WO2023062797A1 - Film for latex ink - Google Patents

Film for latex ink Download PDF

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Publication number
WO2023062797A1
WO2023062797A1 PCT/JP2021/038136 JP2021038136W WO2023062797A1 WO 2023062797 A1 WO2023062797 A1 WO 2023062797A1 JP 2021038136 W JP2021038136 W JP 2021038136W WO 2023062797 A1 WO2023062797 A1 WO 2023062797A1
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WIPO (PCT)
Prior art keywords
latex ink
film
ink
latex
mass
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PCT/JP2021/038136
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French (fr)
Japanese (ja)
Inventor
拓磨 大久保
鉄也 荒添
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リンテック株式会社
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Priority to PCT/JP2021/038136 priority Critical patent/WO2023062797A1/en
Publication of WO2023062797A1 publication Critical patent/WO2023062797A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating

Definitions

  • the present invention relates to a film for latex ink.
  • 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.
  • VOC volatile organic substances
  • 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.
  • 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.
  • the present inventors have investigated latex ink receiving layers containing acrylic resins, which are highly versatile resins.
  • the latex ink-receiving layer containing an acrylic resin on the substrate surface and manufacturing a laminate of the substrate and the latex ink-receiving layer
  • the latex ink-receiving layer It was found that sticking to the back surface of the base material easily occurred. Therefore, it was found that static electricity is generated and the surface of the latex ink-receiving layer is roughened due to the sticking when the wound laminate is unwound. Since electrostatic discharge and surface roughness lead to poor printing, it is desirable to solve such problems from the viewpoint of improving the quality of latex ink films.
  • a process of forming a latex ink-receiving layer containing an acrylic resin on the surface of a base material and manufacturing a laminate of the base material and the latex ink-receiving layer involves winding up the laminate.
  • the property of suppressing sticking between the latex ink-receiving layer and the back surface of the substrate, which occurs when the ink is applied, is also simply referred to as "sticking resistance”.
  • an object of the present invention is to provide a latex ink film having a latex ink receiving layer with excellent sticking resistance and ink adhesion.
  • the present inventors have made intensive studies to solve the above problems, and have found that the latex ink-receiving layer formed from a resin composition in which a specific cross-linking agent is blended with an acrylic resin having a cross-linkable functional group is the above-mentioned. I came to know that the problem can be solved. 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 [11].
  • the latex ink-receiving layer (X) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group and a crosslinker (B), A film for latex ink, wherein the cross-linking agent (B) contains an aromatic polyisocyanate (B1).
  • the cross-linking agent (B) further contains an isocyanurate compound (B2),
  • the isocyanurate compound (B2) includes an isocyanurate compound (B2-1) and a modified isocyanurate compound (B2-2),
  • the isocyanurate compound (B2-1) is a trimer of 1,6-hexamethylene diisocyanate
  • the latex ink according to [1] above, wherein the modified isocyanurate compound (B2-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups.
  • the film [3] The film for latex ink according to [1] or [2] above, wherein the substrate (Y) contains a polyester resin.
  • 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 [1] to [3] above, wherein an adhesive layer (Z) is provided on the other surface of the substrate (Y).
  • an adhesive layer (Z) is provided on the other surface of the substrate (Y).
  • the adhesive surface of the adhesive layer (Z) is covered with a release liner.
  • the content of the aromatic polyisocyanate (B1) is 7.0 parts by mass or more relative to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group.
  • 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 [7] above.
  • the present invention it is possible to provide a latex ink film having a latex ink receiving layer with excellent sticking resistance and ink adhesion.
  • 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.
  • a diluent solvent such as water or an organic solvent among the components contained in the target composition.
  • (meth)acrylic acid indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the lower limit and upper limit values described stepwise for preferred numerical ranges can be independently combined.
  • 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) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group and a crosslinker (B). And the cross-linking agent (B) contains an aromatic polyisocyanate (B1).
  • the present inventors have found a resin composition ( The inventors have found that the latex ink-receiving layer formed from x1) is excellent in sticking resistance and ink adhesion.
  • the latex ink film of the present invention will be described below with respect to the structure of the latex ink film, the members constituting the latex ink film (base material, latex ink receiving layer, adhesive layer, and release liner), and the production of the latex ink film.
  • the method and application of the film for latex inks are described in detail.
  • 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).
  • 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).
  • the film for latex ink can be suitably used as an adhesive film.
  • 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).
  • 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
  • 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.
  • 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.
  • the thickness of the latex ink-receiving layer (X) is not particularly limited, it is preferably 0.05 ⁇ m to 50 ⁇ m, more preferably 0.1 ⁇ m to 25 ⁇ m, still more preferably 0.1 ⁇ m to 10 ⁇ m.
  • the latex ink-receiving layer (X) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group and a crosslinker (B).
  • the cross-linking agent (B) contains an aromatic polyisocyanate (B1).
  • acrylic resin (A) having a crosslinkable functional group and “crosslinking agent (B)” are also referred to as “component (A)” and “component (B)", respectively.
  • the resin composition (x1) which is the material for forming the latex ink-receiving layer (X) may be composed only of the component (A) and the component (B).
  • other components other than the component (A) and the component (B) may be contained within a range that does not impair the.
  • the total content of component (A) and component (B) is preferably 80% by mass to 100% by mass, more preferably 85% by mass, based on the total amount of active ingredients in the resin composition (x1). % to 100% by mass, more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass.
  • the acrylic resin (A) having a crosslinkable functional group and the crosslinker (B) contained in the resin composition (x1) will be described in detail below.
  • the resin composition (x1) used in the present invention contains an 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, so that the crosslinked structure formed by the reaction with the aromatic polyisocyanate (B1) described later is It is speculated that the structure is suitable for improving sticking resistance and ink adhesion, and the effect of the present invention is exerted.
  • 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′).
  • hydroxyl group-containing monomers examples 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; ⁇ -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.
  • 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. From the viewpoint of making it easier to exhibit the effects of the present invention by adjusting the glass transition temperature (Tg) of the acrylic resin (A) to an appropriate range, the number of carbon atoms in the alkyl group is preferably 2 to 20. .
  • 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.
  • 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).
  • Monomers (a3′) include, for example, 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)acrylate; styrene, ⁇ -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acryloylmorpholine, and N-vinylpyr
  • 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.
  • 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.
  • the said number average molecular weight is a polystyrene conversion value by the gel permeation chromatography (GPC) measurement using a differential refractometer detection.
  • 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.
  • 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.
  • the coating liquid used for forming the latex ink-receiving layer (X) solution containing the resin composition (x) ) to improve stability.
  • 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.
  • 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. °C or less.
  • 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.
  • 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.
  • the glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group is based on JIS K 7121: 1987 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.
  • the content of the acrylic resin (A) having a crosslinkable functional group is not particularly limited as long as the effects of the present invention are exhibited. It is 0% by mass or more, more preferably 65.0% by mass or more, and still more preferably 70.0% by mass or more. Also, it is preferably 93.0% by mass or less, more preferably 92.5% by mass or less, and still more preferably 92.0% by mass or less.
  • the resin composition (x1) used in the present invention contains a cross-linking agent (B).
  • the cross-linking agent (B) contains an aromatic polyisocyanate (B1). If the cross-linking agent (B) does not contain the aromatic polyisocyanate (B1), the latex ink-receiving layer (X) cannot have good sticking resistance and ink adhesion.
  • the cross-linking agent (B) containing the aromatic polyisocyanate (B1) when a coating film of the resin composition (x1) is formed on the substrate (Y), a cross-linking reaction occurs quickly. Cheap.
  • the latex ink-receiving layer (X) has appropriate hardness due to the crosslinked structure formed by the reaction with the acrylic resin (A) having a crosslinkable functional group. Therefore, it is presumed that the latex ink-receiving layer (X) having excellent sticking resistance is formed. In addition, it is presumed that the crosslinked structure formed by the reaction with the acrylic resin (A) having a crosslinkable functional group contributes to the ink adhesion and makes the adhesion excellent.
  • the cross-linking agent (B) may contain only the aromatic polyisocyanate (B1), but may contain a cross-linking agent other than the aromatic polyisocyanate (B1) within a range that does not impair the effects of the present invention. good.
  • the crosslinking agent (B ) preferably further contains an isocyanurate compound (B2).
  • a film for latex ink having a latex ink-receiving layer with excellent water abrasion resistance can suppress peeling of the printed portion during application with water.
  • the content of the aromatic polyisocyanate (B1) is the cross-linking agent ( Based on the total amount of B), it is preferably 80% to 100% by mass, more preferably 90% to 100% by mass, and still more preferably 95% to 100% by mass.
  • the cross-linking agent (B) contains an aromatic polyisocyanate (B1) and an isocyanurate compound (B2)
  • the aromatic polyisocyanate (B1) and the isocyanurate compound (B2) The total content is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, still more preferably 95% by mass to 100% by mass, based on the total amount of the cross-linking agent (B).
  • aromatic polyisocyanate (B1) and the isocyanurate compound (B2) are described in detail below.
  • Aromatic polyisocyanate (B1) is a compound having an aromatic ring and two or more isocyanate groups. Since the aromatic polyisocyanate (B1) has an isocyanate group bonded to an aromatic ring which is an electron-withdrawing group, the isocyanate group has very high reaction activity, and a cross-linking reaction tends to occur quickly.
  • the latex ink-receiving layer (X) has appropriate hardness due to the crosslinked structure formed by the reaction with the acrylic resin (A) having a crosslinkable functional group.
  • the latex ink-receiving layer (X) can have excellent sticking resistance.
  • the crosslinked structure formed by the reaction with the acrylic resin (A) having a crosslinkable functional group contributes to the adhesion of the latex ink to the printed area, making the adhesion excellent. be done.
  • the aromatic ring and the isocyanate group may be directly bonded or may be bonded via a linker such as an alkylene group. from the viewpoint of further increasing the reactivity of the isocyanate group, making it easier for the cross-linking reaction to occur more quickly, and making it easier to improve the sticking resistance of the latex ink-receiving layer (X). or is preferably bonded via a methylene group, and more preferably directly bonded.
  • the number of isocyanate groups should be 2 or more, preferably 2 to 3, more preferably 2.
  • aromatic polyisocyanate (B1) examples include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4, 4′,4′′-triphenylmethane triisocyanate, ⁇ , ⁇ ′-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4 -diethylbenzene, 1,4
  • the aromatic polyisocyanate (B1) may be, for example, an adduct with a polyol, a biuret, an allophanate, or a trimer.
  • An adduct with methylolpropane is more preferred.
  • Examples of adducts with trimethylolpropane include trimethylolpropane adduct tolylene diisocyanate and trimethylolpropane adduct xylylene diisocyanate.
  • aromatic polyisocyanates (B1) include, for example, “Coronate L” (trimethylolpropane adduct tolylene diisocyanate, Tosoh Corporation), "Takenate D-110N” (trimethylolpropane adduct xylylene diisocyanate, Mitsui Chemicals, Inc.). Co., Ltd.), etc.
  • the aromatic polyisocyanate (B1) may be used alone or in combination of two or more.
  • the cross-linking agent (B) preferably contains an isocyanurate compound (B2) together with the aromatic polyisocyanate (B1).
  • the isocyanurate compound (B2) includes an isocyanurate compound (B2-1) and a modified isocyanurate compound (B2-2).
  • the total content of the isocyanurate compound (B2-1) and the modified isocyanurate compound (B2-2) in the isocyanurate compound (B2) is from the viewpoint of making it easier to improve sticking resistance and ink adhesion.
  • the total amount of the isocyanurate compound (B2) is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, more preferably 95% to 100% by mass.
  • the isocyanurate compound (B2) includes an isocyanurate compound (B2-1).
  • the isocyanurate compound (B2-1) is a trimer of 1,6-hexamethylene diisocyanate, specifically a compound of the following formula (1).
  • the isocyanurate compound (B2) includes a modified isocyanurate compound (B2-2).
  • the modified isocyanurate compound (B2-2) 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.
  • 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 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.
  • the isocyanurate-based compound (B2) 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.
  • the isocyanurate compound (B2-1) and modified isocyanurate compounds An isocyanurate compound (B2) containing (B2-2) can be prepared.
  • the content of the modified isocyanurate compound (B2-2) is preferably 0.5 mol% to 10 mol%, more preferably 1 mol% to 5 mol%, based on the total amount of the isocyanurate compound (B2). in mol %.
  • the content of the aromatic polyisocyanate (B1) with respect to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group is preferably 7.0 parts by mass or more from the viewpoint of improving sticking resistance and ink adhesion. , more preferably 8.0 parts by mass or more, and still more preferably 9.0 parts by mass or more. Moreover, it is preferably 30 parts by mass or less. From the viewpoint of improving bending resistance, it is preferably less than 24.2 parts by mass, more preferably 20.0 parts by mass or less, even more preferably 15.0 parts by mass or less, and even more preferably 10.0 parts by mass or less. is. Since the latex ink film has excellent bending resistance, it is possible to suppress the whitening that occurs when the latex ink film is bent, and the appearance of the latex ink film on which the printed part is formed can be maintained in good condition. can.
  • the content of the isocyanurate compound (B2) with respect to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group is the sticking resistance.
  • the content of the isocyanurate compound (B2) with respect to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group is the sticking resistance.
  • 1.0 parts by mass or more more preferably 3.0 parts by mass or more.
  • more preferably 5.0 parts by mass or more still more preferably 7.0 parts by mass or more.
  • it is preferably 25.0 parts by mass or less, more preferably 22.0 parts by mass or less, and even more preferably 20.0 parts by mass or less.
