Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • 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
• • 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
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

• the present invention relates to a photocurable adhesive composition for printing.
• the present invention also relates to a cured product and a laminate obtained by using the photocurable adhesive composition for printing.
• Adhesives are used to bond electronic components inside electronic devices such as smartphones and PCs.
• a typical method of bonding using an adhesive first, an adhesive sheet is prepared in which separators are arranged on both sides of the adhesive, and then the adhesive sheet is cut into a desired shape. Then, one separator is peeled off from the cut adhesive sheet, and one side of the exposed adhesive is bonded to a first adherend, and then the other separator is peeled off, and the other side of the exposed adhesive is bonded to a second adherend.
• a part of the adhesive sheet is discarded after cutting, resulting in waste.
• a method has been studied in which a pressure-sensitive adhesive composition is printed in a desired shape and then attached to an adherend without preparing a pressure-sensitive adhesive sheet, which can reduce the generation of waste.
• Patent Document 1 discloses an invention for providing a radiation-curable adhesive composition that allows fine patterning and exhibits high adhesion to various adherends such as metals and plastics.
• Patent Document 1 describes a radiation-curable adhesive composition that contains 10 to 70% by weight of an ethylenically unsaturated monomer that does not contain an aromatic ring, 1 to 10% by weight of a photopolymerization initiator, and 10 to 55% by weight of a crosslinking agent.
• Patent Document 2 discloses an invention for providing a photocurable adhesive composition that, even when irradiated with light in the presence of oxygen, gives a laminate having adhesive strength equivalent to that in the absence of oxygen.
• Patent Document 2 describes a photocurable adhesive composition that contains (A) a (meth)acrylate oligomer, (B) a monofunctional (meth)acrylic monomer, (C) a di- to tetrafunctional (meth)acrylic monomer, (D) a photoinitiator, (E) a tackifier having a softening point of 70 to 150°C, and (F) a liquid plasticizer.
• the method of printing the adhesive composition in a desired shape and then laminating it to an adherend without preparing an adhesive sheet can reduce waste generation.
• photocuring is preferable to avoid heating the adherend, but conventional adhesive compositions have problems such as requiring replacement after each use and poor reprintability, difficulty in curing sufficiently when irradiated with light in the presence of oxygen, and insufficient adhesion and retention performance (creep resistance) after curing.
• the present invention aims to provide a photocurable adhesive composition for printing that has excellent repeatable printability, photocurability in the presence of oxygen, and adhesion and retention properties after curing.
• the present invention also aims to provide a cured product and a laminate made using the photocurable adhesive composition for printing.
• the present disclosure 1 relates to a photocurable pressure-sensitive adhesive composition for printing, which contains a (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, but does not contain a moisture-curable resin, and the photopolymerization initiator has a weight-average molecular weight of 800 or more.
• Disclosure 2 relates to a photocurable pressure-sensitive adhesive composition for printing, the photocurable pressure-sensitive adhesive composition for printing comprising a (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, but not comprising a moisture-curable resin, the photocurable pressure-sensitive adhesive composition for printing being coated on a substrate to a thickness of 40 ⁇ m or more and 60 ⁇ m or less, and irradiating an upper surface of the coated substrate, without sealing it, with light having a wavelength of 365 nm and an illuminance of 500 mW/ cm2 in an atmospheric environment at an irradiation dose of 3,000 mJ/ cm2 , to obtain a cured product having a solid fraction of 90% or more and a gel fraction of the cured product of 25% by mass or more and 60% by mass or less.
• the present disclosure 3 is the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 2, wherein the photopolymerization initiator has a weight average molecular weight of 800 or more.
• the present disclosure 4 relates to the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1 or 2, wherein the photopolymerization initiator is a Norrish I type photopolymerization initiator having a weight average molecular weight of 800 or more.
• the present disclosure 5 is the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 4, wherein the photopolymerization initiator has two or more carbonyl groups in one molecule that contribute to a Norrish I type cleavage reaction.
• the present disclosure 6 is the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1, 2, 3, 4, or 5, wherein the thermoplastic resin has a weight average molecular weight of 100,000 or more and 1,000,000 or less.
• the present disclosure 7 is the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1, 2, 3, 4, 5, or 6, wherein the thermoplastic resin is a block copolymer.
• the present disclosure 8 relates to the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 7, wherein the thermoplastic resin is a (meth)acrylic/styrene block copolymer.
• the present disclosure 9 is the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1, 2, 3, 4, 5, 6, 7, or 8, further comprising a nitrogen-containing vinyl compound, and the content of the nitrogen-containing vinyl compound in 100 parts by mass of the photocurable pressure-sensitive adhesive composition for printing is 0.1 parts by mass or more and 5.0 parts by mass or less.
• the present disclosure 10 is the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, or 9, further comprising an antifoaming agent.
• the present disclosure 11 is the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, further comprising a leveling agent.
