ink receiving layer (X) and the substrate (Y). Examples of such another layer include an easy-adhesion layer.

[0021] [Components that make up latex ink film] The film for latex ink of the present invention has a latex ink-receiving layer (X) and a substrate (Y). As described above, the film for latex ink according to one embodiment of the present invention may further include a pressure-sensitive adhesive layer (Z) in addition to the latex ink-receiving layer (X) and the substrate (Y). Alternatively, the film for latex ink according to one embodiment of the present invention may further include a pressure-sensitive adhesive layer (Z) and a release liner in addition to the latex ink-receiving layer (X) and the substrate (Y). The latex ink-receiving layer (X), the substrate (Y), the pressure-sensitive adhesive layer (Z), and the release liner will be described in detail below.

[0022] <Latex ink receiving layer (X)> The film for latex ink of the present invention has a latex ink-receiving layer (X). The latex ink receiving layer (X) is the portion to which latex ink is applied, and has the function of fixing the printed portion of the applied latex ink. The thickness of the latex ink receiving layer (X) is not particularly limited, but is preferably 0.05 μm to 50 μm, more preferably 0.1 μm to 25 μm, and even more preferably 0.1 μm to 10 μm.

[0023] The latex ink receiving layer (X) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group, a crosslinking agent (B), an ultraviolet-curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary amine (E). The resin composition (x1) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group, a crosslinking agent (B), a UV-curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary amine (E), so that a crosslinked structure formed by the reaction between the acrylic resin (A) having a crosslinkable functional group and the crosslinking agent (B) and a polymer structure formed between the UV-curable acrylate compound (C) and the photopolymerization initiator (D) coexist on the surface of the latex ink-receiving layer (X). This is presumably why the layer has excellent ink adhesion and abrasion resistance. In addition, it is presumed that the polymerizable tertiary amine (E) is incorporated into the polymer structure formed by the ultraviolet-curable acrylate compound (C) and the photopolymerization initiator (D), causing the polymerizable tertiary amine (E) to interact with the latex ink, resulting in the formation of a latex ink-receiving layer (X) that also has excellent water-resistant adhesion of the ink.

[0024] In the following explanation, the "acrylic resin (A) having a crosslinkable functional group," "crosslinking agent (B)," "ultraviolet-curable acrylate compound (C)," "photopolymerization initiator (D)," and "polymerizable tertiary amine (E)" will also be referred to as "component (A)," "component (B)," "component (C)," "component (D)," and "component (E)," respectively.

[0025] In one embodiment of the present invention, the resin composition (x1) that is the material for forming the latex ink-receiving layer (X) may be composed only of components (A), (B), (C), (D), and (E), or may contain components other than components (A), (B), (C), (D), and (E) in addition to components (A), (B), (C), (D), and (E) to the extent that the effects of the present invention are not impaired. Examples of such components include additives for ink-receiving layers that are commonly used in ink-receiving layers such as latex ink-receiving layers, such as reaction accelerators (catalysts), surface conditioners, plasticizers, fillers, and colorants.

[0026] In one embodiment of the present invention, the total content of component (A), component (B), component (C), component (D), and component (E) is preferably 80% by mass to 100% by mass, more preferably 85% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass, based on the total amount of active ingredients in resin composition (x1).

[0027] The acrylic resin (A) having a crosslinkable functional group, the crosslinking agent (B), the ultraviolet-curable acrylate compound (C), the photopolymerization initiator (D), and the polymerizable tertiary amine (E) contained in the resin composition (x1) will be described in detail below.

[0028] (Acrylic resin (A) having crosslinkable functional groups) The resin composition (x1) used in the present invention contains an acrylic resin (A) having a crosslinkable functional group. The acrylic resin (A) having a crosslinkable functional group is preferably an acrylic resin (A1) having a structural unit (a1) derived from a crosslinkable functional group-containing monomer (a1') (hereinafter also referred to as monomer (a1')).

[0029] Examples of the crosslinkable functional group contained in the monomer (a1') include one or more groups selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. That is, examples of the monomer (a1') include hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers, etc. Also included are monomers containing two or more crosslinkable functional groups selected from hydroxyl groups, carboxyl groups, amino groups, and epoxy groups, etc. These monomers (a1') may be used singly or in combination of two or more. Among these, hydroxyl group-containing monomers and carboxy group-containing monomers are preferred as the monomer (a1').

[0030] Examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; N-methylol acrylamide; ε-caprolactone-modified hydroxy(meth)acrylate; and carbonate-modified (meth)acrylate.

[0031] Examples of the carboxyl group-containing monomer include (meth)acrylic acid; and compounds obtained by reacting the terminal hydroxyl group of the hydroxyl group-containing monomer described above with an acid anhydride such as one or more aliphatic dicarboxylic acids selected from succinic anhydride, glutaric anhydride, and the like.

[0032] Here, the acrylic resin (A) having a crosslinkable functional group may be an acrylic copolymer (A2) having a structural unit (a2) derived from an alkyl (meth)acrylate (a2') (hereinafter also referred to as "monomer (a2')") together with the crosslinkable functional group-containing monomer (a1').