  • Total content of aromatic polyisocyanate (B1) and isocyanurate compound (B2) When the cross-linking agent (B) contains the isocyanurate compound (B2), the aromatic polyisocyanate (B1) and the isocyanurate compound (B2) are added to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group.
  • the total content is preferably 8.0 parts by mass or more from the viewpoint of easily improving the sticking resistance, the viewpoint of easily improving the ink adhesion, and the viewpoint of easily improving the water scratch resistance. It is more preferably 11.0 parts by mass or more, still more preferably 14.0 parts by mass or more, and even more preferably 16.0 parts by mass or more. From the viewpoint of improving bending resistance, the content is preferably 41.4 parts by mass or less, more preferably 28.0 parts by mass or less, and even more preferably 20.0 parts by mass or less.
  • the mass ratio is preferably 0.2 to 5.0, more preferably 0.2 to 5.0. 0.3 to 3.0, more preferably 0.5 to 2.0.
  • 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 functions as a support for supporting the printed portion formed on the latex ink-receiving layer (X).
  • the base material (Y) is not particularly limited, it is preferably a resin film.
  • 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.
  • 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.
  • the resin constituting the resin film examples 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.
  • 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
  • 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. According to the present invention, the adhesiveness between the latex ink-receiving layer (X) and the base material (Y), which constitute the latex ink film, is sufficiently ensured, and the sticking resistance is excellent.
  • the sticking of the latex ink-receiving layer (X) to the back surface of the substrate (Y) is suppressed. . Therefore, the surface of the latex ink-receiving layer (X) is prevented from becoming rough due to the sticking.
  • the resin film may be composed of only one type of resin, or may be composed of two or more types of resin.
  • the resin film is a multilayer body.
  • 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.
  • the resin film may be unstretched, or may be stretched in a uniaxial direction such as longitudinally or laterally or in a biaxial direction.
  • the resin film may contain substrate additives such as surface conditioners, plasticizers, UV absorbers, light stabilizers, and colorants along with these resins.
  • 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).
  • the thickness of the base material is not particularly limited, it is preferably 15 ⁇ m to 300 ⁇ m, more preferably 30 ⁇ m to 200 ⁇ m.
  • 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.
  • the thickness of the pressure-sensitive adhesive layer (Z) is not particularly limited, it is preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, from the viewpoint of improving handleability when using the film for latex ink as an adhesive film. It is preferably 15 ⁇ m to 50 ⁇ m.
  • 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.
  • film substrates include polyester resins such as polyethylene terephthalate, and polyolefin resins such as polyethylene resins and polypropylene resins.
  • paper substrates include papers such as woodfree paper, kraft paper, and glassine paper.
  • Materials constituting the release layer include, for example, silicone-based resins, long-chain alkyl-based resins, and fluorine-based resins.
  • the thickness of the release liner is not particularly limited, it is preferably 10 ⁇ m to 200 ⁇ m, more preferably 15 ⁇ m to 150 ⁇ m, still more preferably 20 ⁇ m to 120 ⁇ m.
  • 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. It is preferable to form the latex ink-receiving layer (X) by subsequently 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.
  • 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.
  • the heating conditions for drying the coating film are not particularly limited, and are, for example, a drying temperature of 60° C. to 120° C. and a drying time of 30 seconds to 3 minutes.
  • the crosslinking conditions are not particularly limited.
  • 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 drying step and the cross-linking step may be performed collectively.
  • 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).
  • 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).
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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 %.
  • 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.
  • the latex ink may contain components (other ingredients) other than those already described.
  • components include dispersants, antifungal agents, antirust agents, pH adjusters, surfactants, plasticizers, ultraviolet absorbers, light stabilizers, and the like.
  • 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.
  • 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.
  • Methods for measuring various physical property values in the examples are as described below.
  • Hydroxyl value The hydroxyl value of the acrylic resin (A) having a crosslinkable functional group was measured according to JIS K0070:1992.
  • Acid value The acid value of the acrylic resin (A) having a crosslinkable functional group was measured according to JIS K0070:1992.
  • Glass transition temperature (Tg) The glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group conforms to JIS K 7121: 1987 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.
  • 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.
  • Example 1 to 4 Comparative Example 1
  • the latex ink films of Examples 1 to 4 and Comparative Example 1 were produced by the following procedure.
  • 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.
  • Each resin composition was prepared according to the formulation shown in Table 1 (the compounding amount is calculated as an active ingredient) (active ingredient concentration: 10% by mass, dilution solvent: ethyl acetate), and a polyethylene terephthalate (PET) base material (thickness : 50 ⁇ m) was coated on one side of the film using a Meyer bar so that the film thickness after drying would be 1 ⁇ m.
  • active ingredient concentration 10% by mass
  • dilution solvent ethyl acetate
  • PET polyethylene terephthalate
  • the solvent contained in the resin composition applied to the substrate is removed by heating at 90 ° C. for 1 minute, and further in an environment of 23 ° C. and a relative humidity of 50%. Crosslinked by leaving at room temperature for 7 days.
  • a latex ink-receiving layer (X) having a thickness of 1 ⁇ m was formed to obtain a latex ink film.
  • a test sample for evaluation of sticking resistance was prepared without performing the standing step for 7 days after removing the solvent, and was subjected to the sticking resistance evaluation test immediately after removing the solvent.
  • Residual rate less than 20% 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 has excellent ink adhesion.
  • Latex ink films of Examples 1 to 4 and Comparative Example 1 (latex ink film immediately after removing the solvent, which is a test sample for evaluating sticking resistance described above) was cut into pieces each having a size of 5 cm ⁇ 10 cm, and 10 sheets were stacked to prepare a laminate.
  • the laminate was sandwiched between glass plates having a thickness of 3 mm, and with a weight of 2 kg placed on the glass plates, the laminate was allowed to stand in an environment of 40° C. and a relative humidity of 80% for 7 days. Next, the laminate was taken out from between the glass plates and allowed to stand in an environment of 23° C. and a relative humidity of 50% for 24 hours.
  • the peeling sound was evaluated on a scale of 1, 2, 3, 4, and 5 in descending order of sound. The evaluation value was set to 5 when no peeling sound was heard. The smaller the peeling sound (the larger the evaluation value), the better the sticking resistance.
  • the results of evaluation 1 are shown in Table 1.
  • the content ratio [(B1)/(B2)] between the aromatic polyisocyanate (B1) and the isocyanurate compound (B2) in Example 3 was 1.13 in mass ratio.
  • the content ratio [(B1)/(B2)] in Example 4 is 1.41 in mass ratio.
  • Table 1 shows the following. It can be seen that the latex ink films of Examples 1 to 4 are excellent in ink adhesion and sticking resistance. On the other hand, when only the unmodified isocyanate compound (B2-1) was used as the cross-linking agent as in Comparative Example 1, the ink adhesion was inferior and the sticking resistance was also inferior.
  • ⁇ Evaluation 2> (1) Evaluation of water scratch resistance For each of the latex ink films of Examples 1 to 4 and Comparative Example 1, a predetermined test pattern was printed in the same manner as in Ink Adhesion Evaluation 1. layer) was formed. Then, the latex ink films of Examples 1 to 4 and Comparative Example 1 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, and the test sample was obtained. 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.
  • an anionic surfactant sodium laureth sulfate
  • Residual rate less than 20% 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 more excellent the latex ink-receiving layer is in water scratch resistance.
  • Table 2 shows the results of evaluation 2.
  • Table 2 shows the following. It can be seen that the latex ink films of Examples 1 to 4 are excellent in water scratch resistance and bending resistance. Among these, the latex ink films of Examples 3 and 4 are found to be extremely excellent in water scratch resistance. Moreover, it can be seen that the latex ink films of Examples 1 and 3 are extremely excellent in bending resistance.
  • 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

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Abstract

The present invention addresses the problem of providing a film for a latex ink, the film having a latex-ink-receiving layer having exceptional sticking resistance and ink adhesion. The aforementioned problem is solved by achieving a film for latex ink, the film having a laminate structure in which a latex-ink-receiving layer (X) and a base material (Y) are laminated, the latex-ink-receiving layer (X) being formed from a resin composition (x1) that contains an acrylic resin (A) having a cross-linkable functional group and a cross-linker (B), and the cross-linker (B) containing an aromatic polyisocyanate (B1).

Description

ラテックスインク用フィルムFilm for latex ink
　本発明は、ラテックスインク用フィルムに関する。 The present invention relates to a film for latex ink.
　近年、ラテックスインクを用いた印刷法が注目されている（例えば、特許文献１を参照）。
　ラテックスインクは、顔料を有機溶剤に溶解させる溶剤インクとは異なり、顔料をラテックス（ポリマー）と共に水に分散させた水性インクである。したがって、溶剤インクを使用する場合に問題となる、有機溶剤に起因する揮発性有機物（ＶＯＣ）の排出がないことから、ラテックスインクを用いた印刷物は、飲食店、教育機関、医療機関、及び商業施設等の様々な場所に安心して使用できる利点がある。 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.
　かかる利点を踏まえ、本件出願人は、ラテックスインク用フィルムを特許文献２において提案している。特許文献２に記載のラテックスインク用フィルムは、基材と、ラテックスインクが付与される印刷用コート層とを備える。当該印刷用コート層には、塩化ビニル、酢酸ビニル、及び架橋性モノマーを構成モノマーとする高分子材料が架橋剤により架橋された構造を有する材料が含まれている。これにより、ラテックスインクによる印刷部及び基材の双方との密着性に優れた印刷用コート層を有するラテックスインク用フィルムとしている。 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.
　なお、特許文献２における「印刷用コート層」を、本明細書では「ラテックスインク受理層」と呼ぶ。すなわち、「ラテックスインク受理層」とは、ラテックスインクが付与される部位であり、付与されたラテックスインクによる印刷部を定着させる機能を有する層を意味する。 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.
特開２０１６－１２０７１９号公報JP 2016-120719 A 特開２０１９－１７２８７７号公報JP 2019-172877 A
　近年、ラテックスインクを用いた印刷法が広く採用されつつあり、その際に用いられるラテックスインク用フィルムについても、様々な要求が増えつつある。また、環境保護の観点から非ハロゲン系樹脂を使用することも求められている。したがって、特許文献２とは異なるラテックスインク受理層を備えるラテックスインク用フィルムの開発も望まれる。 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. Moreover, from the viewpoint of environmental protection, the use of non-halogen resins is also required. Therefore, development of a film for latex ink having a latex ink-receiving layer different from that of Patent Document 2 is also desired.
　そこで、本発明者らは、汎用性の高い樹脂であるアクリル系樹脂を含有するラテックスインク受理層について検討を行った。ところが、アクリル系樹脂を含有するラテックスインク受理層を基材表面に形成して、基材とラテックスインク受理層との積層体を製造する過程で、当該積層体を巻き取ると、ラテックスインク受理層と基材裏面との貼り付きが起こりやすいことがわかった。そのため、巻き取った積層体を繰り出す際に、当該貼り付きに起因して、静電気が発生したり、ラテックスインク受理層の表面に荒れが生じたりすることがわかった。静電気放電や表面の荒れは印刷不良に繋がるため、ラテックスインク用フィルムの品質向上の観点からは、このような問題点を解決することが望まれる。
　なお、以降の説明では、「アクリル系樹脂を含有するラテックスインク受理層を基材表面に形成して、基材とラテックスインク受理層との積層体を製造する過程で、当該積層体を巻き取った際に生じる、ラテックスインク受理層と基材裏面との貼り付きを抑制する性質」のことを、単に「耐貼り付き性」ともいう。 Accordingly, the present inventors have investigated latex ink receiving layers containing acrylic resins, which are highly versatile resins. However, in the process of forming a latex ink-receiving layer containing an acrylic resin on the substrate surface and manufacturing a laminate of the substrate and the latex ink-receiving layer, when the laminate is taken up, the latex ink-receiving layer It was found that sticking to the back surface of the base material easily occurred. Therefore, it was found that static electricity is generated and the surface of the latex ink-receiving layer is roughened due to the sticking when the wound laminate is unwound. Since electrostatic discharge and surface roughness lead to poor printing, it is desirable to solve such problems from the viewpoint of improving the quality of latex ink films.
In the following description, "a process of forming a latex ink-receiving layer containing an acrylic resin on the surface of a base material and manufacturing a laminate of the base material and the latex ink-receiving layer involves winding up the laminate. The property of suppressing sticking between the latex ink-receiving layer and the back surface of the substrate, which occurs when the ink is applied, is also simply referred to as "sticking resistance".
　また、アクリル系樹脂を含有するラテックスインク受理層を用いた場合、ラテックスインク受理層のラテックスインクによる印刷部との密着性を確保することも容易ではないことがわかった。
　なお、以降の説明では、「ラテックスインクによる印刷部との密着性」を、単に「インク密着性」ともいう。 It was also found that when a latex ink-receiving layer containing an acrylic resin is used, it is not easy to ensure the adhesion of the latex ink-receiving layer to the printed portion of the latex ink.
In the following description, "adhesion of the latex ink to the printed portion" is also simply referred to as "ink adhesion".
　そこで、本発明は、耐貼り付き性及びインク密着性に優れるラテックスインク受理層を有するラテックスインク用フィルムを提供することを課題とする。 Therefore, an object of the present invention is to provide a latex ink film having a latex ink receiving layer with excellent sticking resistance and ink adhesion.
