WO2017170881A1 - 硬化性組成物、硬化物の製造方法、およびその硬化物 - Google Patents

硬化性組成物、硬化物の製造方法、およびその硬化物 Download PDF

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WO2017170881A1
WO2017170881A1 PCT/JP2017/013286 JP2017013286W WO2017170881A1 WO 2017170881 A1 WO2017170881 A1 WO 2017170881A1 JP 2017013286 W JP2017013286 W JP 2017013286W WO 2017170881 A1 WO2017170881 A1 WO 2017170881A1
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group
formula
carbon atoms
curable composition
polymerizable component
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PCT/JP2017/013286
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English (en)
French (fr)
Japanese (ja)
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WO2017170881A9 (ja
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和彦 松土
智志 渡辺
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株式会社Adeka
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Priority to KR1020187028587A priority Critical patent/KR102356563B1/ko
Priority to JP2018509444A priority patent/JP6910347B2/ja
Priority to CN201780019743.5A priority patent/CN108779321B/zh
Publication of WO2017170881A1 publication Critical patent/WO2017170881A1/ja
Publication of WO2017170881A9 publication Critical patent/WO2017170881A9/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
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a curable composition, a method for producing a cured product, and a cured product thereof, and more specifically, a curable composition having a high glass transition temperature and excellent adhesion, and a method for producing the cured product. It relates to the cured product.
  • Curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like. Various reports have been made regarding the improvement of such a curable composition.
  • Patent Documents 1 to 4 propose an energy ray curable composition containing a cationic polymerizable component and a radical polymerizable component or a cured product thereof.
  • Patent Document 1 proposes an adhesive composition for polarizing plates that is excellent in initial curability and adhesiveness.
  • patent document 2, 3 even when it is a case where a resin film with low moisture permeability is used as a protective film, it expresses an adhesive force immediately after light irradiation, and the adhesive force after a lapse of a certain time against various forces.
  • a low-viscosity photo-curing adhesive has been proposed that is good, does not cause problems even after the endurance test, and has good adhesive strength after the end of the moist heat test.
  • Patent Document 4 proposes an active energy ray-polymerizable resin composition that can satisfy both high heat resistance, high refractive index and transparency, including an unsaturated alicyclic epoxy ester compound.
  • JP 2014-105218 A Japanese Patent Laying-Open No. 2015-040283 JP2015-143352A JP2015-168757A
  • an object of the present invention is to provide a curable composition having a high glass transition temperature of a hard cured product and excellent adhesion, a method for producing the cured product, and a cured product thereof.
  • the curable composition of the present invention comprises a cationic polymerizable component (A), a cationic polymerization initiator (B), a radical polymerizable component (C), a radical polymerization initiator (D), and the following formula ( I), (Wherein X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or a carbon atom) An alicyclic hydrocarbon group of 6 to 10 or a hydrogen atom in these groups substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group A polymer obtained from a monomer represented by the formula (II): (Wherein R 1 represents a hydrogen atom, a methyl group or a halogen atom, and X ′ represents an alkyl group having
  • the cation polymerizable component (A) includes a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1) and an oxetane compound (A2) as essential components.
  • the radical polymerizable component (C) is an epoxy group and an ethylenically unsaturated group compound (C1), an acrylate ester of an alcohol having 2 to 20 carbon atoms, or an alcohol having 2 to 20 carbon atoms.
  • Methacrylic acid ester (C2) is an essential component.
  • the weight average molecular weight is a weight average molecular weight measured by GPC in a tetrahydrofuran (THF) solvent and obtained in terms of styrene.
  • the curable composition of the present invention it is preferable to further contain an alicyclic epoxy compound (A3) as the cationic polymerizable component (A).
  • the polyhydric alcohol in the glycidylated product of the polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of the polyhydric alcohol alkylene oxide adduct is a polyvalent alcohol having a condensed ring.
  • An alcohol is preferred.
  • the polymer (E) is a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II).
  • X in the formula (I) is an aryl group having 6 to 12 carbon atoms
  • X ′ in the formula (II) is an alkyl group having 1 to 7 carbon atoms, It is preferred that the group is substituted with an epoxy group.