[0033] The number of carbon atoms in the alkyl group of the monomer (a2') is preferably 1 to 24. From the viewpoint of adjusting the glass transition temperature (Tg) of the acrylic resin (A) within an appropriate range and making it easier to exhibit ink adhesion, the number of carbon atoms in the alkyl group is preferably 2 to 20. The alkyl group contained in the monomer (a2') may be a linear alkyl group or a branched alkyl group.

[0034] Examples of the monomer (a2') include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate. These monomers (a2') may be used singly or in combination of two or more.

[0035] In the acrylic copolymer (A2) containing the structural unit (a2), the content of the structural unit (a2) is preferably 1 to 99 mass%, more preferably 5 to 95 mass%, and even more preferably 10 to 90 mass%, based on the total amount of the acrylic copolymer (A2).

[0036] The acrylic resin (A1) and the acrylic copolymer (A2) may be an acrylic copolymer (A3) further having a structural unit (a3) ​​derived from a monomer (a3') other than the monomers (a1') and (a2').

[0037] Examples of the monomer (a3') include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene, and chloroprene; (meth)acrylates having a cyclic structure such as cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and imide (meth)acrylate; styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, and (meth)acrylonitrile.

[0038] In the acrylic copolymer (A3) containing the structural unit (a3), the content of the structural unit (a3) ​​is preferably 1 to 99 mass%, more preferably 5 to 95 mass%, and even more preferably 10 to 90 mass%, based on the total amount of the acrylic copolymer (A3).

[0039] The molecular weight of the acrylic resin (A) having a crosslinkable functional group is not particularly limited, but the number average molecular weight is preferably 3,000 to 100,000. The number average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) using a differential refractometer.

[0040] The hydroxyl value of the acrylic resin (A) having a crosslinkable functional group is preferably 5.0 mgKOH / g to 25.0 mgKOH / g, more preferably 6.0 mgKOH / g to 24.0 mgKOH / g, and even more preferably 7.0 mgKOH / g to 23.0 mgKOH / g. When the hydroxyl value of the acrylic resin (A) having a crosslinkable functional group is at least the above lower limit, ink adhesion is likely to be improved, and the stability of the latex ink-receiving layer is likely to be improved. When the hydroxyl value of the acrylic resin (A) having a crosslinkable functional group is the above upper limit or less, the stability of the coating liquid (solution containing the resin composition (x1)) used in forming the latex ink-receiving layer (X) is easily improved. In this specification, the hydroxyl value of the acrylic resin (A) having a crosslinkable functional group means a value measured in accordance with JIS K0070:1992.

[0041] The acid value of the acrylic resin (A) having a crosslinkable functional group is preferably 10.0 mgKOH / g or less, more preferably 1.0 mgKOH / g to 9.0 mgKOH / g, and even more preferably 2.0 mgKOH / g to 8.0 mgKOH / g. In this specification, the acid value of the acrylic resin (A) having a crosslinkable functional group means a value measured in accordance with JIS K0070:1992.

[0042] From the viewpoint of further improving ink adhesion, the glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group is preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower. In particular, when the glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group is lower than the curing temperature of the latex ink, ink adhesion is more likely to be improved. The glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group is usually 30°C or higher, preferably 40°C or higher, and more preferably 50°C or higher, from the viewpoint of further improving the sticking resistance. Here, "anti-sticking property" means "the property of suppressing sticking between the latex ink receiving layer (X) and the back surface of the substrate (Y) that occurs when the laminate is wound up in the process of forming the latex ink receiving layer (X) on the surface of the substrate (Y) and manufacturing the laminate of the substrate (Y) and the latex ink receiving layer (X)." In this specification, the glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group refers to a value measured in accordance with JIS K 7121:2012 using a differential scanning calorimeter (manufactured by TA Instruments Japan, product name "DSC Q2000") at a heating rate of 20°C / min.

[0043] (Crosslinking agent (B)) The resin composition (x1) used in the present invention contains a crosslinking agent (B). The crosslinking agent (B) contains an isocyanurate compound (B1). If the crosslinking agent (B) does not contain an isocyanurate compound (B1), the ink adhesion of the latex ink-receiving layer (X) cannot be improved. In the present invention, it is presumed that the use of a crosslinking agent (B) containing an isocyanurate compound (B1) results in a crosslinked structure formed by reaction with the acrylic resin (A) having a crosslinkable functional group, contributing to excellent ink adhesion. Furthermore, if the crosslinking agent (B) does not contain an isocyanurate compound (B1), it is also impossible to ensure adhesion between the latex ink-receiving layer (X) and the substrate (Y). It is presumed that the use of a crosslinking agent (B) containing an isocyanurate compound (B1) results in the formation of a latex ink-receiving layer (X) having a crosslinked structure that exhibits excellent adhesion to the substrate (Y), particularly to substrates (Y) containing polyester resins such as polyethylene terephthalate, due to the influence of the polar groups of the crosslinking agent (B).

[0044] In one embodiment of the present invention, the content of the isocyanurate compound (B1) is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass, based on the total amount of the crosslinking agent (B), from the viewpoint of further improving ink adhesion. The isocyanurate compound (B1) will be described in detail below.