　本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、架橋性官能基を有するアクリル系樹脂に特定の架橋剤を配合した樹脂組成物から形成されるラテックスインク受理層が、上記課題を解決し得ることを知見するに至った。本発明者らは、かかる知見に基づき更に種々検討を重ね、本発明を完成するに至った。
　すなわち、本発明は、下記［１］～［１１］に関する。
　［１］ラテックスインク受理層（Ｘ）と基材（Ｙ）とが積層された積層構造を有し、
　前記ラテックスインク受理層（Ｘ）は、架橋性官能基を有するアクリル系樹脂（Ａ）及び架橋剤（Ｂ）を含有する樹脂組成物（ｘ１）から形成され、
　前記架橋剤（Ｂ）は、芳香族ポリイソシアネート（Ｂ１）を含む、ラテックスインク用フィルム。
　［２］前記架橋剤（Ｂ）は、さらに、イソシアヌレート系化合物（Ｂ２）を含み、
　前記イソシアヌレート系化合物（Ｂ２）は、イソシアヌレート化合物（Ｂ２－１）及びイソシアヌレート化合物の変性体（Ｂ２－２）を含み、
　前記イソシアヌレート化合物（Ｂ２－１）は、１，６－ヘキサメチレンジイソシアネートの３量体であり、
　前記イソシアヌレート化合物の変性体（Ｂ２－２）は、１，６－ヘキサメチレンジイソシアネートの３量体であって、且つ１以上の３級アミノ基を有する、上記［１］に記載のラテックスインク用フィルム。
　［３］前記基材（Ｙ）は、ポリエステル系樹脂を含む、上記［１］又は［２］に記載のラテックスインク用フィルム。
　［４］前記基材（Ｙ）の一方の面に前記ラテックスインク受理層（Ｘ）が積層され、
　前記基材（Ｙ）の他方の面に粘着剤層（Ｚ）が設けられている、上記［１］～［３］のいずれかに記載のラテックスインク用フィルム。
　［５］前記粘着剤層（Ｚ）の粘着表面が剥離ライナーで覆われている、上記［４］に記載のラテックスインク用フィルム。
　［６］前記架橋性官能基を有するアクリル系樹脂（Ａ）１００質量部に対する、前記芳香族ポリイソシアネート（Ｂ１）の含有量が、７．０質量部以上である、上記［１］～［５］のいずれかに記載のラテックスインク用フィルム。
　［７］前記架橋性官能基を有するアクリル系樹脂（Ａ）１００質量部に対する、前記芳香族ポリイソシアネート（Ｂ１）の含有量が、２４．２質量部未満である、上記［１］～［６］のいずれかに記載のラテックスインク用フィルム。
　［８］アクリル系樹脂を含むラテックスインクを使用した印刷に用いられる、上記［１］～［７］のいずれかに記載のラテックスインク用フィルム。
　［９］上記［１］～［７］のいずれかに記載のラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクを用いて印刷部を形成するために、前記ラテックスインク用フィルムを使用する、使用方法。
　［１０］上記［１］～［７］のいずれかに記載のラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクを用いて印刷部を形成する工程を含む、印刷物の製造方法。
　［１１］上記［１］～［７］のいずれかに記載のラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクによる印刷部を有する、印刷物。 The present inventors have made intensive studies to solve the above problems, and have found that the latex ink-receiving layer formed from a resin composition in which a specific cross-linking agent is blended with an acrylic resin having a cross-linkable functional group is the above-mentioned. I came to know that the problem can be solved. 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 [11].
[1] Having a laminated structure in which the latex ink-receiving layer (X) and the base material (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 and a crosslinker (B),
A film for latex ink, wherein the cross-linking agent (B) contains an aromatic polyisocyanate (B1).
[2] The cross-linking agent (B) further contains an isocyanurate compound (B2),
The isocyanurate compound (B2) includes an isocyanurate compound (B2-1) and a modified isocyanurate compound (B2-2),
The isocyanurate compound (B2-1) is a trimer of 1,6-hexamethylene diisocyanate,
The latex ink according to [1] above, wherein the modified isocyanurate compound (B2-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups. the film.
[3] The film for latex ink according to [1] or [2] above, wherein the substrate (Y) contains a polyester resin.
[4] 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 [1] to [3] above, wherein an adhesive layer (Z) is provided on the other surface of the substrate (Y).
[5] The film for latex ink according to [4] above, wherein the adhesive surface of the adhesive layer (Z) is covered with a release liner.
[6] The above [1] to [5], wherein the content of the aromatic polyisocyanate (B1) is 7.0 parts by mass or more relative to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group. ] The film for latex ink according to any one of the above.
[7] The above [1] to [6], wherein the content of the aromatic polyisocyanate (B1) is less than 24.2 parts by mass with respect to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group. ] The film for latex ink according to any one of the above.
[8] The film for latex ink according to any one of [1] to [7], which is used for printing using latex ink containing acrylic resin.
[9] 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 [7] above. ,how to use.
[10] 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 [7] above.
[11] 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 [7] above.
　本発明によれば、耐貼り付き性及びインク密着性に優れるラテックスインク受理層を有するラテックスインク用フィルムを提供することが可能となる。 According to the present invention, it is possible to provide a latex ink film having a latex ink receiving layer with excellent sticking resistance and ink adhesion.
本発明のラテックスインク用フィルムの一態様を示す断面模式図である。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.
　本明細書において、「有効成分」とは、対象となる組成物に含まれる成分のうち、水や有機溶媒等の希釈溶媒を除いた成分を指す。
　また、本明細書において、「（メタ）アクリル酸」とは、「アクリル酸」と「メタクリル酸」との双方を示し、他の類似用語も同様である。
　また、本明細書において、好ましい数値範囲（例えば、含有量等の範囲）について、段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、「好ましくは１０～９０、より好ましくは３０～６０」という記載から、「好ましい下限値（１０）」と「より好ましい上限値（６０）」とを組み合わせて、「１０～６０」とすることもできる。
　また、本明細書において、実施例の数値は、上限値又は下限値として用いられ得る数値である。 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", and the same applies to other similar terms.
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.
［本発明のラテックスインク用フィルムの態様］
　本発明のラテックスインク用フィルムは、ラテックスインク受理層（Ｘ）と基材（Ｙ）とが積層された積層構造を有する。
　ラテックスインク受理層（Ｘ）は、架橋性官能基を有するアクリル系樹脂（Ａ）及び架橋剤（Ｂ）を含有する樹脂組成物（ｘ１）から形成される。
　そして、架橋剤（Ｂ）は、芳香族ポリイソシアネート（Ｂ１）を含む。 [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) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group and a crosslinker (B).
And the cross-linking agent (B) contains an aromatic polyisocyanate (B1).
　本発明者らは、鋭意検討を重ねた結果、「架橋性官能基を有するアクリル樹脂（Ａ）」及び「芳香族ポリイソシアネート（Ｂ１）を含む架橋剤（Ｂ）」を含有する樹脂組成物（ｘ１）から形成されるラテックスインク受理層が、耐貼り付き性及びインク密着性に優れることを見出し、さらに種々検討を重ねて、本発明を完成するに至った。 As a result of extensive studies, the present inventors have found a resin composition ( The inventors have found that the latex ink-receiving layer formed from x1) is excellent in sticking resistance and ink adhesion.
　以下、本発明のラテックスインク用フィルムについて、ラテックスインク用フィルムの構成、ラテックスインク用フィルムを構成する部材（基材、ラテックスインク受理層、粘着剤層、及び剥離ライナー）、ラテックスインク用フィルムの製造方法、並びにラテックスインク用フィルムの用途について、詳細に説明する。 The latex ink film of the present invention will be described below with respect to the structure of the latex ink film, the members constituting the latex ink film (base material, latex ink receiving layer, adhesive layer, and release liner), and the production of the latex ink film. The method and application of the film for latex inks are described in detail.
［ラテックスインク用フィルムの構成］
　本発明のラテックスインク用フィルムは、ラテックスインク受理層（Ｘ）と基材（Ｙ）とが積層された積層構造を有する。 [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.
　図１に、本発明のラテックスインク用フィルムの一態様の断面模式図を示す。図１に示すラテックスインク用フィルム１は、基材（Ｙ）の一方の面（Ｙａ）にラテックスインク受理層（Ｘ）が積層された積層構造を有する。
　ここで、図１に示すように、本発明の一態様のラテックスインク用フィルムは、基材（Ｙ）の他方の面（Ｙｂ）に粘着剤層（Ｚ）が設けられていることが好ましい。これにより、ラテックスインク用フィルムを、粘着フィルムとして好適に用いることができる。 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.
　また、図示省略するが、粘着剤層（Ｚ）の粘着表面は、剥離ライナーで被覆されていてもよい。そして、被着体への貼着の際に当該剥離ライナーを剥がし、粘着剤層（Ｚ）の粘着表面を表出させるようにしてもよい。
　また、図示省略するが、粘着剤層（Ｚ）を設けることなく、基材（Ｙ）の一方の面（Ｙａ）及び他方の面（Ｙｂ）の両面に、ラテックスインク受理層（Ｘ）が備えられていてもよい。 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
［ラテックスインク用フィルムを構成する部材］
　本発明のラテックスインク用フィルムは、ラテックスインク受理層（Ｘ）及び基材（Ｙ）を有する。
　また、本発明の一態様のラテックスインク用フィルムは、既述したように、ラテックスインク受理層（Ｘ）及び基材（Ｙ）に加えて、更に粘着剤層（Ｚ）を有していてもよい。また、ラテックスインク受理層（Ｘ）及び基材（Ｙ）に加えて、更に、粘着剤層（Ｚ）及び剥離ライナーを有していてもよい。
　以下、ラテックスインク受理層（Ｘ）、基材（Ｙ）、粘着剤層（Ｚ）、及び剥離ライナーについて、詳細に説明する。 [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.
＜ラテックスインク受理層（Ｘ）＞
　本発明のラテックスインク用フィルムは、ラテックスインク受理層（Ｘ）を有する。
　ラテックスインク受理層（Ｘ）は、ラテックスインクが付与される部位であり、付与されたラテックスインクによる印刷部を定着させる機能を有する。
　ラテックスインク受理層（Ｘ）の厚さは、特に限定されないが、好ましくは０．０５μｍ～５０μｍ、より好ましくは０．１μｍ～２５μｍ、更に好ましくは０．１μｍ～１０μｍである。 <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.
　ラテックスインク受理層（Ｘ）は、架橋性官能基を有するアクリル系樹脂（Ａ）及び架橋剤（Ｂ）を含有する樹脂組成物（ｘ１）から形成される。架橋剤（Ｂ）は、芳香族ポリイソシアネート（Ｂ１）を含む。 The latex ink-receiving layer (X) is formed from a resin composition (x1) containing an acrylic resin (A) having a crosslinkable functional group and a crosslinker (B). The cross-linking agent (B) contains an aromatic polyisocyanate (B1).
　以降の説明では、「架橋性官能基を有するアクリル系樹脂（Ａ）」及び「架橋剤（Ｂ）」を、それぞれ「成分（Ａ）」及び「成分（Ｂ）」ともいう。 In the following description, "acrylic resin (A) having a crosslinkable functional group" and "crosslinking agent (B)" are also referred to as "component (A)" and "component (B)", respectively.
　本発明の一態様において、ラテックスインク受理層（Ｘ）の形成材料である樹脂組成物（ｘ１）は、成分（Ａ）及び成分（Ｂ）のみから構成されていてもよいが、本発明の効果を損なわない範囲で、成分（Ａ）及び成分（Ｂ）と共に、成分（Ａ）及び成分（Ｂ）以外の他の成分を含有していてもよい。当該他の成分としては、例えば、ラテックスインク受理層等のインク受理層に一般的に用いられるインク受理層用の添加剤、例えば、反応促進剤（触媒）、表面調整剤、可塑剤、紫外線吸収剤、光安定剤、フィラー、及び着色剤等が挙げられる。 In one aspect of the present invention, the resin composition (x1), which is the material for forming the latex ink-receiving layer (X), may be composed only of the component (A) and the component (B). In addition to the component (A) and the component (B), other components other than the component (A) and the component (B) may be contained within a range that does not impair the. 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 control agents, plasticizers, and ultraviolet absorbers. agents, light stabilizers, fillers, colorants, and the like.
　本発明の一態様において、成分（Ａ）及び成分（Ｂ）の合計含有量は、樹脂組成物（ｘ１）の有効成分の全量基準で、好ましくは８０質量％～１００質量％、より好ましくは８５質量％～１００質量％、更に好ましくは９０質量％～１００質量％、より更に好ましくは９５質量％～１００質量％である。 In one aspect of the present invention, the total content of component (A) and component (B) is preferably 80% by mass to 100% by mass, more preferably 85% by mass, based on the total amount of active ingredients in the resin composition (x1). % to 100% by mass, more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass.
　以下、樹脂組成物（ｘ１）が含有する、架橋性官能基を有するアクリル系樹脂（Ａ）及び架橋剤（Ｂ）について、詳細に説明する。 The acrylic resin (A) having a crosslinkable functional group and the crosslinker (B) contained in the resin composition (x1) will be described in detail below.
（架橋性官能基を有するアクリル系樹脂（Ａ））
　本発明で用いる樹脂組成物（ｘ１）は、架橋性官能基を有するアクリル系樹脂（Ａ）を含有する。本発明で用いる樹脂組成物（ｘ１）が、架橋性官能基を有するアクリル系樹脂（Ａ）を含有することで、後述する芳香族ポリイソシアネート（Ｂ１）との反応により形成される架橋構造が、耐貼り付き性を向上させるとともに、インク密着性を向上させるのに適した構造となり、本発明の効果が発揮されるものと推察される。 (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. The resin composition (x1) used in the present invention contains an acrylic resin (A) having a crosslinkable functional group, so that the crosslinked structure formed by the reaction with the aromatic polyisocyanate (B1) described later is It is speculated that the structure is suitable for improving sticking resistance and ink adhesion, and the effect of the present invention is exerted.