  • the cationic polymerizable component (A) is 30 to 70 parts by mass
  • the cationic polymerization initiator (B) is 0.001 to 10 parts by mass
  • the radical polymerizable component (C) is 30 to 60 parts by mass
  • the radical polymerization initiator (D) is 1 to 10 parts by mass
  • the polymer (E) is 1 to 20 parts by mass
  • the total of the polymer (E) is preferably 100 parts by mass.
  • the method for producing a cured product of the present invention is characterized in that the curable composition of the present invention is irradiated with active energy rays or heated.
  • the cured product of the present invention is a cured product of the curable composition of the present invention.
  • the present invention it is possible to provide a curable composition having a high glass transition temperature of a hard cured product and excellent adhesion, a method for producing the cured product, and a cured product thereof.
  • the curable composition of the present invention is particularly useful for adhesives.
  • the curable composition of the present invention comprises a cationic polymerizable component (A), a cationic polymerization initiator (B), a radical polymerizable component (C), a radical polymerization initiator (D), and the following formula (I):
  • a polymer obtained from a monomer represented by formula (II) a polymer obtained from a monomer represented by formula (II)
  • the cationic polymerizable component (A) includes a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct, and an oxetane compound (A2).
  • the radical polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylate ester of an alcohol having 2 to 20 carbon atoms, or the number of carbon atoms
  • the methacrylic acid ester (C2) of alcohol 2 to 20 is an essential component.
  • X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • An oxy group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a hydrogen atom in these groups is one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group; Has been replaced.
  • R 1 represents a hydrogen atom, a methyl group or a halogen atom
  • X ′ represents an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms or a carbon atom.
  • An alicyclic hydrocarbon group of 6 to 10 or a hydrogen atom in these groups substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group is there.
  • the cationically polymerizable component (A) according to the curable composition of the present invention is a compound that undergoes polymerization or crosslinking reaction by a cationic polymerization initiator activated by irradiation with energy rays or heating.
  • a cationic polymerization initiator activated by irradiation with energy rays or heating.
  • An epoxy compound, an oxetane compound, a vinyl ether compound, etc. are mentioned.
  • the cationic polymerizable component (A) according to the curable composition of the present invention includes a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1), an oxetane compound (A2),
  • A1 polyhydric alcohol alkylene oxide adduct
  • A2 an oxetane compound
  • other epoxy compounds alicyclic epoxy compounds (A3), aromatic epoxy compounds (A4), and the like can also be used.
  • Examples of the glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct include those obtained by glycidylating a polyhydric alcohol or a polyhydric alcohol alkylene oxide adduct.
  • the molecular weight of the compound is 200 or more.
  • Examples of the glycidylated product of polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neo Pentyl glycol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclo Glycidyl ethers of polyhydric alcohols such as pentadiene dimethanol diglycidyl ether, propylene glycol, trimethyl
  • glycidylated polyhydric alcohol or glycidylated polyhydric alcohol alkylene oxide adduct (A1) monoglycidyl ether of higher aliphatic alcohol, glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxy stearate , Epoxy butyl stearate, epoxidized soybean oil, epoxidized polybutadiene and the like.
  • glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct those having a saturated condensed ring are preferable because the curability and adhesion of the cured product are improved.
  • glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct commercially available products can be used.
  • Examples of the oxetane compound (A2) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2- Bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, Bifunctional aliphatic oxygen such as 1,6-bis (3-ethyl-3-o
  • oxetane compound (A2) commercially available products can be used.
  • the above alicyclic epoxy compound (A3) refers to a saturated ring in which an oxirane ring is directly formed without a bonding group.
  • Specific examples of the alicyclic epoxy compound (A3) are obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples include cyclohexene oxide and cyclopentene oxide-containing compounds.
  • 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5 -Methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxy Cyclohexane), propane-2,2-diyl-bis (3,
  • alicyclic epoxy compound (A3) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxyl
  • the rate is preferable from the viewpoint of improving adhesion.