• the present disclosure 12 is the photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, which does not contain a solvent or contains 1 part by mass or less of a solvent per 100 parts by mass of the photocurable pressure-sensitive adhesive composition for printing.
• the present disclosure 13 is a photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, which is used for screen printing and has a viscosity of 1 Pa ⁇ s or more and 400 Pa ⁇ s or less, measured using an E-type viscometer at 25°C and 10 rpm.
• the present disclosure 14 is a photocurable pressure-sensitive adhesive composition for printing according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, which is used for inkjet printing and has a viscosity of 0.001 Pa ⁇ s or more and 10 Pa ⁇ s or less, measured using an E-type viscometer at 25°C and 10 rpm.
• the present disclosure 15 is a cured product obtained by curing the photocurable pressure-sensitive adhesive composition for printing of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14.
• the present disclosure 16 is the cured product of the present disclosure 15, having a solid fraction of 90% or more and a gel fraction of 25% by mass or more and 60% by mass or less.
• the present disclosure 17 is a laminate having a release-treated film on at least one side of the cured product of the present disclosure 15 or 16.
• the present invention will be described in detail below.
• the photocurable pressure-sensitive adhesive composition for printing of Disclosure 1 will also be referred to as the "photocurable pressure-sensitive adhesive composition for printing of Invention 1”
• the photocurable pressure-sensitive adhesive composition for printing of Disclosure 2 will also be referred to as the "photocurable pressure-sensitive adhesive composition for printing of Invention 2.”
• matters common to the photocurable pressure-sensitive adhesive composition for printing of Invention 1 and the photocurable pressure-sensitive adhesive composition for printing of Invention 2 will be described as the "photocurable pressure-sensitive adhesive composition for printing of the present invention.”
• the present inventors have investigated the use of a photopolymerization initiator having a weight average molecular weight of a specific value or more for a photocurable pressure-sensitive adhesive composition for printing that contains a (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, but does not contain a moisture-curable resin.
• a photocurable pressure-sensitive adhesive composition for printing that is excellent in repeated printability, photocurability in the presence of oxygen, and adhesiveness and retention performance after curing can be obtained, and have completed the present invention 1.
• the present inventors also investigated a printing photocurable pressure-sensitive adhesive composition that contains a (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, but does not contain a moisture-curable resin, and that is photocured in the presence of oxygen to obtain a cured product with a solid content of 90% or more and a gel content of the cured product of 25% by mass or more and 60% by mass or less.
• a printing photocurable pressure-sensitive adhesive composition that is excellent in repeated printability, photocurability in the presence of oxygen, and adhesiveness and retention performance after curing can be obtained, and thus completed the present invention 2.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention contains a (meth)acrylic monomer.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention preferably contains a monofunctional (meth)acrylic monomer and a polyfunctional (meth)acrylic monomer.
• (meth)acrylic means acrylic or methacrylic
• (meth)acrylic monomer means a monomer having a (meth)acryloyl group
• (meth)acryloyl means acryloyl or methacryloyl.
• the term "monofunctional (meth)acrylic monomer” means a monomer having one (meth)acryloyl group in one molecule
• the term “polyfunctional (meth)acrylic monomer” means a monomer having two or more (meth)acryloyl groups in one molecule.
• the monofunctional (meth)acrylic monomer is a polymerizable monomer that is polymerized by a reaction with a photopolymerization initiator described below.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention has excellent adhesion to various substrates.
• the monofunctional (meth)acrylic monomer include a monofunctional (meth)acrylic acid ester compound, a monofunctional (meth)acrylamide compound, and a monofunctional (meth)acrylimide compound.
• Examples of the monofunctional (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-heptyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxybutyl (meth)
• Examples of the monofunctional (meth)acrylamide compounds include N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide.
• Examples of the monofunctional (meth)acrylimide compound include N-(meth)acryloyloxyethylhexahydrophthalimide.
• the preferred lower limit of the content of the monofunctional (meth)acrylic monomer in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 45 parts by mass, and the preferred upper limit is 75 parts by mass.
• the content of the monofunctional (meth)acrylic monomer is within this range, the obtained cured product has better adhesion to various substrates.
• the more preferred lower limit of the content of the monofunctional (meth)acrylic monomer is 50 parts by mass, and the more preferred upper limit is 70 parts by mass.
• the polyfunctional (meth)acrylic monomer is a polymerizable monomer that is polymerized by the reaction of a photopolymerization initiator described below, and the polyfunctional (meth)acrylic monomer serves as a crosslinking component.
• the polyfunctional (meth)acrylic monomer include polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylic acid ester compounds, and polyfunctional epoxy (meth)acrylates.
• epoxy (meth)acrylate refers to a compound in which all epoxy groups in an epoxy compound have been reacted with (meth)acrylic acid.