　架橋性官能基を有するアクリル系樹脂（Ａ）としては、架橋性官能基含有モノマー（ａ１’）（以下、モノマー（ａ１’）ともいう）に由来する構成単位（ａ１）を有するアクリル系樹脂（Ａ１）が好ましい。 As the acrylic resin (A) having a crosslinkable functional group, an acrylic resin ( A1) is preferred.
　モノマー（ａ１’）が有する架橋性官能基としては、例えば、水酸基、カルボキシ基、アミノ基、及びエポキシ基等から選択される１種以上が挙げられる。
　つまり、モノマー（ａ１’）としては、例えば、水酸基含有モノマー、カルボキシ基含有モノマー、アミノ基含有モノマー、及びエポキシ基含有モノマー等が挙げられる。また、水酸基、カルボキシ基、アミノ基、及びエポキシ基等から選択される２種以上の架橋性官能基を含有するモノマーも挙げられる。
　これらのモノマー（ａ１’）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、モノマー（ａ１’）としては、水酸基含有モノマー及びカルボキシ基含有モノマーが好ましい。 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′).
　水酸基含有モノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、及び４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類；Ｎ－メチロール化アクリルアミド；ε－カプロラクトン変性ヒドロキシ（メタ）アクリレート；カーボネート変性（メタ）アクリレート等が挙げられる。 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.
　カルボキシ基含有モノマーとしては、例えば、（メタ）アクリル酸；既述の水酸基含有モノマーの末端水酸基を、無水コハク酸及び無水グルタル酸等から選択される１種以上の脂肪族ジカルボン酸等の酸無水物と反応させて得られる化合物等が挙げられる。 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.
　ここで、架橋性官能基を有するアクリル系樹脂（Ａ）は、架橋性官能基含有モノマー（ａ１’）と共に、アルキル（メタ）アクリレート（ａ２’）（以下、「モノマー（ａ２’）」ともいう）に由来する構成単位（ａ２）を有するアクリル系共重合体（Ａ２）であってもよい。 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 ).
　モノマー（ａ２’）が有するアルキル基の炭素数は、好ましくは１～２４である。なお、アクリル系樹脂（Ａ）のガラス転移温度（Ｔｇ）を適切な範囲に調整して本発明の効果をより発揮させやすくする観点から、アルキル基の炭素数は、好ましくは２～２０である。
　なお、モノマー（ａ２’）が有するアルキル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。 The number of carbon atoms in the alkyl group of the monomer (a2') is preferably 1-24. From the viewpoint of making it easier to exhibit the effects of the present invention by adjusting the glass transition temperature (Tg) of the acrylic resin (A) to an appropriate range, the number of carbon atoms in the alkyl group is preferably 2 to 20. .
The alkyl group possessed by the monomer (a2') may be a straight-chain alkyl group or a branched-chain alkyl group.
　モノマー（ａ２’）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、及びステアリル（メタ）アクリレート等が挙げられる。
　これらのモノマー（ａ２’）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 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.
　構成単位（ａ２）を含むアクリル系共重合体（Ａ２）において、構成単位（ａ２）の含有量は、アクリル系共重合体（Ａ２）の全量基準で、好ましくは１～９９質量％、より好ましくは５～９５質量％、更に好ましくは１０～９０質量％である。 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.
　アクリル系樹脂（Ａ１）及びアクリル系共重合体（Ａ２）は、さらにモノマー（ａ１’）及び（ａ２’）以外の他のモノマー（ａ３’）に由来の構成単位（ａ３）を有するアクリル系共重合体（Ａ３）であってもよい。 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).
　モノマー（ａ３’）としては、例えば、エチレン、プロピレン、及びイソブチレン等のオレフィン類；塩化ビニル及びビニリデンクロリド等のハロゲン化オレフィン類；ブタジエン、イソプレン、及びクロロプレン等のジエン系モノマー類；シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、及びイミド（メタ）アクリレート等の環状構造を有する（メタ）アクリレート；スチレン、α－メチルスチレン、ビニルトルエン、ギ酸ビニル、酢酸ビニル、アクリロニトリル、（メタ）アクリルアミド、（メタ）アクリロニトリル、（メタ）アクリロイルモルホリン、及びＮ－ビニルピロリドン等が挙げられる。 Monomers (a3′) include, for example, 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)acrylate; styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acryloylmorpholine, and N-vinylpyrrolidone be done.
　構成単位（ａ３）を含むアクリル系共重合体（Ａ３）において、構成単位（ａ３）の含有量は、アクリル系共重合体（Ａ３）の全量基準で、好ましくは１～９９質量％、より好ましくは５～９５質量％、更に好ましくは１０～９０質量％である。 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.
　架橋性官能基を有するアクリル系樹脂（Ａ）の分子量は、特に限定されないが、数平均分子量が３，０００～１００，０００であることが好ましい。
　なお、当該数平均分子量は、示差屈折率計検出を用いたゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定による、ポリスチレン換算値である。 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.
　ここで、架橋性官能基を有するアクリル系樹脂（Ａ）の水酸基価は、好ましくは５．０ｍｇＫＯＨ／ｇ～２５．０ｍｇＫＯＨ／ｇ、より好ましくは６．０ｍｇＫＯＨ／ｇ～２４．０ｍｇＫＯＨ／ｇ、更に好ましくは７．０ｍｇＫＯＨ／ｇ～２３．０ｍｇＫＯＨ／ｇである。
　架橋性官能基を有するアクリル系樹脂（Ａ）の水酸基価が上記下限値以上であると、インク密着性を向上させやすい。また、ラテックスインク受理層の安定性を向上させやすい。
　架橋性官能基を有するアクリル系樹脂（Ａ）の水酸基価が上記上限値以下であると、ラテックスインク受理層（Ｘ）を形成する際に用いる塗工液（樹脂組成物（ｘ）を含む溶液）の安定性を向上させやすい。また、架橋が密になることにより生じるラテックスインク受理層（Ｘ）の硬化収縮に起因する収縮カールを抑制しやすい。
　なお、本明細書において、架橋性官能基を有するアクリル系樹脂（Ａ）の水酸基価は、ＪＩＳ　Ｋ００７０：１９９２に準拠して測定された値を意味する。 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 (x) ) to improve stability. In addition, it is easy to suppress shrinkage curl caused by curing shrinkage of the latex ink-receiving layer (X) caused by dense cross-linking.
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.
　架橋性官能基を有するアクリル系樹脂（Ａ）の酸価は、好ましくは１０．０ｍｇＫＯＨ／ｇ以下、より好ましくは１．０ｍｇＫＯＨ／ｇ～９．０ｍｇＫＯＨ／ｇ、更に好ましくは２．０ｍｇＫＯＨ／ｇ～８．０ｍｇＫＯＨ／ｇである。
　なお、本明細書において、架橋性官能基を有するアクリル系樹脂（Ａ）の酸価は、ＪＩＳ　Ｋ００７０：１９９２に準拠して測定された値を意味する。 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.
　架橋性官能基を有するアクリル系樹脂（Ａ）のガラス転移温度（Ｔｇ）は、インク密着性をより向上させやすくする観点から、好ましくは１００℃以下、より好ましくは９５℃以下、更に好ましくは９０℃以下である。特に、架橋性官能基を有するアクリル系樹脂（Ａ）のガラス転移温度（Ｔｇ）が、ラテックスインクの硬化温度よりも低いと、インク密着性を更に向上させやすい。
　また、架橋性官能基を有するアクリル系樹脂（Ａ）のガラス転移温度（Ｔｇ）は、耐貼り付き性をより向上させやすくする観点から、通常３０℃以上、好ましくは４０℃以上、より好ましくは５０℃以上である。
　なお、本明細書において、架橋性官能基を有するアクリル系樹脂（Ａ）のガラス転移温度（Ｔｇ）は、ＪＩＳ　Ｋ　７１２１：１９８７に準拠し、示差走査熱量計（ティー・エイ・インスツルメント・ジャパン株式会社製、製品名「ＤＳＣ　Ｑ２０００」）を用いて、昇温速度２０℃／分にて測定した値を意味する。 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.
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: 1987 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.
　架橋性官能基を有するアクリル系樹脂（Ａ）の含有量は、本発明の効果が発揮される限り、特に限定されないが、樹脂組成物（ｘ１）の有効成分の全量基準で、好ましくは６０．０質量％以上、より好ましくは６５．０質量％以上、更に好ましくは７０．０質量％以上である。また、好ましくは９３．０質量％以下、より好ましくは９２．５質量％以下、更に好ましくは９２．０質量％以下である。 The content of the acrylic resin (A) having a crosslinkable functional group is not particularly limited as long as the effects of the present invention are exhibited. It is 0% by mass or more, more preferably 65.0% by mass or more, and still more preferably 70.0% by mass or more. Also, it is preferably 93.0% by mass or less, more preferably 92.5% by mass or less, and still more preferably 92.0% by mass or less.
（架橋剤（Ｂ））
　本発明で用いる樹脂組成物（ｘ１）は、架橋剤（Ｂ）を含有する。
　架橋剤（Ｂ）は、芳香族ポリイソシアネート（Ｂ１）を含む。
　架橋剤（Ｂ）が、芳香族ポリイソシアネート（Ｂ１）を含まない場合、ラテックスインク受理層（Ｘ）の耐貼り付き性及びインク密着性を良好なものとできない。本発明では、芳香族ポリイソシアネート（Ｂ１）を含む架橋剤（Ｂ）を用いることで、樹脂組成物（ｘ１）の塗膜を基材（Ｙ）に形成した際に、架橋反応が速やかに起こりやすい。また、架橋性官能基を有するアクリル系樹脂（Ａ）との反応により形成される架橋構造によって、ラテックスインク受理層（Ｘ）が適度な硬さとなる。そのため、耐貼り付き性に優れるラテックスインク受理層（Ｘ）が形成されるものと推察される。また、架橋性官能基を有するアクリル系樹脂（Ａ）との反応により形成される架橋構造が、インク密着性に寄与し、当該密着性を優れたものにしていると推察される。 (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 aromatic polyisocyanate (B1).
If the cross-linking agent (B) does not contain the aromatic polyisocyanate (B1), the latex ink-receiving layer (X) cannot have good sticking resistance and ink adhesion. In the present invention, by using the cross-linking agent (B) containing the aromatic polyisocyanate (B1), when a coating film of the resin composition (x1) is formed on the substrate (Y), a cross-linking reaction occurs quickly. Cheap. In addition, the latex ink-receiving layer (X) has appropriate hardness due to the crosslinked structure formed by the reaction with the acrylic resin (A) having a crosslinkable functional group. Therefore, it is presumed that the latex ink-receiving layer (X) having excellent sticking resistance is formed. In addition, it is presumed that the crosslinked structure formed by the reaction with the acrylic resin (A) having a crosslinkable functional group contributes to the ink adhesion and makes the adhesion excellent.
　架橋剤（Ｂ）は、芳香族ポリイソシアネート（Ｂ１）のみを含んでいてもよいが、本発明の効果を損なわない範囲で、芳香族ポリイソシアネート（Ｂ１）以外の架橋剤を含有していてもよい。
　ここで、本発明の一態様において、耐貼り付き性をより向上させやすくする観点、インク密着性をより向上させやすくする観点、さらには耐水擦過性を向上させやすくする観点から、架橋剤（Ｂ）は、さらにイソシアヌレート系化合物（Ｂ２）を含むことが好ましい。
　なお、耐水擦過性に優れるラテックスインク受理層を有するラテックスインク用フィルムは、水貼り施工時における印刷部の剥がれを抑制することができる。 The cross-linking agent (B) may contain only the aromatic polyisocyanate (B1), but may contain a cross-linking agent other than the aromatic polyisocyanate (B1) within a range that does not impair the effects of the present invention. good.
Here, in one aspect of the present invention, from the viewpoint of facilitating the improvement of sticking resistance, the viewpoint of facilitating improvement of ink adhesion, and the viewpoint of facilitating improvement of water scratch resistance, the crosslinking agent (B ) preferably further contains an isocyanurate compound (B2).
A film for latex ink having a latex ink-receiving layer with excellent water abrasion resistance can suppress peeling of the printed portion during application with water.
　本発明の一態様において、架橋剤（Ｂ）が芳香族ポリイソシアネート（Ｂ１）を含み、イソシアヌレート系化合物（Ｂ２）を含まない場合、芳香族ポリイソシアネート（Ｂ１）の含有量は、架橋剤（Ｂ）の全量基準で、好ましくは８０質量％～１００質量％、より好ましくは９０質量％～１００質量％、更に好ましくは９５質量％～１００質量％である。
　また、本発明の一態様において、架橋剤（Ｂ）が芳香族ポリイソシアネート（Ｂ１）及びイソシアヌレート系化合物（Ｂ２）を含む場合、芳香族ポリイソシアネート（Ｂ１）及びイソシアヌレート系化合物（Ｂ２）の合計含有量は、架橋剤（Ｂ）の全量基準で、好ましくは８０質量％～１００質量％、より好ましくは９０質量％～１００質量％、更に好ましくは９５質量％～１００質量％である。 In one aspect of the present invention, when the cross-linking agent (B) contains an aromatic polyisocyanate (B1) and does not contain an isocyanurate compound (B2), the content of the aromatic polyisocyanate (B1) is the cross-linking agent ( Based on the total amount of B), it is preferably 80% to 100% by mass, more preferably 90% to 100% by mass, and still more preferably 95% to 100% by mass.