[0045] (Isocyanurate Compound (B1)) In the present invention, the isocyanurate compound (B1) includes an isocyanurate compound (B1-1) and a modified product of the isocyanurate compound (B1-2). From the viewpoint of further improving ink adhesion, the total content of the isocyanurate compound (B1-1) and the modified isocyanurate compound (B1-2) in the isocyanurate compound (B1) is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and even more preferably 95% by mass to 100% by mass, based on the total amount of the isocyanurate compound (B1).

[0046] -Isocyanurate compound (B1-1)- The isocyanurate compound (B1) includes an isocyanurate compound (B1-1). The isocyanurate compound (B1-1) is a trimer of 1,6-hexamethylene diisocyanate, and specifically, is a compound of the following formula (1). [ka]

[0047] -Isocyanurate compound (B1-2)- The isocyanurate compound (B1) includes a modified product (B1-2) of an isocyanurate compound. The modified isocyanurate compound (B1-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups.

[0048] An example of a method for introducing one or more tertiary amino groups into the compound of formula (1) to form a modified product is to react the compound of formula (1) with a modifying agent having a hydroxyl group and a tertiary amino group. Examples of such denaturing agents include N,N-dimethylaminohexanol (e.g., Kao Corporation, Kao Raiser No. 25), N,N-dimethylaminoethoxyethoxyethanol (e.g., Kao Corporation, Kao Raiser No. 23NP), N,N-dimethylaminoethoxyethanol (e.g., Kao Corporation, Kao Raiser No. 26), N,N,N'-trimethylaminoethylethanolamine (e.g., Tosoh Corporation, TOYOCAT RX5), 2-[[3-(dimethylamino)propyl]methylamino]ethanol (e.g., Evónik, POLYCAT 17), and N,N-dimethylethanolamine (e.g., Huntsman, JEFFCAT DMEA). The modifier may have a ring structure, but is preferably a compound as described above that does not have a ring structure. The modifier is preferably an organic nonmetallic compound as described above that does not contain a metal element. That is, the modifier is preferably an acyclic organic nonmetallic compound that has a hydroxyl group and a tertiary amino group.

[0049] The reaction of the compound of formula (1) with the modifier is preferably carried out, for example, by placing the compound of formula (1) and the modifier in a nitrogen-substituted reaction vessel and stirring at a reaction temperature of 60°C to 100°C for 1 hour to 5 hours.

[0050] -Preparation of isocyanurate compound (B1)- The isocyanurate compound (B1) can be prepared, for example, by appropriately adjusting the ratio of the amounts of the compound of formula (1) and the modifier added to a reaction vessel when the compound of formula (1) and the modifier are reacted. The proportion of the modifier added to the compound of formula (1) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the compound of formula (1). As a result, only a portion of the many compounds of formula (1) have one or more tertiary amino groups, and an isocyanurate compound (B1) containing an isocyanurate compound (B1-1) and a modified product (B1-2) of the isocyanurate compound can be prepared. The content of the modified isocyanurate compound (B1-2) is preferably 0.5 mol % to 10 mol %, more preferably 1 mol % to 5 mol %, based on the total amount of the isocyanurate compound (B1).

[0051] (Content of crosslinking agent (B)) To more easily achieve the effects of the present invention, the content of the crosslinking agent (B) is preferably 3.0 parts by mass or more, more preferably 5.0 parts by mass or more, and even more preferably 7.0 parts by mass or more, relative to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group, and is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

[0052] (UV-curable acrylate compound (C)) The ultraviolet-curable acrylate compound (C) is a component that can be cured (polymerized) by irradiation with ultraviolet light. As the ultraviolet-curable acrylate compound (C), ultraviolet-curable monomers and oligomers are used. The compound (C) that is an oligomer has a mass average molecular weight (Mw) of less than 10,000. The ultraviolet-curable acrylate compound (C) may be used alone or in combination of two or more.

[0053] The ultraviolet-curable acrylate compound (C) may be a polymerizable acrylate compound having one or more ultraviolet-polymerizable groups in one molecule. The ultraviolet-polymerizable group may be one having an ultraviolet-polymerizable carbon-carbon double bond, and a (meth)acryloyl group is more preferred. The ultraviolet-curable acrylate compound (C) preferably has two or more ultraviolet-polymerizable groups (for example, (meth)acryloyl groups) in one molecule, and preferably has 2 to 6. Specific examples of the ultraviolet-curable acrylate compound (C) include (meth)acrylate monomers and (meth)acrylate oligomers.

[0054] Specific examples of the (meth)acrylate monomer include trimethylolpropane tri(meth)acrylate, tetramethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Specific examples of the (meth)acrylate oligomer include urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyethylene glycol di(meth)acrylate. Here, from the viewpoint of making it easier to improve abrasion resistance, a (meth)acrylate monomer is preferred, and from the viewpoint of making it easier to improve ink adhesion by smoothly progressing the crosslinking reaction between the acrylic resin (A) having a crosslinkable functional group and the crosslinking agent (B), a (meth)acrylate monomer not having a crosslinkable functional group that reacts with the crosslinking agent (B) is more preferred. Examples of the (meth)acrylate monomer that does not have a crosslinkable functional group that reacts with the crosslinking agent (B) include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate, and among these, dipentaerythritol hexaacrylate is preferred.

