WO2023135711A1 - Film pour encre au latex - Google Patents

Film pour encre au latex Download PDF

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Publication number
WO2023135711A1
WO2023135711A1 PCT/JP2022/000968 JP2022000968W WO2023135711A1 WO 2023135711 A1 WO2023135711 A1 WO 2023135711A1 JP 2022000968 W JP2022000968 W JP 2022000968W WO 2023135711 A1 WO2023135711 A1 WO 2023135711A1
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WIPO (PCT)
Prior art keywords
latex ink
ink
film
latex
receiving layer
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PCT/JP2022/000968
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English (en)
Japanese (ja)
Inventor
鉄也 荒添
拓磨 大久保
枝保 日野
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リンテック株式会社
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Priority to PCT/JP2022/000968 priority Critical patent/WO2023135711A1/fr
Publication of WO2023135711A1 publication Critical patent/WO2023135711A1/fr

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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
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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

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 printing method using latex ink has been widely adopted, and various demands are increasing for the latex ink film used at that time.
  • the latex ink-receiving layer of the latex ink film may be required to have scratch resistance.
  • the latex ink-receiving layer needs to be soft to some extent. be.
  • the surface of the latex ink-receiving layer is easily scratched and has poor scratch resistance.
  • the "printing coat layer” in Patent Document 2 is also inferior in abrasion resistance.
  • the latex ink-receiving layer there is a problem that it is difficult to achieve both ink adhesion and scratch resistance.
  • Films for latex ink are sometimes applied to glass surfaces of shops, showrooms, offices, etc., and used for advertisement and decoration purposes.
  • an adherend such as a glass surface
  • water or an aqueous solution containing a surfactant is sprayed onto the bonding surfaces of the adherends, and after the two are brought into close contact with each other and positioned, water, etc. is removed together with air from the latex ink film side using a squeegee.
  • a so-called wet application in which the adhesive is applied by scraping, is generally performed.
  • the latex-ink-receiving layer of the latex-ink film which is applied with water, maintains the adhesion between the latex-ink-receiving layer and the printed portion of the latex ink even when it is rubbed with a squeegee while in contact with water.
  • water-resistant adhesion of ink it is also referred to as “water-resistant adhesion of ink”.
  • a film for latex ink that has not only ink adhesion and scratch resistance but also water-resistant adhesion of ink has not yet been created.
  • the present invention has been made in view of such problems, and provides a film for latex ink having a latex ink-receiving layer that is excellent in both ink adhesion and abrasion resistance, and is also excellent in water-resistant adhesion of ink.
  • the challenge is to
  • the term “ink adhesion” refers to the relationship between the latex ink receiving layer and the printed area when the latex ink printed area formed on the latex ink receiving layer is not in contact with liquid water. means the adhesion of The quality is evaluated by, for example, an ink adhesion test in Examples described later.
  • the term “water-resistant adhesion of the ink” refers to the degree of adhesion between the latex ink-receiving layer and the printing when the latex-ink-printed portion formed on the latex-ink-receiving layer is in contact with liquid water. It means the adhesion with the part.
  • the quality is evaluated, for example, by a water-resistant adhesion test of ink in Examples described later.
  • the present inventors have found that an acrylic resin having a crosslinkable functional group, a specific crosslinker, an ultraviolet curable acrylate compound, a photopolymerization initiator, and a polymerizable third
  • the present inventors have found that a latex ink-receiving layer formed from a resin composition containing a group amine can solve the above problems.
  • the inventors of the present invention have further conducted various studies based on such findings, and have completed the present invention. That is, the present invention relates to the following [1] to [8].
  • the latex ink-receiving layer (X) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable Formed from a resin composition (x1) containing a tertiary amine (E),
  • the cross-linking agent (B) contains an isocyanurate compound (B1)
  • the isocyanurate compound (B1) includes an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2),
  • the isocyanurate compound (B1-1) is a trimer of 1,6-hexamethylene diisocyanate, A film for latex ink, wherein the modified isocyanurate compound (B1-2) is a trimer of 1,6-hexamethylene diiso
  • the film for latex ink is used to form a printed portion using latex ink on the latex ink-receiving layer of the film for latex ink according to any one of [1] to [5] above. ,how to use.
  • a method for producing a printed matter comprising the step of forming a printed portion using latex ink on the latex ink-receiving layer of the film for latex ink according to any one of [1] to [5] above.
  • a film for latex ink having a latex ink-receiving layer that is excellent in both ink adhesion and abrasion resistance, and is also excellent in water-resistant adhesion of ink.
