WO2014092058A1 - 光硬化性組成物 - Google Patents

光硬化性組成物 Download PDF

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Publication number
WO2014092058A1
WO2014092058A1 PCT/JP2013/083009 JP2013083009W WO2014092058A1 WO 2014092058 A1 WO2014092058 A1 WO 2014092058A1 JP 2013083009 W JP2013083009 W JP 2013083009W WO 2014092058 A1 WO2014092058 A1 WO 2014092058A1
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compound
photocurable composition
group
hydroxyl group
acrylate
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PCT/JP2013/083009
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English (en)
French (fr)
Japanese (ja)
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高橋　利行
和彦 松土
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株式会社Adeka
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Priority to CN201380065388.7A priority Critical patent/CN104854155B/zh
Priority to JP2014552037A priority patent/JP6226388B2/ja
Priority to KR1020157018247A priority patent/KR102083250B1/ko
Publication of WO2014092058A1 publication Critical patent/WO2014092058A1/ja

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    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09J161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Definitions

  • the present invention relates to a photocurable composition and a cured product of the photocurable composition, and more specifically, a photocurable composition capable of obtaining a cured product having excellent adhesion to a substrate and light using the same.
  • the present invention relates to a curable adhesive.
  • a photocurable composition is a composition that is cured by irradiation with active energy rays such as ultraviolet rays, and has the advantage of being excellent in rapid curability, so it can be used in various fields such as adhesives, paints, and various resists. Is used.
  • active energy rays such as ultraviolet rays
  • the photocurable composition those containing an acrylate compound are known.
  • Patent Document 1 discloses urethane acrylate, polyester acrylate, a photocurable material that is a mixture of urethane acrylate and polyester acrylate, and solid polyvinyl acetal. And a solid photocurable film adhesive comprising a photoinitiator.
  • thermosetting resins melamine resins and urea resins obtained through compounds having active methylol groups are known as thermosetting resins and are used as thermosetting agents and thermal crosslinking agents.
  • Patent Document 2 discloses a photocurable acrylic coloring composition using methoxymethylmelamine as an adhesion improver
  • Patent Document 3 discloses a photocurable coating that can use a melamine-based crosslinking agent
  • Patent Document 4 discloses a light and thermosetting composition that can use a melamine resin as a curing agent
  • Patent Document 5 discloses a melamine compound as a crosslinking agent or an adhesive improvement. Although the curable composition contained as an agent is disclosed, these do not use a melamine compound as an active ingredient of an adhesive.
  • JP 05-214302 A Japanese Patent Laid-Open No. 5-188591 Japanese Patent Publication No. 7-015011 Japanese Patent Laid-Open No. 10-147745 JP 2005-089651 A
  • the photocurable resin has the advantages as described above, there is still room for improvement in the adhesion with a substrate such as a film made of various resins. Then, the objective of this invention is providing the photocurable composition which can obtain the hardened
  • thermosetting component an active methylol group known as a thermosetting component
  • alcohol compound an alcohol compound as a main component
  • the photocurable composition of the present invention contains (A) a compound having a plurality of active alkylol groups, (B) an alcohol compound, (C) a polyfunctional acrylic oligomer, and (D) a photoinitiator. It is characterized by.
  • the (B) alcohol compound is preferably an acrylate compound having a hydroxyl group, a methacrylate compound having a hydroxyl group, an acrylamide compound having a hydroxyl group, or a methacrylamide compound having a hydroxyl group.
  • the (B) alcohol compound is preferably a polyol compound.
  • the compound (A) having a plurality of active alkylol groups is polyalkylolated melamine, polyalkylolated glycoluril, polyalkylolated hydroxyethylene urea, polyalkylolated. It is preferably one or more compounds selected from the group consisting of urea, polyalkylolated benzoguanamine, polyalkylolated spiroguanamine, and polyalkylolated acrylamide.
  • the compound (A) having a plurality of active alkylol groups is preferably a compound having one or more skeletons selected from Group 1 below. ⁇ Group 1>
  • the compound (A) having a plurality of active alkylol groups is preferably a polyalkylolated melamine represented by the following general formula (I).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group.
  • the methylene group in the alkyl group may be interrupted by an oxygen atom.