• the above-mentioned polyfunctional urethane (meth)acrylate can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
• MDI diphenylmethane-4,4'-
• isocyanate compound serving as a raw material for the polyfunctional urethane (meth)acrylate a chain-extended isocyanate compound obtained by reacting a polyol with an excess of an isocyanate compound can also be used.
• the polyol include ethylene glycol, propylene glycol, tetraethylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
• Examples of the (meth)acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of dihydric alcohols, and mono(meth)acrylates or di(meth)acrylates of trihydric alcohols.
• Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate.
• Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
• Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.
• polyfunctional (meth)acrylic acid ester compounds examples include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-added
• polyfunctional epoxy (meth)acrylate examples include bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, and caprolactone modified versions of these.
• the preferred lower limit of the content of the polyfunctional (meth)acrylic monomer in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 1 part by mass, and the preferred upper limit is 8 parts by mass.
• the content of the polyfunctional (meth)acrylic monomer in this range the obtained cured product has better adhesion and retention performance to various substrates.
• a more preferred lower limit of the content of the polyfunctional (meth)acrylic monomer is 2 parts by mass, and a more preferred upper limit is 5 parts by mass.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention contains a photopolymerization initiator.
• the photopolymerization initiator has a weight-average molecular weight of at least 800.
• the photopolymerization initiator preferably has a weight-average molecular weight of at least 800.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention can easily adjust the solid fraction and gel fraction of the cured product to within the ranges described below, and as a result, the photocurable pressure-sensitive adhesive composition for printing of the present invention has excellent photocurability in the presence of oxygen, and excellent adhesion and retention performance after curing.
• the lower limit of the weight-average molecular weight of the photopolymerization initiator is preferably 1,000, more preferably 1,100.
• the lower limit of the weight-average molecular weight of the photopolymerization initiator is more preferably 1,000, even more preferably 1,100.
• the upper limit of the weight-average molecular weight of the photopolymerization initiator in the photocurable pressure-sensitive adhesive composition for printing of the present invention is not particularly limited. However, from the viewpoint of deterioration in solubility and handleability when the molecular weight is significantly large, the upper limit is preferably 10,000, and more preferably 5,000.
• the "weight average molecular weight” can be determined by, for example, measuring the molecular weight distribution in terms of polystyrene using gel permeation chromatography (GPC). Specifically, for example, it can be determined by measuring under the following conditions using gel permeation chromatography (Waters Corporation, "2690 Separations Module” or the like).
• Solvent Tetrahydrofuran Sample flow rate: 1 mL/min Detector: Differential refractometer RI Column: GPC KF-806L (Showa Denko) Column temperature (measurement temperature): 40°C Injection volume: 20 ⁇ L
• the photopolymerization initiator is preferably a Norrish I type photopolymerization initiator having a weight average molecular weight of 800 or more.
• the photocurable adhesive composition for printing of the present invention makes it easier to adjust the solid content and gel content of the cured product to the ranges described below.
• the photopolymerization initiator preferably has two or more carbonyl groups in one molecule that contribute to the Norrish I type cleavage reaction.
• Norrish type I photopolymerization initiators with a weight average molecular weight of 800 or more include polymers of ethyl (2,4,6-trimethylbenzoyl)-phenyl phosphonate, polyethylene glycol di( ⁇ -4(4-(2-dimethylamino-2-benzyl)butanoylphenyl)piperazine)propionate, and bis(benzophenone-2-carboxylic acid) polyethylene glycol ester.
• Norrish I type photopolymerization initiators with a weight average molecular weight of 800 or more include, for example, Omnipol TP and Omnipol 910 (both manufactured by IGM Resins).
• the preferred lower limit of the content of the photopolymerization initiator in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 1 part by mass, and the preferred upper limit is 20 parts by mass.
• the resulting photocurable adhesive composition for printing has superior photocurability in the presence of oxygen, and superior adhesion and retention performance after curing.
• a more preferred lower limit of the content of the photopolymerization initiator is 3 parts by mass, and a more preferred upper limit is 10 parts by mass.
• the photocurable adhesive composition for printing of the present invention contains a thermoplastic resin. By containing the above-mentioned thermoplastic resin, the photocurable adhesive composition for printing of the present invention has excellent retention performance when cured.
• the thermoplastic resin has a weight-average molecular weight of preferably 100,000 at the lower limit and 1,000,000 at the upper limit. When the weight-average molecular weight of the thermoplastic resin is within this range, the printing performance is excellent and the obtained cured product has better retention performance.
• the more preferable lower limit of the weight-average molecular weight of the thermoplastic resin is 200,000 and the more preferable upper limit is 500,000.
• the thermoplastic resin is preferably a block copolymer.
• the obtained cured product has better retention performance.
• the thermoplastic resin preferably contains a triblock copolymer.
• the preferred lower limit of the content of the triblock copolymer in the thermoplastic resin is 50% by mass.
• the more preferred lower limit of the content of the triblock copolymer is 70% by mass.