  • the 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”.
  • (meth)acryloyl group” indicates both “acryloyl group” and “methacryloyl group”.
  • 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) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable third It is formed from a resin composition (x1) containing a class amine (E).
  • the cross-linking agent (B) contains an isocyanurate compound (B1).
  • the isocyanurate compound (B1) includes an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2).
  • the isocyanurate compound (B1-1) is a trimer of 1,6-hexamethylene diisocyanate
  • the modified isocyanurate compound (B1-2) is a trimer of 1,6-hexamethylene diisocyanate. and has one or more tertiary amino groups.
  • acrylic resin (A) having a crosslinkable functional group "crosslinking agent (B) containing isocyanurate compound (B1)”, "ultraviolet curable acrylate
  • a latex ink-receiving layer formed from a resin composition (x1) containing a compound (C), a photoinitiator (D), and a polymerizable tertiary amine (E) has good ink adhesion.
  • the present inventors have found that the ink is excellent in both abrasion resistance and abrasion resistance, and is also excellent in water-resistant adhesion of the ink.
  • the structure of the film for latex ink, the members constituting the film for latex ink (base material, latex ink receiving layer, adhesive layer, and release liner), and the production of the film for latex ink The method and application of the film for latex inks are described in detail.
  • 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
  • another layer may be provided between the latex ink receiving layer (X) and the substrate (Y). Examples of the other layer include an easy-adhesion layer.
  • 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) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable third It is formed from a resin composition (x1) containing a class amine (E).
  • the resin composition (x1) comprises an acrylic resin (A) having a crosslinkable functional group, a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary
  • an acrylic resin (A) having a crosslinkable functional group a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary
  • the crosslinked structure formed by the reaction between the acrylic resin (A) having a crosslinkable functional group and the crosslinking agent (B), and the ultraviolet light A polymer structure formed by the curable acrylate compound (C) and the photopolymerization initiator (D) is mixed on the surface of the latex ink-receiving layer (X). Therefore, it is presumed that both ink adhesion and abrasion resistance are excellent.
  • the polymerizable tertiary amine (E) is incorporated into the polymer structure formed by the UV-curable acrylate compound (C) and the photopolymerization initiator (D) to form a polymerizable tertiary It is presumed that the amine (E) interacts with the latex ink to form a latex ink-receiving layer (X) that is also excellent in water-resistant adhesion of the ink.
  • acrylic resin (A) having a crosslinkable functional group "crosslinking agent (B)”, “ultraviolet curable acrylate compound (C)”, “photopolymerization initiator (D)”, and “Polymerizable tertiary amine (E)” is also referred to as “Component (A)”, “Component (B)”, “Component (C)”, “Component (D)”, and “Component (E)” respectively. say.
  • the resin composition (x1) which is the material for forming the latex ink-receiving layer (X), comprises component (A), component (B), component (C), component (D), and component ( E) may be composed only, but within the range that does not impair the effects of the present invention, along with component (A), component (B), component (C), component (D), and component (E), component Components other than (A), component (B), component (C), component (D), and component (E) may be contained.
  • additives for ink-receiving layers generally used in ink-receiving layers such as latex ink-receiving layers, such as reaction accelerators (catalysts), surface modifiers, plasticizers, fillers, and coloring agents.
  • the total content of component (A), component (B), component (C), component (D), and component (E) is based on the total amount of active ingredients in the resin composition (x1). , preferably 80% to 100% by mass, more preferably 85% to 100% by mass, still more preferably 90% to 100% by mass.
  • the resin composition (x1) contains an acrylic resin having a crosslinkable functional group (A), a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and polymerization
  • the functional tertiary amine (E) will be explained in detail.
  • the resin composition (x1) used in the present invention contains an acrylic resin (A) having a crosslinkable functional group.
  • an acrylic resin ( A1) is preferred.
  • Examples of the crosslinkable functional group possessed by the monomer (a1′) include one or more selected from a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and the like. That is, examples of the monomer (a1′) include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers. Also included are monomers containing two or more crosslinkable functional groups selected from a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and the like. These monomers (a1') may be used singly or in combination of two or more. Among these, hydroxyl group-containing monomers and carboxy group-containing monomers are preferable as the monomer (a1′).
  • 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.
  • the number of carbon atoms in the alkyl group is preferably 2 to 20 from the viewpoint of adjusting the glass transition temperature (Tg) of the acrylic resin (A) to an appropriate range so that the ink adhesion can be exhibited more easily.
