WO2023135711A1

WO2023135711A1 - Film for latex ink

Info

Publication number: WO2023135711A1
Application number: PCT/JP2022/000968
Authority: WO
Inventors: 鉄也荒添; 拓磨大久保; 枝保日野
Original assignee: リンテック株式会社
Priority date: 2022-01-13
Filing date: 2022-01-13
Publication date: 2023-07-20

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

Film for latex ink

The present invention relates to a film for latex ink.

In recent years, a printing method using latex ink has attracted attention (see, for example, Patent Document 1).
Latex ink is water-based ink in which pigment is dispersed in water together with latex (polymer), unlike solvent ink in which pigment is dissolved in an organic solvent. Therefore, since there is no emission of volatile organic substances (VOC) caused by organic solvents, which is a problem when using solvent ink, printed matter using latex ink is widely used in restaurants, educational institutions, medical institutions, and commercial establishments. There is an advantage that it can be used safely in various places such as facilities.

Based on these advantages, the applicant of the present application has proposed a film for latex ink in Patent Document 2. The film for latex ink described in Patent Document 2 includes a substrate and a printing coat layer to which latex ink is applied. The printing coat layer contains a material having a structure in which a polymeric material composed of vinyl chloride, vinyl acetate, and a cross-linking monomer is cross-linked with a cross-linking agent. As a result, the latex ink film has a printing coat layer with excellent adhesion to both the latex ink printed portion and the base material.

The "printing coat layer" in Patent Document 2 is referred to as the "latex ink receiving layer" in this specification. That is, the "latex ink receiving layer" is a portion to which the latex ink is applied, and means a layer having a function of fixing the printed portion by the applied latex ink.

JP 2016-120719 A JP 2019-172877 A

In recent years, the printing method using latex ink has been widely adopted, and various demands are increasing for the latex ink film used at that time. Specifically, from the viewpoint of preventing damage to the surface of the latex ink-receiving layer, the latex ink-receiving layer of the latex ink film may be required to have scratch resistance.

However, in order to ensure the adhesion of the latex ink-receiving layer to the printed portion of the latex ink (hereinafter also simply referred to as "ink adhesion"), the latex ink-receiving layer needs to be soft to some extent. be. As a result, the surface of the latex ink-receiving layer is easily scratched and has poor scratch resistance. For this reason, the "printing coat layer" in Patent Document 2 is also inferior in abrasion resistance. Thus, in the latex ink-receiving layer, there is a problem that it is difficult to achieve both ink adhesion and scratch resistance.

Films for latex ink are sometimes applied to glass surfaces of shops, showrooms, offices, etc., and used for advertisement and decoration purposes. When attaching the latex ink film to an adherend such as a glass surface, be careful not to allow air to enter between the latex ink film and the adherend. Alternatively, water or an aqueous solution containing a surfactant is sprayed onto the bonding surfaces of the adherends, and after the two are brought into close contact with each other and positioned, water, etc. is removed together with air from the latex ink film side using a squeegee. A so-called wet application, in which the adhesive is applied by scraping, is generally performed. At this time, an aqueous solution or the like is sometimes sprayed on the side of the latex ink-receiving layer, which is the side opposite to the adhesive layer, in order to increase the slipperiness of the squeegee.
Therefore, the latex-ink-receiving layer of the latex-ink film, which is applied with water, maintains the adhesion between the latex-ink-receiving layer and the printed portion of the latex ink even when it is rubbed with a squeegee while in contact with water. (In the following description, it is also referred to as “water-resistant adhesion of ink”).
However, a film for latex ink that has not only ink adhesion and scratch resistance but also water-resistant adhesion of ink has not yet been created.

The present invention has been made in view of such problems, and provides a film for latex ink having a latex ink-receiving layer that is excellent in both ink adhesion and abrasion resistance, and is also excellent in water-resistant adhesion of ink. The challenge is to

In this specification, the term "ink adhesion" refers to the relationship between the latex ink receiving layer and the printed area when the latex ink printed area formed on the latex ink receiving layer is not in contact with liquid water. means the adhesion of The quality is evaluated by, for example, an ink adhesion test in Examples described later.
In this specification, the term "water-resistant adhesion of the ink" refers to the degree of adhesion between the latex ink-receiving layer and the printing when the latex-ink-printed portion formed on the latex-ink-receiving layer is in contact with liquid water. It means the adhesion with the part. The quality is evaluated, for example, by a water-resistant adhesion test of ink in Examples described later.