[0055] (Photopolymerization initiator (D)) As the photopolymerization initiator (D), any photopolymerization initiator generally used when curing the ultraviolet-curable acrylate compound (C) with ultraviolet light can be used as appropriate. Specific examples include 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, β-chloroanthraquinone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylzoyldiphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.

[0056] The content of the photopolymerization initiator (D) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass in total of the ultraviolet-curable acrylate compound (C) and the polymerizable tertiary amine (E).

[0057] (Polymerizable tertiary amine (E)) The resin composition (x1) used in the present invention contains a polymerizable tertiary amine (E). If the resin composition (x1) does not contain the polymerizable tertiary amine (E), the latex ink-receiving layer (X) cannot have excellent water-resistant ink adhesion. The resin composition (x1) used in the present invention contains a polymerizable tertiary amine (E), which allows the latex ink-receiving layer (X) to have excellent water-resistant ink adhesion. Moreover, even when the polymerizable tertiary amine (E) is blended, the ink adhesion and abrasion resistance of the latex ink-receiving layer (X) remain sufficiently excellent.

[0058] The polymerizable tertiary amine (E) may be a tertiary amine having one or more polymerizable groups in one molecule. Examples of the polymerizable group contained in the polymerizable tertiary amine (E) include a group having an ultraviolet-polymerizable carbon-carbon double bond, and a vinyl group or a (meth)acryloyl group is preferred.

[0059] Specific examples of the polymerizable tertiary amine (E) include N-vinyl-2-pyrrolidone, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, and (meth)acryloylmorpholine. These may be used alone or in combination of two or more.

[0060] The content of the polymerizable tertiary amine (E) is preferably 0.1 to 25 mass%, more preferably 1 to 20 mass%, and even more preferably 3 to 20 mass%, relative to 100 mass% of the total amount of the acrylic resin (A) having a crosslinkable functional group, the ultraviolet-curable acrylate compound (C), and the polymerizable tertiary amine (E).

[0061] (Total content of acrylic resin having crosslinkable functional group (A), ultraviolet-curable acrylate compound (C), and polymerizable tertiary amine (E)) In one embodiment of the present invention, the total content of the acrylic resin (A) having a crosslinkable functional group, the ultraviolet-curable acrylate compound (C), and the polymerizable tertiary amine (E) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more, based on the total content (100% by mass) of the acrylic resin (A) having a crosslinkable functional group, the crosslinking agent (B), the ultraviolet-curable acrylate compound (C), the photopolymerization initiator (D), and the polymerizable tertiary amine (E), from the viewpoint of more easily achieving the effects of the present invention. Also, it is preferably 97% by mass or less, more preferably 95% by mass or less.

[0062] (Content ratio of acrylic resin (A) having crosslinkable functional group and ultraviolet-curable acrylate compound (C)) In one embodiment of the present invention, the content ratio [(A) / (C)] of the acrylic resin (A) having a crosslinkable functional group to the ultraviolet-curable acrylate compound (C) is, in terms of mass ratio, preferably 0.3 to 3.5, more preferably 0.5 to 3.0, even more preferably 0.7 to 3.0, and still more preferably 1.0 to 3.0, from the viewpoint of forming a latex ink-receiving layer (X) that has excellent ink adhesion and abrasion resistance and that has even more excellent water-resistant ink adhesion.

[0063] <Base material (Y)> The film for latex ink of the present invention has a substrate (Y). The substrate (Y) supports the latex ink receiving layer (X) and also functions as a support for supporting the printed portion formed on the latex ink receiving layer (X).

[0064] The substrate (Y) is not particularly limited, but is preferably a resin film. The substrate (Y) being a resin film improves the rigidity and flexibility of the film for latex ink, improving the ease of handling of the film for latex ink. This is also advantageous from the viewpoint of reducing the production cost and weight of the film for latex ink.

[0065] Here, the substrate (Y) is preferably a transparent resin film. By using the substrate (Y) as a transparent resin film, a printed matter having a printed portion formed on the latex ink-receiving layer of the film for latex ink can be suitably used as glass decoration in stores, showrooms, offices, etc. Furthermore, when the substrate (Y) is a transparent resin film, the latex ink-receiving layer (X) also preferably has transparency. Specifically, the total light transmittance of the film for latex ink composed of the substrate (Y) and the latex ink-receiving layer (X) is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The total light transmittance refers to a value measured in accordance with JIS K7361-1:1997 using a haze meter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0066] Examples of resins that may be used to form the resin film include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polyethylene and polypropylene; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resins such as polyurethane and acrylic-modified polyurethane; polymethylpentene; polysulfone; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resins such as polyetherimide and polyimide; polyamide resins; acrylic resins; and fluorine-based resins. Among these, from the viewpoint of easily improving the adhesion between the latex ink receiving layer (X) and the substrate (Y), polyester-based resins and polyolefin-based resins are preferred, polyester-based resins are more preferred, and polyethylene terephthalate is even more preferred.