  • the alkyl group possessed by the monomer (a2') may be a straight-chain alkyl group or a branched-chain alkyl group.
  • Examples of the monomer (a2′) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate etc. These monomers (a2') may be used singly or in combination of two or more.
  • the content of the structural unit (a2) is preferably 1 to 99% by mass, more preferably 1 to 99% by mass, based on the total amount of the acrylic copolymer (A2). is 5 to 95% by mass, more preferably 10 to 90% by mass.
  • the acrylic resin (A1) and the acrylic copolymer (A2) are acrylic copolymers further having a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2'). It may be a polymer (A3).
  • Examples of the monomer (a3′) include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene, and chloroprene; Cyclic acrylates such as acrylates, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and imido (meth)acrylate Structured (meth)acrylates; styrene, ⁇ -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, and (meth)acrylonitrile.
  • olefins such as ethylene, propylene, and is
  • 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 (x1) ) 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 term “sticking resistance” means that "a laminate of the substrate (Y) and the latex ink-receiving layer (X) is formed by forming the latex ink-receiving layer (X) on the surface of the substrate (Y). It means the property of suppressing sticking between the latex ink-receiving layer (X) and the back surface of the substrate (Y), which occurs when the laminate is wound during the manufacturing process.
  • the glass transition temperature (Tg) of the acrylic resin (A) having a crosslinkable functional group is based on JIS K 7121:2012 and measured by a differential scanning calorimeter (T.A. Instruments, Inc.). Japan Co., Ltd., product name “DSC Q2000”), and means a value measured at a temperature increase rate of 20° C./min.
  • the resin composition (x1) used in the present invention contains a cross-linking agent (B).
  • the cross-linking agent (B) contains an isocyanurate compound (B1). If the cross-linking agent (B) does not contain the isocyanurate compound (B1), the latex ink-receiving layer (X) cannot have good ink adhesion.
  • the cross-linking agent (B) containing the isocyanurate-based compound (B1) by using the cross-linking agent (B) containing the isocyanurate-based compound (B1), the cross-linked structure formed by the reaction with the acrylic resin (A) having a cross-linkable functional group contributes to the ink adhesion. It is presumed that this contributes to the excellent ink adhesion.
  • the cross-linking agent (B) does not contain the isocyanurate compound (B1)
  • the adhesion between the latex ink-receiving layer (X) and the substrate (Y) cannot be ensured.
  • the cross-linking agent (B) containing the isocyanurate compound (B1) the adhesion of the latex ink-receiving layer (X) to the substrate (Y) is improved by the influence of the polar group of the cross-linking agent (B).
  • the latex ink receiving layer (X) having a crosslinked structure with excellent adhesion to the substrate (Y) containing a polyester resin such as polyethylene terephthalate is formed.
  • the content of the isocyanurate compound (B1) is preferably 50% by mass to 100% by mass based on the total amount of the cross-linking agent (B) from the viewpoint of facilitating the improvement of ink adhesion. , more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
  • the isocyanurate compound (B1) will be described in detail below.
  • the isocyanurate compound (B1) includes an isocyanurate compound (B1-1) and a modified isocyanurate compound (B1-2).
  • the total content of the isocyanurate compound (B1-1) and the modified isocyanurate compound (B1-2) in the isocyanurate compound (B1) is the isocyanurate compound from the viewpoint of making it easier to improve ink adhesion. Based on the total amount of compound (B1), it is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and still more preferably 95% by mass to 100% by mass.
  • the isocyanurate compound (B1) includes an isocyanurate compound (B1-1).
  • the isocyanurate compound (B1-1) is a trimer of 1,6-hexamethylene diisocyanate, specifically a compound of the following formula (1).
  • the isocyanurate compound (B1) includes a modified isocyanurate compound (B1-2).
  • the modified isocyanurate compound (B1-2) is a trimer of 1,6-hexamethylene diisocyanate and has one or more tertiary amino groups.
  • the method of introducing one or more tertiary amino groups into the compound of formula (1) to obtain a modified product includes, for example, a modifier having a hydroxyl group and a tertiary amino group, and the compound of formula (1). Methods of reacting are included.
  • Such modifiers include, for example, N,N-dimethylaminohexanol (eg, Kao Riser No. 25, manufactured by Kao Corporation), N,N-dimethylaminoethoxyethoxyethanol (eg, Kao Corporation, manufactured by Kao Corporation). Riser No. 23NP), N,N-dimethylaminoethoxyethanol (for example, Kao Riser No.