  • the compound (A) having a plurality of active alkylol groups is preferably a polyalkylolated urea represented by the following general formula (III).
  • R 51 and R 54 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group, and the methylene group in the alkyl group is interrupted by an oxygen atom
  • the (C) polyfunctional acrylic oligomer is preferably a urethane acrylate oligomer or a urethane methacrylate oligomer.
  • the (D) photoinitiator is preferably a photoacid generator.
  • the photocurable composition of the present invention preferably further contains (E) a polyfunctional acrylate compound or a polyfunctional methacrylate compound.
  • the photocurable composition of the present invention preferably further contains (F) a monofunctional acrylic monomer.
  • the photocurable adhesive of the present invention is obtained from any one of the above photocurable compositions.
  • a photocurable composition capable of obtaining a cured product excellent in adhesion to a substrate and a photocurable adhesive using the same.
  • the component (A) in the present invention is a compound having a plurality of active alkylol groups.
  • An active alkylol group has a methylene group adjacent to an oxygen atom, and is highly reactive with an acid catalyst. The number of carbon atoms of the active alkylol group is preferably 1-5.
  • component of this invention shows a polymerization reaction by the effect
  • the compound having a plurality of active alkylol groups is not particularly limited as long as it has a plurality of active alkylol groups in the molecule.
  • amino resins such as melamine resin, guanamine resin, sulfoamide resin, urea resin, aniline resin; melamine monomer, urea, hydroxyethylene urea (glyoxalurea), glycoluril, benzoguanamine, spiroguanamine, guanidine, isocyanuric acid dicyandiamide,
  • An amino compound such as acrylamide, or an amino group of an amide compound alkylated can be used.
  • the alkylolation can be performed by a known method.
  • the compound (A) having a plurality of active alkylol groups used in the present invention include polyalkylolated melamine, polyalkylolated glycoluril, polyalkylolated hydroxyethylene urea, and polyalkylolated. Examples include urea, polyalkylolated benzoguanamine, polyalkylolated spiroguanamine, polyalkylolated acrylamide, and the like, which may contain a partially self-condensed oligomer component.
  • the compound which has several active alkylol group may be used individually by 1 type, or may be used in mixture of multiple.
  • polyalkylolated melamine represented by the following general formula (I) is preferable because synthesis is easy and high adhesion is obtained.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group.
  • the methylene group in the alkyl group may be interrupted by an oxygen atom.
  • the alkyl group having 1 to 5 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 includes methyl, ethyl, propyl, isopropyl, butyl , S-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, methoxyethoxyethyl, 3-methoxybutyl and the like.
  • polyalkylolated urea represented by the following general formula (III) is easy to synthesize and high adhesion can be obtained.
  • R 51 and R 54 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group, and the methylene group in the alkyl group is interrupted by an oxygen atom
  • polyalkylolated urea represented by the following general formula (IV) or (V) is easy to synthesize and has high adhesion. Is preferable.
  • R 55 and R 60 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group, and the methylene group in the alkyl group is interrupted by an oxygen atom
  • R 56 , R 57 , R 58 and R 59 each independently represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms.
  • R 61 , R 62 , R 63 and R 64 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group, and a methylene group in the alkyl group) May be interrupted by an oxygen atom.
  • Examples of the alkyl group having 1 to 5 carbon atoms that can be taken by R 51 , R 54 , R 55 , R 60 , and R 61 to R 64 include those described above.
  • Examples of the alkoxy group having 1 to 5 carbon atoms that R 52 , R 53 , and R 56 to R 59 can include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
  • the active alkylol groups may be condensed with each other to form an oligomer.
  • the compound having a plurality of active alkylol groups may be composed only of monomers, or may be used in the form of a resin by mixing monomers and oligomers.
  • Cymel 303, 235, 254, 325, 1128, 1156, 1170 (manufactured by MT Aquapolymer), My Coat 102, 105 506 (manufactured by MT Aquapolymer), Uban 20N, 20SB, 20SE60, 122, 125, 128, 220, 225, 2020 (manufactured by Mitsui Chemicals), Nikarac MW-30M, MW-30HM, MW-390, MW- Melamine resins such as 100LM, MX-750LM, MX-45, MX-410 (manufactured by Sanwa Chemical Co., Ltd.); guanamine resins such as Nicalac BL-60, BX-4000; Nicalac MX-270, MX-280, MX-290 And urea resins.
