WO2016158522A1 - Composition - Google Patents

Composition Download PDF

Info

Publication number
WO2016158522A1
WO2016158522A1 PCT/JP2016/058815 JP2016058815W WO2016158522A1 WO 2016158522 A1 WO2016158522 A1 WO 2016158522A1 JP 2016058815 W JP2016058815 W JP 2016058815W WO 2016158522 A1 WO2016158522 A1 WO 2016158522A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
composition
carbon atoms
mass
parts
Prior art date
Application number
PCT/JP2016/058815
Other languages
French (fr)
Japanese (ja)
Inventor
英里 本間
和彦 松土
Original Assignee
株式会社Adeka
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社Adeka filed Critical 株式会社Adeka
Priority to KR1020177011479A priority Critical patent/KR102563226B1/en
Priority to JP2017509582A priority patent/JP6879903B2/en
Priority to CN201680003405.8A priority patent/CN107075082B/en
Publication of WO2016158522A1 publication Critical patent/WO2016158522A1/en

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to a composition and a cured product obtained by irradiating the composition with active energy rays.
  • the composition is particularly useful for adhesives.
  • Cationic polymerizable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.
  • Patent Documents 1 to 3 disclose various cationic polymerizable compositions.
  • the cured product of the cationically polymerizable composition described in these documents is not sufficient in adhesiveness or heat resistance.
  • An object of the present invention is to provide a composition excellent in adhesiveness, heat resistance and liquid storage stability.
  • the present invention has been made on the basis of the above knowledge, and comprises a mixture (1) of cationically polymerizable compounds, and the mixture (1) is an aromatic ring-containing epoxy compound represented by the following general formula (I):
  • a composition comprising (1A) as a main component and further comprising at least one selected from an aliphatic epoxy compound (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D) is provided.
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 5 carbon atoms. Represents an alkenyl group or a halogen atom, and m is an integer of 0 to 10.
  • the present invention also provides an adhesive comprising the above composition.
  • composition of the present invention is particularly useful as an adhesive because it has excellent adhesion and heat resistance.
  • composition of the present invention and the adhesive comprising the composition will be described in detail based on preferred embodiments.
  • the cationic polymerizable compound constituting the mixture is a compound that undergoes a polymerization or a crosslinking reaction by a cationic polymerization initiator activated by light irradiation.
  • a cationic polymerizable compound an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl ether, or the like can be used, and the fragrance represented by the above general formula (I) It is essential to contain the ring-containing epoxy compound (1A) as a main component.
  • a main component means what mixes several kinds of cationically polymerizable compounds, and has the largest total mass of the same kind of cationically polymerizable compounds.
  • R 1 , R 2 , R 3 and R 4 having 1 to 5 carbon atoms are represented.
  • alkyl group include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl and the like.
  • Examples of the alkoxy group having 1 to 8 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include methoxy, ethoxy, propyloxy, iso-propyloxy, butoxy, pentyloxy, iso-pentyloxy, Xyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and the like,
  • Examples of the alkenyl group having 2 to 5 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include vinyl, allyl, butenyl, propenyl
  • Examples of the halogen atom represented by R 1 , R 2 , R 3 and R 4 include fluorine, chlorine, bromine and iodine. In addition, all the halogen atoms in this specification are the same as this.
  • aromatic ring-containing epoxy compound (1A) represented by the general formula (I) those in which R 1 , R 2 , R 3 and R 4 are hydrogen or a methyl group are preferable from the viewpoint that the epoxy equivalent becomes small Particularly preferred is hydrogen.
  • Examples of the aliphatic epoxy compound (1B) include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids, polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, Examples include polyfunctional epoxy compounds such as polyglycidyl esters of aliphatic long-chain polybasic acids.
  • Representative compounds include allyl glycidyl ether, butyl glycidyl ether, sec-butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, neopentyl glycol diglycidyl ether, diglycidyl ether of polyethylene glycol, polypropylene glycol Polyglycol glycidyl ether such as diglycidyl ether, propylene glycol, Examples include poly
  • the aliphatic epoxy compound (1B) is preferably a diglycidyl ether of an aliphatic diol having 1 to 6 carbon atoms from the viewpoint of the viscosity of the adhesive and the heat resistance of the cured product.
  • aliphatic epoxy compound (1B) commercially available products can be used.
  • the alicyclic epoxy compound (1C) is a cyclohexene oxide 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. And cyclopentene oxide-containing compounds.
  • the alicyclic epoxy compound (1C) is preferably 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate from the viewpoint of the viscosity of the adhesive and the heat resistance of the cured product.
  • alicyclic epoxy compound (1C) Commercially available products can be used as the alicyclic epoxy compound (1C), and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel Corporation).
  • Examples of the oxetane compound (1D) 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) Bifunctional such as butane and 1,6-bis (3-ethyl-3-oxe
  • the oxetane compound (1D) is particularly preferably 3-ethyl- ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane from the viewpoints of the viscosity of the adhesive and the heat resistance of the cured product.
  • oxetane compound (1D) such as Aron Oxetane EXOH, POX, OXA, OXT-101, OXT-211, OXT-212, OXT-221 (manufactured by Toagosei Co., Ltd.), and the like. Can be mentioned.
  • the aromatic epoxy compound (1A), the aliphatic epoxy compound (1B), the alicyclic epoxy compound (1C), and the oxetane compound represented by the general formula (I) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, more preferably 30 to 70 parts by mass of the aromatic polyfunctional epoxy compound (1A) in 100 parts by mass of the mixture (1) of the cationic polymerizable compound.
  • Is 30 to 60 parts by mass, and the aliphatic epoxy compound (1B) is 0 to 70 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass.
  • (1C) is 0 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and the oxetane compound (1D) is 0 to 70 parts by mass
  • Mashiku is preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by weight.
  • the aromatic epoxy compound (1A) represented by the general formula (I) is a main component, the content thereof is the highest as compared with other compounds.
  • Examples of the cationic polymerizable compound include aromatic ring-containing epoxy compounds other than the aromatic ring-containing epoxy compound (1A) represented by the general formula (I), and aromatic ring-containing epoxy compounds represented by the general formula (I). (1A) can be used in combination.
  • aromatic ring-containing epoxy compound examples include monovalent phenols having at least one aromatic ring such as phenol, cresol, and butylphenol, or glycidyl etherified products of alkylene oxide adducts thereof such as bisphenol A, bisphenol F, or Glycidyl etherified compounds and epoxy novolac resins of compounds further added with alkylene oxide; glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; benzenedimethanol, benzenediethanol and benzenedi Mono / polyglycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as butanol; two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid Glycidyl esters of polybasic acid aromatic compound having, benzoic acid and toluic acid, glycidyl esters of benzoic acids such as naphtho
  • the content of the aromatic ring-containing epoxy compound other than the aromatic ring-containing epoxy compound (1A) represented by the general formula (I) is the aromatic ring-containing epoxy compound (1A) represented by the general formula (I).
  • the composition of the present invention may further contain a cationic polymerization initiator (2).
  • the cationic polymerization initiator (2) used in the present invention may be any compound that can generate an acid upon irradiation with energy rays. It is a double salt that is an onium salt that releases an acid, or a derivative thereof. Representative examples of such compounds include the following general formula: p [A] q + ⁇ s [B] t ⁇ (A represents a cationic species, B represents an anionic species, q and t each independently represents 1 or 2, and p and s represent charges. And a salt of a cation and an anion.
  • the cation [A] q + is preferably onium, and the structure thereof is, for example, the following general formula: [(R 10 ) a Q] q + Can be expressed as
  • R 10 is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms.
  • a is an integer of 1 to 5.
  • the a R 10 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] t- is preferably a halide complex, and the structure thereof is, for example, the following general formula: [LX b ] t- Can be expressed as
  • 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.
  • X is a halogen atom.
  • b is an integer of 3 to 7.
  • anion [LX b ] 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.
  • the anion [B] t ⁇ is represented by the following general formula: [LX b-1 (OH)] t-
  • L, X, and b are the same as described above.
  • Other anions that can be used include perchlorate ion (ClO 4 ) ⁇ , trifluoromethyl sulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonate ion (FSO 3 ) ⁇ , and toluenesulfonate anion.
  • Trinitrobenzenesulfonic acid 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 (a) to (c).
  • aromatic onium salts (a) to (c) one of them can be used alone, or two or more can be mixed and used.
  • Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate
  • Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
  • (C) sulfonium salts such as sulfonium cations represented by the following group I or group II, hexafluoroantimony ions, tetrakis (pentafluorophenyl) borate ions, etc.
  • preferable examples include ( ⁇ 5 -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6- ⁇ )-(1-methylethyl) benzene] -iron.
  • -Iron-arene complexes such as hexafluorophosphate
  • aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum, and silanols such as triphenylsilanol
  • silanols such as triphenylsilanol
  • aromatic iodonium salts aromatic sulfonium salts, and iron-arene complexes are preferably used from the viewpoints of practical use and photosensitivity.
  • the use ratio of the cationic polymerization initiator (2) to the mixture (1) of the cationic polymerizable 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.
  • the cationic polymerization initiator (2) can be preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the mixture (1) of the cationic polymerizable compound. . 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.
  • composition of the present invention preferably contains 0.05 to 3 parts by mass of water with respect to 100 parts by mass of the total composition (excluding the solvent).
  • 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 amino
  • the amount of the silane coupling agent used is not particularly limited, but is usually in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of solids in the composition.
  • thermal polymerization initiator is a compound that generates a cationic species or Lewis acid by heating, such as a salt of sulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; diethylenetriamine, triethylenetriamine, tetraethylenepenta Polyalkylpolyamines such as min; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Aromatic polyamines such as; such polyamines; phenyl glycidyl ether, butyl glycidyl ether, bisphenol
  • Mannich-modified products produced by reacting phenols having sex sites by a conventional method polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain Acid, sebacic acid, do Candiic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecane Aliphatic dicarboxylic acids such as diacids, hydrogenated dimer acids and dimer acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid , Tricar
  • thermal polymerization initiator Commercially available products may be used as the thermal polymerization initiator.
  • Adeka Opton® CP77 Adeka Opton CP66 (manufactured by ADEKA), CI-2539, CI-2624 (manufactured by Nippon Soda Co., Ltd.), Sun-Aid® SI-60L, Sun-Aid SI -80L, Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.
  • the amount of the thermal polymerization initiator used is not particularly limited, but is usually in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solids in the composition.
  • the composition of the present invention is preferably heated at 130 to 180 ° C. for 20 minutes to 1 hour when it is cured.
  • thermoplastic organic polymer examples include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.
  • the composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (1) to (4) that are usually used can be used.
  • a solvent that can dissolve or disperse the components (1) to (4) that are usually used can be used.
  • methyl ethyl ketone, methyl amyl ketone, diethyl ketone, Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol Ether solvents such as dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl
  • composition of the present invention preferably has a viscosity of 1 to 200 mPa ⁇ s because it is excellent in curability and coatability.
  • 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 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 Polyester such as ethane-4,4′-dicarboxylate, polybutylene terephthalate, etc .; polystyrene; polyethylene, polypropylene, polymethylpentene, etc.
  • Polyolefins Vinyl compounds such as polyvinyl alcohol (PVA), polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone Polyetherimide; polymer materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP).
  • the support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.
  • Polymerization initiators radical polymerization initiators, inorganic fillers, organic fillers, colorants such as pigments, dyes, photosensitizers, antifoaming agents, thickeners, surfactants, leveling agents, flame retardants, thixotropic agents, dilution
  • resin additives such as an agent, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, a flow regulator, and an adhesion promoter can be added.
  • the composition of the present invention is cured by irradiation with active energy rays
  • the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are most preferable economically.
  • the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
  • composition of the present invention include glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, insulating varnishes, insulating materials. Sheets, laminates, printed circuit boards, semiconductor devices, LED packages, liquid crystal injection ports, organic ELs, optical elements, electrical insulation, electronic components, separation membranes, sealing materials, molding materials, putty Glass fiber impregnating agent, sealing agent, passivation film for semiconductors and solar cells, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, screen for projection TV etc.
  • My lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets, or backlights using such sheets, etc.
  • Examples include optical lenses such as Lolens, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, etc.
  • Examples of substrates that can be used as coating agents include metals, wood, rubber, plastics, glass, ceramics Product etc. can be mentioned.
  • composition of the present invention and the cured product obtained by curing the composition will be specifically described with reference to examples, evaluation examples, and comparative examples, but the present invention is not limited to the examples.
  • “part” means “part by mass”.
  • Examples 1 to 16 and Comparative Examples 1 to 4 The components shown in [Table 1] to [Table 4] below were mixed thoroughly to obtain Example Compositions 1 to 16 and Comparative Compositions 1 to 4, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention of the present application provides a composition having excellent adhesive properties, heat resistance and liquid storage stability, and more specifically provides a composition that is characterized by containing a mixture (1) of cationic polymerizable compounds, with the mixture (1) containing an aromatic ring-containing epoxy compound (1A) represented by general formula (I) as a primary component and further containing at least one compound selected from among an aliphatic epoxy compound (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D). (In the formula, R1, R2, R3 and R4 each independently denote a hydrogen atom, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-8 carbon atoms, an alkenyl group having 2-5 carbon atoms, or a halogen atom, and m is an integer between 0 and 10.)

