WO2015005211A1 - Cation-polymerizable composition - Google Patents

Cation-polymerizable composition Download PDF

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Publication number
WO2015005211A1
WO2015005211A1 PCT/JP2014/067779 JP2014067779W WO2015005211A1 WO 2015005211 A1 WO2015005211 A1 WO 2015005211A1 JP 2014067779 W JP2014067779 W JP 2014067779W WO 2015005211 A1 WO2015005211 A1 WO 2015005211A1
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WIPO (PCT)
Prior art keywords
epoxy compound
polymerizable composition
compound
cationically polymerizable
composition according
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PCT/JP2014/067779
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French (fr)
Japanese (ja)
Inventor
俊輔 高日
和彦 松土
智幸 岩島
浩之 五十嵐
英里 本間
智志 渡辺
泰延 大野
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株式会社Adeka
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Application filed by 株式会社Adeka filed Critical 株式会社Adeka
Priority to CN201480005618.5A priority Critical patent/CN104955866B/en
Priority to KR1020157020637A priority patent/KR102219443B1/en
Priority to JP2015526295A priority patent/JP6400006B2/en
Publication of WO2015005211A1 publication Critical patent/WO2015005211A1/en

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    • 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

Definitions

  • the present invention relates to a cationic polymerizable composition and a cured product obtained by irradiating the cationic polymerizable composition with active energy rays.
  • the cationically polymerizable 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 photocurable adhesives.
  • An object of the present invention is to provide a cationically polymerizable composition having excellent curability, adhesion and water resistance.
  • the present invention has been made on the basis of the above findings, and includes (1) an aromatic epoxy compound (1A) as a main component as a cationically polymerizable organic substance, and further an aliphatic epoxy compound (1B) or an alicyclic type.
  • an aromatic epoxy compound (1A) as a main component as a cationically polymerizable organic substance
  • an aliphatic epoxy compound (1B) or an alicyclic type By providing a cationically polymerizable composition characterized by comprising a cationically polymerizable organic substance mixture containing at least one of the epoxy compound (1C) and (2) an energy ray-sensitive cationic polymerization initiator. Is achieved.
  • the present invention also provides an adhesive comprising the above cationic polymerizable composition.
  • the cationically polymerizable composition of the present invention is particularly useful as an adhesive because it is excellent in curability, adhesiveness and water resistance.
  • the cationic polymerizable organic substance constituting the mixture is polymerized or crosslinked by an energy ray sensitive cationic polymerization initiator activated by light irradiation.
  • An epoxy compound is preferable.
  • an aromatic epoxy compound (1A), an alicyclic epoxy compound (1C), an aliphatic epoxy compound (1B), or a high molecular weight compound (1D) having an epoxy group and having a weight average molecular weight of 1,000 to 1,000,000 is used. be able to.
  • a vinyl ether compound or an oxetane compound (1E) is used as the cationically polymerizable organic substance.
  • the aromatic epoxy compound (1A) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include monovalent phenols having at least one aromatic ring such as phenol, cresol, and butylphenol.
  • mono / polyglycidyl etherified products of the alkylene oxide adducts such as bisphenol A, bisphenol F, or glycidyl etherified products of compounds obtained by further adding alkylene oxide to these and epoxy novolac resins; two such as resorcinol, hydroquinone and catechol Glycidyl ethers of aromatic compounds having the above phenolic hydroxyl groups; mono / polyglycidic aromatic compounds having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol Ruetherified products: glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, gly
  • glycidyl ethers of phenols glycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups
  • glycidyl ethers of polyphenols glycidyl esters of benzoic acids
  • glycidyl esters of polybasic acids glycidyl esters of polybasic acids
  • styrene oxide or divinyl It is preferable to contain at least one selected from the group of epoxidized benzene from the viewpoint of reducing the viscosity of the composition.
  • aromatic epoxy compound those having an epoxy equivalent of 80 to 500 are preferable because of excellent curability.
  • the aromatic epoxy compound (1A) commercially available products can be used.
  • the aromatic epoxy compound (1A) preferably contains at least one polyfunctional epoxy compound from the viewpoints of curability and adhesiveness.
  • the cationically polymerizable composition of the present invention preferably contains 25 to 70 parts by mass of the polyfunctional aromatic epoxy compound (1A) with respect to 100 parts by mass of (1) the cationically polymerizable organic substance mixture, More preferably, 60 parts by mass is contained.
  • the amount of (1A) includes the amount corresponding to (1D).
  • alicyclic epoxy compound (1C) is 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.
  • 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).
  • the aliphatic epoxy compound (1B) refers to an epoxy compound that is not classified as the aromatic epoxy compound (1A) or the alicyclic epoxy compound (1C).
  • Specific examples of the aliphatic epoxy compound include aliphatic alcohols.
  • An epoxy compound is mentioned.
  • Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C 1 2-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, glycidyl ether of polyhydric alcohol such as diglycidyl ether of polypropylene glycol, In addition, one or two or more alkyl polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin are used.
  • Polyglycidyl ethers of polyether polyols obtained by adding emission oxide include 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. As the aliphatic epoxy compound (1B), those having an epoxy equivalent of 80 to 500 are preferable.
  • aliphatic epoxy compound (1B) commercially available products can be used.
  • the cationically polymerizable composition of this invention contains at least 1 type of a polyfunctional epoxy compound as said aliphatic epoxy compound (1B) or alicyclic epoxy compound (1C).
  • the cationically polymerizable composition of the present invention is (1) the sum of the polyfunctional aliphatic epoxy compound (1B) and the polyfunctional alicyclic epoxy compound (1C) with respect to 100 parts by mass of the cationically polymerizable organic substance mixture.
  • the amount is preferably 10 to 65 parts by mass, particularly 20 to 50 parts by mass.
  • the content of the polyfunctional aliphatic epoxy compound (1B) is preferably 10 to 45 parts by mass with respect to (1) 100 parts by mass of the cation polymerizable organic substance mixture, and the polyfunctional alicyclic epoxy compound
  • the content of (1C) is preferably 0 to 10 parts by mass.
  • the amounts of (1B) and (1C) are amounts including those corresponding to (1D).
  • Examples of the high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group include a polymer obtained by radical polymerization, and homopolymerizing one kind of ethylenically unsaturated monomer having a cationic polymerizable substituent. Preferred is a polymer copolymerized with an ethylenically unsaturated monomer that does not have a polymer or a cationically polymerizable substituent.