As a result of intensive studies to solve the above problems, the present inventors have found that an acrylic resin having a crosslinkable functional group, a specific crosslinker, an ultraviolet curable acrylate compound, a photopolymerization initiator, and a polymerizable third The present inventors have found that a latex ink-receiving layer formed from a resin composition containing a group amine can solve the above problems. The inventors of the present invention have further conducted various studies based on such findings, and have completed the present invention.
That is, the present invention relates to the following [1] to [8].
[1] Having a laminated structure in which the latex ink-receiving layer (X) and the substrate (Y) are laminated,
The latex ink-receiving layer (X) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable Formed from a resin composition (x1) containing a tertiary amine (E),
The cross-linking 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,
A film for latex ink, wherein 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-based 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 the pressure-sensitive adhesive layer (Z) is provided on the other surface of the substrate (Y).
[4] The film for latex ink according to [3] above, 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], which is used for printing using latex ink containing acrylic resin.
[6] The film for latex ink is used to form 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. ,how to use.
[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 material having a latex ink printed portion on the latex ink receiving layer of the film for latex ink according to any one of [1] to [5] above.

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, and is also excellent in water-resistant adhesion of ink.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows one aspect|mode of the film for latex inks of this invention.

As used herein, the term “active ingredient” refers to a component excluding a diluent solvent such as water or an organic solvent among the components contained in the target composition.
Moreover, in this specification, "(meth)acrylic acid" indicates both "acrylic acid" and "methacrylic acid". Moreover, "(meth)acryloyl group" indicates both "acryloyl group" and "methacryloyl group".
In addition, in this specification, the lower limit and upper limit values described stepwise for preferred numerical ranges (for example, ranges of contents, etc.) can be independently combined. For example, from the statement "preferably 10 to 90, more preferably 30 to 60", combining "preferred lower limit (10)" and "more preferred upper limit (60)" to "10 to 60" can also
In addition, in this specification, numerical values in the examples are numerical values that can be used as upper limit values or lower limit values.

[Aspect 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 the latex ink-receiving layer (X) and the substrate (Y) are laminated.
The latex ink-receiving layer (X) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable third It is formed from a resin composition (x1) containing a class amine (E).
The cross-linking 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.

As a result of intensive studies, the present inventors have found "acrylic resin (A) having a crosslinkable functional group", "crosslinking agent (B) containing isocyanurate compound (B1)", "ultraviolet curable acrylate A latex ink-receiving layer formed from a resin composition (x1) containing a compound (C), a photoinitiator (D), and a polymerizable tertiary amine (E) has good ink adhesion. The present inventors have found that the ink is excellent in both abrasion resistance and abrasion resistance, and is also excellent in water-resistant adhesion of the ink.

Hereinafter, regarding the film for latex ink of the present invention, the structure of the film for latex ink, the members constituting the film for latex ink (base material, latex ink receiving layer, adhesive layer, and release liner), and the production of the film for latex ink The method and application of the film for latex inks are described in detail.

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

FIG. 1 shows a schematic cross-sectional view of one embodiment of the film for latex ink of the present invention. The latex ink film 1 shown in FIG. 1 has a laminated structure in which a latex ink receiving layer (X) is laminated on one surface (Ya) of a substrate (Y).
Here, as shown in FIG. 1, the film for latex ink of one embodiment of the present invention preferably has an adhesive layer (Z) provided on the other surface (Yb) of the substrate (Y). Thereby, the film for latex ink can be suitably used as an adhesive film.

Although not shown, the adhesive surface of the adhesive layer (Z) may be covered with a release liner. Then, the release liner may be peeled off at the time of sticking to the adherend to expose the adhesive surface of the adhesive layer (Z).
In addition, although not shown, latex ink-receiving layers (X) are provided on both one surface (Ya) and the other surface (Yb) of the substrate (Y) without providing an adhesive layer (Z). may have been
Although not shown, another layer may be provided between the latex ink receiving layer (X) and the substrate (Y). Examples of the other layer include an easy-adhesion layer.

[Members Constituting Latex Ink Film]
The film for latex ink of the present invention has a latex ink-receiving layer (X) and a substrate (Y).
Further, as described above, the latex ink film of one embodiment of the present invention may further have an adhesive layer (Z) in addition to the latex ink receiving layer (X) and the substrate (Y). good. In addition to the latex ink-receiving layer (X) and substrate (Y), the adhesive layer (Z) and release liner may also be provided.
The latex ink-receiving layer (X), substrate (Y), pressure-sensitive adhesive layer (Z), and release liner are described in detail below.

<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 a portion to which latex ink is applied, and has a function of fixing the printed portion by the applied latex ink.
Although the thickness of the latex ink-receiving layer (X) is not particularly limited, it is preferably 0.05 μm to 50 μm, more preferably 0.1 μm to 25 μm, still more preferably 0.1 μm to 10 μm.