  • alicyclic epoxy compound (A3) Commercially available products can be used as the alicyclic epoxy compound (A3), and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel Corporation).
  • the aromatic epoxy compound (A4) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound (A4) include polyphenols having at least one aromatic ring such as phenol, cresol, and butylphenol. Mono- or polyglycidyl etherified products of polyhydric phenols or alkylene oxide adducts thereof, such as glycidyl etherified products of epoxy compounds and bisphenol A, bisphenol F, or compounds obtained by further adding alkylene oxide to these, epoxy novolac resins; resorcinol, hydroquinone, catechol, etc.
  • aromatic epoxy compound (A4) commercially available products can be used.
  • Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX -721, on-coat EX-1020, on-coat EX-1030, on-coat EX-1040, on-coat EX-1050, on-coat EX-1051, on-coat EX-1010, on-coat EX-1011, on-coat 1012 (Nagase Chemtex Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (DIC Corporation) ESN-475 (Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epicoat YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA,
  • Examples of the vinyl ether compound include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2- Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether.
  • a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct, an oxetane compound (A2), an alicyclic epoxy compound (A3) ), Aromatic epoxy compound (A4) and vinyl ether compound are used in a proportion of glycidylated polyhydric alcohol or polyhydric alcohol alkylene oxide adduct having a molecular weight of 200 or more with respect to 100 parts by mass of the cationic polymerizable component (A).
  • the vinyl ether compound 0 to 20 parts by mass is viscosity, coatability, Sex and curability preferably improved.
  • the cationic polymerization initiator (B) may be any compound as long as it can release a substance that initiates cationic polymerization by energy ray irradiation or heating.
  • it is a double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof.
  • Representative examples of such compounds include the following general formula: [A] r + [B] r- And cation and anion salts represented by the formula:
  • the cation [A] r + is preferably onium, and the structure thereof is, for example, the following general formula: [(R 2 ) a Q] r + Can be expressed as
  • R 2 is an organic group having 1 to 60 carbon atoms and any number of atoms other than carbon atoms.
  • a is an integer of 1 to 5.
  • the a R 2 s are independent and may be the same or different.
  • at least one is preferably an organic group as described above having an aromatic ring.
  • the anion [B] r- is preferably a halide complex, and the structure thereof is, for example, the following general formula: [LY b ] r- .
  • 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 and the like.
  • Y is a halogen atom.
  • b is an integer of 3 to 7.
  • anion [LY b ] r- 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.
  • the anion [B] r- is represented by the following general formula: [LY b-1 (OH)] r-
  • the thing of the structure represented by can also be used preferably. L, Y, and b 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.
  • the onium salts it is particularly effective to use the following aromatic onium salts (a) to (c).
  • aromatic onium salts (a) to (c) 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, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
  • Sulfonium salts such as sulfonium cations represented by the following group I or group II and hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions, etc.
  • Aromatic sulfonium salts having the following structure are used as cationic polymerization initiators (B ) It is more preferable to contain at least 0.1% by mass with respect to 100% by mass.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are each independently a hydrogen atom, a halogen atom, or a carbon atom number.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 26 , R 27 , R 28 , R 29 , R 35 , R 36 , R 37 , R 38 and R 39 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom.
  • R 30 , R 31 , R 32 , R 33 and R 34 each independently represents a hydrogen atom, a halogen atom or 1 to 10 carbon atoms. Represents an alkyl group.
  • Examples of the halogen atom represented include fluorine, chlorine, bromine and iodine.
  • R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 and R 39 Is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3- Methoxypropyl, 4-methoxybutyl, 2-
  • the alkoxy group having 1 to 10 carbon atoms includes methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4- Methoxybutyloxy, 2-butoxye
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 26 , R 27 , R 28 R 29 , R 35 , R 36 , R 37 , R 38 and R 39 are ester groups having 2 to 10 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyl Examples include oxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.
  • the proportion of the cationic polymerization initiator (B) used relative to 100 parts by mass of the total of the cationic polymerizable component (A), the radical polymerizable component (C), and the polymer (E) is as follows: cationic polymerization initiator (B) 0 0.001 to 10 parts by mass, preferably 0.1 to 10 parts by mass. If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.