  • the ethylenically unsaturated monomer constituting the high molecular weight product (1D) having a weight average molecular weight of 1,000 to 1,000,000 having the epoxy group is not particularly limited, and known ones can be used.
  • an example of an ethylenically unsaturated monomer having no cationically polymerizable substituent includes a group represented by the following general formula (1), and an ethylenically unsaturated group having a cationically polymerizable substituent.
  • the monomer one or more hydrogen atoms in the alkyl group, aryl group or alicyclic hydrocarbon group in the following general formula (1) are substituted with an epoxy group, an oxetane group or a vinyl ether group. Groups.
  • R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or 6 to 12 carbon atoms.
  • An aryl group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, and a methylene group in these groups may be substituted with —CO—, —O— or —COO—)
  • the high molecular weight body (1D) contains 10 to 10 ethylenically unsaturated monomers having a structure substituted with a cationic polymerizable substituent such as an epoxy group, an oxetane group or a vinyl ether group.
  • methyl group, ethyl group or branched alkyl group having 3 to 7 carbon atoms, aryl group having 6 to 12 carbon atoms, 6 to 10 carbon atoms, which is not substituted with a cationic polymerizable substituent The content of the ethylenically unsaturated monomer substituted with an alicyclic hydrocarbon group is preferably 20 to 90% by mass, and the total together with other ethylenically unsaturated monomers is preferably 100% by mass.
  • the high molecular weight product (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group preferably has a weight average molecular weight of 5,000 to 100,000, more preferably 7,000 to 70,000.
  • Examples of the vinyl ether compound or oxetane compound (1E) include ethylene glycol divinyl 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.
  • the vinyl ether compound preferably has a molecular weight of 58 to 500, more preferably 70 to 300.
  • the oxetane compound preferably has a molecular weight of 100 to 1000, more preferably 110 to 500.
  • the vinyl ether compound or oxetane compound (1E) may be monofunctional or polyfunctional, but has one or two vinyl ether groups or oxetane groups having one or two vinyl ether groups. It is preferable to use an oxetane compound.
  • vinyl ether compound or oxetane compound (1E) commercially available products mainly composed of a cationic polymerizable monomer can be used.
  • the molecular weight (1D), vinyl ether compound, or oxetane compound (1E) is used in an amount of (1) 25 to 70 parts by mass, especially 30 parts by mass of the aromatic epoxy compound (1A) with respect to 100 parts by mass of the cationic polymerizable organic substance mixture.
  • the amounts of (1B) and (1C) are amounts excluding those corresponding to the above (1D), and the amount of (1A) is an amount including those corresponding to (1D).
  • the main component means a mixture of several types of epoxy compounds and the largest total amount of the same type of epoxy compounds, and the cationically polymerizable organic substance mixture contains a cationically polymerizable organic substance other than the epoxy compound.
  • the total amount of the several types of epoxy compounds having the largest total amount is greater than the total amount of the cationically polymerizable organic material other than the epoxy compound.
  • the total amount of each type of epoxy compound includes those corresponding to (1D).
  • the (2) energy ray-sensitive cationic polymerization initiator used in the present invention may be any compound that can release a substance that initiates cationic polymerization by irradiation with energy rays, but is preferably 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: Listed is a salt of a cation and an anion represented by [A] r + [B] r- (wherein A represents a cation species, B represents an anion species, and r represents a valence). be able to.
  • the cation [A] r + is preferably onium, and the structure thereof is, for example, the following general formula: [(R 1 ) a Q] r + It can be expressed as
  • R 1 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 1 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.
  • anion [B] r- is preferably a halide complex, and the structure thereof is, for example, the following general formula: [LX b ] r- It 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 ] r- in 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: [LX b-1 (OH)] r-
  • 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.
  • Trinitrobenzenesulfonate anion camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
  • onium salts it is particularly effective to use the following aromatic onium salts (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
  • 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 (2) energy ray sensitive cationic polymerization initiator to the above (1) cationic polymerizable organic substance mixture is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention.
  • a silane coupling agent can be used as necessary.
  • the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane.
  • 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 cationic polymerizable 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 glycid
  • 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, Decanedioic 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 diacid, hydrogenated dimer acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, Tri
  • 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 amount of solids in the cationic polymerizable composition.
  • an initiator it is preferable to heat the cationically polymerizable composition of the present invention at 130 to 180 ° C. for 20 minutes to 1 hour.
  • a cured product can be obtained by using a thermoplastic organic polymer (excluding a high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group) as necessary. It is possible to improve the characteristics.
  • a thermoplastic organic polymer excluding a high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group
  • 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 cationically polymerizable composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (1) and (2) that are usually used can be used.
  • a solvent that can dissolve or disperse the components (1) and (2) that are usually used can be used.
  • methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, Ether solvents such as dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate,
  • BTX solvents aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; terpenes such as turpentine oil, D-limonene, and pinene Hydrocarbon oils; paraffinic solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2- Halogenated aliphatic hydrocarbon solvents such as dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- Examples thereof include dimethylformamide, N, N-dimethylacetamide, N-methylpyrrol
  • the total amount of optional components other than (1) the cationic polymerizable organic substance mixture and (2) the energy ray sensitive cationic polymerization initiator depends on the use of the present invention, etc. From the viewpoint of further enhancing the effects of the present invention, (1) it is preferably 20 parts by mass or less, particularly 10 parts by mass or less with respect to 100 parts by mass of the cationically polymerizable organic substance mixture.
  • the cationically polymerizable composition of the present invention has a water content of preferably 5% by mass or less, and more preferably 3% by mass or less from the viewpoints of curability, adhesiveness, and liquid storage stability. Too much moisture is not preferable because it may cause cloudiness or components may precipitate. The amount of water is measured by the method described in the examples described later.
  • the cationic polymerizable composition of the present invention preferably has a viscosity of 200 mPa ⁇ s or less, more preferably 10 to 150 mPa ⁇ s, from the viewpoint of coating properties.
  • This viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.
  • the cationically polymerizable 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 acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polymer materials such as oxyethylene, norbornene resin, and cycloolefin polymer (COP) can be used.
  • 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.
  • the cationic polymerizable composition of the present invention is cured by irradiation with active energy rays.