  • the (B) alcohol compound is added to improve adhesion, and any known compound can be used without particular limitation.
  • any known compound can be used without particular limitation.
  • Alcohols and their alkylene oxide adducts pentaerythritol, dipenta Polyhydric alcohols such as lithritol, tetramethylolpropane, sorbitol and their alkylene oxide adducts; tris-2-hydroxyethyl isocyanurate, oxetane alcohol, 3-ethyl-3-hydroxymethyloxetane, 2-hydroxyethyl (3-ethyl) -3-Ocetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether and other oxetane compounds having a hydroxyl group; hydroxyl group-containing acrylate compounds; hydroxyl group-containing methacrylate compounds; hydroxyl group-containing acrylamide compounds; And methacrylamide compounds having a hydroxyl group.
  • the use ratio of the (B) alcohol compound to the compound (A) having a plurality of alkylol groups is such that (B) the alcohol compound is 20 to 800 masses per 100 parts by mass of the compound (A) having a plurality of alkylol groups. Parts, and more preferably in the range of 50 to 300 parts by weight.
  • Polyfunctional acrylic oligomer used in the present invention includes urethane acrylate oligomer, epoxy acrylate oligomer, polyether acrylate oligomer, polyester acrylate oligomer, urethane methacrylate oligomer, epoxy methacrylate oligomer, polyether methacrylate oligomer, polyester methacrylate oligomer, etc. Among them, urethane acrylate oligomer or urethane methacrylate oligomer is preferable.
  • urethane acrylate oligomer examples include polycarbonate-based urethane acrylate, polyester-based urethane acrylate, polyether-based urethane acrylate, caprolactone-based urethane acrylate, and the like.
  • the polyol include polycarbonate diol, polyester polyol, polyether polyol, and polycaprolactone polyol.
  • the epoxy acrylate oligomer can be obtained, for example, by an esterification reaction between an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin and acrylic acid.
  • the polyether acrylate oligomer is obtained by obtaining a polyether oligomer having hydroxyl groups at both ends by dehydration condensation reaction of polyol, and then esterifying the hydroxyl groups at both ends with acrylic acid.
  • the polyester acrylate oligomer can be obtained, for example, by obtaining a polyester oligomer having hydroxyl groups at both ends by condensation of polycarboxylic acid and polyol, and then esterifying the hydroxyl groups at both ends with acrylic acid.
  • polyfunctional means bifunctional or higher, but usually 20 functional or lower.
  • the molecular weight of the (C) polyfunctional acrylic oligomer used in the present invention is preferably 500 to 5,000.
  • Examples of the (D) photoinitiator used in the present invention include a photoacid generator and a photoradical generator, and one kind may be used alone, or two or more kinds may be mixed and used.
  • the photoinitiator generates an acid to react (A) a compound having a plurality of active alkylol groups with (B) an alcohol compound, or (C) a polyfunctional acrylic oligomer or (F) polyfunctional acrylate described below. It functions to cure the compound or polyfunctional methacrylate compound.
  • the photoacid generator is not particularly limited as long as it generates a Lewis acid by light irradiation, and any known one can be used.
  • a sulfonic acid derivative, a carboxylic acid derivative, an onium salt or a derivative thereof, a phosphate ester, an oxime sulfonate, a hydroxyimide ester, a metal salt, and the like can be used, and among them, an onium salt is preferable because of its high acid generating ability.
  • a salt of a cation and an anion represented by the following general formula: [A] r + [B] s t- (where r is a number of 1 to 4, t is 1) The number of ⁇ 4, s is a coefficient for keeping the charge neutral).
  • the cation [A] r + is preferably onium, and the structure thereof can be represented by, for example, the following general formula: [(R 7 ) f Q] r + .
  • R 7 is an organic group having 1 to 60 carbon atoms and any number of atoms other than carbon atoms.
  • f is an integer from 1 to 5.
  • the f R 7 s are independent and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring.
  • the anion [B] t- is preferably a halide complex, and the structure thereof can be represented by, for example, the general formula [LX g ] t- .