  • 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 (B1) is, for example, the amount of the compound of the formula (1) and the modifier put into the reaction vessel when performing the reaction of the compound of the formula (1) and the modifier. It can be prepared by appropriately adjusting the ratio.
  • the ratio of the modifier added to the compound of formula (1) is preferably 0.01 to 10 parts by mass, preferably 0.05, per 100 parts by mass of the compound of formula (1). It is more preferably from 1 part by mass to 5 parts by mass.
  • the isocyanurate compound (B1-1) and the modified isocyanurate compound An isocyanurate compound (B1) containing (B1-2) can be prepared.
  • the content of the modified isocyanurate compound (B1-2) is preferably 0.5 mol% to 10 mol%, more preferably 1 mol% to 5 mol%, based on the total amount of the isocyanurate compound (B1). in mol %.
  • the content of the cross-linking agent (B) is preferably 3.0 parts by mass or more with respect to 100 parts by mass of the acrylic resin (A) having a cross-linkable functional group, from the viewpoint of making it easier to exhibit the effects of the present invention. It is more preferably 5.0 parts by mass or more, still more preferably 7.0 parts by mass or more. Also, it is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.
  • UV-curable acrylate compound (C) The UV-curable acrylate compound (C) is a component that can be cured (polymerized) by UV irradiation. UV-curable monomers and oligomers are used as the UV-curable acrylate compound (C).
  • Compound (C), which is an oligomer, has a mass average molecular weight (Mw) of less than 10,000.
  • Mw mass average molecular weight
  • One of the ultraviolet-curable acrylate compounds (C) may be used alone, or two or more thereof may be used in combination.
  • Examples of the UV-curable acrylate compound (C) include polymerizable acrylate compounds having one or more UV-polymerizable groups in one molecule.
  • Examples of the UV-polymerizable group include those having a UV-polymerizable carbon-carbon double bond, and a (meth)acryloyl group is more preferred.
  • the UV-curable acrylate compound (C) preferably has two or more UV-polymerizable groups (eg, (meth)acryloyl groups) in one molecule, preferably two to six.
  • specific examples of the ultraviolet curable acrylate compound (C) include (meth)acrylate monomers and (meth)acrylate oligomers.
  • (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, tetramethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta( meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate and the like.
  • (meth)acrylate oligomers include urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyethylene glycol di(meth)acrylate.
  • a (meth)acrylate monomer is preferable, and the cross-linking reaction between the acrylic resin (A) having a cross-linkable functional group and the cross-linking agent (B) proceeds favorably.
  • a (meth)acrylate monomer that does not have a crosslinkable functional group that reacts with the crosslinker (B) is more preferable from the viewpoint of making it easier to improve the ink adhesion.
  • (Meth)acrylate monomers having no crosslinkable functional group that reacts with the crosslinker (B) include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1 ,4-butylene glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate, among which dipentaerythritol hexaacrylate is preferred.
  • Photopolymerization initiator (D) As the photopolymerization initiator (D), a photopolymerization initiator generally used for curing the ultraviolet-curable acrylate compound (C) with ultraviolet rays can be appropriately used. Specifically, 1-hydroxycyclohexylphenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, ⁇ -chloranthraquinone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl- pentylphosphine oxide and the
  • the content of the photopolymerization initiator (D) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the UV-curable acrylate compound (C) and the polymerizable tertiary amine (E). .
  • the resin composition (x1) used in the present invention contains a polymerizable tertiary amine (E). If the resin composition (x1) does not contain the polymerizable tertiary amine (E), the latex ink-receiving layer (X) cannot have excellent ink water-resistant adhesion.
  • the resin composition (x1) used in the present invention can improve the water-resistant adhesion of the ink of the latex ink-receiving layer (X). Moreover, even when the polymerizable tertiary amine (E) is incorporated, the latex ink-receiving layer (X) maintains sufficiently excellent ink adhesion and abrasion resistance.
  • Examples of the polymerizable tertiary amine (E) include tertiary amines having one or more polymerizable groups in one molecule.
  • the polymerizable group possessed by the polymerizable tertiary amine (E) includes, for example, a group having a UV-polymerizable carbon-carbon double bond, preferably a vinyl group or a (meth)acryloyl group.
  • polymerizable tertiary amine (E) examples include N-vinyl-2-pyrrolidone, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N -dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acryloylmorpholine and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the polymerizable tertiary amine (E) is the total amount of 100 masses of the acrylic resin (A) having a crosslinkable functional group, the UV-curable acrylate compound (C), and the polymerizable tertiary amine (E). %, preferably 0.1 to 25% by mass, more preferably 1 to 20% by mass, and still more preferably 3 to 20% by mass.