  • active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are the most economical.
  • ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
  • cationically polymerizable 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, and insulation. Varnish, insulating sheet, laminate, printed circuit board, sealing agent for molding of semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic components, separation membranes, etc. Materials, putty, glass fiber impregnating agent, sealant, semiconductor / solar cell passivation film, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display, screen for projection TV, etc.
  • the lens portion of a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet, or a bag using such a sheet.
  • a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet, or a bag using such a sheet.
  • Examples include light, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical molding casting agents, etc.
  • substrates that can be used as coating agents include metals, wood, rubber, and plastics. , Glass, ceramic products and the like.
  • cationic polymerizable composition of the present invention and the cured product obtained by curing the cationic polymerizable composition will be described in detail with reference to examples, evaluation examples, and comparative examples.
  • “part” means “part by mass”
  • “%” means “% by mass”.
  • Examples 1-30, Comparative Examples 1-2 The components shown in [Table 1] to [Table 3] below were mixed thoroughly to obtain Example Compositions 1 to 30 and Comparative Compositions 1 and 2, respectively.
  • Compound 1A-1 Resorcinol diglycidyl ether compound 1A-2: Diglycidyl o-phthalate compound 1A-3: Divinylbenzene oxide compound 1A-4: Phenyl glycidyl ether compound 1A-5: Styrene oxide compound 1A-6: EP-4100L ( Bisphenol A epoxy: manufactured by ADEKA) Compound 1A-7: Adeka Resin EP-4901L Compound 1A-8: Adeka Resin EP-4000L Compound 1A-9: TECHMORE VG-3101L Compound 1A-10: Adekaglycil ED-509S (manufactured by ADEKA) Compound 1A-11: Adekaglycilol ED-501 (manufactured by ADEKA) Compound 1A-12: Adekaglycil ED-529 (manufactured by ADEKA) Compound 1B-1: Neopentyl glycol diglycidyl ether compound 1B-2: Triglycid
  • Example Compositions 1 to 30 and Comparative Compositions 1 to 2 were applied to a COP (cycloolefin polymer) film that had been subjected to corona discharge treatment, and then the film was laminated using a laminator.
  • COP cycloolefin polymer
  • a test piece was obtained by bonding to another COP (cycloolefin polymer) film that had been subjected to corona discharge treatment, and using an electrodeless ultraviolet lamp to irradiate with 1000 mJ / cm 2 of energy.
  • a 90 degree peel test is performed on the obtained test piece.
  • a specimen having a strength of 2.0 N / cm or more is indicated by ⁇ , a specimen having a strength of 1.0 to 2.0 N / cm is ⁇ , and a specimen having a strength of 1.0 N / cm or less.
  • the results are shown in [Table 1] to [Table 5].
  • (amount of water) The water content of each of the obtained practical compositions 1-30 and the comparative compositions 1-2 was measured according to the Karl Fischer method. The results are shown in the above [Table 1] to [Table 5].

Abstract

A cation-polymerizable composition according to the present invention comprises: (1) a cation-polymerizable organic substance mixture that contains an aromatic epoxy compound (1A), which serves as the main component, and also contains an aliphatic epoxy compound (1B) and/or an alicyclic epoxy compound (1C) as cation-polymerizable organic substances; and (2) an energy ray-sensitive cation polymerization initiator. It is preferred that at least one polyfunctional epoxy compound is contained as the aliphatic epoxy compound (1B) or the alicyclic epoxy compound (1C).

Description

カチオン重合性組成物Cationic polymerizable composition
　本発明は、カチオン重合性組成物及び該カチオン重合性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。該カチオン重合性組成物は、特に接着剤に有用である。 The present invention relates to a cationic polymerizable composition and a cured product obtained by irradiating the cationic polymerizable composition with active energy rays. The cationically polymerizable 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、種々の光硬化性接着剤が開示されている。 For example, the following Patent Documents 1 to 3 disclose various photocurable adhesives.
特開２０１１－２３６３８９号公報JP 2011-236389 A 特開２０１２－１４９２６２号公報JP 2012-149262 A 国際公開２００８／１１１５８４号公報International Publication No. 2008/111484
　本発明の目的は、硬化性、接着性及び耐水性に優れるカチオン重合性組成物を提供することにある。 An object of the present invention is to provide a cationically polymerizable composition having excellent curability, adhesion and water resistance.
　本発明は、上記知見に基づいてなされたもので、（１）カチオン重合性有機物質として、芳香族エポキシ化合物（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）又は脂環式エポキシ化合物（１Ｃ）の少なくとも一方を含有するカチオン重合性有機物質混合物、及び（２）エネルギー線感受性カチオン重合開始剤を含有することを特徴とするカチオン重合性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 findings, and includes (1) an aromatic epoxy compound (1A) as a main component as a cationically polymerizable organic substance, and further an aliphatic epoxy compound (1B) or an alicyclic type. By providing a cationically polymerizable composition characterized by comprising a cationically polymerizable organic substance mixture containing at least one of the epoxy compound (1C) and (2) an energy ray-sensitive cationic polymerization initiator. Is achieved.
　また、本発明は、上記カチオン重合性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 cationic polymerizable composition.
　本発明のカチオン重合性組成物は、硬化性、接着性及び耐水性に優れるため、接着剤用途として特に有用なものである。 The cationically polymerizable composition of the present invention is particularly useful as an adhesive because it is excellent in curability, adhesiveness and water resistance.
　以下、本発明のカチオン重合性組成物及び該カチオン重合性組成物からなる接着剤について詳細に説明する。 Hereinafter, the cationic polymerizable composition of the present invention and the adhesive comprising the cationic polymerizable composition will be described in detail.