  • L is a metal or metalloid which is a central atom of a halide complex
  • B P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr , Mn, Co, etc.
  • X is a halogen atom.
  • anion [LX g ] t- of the above general formula examples include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF 4 ) ⁇ , Examples include hexafluorophosphate (PF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , hexafluoroarsenate (AsF 6 ) ⁇ , hexachloroantimonate (SbCl 6 ) ⁇ and the like.
  • a structure represented by the following general formula, [LX g-1 (OH)] t- can also be preferably used.
  • L, X, and g are the same as described above.
  • Other anions that can be used include perchlorate ion (ClO 4 ) ⁇ , trifluoromethylsulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonate ion (FSO 3 ) ⁇ , and toluenesulfonate anion.
  • Trinitrobenzenesulfonate anion camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
  • onium salts it is particularly effective to use the following aromatic onium salts (1) to (3).
  • aromatic onium salts (1) to (3) one of them can be used alone, or two or more of them can be mixed and used.
  • Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
  • Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
  • Sulfonium salts such as sulfonium cations and hexafluoroantimony ions, tetrakis (pentafluorophenyl) borate ions represented by the following group 2 or group 3
  • photoacid generators As other photoacid generators, ( ⁇ 5 -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6- ⁇ )-(1- Iron-arene complexes such as methylethyl) benzene] -iron-hexafluorophosphate, and aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum
  • silanols such as phenylsilanol can also be mentioned.
  • aromatic iodonium salts aromatic sulfonium salts, and iron-arene complexes are preferably used from the viewpoints of practical use and photosensitivity, and aromatic sulfoniums represented by the following general formula (II)
  • aromatic sulfoniums represented by the following general formula (II) A salt is more preferable from the viewpoint of sensitivity.
  • R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 39 , R 40 , R 41 , R 42 and R 43 are Each independently a hydrogen atom; a halogen atom; a linear or branched chain having 1 to 10 carbon atoms which may be substituted with a halogen atom or an epoxy group, and may be interrupted with an oxygen atom or a sulfur atom Represents an alkyl group; an alkoxy group having 1 to 10 carbon atoms; or an ester group having 2 to 10 carbon atoms; and R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 each independently represent a hydrogen atom; a halogen atom; or a halogen atom or an epoxy group may be substituted by, it may be interrupted by an oxygen atom or a sulfur atom, a straight-chain having 1 to 10
  • Examples of the halogen atom represented by 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 and R 43 include fluorine, chlorine, bromine and iodine. It is done.
  • Examples of the linear or branched alkyl group having 1 to 10 atoms include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, Octyl, nonyl, ethyloctyl, 2-methoxyethy
  • Examples of the alkoxy group of 1 to 10 include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexyl Methyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethoxye
  • Examples of the ester group of 2 to 10 include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butyl Examples include carbonyloxy, methoxyacetyloxy, benzoyloxy and the like.
  • photo radical initiator conventionally known compounds can be used.
  • benzophenone phenyl biphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyl dimethyl ketal, 1-benzyl-1-dimethyl Amino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4 -Benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4- Tylbenzoyltrichloromethane, 4-phenoxybenzoy
  • the use ratio of the (D) photoinitiator to the compound having a plurality of (A) active alkylol groups is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention.
  • 0.05 to 10 parts by mass of (C) photoinitiator is preferable, and more preferably 0.5 to 10 parts by mass. . If the amount is too small, curing tends to be insufficient, and if the amount is too large, the strength of the cured product may be adversely affected.
  • a polyfunctional acrylate compound or a polyfunctional methacrylate compound can be further added to the photocurable composition of the present invention.
  • the polyfunctional acrylate compound include epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, and acrylic ester of alcohols.
  • the polyfunctional methacrylate compound include epoxy methacrylate, urethane methacrylate, and polyester methacrylate. Examples thereof include acrylates, polyether methacrylates, and methacrylic acid esters of alcohols.
  • the epoxy acrylate is, for example, an acrylate obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with acrylic acid.
  • a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like is particularly preferred.
  • an acrylate of an aromatic epoxy resin particularly preferred is an acrylate of an aromatic epoxy resin, and a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof is reacted with acrylic acid.