  • the radical polymerizable component (C) according to the curable composition of the present invention is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylate ester of an alcohol having 2 to 20 carbon atoms, or the number of carbon atoms.
  • the methacrylic acid ester (C2) of alcohol 2 to 20 is an essential component.
  • Examples of the compound (C1) having an epoxy group and an ethylenically unsaturated group include epoxy acrylate or epoxy methacrylate.
  • epoxy acrylate or epoxy methacrylate Specifically, conventionally known aromatic epoxy resins, alicyclic epoxy resins, An acrylate obtained by reacting an aliphatic epoxy resin or the like with acrylic acid or methacrylic acid.
  • epoxy acrylates or epoxy methacrylates particularly preferred are acrylates or methacrylates of glycidyl ethers of alcohols.
  • Examples of the acrylate of alcohol having 2 to 20 carbon atoms or the methacrylate (C2) of alcohol having 2 to 20 carbon atoms include aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule, and alkylenes thereof. Examples thereof include acrylates or methacrylates obtained by reacting an oxide adduct with acrylic acid or methacrylic acid.
  • radically polymerizable component (C) a compound that is polymerized or cross-linked by a radical polymerization initiator activated by energy ray irradiation or heating other than (C1) or (C2) can be used. Examples include urethane compounds, unsaturated polyester compounds, and styrene compounds.
  • the proportion of the component (C1) and the component (C2) in the radical polymerizable component (C) is preferably 50% by mass or more.
  • the radical initiator (D) according to the curable composition of the present invention is not particularly limited, and known ones can be used.
  • ketone compounds such as acetophenone compounds, benzyl compounds, benzophenone compounds, and thioxanthone compounds, oxime compounds, and the like can be used.
  • the polymer (E) according to the curable composition of the present invention is a polymer obtained from the monomer represented by the above formula (I), a polymer obtained from the monomer represented by the above formula (II), Polymer obtained from two or more monomers selected from monomers represented by formula (I), two or more monomers selected from monomers represented by formula (II) Selected from the group consisting of a polymer obtained from the above, a monomer represented by the above formula (I) and a polymer obtained from the monomer represented by the above formula (II), and the weight average molecular weight is in terms of polystyrene 1,000 to 30,000.
  • alkyl group having 1 to 7 carbon atoms represented by X in the formula (I) examples include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, Examples include iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl and the like.
  • an alkyl group having 1 to 4 carbon atoms, or 1 to 1 carbon atom partially substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group 4 alkyl groups are preferable from the viewpoint of curability.
  • alkoxy group having 1 to 7 carbon atoms represented by X in the formula (I) examples include methoxy, ethoxy, propyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, Amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, and tert-heptyloxy.
  • an alkoxy group having 1 to 4 carbon atoms, or 1 to 1 carbon atoms partially substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group 4 alkoxy groups are preferred from the viewpoint of curability.
  • Examples of the aryl group having 6 to 12 carbon atoms represented by X in the above formula (I) include phenyl, methylphenyl, naphthyl and the like.
  • Examples of the aryloxy group having 6 to 12 carbon atoms represented by X in the above formula (I) include phenyloxy, methylphenyloxy, naphthyloxy and the like.
  • Examples of the alicyclic hydrocarbon group having 6 to 10 carbon atoms represented by X in the formula (I) include cyclohexyl, methylcyclohexyl, norbornyl, bicyclopentyl, bicyclooctyl, trimethylbicycloheptyl, tricyclooctyl. , Tricyclodecanyl, spirooctyl, spirobicyclopentyl, adamantyl, isobornyl and the like.
  • alkyl group, alkoxy group, aryl group, aryloxy group, and alicyclic hydrocarbon group are selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group, and a carboxyl group in which the hydrogen atom in these groups is 1 It may be substituted with more than one group.
  • examples of the monomer represented by the formula (I) include the following formulas (1) to (3): The monomer represented by these is mentioned.
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6.
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.
  • R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6.
  • examples of the halogen atom represented by R 1 include fluorine, chlorine, bromine and iodine.