Further, in one aspect of the present invention, when the cross-linking agent (B) contains an aromatic polyisocyanate (B1) and an isocyanurate compound (B2), the aromatic polyisocyanate (B1) and the isocyanurate compound (B2) The total content is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, still more preferably 95% by mass to 100% by mass, based on the total amount of the cross-linking agent (B).
　以下、芳香族ポリイソシアネート（Ｂ１）及びイソシアヌレート系化合物（Ｂ２）について、詳細に説明する。 The aromatic polyisocyanate (B1) and the isocyanurate compound (B2) are described in detail below.
（芳香族ポリイソシアネート（Ｂ１））
　架橋剤（Ｂ）は、芳香族ポリイソシアネート（Ｂ１）を含む。
　芳香族ポリイソシアネート（Ｂ１）は、芳香環を有し、且つイソシアネート基を２つ以上有する化合物である。
　芳香族ポリイソシアネート（Ｂ１）は、電子吸引基である芳香環にイソシアネート基が結合しているため、イソシアネート基の反応活性が非常に高く、架橋反応が速やかに起こりやすい。また、架橋性官能基を有するアクリル系樹脂（Ａ）との反応により形成される架橋構造によって、ラテックスインク受理層（Ｘ）が適度な硬さとなる。そのため、ラテックスインク受理層（Ｘ）の耐貼り付き性を優れたものとできると推察される。また、架橋性官能基を有するアクリル系樹脂（Ａ）との反応により形成される架橋構造が、ラテックスインクによる印刷部との密着性に寄与し、当該密着性を優れたものにしていると推察される。 (Aromatic polyisocyanate (B1))
The cross-linking agent (B) contains an aromatic polyisocyanate (B1).
Aromatic polyisocyanate (B1) is a compound having an aromatic ring and two or more isocyanate groups.
Since the aromatic polyisocyanate (B1) has an isocyanate group bonded to an aromatic ring which is an electron-withdrawing group, the isocyanate group has very high reaction activity, and a cross-linking reaction tends to occur quickly. In addition, the latex ink-receiving layer (X) has appropriate hardness due to the crosslinked structure formed by the reaction with the acrylic resin (A) having a crosslinkable functional group. Therefore, it is presumed that the latex ink-receiving layer (X) can have excellent sticking resistance. In addition, it is speculated that the crosslinked structure formed by the reaction with the acrylic resin (A) having a crosslinkable functional group contributes to the adhesion of the latex ink to the printed area, making the adhesion excellent. be done.
　ここで、芳香族ポリイソシアネート（Ｂ１）において、芳香環とイソシアネート基は、直接結合していてもよく、アルキレン基等のリンカーを介して結合していてもよいが、芳香族ポリイソシアネート（Ｂ１）の反応性をより高めて、架橋反応をより速やかに起こりやすくし、ラテックスインク受理層（Ｘ）の耐貼り付き性をより向上させやすくする観点から、芳香環とイソシアネート基とは、直接結合しているか、又は、メチレン基を介して結合していることが好ましく、直接結合していることがより好ましい。
　また、芳香族ポリイソシアネート（Ｂ１）において、イソシアネート基の数は、２以上であればよいが、好ましくは２～３、より好ましくは２である。 Here, in the aromatic polyisocyanate (B1), the aromatic ring and the isocyanate group may be directly bonded or may be bonded via a linker such as an alkylene group. from the viewpoint of further increasing the reactivity of the isocyanate group, making it easier for the cross-linking reaction to occur more quickly, and making it easier to improve the sticking resistance of the latex ink-receiving layer (X). or is preferably bonded via a methylene group, and more preferably directly bonded.
In the aromatic polyisocyanate (B1), the number of isocyanate groups should be 2 or more, preferably 2 to 3, more preferably 2.
　芳香族ポリイソシアネート（Ｂ１）としては、例えば、１，３－フェニレンジイソシアネート、４，４’－ジフェニルジイソシアネート、１，４－フェニレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４’－トルイジンジイソシアネート、２，４，６－トリイソシアネートトルエン、１，３，５－トリイソシアネートベンゼン、ジアニシジンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、４，４’，４”－トリフェニルメタントリイソシアネート、ω，ω’－ジイソシアネート－１，３－ジメチルベンゼン、ω，ω’－ジイソシアネート－１，４－ジメチルベンゼン、ω，ω’－ジイソシアネート－１，４－ジエチルベンゼン、１，４－テトラメチルキシリレンジイソシアネート、及び１，３－テトラメチルキシリレンジイソシアネート等が挙げられる。 Examples of the aromatic polyisocyanate (B1) include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4, 4′,4″-triphenylmethane triisocyanate, ω,ω′-diisocyanate-1,3-dimethylbenzene, ω,ω′-diisocyanate-1,4-dimethylbenzene, ω,ω′-diisocyanate-1,4 -diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.
　また、芳香族ポリイソシアネート（Ｂ１）は、例えば、ポリオールとのアダクト体、ビウレット体、アロファネート体、及び３量体等であってもよいが、これらの中でも、ポリオールとのアダクト体が好ましく、トリメチロールプロパンとのアダクト体がより好ましい。トリメチロールプロパンとのアダクト体としては、例えば、トリメチロールプロパンアダクトトリレンジイソシアネート、トリメチロールプロパンアダクトキシリレンジイソシアネート等が挙げられる。 Further, the aromatic polyisocyanate (B1) may be, for example, an adduct with a polyol, a biuret, an allophanate, or a trimer. An adduct with methylolpropane is more preferred. Examples of adducts with trimethylolpropane include trimethylolpropane adduct tolylene diisocyanate and trimethylolpropane adduct xylylene diisocyanate.
　芳香族ポリイソシアネート（Ｂ１）の市販品としては、例えば、「コロネート　Ｌ」（トリメチロールプロパンアダクトトリレンジイソシアネート、東ソー株式会社）、「タケネート　Ｄ－１１０Ｎ」（トリメチロールプロパンアダクトキシリレンジイソシアネート、三井化学株式会社）等が挙げられる。 Commercially available aromatic polyisocyanates (B1) include, for example, "Coronate L" (trimethylolpropane adduct tolylene diisocyanate, Tosoh Corporation), "Takenate D-110N" (trimethylolpropane adduct xylylene diisocyanate, Mitsui Chemicals, Inc.). Co., Ltd.), etc.
　芳香族ポリイソシアネート（Ｂ１）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The aromatic polyisocyanate (B1) may be used alone or in combination of two or more.
（イソシアヌレート系化合物（Ｂ２））
　架橋剤（Ｂ）は、芳香族ポリイソシアネート（Ｂ１）とともに、イソシアヌレート系化合物（Ｂ２）を含むことが好ましい。
　イソシアヌレート系化合物（Ｂ２）は、イソシアヌレート化合物（Ｂ２－１）及びイソシアヌレート化合物の変性体（Ｂ２－２）を含む。
　イソシアヌレート系化合物（Ｂ２）中のイソシアヌレート化合物（Ｂ２－１）及びイソシアヌレート化合物の変性体（Ｂ２－２）の合計含有量は、耐貼り付き性をより向上させやすくする観点、インク密着性をより向上させやすくする観点、さらには耐水擦過性を向上させやすくする観点から、イソシアヌレート系化合物（Ｂ２）の全量基準で、好ましくは８０質量％～１００質量％、より好ましくは９０質量％～１００質量％、更に好ましくは９５質量％～１００質量％である。 (Isocyanurate compound (B2))
The cross-linking agent (B) preferably contains an isocyanurate compound (B2) together with the aromatic polyisocyanate (B1).
The isocyanurate compound (B2) includes an isocyanurate compound (B2-1) and a modified isocyanurate compound (B2-2).
The total content of the isocyanurate compound (B2-1) and the modified isocyanurate compound (B2-2) in the isocyanurate compound (B2) is from the viewpoint of making it easier to improve sticking resistance and ink adhesion. From the viewpoint of making it easier to improve the water abrasion resistance, the total amount of the isocyanurate compound (B2) is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, more preferably 95% to 100% by mass.
－イソシアヌレート化合物（Ｂ２－１）－
　イソシアヌレート系化合物（Ｂ２）は、イソシアヌレート化合物（Ｂ２－１）を含む。
　イソシアヌレート化合物（Ｂ２－１）は、１，６－ヘキサメチレンジイソシアネートの３量体であり、具体的には下記式（１）の化合物である。
Figure JPOXMLDOC01-appb-C000001
 -Isocyanurate compound (B2-1)-
The isocyanurate compound (B2) includes an isocyanurate compound (B2-1).
The isocyanurate compound (B2-1) is a trimer of 1,6-hexamethylene diisocyanate, specifically a compound of the following formula (1).
Figure JPOXMLDOC01-appb-C000001
－イソシアヌレート化合物（Ｂ２－２）－
　イソシアヌレート系化合物（Ｂ２）は、イソシアヌレート化合物の変性体（Ｂ２－２）を含む。
　イソシアヌレート化合物の変性体（Ｂ２－２）は、１，６－ヘキサメチレンジイソシアネートの３量体であって、且つ１以上の３級アミノ基を有する。 -Isocyanurate compound (B2-2)-
The isocyanurate compound (B2) includes a modified isocyanurate compound (B2-2).
The modified isocyanurate compound (B2-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups.
　１以上の３級アミノ基を、上記式（１）の化合物に導入して変性体とする方法としては、例えば、水酸基及び３級アミノ基を有する変性剤を、上記式（１）の化合物と反応させる方法が、挙げられる。
　このような変性剤としては、例えば、Ｎ，Ｎ－ジメチルアミノヘキサノール（例えば、花王株式会社製、カオーライザーＮｏ．２５）、Ｎ，Ｎ－ジメチルアミノエトキシエトキシエタノール（例えば、花王株式会社製、カオーライザーＮｏ．２３ＮＰ）、Ｎ，Ｎ－ジメチルアミノエトキシエタノール（例えば、花王株式会社製、カオーライザーＮｏ．２６）、Ｎ，Ｎ，Ｎ’－トリメチルアミノエチルエタノールアミン（例えば、東ソー株式会社製、ＴＯＹＯＣＡＴ　ＲＸ５）、２－［［３－（ジメチルアミノ）プロピル］メチルアミノ］エタノール（例えば、Ｅｖоｎｉｋ社製、ＰＯＬＹＣＡＴ　１７）、Ｎ，Ｎ－ジメチルエタノールアミン（例えば、Ｈｕｎｔｓｍａｎ社製、ＪＥＦＦＣＡＴ　ＤＭＥＡ）等が挙げられる。
　なお、変性剤は、環構造を有していてもよいが、環構造を有していない、既述のような化合物であることが好ましい。また、変性剤は、金属元素を有していない、既述のような有機非金属化合物であることが好ましい。すなわち、変性剤は、水酸基及び３級アミノ基を有する、非環式有機非金属化合物であることが好ましい。 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.
　上記式（１）の化合物と変性剤との反応は、例えば、窒素置換された反応容器中に上記式（１）の化合物と変性剤とを投入し、反応温度６０℃～１００℃にて、１時間～５時間撹拌することにより行うことが好ましい。 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.
－イソシアヌレート系化合物（Ｂ２）の調製－
　イソシアヌレート系化合物（Ｂ２）は、例えば、既述した上記式（１）の化合物と変性剤との反応を行う際に、上記式（１）の化合物と変性剤との反応容器への投入量比を適宜調整することで、調製することができる。
　上記式（１）の化合物に対する変性剤の投入割合は、上記式（１）の化合物１００質量部に対し、変性剤の含有量が０．０１～１０質量部であることが好ましく、０．０５質量部～５質量部であることがより好ましい。これにより、多数の上記式（１）の化合物のうち、一部の化合物のみが１以上の３級アミノ基を有する化合物となるため、イソシアヌレート化合物（Ｂ２－１）及びイソシアヌレート化合物の変性体（Ｂ２－２）を含むイソシアヌレート系化合物（Ｂ２）を調製することができる。
　なお、イソシアヌレート化合物の変性体（Ｂ２－２）の含有量は、イソシアヌレート系化合物（Ｂ２）の全量基準で、好ましくは０．５モル％～１０モル％、より好ましくは１モル％～５モル％である。 -Preparation of isocyanurate compound (B2)-
The isocyanurate-based compound (B2) 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, of the many compounds of formula (1), only some of the compounds become compounds having one or more tertiary amino groups, so the isocyanurate compound (B2-1) and modified isocyanurate compounds An isocyanurate compound (B2) containing (B2-2) can be prepared.
The content of the modified isocyanurate compound (B2-2) is preferably 0.5 mol% to 10 mol%, more preferably 1 mol% to 5 mol%, based on the total amount of the isocyanurate compound (B2). in mol %.
（芳香族ポリイソシアネート（Ｂ１）の含有量）
　架橋性官能基を有するアクリル系樹脂（Ａ）１００質量部に対する、芳香族ポリイソシアネート（Ｂ１）の含有量は、耐貼り付き性及びインク密着性向上の観点から、好ましくは７．０質量部以上、より好ましくは８．０質量部以上、更に好ましくは９．０質量部以上である。また、好ましくは３０質量部以下である。
　なお、耐折り曲げ性を向上させる観点から、好ましくは２４．２質量部未満、より好ましくは２０．０質量部以下、更に好ましくは１５．０質量部以下、より更に好ましくは１０．０質量部以下である。
　ラテックスインク用フィルムが耐折り曲げ性に優れることで、ラテックスインク用フィルムを折り曲げた際に生じる白化等を抑制することができ、印刷部が形成されたラテックスインク用フィルムの外観を良好な状態に保持し得る。 (Content of aromatic polyisocyanate (B1))
The content of the aromatic polyisocyanate (B1) with respect to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group is preferably 7.0 parts by mass or more from the viewpoint of improving sticking resistance and ink adhesion. , more preferably 8.0 parts by mass or more, and still more preferably 9.0 parts by mass or more. Moreover, it is preferably 30 parts by mass or less.