• the content of the triblock copolymer in the thermoplastic resin may be 100% by mass, that is, the thermoplastic resin may contain only the triblock copolymer.
• thermoplastic resin block copolymer is preferably a (meth)acrylic/styrene block copolymer, and more preferably a (meth)acrylic/styrene triblock copolymer.
• the preferred lower limit of the content of the styrene-derived structure in the (meth)acrylic/styrene block copolymer is 3% by mass.
• the content of the styrene-derived structure is 3% by mass or more, so that the obtained cured product has better retention performance.
• the more preferred lower limit of the content of the styrene-derived structure is 4% by mass.
• the upper limit of the content of the structure derived from the styrene is preferably 40% by mass, and more preferably 30% by mass.
• the preferred lower limit of the content of the thermoplastic resin in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 1 part by mass, and the preferred upper limit is 60 parts by mass.
• the content of the thermoplastic resin is within this range, the obtained cured product has better retention performance.
• a more preferred lower limit of the content of the thermoplastic resin is 10 parts by mass, and a more preferred upper limit is 40 parts by mass.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention does not contain a moisture-curable resin.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention does not need to be replaced after each use and has excellent repeat printability.
• moisture-curable resin refers to a curable resin whose curing reaction proceeds when triggered by moisture in the air, such as a moisture-curable urethane resin or a resin having a crosslinkable silyl group.
• the photocurable adhesive composition for printing of the present invention preferably further contains a nitrogen-containing vinyl compound as a polymerizable monomer.
• a nitrogen-containing vinyl compound as a polymerizable monomer.
• the nitrogen-containing vinyl compound preferably contains at least one selected from the group consisting of monofunctional radically polymerizable monomers having a lactam structure and maleimide derivatives, and more preferably contains a maleimide derivative.
• the reaction system of the monofunctional radical polymerizable monomer having the lactam structure and the maleimide derivative basically proceeds by a hydrogen abstraction reaction. Photoradical polymerization by hydrogen abstraction reaction is less susceptible to oxygen inhibition, and can therefore increase surface curability. In addition, photoradical polymerization by hydrogen abstraction reaction produces a branched polymer and also increases cohesive strength.
• the photocurable pressure-sensitive adhesive composition for printing can produce a cured product that is less susceptible to bleeding due to a decrease in surface curability and cohesive failure due to a decrease in surface curability and cohesive strength.
• the above "maleimide derivative” means a compound having a maleimide group.
• examples of the monofunctional maleimide include N-cyclohexylmaleimide, N-laurylmaleimide, 4-hydroxyphenylmaleimide, N-(4-carboxycyclohexylmethyl)maleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and N- Examples of the monofunctional maleimide include butylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, N-(2,4,6-tribromophenyl)maleimide, N-(3-(triethoxysilyl)propyl)maleimide, N-octadecenyl
• the monofunctional maleimide is preferably at least one selected from the group consisting of N-cyclohexylmaleimide, 4-hydroxyphenylmaleimide, and N-(4-carboxycyclohexylmethyl)maleimide, and more preferably N-cyclohexylmaleimide.
• examples of polyfunctional maleimides include N,N'-methylene bismaleimide, N,N'-trimethylene bismaleimide, N,N'-dodecamethylene bismaleimide, N,N'-(4,4'-diphenylmethane) bismaleimide, 1,4-dimaleimidecyclohexane, isophorone bisurethane bis(N-ethylmaleimide), N,N'-P-phenylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-m-toluylene bismaleimide, and N,N'-4,4'-biphenyl.
• maleimide derivatives examples include N,N'-4,4'-(3,3'-dimethyl-biphenylene)bismaleimide, N,N'-4,4'-(3,3'-dimethyldiphenylmethane)bismaleimide, N,N'-4,4'-(3,3'-diethyldiphenylmethane)bismaleimide, N,N'-4,4'-diphenylpropane bismaleimide, N,N'-4,4'-diphenylether bismaleimide, N,N'-3,3'-diphenylsulfone bismaleimide, and N,N'-4,4'-diphenylsulfone bismaleimide. From the viewpoint of increasing the reaction rate, the above monofunctional maleimide may be used in combination with these polyfunctional maleimides as the maleimide derivatives, but it is not preferable to use a large amount of polyfunctional maleimide in combination since the gel fraction increases.
• the monofunctional radically polymerizable monomer having a lactam structure is preferably a compound represented by the following formula (1):
• n represents an integer from 2 to 6.
• Examples of the compound represented by the above formula (1) include N-vinyl-2-pyrrolidone and N-vinyl- ⁇ -caprolactam. Of these, N-vinyl- ⁇ -caprolactam is preferred.
• the preferred lower limit of the content of the nitrogen-containing vinyl compound in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 0.1 parts by mass, and the preferred upper limit is 5.0 parts by mass.
• the content of the nitrogen-containing vinyl compound is within this range, the obtained cured product has superior surface curability and adhesion to various substrates.