　本発明に使用する前記（１）カチオン重合性有機物質混合物において、該混合物を構成するカチオン重合性有機物質は、光照射により活性化したエネルギー線感受性カチオン重合開始剤により高分子化または、架橋反応を起こす化合物であり、エポキシ化合物が好ましい。該エポキシ化合物としては、芳香族エポキシ化合物（１Ａ）、脂環式エポキシ化合物（１Ｃ）、脂肪族エポキシ化合物（１Ｂ）、エポキシ基を有する重量平均分子量１０００～１００００００の高分子量体（１Ｄ）を用いることができる。また、カチオン重合性有機物質としては、その他、ビニルエーテル化合物又はオキセタン化合物（１Ｅ）が用いられる。 In the (1) cationic polymerizable organic substance mixture used in the present invention, the cationic polymerizable organic substance constituting the mixture is polymerized or crosslinked by an energy ray sensitive cationic polymerization initiator activated by light irradiation. An epoxy compound is preferable. As the epoxy compound, an aromatic epoxy compound (1A), an alicyclic epoxy compound (1C), an aliphatic epoxy compound (1B), or a high molecular weight compound (1D) having an epoxy group and having a weight average molecular weight of 1,000 to 1,000,000 is used. be able to. In addition, as the cationically polymerizable organic substance, a vinyl ether compound or an oxetane compound (1E) is used.
　上記芳香族エポキシ化合物（１Ａ）とは、芳香環を含むエポキシ化合物を指し、該芳香族エポキシ化合物の具体例としては、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モノ／ポリ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。
　中でも、フェノール類のグリシジルエーテル、アルコール性水酸基を２個以上有する芳香族化合物のグリシジルエーテル化物、多価フェノール類のグリシジルエーテル化物、安息香酸類のグリシジルエステル、多塩基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の群から選ばれる少なくとも一種含有することが組成物の低粘度化の観点から好ましい。
　上記芳香族エポキシ化合物としては、エポキシ当量が８０～５００であるものが、硬化性に優れるため好ましい。 The aromatic epoxy compound (1A) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include monovalent phenols having at least one aromatic ring such as phenol, cresol, and butylphenol. Alternatively, mono / polyglycidyl etherified products of the alkylene oxide adducts such as bisphenol A, bisphenol F, or glycidyl etherified products of compounds obtained by further adding alkylene oxide to these and epoxy novolac resins; two such as resorcinol, hydroquinone and catechol Glycidyl ethers of aromatic compounds having the above phenolic hydroxyl groups; mono / polyglycidic aromatic compounds having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol Ruetherified products: glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, glycidyl esters of benzoic acids such as benzoic acid, toluic acid, naphthoic acid, styrene oxide Or the epoxidized substance of divinylbenzene etc. are mentioned.
Among them, glycidyl ethers of phenols, glycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, glycidyl ethers of polyphenols, glycidyl esters of benzoic acids, glycidyl esters of polybasic acids, styrene oxide or divinyl It is preferable to contain at least one selected from the group of epoxidized benzene from the viewpoint of reducing the viscosity of the composition.
As the aromatic epoxy compound, those having an epoxy equivalent of 80 to 500 are preferable because of excellent curability.
　上記芳香族エポキシ化合物（１Ａ）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－１４１、デナコールＥＸ－１４２、デナコールＥＸ－１４５、デナコールＥＸ－１４６、デナコールＥＸ－１４７、デナコールＥＸ－２０１、デナコールＥＸ－２０３、デナコールＥＸ－７１１、デナコールＥＸ－７２１、オンコートＥＸ－１０２０、オンコートＥＸ－１０３０、オンコートＥＸ－１０４０、オンコートＥＸ－１０５０、オンコートＥＸ－１０５１、オンコートＥＸ－１０１０、オンコートＥＸ－１０１１、オンコート１０１２（ナガセケムテックス社製）；オグソールＰＧ－１００、オグソールＥＧ－２００、オグソールＥＧ－２１０、オグソールＥＧ－２５０（大阪ガスケミカル社製）；ＨＰ４０３２、ＨＰ４０３２Ｄ、ＨＰ４７００（ＤＩＣ社製）；ＥＳＮ－４７５Ｖ（新日鉄住金化学社製）；エピコートＹＸ８８００（三菱化学社製）；マープルーフＧ－０１０５ＳＡ、マープルーフＧ－０１３０ＳＰ（日油社製）；エピクロンＮ－６６５、エピクロンＨＰ－７２００（ＤＩＣ社製）；ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＸＤ－１０００、ＮＣ－３０００、ＥＰＰＮ－５０１Ｈ、ＥＰＰＮ－５０１ＨＹ、ＥＰＰＮ－５０２Ｈ、ＮＣ－７０００Ｌ（日本化薬社製）；アデカグリシロールＥＤ－５０１、アデカグリシロールＥＤ－５０２、アデカグリシロールＥＤ－５０９、アデカグリシロールＥＤ－５２９、アデカレジンＥＰ－４０００、アデカレジンＥＰ－４００５、アデカレジンＥＰ－４１００、アデカレジンＥＰ－４９０１（ＡＤＥＫＡ社製）；ＴＥＣＨＭＯＲＥ　ＶＧ－３１０１Ｌ、ＥＰＯＸ－ＭＫＲ７１０、ＥＰＯＸ－ＭＫＲ１５１（プリンテック社製）等が挙げられる。 As the aromatic epoxy compound (1A), commercially available products can be used. For example, Denacol EX-121, Denacol EX-141, Denacol EX-142, Denacol EX-145, Denacol EX-146, Denacol EX -147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX -1051, ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT 1012 (manufactured by Nagase ChemteX); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical Co., Ltd.) ); HP4032, HP4032D, HP4700 (manufactured by DIC); ESN-475V (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epicoat YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation) Epicron N-665, Epicron HP-7200 (manufactured by DIC); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN- 502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); Adekaglycilol ED-501, Adekaglycilol ED-502, Adekaglycilol ED-509, Adekaglycilol ED-529, Adekaresin EP-4000, Adekaresin EP-400 , Adecaresin EP-4100, ADEKA RESIN EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L, EPOX-MKR710, etc. EPOX-MKR151 (manufactured by purine Tech Co., Ltd.).
　上記芳香族エポキシ化合物（１Ａ）として、多官能エポキシ化合物を少なくとも一種含有することが、硬化性及び接着性の観点から好ましい。本発明のカチオン重合性組成物は、（１）カチオン重合性有機物質混合物１００質量部に対し、多官能の芳香族エポキシ化合物（１Ａ）を、２５～７０質量部含有することが好ましく、３０～６０質量部含有することが更に好ましい。
　ここで上記（１Ａ）の量は（１Ｄ）に該当するものを含む量である。 The aromatic epoxy compound (1A) preferably contains at least one polyfunctional epoxy compound from the viewpoints of curability and adhesiveness. The cationically polymerizable composition of the present invention preferably contains 25 to 70 parts by mass of the polyfunctional aromatic epoxy compound (1A) with respect to 100 parts by mass of (1) the cationically polymerizable organic substance mixture, More preferably, 60 parts by mass is contained.