Description

組成物Composition
　本発明は、組成物及び該組成物に活性エネルギー線を照射することによって得られる硬化物に関する。該組成物は、特に接着剤に有用である。 The present invention relates to a composition and a cured product obtained by irradiating the composition with active energy rays. The composition is particularly useful for adhesives.
　カチオン重合性組成物は、インキ、塗料、各種コーティング剤、接着剤、光学部材等の分野において用いられている。 Cationic polymerizable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.
　例えば、下記特許文献１～３には、種々のカチオン重合性組成物が開示されている。
　しかしながら、これらの文献に記載のカチオン重合性組成物の硬化物は、接着性又は耐熱性において十分ではなかった。 For example, the following Patent Documents 1 to 3 disclose various cationic polymerizable compositions.
However, the cured product of the cationically polymerizable composition described in these documents is not sufficient in adhesiveness or heat resistance.
特開平１０－２７９６５８号公報JP-A-10-279658 特開２００３－３１３２７４号公報JP 2003-313274 A 特開２０１０－２２９３９２号公報JP 2010-229392 A
　本発明の目的は、接着性、耐熱性及び液保存安定性に優れる組成物を提供することにある。 An object of the present invention is to provide a composition excellent in adhesiveness, heat resistance and liquid storage stability.
　本発明は、上記知見に基づいてなされたもので、カチオン重合性化合物の混合物（１）を含んでなり、該混合物（１）が、下記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）を主成分として含有し、さらに脂肪族エポキシ化合物（１Ｂ）、脂環式エポキシ化合物（１Ｃ）及びオキセタン化合物（１Ｄ）から選ばれる少なくとも一種を含むことを特徴とする組成物を提供することで、上記目的を達成したものである。 The present invention has been made on the basis of the above knowledge, and comprises a mixture (1) of cationically polymerizable compounds, and the mixture (1) is an aromatic ring-containing epoxy compound represented by the following general formula (I): A composition comprising (1A) as a main component and further comprising at least one selected from an aliphatic epoxy compound (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D) is provided. Thus, the above-mentioned purpose has been achieved.
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に、水素原子、炭素原子数１～５のアルキル基、炭素原子数１～８のアルコキシ基、炭素原子数２～５のアルケニル基又はハロゲン原子を表し、ｍは０～１０の整数である。）
Figure JPOXMLDOC01-appb-C000002
 Wherein R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 5 carbon atoms. Represents an alkenyl group or a halogen atom, and m is an integer of 0 to 10.)
　また、本発明は、上記組成物からなる接着剤を提供するものである。 The present invention also provides an adhesive comprising the above composition.
　本発明の組成物は、接着性及び耐熱性に優れるため、接着剤用途として特に有用なものである。 The composition of the present invention is particularly useful as an adhesive because it has excellent adhesion and heat resistance.
　以下、本発明の組成物及び該組成物からなる接着剤について好ましい実施形態に基づき詳細に説明する。 Hereinafter, the composition of the present invention and the adhesive comprising the composition will be described in detail based on preferred embodiments.
　本発明に使用する前記カチオン重合性化合物の混合物（１）において、該混合物を構成するカチオン重合性化合物は、光照射により活性化したカチオン重合開始剤により高分子化又は架橋反応を起こす化合物であり、カチオン重合性化合物として、エポキシ化合物、オキセタン化合物、環状ラクトン化合物、環状アセタール化合物、環状チオエーテル化合物、スピロオルトエステル化合物、ビニルエーテル等を用いることができるが、上記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）を主成分として含有していることが必須である。これに加えて、脂肪族エポキシ化合物（１Ｂ）、脂環式エポキシ化合物（１Ｃ）及びオキセタン化合物（１Ｄ）の少なくとも一種を含有していることが必須である。尚、主成分とは、カチオン重合性化合物を数種類混ぜて、同じ種類のカチオン重合性化合物の合計質量が一番多いものを言う。 In the mixture (1) of the cationic polymerizable compound used in the present invention, the cationic polymerizable compound constituting the mixture is a compound that undergoes a polymerization or a crosslinking reaction by a cationic polymerization initiator activated by light irradiation. As the cationic polymerizable compound, an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl ether, or the like can be used, and the fragrance represented by the above general formula (I) It is essential to contain the ring-containing epoxy compound (1A) as a main component. In addition to this, it is essential to contain at least one of the aliphatic epoxy compound (1B), the alicyclic epoxy compound (1C) and the oxetane compound (1D). In addition, a main component means what mixes several kinds of cationically polymerizable compounds, and has the largest total mass of the same kind of cationically polymerizable compounds.
　上記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）において、上記一般式（Ｉ）中、Ｒ1、Ｒ2、Ｒ3及びＲ4で表される炭素原子数１～５のアルキル基としては、メチル、エチル、プロピル、ｉｓｏ－プロピル、ブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、ｉｓｏ－ブチル、アミル、ｉｓｏ－アミル、ｔｅｒｔ－アミル等が挙げられ、
　Ｒ1、Ｒ2、Ｒ3及びＲ4で表される炭素原子数１～８のアルコキシ基としては、メトキシ、エトキシ、プロピルオキシ、ｉｓｏ－プロピルオキシ、ブトキシ、ペンチルオキシ、ｉｓｏ－ペンチルオキシ、へキシルオキシ、へプチルオキシ、オクチルオキシ、２－エチルへキシルオキシ等が挙げられ、
　Ｒ1、Ｒ2、Ｒ3及びＲ4で表される炭素原子数２～５のアルケニル基としては、ビニル、アリル、ブテニル、プロペニル等が挙げられ、
　Ｒ1、Ｒ2、Ｒ3及びＲ4で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。尚、本明細書中におけるハロゲン原子はすべてこれと同様である。 In the aromatic ring-containing epoxy compound (1A) represented by the above general formula (I), in the above general formula (I), R 1 , R 2 , R 3 and R 4 having 1 to 5 carbon atoms are represented. Examples of the alkyl group include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl and the like.
Examples of the alkoxy group having 1 to 8 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include methoxy, ethoxy, propyloxy, iso-propyloxy, butoxy, pentyloxy, iso-pentyloxy, Xyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and the like,
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include vinyl, allyl, butenyl, propenyl,
Examples of the halogen atom represented by R 1 , R 2 , R 3 and R 4 include fluorine, chlorine, bromine and iodine. In addition, all the halogen atoms in this specification are the same as this.
　上記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）としては、エポキシ当量が小さくなる点から、Ｒ1、Ｒ2、Ｒ3及びＲ4が水素又はメチル基であるものが好ましく、水素であるものが特に好ましい。 As the aromatic ring-containing epoxy compound (1A) represented by the general formula (I), those in which R 1 , R 2 , R 3 and R 4 are hydrogen or a methyl group are preferable from the viewpoint that the epoxy equivalent becomes small Particularly preferred is hydrogen.
　上記脂肪族エポキシ化合物（１Ｂ）としては、脂肪族アルコールのグリシジルエーテル化物、アルキルカルボン酸のグリシジルエステル等の単官能エポキシ化合物や、脂肪族多価アルコール又はそのアルキレンオキサイド付加物のポリグリシジルエーテル化物、脂肪族長鎖多塩基酸のポリグリシジルエステル等の多官能エポキシ化合物が挙げられる。代表的な化合物として、アリルグリシジルエーテル、ブチルグリシジルエーテル、ｓｅｃ‐ブチルフェニルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、Ｃ１２～１３混合アルキルグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ソルビトールのテトラグリシジルエーテル、ジペンタエリスリトールのヘキサグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル、ポリプロピレングリコールのジグリシジルエーテル等の多価アルコールのグリシジルエーテル、またプロピレングリコール、トリメチロールプロパン、グリセリン等の脂肪族多価アルコールに１種又は２種以上のアルキレンオキサイドを付加することによって得られるポリエーテルポリオールのポリグリシジルエーテル化物、脂肪族長鎖二塩基酸のジグリシジルエステルが挙げられる。更に、脂肪族高級アルコールのモノグリシジルエーテルや高級脂肪酸のグリシジルエステル、エポキシ化大豆油、エポキシステアリン酸オクチル、エポキシステアリン酸ブチル、エポキシ化大豆油、エポキシ化ポリブタジエン等が挙げられる。 Examples of the aliphatic epoxy compound (1B) include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids, polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, Examples include polyfunctional epoxy compounds such as polyglycidyl esters of aliphatic long-chain polybasic acids. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, sec-butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, neopentyl glycol diglycidyl ether, diglycidyl ether of polyethylene glycol, polypropylene glycol Polyglycol glycidyl ether such as diglycidyl ether, propylene glycol, Examples include polyglycidyl etherified products of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as methylolpropane and glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids. . Furthermore, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, epoxidized polybutadiene and the like.