  • the resulting acrylate for example, acrylate obtained by reacting glycidyl ether obtained by reacting bisphenol A or its alkylene oxide adduct with epichlorohydrin with acrylic acid, acrylate obtained by reacting epoxy novolac resin with acrylic acid, etc. Is mentioned.
  • the epoxy methacrylate is, for example, an acrylate obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with methacrylic acid.
  • these epoxy methacrylates particularly preferred are aromatic epoxy resin methacrylates, polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof, and methacrylic acid. It is a methacrylate obtained by reaction.
  • bisphenol A or its alkylene oxide adduct is obtained by reacting glycidyl ether obtained by reacting with epichlorohydrin with methacrylic acid, methacrylate, epoxy novolac resin and methacrylic acid.
  • methacrylates is, for example, an acrylate obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with methacrylic acid.
  • aromatic epoxy resin methacrylates particularly preferred are aromatic epoxy resin
  • the urethane acrylate is an acrylate obtained by reacting a hydroxyl group-containing acrylate ester and an isocyanate group with one or two or more hydroxyl group-containing polyesters or a hydroxyl group-containing polyether, or a hydroxyl group-containing acrylate ester and an isocyanate group.
  • Preferred as the urethane methacrylate is a methacrylate obtained by reacting a hydroxyl group-containing methacrylate and an isocyanate with one or more hydroxyl group-containing polyester or hydroxyl group-containing polyether, or a hydroxyl group-containing methacrylate. And methacrylate obtained by reacting with isocyanates.
  • the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by reaction of one or more aliphatic polyhydric alcohols with one or more polybasic acids
  • the aliphatic polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, and glycerin.
  • the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid, and the like.
  • hydroxyl group-containing polyether is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol, and the aliphatic polyhydric alcohol includes the compounds described above. The same thing can be illustrated.
  • alkylene oxide include ethylene oxide and propylene oxide.
  • the hydroxyl group-containing acrylate ester is a hydroxyl group-containing acrylate ester obtained by an esterification reaction of an aliphatic polyhydric alcohol and acrylic acid, and the aliphatic polyhydric alcohol is the same as the compound described above. It can be illustrated.
  • a hydroxyl group-containing acrylic ester obtained by esterification of an aliphatic dihydric alcohol and acrylic acid is particularly preferred, and examples thereof include 2-hydroxyethyl acrylate.
  • the hydroxyl group-containing methacrylic acid ester is a hydroxyl group-containing methacrylic acid ester obtained by esterification reaction of an aliphatic polyhydric alcohol and methacrylic acid, and the aliphatic polyhydric alcohol is the same as the compound described above. Can be exemplified.
  • a hydroxyl group-containing methacrylic acid ester obtained by esterification reaction of an aliphatic dihydric alcohol and methacrylic acid is particularly preferred, and examples thereof include 2-hydroxyethyl methacrylate.
  • isocyanates compounds having one or more isocyanate groups in the molecule are preferable, and divalent isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.
  • the polyester acrylate is preferably a polyester acrylate obtained by reacting a hydroxyl group-containing polyester with acrylic acid
  • the polyester methacrylate is preferably a polyester obtained by reacting a hydroxyl group-containing polyester with methacrylic acid.
  • Preferred as the hydroxyl group-containing polyester used here is an esterification reaction of one or more aliphatic polyhydric alcohols with one or more monobasic acids, polybasic acids, and phenols.
  • examples of the aliphatic polyhydric alcohol include the same compounds as those described above.
  • monobasic acids include formic acid, acetic acid, butyl carboxylic acid, benzoic acid and the like.
  • the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid and the like.
  • phenols include phenol, p-nonylphenol, bisphenol A, and the like.
  • the polyether acrylate is a polyether acrylate obtained by reacting a hydroxyl group-containing polyether with acrylic acid
  • preferred as the polyether methacrylate is a hydroxyl group-containing polyether, methacrylic acid
  • What is preferable as the hydroxyl group-containing polyether used here is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol, The same compounds as those described above can be exemplified.
  • the alkylene oxide include ethylene oxide and propylene oxide.