Here, the amount of (1A) includes the amount corresponding to (1D).
　上記脂環式エポキシ化合物（１Ｃ）の具体例としては、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また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。たとえば、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、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－メチルシクロヘキサンカルボキシレート、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、α－ピネンオキシド、リモネンジオキシド等が挙げられる。
　脂環式エポキシ化合物（１Ｃ）としては、エポキシ当量が８０～５００であるものが好ましい。 Specific examples of the alicyclic epoxy compound (1C) 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. 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, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexa Carboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diene Epoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy -2-Epoxyethylcyclohexane, α-pinene oxide, limonene dioxide and the like.
As the alicyclic epoxy compound (1C), those having an epoxy equivalent of 80 to 500 are preferable.
　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).
　上記脂肪族エポキシ化合物（１Ｂ）とは、上記芳香族エポキシ化合物（１Ａ）や脂環式エポキシ化合物（１Ｃ）に分類されないエポキシ化合物を指し、該脂肪族エポキシ化合物の具体例としては、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また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、２-エチルヘキシルグリシジルエーテル、Ｃ １ ２～１３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、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など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種または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。
　脂肪族エポキシ化合物（１Ｂ）としては、エポキシ当量が８０～５００であるものが好ましい。 The aliphatic epoxy compound (1B) refers to an epoxy compound that is not classified as the aromatic epoxy compound (1A) or the alicyclic epoxy compound (1C). Specific examples of the aliphatic epoxy compound include aliphatic alcohols. Polyfunctional glycidyl ethers, monofunctional epoxy compounds such as glycidyl esters of alkyl carboxylic acids, polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyfunctional glycidyl esters of aliphatic long-chain polybasic acids, etc. An epoxy compound is mentioned. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C 1 2-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, glycidyl ether of polyhydric alcohol such as diglycidyl ether of polypropylene glycol, In addition, one or two or more alkyl polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin are used. Polyglycidyl ethers of polyether polyols obtained by adding emission oxide include 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.
As the aliphatic epoxy compound (1B), those having an epoxy equivalent of 80 to 500 are preferable.
　前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）、アデカグリシロールＥＤ－５０３、アデカグリシロールＥＤ－５０３Ｇ、アデカグリシロールＥＤ－５０６、アデカグリシロールＥＤ－５２３Ｔ（ＡＤＥＫＡ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.), Adeka Glycilol ED-503, Adeka Glycilol ED-503G, Adeka Glycilol ED-506, Adeka Glycilol ED-523T (made by ADEKA) etc. are mentioned.
　また、本発明のカチオン重合性組成物は、上記の脂肪族エポキシ化合物（１Ｂ）又は脂環式エポキシ化合物（１Ｃ）として、多官能エポキシ化合物を少なくとも一種含有することが好ましい。本発明のカチオン重合性組成物は、（１）カチオン重合性有機物質混合物１００質量部に対して、多官能の脂肪族エポキシ化合物（１Ｂ）及び多官能の脂環式エポキシ化合物（１Ｃ）の合計量が、１０～６５質量部、特に２０～５０質量部であることが好ましい。また、（１）カチオン重合性有機物質混合物１００質量部に対し、多官能の脂肪族エポキシ化合物（１Ｂ）の含有量が１０～４５質量部であることが好ましく、多官能の脂環式エポキシ化合物（１Ｃ）の含有量が０～１０質量部であることが好ましい。
ここで上記（１Ｂ）及び（１Ｃ）の量は（１Ｄ）に該当するものを含む量である。 Moreover, it is preferable that the cationically polymerizable composition of this invention contains at least 1 type of a polyfunctional epoxy compound as said aliphatic epoxy compound (1B) or alicyclic epoxy compound (1C). The cationically polymerizable composition of the present invention is (1) the sum of the polyfunctional aliphatic epoxy compound (1B) and the polyfunctional alicyclic epoxy compound (1C) with respect to 100 parts by mass of the cationically polymerizable organic substance mixture. The amount is preferably 10 to 65 parts by mass, particularly 20 to 50 parts by mass. The content of the polyfunctional aliphatic epoxy compound (1B) is preferably 10 to 45 parts by mass with respect to (1) 100 parts by mass of the cation polymerizable organic substance mixture, and the polyfunctional alicyclic epoxy compound The content of (1C) is preferably 0 to 10 parts by mass.
Here, the amounts of (1B) and (1C) are amounts including those corresponding to (1D).
　上記エポキシ基を有する重量平均分子量１０００～１００００００の高分子量体（１Ｄ）としては、ラジカル重合により得られる重合体が挙げられ、カチオン重合性置換基を有するエチレン性不飽和単量体一種を単独重合した重合体あるいはカチオン重合性置換基を有さないエチレン性不飽和単量体と共重合した重合体が好ましい。 Examples of the high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group include a polymer obtained by radical polymerization, and homopolymerizing one kind of ethylenically unsaturated monomer having a cationic polymerizable substituent. Preferred is a polymer copolymerized with an ethylenically unsaturated monomer that does not have a polymer or a cationically polymerizable substituent.
　上記エポキシ基を有する重量平均分子量１０００～１００００００の高分子量体（１Ｄ）を構成するエチレン性不飽和単量体としては、特に制限されず公知のものを用いることができる。例えば、カチオン重合性置換基を有さないエチレン性不飽和単量体の一例としては、以下の一般式（１）で表される基が挙げられ、カチオン重合性置換基を有するエチレン性不飽和単量体の一例としては、以下の一般式（１）におけるアルキル基、アリール基又は脂環式炭化水素基中の１又は２以上の水素原子がエポキシ基、オキセタン基又はビニルエーテル基に置換された基が挙げられる。 The ethylenically unsaturated monomer constituting the high molecular weight product (1D) having a weight average molecular weight of 1,000 to 1,000,000 having the epoxy group is not particularly limited, and known ones can be used. For example, an example of an ethylenically unsaturated monomer having no cationically polymerizable substituent includes a group represented by the following general formula (1), and an ethylenically unsaturated group having a cationically polymerizable substituent. As an example of the monomer, one or more hydrogen atoms in the alkyl group, aryl group or alicyclic hydrocarbon group in the following general formula (1) are substituted with an epoxy group, an oxetane group or a vinyl ether group. Groups.