　上記脂肪族エポキシ化合物（１Ｂ）としては、接着剤の粘度及び硬化物の耐熱性の点から、炭素原子数１～６の脂肪族ジオールのジグリシジルエーテルが好ましい。 The aliphatic epoxy compound (1B) is preferably a diglycidyl ether of an aliphatic diol having 1 to 6 carbon atoms from the viewpoint of the viscosity of the adhesive and the heat resistance of the cured product.
　上記脂肪族エポキシ化合物（１Ｂ）としては、市販品のものを用いることができ、例えば、デナコールＥＸ－１２１、デナコールＥＸ－１７１、デナコールＥＸ－１９２、デナコールＥＸ－２１１、デナコールＥＸ－２１２、デナコールＥＸ－３１３、デナコールＥＸ－３１４、デナコールＥＸ－３２１、デナコールＥＸ－４１１、デナコールＥＸ－４２１、デナコールＥＸ－５１２、デナコールＥＸ－５２１、デナコールＥＸ－６１１、デナコールＥＸ－６１２、デナコールＥＸ－６１４、デナコールＥＸ－６２２、デナコールＥＸ－８１０、デナコールＥＸ－８１１、デナコールＥＸ－８５０、デナコールＥＸ－８５１、デナコールＥＸ－８２１、デナコールＥＸ－８３０、デナコールＥＸ－８３２、デナコールＥＸ－８４１、デナコールＥＸ－８６１、デナコールＥＸ－９１１、デナコールＥＸ－９４１、デナコールＥＸ－９２０、デナコールＥＸ－９３１（ナガセケムテックス社製）；エポライトＭ－１２３０、エポライト４０Ｅ、エポライト１００Ｅ、エポライト２００Ｅ、エポライト４００Ｅ、エポライト７０Ｐ、エポライト２００Ｐ、エポライト４００Ｐ、エポライト１５００ＮＰ、エポライト１６００、エポライト８０ＭＦ、エポライト１００ＭＦ（共栄社化学社製）等が挙げられる。 As the aliphatic epoxy compound (1B), commercially available products can be used. For example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX -313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX -622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denaco EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
　上記脂環式エポキシ化合物（１Ｃ）としては、少なくとも１個の脂環式環を有する多価アルコールのポリグリシジルエーテル化物又はシクロヘキセンやシクロペンテン環含有化合物を酸化剤でエポキシ化することによって得られるシクロヘキセンオキサイドやシクロペンテンオキサイド含有化合物が挙げられる。例えば、水素添加ビスフェノールＡジグリシジルエーテル、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－１－メチルシクロヘキシル－３，４－エポキシ－１－メチルヘキサンカルボキシレート、６－メチル－３，４－エポキシシクロヘキシルメチル－６－メチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－３－メチルシクロヘキシルメチル－３，４－エポキシ－３－メチルシクロヘキサンカルボキシレート、３，４－エポキシ－５－メチルシクロヘキシルメチル－３，４－エポキシ－５－メチルシクロヘキサンカルボキシレート、２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサン－メタジオキサン、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、３，４－エポキシ－６－メチルシクロヘキシルカルボキシレート、メチレンビス（３，４－エポキシシクロヘキサン）、プロパン－２，２－ジイル－ビス（３，４－エポキシシクロヘキサン）、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、ジシクロペンタジエンジエポキサイド、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ－２－エチルヘキシル、１－エポキシエチル－３，４－エポキシシクロヘキサン、１，２－エポキシ－２－エポキシエチルシクロヘキサン等が挙げられる。 The alicyclic epoxy compound (1C) is a cyclohexene oxide 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. And cyclopentene oxide-containing compounds. For example, hydrogenated bisphenol A diglycidyl ether, 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, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Metajiki , Bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4 -Epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, epoxy hexahydrophthal Examples include di-2-ethylhexyl acid, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, and the like.
　上記脂環式エポキシ化合物（１Ｃ）としては、接着剤の粘度及び硬化物の耐熱性の点から、３，４-エポキシシクロヘキシルメチルー３，４－エポキシシクロヘキサンカルボキシレートが好ましい。 The alicyclic epoxy compound (1C) is preferably 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate from the viewpoint of the viscosity of the adhesive and the heat resistance of the cured product.
　上記脂環式エポキシ化合物（１Ｃ）としては、市販品のものを用いることができ、例えば、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０００、セロキサイド３０００（ダイセル社製）等が挙げられる。 Commercially available products can be used as the alicyclic epoxy compound (1C), and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel Corporation).
　上記オキセタン化合物（１Ｄ）としては、例えば、３，７－ビス（３－オキセタニル）－５－オキサ－ノナン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、１，２－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］エタン、１，３－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］プロパン、エチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、トリエチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、テトラエチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、１，４－ビス（３－エチル－３－オキセタニルメトキシ）ブタン、１，６－ビス（３－エチル－３－オキセタニルメトキシ）ヘキサン等の二官能脂肪族オキセタン化合物、３―エチル―３－［（フェノキシ）メチル］オキセタン、３―エチル―３－（ヘキシロキシメチル）オキセタン、３―エチル―３－（２－エチルヘキシロキシメチル）オキセタン、３―エチル―３－（ヒドロキシメチル）オキセタン、３―エチル―３－（クロロメチル）オキセタン等の単官能オキセタン化合物が挙げられ、中でも二官能脂肪族オキセタンが、反応性、硬化性の点から好ましい。 Examples of the oxetane compound (1D) 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) Bifunctional such as butane and 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane Aliphatic oxetane compounds, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3- Examples thereof include monofunctional oxetane compounds such as ethyl-3- (hydroxymethyl) oxetane and 3-ethyl-3- (chloromethyl) oxetane. Among them, bifunctional aliphatic oxetane is preferable from the viewpoint of reactivity and curability.
　上記オキセタン化合物（１Ｄ）としては、接着剤の粘度及び硬化物の耐熱性の点から、３－エチルー｛［（３－エチルオキセタンー３－イル）メトキシ］メチル｝オキセタンが特に好ましい。 The oxetane compound (1D) is particularly preferably 3-ethyl-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane from the viewpoints of the viscosity of the adhesive and the heat resistance of the cured product.
　上記オキセタン化合物（１Ｄ）としては、市販品を用いることができ、例えば、アロンオキセタンＥＸＯＨ、ＰＯＸ、ＯＸＡ、ＯＸＴ－１０１、ＯＸＴ－２１１、ＯＸＴ－２１２、ＯＸＴ－２２１（東亞合成社製）等が挙げられる。 Commercially available products can be used as the oxetane compound (1D), such as Aron Oxetane EXOH, POX, OXA, OXT-101, OXT-211, OXT-212, OXT-221 (manufactured by Toagosei Co., Ltd.), and the like. Can be mentioned.
　上記カチオン重合性化合物の混合物（１）において、上記一般式（Ｉ）で表される芳香族エポキシ化合物（１Ａ）、脂肪族エポキシ化合物（１Ｂ）、脂環式エポキシ化合物（１Ｃ）及びオキセタン化合物（１Ｄ）の混合割合は、上記カチオン重合性化合物の混合物（１）１００質量部中、上記芳香族多官能エポキシ化合物（１Ａ）が２０～８０質量部、好ましくは、３０～７０質量部、より好ましくは３０～６０質量部であり、上記脂肪族エポキシ化合物（１Ｂ）が０～７０質量部、好ましくは、５～６０質量部、より好ましくは１０～５０質量部であり、上記脂環式エポキシ化合物（１Ｃ）が０～２０質量部、好ましくは、０．５～１５質量部、より好ましくは１～１０質量部であり、上記オキセタン化合物（１Ｄ）が０～７０質量部、好ましくは、５～６０質量部、より好ましくは１０～５０質量部であることが好ましい。但し、上記一般式（Ｉ）で表される芳香族エポキシ化合物（１Ａ）は主成分であることから、その含有量は、他の化合物に比して最も多い値をとる。 In the mixture (1) of the cationic polymerizable compound, the aromatic epoxy compound (1A), the aliphatic epoxy compound (1B), the alicyclic epoxy compound (1C), and the oxetane compound represented by the general formula (I) ( The mixing ratio of 1D) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, more preferably 30 to 70 parts by mass of the aromatic polyfunctional epoxy compound (1A) in 100 parts by mass of the mixture (1) of the cationic polymerizable compound. Is 30 to 60 parts by mass, and the aliphatic epoxy compound (1B) is 0 to 70 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass. (1C) is 0 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and the oxetane compound (1D) is 0 to 70 parts by mass, Mashiku is preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by weight. However, since the aromatic epoxy compound (1A) represented by the general formula (I) is a main component, the content thereof is the highest as compared with other compounds.