[0067] The resin film may be composed of only one type of resin, or may be composed of two or more types of resin. When the resin film is composed of two or more types of resin, it is preferably a multi-layered film. Furthermore, the uppermost layer of the multi-layered film (the layer in contact with the latex ink-receiving layer) is preferably a polyester resin, more preferably polyethylene terephthalate, from the viewpoint of easily improving the adhesion between the latex ink-receiving layer (X) and the substrate (Y).

[0068] The resin film may be unstretched or may be stretched uniaxially, such as longitudinally or transversely, or biaxially.

[0069] In addition, the resin film may contain, together with these resins, additives for the substrate, such as a surface conditioner, a plasticizer, an ultraviolet absorber, a light stabilizer, and a colorant. The content of the additive for the substrate is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the total amount of the substrate (Y).

[0070] The thickness of the substrate (Y) is not particularly limited, but is preferably 15 μm to 300 μm, more preferably 30 μm to 200 μm.

[0071] <Adhesive layer (Z)> The film for latex ink according to one embodiment of the present invention may have a pressure-sensitive adhesive layer (Z). The film for latex ink according to one embodiment of the present invention has the pressure-sensitive adhesive layer (Z), and therefore the film for latex ink can be suitably used as a pressure-sensitive adhesive film.

[0072] The adhesive constituting the adhesive layer is not particularly limited, and examples thereof include acrylic adhesives, urethane adhesives, and silicone adhesives.

[0073] The thickness of the adhesive layer (Z) is not particularly limited, but from the viewpoint of improving the handleability when using the film for latex ink as an adhesive film, it is preferably 5 μm to 100 μm, more preferably 10 μm to 70 μm, and even more preferably 15 μm to 50 μm.

[0074] <Release liner> The film for latex ink of one embodiment of the present invention may have a release liner together with the pressure-sensitive adhesive layer (Z). By covering the adhesive surface of the adhesive layer (Z) of one embodiment of the latex ink film of the present invention with a release liner, the adhesive surface of the adhesive layer (Z) can be suitably protected during transportation and storage of the latex ink film.

[0075] The release liner is not particularly limited, and any release liner commonly used in the field of pressure-sensitive adhesive films can be used as appropriate. Examples of release liners include laminates in which a release layer is provided on the surface of a film or paper substrate. Examples of the film substrate include polyester resins such as polyethylene terephthalate, and polyolefin resins such as polyethylene resin and polypropylene resin. Examples of the paper substrate include fine paper, kraft paper, and glassine paper. Examples of materials that can be used to form the release layer include silicone, long-chain alkyl resins, and fluorine-based resins.

[0076] The thickness of the release liner is not particularly limited, but is preferably 10 μm to 150 μm, more preferably 20 μm to 130 μm, and even more preferably 30 μm to 100 μm.

[0077] [Latex ink film manufacturing method] The method for producing the film for latex ink of the present invention is not particularly limited, and may be appropriately selected depending on the configuration of the film for latex ink.

[0078] <Method of forming latex ink receiving layer (X)> A preferred method for forming the latex ink receiving layer (X) is to apply the resin composition (x1) to one surface (Ya) of the substrate (Y) to form a coating film, dry the coating film, and then UV-cur and crosslink the coating film to form the latex ink receiving layer (X). In order to improve the workability of application to the substrate (Y), the resin composition (x1) is preferably further diluted with a dilution solvent to form a solution.

[0079] Examples of dilution solvents include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, and isopropanol. The concentration of the active ingredient in the solution of the resin composition (x1) is preferably 10 to 50% by mass.

[0080] Examples of methods for applying the solution of the resin composition (x1) include Mayer bar coating, gravure coating, roll coating, knife coating, and die coating.

[0081] After the resin composition (x1) is applied to one surface (Ya) of the substrate (Y) to form a coating film, the coating film is dried to remove the dilution solvent from the coating film (drying step). The heating conditions for drying the coating film are, for example, a drying temperature of 60°C to 120°C and a drying time of 30 seconds to 3 minutes.

[0082] After drying the coating film, the coating film is irradiated with ultraviolet light to cure (polymerize) the ultraviolet-curable acrylate compound (C) (ultraviolet light irradiation step). At this time, the polymerizable tertiary amine (E) is incorporated into the cured product of the ultraviolet-curable acrylate compound (C). The ultraviolet irradiation conditions are cumulative irradiation dose (cumulative light amount) of 5 to 1200 mJ / cm 2 is preferred, and 50 to 500 mJ / cm 2 is more preferred. The ultraviolet light can be irradiated using, for example, a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, an LED, or the like as an ultraviolet light source.

[0083] After the ultraviolet-curable acrylate compound (C) is cured (polymerized), the acrylic resin (A) having a crosslinkable functional group is reacted with the crosslinking agent (B) to form a crosslinked structure (crosslinking step). The crosslinking conditions are not particularly limited, and for example, the crosslinking may be carried out by leaving the composition in a normal environment (e.g., 23°C, relative humidity 50°C) for 1 to 14 days, or by leaving the composition in an environment of 40 to 60°C for 1 to 3 days.