  • the alkyl group having 1 to 7 carbon atoms, the aryl group having 6 to 12 carbon atoms, or the alicyclic hydrocarbon group having 6 to 10 carbon atoms as X ′ can be represented by the above formula (I ).
  • R 1 is the same as in the above formula (II)
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • t is an integer of 1 to 6 It is.
  • R 1 is the same as in Formula (II) above, R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6 It is.
  • R 1 is the same as in the above formula (II)
  • R 8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • y is an integer of 1 to 6 It is.
  • the proportion of the monomer constituting the polymer is such that X is a carbon substituted with one or more groups selected from the group consisting of epoxy groups, oxetane groups, hydroxyl groups and carboxyl groups.
  • X is a carbon substituted with one or more groups selected from the group consisting of epoxy groups, oxetane groups, hydroxyl groups and carboxyl groups.
  • an alkyl group having 1 to 7 atoms, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms the single group represented by the above (I) or (II) It is preferable to use the polymer in an amount of 10 to 100% by mass because the adhesiveness is improved.
  • the total amount of the cationic polymerizable component (A), the radical polymerizable component (C), and the polymer (E) is 100 parts by mass, and the cationic polymerizable component (A ) Is 30 to 70 parts by mass, the cationic polymerization initiator (B) is 0.001 to 10 parts by mass, the radical polymerizable component (C) is 30 to 60 parts by mass, and the radical polymerization initiator (D) is 1 -10 parts by mass, and the polymer (E) is preferably 1-20 parts by mass. If the blending ratio is other than the above, the curability and adhesion of the cured product may be deteriorated.
  • a sensitizer and / or a sensitization aid can be further used as necessary.
  • the sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength indicated by the cationic polymerization initiator (B) and promotes the polymerization initiation reaction by the cationic polymerization initiator (B).
  • the sensitization aid is a compound that further promotes the action of the sensitizer.
  • Sensitizers and sensitizers include anthracene compounds and naphthalene compounds.
  • anthracene compound examples include those represented by the following formula (7).
  • R 50 and R 51 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms
  • R 52 represents a hydrogen atom. Or an alkyl group having 1 to 6 carbon atoms.
  • anthracene compound represented by the above formula (7) include the following compounds.
  • naphthalene compound examples include those represented by the following formula (8).
  • R 53 and R 54 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • naphthalene compound represented by the above formula (8) include the following compounds.
  • 4-methoxy-1-naphthol 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene
  • Examples thereof include 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene and the like.
  • the use ratio of the sensitizer and the sensitization aid to the cationic polymerizable component (A) is not particularly limited, and may be used at a generally normal use ratio within a range not inhibiting the purpose of the present invention. From the viewpoint of improving curability, the amount of the sensitizer and the sensitizer is 0.1 to 3 parts by mass with respect to 100 parts by mass of the cationic polymerizable component (A).
  • 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-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, ⁇ Epoxy-functional alkoxysilanes such as glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ Aminofunctional alkoxysilanes such as amino
  • the amount of the silane coupling agent used is not particularly limited, but is usually in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of solids in the curable composition.
  • the properties of the cured product can be improved by using a thermoplastic organic polymer as necessary.
  • the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate ethyl acrylate copolymer, methyl methacrylate glycidyl methacrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, Examples include (meth) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.
  • the UV-absorbing agent is inactivated at room temperature, and the protective group is released by heating to a predetermined temperature, light irradiation, acid, etc. and activated.
  • a compound exhibiting ultraviolet absorbing ability can also be used.
  • coloring agents such as polyols, inorganic fillers, organic fillers, pigments, dyes, antifoaming agents, thickeners, surfactants, leveling agents, difficulty
  • resin additives such as flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, etc. may be added. it can.
  • the curable composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (A), (B), (C), (D) and (E) which are usually used is used.
  • a solvent that can dissolve or disperse the components (A), (B), (C), (D) and (E) which are usually used is used.
  • the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 Ether solvents such as 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n
  • Paraffin solvents Paraffin solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; propylene carbonate, carbitol solvents Aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like. These solvents can be used as one or a mixture of two or more.