  • the acrylate ester of the alcohol is an acrylate obtained by reacting an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule, and an alkylene oxide adduct thereof with acrylic acid, for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, benzyl acrylate, 1,3-butanediol Diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene Examples include glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolprop
  • polyacrylates of polyhydric alcohols are particularly preferred.
  • Preferred as the methacrylic acid ester of the alcohol is an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule, and a methacrylate obtained by reacting the alkylene oxide adduct with methacrylic acid.
  • the content of the above-mentioned (E) polyfunctional acrylate compound or polyfunctional methacrylate compound is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention.
  • (A) The amount of (E) the polyfunctional acrylate compound or polyfunctional methacrylate compound is preferably 0.5 to 100 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the compound having a plurality of active alkylol groups. It is. If the amount is too small, the adhesion tends to be insufficient. If the amount is too large, the strength of the cured product may be adversely affected.
  • a monofunctional acrylic monomer can be further added to the photocurable composition of the present invention.
  • functional acrylic monomers include monofunctional acrylate compounds, monofunctional methacrylate compounds, monofunctional acrylamide compounds, and monofunctional methacrylamide compounds, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic 4-hydroxybutyl acid, isobutyl acrylate, tertiary butyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, stearyl acrylate, lauryl acrylate, behenyl acrylate, methoxy acrylate Monofunctional acrylate compounds such as ethyl, dimethylaminoethyl acrylate, and zinc acrylate; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl methacrylate, Monofunctional methacrylate compounds such as butyl,
  • a photosensitizer can be further added to the photocurable composition of the present invention, and examples thereof include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone.
  • Polymethine dyes such as 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives , Acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphen
  • Derivatives acridine derivatives, benzothiazole derivatives, and the like. More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Nobu Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori, “Special Function” Examples thereof include, but are not limited to, the dyes and sensitizers described in “Materials” (1986, CMC), and other dyes and sensitizers that absorb light in the ultraviolet to near infrared region. Agents. These may be used alone or in combination.
  • a thermal polymerization initiator can be used in the photocurable composition of the present invention as necessary.
  • the thermal polymerization initiator is a compound that generates a cationic species or a Lewis acid by heating.
  • sulfonium salt, thiophenium salt, thioranium salt, benzylammonium, pyridinium salt, hydrazinium salt, etc . polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4 -Cycloaliphatic polyamines such as diamino-3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; the polyamines and phenylglycidyl ether, butylglycidyl
  • Mannich modified product produced by: polyvalent carboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyl adipic acid, 3-methyl Aliphatic dicarboxylic acids such as dipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid; Aromatic dicarboxylic acids such as acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic
  • thermal polymerization initiator for example, Adeka Opton CP77, Adeka Opton CP66 (ADEKA), CI-2939, CI-2624 (Nihon Soda Co., Ltd.), SunAid SI-60L, SunAid SI -80L, Sun-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.)
  • the amount of the thermal polymerization initiator used is not particularly limited, but is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photocurable composition.
  • the thermal polymerization initiator is preferably heated at 130 to 180 ° C. for 20 minutes to 1 hour when the photocurable composition of the present invention is cured.
  • a silane coupling agent can be used as necessary.
  • the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane.
  • Alkyl-functional alkoxysilanes vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane Epoxy-functional alkoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- ⁇ (aminoethyl) Aminofunctional alkoxysilanes such as ⁇ -amin
  • the stress can be relieved by adding a polymer having no hydroxyl group to the photocurable composition of the present invention.
  • the molecular weight of the polymer is preferably 5000 to 50000.
  • a solvent capable of dissolving or dispersing each of the components (A) to (D) can be used as required.
  • acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol can be added.
  • the photocurable composition of the present invention is applied onto a supporting substrate by a known means such as a roll coater, a curtain coater, various types of printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
  • the support substrate is not particularly limited, but preferred examples thereof include glass plate, polyethylene terephthalate plate, polycarbonate plate, polyimide plate, polyamide plate, polymethyl methacrylate plate, polystyrene plate, polyvinyl chloride plate, polyolefin plate, cyclohexane plate, Olefin polymer plate, polytetrafluoroethylene plate, triacetylcellulose plate, norbornene plate, polyvinyl alcohol plate, cellulose acetate plate, polyarylate plate, polysulfone plate, polyethersulfone plate, silicon wafer, reflector, calcite plate, quartz plate, A glass plate, paper, wood, a metal plate, etc. are mentioned.