The latex ink-receiving layer (X) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable third It is formed from a resin composition (x1) containing a class amine (E).
The resin composition (x1) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary By forming from the resin composition (x1) containing the amine (E), the crosslinked structure formed by the reaction between the acrylic resin (A) having a crosslinkable functional group and the crosslinking agent (B), and the ultraviolet light A polymer structure formed by the curable acrylate compound (C) and the photopolymerization initiator (D) is mixed on the surface of the latex ink-receiving layer (X). Therefore, it is presumed that both ink adhesion and abrasion resistance are excellent.
In addition, the polymerizable tertiary amine (E) is incorporated into the polymer structure formed by the UV-curable acrylate compound (C) and the photopolymerization initiator (D) to form a polymerizable tertiary It is presumed that the amine (E) interacts with the latex ink to form a latex ink-receiving layer (X) that is also excellent in water-resistant adhesion of the ink.

In the following description, "acrylic resin (A) having a crosslinkable functional group", "crosslinking agent (B)", "ultraviolet curable acrylate compound (C)", "photopolymerization initiator (D)", and "Polymerizable tertiary amine (E)" is also referred to as "Component (A)", "Component (B)", "Component (C)", "Component (D)", and "Component (E)" respectively. say.

In one aspect of the present invention, the resin composition (x1), which is the material for forming the latex ink-receiving layer (X), comprises component (A), component (B), component (C), component (D), and component ( E) may be composed only, but within the range that does not impair the effects of the present invention, along with component (A), component (B), component (C), component (D), and component (E), component Components other than (A), component (B), component (C), component (D), and component (E) may be contained. Examples of such other components include additives for ink-receiving layers generally used in ink-receiving layers such as latex ink-receiving layers, such as reaction accelerators (catalysts), surface modifiers, plasticizers, fillers, and coloring agents.

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

Hereinafter, the resin composition (x1) contains an acrylic resin having a crosslinkable functional group (A), a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and polymerization The functional tertiary amine (E) will be explained in detail.

(Acrylic resin (A) having a crosslinkable functional group)
The resin composition (x1) used in the present invention contains an acrylic resin (A) having a crosslinkable functional group.
As the acrylic resin (A) having a crosslinkable functional group, an acrylic resin ( A1) is preferred.

Examples of the crosslinkable functional group possessed by the monomer (a1′) include one or more selected from a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and the like.
That is, examples of the monomer (a1′) include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers. Also included are monomers containing two or more crosslinkable functional groups selected from a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and the like.
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 preferable as the monomer (a1′).

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

Carboxy group-containing monomers include, for example, (meth)acrylic acid; acid anhydrides such as one or more aliphatic dicarboxylic acids selected from succinic anhydride, glutaric anhydride, etc., for the terminal hydroxyl group of the hydroxyl group-containing monomer described above; Examples include compounds obtained by reacting with substances.

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

The number of carbon atoms in the alkyl group of the monomer (a2') is preferably 1-24. The number of carbon atoms in the alkyl group is preferably 2 to 20 from the viewpoint of adjusting the glass transition temperature (Tg) of the acrylic resin (A) to an appropriate range so that the ink adhesion can be exhibited more easily.
The alkyl group possessed by the monomer (a2') may be a straight-chain alkyl group or a branched-chain alkyl group.

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 etc.
These monomers (a2') may be used singly or in combination of two or more.

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

The acrylic resin (A1) and the acrylic copolymer (A2) are acrylic copolymers further having a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2'). It may be a polymer (A3).

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; Cyclic acrylates such as acrylates, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and imido (meth)acrylate Structured (meth)acrylates; styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, and (meth)acrylonitrile.

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

Although the molecular weight of the acrylic resin (A) having a crosslinkable functional group is not particularly limited, it preferably has a number average molecular weight of 3,000 to 100,000.
In addition, the said number average molecular weight is a polystyrene conversion value by the gel permeation chromatography (GPC) measurement using a differential refractometer detection.

Here, 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 further It is 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, it is easy to improve ink adhesion. In addition, it is easy to improve the stability of the latex ink-receiving layer.
When the hydroxyl value of the acrylic resin (A) having a crosslinkable functional group is equal to or less than the above upper limit, the coating liquid used for forming the latex ink-receiving layer (X) (solution containing the resin composition (x1) ) to improve stability.
In addition, in this specification, the hydroxyl value of acrylic resin (A) which has a crosslinkable functional group means the value measured based on JISK0070:1992.

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, still more preferably 2.0 mgKOH/g to 8.0 mg KOH/g.
In addition, in this specification, the acid value of acrylic resin (A) which has a crosslinkable functional group means the value measured based on JISK0070:1992.

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., from the viewpoint of making it easier to improve ink adhesion. ℃ or less. 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, the ink adhesion can be further improved.
Further, 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, more preferably 40° C. or higher, from the viewpoint of making it easier to improve sticking resistance. 50°C or higher.
Here, the term "sticking resistance" means that "a laminate of the substrate (Y) and the latex ink-receiving layer (X) is formed by forming the latex ink-receiving layer (X) on the surface of the substrate (Y). It means the property of suppressing sticking between the latex ink-receiving layer (X) and the back surface of the substrate (Y), which occurs when the laminate is wound during the manufacturing process.
In the present specification, the glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group is based on JIS K 7121:2012 and measured by a differential scanning calorimeter (T.A. Instruments, Inc.). Japan Co., Ltd., product name “DSC Q2000”), and means a value measured at a temperature increase rate of 20° C./min.