　上記カチオン重合性化合物としては、上記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）以外の芳香環含有エポキシ化合物を、上記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）と併用することができる。該芳香環含有エポキシ化合物としては、例えば、フェノール、クレゾール、ブチルフェノール等、少なくとも１個の芳香族環を有する１価フェノール又は、そのアルキレンオキサイド付加物のグリシジルエーテル化物、例えばビスフェノールＡ、ビスフェノールＦ、又はこれらに更にアルキレンオキサイドを付加した化合物のグリシジルエーテル化物やエポキシノボラック樹脂；レゾルシノールやハイドロキノン、カテコール等の２個以上のフェノール性水酸基を有する芳香族化合物のグリシジルエーテル；ベンゼンジメタノールやベンゼンジエタノール、ベンゼンジブタノール等のアルコール性水酸基を２個以上有する芳香族化合物のモノ／ポリグリシジルエーテル化物；フタル酸、テレフタル酸、トリメリット酸等の２個以上のカルボン酸を有する多塩基酸芳香族化合物のグリシジルエステル、安息香酸やトルイル酸、ナフトエ酸等の安息香酸類のグリシジルエステル、スチレンオキサイド又はジビニルベンゼンのエポキシ化物等が挙げられる。この場合、上記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）以外の芳香環含有エポキシ化合物の含有量は、上記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）１００質量部に対し好ましくは９０質量部以下、より好ましくは６０質量部以下とする Examples of the cationic polymerizable compound include aromatic ring-containing epoxy compounds other than the aromatic ring-containing epoxy compound (1A) represented by the general formula (I), and aromatic ring-containing epoxy compounds represented by the general formula (I). (1A) can be used in combination. Examples of the aromatic ring-containing epoxy compound include monovalent phenols having at least one aromatic ring such as phenol, cresol, and butylphenol, or glycidyl etherified products of alkylene oxide adducts thereof such as bisphenol A, bisphenol F, or Glycidyl etherified compounds and epoxy novolac resins of compounds further added with alkylene oxide; glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; benzenedimethanol, benzenediethanol and benzenedi Mono / polyglycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as butanol; two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid Glycidyl esters of polybasic acid aromatic compound having, benzoic acid and toluic acid, glycidyl esters of benzoic acids such as naphthoic acid, epoxides and the like of styrene oxide or divinylbenzene. In this case, the content of the aromatic ring-containing epoxy compound other than the aromatic ring-containing epoxy compound (1A) represented by the general formula (I) is the aromatic ring-containing epoxy compound (1A) represented by the general formula (I). ) Preferably not more than 90 parts by mass, more preferably not more than 60 parts by mass with respect to 100 parts by mass.
　本発明の組成物は、更にカチオン重合開始剤（２）を含有してもよい。
　本発明に使用する上記カチオン重合開始剤（２）とは、エネルギー線照射により酸を発生することが可能な化合物であればどのようなものでも差し支えないが、好ましくは、エネルギー線の照射によってルイス酸を放出するオニウム塩である複塩、又はその誘導体である。かかる化合物の代表的なものとしては、下記一般式、
ｐ［Ａ］q+・ｓ［Ｂ］t-（Ａは陽イオン種を表し、Ｂは陰イオン種を表し、ｑ及びｔは、それぞれ独立に１又は２を表し、ｐ及びｓは、電荷を中性に保つ係数を表す。）で表される陽イオンと陰イオンの塩を挙げることができる。 The composition of the present invention may further contain a cationic polymerization initiator (2).
The cationic polymerization initiator (2) used in the present invention may be any compound that can generate an acid upon irradiation with energy rays. It is a double salt that is an onium salt that releases an acid, or a derivative thereof. Representative examples of such compounds include the following general formula:
p [A] q + · s [B] t− (A represents a cationic species, B represents an anionic species, q and t each independently represents 1 or 2, and p and s represent charges. And a salt of a cation and an anion.
　ここで陽イオン［Ａ］q+はオニウムであることが好ましく、その構造は、例えば、下記一般式、
［（Ｒ10）aＱ］q+
で表すことができる。 Here, the cation [A] q + is preferably onium, and the structure thereof is, for example, the following general formula:
[(R 10 ) a Q] q +
Can be expressed as
　更にここで、Ｒ10は炭素原子数が１～６０であり、炭素原子以外の原子をいくつ含んでいてもよい有機の基である。ａは１～５なる整数である。ａ個のＲ10は各々独立で、同一でも異なっていてもよい。また、少なくとも１つは、芳香環を有する上記の如き有機の基であることが好ましい。ＱはＳ，Ｎ，Ｓｅ，Ｔｅ，Ｐ，Ａｓ，Ｓｂ，Ｂｉ，Ｏ，Ｉ，Ｂｒ，Ｃｌ，Ｆ，Ｎ＝Ｎからなる群から選ばれる原子或いは原子団である。また、陽イオン［Ａ］q+中のＱの原子価をｔとしたとき、ｑ＝ａ－ｔなる関係が成り立つことが必要である（但し、Ｎ＝Ｎは原子価０として扱う）。 Further, here, R 10 is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a R 10 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. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] q + is t, it is necessary that the relationship q = at is satisfied (however, N = N is treated as a valence of 0).
　また、陰イオン［Ｂ］t-は、ハロゲン化物錯体であることが好ましく、その構造は、例えば、下記一般式、
［ＬＸb］t-
で表すことができる。 The anion [B] t- is preferably a halide complex, and the structure thereof is, for example, the following general formula:
[LX b ] t-
Can be expressed as
　更にここで、Ｌはハロゲン化物錯体の中心原子である金属又は半金属（Ｍｅｔａｌｌｏｉｄ）であり、Ｂ，Ｐ，Ａｓ，Ｓｂ，Ｆｅ，Ｓｎ，Ｂｉ，Ａｌ，Ｃａ，Ｉｎ，Ｔｉ，Ｚｎ，Ｓｃ，Ｖ，Ｃｒ，Ｍｎ，Ｃｏ等である。Ｘはハロゲン原子である。ｂは３～７なる整数である。また、陰イオン［Ｂ］t-中のＬの原子価をｐとしたとき、ｒ＝ｂ－ｐなる関係が成り立つことが必要である。 Further, here, L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen atom. b is an integer of 3 to 7. Further, when the valence of L in the anion [B] t− is p, it is necessary that the relationship r = b−p holds.
　上記一般式の陰イオン［ＬＸb］t-の具体例としては、テトラキス（ペンタフルオロフェニル）ボレート、テトラ（３，５－ジフルオロ－４－メトキシフェニル）ボレート、テトラフルオロボレート（ＢＦ4）-、ヘキサフルオロフォスフェート（ＰＦ6）-、ヘキサフルオロアンチモネート（ＳｂＦ6）-、ヘキサフルオロアルセネート（ＡｓＦ6）-、ヘキサクロロアンチモネート（ＳｂＣｌ6）-等を挙げることができる。 Specific examples of the anion [LX b ] t- of the above general formula 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.
　また、陰イオン［Ｂ］t-は、下記一般式、
［ＬＸb-1（ＯＨ）］t-
で表される構造のものも好ましく用いることができる。Ｌ，Ｘ，ｂは上記と同様である。また、その他用いることのできる陰イオンとしては、過塩素酸イオン（ＣｌＯ4）-、トリフルオロメチル亜硫酸イオン（ＣＦ3ＳＯ3）-、フルオロスルホン酸イオン（ＦＳＯ3）-、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフルオロブタンスルフォネート、ヘキサデカフルオロオクタンスルフォネート、テトラアリールボレート、テトラキス（ペンタフルオロフェニル）ボレート等を挙げることができる。 Further, the anion [B] t− is represented by the following general formula:
[LX b-1 (OH)] t-
The thing of the structure represented by can also be used preferably. L, X, and b are the same as described above. Other anions that can be used include perchlorate ion (ClO 4 ) − , trifluoromethyl sulfite ion (CF 3 SO 3 ) − , fluorosulfonate ion (FSO 3 ) − , and toluenesulfonate anion. , Trinitrobenzenesulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
　本発明では、このようなオニウム塩の中でも、下記の（イ）～（ハ）の芳香族オニウム塩を使用することが特に有効である。これらの中から、その１種を単独で、又は２種以上を混合して使用することができる。 In the present invention, among these onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more can be mixed and used.
（イ） フェニルジアゾニウムヘキサフルオロホスフェート、４－メトキシフェニルジアゾニウムヘキサフルオロアンチモネート、４－メチルフェニルジアゾニウムヘキサフルオロホスフェート等のアリールジアゾニウム塩 (Ii) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate
（ロ） ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ（４－メチルフェニル）ヨードニウムヘキサフルオロホスフェート、ジ（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムヘキサフルオロホスフェート、トリルクミルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート等のジアリールヨードニウム塩 (B) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
（ハ）下記群Ｉ又は群ＩＩで表されるスルホニウムカチオンとヘキサフルオロアンチモンイオン、テトラキス（ペンタフルオロフェニル）ボレートイオン等のスルホニウム塩 (C) sulfonium salts such as sulfonium cations represented by the following group I or group II, hexafluoroantimony ions, tetrakis (pentafluorophenyl) borate ions, etc.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003

Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　また、その他好ましいものとしては、（η5－２，４－シクロペンタジエン－１－イル）〔（１，２，３，４，５，６－η）－（１－メチルエチル）ベンゼン〕－アイアン－ヘキサフルオロホスフェート等の鉄－アレーン錯体や、トリス（アセチルアセトナト）アルミニウム、トリス（エチルアセトナトアセタト）アルミニウム、トリス（サリチルアルデヒダト）アルミニウム等のアルミニウム錯体とトリフェニルシラノール等のシラノール類との混合物等も挙げることができる。 Other preferable examples include (η 5 -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum, and silanols such as triphenylsilanol The mixture of these can also be mentioned.
　これらの中でも、実用面と光感度の観点から、芳香族ヨードニウム塩、芳香族スルホニウム塩、鉄－アレーン錯体を用いることが好ましい。 Of these, aromatic iodonium salts, aromatic sulfonium salts, and iron-arene complexes are preferably used from the viewpoints of practical use and photosensitivity.
　上記カチオン重合性化合物の混合物（１）に対するカチオン重合開始剤（２）の使用割合は特に限定されず、本発明の目的を阻害しない範囲内で概ね通常の使用割合で使用すればよいが、例えば、カチオン重合性化合物の混合物（１）１００質量部に対して、カチオン重合開始剤（２）を好ましくは０．１～２０質量部、より好ましくは０．５～１０質量部とすることができる。少なすぎると硬化が不十分となりやすく、多すぎると硬化物の吸水率や硬化物強度等の諸物性に悪影響を与える場合がある。 The use ratio of the cationic polymerization initiator (2) to the mixture (1) of the cationic polymerizable 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. The cationic polymerization initiator (2) can be preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the mixture (1) of the cationic polymerizable compound. . 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.
　本発明の組成物は、組成物全量（但し、溶媒は除く）の１００質量部に対し、水分を０．０５～３質量部含むことが好ましい。 The composition of the present invention preferably contains 0.05 to 3 parts by mass of water with respect to 100 parts by mass of the total composition (excluding the solvent).
　本発明の組成物には、必要に応じてシランカップリング剤を用いることができる。
　シランカップリング剤としては、例えば、ジメチルジメトキシシラン、ジメチルジエトキシシラン、メチルエチルジメトキシシラン、メチルエチルジエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリメトキシシラン等のアルキル官能性アルコキシシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン等のアルケニル官能性アルコキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、２－メタクリロキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ官能性アルコキシシラン、Ｎ－β（アミノエチル）－γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ官能性アルコキシシラン、γ－メルカプトプロピルトリメトキシシラン等のメルカプト官能性アルコキシシラン、チタンテトライソプロポキシド、チタンテトラノルマルブトキシド等のチタンアルコキシド類、チタンジオクチロキシビス（オクチレングリコレート）、チタンジイソプロポキシビス（エチルアセトアセテート）等のチタンキレート類、ジルコウニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート等のジルコニウムキレート類、ジルコニウムトリブトキシモノステアレート等のジルコニウムアシレート類、メチルトリイソシアネートシラン等のイソシアネートシラン類等を用いることができる。 In the composition of the present invention, a silane coupling agent can be used as necessary.
Examples of 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, γ Epoxy-functional alkoxysilanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ Aminofunctional alkoxysilanes such as aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium Titanium alkoxides such as tetraisopropoxide and titanium tetranormal butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), zirconi Arm tetraacetyl acetonate, zirconium chelates such as zirconium tributoxy monoacetylacetonate, zirconium acylates such as zirconium tributoxy monostearate, an isocyanate silane such as methyl triisocyanate silane.
　上記シランカップリング剤の使用量は、特に限定されないが、通常、組成物中の固形物の全量１００質量部に対して、１～２０質量部の範囲である。 The amount of the silane coupling agent used is not particularly limited, but is usually in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of solids in the composition.
　本発明の組成物には、必要に応じて熱重合開始剤を用いることができる。
　熱重合開始剤とは、加熱によりカチオン種又はルイス酸を発生する化合物として、スルホニウム塩、チオフェニウム塩、チオラニウム塩、ベンジルアンモニウム、ピリジニウム塩、ヒドラジニウム塩等の塩；ジエチレントリアミン、トリエチレントリアミン、テトラエチレンペンタミン等のポリアルキルポリアミン類；１，２－ジアミノシクロヘキサン、１，４－ジアミノ－３，６－ジエチルシクロヘキサン、イソホロンジアミン等の脂環式ポリアミン類；ｍ－キシリレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族ポリアミン類；前記ポリアミン類と、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールＡ－ジグリシジルエーテル、ビスフェノールＦ－ジグリシジルエーテル等のグリシジルエーテル類又はカルボン酸のグリシジルエステル類等の各種エポキシ樹脂とを常法によって反応させることによって製造されるポリエポキシ付加変性物；前記有機ポリアミン類と、フタル酸、イソフタル酸、ダイマー酸等のカルボン酸類とを常法によって反応させることによって製造されるアミド化変性物；前記ポリアミン類とホルムアルデヒド等のアルデヒド類及びフェノール、クレゾール、キシレノール、第三ブチルフェノール、レゾルシン等の核に少なくとも一個のアルデヒド化反応性場所を有するフェノール類とを常法によって反応させることによって製造されるマンニッヒ化変性物；多価カルボン酸（シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、２－メチルコハク酸、２－メチルアジピン酸、３－メチルアジピン酸、３－メチルペンタン二酸、２－メチルオクタン二酸、３，８－ジメチルデカン二酸、３，７－ジメチルデカン二酸、水添ダイマー酸、ダイマー酸等の脂肪族ジカルボン酸類；フタル酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸類；シクロヘキサンジカルボン酸等の脂環式ジカルボン酸類；トリメリット酸、トリメシン酸、ひまし油脂肪酸の三量体等のトリカルボン酸類；ピロメリット酸等のテトラカルボン酸類等）の酸無水物；ジシアンジアミド、イミダゾール類、カルボン酸エステル、スルホン酸エステル、アミンイミド等を挙げることができる。 In the composition of the present invention, a thermal polymerization initiator can be used as necessary.
Thermal polymerization initiator is a compound that generates a cationic species or Lewis acid by heating, such as a salt of sulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; diethylenetriamine, triethylenetriamine, tetraethylenepenta Polyalkylpolyamines such as min; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Aromatic polyamines such as; such polyamines; phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. Polyepoxy addition-modified products produced by reacting various types of epoxy resins such as glycidyl ethers or glycidyl esters of carboxylic acids in a conventional manner; the organic polyamines, phthalic acid, isophthalic acid, dimer acid, etc. An amidation modified product produced by reacting carboxylic acids with a conventional method; at least one aldehyde reaction in the nucleus of polyamines and aldehydes such as formaldehyde and phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. Mannich-modified products produced by reacting phenols having sex sites by a conventional method; polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain Acid, sebacic acid, do Candiic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecane Aliphatic dicarboxylic acids such as diacids, hydrogenated dimer acids and dimer acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid , Tricarboxylic acids such as trimesic acid and trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, etc. .
　上記熱重合開始剤としては、市販品を用いることもでき、例えば、アデカオプトン ＣＰ７７、アデカオプトンＣＰ６６（ＡＤＥＫＡ社製）、ＣＩ－２６３９、ＣＩ－２６２４（日本曹達社製）、サンエイド ＳＩ－６０Ｌ、サンエイドＳＩ－８０Ｌ、サンエイド ＳＩ－１００Ｌ（三新化学工業社製）等が挙げられる。 Commercially available products may be used as the thermal polymerization initiator. For example, Adeka Opton® CP77, Adeka Opton CP66 (manufactured by ADEKA), CI-2539, CI-2624 (manufactured by Nippon Soda Co., Ltd.), Sun-Aid® SI-60L, Sun-Aid SI -80L, Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.
　上記熱重合開始剤の使用量は、特に限定されないが、通常、組成物中の固形物の全量１００質量部に対して、０．００１～１０質量部の範囲であり、該熱重合開始剤を用いる場合には、本発明の組成物を硬化させる際に１３０～１８０℃で２０分～１時間加熱するのが好ましい。 The amount of the thermal polymerization initiator used is not particularly limited, but is usually in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solids in the composition. When used, the composition of the present invention is preferably heated at 130 to 180 ° C. for 20 minutes to 1 hour when it is cured.
　本発明の組成物には、必要に応じて熱可塑性有機重合体を用いることによって、硬化物の特性を改善することもできる。該熱可塑性有機重合体としては、例えば、ポリスチレン、ポリメチルメタクリレート、メチルメタクリレート－エチルアクリレート共重合体、ポリ（メタ）アクリル酸、スチレン－（メタ）アクリル酸共重合体、（メタ）アクリル酸－メチルメタクリレート共重合体、グリシジル（メタ）アクリレート－ポリメチル（メタ）アクリレート共重合体、ポリビニルブチラール、セルロースエステル、ポリアクリルアミド、飽和ポリエステル等が挙げられる。 In the composition of the present invention, the properties of the cured product can be improved by using a thermoplastic organic polymer as necessary. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.
　本発明の組成物には、特に制限されず通常用いられる上記（１）～（４）の各成分を溶解又は分散しえる溶媒を用いることができ、例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルイソブチルケトン、シクロヘキサノン、２－ヘプタノン等のケトン類；エチルエーテル、ジオキサン、テトラヒドロフラン、１，２－ジメトキシエタン、１，２－ジエトキシエタン、プロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル等のエーテル系溶媒；酢酸メチル、酢酸エチル、酢酸－ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸シクロヘキシル、乳酸エチル、コハク酸ジメチル、テキサノール等のエステル系溶媒；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のセロソルブ系溶媒；メタノール、エタノール、イソ－又はｎ－プロパノール、イソ－又はｎ－ブタノール、アミルアルコール等のアルコール系溶媒；エチレングリコールモノメチルアセテート、エチレングリコールモノエチルアセテート、プロピレングリコール－１－モノメチルエーテル－２－アセテート（ＰＧＭＥＡ）、ジプロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート、エトキシエチルプロピオネート等のエーテルエステル系溶媒；ベンゼン、トルエン、キシレン等のＢＴＸ系溶媒；ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶媒；テレピン油、Ｄ－リモネン、ピネン等のテルペン系炭化水素油；ミネラルスピリット、スワゾール＃３１０（コスモ松山石油（株））、ソルベッソ＃１００（エクソン化学（株））等のパラフィン系溶媒；四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、１，２－ジクロロエタン等のハロゲン化脂肪族炭化水素系溶媒；クロロベンゼン等のハロゲン化芳香族炭化水素系溶媒；プロピレンカーボネート、カルビトール系溶媒、アニリン、トリエチルアミン、ピリジン、酢酸、アセトニトリル、二硫化炭素、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、水等が挙げられ、これらの溶媒は１種又は２種以上の混合溶媒として使用することができる。 The composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (1) to (4) that are usually used can be used. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol Ether solvents such as dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; ethylene glycol Cellosolve solvents such as nomethyl ether, ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl Ether ester solvents such as acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; BTX such as benzene, toluene, xylene Solvents: aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, pinene; Parasitic solvents such as Luspirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogens such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 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, and these solvents can be used as one or a mixture of two or more.