From the viewpoint of improving bending resistance, it is preferably less than 24.2 parts by mass, more preferably 20.0 parts by mass or less, even more preferably 15.0 parts by mass or less, and even more preferably 10.0 parts by mass or less. is.
Since the latex ink film has excellent bending resistance, it is possible to suppress the whitening that occurs when the latex ink film is bent, and the appearance of the latex ink film on which the printed part is formed can be maintained in good condition. can.
（イソシアヌレート系化合物（Ｂ２）の含有量）
　架橋剤（Ｂ）がイソシアヌレート系化合物（Ｂ２）を含む場合、架橋性官能基を有するアクリル系樹脂（Ａ）１００質量部に対する、イソシアヌレート系化合物（Ｂ２）の含有量は、耐貼り付き性をより向上させやすくする観点、インク密着性をより向上させやすくする観点、さらには耐水擦過性を向上させやすくする観点から、好ましくは１．０質量部以上、より好ましくは３．０質量部以上、更に好ましくは５．０質量部以上、より更に好ましくは７．０質量部以上である。また、好ましくは２５．０質量部以下、より好ましくは２２．０質量部以下、更に好ましくは２０．０質量部以下である。 (Content of isocyanurate compound (B2))
When the cross-linking agent (B) contains the isocyanurate compound (B2), the content of the isocyanurate compound (B2) with respect to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group is the sticking resistance. from the viewpoint of making it easier to improve the ink adhesion, and the viewpoint of making it easier to improve the water scratch resistance, preferably 1.0 parts by mass or more, more preferably 3.0 parts by mass or more. , more preferably 5.0 parts by mass or more, still more preferably 7.0 parts by mass or more. Also, it is preferably 25.0 parts by mass or less, more preferably 22.0 parts by mass or less, and even more preferably 20.0 parts by mass or less.
（芳香族ポリイソシアネート（Ｂ１）及びイソシアヌレート系化合物（Ｂ２）の合計含有量）
　架橋剤（Ｂ）がイソシアヌレート系化合物（Ｂ２）を含む場合、架橋性官能基を有するアクリル系樹脂（Ａ）１００質量部に対する、芳香族ポリイソシアネート（Ｂ１）及びイソシアヌレート系化合物（Ｂ２）の合計含有量は、耐貼り付き性をより向上させやすくする観点、インク密着性をより向上させやすくする観点、さらには耐水擦過性を向上させやすくする観点から、好ましくは８．０質量部以上、より好ましくは１１．０質量部以上、更に好ましくは１４．０質量部以上、より更に好ましくは１６．０質量部以上である。
　また、耐折り曲げ性を向上させる観点から、好ましくは４１．４質量部以下、より好ましくは２８．０質量部以下、更に好ましくは２０．０質量部以下である。 (Total content of aromatic polyisocyanate (B1) and isocyanurate compound (B2))
When the cross-linking agent (B) contains the isocyanurate compound (B2), the aromatic polyisocyanate (B1) and the isocyanurate compound (B2) are added to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group. The total content is preferably 8.0 parts by mass or more from the viewpoint of easily improving the sticking resistance, the viewpoint of easily improving the ink adhesion, and the viewpoint of easily improving the water scratch resistance. It is more preferably 11.0 parts by mass or more, still more preferably 14.0 parts by mass or more, and even more preferably 16.0 parts by mass or more.
From the viewpoint of improving bending resistance, the content is preferably 41.4 parts by mass or less, more preferably 28.0 parts by mass or less, and even more preferably 20.0 parts by mass or less.
（芳香族ポリイソシアネート（Ｂ１）とイソシアヌレート系化合物（Ｂ２）との含有比率）
　架橋剤（Ｂ）がイソシアヌレート系化合物（Ｂ２）を含む場合、芳香族ポリイソシアネート（Ｂ１）とイソシアヌレート系化合物（Ｂ２）との含有比率［（Ｂ１）／（Ｂ２）］は、耐貼り付き性をより向上させやすくする観点、インク密着性をより向上させやすくする観点、さらには耐水擦過性を向上させやすくする観点から、質量比で、好ましくは０．２～５．０、より好ましくは０．３～３．０、更に好ましくは０．５～２．０である。 (Content ratio of aromatic polyisocyanate (B1) and isocyanurate compound (B2))
When the cross-linking agent (B) contains the isocyanurate compound (B2), the content ratio [(B1)/(B2)] of the aromatic polyisocyanate (B1) and the isocyanurate compound (B2) is the anti-sticking From the viewpoint of facilitating improvement of the properties, the viewpoint of facilitating improvement of ink adhesion, and the viewpoint of facilitating improvement of water scratch resistance, the mass ratio is preferably 0.2 to 5.0, more preferably 0.2 to 5.0. 0.3 to 3.0, more preferably 0.5 to 2.0.
＜基材（Ｙ）＞
　本発明のラテックスインク用フィルムは、基材（Ｙ）を有する。
　基材（Ｙ）は、ラテックスインク受理層（Ｘ）を支持すると共に、ラテックスインク受理層（Ｘ）上に形成される印刷部を支持する支持体としての機能を有する。 <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 functions as a support for supporting the printed portion formed on the latex ink-receiving layer (X).
　基材（Ｙ）は、特に限定されないが、樹脂フィルムであることが好ましい。基材（Ｙ）が樹脂フィルムであることにより、ラテックスインク用フィルムの剛性及び可撓性等を良好なものとし、ラテックスインク用フィルムの取扱性を良好なものとできる。また、ラテックスインク用フィルムの生産コストの低減及び軽量化の観点からも有利である。 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.
　ここで、基材（Ｙ）は、透明性を有する樹脂フィルムであることが好ましい。基材（Ｙ）が、透明性を有する樹脂フィルムであることにより、ラテックスインク用フィルムのラテックスインク受理層上に印刷部が形成された印刷物を、店舗、ショールーム、オフィス等のガラス装飾としての用途等に好適に用いることができる。 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.
　樹脂フィルムを構成する樹脂としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、及びポリエチレンナフタレート等のポリエステル系樹脂；ポリエチレン及びポリプロピレン等のポリオレフィン樹脂；ポリスチレン；アクリロニトリル－ブタジエン－スチレン共重合体；三酢酸セルロース；ポリカーボネート；ポリウレタン及びアクリル変性ポリウレタン等のウレタン樹脂；ポリメチルペンテン；ポリスルホン；ポリエーテルエーテルケトン；ポリエーテルスルホン；ポリフェニレンスルフィド；ポリエーテルイミド、ポリイミド等のポリイミド系樹脂；ポリアミド系樹脂；アクリル樹脂；フッ素系樹脂等が挙げられる。
　これらの中でも、ラテックスインク受理層（Ｘ）と基材（Ｙ）との密着性を向上させやすくする観点から、ポリエステル系樹脂、ポリオレフィン系樹脂であることが好ましく、ポリエステル系樹脂であることがより好ましく、ポリエチレンテレフタレートであることが更に好ましい。なお、本発明によれば、ラテックスインク用フィルムを構成するラテックスインク受理層（Ｘ）と基材（Ｙ）との密着性を十分に確保しつつも、耐貼り付き性に優れるため、巻き取り時等にラテックスインク受理層（Ｘ）の表面と基材（Ｙ）の裏面とが接触した際に、基材（Ｙ）の裏面へのラテックスインク受理層（Ｘ）の貼り付きが抑制される。したがって、当該貼り付きに起因して、ラテックスインク受理層（Ｘ）の表面に荒れが生じたりすることが抑制される。 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. According to the present invention, the adhesiveness between the latex ink-receiving layer (X) and the base material (Y), which constitute the latex ink film, is sufficiently ensured, and the sticking resistance is excellent. When the surface of the latex ink-receiving layer (X) and the back surface of the substrate (Y) come into contact with each other, the sticking of the latex ink-receiving layer (X) to the back surface of the substrate (Y) is suppressed. . Therefore, the surface of the latex ink-receiving layer (X) is prevented from becoming rough due to the sticking.
　樹脂フィルムは、１種の樹脂のみから構成されたものであってもよく、２種以上の樹脂から構成されたものであってもよい。樹脂フィルムが２種以上の樹脂から構成されている場合、樹脂フィルムは複層体であることが好ましい。また、複層体の最上層（ラテックスインク受理層に接する層）は、ラテックスインク受理層（Ｘ）と基材（Ｙ）との密着性を向上させやすくする観点から、ポリエステル系樹脂であることが好ましく、ポリエチレンテレフタレートであることがより好ましい。 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.
　また、樹脂フィルムは、未延伸でもよいし、縦又は横等の一軸方向あるいは二軸方向に延伸されていてもよい。 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.
　加えて、樹脂フィルムは、これらの樹脂と共に、表面調整剤、可塑剤、紫外線吸収剤、光安定剤、及び着色剤等の、基材用添加剤を含有していてもよい。
　基材用添加剤の含有量は、基材（Ｙ）の全量基準で、好ましくは１０質量％以下、より好ましくは５質量％以下、更に好ましくは３質量％以下である。 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).
　基材の厚さは、特に限定されないが、好ましくは１５μｍ～３００μｍ、より好ましくは３０μｍ～２００μｍである。 Although the thickness of the base material is not particularly limited, it is preferably 15 μm to 300 μm, more preferably 30 μm to 200 μm.
＜粘着剤層（Ｚ）＞
　本発明の一態様のラテックスインク用フィルムは、粘着剤層（Ｚ）を有していてもよい。
　本発明の一態様のラテックスインク用フィルムが粘着剤層（Ｚ）を有することで、ラテックスインク用フィルムを、粘着フィルムとして好適に用いることができる。 <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.
　粘着剤層を構成する粘着剤は、特に限定されず、例えば、アクリル系粘着剤、ウレタン系粘着剤、及びシリコーン系粘着剤等が挙げられる。 The adhesive that constitutes the adhesive layer is not particularly limited, and examples thereof include acrylic adhesives, urethane adhesives, and silicone adhesives.
　粘着剤層（Ｚ）の厚さは、特に限定されないが、ラテックスインク用フィルムを、粘着フィルムとして用いる際の取扱性の向上の観点から、好ましくは５μｍ～１００μｍ、より好ましくは１０μｍ～７０μｍ、更に好ましくは１５μｍ～５０μｍである。 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, 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.
＜剥離ライナー＞
　本発明の一態様のラテックスインク用フィルムは、粘着剤層（Ｚ）と共に、剥離ライナーを有していてもよい。
　本発明の一態様のラテックスインク用フィルムが有する粘着剤層（Ｚ）の粘着表面が剥離ライナーで覆われていることで、ラテックスインク用フィルムの搬送時や保管時において粘着剤層（Ｚ）の粘着表面を好適に保護することができる。 <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.
　剥離ライナーは、特に限定されず、粘着フィルムの分野で通常使用される剥離ライナーを適宜用いることができる。剥離ライナーとしては、例えば、フィルム基材又は紙基材の表面に、剥離層が設けられた積層体等が挙げられる。
　フィルム基材としては、例えば、ポリエチレンテレフタレート等のポリエステル系樹脂、ポリエチレン樹脂及びポリプロピレン樹脂等のポリオレフィン系樹脂等が挙げられる。
　紙基材としては、例えば、上質紙、クラフト紙、及びグラシン紙等の紙類が挙げられる。
　剥離層の構成材料は、例えば、シリコーン系樹脂、長鎖アルキル系樹脂、及びフッ素系樹脂等が挙げられる。 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-based resins, long-chain alkyl-based resins, and fluorine-based resins.
　剥離ライナーの厚さは、特に限定されないが、好ましくは１０μｍ～２００μｍ、より好ましくは１５μｍ～１５０μｍ、更に好ましくは２０μｍ～１２０μｍである。 Although the thickness of the release liner is not particularly limited, it is preferably 10 μm to 200 μm, more preferably 15 μm to 150 μm, still more preferably 20 μm to 120 μm.
［ラテックスインク用フィルムの製造方法］
　本発明のラテックスインク用フィルムの製造方法としては、特に制限はなく、ラテックスインク用フィルムの構成によって適宜選択される。 [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.
＜ラテックスインク受理層（Ｘ）の形成方法＞
　ラテックスインク受理層（Ｘ）の形成方法としては、基材（Ｙ）の一方の面（Ｙａ）に、樹脂組成物（ｘ１）を塗布して塗膜を形成し、当該塗膜を乾燥させた後、架橋させることで、ラテックスインク受理層（Ｘ）を形成することが好ましい。
　なお、基材（Ｙ）への塗布の作業性を向上させるために、樹脂組成物（ｘ１）は、更に希釈溶媒で希釈して、溶液の形態とすることが好ましい。 <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. It is preferable to form the latex ink-receiving layer (X) by subsequently 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.
　希釈溶媒としては、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサン、ｎ－ヘキサン、トルエン、キシレン、ｎ－プロパノール、及びイソプロパノール等の有機溶剤が挙げられる。
　樹脂組成物（ｘ１）の溶液の有効成分濃度としては、好ましくは１０質量～５０質量％である。 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.
　樹脂組成物（ｘ１）の溶液の塗布方法としては、例えば、マイヤーバーコート法、グラビヤコート法、ロールコート法、ナイフコート法、ダイコート法等が挙げられる。 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.