(Crosslinking agent (B))
The resin composition (x1) used in the present invention contains a cross-linking agent (B).
The cross-linking agent (B) contains an isocyanurate compound (B1).
If the cross-linking agent (B) does not contain the isocyanurate compound (B1), the latex ink-receiving layer (X) cannot have good ink adhesion. In the present invention, by using the cross-linking agent (B) containing the isocyanurate-based compound (B1), the cross-linked structure formed by the reaction with the acrylic resin (A) having a cross-linkable functional group contributes to the ink adhesion. It is presumed that this contributes to the excellent ink adhesion. Moreover, when the cross-linking agent (B) does not contain the isocyanurate compound (B1), the adhesion between the latex ink-receiving layer (X) and the substrate (Y) cannot be ensured. By using the cross-linking agent (B) containing the isocyanurate compound (B1), the adhesion of the latex ink-receiving layer (X) to the substrate (Y) is improved by the influence of the polar group of the cross-linking agent (B). In particular, it is presumed that the latex ink receiving layer (X) having a crosslinked structure with excellent adhesion to the substrate (Y) containing a polyester resin such as polyethylene terephthalate is formed.

In one aspect of the present invention, the content of the isocyanurate compound (B1) is preferably 50% by mass to 100% by mass based on the total amount of the cross-linking agent (B) from the viewpoint of facilitating the improvement of ink adhesion. , more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
The isocyanurate compound (B1) will be described in detail below.

(Isocyanurate compound (B1))
In the present invention, the isocyanurate compound (B1) includes an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2).
The total content of the isocyanurate compound (B1-1) and the modified isocyanurate compound (B1-2) in the isocyanurate compound (B1) is the isocyanurate compound from the viewpoint of making it easier to improve ink adhesion. Based on the total amount of compound (B1), it is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and still more preferably 95% by mass to 100% by mass.

-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, specifically a compound of the following formula (1).

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

The method of introducing one or more tertiary amino groups into the compound of formula (1) to obtain a modified product includes, for example, a modifier having a hydroxyl group and a tertiary amino group, and the compound of formula (1). Methods of reacting are included.
Such modifiers include, for example, N,N-dimethylaminohexanol (eg, Kao Riser No. 25, manufactured by Kao Corporation), N,N-dimethylaminoethoxyethoxyethanol (eg, Kao Corporation, manufactured by Kao Corporation). Riser No. 23NP), N,N-dimethylaminoethoxyethanol (for example, Kao Riser No. 26, manufactured by Kao Corporation), N,N,N'-trimethylaminoethylethanolamine (for example, manufactured by Tosoh Corporation, TOYOCAT RX5), 2-[[3-(dimethylamino)propyl]methylamino]ethanol (eg POLYCAT 17 manufactured by Evonik), N,N-dimethylethanolamine (eg JEFFCAT DMEA manufactured by Huntsman) and the like. be done.
The modifier may have a ring structure, but is preferably a compound as described above that does not have a ring structure. Also, the modifier is preferably an organic non-metallic compound as described above, which does not contain a metal element. That is, the modifier is preferably an acyclic organic nonmetallic compound having a hydroxyl group and a tertiary amino group.

The reaction of the compound of the formula (1) and the modifier can be carried out, for example, by charging the compound of the formula (1) and the modifier into a nitrogen-substituted reaction vessel, and carrying out the reaction at a reaction temperature of 60°C to 100°C. It is preferable to carry out by stirring for 1 hour to 5 hours.

-Preparation of isocyanurate compound (B1)-
The isocyanurate-based compound (B1) is, for example, the amount of the compound of the formula (1) and the modifier put into the reaction vessel when performing the reaction of the compound of the formula (1) and the modifier. It can be prepared by appropriately adjusting the ratio.
The ratio of the modifier added to the compound of formula (1) is preferably 0.01 to 10 parts by mass, preferably 0.05, per 100 parts by mass of the compound of formula (1). It is more preferably from 1 part by mass to 5 parts by mass. As a result, only some of the compounds of the above formula (1) are compounds having one or more tertiary amino groups, so the isocyanurate compound (B1-1) and the modified isocyanurate compound An isocyanurate compound (B1) containing (B1-2) 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). in mol %.

(Content of cross-linking agent (B))
The content of the cross-linking agent (B) is preferably 3.0 parts by mass or more with respect to 100 parts by mass of the acrylic resin (A) having a cross-linkable functional group, from the viewpoint of making it easier to exhibit the effects of the present invention. It is more preferably 5.0 parts by mass or more, still more preferably 7.0 parts by mass or more. Also, it 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.