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ１１、Ｒ１２、Ｒ１３及びＲ１４はそれぞれ独立に、水素原子、炭素原子数１～１０の直鎖状、分岐鎖状若しくは環状のアルキル基、炭素原子数６～１２のアリール基又は炭素原子数６～１０の脂環式炭化水素基であり、これらの基中のメチレン基は－ＣＯ－、－Ｏ－又は－ＣＯＯ－で置換されていてもよい）
Figure JPOXMLDOC01-appb-C000001
 (Wherein R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or 6 to 12 carbon atoms. An aryl group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, and a methylene group in these groups may be substituted with —CO—, —O— or —COO—)
　また、上記の共重合体の場合、高分子量体（１Ｄ）は、エポキシ基、オキセタン基、ビニルエーテル基等のカチオン重合性置換基で置換された構造を有するエチレン性不飽和単量体を１０～８０質量％含有し、カチオン重合性置換基で置換されていないメチル基、エチル基又は炭素原子数３～７の分岐アルキル基、炭素原子数６～１２のアリール基、炭素原子数６～１０の脂環式炭化水素基で置換されたエチレン性不飽和単量体を２０～９０質量％含有し、その他のエチレン性不飽和単量体と合わせて合計で１００質量％となるのが好ましい。 In the case of the above copolymer, the high molecular weight body (1D) contains 10 to 10 ethylenically unsaturated monomers having a structure substituted with a cationic polymerizable substituent such as an epoxy group, an oxetane group or a vinyl ether group. 80% by mass of methyl group, ethyl group or branched alkyl group having 3 to 7 carbon atoms, aryl group having 6 to 12 carbon atoms, 6 to 10 carbon atoms, which is not substituted with a cationic polymerizable substituent The content of the ethylenically unsaturated monomer substituted with an alicyclic hydrocarbon group is preferably 20 to 90% by mass, and the total together with other ethylenically unsaturated monomers is preferably 100% by mass.
　上記エポキシ基を有する重量平均分子量１０００～１００００００の高分子量体（１Ｄ）は、重量平均分子量５０００～１０００００であるのが好ましく、さらに好ましくは７０００～７００００である。 The high molecular weight product (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group preferably has a weight average molecular weight of 5,000 to 100,000, more preferably 7,000 to 70,000.
　上記ビニルエーテル化合物又はオキセタン化合物（１Ｅ）としては、エチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、ｎ－ドデシルビニルエーテル、シクロヘキシルビニルエーテル、２－エチルヘキシルビニルエーテル、２－クロロエチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテル、トリエチレングリコールビニルエーテル、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、１，６－シクロヘキサンジメタノールモノビニルエーテル、１，４－ブタンジオールモノビニルエーテル、ジエチレングリコールモノビニルエーテル、１，４－ブタンジオールジビニルエーテル、１，６－シクロヘキサンジメタノールジビニルエーテル等のビニルエーテル化合物；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、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）オキセタン等のオキセタン化合物等が挙げられる。ビニルエーテル化合物としては、分子量が５８～５００のものが好ましく、７０～３００のものが好ましい。オキセタン化合物としては、分子量が１００～１０００のものが好ましく、１１０～５００のものが好ましい。また上記ビニルエーテル化合物又はオキセタン化合物（１Ｅ）としては、単官能及び多官能のいずれのものを用いることもできるが、ビニルエーテル基を１個若しくは２個有するビニルエーテル化合物又はオキセタン基を１個若しくは２個有するオキセタン化合物を用いることが好ましい。 Examples of the vinyl ether compound or oxetane compound (1E) include ethylene glycol divinyl 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-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, 1,4-butanediol monovinyl ether, diethylene glycol monovinyl ether, 1,4-butanediol divinyl ether, 1,6 -Vinyl ethers such as cyclohexanedimethanol divinyl ether Compound: 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, 1,6-bis ( 3-Ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3-[(phenoxy) methyl] oxeta 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (chloro And oxetane compounds such as methyl) oxetane. The vinyl ether compound preferably has a molecular weight of 58 to 500, more preferably 70 to 300. The oxetane compound preferably has a molecular weight of 100 to 1000, more preferably 110 to 500. The vinyl ether compound or oxetane compound (1E) may be monofunctional or polyfunctional, but has one or two vinyl ether groups or oxetane groups having one or two vinyl ether groups. It is preferable to use an oxetane compound.
　上記ビニルエーテル化合物又はオキセタン化合物（１Ｅ）としては、カチオン重合性モノマーを主成分とする市販品のものを用いることができ、例えば、２－ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル、4－ヒドロキシブチルビニルエーテル（丸善石油化学社製）；アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＥＸＯＨ、ＰＯＸ、ＯＸＡ、ＯＸＴ－１０１、ＯＸＴ－２１１、ＯＸＴ－２１２（東亞合成社製）、エタナコールＯＸＢＰ、ＯＸＴＰ（宇部興産社製）等が挙げられる。 As the vinyl ether compound or oxetane compound (1E), commercially available products mainly composed of a cationic polymerizable monomer can be used. For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen) Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), Etanacol OXBP, OXTP (manufactured by Ube Industries) Etc.