  • the substrate may be subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, or coating such as an anchor coating agent or a primer.
  • the photocurable composition of the present invention is cured by irradiation with active energy rays.
  • active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are the most economical.
  • ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
  • photocurable composition of the present invention include adhesives, paints, coating agents, lining agents, inks, resists, liquid resists, printing plates, insulating varnishes, insulating sheets, laminates, and printed boards.
  • the lens portion of the lens sheet such as a backlight using such a sheet, an optical lens such as a microlens, an optical element, an optical connector, an optical waveguide, a casting for optical modeling, etc.
  • substrates that can be applied as coating agents include metals, wood, rubber, plastic, glass, ceramic Click products and the like can be mentioned.
  • the photocurable composition of the present invention When the photocurable composition of the present invention is used for an adhesive, the photocurable composition is applied to a support substrate, and an ultraviolet ray or the like is applied to a laminate in which another layer such as a protective layer is laminated as necessary. At the same time or before or after light irradiation, the laminate is preheated and pressurized at 40 to 120 ° C. and about 0.01 to 20 kg / cm 2 for 5 to 10 minutes to accelerate curing. May be irradiated with active energy rays.
  • Examples 1 to 54, Comparative Examples 1 to 6 The components shown in Tables 1 to 10 below were mixed thoroughly to obtain photocurable compositions of Examples and Comparative Examples.
  • Various substrates TAC (triacetyl cellulose), COP (cycloolefin polymer), PMMA (polymethyl methacrylate), and PET (polyethylene terephthalate) were coated with the photocurable composition to a thickness of 5 to 10 ⁇ m with a bar coater.
  • the PET substrate was bonded, and ultraviolet light was irradiated with an energy amount of 1000 mJ / cm 2 through the PET substrate using a cold mirror type mercury lamp. After the irradiation, the specimen was left for 24 hours under the condition of 30 ° C. ⁇ 50% Rh to obtain a test piece.
  • (A) The following compounds (A-1) to (A-2) were used as compounds having a plurality of active alkylol groups.
  • Compound A-1 MW-30M (Methylated melamine resin manufactured by Sanwa Chemical Co., Ltd.)
  • Compound A-2 MW-270 (methylated urea resin manufactured by Sanwa Chemical Co., Ltd.)
  • (C) As the polyfunctional acrylic oligomer, the following compounds (C-1) to (C-3) were used.
  • Compound C-1 U-200PA (urethane acrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Compound C-2 UA-4200 (urethane acrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Compound C-3 1,6-hexanediol-based polycarbonate diol + isophorone diisocyanate + HEA reaction product (MW10000)
  • Compound C-4 Reaction product of polyol obtained from polyethylene glycol and adipic acid + isophorone diisocyanate + acrylic acid-2-hydroxyethyl (MW10000)
  • Compound C-5 A-600 (polyethylene glycol diacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • (E) As the polyfunctional acrylate compound or polyfunctional methacrylate compound, the following compounds (E-1) to (E-3) were used.
  • Compound D-1 DPHA (dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate)
  • Compound E-2 Trimethylolpropane triacrylate compound
  • E-3 A-9300S (ethoxylated isocyanuric acid triacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • the photocurable composition of the present invention containing the components (A) to (D) was excellent in adhesion.
  • the photocurable composition concerning the comparative example which does not contain (A) component and (B) component and a polyfunctional acrylate compound is a main component was inferior to adhesiveness. Since the heat treatment is not performed in the production process of the test pieces of the above Examples and Comparative Examples, it can be seen that the component (A) of the present invention acts as a photocuring component, not as a thermosetting agent. Moreover, it was confirmed from the comparison between Examples 7 and 8 and other examples that the adhesiveness can be further improved by containing the component (E) and the component (F).

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US11332559B2 (en) * 2019-07-17 2022-05-17 Rohm And Haas Electronic Materials Llc Polymers for display devices
JP7447206B2 (ja) 2020-12-04 2024-03-11 デクセリアルズ株式会社 積層体の製造方法、及び光硬化性樹脂組成物

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