(Ultraviolet curable acrylate compound (C))
The UV-curable acrylate compound (C) is a component that can be cured (polymerized) by UV irradiation. UV-curable monomers and oligomers are used as the UV-curable acrylate compound (C). Compound (C), which is an oligomer, has a mass average molecular weight (Mw) of less than 10,000.
One of the ultraviolet-curable acrylate compounds (C) may be used alone, or two or more thereof may be used in combination.

Examples of the UV-curable acrylate compound (C) include polymerizable acrylate compounds having one or more UV-polymerizable groups in one molecule. Examples of the UV-polymerizable group include those having a UV-polymerizable carbon-carbon double bond, and a (meth)acryloyl group is more preferred.
The UV-curable acrylate compound (C) preferably has two or more UV-polymerizable groups (eg, (meth)acryloyl groups) in one molecule, preferably two to six. Further, specific examples of the ultraviolet curable acrylate compound (C) include (meth)acrylate monomers and (meth)acrylate oligomers.

Specific examples of (meth)acrylate monomers 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, 1,6-hexanediol di(meth)acrylate and the like.
Specific examples of (meth)acrylate oligomers 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 scratch resistance, a (meth)acrylate monomer is preferable, and the cross-linking reaction between the acrylic resin (A) having a cross-linkable functional group and the cross-linking agent (B) proceeds favorably. A (meth)acrylate monomer that does not have a crosslinkable functional group that reacts with the crosslinker (B) is more preferable from the viewpoint of making it easier to improve the ink adhesion.
(Meth)acrylate monomers having no crosslinkable functional group that reacts with the crosslinker (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, among which dipentaerythritol hexaacrylate is preferred.

(Photoinitiator (D))
As the photopolymerization initiator (D), a photopolymerization initiator generally used for curing the ultraviolet-curable acrylate compound (C) with ultraviolet rays can be appropriately used.
Specifically, 1-hydroxycyclohexylphenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, β -chloranthraquinone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl- pentylphosphine oxide and the like.

The content of the photopolymerization initiator (D) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the UV-curable acrylate compound (C) and the polymerizable tertiary amine (E). .

(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 ink water-resistant adhesion.
By containing the polymerizable tertiary amine (E), the resin composition (x1) used in the present invention can improve the water-resistant adhesion of the ink of the latex ink-receiving layer (X). Moreover, even when the polymerizable tertiary amine (E) is incorporated, the latex ink-receiving layer (X) maintains sufficiently excellent ink adhesion and abrasion resistance.

Examples of the polymerizable tertiary amine (E) include tertiary amines having one or more polymerizable groups in one molecule.
The polymerizable group possessed by the polymerizable tertiary amine (E) includes, for example, a group having a UV-polymerizable carbon-carbon double bond, preferably a vinyl group or a (meth)acryloyl group.

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, (meth)acryloylmorpholine and the like.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

(Total content of acrylic resin (A) having a crosslinkable functional group, UV-curable acrylate compound (C), and polymerizable tertiary amine (E))
In one aspect of the present invention, the total content of the acrylic resin (A) having a crosslinkable functional group, the UV-curable acrylate compound (C), and the polymerizable tertiary amine (E) is the effect of the present invention. From the viewpoint of making it easier to exhibit, an acrylic resin having a crosslinkable functional group (A), a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary It is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more relative to the total content (100% by mass) of the amine (E). Also, it is preferably 97% by mass or less, more preferably 95% by mass or less.

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

<Base material (Y)>
The film for latex ink of the present invention has a substrate (Y).
The base material (Y) supports the latex ink-receiving layer (X) and has a function as a support that supports the printed portion formed on the latex ink-receiving layer (X).

Although the base material (Y) is not particularly limited, it is preferably a resin film. By using a resin film as the substrate (Y), the rigidity and flexibility of the film for latex ink can be improved, and the handleability of the film for latex ink can be improved. It is also advantageous from the viewpoint of reducing the production cost and weight of the film for latex ink.

Here, the substrate (Y) is preferably a transparent resin film. Since the base material (Y) is a resin film having transparency, the printed material in which the printed part is formed on the latex ink receiving layer of the latex ink film can be used as glass decoration for shops, showrooms, offices, etc. etc. can be suitably used.
Moreover, when the base material (Y) is a transparent resin film, the latex ink-receiving layer (X) is also preferably transparent. Specifically, the total light transmittance of the latex ink film composed of the substrate (Y) and the latex ink-receiving layer (X) is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.
The total light transmittance means a value measured according to JIS K7361-1:1997 using a haze meter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

Examples of the resin constituting 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; ; Polycarbonate; Urethane resin such as polyurethane and acrylic-modified polyurethane; Polymethylpentene; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; system resin and the like.
Among these, polyester-based resins and polyolefin-based resins are preferable, and polyester-based resins are more preferable, from the viewpoint of easily improving the adhesion between the latex ink-receiving layer (X) and the substrate (Y). It is preferably polyethylene terephthalate, more preferably polyethylene terephthalate.