　上記（１）カチオン重合性有機物質混合物において、上記芳香族エポキシ化合物（１Ａ）、脂環式エポキシ化合物（１Ｃ）、脂肪族エポキシ化合物（１Ｂ）、エポキシ基を有する重量平均分子量１０００～１００００００の高分子量体（１Ｄ）、ビニルエーテル化合物又はオキセタン化合物（１Ｅ）の使用割合は、（１）カチオン重合性有機物質混合物１００質量部に対して、芳香族エポキシ化合物（１Ａ）２５～７０質量部、特に３０～６０質量部、脂環式エポキシ化合物（１Ｃ）０～４５質量部、特に０～３０質量部、脂肪族エポキシ化合物（１Ｂ）０～４５質量部、特に１０～４０質量部、エポキシ基を有する重量平均分子量１０００～１００００００の高分子量体（１Ｄ）０～５０質量部、特に０～１５質量部、ビニルエーテル化合物又はオキセタン化合物（１Ｅ）０～３０質量部、特に０～２５質量部であり、脂環式エポキシ化合物（１Ｃ）と脂肪族エポキシ化合物（１Ｂ）の和は０ではなく、芳香族エポキシ化合物（１Ａ）が主成分となるように用いるのが好ましい。
　ただし、ここで（１Ｂ）及び（１Ｃ）の量は上記（１Ｄ）に該当するものは除く量であり、（１Ａ）の量は（１Ｄ）に該当するものを含む量である。
　ここで、主成分とは、エポキシ化合物を数種類混ぜて、同じ種類のエポキシ化合物の合計量が一番多いものを言い、カチオン重合性有機物質混合物がエポキシ化合物以外のカチオン重合性有機物質を含む場合、数種類のエポキシ化合物のうち合計量が一番多い種類の該合計量は、エポキシ化合物以外のカチオン重合性有機物質の合計量よりも多いものとする。ここでいう各種類のエポキシ化合物の合計量には、（１Ｄ）に該当するものを含む。 (1) In the cationically polymerizable organic substance mixture, the aromatic epoxy compound (1A), the alicyclic epoxy compound (1C), the aliphatic epoxy compound (1B), a high weight average molecular weight of 1,000 to 1,000,000 having an epoxy group The molecular weight (1D), vinyl ether compound, or oxetane compound (1E) is used in an amount of (1) 25 to 70 parts by mass, especially 30 parts by mass of the aromatic epoxy compound (1A) with respect to 100 parts by mass of the cationic polymerizable organic substance mixture. ~ 60 parts by weight, alicyclic epoxy compound (1C) 0 to 45 parts by weight, especially 0 to 30 parts by weight, aliphatic epoxy compound (1B) 0 to 45 parts by weight, especially 10 to 40 parts by weight, having an epoxy group 0 to 50 parts by mass, particularly 0 to 15 parts by mass of a high molecular weight product (1D) having a weight average molecular weight of 1,000 to 1,000,000, vinyl ether compound Or 0 to 30 parts by mass, particularly 0 to 25 parts by mass of the oxetane compound (1E), and the sum of the alicyclic epoxy compound (1C) and the aliphatic epoxy compound (1B) is not 0, and the aromatic epoxy compound (1A ) Is preferably used as a main component.
Here, the amounts of (1B) and (1C) are amounts excluding those corresponding to the above (1D), and the amount of (1A) is an amount including those corresponding to (1D).
Here, the main component means a mixture of several types of epoxy compounds and the largest total amount of the same type of epoxy compounds, and the cationically polymerizable organic substance mixture contains a cationically polymerizable organic substance other than the epoxy compound. The total amount of the several types of epoxy compounds having the largest total amount is greater than the total amount of the cationically polymerizable organic material other than the epoxy compound. Here, the total amount of each type of epoxy compound includes those corresponding to (1D).
　本発明に使用する前記（２）エネルギー線感受性カチオン重合開始剤とは、エネルギー線照射によりカチオン重合を開始させる物質を放出させ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、また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、
［Ａ］r+［Ｂ］r-（式中、Ａは陽イオン種を表し、Ｂは陰イオン種を表し、ｒは価数を表す。）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 (2) energy ray-sensitive cationic polymerization initiator used in the present invention may be any compound that can release a substance that initiates cationic polymerization by irradiation with energy rays, but is preferably 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:
Listed is a salt of a cation and an anion represented by [A] r + [B] r- (wherein A represents a cation species, B represents an anion species, and r represents a valence). be able to.
　ここで陽イオン［Ａ］r+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、
［（Ｒ1）aＱ］r+
で表すことができる。 Here, the cation [A] r + is preferably onium, and the structure thereof is, for example, the following general formula:
[(R 1 ) a Q] r +
It can be expressed as
　更にここで、Ｒ1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Ｒ1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あるいは原子団である。また、陽イオン［Ａ］r+中のＱの原子価をｑとしたとき、ｒ＝ａ－ｑ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, R 1 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 1 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] r + is q, it is necessary that the relationship r = aq is established (however, N = N is treated as a valence of 0).
　また、陰イオン［Ｂ］r-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］r-
で表すことができる。 Further, the anion [B] r- is preferably a halide complex, and the structure thereof is, for example, the following general formula:
[LX b ] r-
It 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または半金属（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］r-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] r− is p, it is necessary that the relationship r = b−p holds.
　上記一般式の陰イオン［ＬＸb］r-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 ] r- in 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］r-は、下記一般式、
［ＬＸb-1（ＯＨ）］r-
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、ノナフロロブタンスルフォネート、ヘキサデカフロ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] r− is represented by the following general formula:
[LX b-1 (OH)] r-
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. , Trinitrobenzenesulfonate 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、または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 of them 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) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
　（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、ヘキサフルオロフォスフェートイオン、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 and hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions represented by the following group I or group II
Figure JPOXMLDOC01-appb-C000002
 　　
Figure JPOXMLDOC01-appb-C000002
 　　
Figure JPOXMLDOC01-appb-C000003
  
Figure JPOXMLDOC01-appb-C000003
  
　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（１）カチオン重合性有機物質混合物に対する（２）エネルギー線感受性カチオン重合開始剤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、（１）カチオン重合性有機物質混合物１００質量部に対して、（２）エネルギー線感受性カチオン重合開始剤０．００１～１０質量部、好ましくは０．１～５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などの諸物性に悪影響を与える場合がある。 The use ratio of the (2) energy ray sensitive cationic polymerization initiator to the above (1) cationic polymerizable organic substance mixture 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. However, for example, (1) with respect to 100 parts by weight of the cationically polymerizable organic substance mixture, (2) 0.001 to 10 parts by weight, preferably 0.1 to 5 parts by weight of the energy ray sensitive cationic polymerization initiator Can do. 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.
　本発明のカチオン重合性組成物には、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など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などのアルケニル官能性アルコキシシラン、３－メタクリロキシブロピルトリエトキシシラン、３－メタクリロキシブ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など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）など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など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など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など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 cationically polymerizable 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 alkoxysilane, 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 γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) Aminofunctional alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane , Titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), di Kou tetra acetylacetonate, 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、カチオン重合性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 cationic polymerizable composition.
　本発明のカチオン重合性組成物には、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、ダイマー酸など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 cationic polymerizable 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 kinds of epoxy resins such as glycidyl ethers or glycidyl esters of carboxylic acids in a conventional manner; such organic polyamines as 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, Decanedioic 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 diacid, hydrogenated dimer acid and dimer acid; 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; acid anhydrides of tetracarboxylic acids such as pyromellitic acid); dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides and the like.