　塗膜を乾燥させる際の加熱条件は、特に限定されず、例えば、乾燥温度６０℃～１２０℃、乾燥時間３０秒間～３分間である。
　架橋条件は、特に限定されず、例えば、通常環境（例えば２３℃、相対湿度５０℃）に１日以上１４日以下放置して架橋させてもよいし、４０℃～６０℃の環境下に１日～３日間放置して架橋させてもよい。また、乾燥工程と架橋工程を一括して行うようにしてもよい。 The heating conditions for drying the coating film are not particularly limited, and are, for example, a drying temperature of 60° C. to 120° C. and a drying time of 30 seconds to 3 minutes.
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. Alternatively, the drying step and the cross-linking step may be performed collectively.
＜粘着剤層（Ｚ）の形成方法＞
　本発明の一態様のラテックスインク用フィルムが粘着剤層（Ｚ）を有する場合、粘着剤層（Ｚ）は、ラテックスインク受理層（Ｘ）が形成されていない、基材（Ｙ）の他方の面（Ｙｂ）に形成される。
　粘着剤層（Ｚ）は、例えば、基材（Ｙ）の他方の面（Ｙｂ）に、粘着剤層（Ｚ）を形成するための組成物（粘着剤層形成用組成物）を塗布することにより形成される。あるいは、剥離ライナーの剥離面に粘着剤層形成用組成物を塗布して粘着剤層（Ｚ）を形成し、これを基材（Ｙ）の他方の面（Ｙｂ）に貼り合わせる（転写する）ようにしてもよい。
　粘着剤層形成用組成物の塗布方法は、樹脂組成物（ｘ１）として既述したものと同じである。 <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).
［ラテックスインク用フィルムの用途等］
　本発明のラテックスインク用フィルムは、ラテックスインクを使用した印刷に用いられることが好ましい。
　したがって、本発明によれば、前記ラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクを用いて印刷部を形成するために、前記ラテックスインク用フィルムを使用する、使用方法が提供される。
　また、本発明によれば、前記ラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクを用いて印刷部を形成する工程を含む、印刷物の製造方法が提供される。
　さらに、本発明によれば、前記ラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクによる印刷部を有する、印刷物が提供される。 [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.
　以下、本発明のラテックスインク用フィルムのラテックスインク受理層上に印刷部を形成するための、ラテックスインクについて説明した後、本発明のラテックスインク用フィルムのラテックスインク受理層上に印刷部を形成する方法について説明する。 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.
＜ラテックスインク＞
　ラテックスインクは、液状の分散媒と、当該分散媒中に分散（乳濁および／または懸濁）している、少なくとも樹脂を含む材料で構成された分散質を含有する。
　ラテックスインクは、環境に対する負荷が低い。また、ラテックスインクは、薄い層で濃い色を表現できるという利点がある。また、ラテックスインクを構成するラテックス粒子は、バインダー（樹脂）を含み、一般に、顔料着色剤の記録媒体への密着性を向上させる上で有利である。また、インクジェット法を利用できるため、オンデマンドで印刷することができるという利点がある。
　また、ラテックスインクは、水系インクであることが好ましい。水系インクは、有機溶剤に起因する揮発性有機物の発生が抑えられるため、安全性がより高く、環境に対する負荷がより少ない。 <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.
（樹脂）
　ラテックスインクに含まれる樹脂は、特に限定されないが、例えば、ビニル系樹脂、アクリル系樹脂、スチレン系樹脂、アルキッド系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、シリコーン系樹脂、フッ素系樹脂、エポキシ系樹脂、フェノキシ系樹脂、ポリオレフィン系樹脂等、およびこれらの変性樹脂（例えば、水溶性に変性された変性樹脂）等が挙げられ、これらから選択される１種または２種以上を組み合わせて用いることができる。この中でも、アクリル系樹脂、スチレン系樹脂、水溶性ポリウレタン系樹脂、水溶性ポリエステル系樹脂、水溶性アクリル系樹脂が好ましく、アクリル系樹脂がより好ましい。
　本発明の一態様のラテックスインク用フィルムにおいて用いられるラテックスインクは、ラテックスインク受理層（Ｘ）と印刷部との密着性をより向上させる観点から、アクリル系樹脂を含むラテックスインクであることが好ましい。
　ラテックスインク中における樹脂の含有率は、ラテックスインクの全量基準で、１質量％～２０質量％であるのが好ましく、２質量％～１０質量％であるのがより好ましい。 (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.
（分散媒）
　ラテックスインクは、分散媒として水を含む。
　ラテックスインク中における分散媒（水）の含有率は、ラテックスインクの全量基準で、５０質量％～９８質量％であるのが好ましく、６０質量％～９７質量％であるのがより好ましく、７０質量％～９６質量％であるのが更に好ましい。 (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 %.
（着色剤）
　ラテックスインクは、通常、着色剤を含んでいる。
　着色剤としては、各種染料、各種顔料等を用いることができる。
　ラテックスインク中における着色剤の含有率は、ラテックスインクの全量基準で、０．１質量％～２０質量％であるのが好ましく、０．２質量％～１０質量％であるのがより好ましい。 (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.
（その他の成分）
　ラテックスインクは、既述した以外の成分（その他の成分）を含んでいてもよい。
　このような成分としては、例えば、分散剤、防黴剤、防錆剤、ｐＨ調整剤、界面活性剤、可塑剤、紫外線吸収剤、光安定剤等が挙げられる。 (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.
＜印刷部の形成＞
　ラテックスインクによる印刷部は、ラテックスインク用フィルムのラテックスインク受理層（Ｘ）上にラテックスインクを付与することにより形成される。当該ラテックスインクは、ラテックスインク受理層（Ｘ）と印刷部との密着性をより向上させる観点から、アクリル系樹脂を含むラテックスインクであることが好ましい。
　ラテックスインクを付与する方法は、特に限定されず、各種印刷法を用いることができるが、インクジェット法が好ましい。インクジェットの方式としては、例えば、ピエゾ方式、サーマルジェット方式等が挙げられる。
　ラテックスインクを付与する際、ラテックスインク用フィルムを加熱してもよい。加熱温度は、特に限定されないが、好ましくは４０℃～９０℃である。
　以上の方法により、ラテックスインク用フィルムのラテックスインク受理層（Ｘ）上にラテックスインクによる印刷部を有する印刷物が得られる。当該ラテックスインクは、ラテックスインク受理層（Ｘ）と印刷部との密着性をより向上させる観点から、アクリル系樹脂を含むラテックスインクであることが好ましい。 <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.
　本発明について、以下の実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。 The present invention will be specifically described by the following examples, but the present invention is not limited to the following examples.
［各種物性値の測定方法］
　本実施例における各種物性値の測定方法は、以下に記載のとおりである。
（１）水酸基価
　架橋性官能基を有するアクリル系樹脂（Ａ）の水酸基価は、ＪＩＳ　Ｋ００７０：１９９２に準拠して測定した。
（２）酸価
　架橋性官能基を有するアクリル系樹脂（Ａ）の酸価は、ＪＩＳ　Ｋ００７０：１９９２に準拠して測定した。
（３）ガラス転移温度（Ｔｇ）
　架橋性官能基を有するアクリル系樹脂（Ａ）のガラス転移温度（Ｔｇ）は、ＪＩＳ　Ｋ　７１２１：１９８７に準拠し、示差走査熱量計（ティー・エイ・インスツルメント・ジャパン株式会社製、製品名「ＤＳＣ　Ｑ２０００」）を用いて、昇温速度２０℃／分にて測定した。
（４）各層の厚さ
　各層の厚さは、テクロック社製の定圧厚さ測定器（型番：「ＰＧ－０２Ｊ」、標準規格：ＪＩＳ　Ｋ６７８３：１９９４、ＪＩＳ　Ｚ１７０２：１９９４、ＪＩＳ　Ｚ１７０９：１９９５に準拠）を用いて測定した。 [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: 1987 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.
［実施例１～４、比較例１］
　実施例１～４、比較例１のラテックスインク用フィルムを以下の手順で作製した。 [Examples 1 to 4, Comparative Example 1]
The latex ink films of Examples 1 to 4 and Comparative Example 1 were produced by the following procedure.
＜樹脂組成物の調製＞
　樹脂組成物の調製には、以下に示す樹脂及び架橋剤を用いた。 <Preparation of resin composition>
The following resins and cross-linking agents were used to prepare the resin composition.
（樹脂）
－架橋性官能基を有するアクリル系樹脂（Ａ）－
　水酸基価が１１．０ｍｇＫＯＨ／ｇであり、酸価が３．９ｍｇＫＯＨ／ｇであり、ガラス転移温度（Ｔｇ）が９０℃である、架橋性官能基を有するアクリル系樹脂を用いた。 (resin)
-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.
（架橋剤）
－架橋剤（Ｂ）－
・「芳香族ポリイソシアネート（Ｂ１）」：トリメチロールプロパンアダクトトリレンジイソシアネート
・「イソシアネート系化合物（Ｂ２）」：イソシアヌレート化合物の一部変性品（イソシアヌレート化合物（Ｂ２－１）とイソシアヌレート化合物の変性体（Ｂ２－２）とを含む架橋剤に相当。）
－架橋剤（Ｂ’）－
　イソシアヌレート化合物（未変性品、イソシアヌレート化合物（Ｂ２－１）に相当。）を用いた。 (crosslinking agent)
-Crosslinking agent (B)-
・ “Aromatic polyisocyanate (B1)”: trimethylolpropane adduct tolylene diisocyanate ・ “Isocyanate compound (B2)”: partially modified isocyanurate compound (isocyanurate compound (B2-1) and isocyanurate compound Corresponds to a cross-linking agent containing a modified product (B2-2).)
-Crosslinking agent (B')-
An isocyanurate compound (unmodified product, corresponding to isocyanurate compound (B2-1)) was used.
（その他の添加剤）
　スズ系触媒 (Other additives)
tin catalyst
　樹脂組成物を表１に示す配合（配合量は有効成分換算）にてそれぞれ調製し（有効成分濃度：１０質量％、希釈溶媒：酢酸エチル）、ポリエチレンテレフタレート（ＰＥＴ）製の基材（厚さ：５０μｍ）の一方の面に、マイヤーバーを用いて、乾燥後の膜厚が１μｍとなるように塗布した。 Each resin composition was prepared according to the formulation shown in Table 1 (the compounding amount is calculated as an active ingredient) (active ingredient concentration: 10% by mass, dilution solvent: ethyl acetate), and a polyethylene terephthalate (PET) base material (thickness : 50 μm) was coated on one side of the film using a Meyer bar so that the film thickness after drying would be 1 μm.
　次に、熱風乾燥装置を用いて、９０℃、１分間の条件で加熱することにより、基材に塗布した樹脂組成物に含まれる溶剤を除去し、さらに２３℃、相対湿度５０％の環境下に７日間放置することにより、架橋させた。これにより、厚さ：１μｍのラテックスインク受理層（Ｘ）を形成し、ラテックスインク用フィルムを得た。但し、耐貼りつき性の評価用の試験試料については、溶剤を除去した後の７日間放置工程を行わず作製し、溶剤を除去した直後に耐貼りつき性の評価試験に供した。 Next, using a hot air dryer, the solvent contained in the resin composition applied to the substrate is removed by heating at 90 ° C. for 1 minute, and further in an environment of 23 ° C. and a relative humidity of 50%. Crosslinked by leaving at room temperature for 7 days. Thus, a latex ink-receiving layer (X) having a thickness of 1 μm was formed to obtain a latex ink film. However, a test sample for evaluation of sticking resistance was prepared without performing the standing step for 7 days after removing the solvent, and was subjected to the sticking resistance evaluation test immediately after removing the solvent.
＜評価１＞
（１）インク密着性の評価
　実施例１～４及び比較例１のラテックスインク用フィルムのそれぞれについて、ラテックスインク受理層（Ｘ）の表面にラテックスインク（ヒューレット・パッカード社製、ＨＰ８８２）を用いてインクジェット印刷機（ヒューレット・パッカード社製、ＨＰ　Ｌａｔｅｘ　Ｒ２０００）でインクジェット法により、所定の試験用パターンを印刷し、印刷部（印刷層）を形成した。
　そして、所定の試験用パターンの印刷部が形成された実施例１～４及び比較例１のラテックスインク用フィルムを、２３℃、相対湿度５０％の環境下に１日間静置して、試験試料を準備した。
　そして、試験試料の印刷部が形成された側の面に、１００ｍｍ×２４ｍｍのニチバン社製セロテープ（登録商標）を貼付し、テープ引きはがし後の印刷部の残存率（残存面積／全面積）を求め、以下の基準に従い評価した。
１：残存率２０％未満
２：残存率２０％以上４０％未満
３：残存率４０％以上６０％未満
４：残存率６０％以上９０％未満
５：残存率９０％以上
　残存率が高い程、ラテックスインク受理層がインク密着性に優れる。 <Evaluation 1>
(1) Evaluation of Ink Adhesion For each of the latex ink films of Examples 1 to 4 and Comparative Example 1, 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 4 and Comparative Example 1 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, and the test sample was obtained. prepared.
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 has excellent ink adhesion.