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 resins, it is preferred that the resin film is a multilayer body. In addition, the uppermost layer of the multilayer body (the layer in contact with the latex ink-receiving layer) is made of a polyester-based resin from the viewpoint of facilitating the improvement of the adhesion between the latex ink-receiving layer (X) and the substrate (Y). is preferred, and polyethylene terephthalate is more preferred.

In addition, the resin film may be unstretched, or may be stretched in a uniaxial direction such as longitudinally or laterally or in a biaxial direction.

In addition, the resin film may contain substrate additives such as surface conditioners, plasticizers, UV absorbers, light stabilizers, and colorants along with these resins.
The content of the base material additive 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 base material (Y).

Although the thickness of the substrate (Y) is not particularly limited, it is preferably 15 μm to 300 μm, more preferably 30 μm to 200 μm.

<Adhesive layer (Z)>
The film for latex ink of one embodiment of the present invention may have an adhesive layer (Z).
Since the film for latex ink of one embodiment of the present invention has the pressure-sensitive adhesive layer (Z), the film for latex ink can be suitably used as a pressure-sensitive adhesive film.

The adhesive that constitutes the adhesive layer is not particularly limited, and examples thereof include acrylic adhesives, urethane adhesives, and silicone adhesives.

Although the thickness of the pressure-sensitive adhesive layer (Z) is not particularly limited, it is preferably 5 μm to 100 μm, more preferably 10 μm to 70 μm, and more preferably 10 μm to 70 μm, from the viewpoint of improving handleability when using the film for latex ink as an adhesive film. It is preferably 15 μm to 50 μm.

<Release liner>
The film for latex ink of one embodiment of the present invention may have a release liner together with the adhesive layer (Z).
Since the adhesive surface of the adhesive layer (Z) included in the film for latex ink of one embodiment of the present invention is covered with a release liner, the adhesive layer (Z) can be removed during transportation or storage of the film for latex ink. The adhesive surface can be suitably protected.

The release liner is not particularly limited, and any release liner commonly used in the field of adhesive films can be used as appropriate. The release liner includes, for example, a laminate in which a release layer is provided on the surface of a film substrate or a paper substrate.
Examples of film substrates include polyester resins such as polyethylene terephthalate, and polyolefin resins such as polyethylene resins and polypropylene resins.
Examples of paper substrates include papers such as woodfree paper, kraft paper, and glassine paper.
Materials constituting the release layer include, for example, silicone, long-chain alkyl-based resins, and fluorine-based resins.

Although the thickness of the release liner is not particularly limited, it is preferably 10 μm to 150 μm, more preferably 20 μm to 130 μm, still more preferably 30 μm to 100 μm.

[Manufacturing method of film for latex ink]
The method for producing the film for latex ink of the present invention is not particularly limited, and is appropriately selected depending on the structure of the film for latex ink.

<Method for Forming Latex Ink Receiving Layer (X)>
As a method for forming the latex ink-receiving layer (X), the resin composition (x1) was applied to one surface (Ya) of the substrate (Y) to form a coating film, and the coating film was dried. After that, it is preferable to form the latex ink receiving layer (X) by UV curing and cross-linking.
In addition, in order to improve workability of application to the substrate (Y), it is preferable to further dilute the resin composition (x1) with a diluting solvent to form a solution.

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

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

After forming a coating film by applying the resin composition (x1) to one surface (Ya) of the substrate (Y), the coating film is dried to remove the diluent 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.

After the coating film is dried, it is irradiated with ultraviolet rays to cure (polymerize) the ultraviolet-curable acrylate compound (C) (ultraviolet irradiation step). At that time, the polymerizable tertiary amine (E) is incorporated into the cured product of the UV-curable acrylate compound (C).
The irradiation conditions of the ultraviolet rays are preferably 5 to 1200 mJ/cm ² , more preferably 50 to 500 mJ/cm ² in terms of cumulative irradiation amount (accumulated amount of light).
Ultraviolet rays can be applied by using, for example, a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, an LED, or the like as an ultraviolet light source.

After curing (polymerizing) the UV-curable acrylate compound (C), the acrylic resin (A) having a crosslinkable functional group is reacted with the crosslinker (B) to form a crosslinked structure (crosslinking step). .
The crosslinking conditions are not particularly limited. For example, crosslinking may be performed by standing in a normal environment (eg, 23° C., relative humidity of 50° C.) for 1 to 14 days, or in an environment of 40° C. to 60° C. It may be allowed to stand for 3 days to 3 days for cross-linking.