  • Total content of acrylic resin (A) having a crosslinkable functional group, UV-curable acrylate compound (C), and polymerizable tertiary amine (E) In one aspect of the present invention, the total content of the acrylic resin (A) having a crosslinkable functional group, the UV-curable acrylate compound (C), and the polymerizable tertiary amine (E) is the effect of the present invention.
  • an acrylic resin having a crosslinkable functional group (A), a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), and a polymerizable tertiary It is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more relative to the total content (100% by mass) of the amine (E). Also, it is preferably 97% by mass or less, more preferably 95% by mass or less.
  • the content ratio [(A)/(C)] of the acrylic resin (A) having a crosslinkable functional group and the UV-curable acrylate compound (C) is From the viewpoint of forming a latex ink-receiving layer (X) that is excellent and has excellent water-resistant adhesion of the ink, the mass ratio is preferably 0.3 to 3.5, more preferably 0.5 to 3.0, and still more preferably. is 0.7 to 3.0, more preferably 1.0 to 3.0.
  • the film for latex ink of the present invention has a substrate (Y).
  • the base material (Y) supports the latex ink-receiving layer (X) and has a function as a support that supports the printed portion formed on the latex ink-receiving layer (X).
  • 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. Moreover, when the base material (Y) is a transparent resin film, the latex ink-receiving layer (X) is also preferably transparent. Specifically, the total light transmittance of the latex ink film composed of the substrate (Y) and the latex ink-receiving layer (X) is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The total light transmittance means a value measured according to JIS K7361-1:1997 using a haze meter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.).
  • 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.
  • 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 substrate (Y) 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, and 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, 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 150 ⁇ m, more preferably 20 ⁇ m to 130 ⁇ m, still more preferably 30 ⁇ m to 100 ⁇ 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. After that, it is preferable to form the latex ink receiving layer (X) by UV curing and cross-linking. In addition, in order to improve workability of application to the substrate (Y), it is preferable to further dilute the resin composition (x1) with a diluting solvent to form a solution.
  • 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 coating film After forming a coating film by applying the resin composition (x1) to one surface (Ya) of the substrate (Y), the coating film is dried to remove the diluent solvent from the coating film (drying step).
  • the heating conditions for drying the coating film are, for example, a drying temperature of 60° C. to 120° C. and a drying time of 30 seconds to 3 minutes.
  • the coating film After the coating film is dried, it is irradiated with ultraviolet rays to cure (polymerize) the ultraviolet-curable acrylate compound (C) (ultraviolet irradiation step). At that time, the polymerizable tertiary amine (E) is incorporated into the cured product of the UV-curable acrylate compound (C).
  • the irradiation conditions of the ultraviolet rays are preferably 5 to 1200 mJ/cm 2 , more preferably 50 to 500 mJ/cm 2 in terms of cumulative irradiation amount (accumulated amount of light).
  • Ultraviolet rays can be applied by using, for example, a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, an LED, or the like as an ultraviolet light source.
  • crosslinking step After curing (polymerizing) the UV-curable acrylate compound (C), the acrylic resin (A) having a crosslinkable functional group is reacted with the crosslinker (B) to form a crosslinked structure (crosslinking step).
  • the crosslinking conditions are not particularly limited. For example, crosslinking may be performed by standing in a normal environment (eg, 23° C., relative humidity of 50° C.) for 1 to 14 days, or in an environment of 40° C. to 60° C. It may be allowed to stand for 3 days to 3 days for cross-linking.
  • the ultraviolet irradiation process may be performed at any timing before the cross-linking process, during the cross-linking process, or after the cross-linking process. Moreover, the cross-linking step and the ultraviolet irradiation step may be performed simultaneously, or the cross-linking step and the ultraviolet irradiation step may be performed in multiple steps. Furthermore, at least one of the ultraviolet irradiation step and the cross-linking step may be performed simultaneously with the drying step.
  • 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: 2012 and is measured using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., product name "DSC Q2000") was used, and the temperature was measured at a heating rate of 20°C/min.
  • 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.
  • Latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4 were produced by the following procedure.