[0084] The ultraviolet irradiation step may be performed before, during, or after the crosslinking step. The crosslinking step and the ultraviolet irradiation step may be performed simultaneously, or the crosslinking step and the ultraviolet irradiation step may each be performed multiple times. Furthermore, at least one of the ultraviolet irradiation step and the crosslinking step may be performed simultaneously with the drying step.

[0085] <Method for forming pressure-sensitive adhesive layer (Z)> When the film for latex ink of one embodiment of the present invention has an adhesive layer (Z), the adhesive layer (Z) is formed on the other surface (Yb) of the substrate (Y) on which the latex ink receiving layer (X) is not formed. The pressure-sensitive adhesive layer (Z) is formed, for example, by applying a composition for forming the pressure-sensitive adhesive layer (Z) (pressure-sensitive adhesive layer-forming composition) to the other surface (Yb) of the substrate (Y). Alternatively, the pressure-sensitive adhesive layer (Z) may be formed by applying the pressure-sensitive adhesive layer-forming composition to the release surface of a release liner, and then the pressure-sensitive adhesive layer (Z) may be laminated (transferred) to the other surface (Yb) of the substrate (Y). The method for applying the composition for forming a pressure-sensitive adhesive layer is the same as that described above for the resin composition (x1).

[0086] [Applications of latex ink film] The film for latex ink of the present invention is preferably used for printing using latex ink. Therefore, the present invention provides a method of using the latex ink-compatible film to form a printed portion on the latex ink-receiving layer of the latex ink-compatible film using latex ink. The present invention also provides a method for producing a printed matter, which includes a step of forming a printed portion on the latex ink-receiving layer of the film for latex ink using latex ink. Furthermore, according to the present invention, there is provided a printed matter having a printed portion printed with latex ink on the latex ink-receiving layer of the film for latex ink.

[0087] Below, we will explain the latex ink used to form a printed area on the latex ink-receiving layer of the latex ink film of the present invention, and then we will explain the method for forming a printed area on the latex ink-receiving layer of the latex ink film of the present invention.

[0088] <Latex ink> Latex ink contains a liquid dispersion medium and a dispersoid made of a material containing at least a resin, which is dispersed (emulsified and / or suspended) in the dispersion medium. Latex inks have a low environmental impact. Another advantage of latex inks is that they can produce deep colors with a thin layer. The latex particles that make up latex inks contain a binder (resin), which generally has the advantage of improving the adhesion of pigment colorants to recording media. Another advantage is that they can be printed on demand using the inkjet method. Furthermore, the latex ink is preferably a water-based ink, which is safer and places less strain on the environment because it suppresses the generation of volatile organic substances resulting from organic solvents.

[0089] (resin) The resin contained in the latex ink is not particularly limited, but examples thereof include vinyl resins, acrylic resins, styrene resins, alkyd resins, polyester resins, polyurethane resins, silicone resins, fluorine resins, epoxy resins, phenoxy resins, polyolefin resins, and modified resins thereof (e.g., modified resins modified to be water-soluble), and one or more selected from these may be used in combination. Among these, acrylic resins, styrene resins, water-soluble polyurethane resins, water-soluble polyester resins, and water-soluble acrylic resins are preferred, with acrylic resins being more preferred. The latex ink used in the film for latex ink of one embodiment of the present invention is preferably a latex ink containing an acrylic resin, from the viewpoint of further improving the adhesion between the latex ink-receiving layer (X) and the printed area. The content of the resin in the latex ink is preferably 1% by mass to 20% by mass, and more preferably 2% by mass to 10% by mass, based on the total amount of the latex ink.

[0090] (dispersion medium) Latex ink contains water as a dispersion medium. The content of the dispersion medium (water) in the latex ink is preferably 50% to 98% by mass, more preferably 60% to 97% by mass, and even more preferably 70% to 96% by mass, based on the total amount of the latex ink.

[0091] (coloring agent) Latex inks typically contain a colorant. As the colorant, various dyes, various pigments, etc. can be used. The content of the colorant in the latex ink is preferably 0.1% by mass to 20% by mass, and more preferably 0.2% by mass to 10% by mass, based on the total amount of the latex ink.

[0092] (Other ingredients) The latex ink may contain components other than those already described (other components). Examples of such components include dispersants, antifungals, anticorrosives, pH adjusters, surfactants, plasticizers, ultraviolet absorbers, and light stabilizers.

[0093] <Formation of the printing part> The printed portion using latex ink is formed by applying latex ink onto the latex ink-receiving layer (X) of the film for latex ink. From the viewpoint of further improving the adhesion between the latex ink-receiving layer (X) and the printed portion, the latex ink is preferably a latex ink containing an acrylic resin. The method for applying the latex ink is not particularly limited, and various printing methods can be used, but inkjet methods are preferred. Examples of inkjet methods include piezo methods and thermal jet methods. When applying the latex ink, the film for latex ink may be heated. The heating temperature is not particularly limited, but is preferably 40°C to 90°C. By the above method, a printed matter having a printed portion printed with latex ink on the latex ink-receiving layer (X) of the film for latex ink can be obtained. The latex ink is preferably a latex ink containing an acrylic resin, from the viewpoint of further improving adhesion between the latex ink-receiving layer (X) and the printed portion. [Example]

[0094] The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples.