（２）耐貼り付き性の評価
　実施例１～４及び比較例１のラテックスインク用フィルム（上述した耐貼りつき性の評価用の試験試料である、溶剤を除去した直後のラテックスインク用フィルム）を、それぞれ５ｃｍ×１０ｃｍの大きさに切断して１０枚重ね、積層体を作製した。当該積層体を厚さ３ｍｍのガラス板で挟み、ガラス板上に２ｋｇの重りを載せた状態で、４０℃、相対湿度８０％の環境下で７日静置した。次いで、当該積層体をガラス板の間から取り出し、２３℃、相対湿度５０％の環境下で２４時間静置した後、ラテックスインク用フィルムを１枚ずつ剥離し、剥離音と貼り付きを評価した。
　剥離音は、音が大きい順に１、２、３、４、及び５の５段階で評価とした。剥離音が聞こえない場合は、評価値は５とした。剥離音が小さい程（評価値が大きい程）、耐貼り付き性に優れる。 (2) Evaluation of sticking resistance Latex ink films of Examples 1 to 4 and Comparative Example 1 (latex ink film immediately after removing the solvent, which is a test sample for evaluating sticking resistance described above) was cut into pieces each having a size of 5 cm×10 cm, and 10 sheets were stacked to prepare a laminate. The laminate was sandwiched between glass plates having a thickness of 3 mm, and with a weight of 2 kg placed on the glass plates, the laminate was allowed to stand in an environment of 40° C. and a relative humidity of 80% for 7 days. Next, the laminate was taken out from between the glass plates and allowed to stand in an environment of 23° C. and a relative humidity of 50% for 24 hours.
The peeling sound was evaluated on a scale of 1, 2, 3, 4, and 5 in descending order of sound. The evaluation value was set to 5 when no peeling sound was heard. The smaller the peeling sound (the larger the evaluation value), the better the sticking resistance.
　評価１の結果を表１に示す。
　なお、実施例３における芳香族ポリイソシアネート（Ｂ１）とイソシアヌレート化合物（Ｂ２）との含有比率［（Ｂ１）／（Ｂ２）］は、質量比で、１．１３である。実施例４における含有比率［（Ｂ１）／（Ｂ２）］は、質量比で、１．４１である。 The results of evaluation 1 are shown in Table 1.
The content ratio [(B1)/(B2)] between the aromatic polyisocyanate (B1) and the isocyanurate compound (B2) in Example 3 was 1.13 in mass ratio. The content ratio [(B1)/(B2)] in Example 4 is 1.41 in mass ratio.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１より、以下のことがわかる。
　実施例１～４のラテックスインク用フィルムは、インク密着性に優れ、耐貼り付き性にも優れることがわかる。
　一方、比較例１のように架橋剤として未変性のイソシアネート化合物（Ｂ２－１）のみを用いた場合には、インク密着性が劣り、耐貼り付き性も劣ることがわかる。 Table 1 shows the following.
It can be seen that the latex ink films of Examples 1 to 4 are excellent in ink adhesion and sticking resistance.
On the other hand, when only the unmodified isocyanate compound (B2-1) was used as the cross-linking agent as in Comparative Example 1, the ink adhesion was inferior and the sticking resistance was also inferior.
＜評価２＞
（１）耐水擦過性の評価
　実施例１～４及び比較例１のラテックスインク用フィルムのそれぞれについて、インク密着性評価１と同様の方法で、所定の試験用パターンを印刷し、印刷部（印刷層）を形成した。
　そして、所定の試験用パターンの印刷部が形成された実施例１～４及び比較例１のラテックスインク用フィルムを、２３℃、相対湿度５０％の環境下に１日間静置して、試験試料を準備した。
　そして、試験試料の印刷部が形成された側の面の全面に、アニオン系界面活性剤（ラウレス硫酸ナトリウム）の３質量％水溶液を吹き付けた後、１０分間静置し、印刷部が形成された側の面の全面をゴム製スキージーで強く擦って、印刷部の残存率（残存面積／全面積）を求め、以下の基準に従い評価した。
１：残存率２０％未満
２：残存率２０％以上４０％未満
３：残存率４０％以上６０％未満
４：残存率６０％以上９０％未満
５：残存率９０％以上
　印刷部の残存率が高い程、ラテックスインク受理層が、耐水擦過性に優れる。
（２）耐折り曲げ性の評価
　実施例１～４及び比較例１のラテックスインク用フィルム（印刷前）をサンプルとし、ＪＩＳ　Ｋ　５６００－５－１：１９９９に基づき、円筒型マンドレル屈曲試験機でマンドレル直径５ｍｍφにて試験を行い、試験後のサンプルの白化度合いを目視で評価した。
　白化が強い順に１、２、３、４、及び５の５段階で評価とした。白化が確認されない場合には、評価値は５とした、白化が弱い程（評価値が大きい程）、耐折り曲げ性に優れる。 <Evaluation 2>
(1) Evaluation of water scratch resistance For each of the latex ink films of Examples 1 to 4 and Comparative Example 1, a predetermined test pattern was printed in the same manner as in Ink Adhesion Evaluation 1. layer) was formed.
Then, the latex ink films of Examples 1 to 4 and Comparative Example 1 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, and the test sample was obtained. 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 more excellent the latex ink-receiving layer is in water scratch resistance.
(2) Evaluation of bending resistance The latex ink films (before printing) of Examples 1 to 4 and Comparative Example 1 were used as samples, and the mandrel was tested with a cylindrical mandrel bending tester according to JIS K 5600-5-1: 1999. The test was performed with a diameter of 5 mmφ, and the degree of whitening of the sample after the test was visually evaluated.
Evaluation was made in five stages of 1, 2, 3, 4, and 5 in descending order of whitening. When no whitening was observed, the evaluation value was set to 5. The weaker the whitening (the higher the evaluation value), the better the bending resistance.
　評価２の結果を表２に示す。 Table 2 shows the results of evaluation 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２より、以下のことがわかる。
　実施例１～４のラテックスインク用フィルムは、耐水擦過性及び耐折り曲げ性に優れることがわかる。
　これらの中でも、実施例３及び実施例４のラテックスインク用フィルムは、耐水擦過性に極めて優れることがわかる。また、実施例１及び実施例３のラテックスインク用フィルムは、耐折り曲げ性に極めて優れることがわかる。 Table 2 shows the following.
It can be seen that the latex ink films of Examples 1 to 4 are excellent in water scratch resistance and bending resistance.
Among these, the latex ink films of Examples 3 and 4 are found to be extremely excellent in water scratch resistance. Moreover, it can be seen that the latex ink films of Examples 1 and 3 are extremely excellent in bending resistance.
１　　ラテックスインク用フィルム
Ｘ　　ラテックスインク受理層
Ｙ　　基材
Ｙａ　基材の一方の面
Ｙｂ　基材の他方の面
Ｚ　　粘着剤層

  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 (11)

  1. 　ラテックスインク受理層（Ｘ）と基材（Ｙ）とが積層された積層構造を有し、
    　前記ラテックスインク受理層（Ｘ）は、架橋性官能基を有するアクリル系樹脂（Ａ）及び架橋剤（Ｂ）を含有する樹脂組成物（ｘ１）から形成され、
    　前記架橋剤（Ｂ）は、芳香族ポリイソシアネート（Ｂ１）を含む、ラテックスインク用フィルム。     Having a laminated structure in which the latex ink-receiving layer (X) and the 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 and a crosslinker (B),
    A film for latex ink, wherein the cross-linking agent (B) contains an aromatic polyisocyanate (B1).
  2. 　前記架橋剤（Ｂ）は、さらに、イソシアヌレート系化合物（Ｂ２）を含み、
    　前記イソシアヌレート系化合物（Ｂ２）は、イソシアヌレート化合物（Ｂ２－１）及びイソシアヌレート化合物の変性体（Ｂ２－２）を含み、
    　前記イソシアヌレート化合物（Ｂ２－１）は、１，６－ヘキサメチレンジイソシアネートの３量体であり、
    　前記イソシアヌレート化合物の変性体（Ｂ２－２）は、１，６－ヘキサメチレンジイソシアネートの３量体であって、且つ１以上の３級アミノ基を有する、請求項１に記載のラテックスインク用フィルム。     The cross-linking agent (B) further contains an isocyanurate compound (B2),
    The isocyanurate compound (B2) includes an isocyanurate compound (B2-1) and a modified isocyanurate compound (B2-2),
    The isocyanurate compound (B2-1) is a trimer of 1,6-hexamethylene diisocyanate,
    2. The latex ink film according to claim 1, wherein the modified isocyanurate compound (B2-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups. .
  3. 　前記基材（Ｙ）は、ポリエステル系樹脂を含む、請求項１又は２に記載のラテックスインク用フィルム。 The film for latex ink according to claim 1 or 2, wherein the substrate (Y) contains a polyester resin.
  4. 　前記基材（Ｙ）の一方の面に前記ラテックスインク受理層（Ｘ）が積層され、
    　前記基材（Ｙ）の他方の面に粘着剤層（Ｚ）が設けられている、請求項１～３のいずれか１項に記載のラテックスインク用フィルム。     The latex ink-receiving layer (X) is laminated on one surface of the substrate (Y),
    4. The latex ink film according to any one of claims 1 to 3, wherein a pressure-sensitive adhesive layer (Z) is provided on the other surface of the substrate (Y).
  5. 　前記粘着剤層（Ｚ）の粘着表面が剥離ライナーで覆われている、請求項４に記載のラテックスインク用フィルム。 The film for latex ink according to claim 4, wherein the adhesive surface of the adhesive layer (Z) is covered with a release liner.
  6. 　前記架橋性官能基を有するアクリル系樹脂（Ａ）１００質量部に対する、前記芳香族ポリイソシアネート（Ｂ１）の含有量が、７．０質量部以上である、請求項１～５のいずれか１項に記載のラテックスインク用フィルム。 Any one of claims 1 to 5, wherein the content of the aromatic polyisocyanate (B1) is 7.0 parts by mass or more relative to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group. The film for latex ink described in .
  7. 　前記架橋性官能基を有するアクリル系樹脂（Ａ）１００質量部に対する、前記芳香族ポリイソシアネート（Ｂ１）の含有量が、２４．２質量部未満である、請求項１～６のいずれか１項に記載のラテックスインク用フィルム。 Any one of claims 1 to 6, wherein the content of the aromatic polyisocyanate (B1) is less than 24.2 parts by mass with respect to 100 parts by mass of the acrylic resin (A) having a crosslinkable functional group. The film for latex ink described in .
  8. 　アクリル系樹脂を含むラテックスインクを使用した印刷に用いられる、請求項１～７のいずれか１項に記載のラテックスインク用フィルム。 The film for latex ink according to any one of claims 1 to 7, which is used for printing using latex ink containing acrylic resin.
  9. 　請求項１～７のいずれか１項に記載のラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクを用いて印刷部を形成するために、前記ラテックスインク用フィルムを使用する、使用方法。 A method of using the film for latex ink according to any one of claims 1 to 7, 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.
  10. 　請求項１～７のいずれか１項に記載のラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクを用いて印刷部を形成する工程を含む、印刷物の製造方法。 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 7.
  11. 　請求項１～７のいずれか１項に記載のラテックスインク用フィルムのラテックスインク受理層上に、ラテックスインクによる印刷部を有する、印刷物。

          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 claims 1 to 7.
PCT/JP2021/038136 2021-10-14 2021-10-14 Film for latex ink WO2023062797A1 (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0872391A (en) * 1994-09-07 1996-03-19 Nippon Paper Ind Co Ltd Material for ink jet recording
JPH10292137A (en) * 1996-04-16 1998-11-04 Canon Inc Coating composition, recording medium, and image formation using the same
JP2000190433A (en) * 1998-12-25 2000-07-11 Oji Yuka Synthetic Paper Co Ltd Recording paper
JP2001138621A (en) * 1999-11-11 2001-05-22 Konica Corp Ink jet recording sheet
JP2002274007A (en) * 2001-03-15 2002-09-25 Toyobo Co Ltd Recording material and recorded matter using the same
JP2002274008A (en) * 2001-03-15 2002-09-25 Toyobo Co Ltd Recording material and recorded matter using the same
JP2002274006A (en) * 2001-03-15 2002-09-25 Toyobo Co Ltd Recording material and recorded matter using the same
JP2007524507A (en) * 2003-12-16 2007-08-30 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Printable article and method of making a printed article
JP2012218318A (en) * 2011-04-11 2012-11-12 Dic Corp Resin composition for forming conductive ink absorbing layer, conductive ink absorbing base material, board for forming circuit, printed matter, conductive pattern, and circuit board
JP2019172877A (en) * 2018-03-29 2019-10-10 リンテック株式会社 Film for latex ink and method for producing film for latex ink

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0872391A (en) * 1994-09-07 1996-03-19 Nippon Paper Ind Co Ltd Material for ink jet recording
JPH10292137A (en) * 1996-04-16 1998-11-04 Canon Inc Coating composition, recording medium, and image formation using the same
JP2000190433A (en) * 1998-12-25 2000-07-11 Oji Yuka Synthetic Paper Co Ltd Recording paper
JP2001138621A (en) * 1999-11-11 2001-05-22 Konica Corp Ink jet recording sheet
JP2002274007A (en) * 2001-03-15 2002-09-25 Toyobo Co Ltd Recording material and recorded matter using the same
JP2002274008A (en) * 2001-03-15 2002-09-25 Toyobo Co Ltd Recording material and recorded matter using the same
JP2002274006A (en) * 2001-03-15 2002-09-25 Toyobo Co Ltd Recording material and recorded matter using the same
JP2007524507A (en) * 2003-12-16 2007-08-30 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Printable article and method of making a printed article
JP2012218318A (en) * 2011-04-11 2012-11-12 Dic Corp Resin composition for forming conductive ink absorbing layer, conductive ink absorbing base material, board for forming circuit, printed matter, conductive pattern, and circuit board
JP2019172877A (en) * 2018-03-29 2019-10-10 リンテック株式会社 Film for latex ink and method for producing film for latex ink

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