  • the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less because the curability, adhesiveness, and liquid storage stability are improved. Too much moisture is not preferred because it may cause cloudiness or components may precipitate.
  • the curable composition of the present invention is applied onto a support 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 material for the support substrate is not particularly limited and may be any commonly used material, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl.
  • inorganic materials such as glass
  • Cellulose esters such as cellulose and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxy Polyesters such as ethane-4,4′-dicarboxylate and polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpente Polyolefin such as polyvinyl acetate, polyvinyl compounds such as polyvinyl chloride and polyvinyl fluoride, acrylic resins such as polymethyl methacrylate and polyacrylate, polycarbonate, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyoxy Polymer materials such as ethylene, norbornene resin, and cycloolefin polymer (COP) can be used.
  • the support substrate may
  • examples of energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies, and the like, and ultraviolet rays are most preferable economically.
  • examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
  • the conditions for the method of curing the curable composition of the present invention by heating are 70 to 250 ° C. and 1 to 100 minutes. After performing pre-baking (PAB), pressurization and post-baking (PEB) may be performed, or baking may be performed at several different temperatures.
  • the heating conditions vary depending on the type and mixing ratio of each component, but are, for example, 70 to 180 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate.
  • a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.
  • curable composition of the present invention or a cured product thereof include adhesives, glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, printing Plates, color TVs, PC monitors, personal digital assistants, digital cameras, organic EL, touch panels and other display elements, insulating varnishes, insulating sheets, laminates, printed boards, semiconductor devices, LED packages, liquid crystal inlets, organic Sealants for EL, optical elements, electrical insulation, electronic parts, separation membranes, molding materials, putty, glass fiber impregnating agents, sealants, passivation films for semiconductors and solar cells, interlayers Insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, Fresnel label used for screen of projection TV, etc. Lens parts of lens sheets such as lens sheets, lenticular lens sheets, or backlights using such sheets, optical lenses such as micro lenses, optical elements, optical connectors, optical waveguides, castings for optical modeling, etc. Can be mentioned
  • a transparent support As a display device, a transparent support, an undercoat layer, an antireflection layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coating layer, a lubricating layer, a protective layer, etc., as necessary
  • cured material of this invention can be used for each layer.
  • Examples 1 to 15, Comparative Examples 1 to 3 The components shown in [Table 1] to [Table 3] below were mixed thoroughly to obtain the curable compositions of Examples 1 to 15 and the curable compositions of Comparative Examples 1 to 3, respectively.
  • the unit of an Example and a comparative example is a mass part.
  • the following compounds (A1-1) to (A1-3) and (A2-1) to (A3-1) were used.
  • Compound (A1-1) Adeka Resin EP-4088L (manufactured by ADEKA Corporation)
  • Compound (A3-1) Celoxide 2021P (alicyclic epoxy: manufactured by Daicel Corporation)
  • the following compound (B-1) was used as the cationic polymerization initiator (B).
  • Compound B-1 50% propylene carbonate solution of a mixture of a compound represented by the following formula (9) and a compound represented by the following formula (10)
  • radical polymerizable component (C) the following compounds (C2-1) to (C2-4) were used.
  • the following compounds (E-1) and (E-2) were used.
  • Compound (E-1) copolymer of 75 parts by mass of methyl methacrylate and 25 parts by mass of glycidyl methacrylate (weight average molecular weight 7,000)
  • Compound (E-2) copolymer of 35 parts by weight of methyl methacrylate, 35 parts by weight of styrene and 30 parts by weight of glycidyl methacrylate (weight average molecular weight 8,000)
  • compositions 1 to 15 of the examples and the compositions 1 to 3 of the comparative examples obtained above were respectively applied to one sheet of corona-treated PMMA film (manufactured by Sumitomo Chemical Co., Ltd .: Technoloy 125S001), A COP (cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd .: Part No. ZEONOR film 14-060) film and a laminator were laminated together using a laminator, and 1000 mJ / using an electrodeless ultraviolet lamp.
  • a test piece was obtained by applying light corresponding to cm 2 through a COP film and bonding. About the obtained test piece, the 90 degree

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