[0095] [Methods for measuring various physical properties] The methods for measuring various physical properties in the examples are as follows. (1) Hydroxyl value The hydroxyl value of the acrylic resin (A) having a crosslinkable functional group was measured in accordance with JIS K0070:1992. (2) Acid value The acid value of the acrylic resin (A) having a crosslinkable functional group was measured in accordance with JIS K0070:1992. (3) Glass transition temperature (Tg) The glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group was measured in accordance with JIS K 7121:2012 using a differential scanning calorimeter (manufactured by TA Instruments Japan, product name "DSC Q2000") at a heating rate of 20°C / min. (4) Thickness of each layer The thickness of each layer was measured using a constant pressure thickness measuring instrument manufactured by Teclock Corporation (model number: "PG-02J", standard specifications: compliant with JIS K6783:1994, JIS Z1702:1994, and JIS Z1709:1995).

[0096] [Examples 1 to 6, Comparative Examples 1 to 4] Films for latex ink of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared by the following procedure.

[0097] <Preparation of Resin Composition> The resin composition was prepared using the following acrylic resin (A) having a crosslinkable functional group, crosslinking agent (B), ultraviolet-curable acrylate compound (C), photopolymerization initiator (D), and polymerizable tertiary amine (E).

[0098] (Acrylic resin (A) having crosslinkable functional groups) An acrylic resin having a crosslinkable functional group, a hydroxyl value of 11.0 mgKOH / g, an acid value of 3.9 mgKOH / g, and a glass transition temperature (Tg) of 90°C was used.

[0099] (Crosslinking agent (B)) "Isocyanurate compound (B1)": A partially modified product of an isocyanurate compound (corresponding to a crosslinking agent containing an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2)).

[0100] (UV-curable acrylate compound (C)) Dipentaerythritol hexaacrylate was used.

[0101] (Photopolymerization initiator (D)) 1-Hydroxycyclohexyl phenyl ketone was used.

[0102] (Polymerizable tertiary amine (E)) Polymerizable tertiary amine (E)-1: N-vinyl-2-pyrrolidone "Polymerizable tertiary amine (E)-2": N,N-dimethylmethacrylamide

[0103] (Other additives) "Catalyst": Tin-based catalyst

[0104] A polyethylene terephthalate sheet (thickness: 50 μm) with an easy-adhesion layer was prepared as the substrate (Y). Then, a coating liquid (active ingredient concentration: 10 mass%, diluent: ethyl acetate) of a resin composition prepared by adjusting the formulation (formulation amount calculated as active ingredient) shown in Table 1, which included an acrylic resin (A) having a crosslinkable functional group, a crosslinking agent (B), an ultraviolet-curable acrylate compound (C), a photopolymerization initiator (D), a polymerizable tertiary amine (E), and a catalyst, was applied to the easy-adhesion layer side of the substrate (Y) using a Mayer bar so that the film thickness after drying would be 1 μm. Next, the dilution solvent contained in the coating film formed by coating on the substrate (Y) is removed by heating at 90°C for 1 minute using a hot air dryer (drying step), and then ultraviolet light having a peak wavelength of 365 nm is applied at an integrated light intensity of 150 mJ / cm 2 The film was then irradiated with ultraviolet light (ultraviolet curing step), and then allowed to stand for 7 days in an environment of 23°C and a relative humidity of 50% to allow crosslinking (crosslinking step). As a result, a latex ink-receiving layer (X) with a thickness of 1 μm was formed, and films for latex ink of Examples 1 to 6 and Comparative Examples 1 to 4 were obtained. However, the film for latex ink of Comparative Example 1 was produced without carrying out the ultraviolet curing step.

[0105] <Rating 1> (1) Evaluation of ink adhesion For each of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, a predetermined test pattern was printed on the surface of the latex ink receiving layer (X) using latex ink (HP882, manufactured by Hewlett-Packard) by the inkjet method with an inkjet printer (HP Latex R2000, manufactured by Hewlett-Packard) to form a printed portion (printed layer). Then, the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, on which a printed portion of a predetermined test pattern was formed, were left to stand for one day in an environment of 23°C and a relative humidity of 50%, to prepare test samples. Then, a 100mm x 24mm piece of Nichiban Cellotape (registered trademark) was applied to the side of the test sample on which the printed area was formed, and the remaining rate of the printed area (remaining area / total area) after the tape was removed was determined and evaluated according to the following criteria. 1: Less than 20% remaining 2: Residual rate 20% to less than 40% 3: Residual rate 40% or more but less than 60% 4: Residual rate 60% to less than 90% 5: Survival rate 90% or more The higher the residual rate, the better the ink adhesion of the latex ink-receiving layer (X).