• the more preferred lower limit of the content of the nitrogen-containing vinyl compound is 0.5 parts by mass, and the more preferred upper limit is 3.0 parts by mass.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention preferably further contains an antifoaming agent.
• the defoaming agent include silicone-based defoaming agents, acrylic polymer-based defoaming agents, vinyl ether polymer-based defoaming agents, and olefin polymer-based defoaming agents.
• the preferred lower limit of the content of the defoaming agent in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 0.1 parts by mass, and the preferred upper limit is 3.0 parts by mass.
• the content of the defoaming agent is within this range, the resulting photocurable adhesive composition for printing has better printability.
• the more preferred lower limit of the content of the defoaming agent is 0.5 parts by mass, and the more preferred upper limit is 2.0 parts by mass.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention further contains a leveling agent.
• the leveling agent include silicone-based leveling agents, acrylic-based leveling agents, and fluorine-based leveling agents.
• the preferred lower limit of the content of the leveling agent in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 0.05 parts by mass, and the preferred upper limit is 3.0 parts by mass. When the content of the leveling agent is within this range, the resulting photocurable adhesive composition for printing has better printability.
• the more preferred lower limit of the content of the leveling agent is 0.1 parts by mass, and the more preferred upper limit is 2.0 parts by mass.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention may further contain a tackifier.
• tackifier include rosin-based resins and terpene-based resins.
• the rosin-based resin includes, for example, rosin diol.
• the rosin diol is not particularly limited as long as it is a rosin-modified diol having two rosin skeletons and two hydroxyl groups in the molecule.
• Diols having a rosin component in the molecule are called rosin polyols, and these include polyether types such as polypropylene glycol (PPG) in which the skeleton excluding the rosin component is polyether, and polyester types such as condensation polyester polyols, lactone polyester polyols, and polycarbonate diols.
• PPG polypropylene glycol
• polyester types such as condensation polyester polyols, lactone polyester polyols, and polycarbonate diols.
• rosin diol examples include rosin ester obtained by reacting rosin with a polyhydric alcohol, epoxy-modified rosin ester obtained by reacting rosin with an epoxy compound, and modified rosin having a hydroxyl group, such as polyether having a rosin skeleton, etc. These can be produced by conventionally known methods.
• rosin components include, for example, abietic acid, abietic acid derivatives such as dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, diabietic acid, and neoabietic acid, pimaric acid-type resin acids such as levopimaric acid, hydrogenated rosins obtained by hydrogenating these, and disproportionated rosins obtained by disproportionating these.
• rosin-based resins include Pine Crystal D-6011, Pine Crystal KE-615-3, Pine Crystal KR-614, Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE-604, and Pine Crystal D-6250 (all manufactured by Arakawa Chemical Industries Co., Ltd.).
• the terpene resin examples include terpene phenol resins.
• the terpene phenol resin is a copolymer of phenol and a terpene resin, which is an essential oil component obtained from natural products such as rosin and orange peel, and also includes partially hydrogenated terpene phenol resins in which at least a portion of the copolymer is hydrogenated, and fully hydrogenated terpene phenol resins in which the copolymer is completely hydrogenated.
• the fully hydrogenated terpene phenolic resin is a terpene resin obtained by substantially completely hydrogenating a terpene phenolic resin
• the partially hydrogenated terpene phenolic resin is a terpene resin obtained by partially hydrogenating a terpene phenolic resin.
• the terpene phenolic resin has a double bond derived from a terpene and an aromatic ring double bond derived from a phenol. Therefore, the fully hydrogenated terpene phenolic resin means a resin in which both the terpene portion and the phenol portion are completely or almost hydrogenated, and the partially hydrogenated terpene phenolic resin means a resin in which the degree of hydrogenation of these portions is not complete but partial.
• the hydrogenation method and reaction form are not particularly limited.
• examples of commercially available ones include YS Polystar NH (fully hydrogenated terpene phenol-based resin) manufactured by Yasuhara Chemical Co., Ltd.
• the preferred lower limit of the content of the tackifier in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 7 parts by mass, and the preferred upper limit is 40 parts by mass.
• the more preferred lower limit of the content of the tackifier is 10 parts by mass, and the more preferred upper limit is 30 parts by mass.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention may contain a filler from the viewpoint of improving printability by adjusting the viscosity.
• a filler from the viewpoint of improving printability by adjusting the viscosity.
• an inorganic filler or an organic filler can be used.
• the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate.
• the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and (meth)acrylic polymer fine particles. Of these, silica is preferred, and fumed silica
• the preferred lower limit of the content of the filler in 100 parts by mass of the photocurable adhesive composition for printing of the present invention is 0.3 parts by mass, and the preferred upper limit is 5.0 parts by mass.