The ultraviolet irradiation process may be performed at any timing before the cross-linking process, during the cross-linking process, or after the cross-linking process. Moreover, the cross-linking step and the ultraviolet irradiation step may be performed simultaneously, or the cross-linking step and the ultraviolet irradiation step may be performed in multiple steps. Furthermore, at least one of the ultraviolet irradiation step and the cross-linking step may be performed simultaneously with the drying step.

<Method for Forming Adhesive Layer (Z)>
When the film for latex ink of one embodiment of the present invention has the adhesive layer (Z), the adhesive layer (Z) is formed on the other side of the substrate (Y) on which the latex ink-receiving layer (X) is not formed. It is formed on the plane (Yb).
The adhesive layer (Z) is formed, for example, by applying a composition for forming the adhesive layer (Z) (composition for forming an adhesive layer) to the other surface (Yb) of the substrate (Y). Formed by Alternatively, a composition for forming an adhesive layer is applied to the release surface of the release liner to form an adhesive layer (Z), which is laminated (transferred) to the other surface (Yb) of the substrate (Y). You may do so.
The method of applying the pressure-sensitive adhesive layer-forming composition is the same as that described above for the resin composition (x1).

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

Hereinafter, the latex ink for forming the printed portion on the latex ink-receiving layer of the film for latex ink of the present invention will be described, and then the printed portion will be formed on the latex ink-receiving layer of the film for latex ink of the present invention. I will explain how.

<Latex ink>
Latex ink contains a liquid dispersion medium and dispersoids composed of at least a resin-containing material dispersed (emulsified and/or suspended) in the dispersion medium.
Latex inks have a low environmental impact. Latex ink also has the advantage of being able to express dark colors with a thin layer. In addition, the latex particles that constitute the latex ink contain a binder (resin) and are generally advantageous in improving the adhesion of the pigment colorant to the recording medium. In addition, since the inkjet method can be used, there is an advantage that printing can be performed on demand.
Also, the latex ink is preferably a water-based ink. Water-based inks suppress the generation of volatile organic substances resulting from organic solvents, and are therefore safer and less burdensome to the environment.

(resin)
The resin contained in the latex ink is not particularly limited, but examples include vinyl resins, acrylic resins, styrene resins, alkyd resins, polyester resins, polyurethane resins, silicone resins, fluorine resins, and epoxy resins. , phenoxy-based resins, polyolefin-based resins, etc., and modified resins thereof (e.g., modified resins modified to be water-soluble), etc., and can be used alone or in combination of two or more selected from these. . Among these, acrylic resins, styrene resins, water-soluble polyurethane resins, water-soluble polyester resins, and water-soluble acrylic resins are preferable, and acrylic resins are more preferable.
The latex ink used in the latex ink film 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 portion. .
The resin content in the latex ink is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 10% by mass, based on the total amount of the latex ink.

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

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

(other ingredients)
The latex ink may contain components (other components) other than those already described.
Examples of such components include dispersants, antifungal agents, antirust agents, pH adjusters, surfactants, plasticizers, ultraviolet absorbers, light stabilizers, and the like.

<Formation of printing part>
The latex ink printed portion is formed by applying the latex ink onto the latex ink receiving layer (X) of the latex ink film. The latex ink 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 portion.
The method of applying the latex ink is not particularly limited, and various printing methods can be used, but an inkjet method is preferred. Examples of inkjet methods include a piezo method and a thermal jet method.
The latex ink film may be heated when the latex ink is applied. Although the heating temperature is not particularly limited, it is preferably 40°C to 90°C.
By the above method, a printed matter having a latex ink printed portion 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 the adhesion between the latex ink receiving layer (X) and the printed portion.

The present invention will be specifically described by the following examples, but the present invention is not limited to the following examples.

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

[Examples 1 to 6, Comparative Examples 1 to 4]
Latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4 were produced by the following procedure.

<Preparation of resin composition>
For the preparation of the resin composition, an acrylic resin (A) having a crosslinkable functional group shown below, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable A tertiary amine (E) was used.

(Acrylic resin (A) having a crosslinkable functional group)
An acrylic resin having a crosslinkable functional group having 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.

(Crosslinking agent (B))
- "Isocyanurate compound (B1)": a partially modified isocyanurate compound (corresponding to a cross-linking agent containing an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2).)

(Ultraviolet curable acrylate compound (C))
Dipentaerythritol hexaacrylate was used.

(Photoinitiator (D))
1-hydroxycyclohexyl phenyl ketone was used.