[0106] (2) Evaluation of ink water-resistant adhesion For each of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, a predetermined test pattern was printed in the same manner as in "(1) Evaluation of ink adhesion (Dry)" to form a printed portion (printed layer). Then, the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, on which a printed portion of a predetermined test pattern was formed, were left to stand for one day in an environment of 23°C and a relative humidity of 50%, to prepare test samples. Then, a 3% by mass aqueous solution of an anionic surfactant (sodium laureth sulfate) was sprayed onto the entire surface of the test sample on which the printed area was formed, and the sample was left to stand for 10 minutes.The entire surface on which the printed area was formed was then rubbed vigorously with a rubber squeegee to determine the remaining rate of the printed area (remaining area / total area), and evaluated according to the following criteria. 1: Less than 20% remaining 2: Residual rate 20% to less than 40% 3: Residual rate 40% or more but less than 60% 4: Residual rate 60% to less than 90% 5: Survival rate 90% or more The higher the remaining rate of the printed portion, the more excellent the water-resistant adhesion of the ink of the latex ink-receiving layer (X).

[0107] (3) Evaluation of abrasion resistance For each of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, the surface (unprinted) of the latex ink receiving layer (X) was wiped with #0000 steel wool at a rate of 250 g / cm 2 After rubbing the sample back and forth 10 times under a load, the degree of damage was checked and evaluated according to the following criteria. S: No scratches. A: Only a few scratches are visible. B: Although some scratches can be seen, the product can still be used. C: Many scratches occurred.

[0108] The results are shown in Table 1.

[0109] [Table 1]

[0110] From Table 1, we can see the following: It can be seen that the films for latex ink of Examples 1 to 6 have excellent ink adhesion and water-resistant ink adhesion, as well as excellent abrasion resistance. On the other hand, as in Comparative Example 1, a film for latex ink having a latex ink-receiving layer formed from a resin composition consisting of an acrylic resin (A) and a crosslinking agent (B) is excellent in ink adhesion and water-resistant ink adhesion, but is poor in abrasion resistance. Furthermore, as in Comparative Example 2, a film for latex ink having a latex ink-receiving layer formed from a resin composition containing an acrylic resin (A), a crosslinking agent (B), a photopolymerization initiator (D), and a polymerizable tertiary amine (E) was also found to have excellent ink adhesion and water-resistant ink adhesion, but poor abrasion resistance, similar to Comparative Example 1. Furthermore, as in Comparative Examples 3 and 4, films for latex inks having a latex ink-receiving layer formed from a resin composition consisting of an acrylic resin (A), a crosslinking agent (B), an ultraviolet-curable acrylate compound (C), and a photopolymerization initiator (D), but not containing a polymerizable tertiary amine (E), are excellent in ink adhesion and abrasion resistance, but are poor in water-resistant ink adhesion.

[0111] <Rating 2> (1) Evaluation of total light transmittance For each of the films for latex ink of Examples 1 to 6 and Comparative Examples 1 to 4, the total light transmittance was measured using a haze meter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361-1:1997. As a result, the total light transmittance of all of the films for latex ink of Examples 1 to 6 and Comparative Examples 1 to 4 was 92%. [Explanation of symbols]

[0112] 1 Latex ink film X Latex ink receiving layer Y base material Ya One side of the substrate The other side of the Yb substrate Z adhesive layer

Claims

1. a laminated structure in which a latex ink-receiving layer (X) and a substrate (Y) are laminated, the latex ink-receiving layer (X) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group, a crosslinking agent (B), an ultraviolet-curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary amine (E); The crosslinking agent (B) contains an isocyanurate compound (B1), The isocyanurate compound (B1) includes an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2), The isocyanurate compound (B1-1) is a trimer of 1,6-hexamethylene diisocyanate, The modified isocyanurate compound (B1-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups, and is a film for latex ink, the ultraviolet-curable acrylate compound (C) is a (meth)acrylate monomer that does not have a crosslinkable functional group that reacts with the crosslinking agent (B), A film for latex ink, wherein the polymerizable tertiary amine (E) has a group having an ultraviolet-polymerizable carbon-carbon double bond.

2. A film for latex ink as described in claim 1, wherein the (meth)acrylate monomer not having a crosslinkable functional group that reacts with the crosslinking agent (B) is one or more selected from the group consisting of trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

3. A film for latex ink as described in claim 1 or 2, wherein the polymerizable tertiary amine (E) is one or more selected from the group consisting of N-vinyl-2-pyrrolidone, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide and (meth)acryloylmorpholine.

4. The film for latex ink according to any one of claims 1 to 3, wherein the substrate (Y) contains a polyester-based resin.

5. the latex ink-receiving layer (X) is laminated on one surface of the substrate (Y); The film for latex ink according to any one of claims 1 to 4, wherein a pressure-sensitive adhesive layer (Z) is provided on the other surface of the substrate (Y).

6. 6. The film for latex ink according to claim 5, wherein the adhesive surface of the adhesive layer (Z) is covered with a release liner.

7. The film for latex ink according to any one of claims 1 to 6, which is used for printing using latex ink containing an acrylic resin.

8. A method for using the film for latex ink according to any one of claims 1 to 7 to form a printed portion on the latex ink-receiving layer of the film for latex ink using latex ink.

9. A method for producing a printed matter, comprising the step of forming a printed portion on the latex ink-receiving layer of the film for latex ink according to any one of claims 1 to 7 using latex ink.

10. A printed matter having a latex ink-printed portion on the latex ink-receiving layer of the film for latex ink according to any one of claims 1 to 7.

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