• the more preferred lower limit of the content of the filler is 0.7 parts by mass, and the more preferred upper limit is 3.0 parts by mass.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention may further contain various known additives such as a plasticizer, a silane coupling agent, a sensitizer, a heat curing agent, a curing retarder, an antioxidant, a storage stabilizer, and a dispersant, within the scope of not impairing the object of the present invention.
• various known additives such as a plasticizer, a silane coupling agent, a sensitizer, a heat curing agent, a curing retarder, an antioxidant, a storage stabilizer, and a dispersant, within the scope of not impairing the object of the present invention.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention does not contain a solvent or contains 1 part by mass or less of a solvent per 100 parts by mass of the photocurable pressure-sensitive adhesive composition for printing.
• the method for preparing the photocurable pressure-sensitive adhesive composition for printing of the present invention can be, for example, a method in which the (meth)acrylic monomer, the photopolymerization initiator, the thermoplastic resin, and additives to be added as necessary are mixed using a mixer.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mixer.
• the printing photocurable pressure-sensitive adhesive composition of the second invention is obtained by applying the printing photocurable pressure-sensitive adhesive composition to a substrate to a thickness of 40 ⁇ m or more and 60 ⁇ m or less, and irradiating the coated surface with light having a wavelength of 365 nm and an illuminance of 500 mW/cm 2 in an atmospheric environment without sealing the coated surface, so that the irradiation amount is 3000 mJ/cm 2.
• the lower limit of the solid content of the cured product obtained by applying the printing photocurable pressure-sensitive adhesive composition to a substrate to a thickness of 40 ⁇ m or more and 60 ⁇ m or less, and irradiating the coated surface with light having a wavelength of 365 nm and an illuminance of 500 mW/cm 2 in an atmospheric environment without sealing the coated surface, is 90%.
• a PET film with a release treatment on the surface is preferably used.
• the preparation conditions of the cured product are that the photocurable pressure-sensitive adhesive composition for printing is applied to the substrate, and then the coated surface is irradiated with light in the presence of oxygen without being covered with a separator or the like.
• the solid content of the cured product reflects the photoreactivity in the presence of oxygen.
• the solid content of the cured product is 90% or more, it can be said that the photoreactivity in the presence of oxygen is sufficiently high, making it possible to apply a method in which the printable photocurable pressure-sensitive adhesive composition is printed in a desired shape and then bonded to an adherend.
• the lower limit of the solid content of the cured product is preferably 92%, more preferably 94%
• the lower limit of the solid content of the cured product is more preferably 92%, even more preferably 94%.
• the higher the solid content of the cured product the more preferable it is, but the practical upper limit is 99%.
• the solid content of the cured product can be measured, for example, according to the following procedure. That is, the photocurable pressure-sensitive adhesive composition for printing is first coated onto a release PET film as a substrate to a thickness of 40 ⁇ m to 60 ⁇ m, and then, without sealing the coated surface, the coated surface is simultaneously irradiated with light having a wavelength of 365 nm and an illuminance of 500 mW/ cm2 at an irradiation dose of 3000 mJ/ cm2 using a light irradiation device in an atmospheric environment to cure the photocurable pressure-sensitive adhesive composition for printing and obtain a cured product.
• Solid content rate (%) of cured product (total mass of aluminum pan and sample after drying ⁇ mass of aluminum pan before drying)/(mass of sample before swelling) ⁇ 100
• the lower limit of the gel fraction of the cured product is 25% by mass, and the upper limit is 60% by mass.
• the preferred lower limit of the gel fraction of the cured product is 25% by mass, and the preferred upper limit is 60% by mass.
• the photocurable adhesive composition for printing of the present invention has excellent adhesion and retention performance after curing.
• the preferred lower limit of the gel fraction of the cured product is 30% by mass, the preferred upper limit is 50% by mass, and the more preferred upper limit is 45% by mass.
• the more preferred lower limit of the gel fraction of the cured product is 30% by mass, the more preferred upper limit is 50% by mass, and the even more preferred upper limit is 45% by mass.
• the photocurable adhesive composition for printing of the present invention is used for printing. If an adhesive layer is formed by applying a desired pattern on an adherend (substrate) by printing, there is an advantage that the cutting process can be omitted compared to the case where an adhesive of a desired shape is obtained by cutting a sheet-like adhesive just before lamination. As a result, it is possible to suppress the generation of waste and reduce the environmental load.
• methods for printing the photocurable pressure-sensitive adhesive composition for printing of the present invention include gravure printing, flexographic printing, slot die coating, knife coating, inkjet printing, spray coating, spin coating, screen printing, stencil printing, reverse offset printing, etc. Among these, screen printing and inkjet printing are preferably used.