　本発明の組成物は、粘度が１～２００ｍＰａ・ｓ以下であるものが、硬化性及び塗工性に優れるため好ましい。 The composition of the present invention preferably has a viscosity of 1 to 200 mPa · s because it is excellent in curability and coatability.
　本発明の組成物は、ロールコーター、カーテンコーター、各種の印刷、浸漬等の公知の手段で、支持基体上に適用される。また、一旦フィルム等の支持基体上に施した後、他の支持基体上に転写することもでき、その適用方法に制限はない。 The 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 | substrate, There is no restriction | limiting in the application method.
　上記支持基体の材料としては、特に制限されず通常用いられるものを使用することができ、例えば、ガラス等の無機材料；ジアセチルセルロース、トリアセチルセルロース（ＴＡＣ）、プロピオニルセルロース、ブチリルセルロース、アセチルプロピオニルセルロース、ニトロセルロース等のセルロースエステル；ポリアミド；ポリイミド；ポリウレタン；エポキシ樹脂；ポリカーボネート；ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリ－１，４－シクロヘキサンジメチレンテレフタレート、ポリエチレン－１，２－ジフェノキシエタン－４，４'－ジカルボキシレート、ポリブチレンテレフタレート等のポリエステル；ポリスチレン；ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン；ポリビニルアルコール（ＰＶＡ）、ポリ酢酸ビニル、ポリ塩化ビニル、ポリフッ化ビニル等のビニル化合物；ポリメチルメタクリレート、ポリアクリル酸エステル等のアクリル系樹脂；ポリカーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテルケトン；ポリエーテルイミド；ポリオキシエチレン、ノルボルネン樹脂、シクロオレフィンポリマー（ＣＯＰ）等の高分子材料が挙げられる。
　尚、上記支持基体に、コロナ放電処理、火炎処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理等の表面活性化処理を行ってもよい。 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. 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 Polyester such as ethane-4,4′-dicarboxylate, polybutylene terephthalate, etc .; polystyrene; polyethylene, polypropylene, polymethylpentene, etc. Polyolefins; Vinyl compounds such as polyvinyl alcohol (PVA), polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone Polyetherimide; polymer materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP).
Note that the support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.
　また、本発明の効果を損なわない範囲（好ましくは組成物中の固形物の全量１００質量部に対して、５０質量部以下）である限り、必要に応じて他のモノマー、他のカチオン重合性重合開始剤、ラジカル重合開始剤、無機フィラー、有機フィラー、顔料、染料等の着色剤、光増感剤、消泡剤、増粘剤、界面活性剤、レベリング剤、難燃剤、チクソ剤、希釈剤、可塑剤、安定剤、重合禁止剤、紫外線吸収剤、酸化防止剤、静電防止剤、流動調整剤、接着促進剤等の各種樹脂添加物等を添加することができる。 Moreover, as long as it is the range which does not impair the effect of this invention (Preferably 50 mass parts or less with respect to 100 mass parts of the total amount of the solid substance in a composition), another monomer and other cationic polymerizability are needed as needed. Polymerization initiators, radical polymerization initiators, inorganic fillers, organic fillers, colorants such as pigments, dyes, photosensitizers, antifoaming agents, thickeners, surfactants, leveling agents, flame retardants, thixotropic agents, dilution Various resin additives such as an agent, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, a flow regulator, and an adhesion promoter can be added.
　本発明の組成物は活性エネルギー線の照射により硬化するが、活性エネルギー線としては、紫外線、電子線、Ｘ線、放射線、高周波等を挙げることができ、紫外線が経済的に最も好ましい。紫外線の光源としては、紫外線レーザ、水銀ランプ、キセノンレーザ、メタルハライドランプ等が挙げられる。 The composition of the present invention is cured by irradiation with active energy rays, and examples of the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, 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.
　本発明の組成物の具体的な用途としては、メガネ、撮像用レンズに代表される光学材料、塗料、コーティング剤、ライニング剤、インキ、レジスト、液状レジスト、接着剤、印刷版、絶縁ワニス、絶縁シート、積層板、プリント基盤、半導体装置用・ＬＥＤパッケージ用・液晶注入口用・有機ＥＬ用・光素子用・電気絶縁用・電子部品用・分離膜用等の封止剤、成形材料、パテ、ガラス繊維含浸剤、目止め剤、半導体用・太陽電池用等のパッシベーション膜、層間絶縁膜、保護膜、液晶表示装置のバックライトに使用されるプリズムレンズシート、プロジェクションテレビ等のスクリーンに使用されるフレネルレンズシート、レンチキュラーレンズシート等のレンズシートのレンズ部、又はこのようなシートを用いたバックライト等、マイクロレンズ等の光学レンズ、光学素子、光コネクター、光導波路、光学的造形用注型剤等を挙げることができ、例えばコーティング剤として適用できる基材としては金属、木材、ゴム、プラスチック、ガラス、セラミック製品等を挙げることができる。 Specific applications of the composition of the present invention include glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, insulating varnishes, insulating materials. Sheets, laminates, printed circuit boards, semiconductor devices, LED packages, liquid crystal injection ports, organic ELs, optical elements, electrical insulation, electronic components, separation membranes, sealing materials, molding materials, putty Glass fiber impregnating agent, sealing agent, passivation film for semiconductors and solar cells, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, screen for projection TV etc. My lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets, or backlights using such sheets, etc. Examples include optical lenses such as Lolens, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, etc. Examples of substrates that can be used as coating agents include metals, wood, rubber, plastics, glass, ceramics Product etc. can be mentioned.
　以下、本発明の組成物及び該組成物を硬化して得られる硬化物に関し、実施例、評価例及び比較例により具体的に説明するが、本発明は実施例等により制限されない。尚、実施例及び比較例では部は質量部を意味する。 Hereinafter, the composition of the present invention and the cured product obtained by curing the composition will be specifically described with reference to examples, evaluation examples, and comparative examples, but the present invention is not limited to the examples. In Examples and Comparative Examples, “part” means “part by mass”.
[実施例１～１６及び比較例１～４]
　下記の[表１]～[表４]に示す配合で各成分を十分に混合して、各々実施組成物１～１６、比較組成物１～４を得た。 [Examples 1 to 16 and Comparative Examples 1 to 4]
The components shown in [Table 1] to [Table 4] below were mixed thoroughly to obtain Example Compositions 1 to 16 and Comparative Compositions 1 to 4, respectively.
　カチオン重合性化合物としては下記の化合物（１Ａ－１）並びに（１Ａ’－１）～（１Ａ’－２）、（１Ｂ－１）～（１Ｂ－３）、（１Ｃ－１）～（１Ｃ－２）、（１Ｄ－１）～（１Ｄ－２）を用いた。
化合物１Ａ－１：ＥＰＯＸ－ＭＫ　Ｒ１７１０（プリンテック社製ビスフェノールＥ型エポキシ樹脂）
化合物１Ａ’－１：ＥＰ－４９０１Ｌ（ＡＤＥＫＡ社製ビスフェノールＦ型エポキシ樹脂）
化合物１Ａ’－２：ＥＰ－４１００Ｌ（ＡＤＥＫＡ社製ビスフェノールＡ型エポキシ樹脂）
化合物１Ｂ－１：１，４－ブタンジオールジグリシジルエーテル
化合物１Ｂ－２：ネオペンチルグリコールジグリシジルエーテル
化合物１Ｃ－１： セロキサイド２０２１Ｐ（ダイセル社製脂環式エポキシ化合物）
化合物１Ｃ－２：（４Ｒ）－１，２－エポキシ－４－（２－メチルオキシラニル）－１－メチルシクロヘキサン
化合物１Ｄ－１：アロンオキセタンＯＸＴ－２２１（東亞合成社製）
化合物１Ｄ－２：アロンオキセタンＯＸＴ－１０１（東亞合成社製） As cationically polymerizable compounds, the following compounds (1A-1), (1A′-1) to (1A′-2), (1B-1) to (1B-3), (1C-1) to (1C— 2), (1D-1) to (1D-2) were used.
Compound 1A-1: EPOX-MK R1710 (Bisphenol E type epoxy resin manufactured by Printec)
Compound 1A′-1: EP-4901L (bisphenol F type epoxy resin manufactured by ADEKA)
Compound 1A′-2: EP-4100L (bisphenol A type epoxy resin manufactured by ADEKA)
Compound 1B-1: 1,4-butanediol diglycidyl ether compound 1B-2: Neopentyl glycol diglycidyl ether compound 1C-1: Celoxide 2021P (alicyclic epoxy compound manufactured by Daicel)
Compound 1C-2: (4R) -1,2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane Compound 1D-1: Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)
Compound 1D-2: Aron Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.)
　カチオン重合開始剤（２）としては下記の化合物（２－１）を用いた。
化合物２－１：[化４]で表される化合物及び[化５]で表される化合物の混合物のプロピレンカーボネート５０％溶液 The following compound (2-1) was used as the cationic polymerization initiator (2).
Compound 2-1: 50% solution of propylene carbonate in a mixture of the compound represented by [Chemical Formula 4] and the compound represented by [Chemical Formula 5]
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
[評価例１～１６及び比較評価例１～４]
　上記実施例１～１６で得られた実施組成物及び比較例１～４で得られた比較組成物について、下記評価を行った。結果を上記[表１]～[表４]に示す。
（密着性）
　得られた実施組成物１～１６、比較組成物の１～４のそれぞれを、一枚のＴＡＣフィルム又はＰＭＭＡフィルムに塗布した後、ラミネーターを用いてコロナ放電処理を施したＣＯＰ（シクロオレフィンポリマー）フィルムと貼り合わせ、コールドミラー型高圧Ｈｇランプを用いて１０００ｍＪ／ｃｍ2のエネルギーを照射して接着して試験片を得た。得られた試験片の９０度ピール試験を行った。
（Ｔｇ）
　得られた実施組成物１～１６、比較組成物の１～４のそれぞれをＰＥＴフィルム上にバーコーターで３μｍの厚さに塗布し、コールドミラー型高圧Hgランプを用いて２０００ｍＪ／ｃｍ2のエネルギーを照射した。２４時間後にフィルムから接着剤硬化物を取り出し、(株)日立ハイテクサイエンス製の粘弾性測定装置（ＤＭＡ７１００）を用いＴｇを測定した。結果を［表１］～［表４］に示す。
（粘度）
　得られた実施組成物の１～１６、比較組成物の１～４のそれぞれを２５℃においてＥ型粘度計で粘度を測定した。結果を［表１］～［表４］に示す。 [Evaluation Examples 1 to 16 and Comparative Evaluation Examples 1 to 4]
The following evaluations were performed on the working compositions obtained in Examples 1 to 16 and the comparative compositions obtained in Comparative Examples 1 to 4. The results are shown in the above [Table 1] to [Table 4].
(Adhesion)
COP (cycloolefin polymer) obtained by applying each of the obtained working compositions 1 to 16 and comparative compositions 1 to 4 to a single TAC film or PMMA film and then applying a corona discharge treatment using a laminator A test piece was obtained by laminating the film and bonding it by applying energy of 1000 mJ / cm 2 using a cold mirror type high-pressure Hg lamp. The obtained test piece was subjected to a 90 degree peel test.
(Tg)
Each of the obtained working compositions 1 to 16 and comparative compositions 1 to 4 was applied to a PET film with a bar coater to a thickness of 3 μm, and an energy of 2000 mJ / cm 2 using a cold mirror type high pressure Hg lamp. Was irradiated. After 24 hours, the cured adhesive was taken out from the film, and Tg was measured using a viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in [Table 1] to [Table 4].
(viscosity)
The viscosity of each of the obtained practical compositions 1 to 16 and the comparative compositions 1 to 4 was measured with an E-type viscometer at 25 ° C. The results are shown in [Table 1] to [Table 4].
　[表１]～[表４]より、本発明の組成物は、接着性及び耐熱性に優れることが明らかである。 [Table 1] to [Table 4] clearly show that the composition of the present invention is excellent in adhesiveness and heat resistance.