(Polymerizable tertiary amine (E))
・ “Polymerizable tertiary amine (E) -1”: N-vinyl-2-pyrrolidone ・ “Polymerizable tertiary amine (E) -2”: N,N-dimethylmethacrylamide

(Other additives)
・"Catalyst": Tin-based catalyst

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

<Evaluation 1>
(1) Evaluation of Ink Adhesion For each of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, latex ink (HP882, manufactured by Hewlett-Packard) was applied to the surface of the latex ink receiving layer (X). A predetermined test pattern was printed by an inkjet method using 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 the printed portion of the predetermined test pattern was formed were allowed to stand in an environment of 23° C. and a relative humidity of 50% for 1 day. , prepared the test samples.
Then, a 100 mm × 24 mm cellotape (registered trademark) manufactured by Nichiban Co., Ltd. was attached to the surface of the test sample on which the printed part was formed, and the residual rate of the printed part after peeling off the tape (remaining area / total area) was measured. and evaluated according to the following criteria.
1: Residual rate less than 20% 2: Residual rate 20% or more and less than 40% 3: Residual rate 40% or more and less than 60% 4: Residual rate 60% or more and less than 90% 5: Residual rate 90% or more The higher the residual rate, The latex ink-receiving layer (X) has excellent ink adhesion.

(2) Evaluation of water-resistant adhesion of ink For each of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, the same method as in "(1) Evaluation of ink adhesion (Dry)" was printed 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 the printed portion of the predetermined test pattern was formed were allowed to stand in an environment of 23° C. and a relative humidity of 50% for 1 day. A test sample was prepared.
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 portion was formed, and then left to stand for 10 minutes to form a printed portion. The entire surface of the side surface was strongly rubbed with a rubber squeegee to determine the residual ratio of the printed area (remaining area/total area) and evaluated according to the following criteria.
1: Residual rate less than 20% 2: Residual rate 20% or more and less than 40% 3: Residual rate 40% or more and less than 60% 4: Residual rate 60% or more and less than 90% 5: Residual rate 90% or more The higher it is, the better the latex ink-receiving layer (X) is in the water-resistant adhesion of the ink.

(3) Evaluation of scratch 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 coated with #0000 steel wool. , and 10 reciprocating rubbings under a load of 250 g/cm ² , the degree of damage was checked and evaluated according to the following criteria.
S: No damage.
A: Scratches are seen only slightly.
B: Usable as a product although scratches are observed.
C: Many scratches occurred.

The results are shown in Table 1.

Table 1 shows the following.
It can be seen that the films for latex inks of Examples 1 to 6 are excellent in ink adhesion, water-resistant adhesion of ink, and 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 cross-linking agent (B) has excellent ink adhesion and ink water-resistant adhesion. It can be seen that the abrasion resistance is inferior although the abrasion resistance is excellent.
Further, as in Comparative Example 2, the acrylic resin (A), the cross-linking agent (B), and the photopolymerization initiator (D) are formed from a resin composition containing a polymerizable tertiary amine (E). Similarly to Comparative Example 1, the film for latex ink having a latex ink-receiving layer is also excellent in ink adhesion and water-resistant adhesion of ink, but inferior in abrasion resistance.
Further, as in Comparative Examples 3 and 4, an acrylic resin (A), a cross-linking agent (B), an ultraviolet-curable acrylate compound (C), and a photopolymerization initiator (D) are composed of a polymerizable tertiary amine. It can be seen that the latex ink film having a latex ink-receiving layer formed from a resin composition containing no (E) is excellent in ink adhesion and scratch resistance, but is inferior in ink water-resistant adhesion.

<Evaluation 2>
(1) Evaluation of total light transmittance For each of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-5000) was used to measure JIS K7361- 1:1997, the total light transmittance was measured.
As a result, all of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4 had a total light transmittance of 92%.

1 Latex ink film X Latex ink receiving layer Y Base material Ya One side of base material Yb The other side of base material Z Adhesive layer

Claims

Having a laminated structure in which the latex ink-receiving layer (X) and the substrate (Y) are laminated,
The latex ink-receiving layer (X) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable Formed from a resin composition (x1) containing a tertiary amine (E),
The cross-linking 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,
A film for latex ink, wherein the modified isocyanurate compound (B1-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups.
The film for latex ink according to claim 1, wherein the substrate (Y) contains a polyester resin.
The latex ink-receiving layer (X) is laminated on one surface of the substrate (Y),
3. The film for latex ink according to claim 1, wherein a pressure-sensitive adhesive layer (Z) is provided on the other surface of the substrate (Y).
The film for latex ink according to claim 3, wherein the adhesive surface of the adhesive layer (Z) is covered with a release liner.
The film for latex ink according to any one of claims 1 to 4, which is used for printing using latex ink containing acrylic resin.
A method of using the film for latex ink according to any one of claims 1 to 5, wherein the film for latex ink is used to form a printed portion using latex ink on the latex ink receiving layer of the film for latex ink.
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 claims 1 to 5.
A printed material having a latex ink-printed portion on the latex ink-receiving layer of the latex ink film according to any one of claims 1 to 5.