  • a polyethylene terephthalate sheet (thickness: 50 ⁇ m) with an easy-adhesion layer was prepared as the substrate (Y). Then, an acrylic resin having a crosslinkable functional group (A), a crosslinker (B), an ultraviolet curable acrylate compound (C), a photopolymerization initiator (D), a polymerizable tertiary amine (E), and a catalyst
  • a coating liquid (active ingredient concentration: 10% by mass, diluent solvent: ethyl acetate) of a resin composition adjusted to the formulation shown in Table 1 (the amount is calculated as an active ingredient) is applied to the easy adhesion layer of the substrate (Y).
  • the film was applied to the side of the film so that the film thickness after drying would be 1 ⁇ m.
  • the diluent solvent contained in the coating film formed by coating the substrate (Y) is removed by heating at 90° C. for 1 minute (drying step). Then, it was irradiated with ultraviolet light having a peak wavelength of 365 nm at an integrated light amount of 150 mJ/cm 2 (ultraviolet curing step), and further left to stand for 7 days in an environment of 23 ° C. and a relative humidity of 50% to crosslink (crosslinking step). .
  • a latex ink-receiving layer (X) having a thickness of 1 ⁇ m was formed, and latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4 were obtained.
  • the latex ink film of Comparative Example 1 was produced without carrying out the ultraviolet curing step.
  • 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
  • Table 1 shows the following. It can be seen that the films for latex inks of Examples 1 to 6 are excellent in ink adhesion, water-resistant adhesion of ink, and abrasion resistance.
  • a film for latex ink having a latex ink receiving layer formed from a resin composition consisting of an acrylic resin (A) and a cross-linking agent (B) has excellent ink adhesion and ink water-resistant adhesion. It can be seen that the abrasion resistance is inferior although the abrasion resistance is excellent.
  • the acrylic resin (A), the cross-linking agent (B), and the photopolymerization initiator (D) are formed from a resin composition containing a polymerizable tertiary amine (E).
  • the film for latex ink having a latex ink-receiving layer is also excellent in ink adhesion and water-resistant adhesion of ink, but inferior in abrasion resistance.
  • an acrylic resin (A), a cross-linking agent (B), an ultraviolet-curable acrylate compound (C), and a photopolymerization initiator (D) are composed of a polymerizable tertiary amine. It can be seen that the latex ink film having a latex ink-receiving layer formed from a resin composition containing no (E) is excellent in ink adhesion and scratch resistance, but is inferior in ink water-resistant adhesion.
  • ⁇ Evaluation 2> (1) Evaluation of total light transmittance For each of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-5000) was used to measure JIS K7361- 1:1997, the total light transmittance was measured. As a result, all of the latex ink films of Examples 1 to 6 and Comparative Examples 1 to 4 had a total light transmittance of 92%.
  • 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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  • Ink Jet (AREA)

Abstract

La présente invention aborde le problème consistant à fournir un film pour encre au latex, le film ayant une couche de réception d'encre au latex qui est excellente en termes à la fois d'adhésion de l'encre et de résistance à l'abrasion et excellente en termes d'adhésion de l'encre résistante à l'eau. Ce problème est résolu en configurant le film pour qu'il présente une structure stratifiée dans laquelle une couche de réception d'encre au latex (X) et un substrat (Y) sont stratifiés, la couche de réception d'encre au latex (X) étant formée à partir d'une composition de résine (x1) qui contient : une résine acrylique (A) ayant un groupe fonctionnel réticulable ; un agent de réticulation spécifique (B) ; un composé acrylate durcissable par UV (C) ; un initiateur de photopolymérisation (D) ; et une amine tertiaire polymérisable (E).
PCT/JP2022/000968 2022-01-13 2022-01-13 Film pour encre au latex WO2023135711A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014144605A (ja) * 2013-01-30 2014-08-14 Lintec Corp 印刷用シートおよびその製造方法
JP2019172877A (ja) * 2018-03-29 2019-10-10 リンテック株式会社 ラテックスインク用フィルムおよびラテックスインク用フィルムの製造方法
JP2020093400A (ja) * 2018-12-10 2020-06-18 Dic株式会社 積層体
WO2022018807A1 (fr) * 2020-07-20 2022-01-27 リンテック株式会社 Film pour encre au latex

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014144605A (ja) * 2013-01-30 2014-08-14 Lintec Corp 印刷用シートおよびその製造方法
JP2019172877A (ja) * 2018-03-29 2019-10-10 リンテック株式会社 ラテックスインク用フィルムおよびラテックスインク用フィルムの製造方法
JP2020093400A (ja) * 2018-12-10 2020-06-18 Dic株式会社 積層体
WO2022018807A1 (fr) * 2020-07-20 2022-01-27 リンテック株式会社 Film pour encre au latex

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