Claims (6)

  1. 　カチオン重合性化合物の混合物（１）を含んでなり、該混合物（１）が、下記一般式（Ｉ）で表される芳香環含有エポキシ化合物（１Ａ）を主成分として含有し、さらに脂肪族エポキシ化合物（１Ｂ）、脂環式エポキシ化合物（１Ｃ）及びオキセタン化合物（１Ｄ）から選ばれる少なくとも一種を含むことを特徴とする組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に、水素原子、炭素原子数１～５のアルキル基、炭素原子数１～８のアルコキシ基、炭素原子数２～５のアルケニル基又はハロゲン原子を表し、ｍは０～１０の整数である。）     Comprising a mixture (1) of a cationically polymerizable compound, the mixture (1) containing an aromatic ring-containing epoxy compound (1A) represented by the following general formula (I) as a main component, and further an aliphatic epoxy A composition comprising at least one selected from a compound (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D).
    Figure JPOXMLDOC01-appb-C000001
     Wherein R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 5 carbon atoms. Represents an alkenyl group or a halogen atom, and m is an integer of 0 to 10.)
  2. 　上記脂肪族エポキシ化合物（１Ｂ）が、炭素原子数１～６の脂肪族ジオールのジグリシジルエーテルであることを特徴とする請求項１記載の組成物。 The composition according to claim 1, wherein the aliphatic epoxy compound (1B) is a diglycidyl ether of an aliphatic diol having 1 to 6 carbon atoms.
  3. 　上記カチオン重合性化合物の混合物（１）１００質量部に対し、カチオン重合開始剤（２）を０．１～２０質量部含むことを特徴とする請求項１又は２に記載の組成物。 The composition according to claim 1 or 2, which comprises 0.1 to 20 parts by mass of the cationic polymerization initiator (2) with respect to 100 parts by mass of the mixture (1) of the cationic polymerizable compound.
  4. 　上記カチオン重合開始剤が、ｐ［Ａ］q+・ｓ［Ｂ］t-（Ａは陽イオン種を表し、Ｂは陰イオン種を表し、ｑ及びｔは、それぞれ独立に１又は２を表し、ｐ及びｓは、電荷を中性に保つ係数を表す。）で表される陽イオンと陰イオンの塩である請求項１～３の何れか一項に記載の組成物。 The cationic polymerization initiator is p [A] q + · s [B] t− (A represents a cationic species, B represents an anionic species, q and t each independently represent 1 or 2, The composition according to any one of claims 1 to 3, which is a salt of a cation and an anion represented by p and s each representing a coefficient for maintaining a neutral charge).
  5. 　組成物全量（但し、溶媒は除く）の１００質量部に対し、水分を０．０５～３質量部含むことを特徴とする請求項１～４の何れか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the composition contains 0.05 to 3 parts by mass of water with respect to 100 parts by mass of the total amount of the composition (excluding the solvent).
  6. 　請求項１～５の何れか一項に記載の組成物からなることを特徴とする接着剤。 An adhesive comprising the composition according to any one of claims 1 to 5.
PCT/JP2016/058815 2015-03-27 2016-03-18 Composition WO2016158522A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020177011479A KR102563226B1 (en) 2015-03-27 2016-03-18 Composition
JP2017509582A JP6879903B2 (en) 2015-03-27 2016-03-18 Composition
CN201680003405.8A CN107075082B (en) 2015-03-27 2016-03-18 Composition comprising a metal oxide and a metal oxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-066954 2015-03-27
JP2015066954 2015-03-27