• the viscosity of the photocurable pressure-sensitive adhesive composition for printing of the present invention measured using an E-type viscometer at 25°C and 10 rpm, preferably has a lower limit of 1 Pa ⁇ s and a higher limit of 400 Pa ⁇ s. When the viscosity is in this range, the photocurable pressure-sensitive adhesive composition for printing of the present invention is more suitable for screen printing. When the photocurable pressure-sensitive adhesive composition for printing of the present invention is used for screen printing, the more preferred lower limit of the viscosity is 5 Pa ⁇ s and the more preferred upper limit is 100 Pa ⁇ s.
• the viscosity of the photocurable pressure-sensitive adhesive composition for printing of the present invention measured using an E-type viscometer at 25°C and 10 rpm, preferably has a lower limit of 0.001 Pa ⁇ s and a preferred upper limit of 10 Pa ⁇ s.
• the photocurable pressure-sensitive adhesive composition for printing of the present invention is more suitable for inkjet printing.
• the more preferred lower limit of the viscosity is 0.005 Pa ⁇ s and the more preferred upper limit is 1 Pa ⁇ s.
• the E-type viscometer for example, a VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) can be used.
• the photocurable adhesive composition for printing of the present invention is cured by irradiation with light to form an adhesive layer, and its method of use may be to form an adhesive layer on a substrate (separator) to produce an adhesive sheet that can be transferred to an adherend, or to form an adhesive layer directly on an adherend.
• the method of forming an adhesive layer directly on an adherend can minimize the number of times of lamination and can prevent air bubbles from entering the interface during lamination.
• the method of forming an adhesive layer on a substrate (separator) has the advantage that there are fewer constraints on construction, since the adhesive layer is placed on the adherend by transfer.
• the present invention also includes a cured product obtained by curing the photocurable adhesive composition for printing of the present invention.
• the cured product of the present invention preferably has the above-mentioned solid content of 90% or more and the above-mentioned gel content of 25% by mass or more and 60% by mass or less.
• a laminate having a release-treated film on at least one side of the cured product of the present invention is also one aspect of the present invention.
• the present invention can provide a photocurable pressure-sensitive adhesive composition for printing that has excellent repeatable printability, photocurability in the presence of oxygen, and adhesiveness and retention performance after curing.
• the present invention can also provide a cured product and a laminate made using the photocurable pressure-sensitive adhesive composition for printing.
• SCT-9001 Acrylic/styrene triblock copolymer (manufactured by Fujikura Chemical Industries, weight average molecular weight 350,000) (Tackifier) KE-359: Rosin ester (manufactured by Arakawa Chemical Industries, Ltd.) (Filler) R805: Fumed silica (manufactured by Nippon Aerosil Co., Ltd.) (Antifoaming agent) KS-66: Silicone-based defoamer (manufactured by Shin-Etsu Chemical Co., Ltd.) (Leveling Agent) ⁇ BYK-302: Silicone-based leveling agent (manufactured by BYK Japan)
• a polymerization initiator solution obtained by diluting 0.2 parts by mass of t-butylperoxy-2-ethylhexanoate with 5 parts by mass of ethyl acetate as a polymerization initiator was added dropwise to the reaction vessel over 2 hours. After that, the mixture was further reacted at 80°C for 6 hours, and then the reaction liquid was cooled to obtain an acrylic polymer solution.
• the obtained acrylic polymer solution was diluted with ethyl acetate to obtain a solution with a solid content of 20% by mass.
• the obtained solution was then applied onto a release PET film using a coater so that the thickness after drying was 100 ⁇ m, and dried at 80° C. for 1 hour and at 110° C. for 1 hour to obtain an acrylic random copolymer A.
• the weight average molecular weight of the resulting acrylic random copolymer A was 300,000.
• a polymerization initiator solution obtained by diluting 0.2 parts by mass of t-butylperoxy-2-ethylhexanoate with 5 parts by mass of ethyl acetate as a polymerization initiator was added dropwise to the reaction vessel over 2 hours. After that, the mixture was further reacted at 80°C for 6 hours, and then the reaction liquid was cooled to obtain an acrylic polymer solution.
• the obtained acrylic polymer solution was diluted with ethyl acetate to obtain a solution with a solid content of 20% by mass.
• the obtained solution was then applied onto a release PET film using a coater so that the thickness after drying was 100 ⁇ m, and dried at 80° C. for 1 hour and at 110° C. for 1 hour to obtain an acrylic random copolymer B.
• the weight average molecular weight of the resulting acrylic random copolymer B was 80,000.
• the obtained photocurable pressure-sensitive adhesive composition for printing was applied to a release PET film (manufactured by Nippa Corporation, "1-E", thickness 50 ⁇ m) using an applicator to a thickness of about 50 ⁇ m.
• the film was irradiated with light having a wavelength of 365 nm and an illuminance of 500 mW/ cm2 in an atmospheric environment using a UV-LED irradiation device (manufactured by CCS Corporation, "UVS01-01”) so that the irradiation amount was 3000 mJ/ cm2 , thereby obtaining a cured product.
• the atmospheric surface of the cured product was sealed with a release PET film (manufactured by Nippa Corporation, "1-C", thickness 38 ⁇ m) to obtain a laminate.