Publications (1)

Publication Number Publication Date
WO2016158522A1 true WO2016158522A1 (en) 2016-10-06

Family

ID=57006141

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/058815 WO2016158522A1 (en) 2015-03-27 2016-03-18 Composition

Country Status (5)

Country Link
JP (1) JP6879903B2 (en)
KR (1) KR102563226B1 (en)
CN (1) CN107075082B (en)
TW (1) TWI764862B (en)
WO (1) WO2016158522A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017071745A (en) * 2015-10-07 2017-04-13 アイカ工業株式会社 Photocurable resin composition and laminate
WO2017110951A1 (en) * 2015-12-25 2017-06-29 株式会社Adeka Curable composition, method for curing same, and cured product obtained thereby
JP2018109143A (en) * 2016-12-28 2018-07-12 日本合成化学工業株式会社 Active energy ray-curable adhesive composition, adhesive composition for polarizing plate, adhesive for polarizing plate and polarizing plate using the same
WO2018159260A1 (en) * 2017-03-02 2018-09-07 東亞合成株式会社 Active-energy-ray-curable adhesive composition for plastic film or sheet
WO2019021934A1 (en) * 2017-07-28 2019-01-31 株式会社ダイセル Monomer mixture and curable composition containing same
JP2019026820A (en) * 2017-07-28 2019-02-21 株式会社ダイセル Monomer mixture and curable composition containing the same
CN109690806A (en) * 2016-12-09 2019-04-26 株式会社Lg化学 Encapsulating composition
JP2020066643A (en) * 2018-10-22 2020-04-30 アイカ工業株式会社 Photocationic curing type epoxy resin composition
JP2020518952A (en) * 2017-04-28 2020-06-25 エルジー・ケム・リミテッド Sealing material composition
US11787971B2 (en) 2017-11-24 2023-10-17 Shanjin Optoelectronics (Suzhou) Co., Ltd. Polarizing plate, image display device comprising same and photocurable composition for polarizing plate protection layer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011138850A (en) * 2009-12-28 2011-07-14 Hitachi High-Technologies Corp Fine structure, method for producing fine structure, and polymerizable resin composition for production of fine structure
JP2012214526A (en) * 2011-03-28 2012-11-08 Hitachi Chemical Co Ltd Film adhesive, adhesive sheet and semiconductor apparatus
JP2013166893A (en) * 2012-02-16 2013-08-29 Jsr Corp Radiation-curable composition for stereophotolithography
JP2015048457A (en) * 2013-09-04 2015-03-16 積水化学工業株式会社 Connection material, connection structure and method for manufacturing connection structure

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0616874B2 (en) * 1985-10-15 1994-03-09 日産自動車株式会社 Wax coating device
JPS62290718A (en) * 1986-06-11 1987-12-17 Hitachi Ltd Epoxy resin composition and production of flyback transformer using same
JPH0735492B2 (en) * 1986-09-26 1995-04-19 三井石油化学工業株式会社 Hot water pipe inner surface coating composition
JPS63130627A (en) * 1986-11-21 1988-06-02 Toshiba Corp Resin composition for optical disk
JP2533348B2 (en) * 1988-01-06 1996-09-11 三井石油化学工業株式会社 Adhesive composition for vinyl halide resin
JPH03250042A (en) * 1990-02-28 1991-11-07 Yokohama Rubber Co Ltd:The Composition for rigid resin mold
JPH04126761A (en) * 1990-06-21 1992-04-27 Toray Ind Inc Thermosetting resin composition
JPH06136099A (en) * 1992-10-29 1994-05-17 Sanyo Chem Ind Ltd Resin composition for fiber-reinforced resin molding and molded product
JPH06287270A (en) * 1993-03-31 1994-10-11 Sanyo Chem Ind Ltd Resin composition for molding fiber-reinforced resin and molded article
JPH10195408A (en) * 1997-01-16 1998-07-28 Hitachi Chem Co Ltd Conductive resin paste composition and semiconductor device using the same
JPH10279658A (en) 1997-04-07 1998-10-20 Nippon Kayaku Co Ltd Active-energy-ray-curable resin composition and laminate prepared therefrom
JPH11181390A (en) * 1997-12-25 1999-07-06 Sumitomo Bakelite Co Ltd Ultraviolet-curable adhesive for sealing device hollow package
JPH11199651A (en) * 1998-01-12 1999-07-27 Sumitomo Bakelite Co Ltd Ultraviolet light-curable adhesive resin composition for sealing hollow package for device
JP2000191751A (en) * 1998-12-25 2000-07-11 Sumitomo Bakelite Co Ltd Ultraviolet light-curable type resin composition
JP2003313274A (en) 2002-04-25 2003-11-06 Dainippon Ink & Chem Inc Ultraviolet-curable composition and optical disk using the same
JP5349854B2 (en) * 2008-06-30 2013-11-20 株式会社日立製作所 Fine structure and manufacturing method thereof
DE112009001633B4 (en) * 2008-06-30 2013-06-27 Hitachi, Ltd. Fine structure and stamping
JP5446902B2 (en) 2009-03-05 2014-03-19 Ｄｉｃ株式会社 Cationic polymerizable adhesive and polarizing plate obtained using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011138850A (en) * 2009-12-28 2011-07-14 Hitachi High-Technologies Corp Fine structure, method for producing fine structure, and polymerizable resin composition for production of fine structure
JP2012214526A (en) * 2011-03-28 2012-11-08 Hitachi Chemical Co Ltd Film adhesive, adhesive sheet and semiconductor apparatus
JP2013166893A (en) * 2012-02-16 2013-08-29 Jsr Corp Radiation-curable composition for stereophotolithography
JP2015048457A (en) * 2013-09-04 2015-03-16 積水化学工業株式会社 Connection material, connection structure and method for manufacturing connection structure

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017071745A (en) * 2015-10-07 2017-04-13 アイカ工業株式会社 Photocurable resin composition and laminate
WO2017110951A1 (en) * 2015-12-25 2017-06-29 株式会社Adeka Curable composition, method for curing same, and cured product obtained thereby
US11171309B2 (en) 2016-12-09 2021-11-09 Lg Chem, Ltd. Encapsulating composition
CN109690806A (en) * 2016-12-09 2019-04-26 株式会社Lg化学 Encapsulating composition
JP2019526691A (en) * 2016-12-09 2019-09-19 エルジー・ケム・リミテッド Sealant composition
JP2018109143A (en) * 2016-12-28 2018-07-12 日本合成化学工業株式会社 Active energy ray-curable adhesive composition, adhesive composition for polarizing plate, adhesive for polarizing plate and polarizing plate using the same
WO2018159260A1 (en) * 2017-03-02 2018-09-07 東亞合成株式会社 Active-energy-ray-curable adhesive composition for plastic film or sheet
JP2020518952A (en) * 2017-04-28 2020-06-25 エルジー・ケム・リミテッド Sealing material composition
JP7020495B2 (en) 2017-04-28 2022-02-16 エルジー・ケム・リミテッド Sealing material composition
KR20190130660A (en) * 2017-07-28 2019-11-22 주식회사 다이셀 Monomer Mixture and Curable Composition Comprising the Same
KR102252659B1 (en) * 2017-07-28 2021-05-20 주식회사 다이셀 Monomer mixture and curable composition comprising the same
TWI741201B (en) * 2017-07-28 2021-10-01 日商大賽璐股份有限公司 Monomer mixture and curable composition containing the same
JP2019026820A (en) * 2017-07-28 2019-02-21 株式会社ダイセル Monomer mixture and curable composition containing the same
WO2019021934A1 (en) * 2017-07-28 2019-01-31 株式会社ダイセル Monomer mixture and curable composition containing same
US11339245B2 (en) 2017-07-28 2022-05-24 Daicel Corporation Monomer mixture and curable composition containing same
US11787971B2 (en) 2017-11-24 2023-10-17 Shanjin Optoelectronics (Suzhou) Co., Ltd. Polarizing plate, image display device comprising same and photocurable composition for polarizing plate protection layer
JP2020066643A (en) * 2018-10-22 2020-04-30 アイカ工業株式会社 Photocationic curing type epoxy resin composition
JP7128716B2 (en) 2018-10-22 2022-08-31 アイカ工業株式会社 Photo cationic curable epoxy resin composition

Also Published As

Publication number Publication date
KR20170133311A (en) 2017-12-05
KR102563226B1 (en) 2023-08-03
TW201700524A (en) 2017-01-01
TWI764862B (en) 2022-05-21
JP6879903B2 (en) 2021-06-02
CN107075082B (en) 2020-10-30
CN107075082A (en) 2017-08-18
JPWO2016158522A1 (en) 2018-01-18

Similar Documents

Publication Publication Date Title
KR102219443B1 (en) Cation-polymerizable composition
KR102563226B1 (en) Composition
JP6400005B2 (en) Cationic polymerizable composition
JP6284721B2 (en) Energy ray sensitive composition
KR102631774B1 (en) Curable composition, method for producing cured product, and cured product of same
TWI797078B (en) Curable composition, method for producing cured product, and cured product
WO2017110951A1 (en) Curable composition, method for curing same, and cured product obtained thereby
KR102265025B1 (en) Curable composition, manufacturing method of cured product, and cured product thereof
JP6251894B2 (en) Energy ray sensitive composition
WO2016158523A1 (en) Composition
JP6817702B2 (en) Curable composition, its curing method, the resulting cured product and adhesive
JP2018012765A (en) Curable composition, method for producing cured product, cured product thereof, and adhesive
JP2018172494A (en) Curable composition, method for producing cured product, cured product thereof, and adhesive using the same
JPWO2017170880A1 (en) Curable composition, method for producing cured product, and cured product thereof
JP2017179202A (en) Curable composition, manufacturing method of cured article and the cured article
JP6705623B2 (en) Cationic polymerizable composition
JP6163043B2 (en) Energy ray sensitive composition
JP2017179161A (en) Curable composition, manufacturing method of cured article and the cured article
JP2018012766A (en) Curable composition, method for producing cured product, and cured product thereof
JP2017179163A (en) Curable composition, manufacturing method of cured article and the cured article

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16772404

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017509582

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20177011479

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16772404

Country of ref document: EP

Kind code of ref document: A1