• Both release films were peeled off from the obtained laminate, and about 0.3 g of the cured product of the photocurable adhesive composition for printing was placed on an aluminum pan with a diameter of 10 cm and a height of 1 cm.
• a mixed solvent containing THF: acetone: ethanol in a mass ratio of 8:1:1 was gently added so that the cured sample would not scatter, and the sample was allowed to swell for about 2 hours. After that, the sample was dried at 110°C for 30 minutes, at 170°C for 1 hour, and at 190°C for 30 minutes.
• Solid content rate (%) of cured product (total mass of aluminum pan and sample after drying ⁇ mass of aluminum pan before drying)/(mass of sample before swelling) ⁇ 100
• a cured product was obtained by irradiating light with a wavelength of 365 nm and an illuminance of 500 mW/cm 2 using a UV-LED irradiation device (manufactured by CCS Corporation, "UVS01-01") so that the irradiation amount was 3000 mJ/cm 2.
• the air surface of the cured product was sealed with a release PET film (manufactured by Nippa Co., Ltd., "1-C", thickness 38 ⁇ m), and cut to a width of 25 mm and a length of 200 mm (adhering surface 25 mm x 125 mm) to prepare a laminated film.
• the release PET film was peeled off from the laminated film, and the exposed surface was attached to a SUS substrate and pressed by reciprocating a 2 kg roller to obtain a test piece.
• the test piece was stored in a 25°C environment for 24 hours, and a 180° peel was performed at a speed of 300 mm/min using a universal testing machine (manufactured by A&D Co., Ltd., "Tensilon RTI-1310") to measure the 180° peel adhesive strength.
• the other release PET film (1-E) was peeled off, and the mirror-polished surface of a similar SUS substrate was bonded to the exposed cured product surface, and then the specimen was pressed at 215 N using a universal testing machine (manufactured by A&D, "Tensilon RTI-1310") and allowed to stand for 48 hours in an environment at 25 ° C. to obtain a test specimen.
• the tensile shear adhesive strength (shear adhesive strength) of the obtained test specimen was measured at 25 ° C. using a universal testing machine (manufactured by A&D, "Tensilon RTI-1310") according to a method conforming to JIS K 6850.
• the other release PET film (1-E) was peeled off, and the mirror-polished surface of a similar SUS substrate was attached to the exposed cured product surface, and then the specimen was pressed at 215 N using a universal testing machine (manufactured by A&D Co., Ltd., "Tensilon RTI-1310") and allowed to stand for 48 hours in an environment of 25°C to obtain a test specimen.
• the obtained test piece was hung using an S-hook, and further, a weight of 1 kg was hung from the lower SUS substrate. This was left at 25° C., and the time until the weight fell was measured, and the retention performance (creep resistance) was evaluated according to the following criteria.
• ⁇ The weight did not fall even after 72 hours.
• ⁇ The time until the weight fell was 24 hours or more but less than 72 hours.
• ⁇ The time until the weight fell was 6 hours or more but less than 24 hours.
• ⁇ The time until the weight fell was less than 6 hours.
• a cured product was obtained by irradiating the film with light having a wavelength of 365 nm and an illuminance of 500 mW/ cm2 using a UV-LED irradiation device (CS Corporation's "UVS01-01") so that the irradiation amount was 3000 mJ/ cm2 .
• Screen printing The obtained photocurable pressure-sensitive adhesive composition for printing was screen-printed by applying a pattern to a thickness of about 50 ⁇ m on the inner treated surface of an easily adhesive polyester film (Toyobo Co., Ltd., "Cosmoshine A4100") using a screen printer (Micro-Tec Co., Ltd., "LABTOP 38").
• a pattern-treated 80-mesh printing plate was used as the screen printing plate.
• a UV-LED irradiation device (CS Inc., "UVS01-01") was used to irradiate light with a wavelength of 365 nm and an illuminance of 500 mW/ cm2 at an irradiation dose of 3000 mJ/ cm2 to obtain a cured product.
• (1-3) Inkjet printing The obtained photocurable pressure-sensitive adhesive composition for printing was applied to a thickness of about 2 ⁇ m on a release PET film (Nippa's "1-E", thickness 50 ⁇ m) using an inkjet device (FUJIFILM Corporation, "Material Printer DMP-2831").
• a cured product was obtained by irradiating the film with light having a wavelength of 365 nm and an illuminance of 500 mW/ cm2 using a UV-LED irradiation device (CS Corporation, "UVS01-01") so that the irradiation amount was 3000 mJ/ cm2 .
• the present invention can provide a photocurable pressure-sensitive adhesive composition for printing that has excellent repeatable printability, photocurability in the presence of oxygen, and adhesiveness and retention performance after curing.
• the present invention can also provide a cured product and a laminate made using the photocurable pressure-sensitive adhesive composition for printing.

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