　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）などが挙げられる。 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、カチオン重合性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、本発明のカチオン重合性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 amount of solids in the cationic polymerizable composition. When using an initiator, it is preferable to heat the cationically polymerizable composition of the present invention at 130 to 180 ° C. for 20 minutes to 1 hour.
　本発明のカチオン重合性組成物には、必要に応じて熱可塑性有機重合体（但し、エポキシ基を有する重量平均分子量１０００～１００００００の高分子量体（１Ｄ）を除く）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 cationic polymerizable composition of the present invention, a cured product can be obtained by using a thermoplastic organic polymer (excluding a high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group) as necessary. It is possible to improve the characteristics. 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.
　本発明のカチオン重合性組成物には、特に制限されず通常用いられる前記（１）及び（２）の各成分を溶解また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 cationically polymerizable composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (1) and (2) that are usually used can be used. For example, methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, Ether solvents such as dipropylene glycol 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, texanol; Cellosolve solvents such as tylene glycol monomethyl ether and 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 mono Ether ester solvents such as ethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; benzene, toluene, xylene, etc. BTX solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; terpenes such as turpentine oil, D-limonene, and pinene Hydrocarbon oils; paraffinic solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2- Halogenated aliphatic hydrocarbon solvents such as dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- Examples thereof include 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.
　本発明のカチオン重合性組成物における、（１）カチオン重合性有機物質混合物、及び（２）エネルギー線感受性カチオン重合開始剤以外の任意成分の合計量は、本発明の用途等にもよるが、本発明の効果を一層高める観点から、（１）カチオン重合性有機物質混合物１００質量部に対して２０質量部以下、特に１０質量部以下とすることが好ましい。 In the cationic polymerizable composition of the present invention, the total amount of optional components other than (1) the cationic polymerizable organic substance mixture and (2) the energy ray sensitive cationic polymerization initiator depends on the use of the present invention, etc. From the viewpoint of further enhancing the effects of the present invention, (1) it is preferably 20 parts by mass or less, particularly 10 parts by mass or less with respect to 100 parts by mass of the cationically polymerizable organic substance mixture.
本発明のカチオン重合性組成物は、硬化性、接着性、液保存安定性の観点から水分量が５質量％以下であることが好ましく、３質量％以下であることがさらに好ましい。水分が多すぎると、白濁したり成分が析出したりする恐れがあるので好ましくない。水分量は、後述する実施例に記載の方法により測定される。 The cationically polymerizable composition of the present invention has a water content of preferably 5% by mass or less, and more preferably 3% by mass or less from the viewpoints of curability, adhesiveness, and liquid storage stability. Too much moisture is not preferable because it may cause cloudiness or components may precipitate. The amount of water is measured by the method described in the examples described later.
　本発明のカチオン重合性組成物は、塗工性の観点から粘度が２００ｍＰａ・ｓ以下であるのが好ましく、１０～１５０ｍＰａ・ｓであるのが更に好ましい。この粘度は、２５℃における粘度であり、後述する実施例に記載の方法によって測定される。 The cationic polymerizable composition of the present invention preferably has a viscosity of 200 mPa · s or less, more preferably 10 to 150 mPa · s, from the viewpoint of coating properties. This viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.
　本発明のカチオン重合性組成物は、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 cationically polymerizable 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 acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polymer materials such as oxyethylene, norbornene resin, and cycloolefin polymer (COP) can be used.
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限り、必要に応じて他のモノマー、他のエネルギー線感受性重合開始剤、無機フィラー、有機フィラー、顔料、染料などの着色剤、光増感剤、消泡剤、増粘剤、界面活性剤、レべリング剤、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。 In addition, as long as the effects of the present invention are not impaired, other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes and other colorants, photosensitizers and antifoaming agents as necessary. , Thickener, surfactant, leveling agent, flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, antistatic agent, flow regulator, Various resin additives such as an adhesion promoter can be added.
　本発明のカチオン重合性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、高周波など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などが挙げられる。 The cationic polymerizable composition of the present invention is cured by irradiation with active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are the most economical. . Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
　本発明のカチオン重合性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、また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 uses of the cationically polymerizable 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, and insulation. Varnish, insulating sheet, laminate, printed circuit board, sealing agent for molding of semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic components, separation membranes, etc. Materials, putty, glass fiber impregnating agent, sealant, semiconductor / solar cell passivation film, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display, screen for projection TV, etc. The lens portion of a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet, or a bag using such a sheet. Examples include light, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical molding casting agents, etc. Examples of substrates that can be used as coating agents include metals, wood, rubber, and plastics. , Glass, ceramic products and the like.
　以下、実施例等を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples.
　以下、本発明のカチオン重合性組成物及び該カチオン重合性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。なお、実施例及び比較例では部は質量部を意味し、％は質量％を意味する。 Hereinafter, the cationic polymerizable composition of the present invention and the cured product obtained by curing the cationic polymerizable composition will be described in detail with reference to examples, evaluation examples, and comparative examples. In Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
[実施例１～３０、比較例１～２]
　下記の[表１]～[表３]に示す配合で各成分を十分に混合して、各々実施組成物１～３０、比較組成物１～２を得た。 [Examples 1-30, Comparative Examples 1-2]
The components shown in [Table 1] to [Table 3] below were mixed thoroughly to obtain Example Compositions 1 to 30 and Comparative Compositions 1 and 2, respectively.
　（１）カチオン重合性有機物質としては下記の化合物（１Ａ－１）～（１Ａ－１２）、（１Ｂ－１）～（１Ｂ－４）、（１Ｃ－１）～（１Ｃ－３）、（１Ｄ－１）～（１Ｄ－２）並びに（１Ｅ－１）～（１Ｅ－４）を用いた。これらのエポキシ当量を、[表１]～[表５]に合わせて示す。
化合物１Ａ－１： レゾルシノールジグリシジルエーテル
化合物１Ａ－２： ジグリシジルｏ－フタレート
化合物１Ａ－３： ジビニルベンゼンオキサイド
化合物１Ａ－４：フェニルグリシジルエーテル
化合物１Ａ－５：スチレンオキサイド
化合物１Ａ－６：ＥＰ－４１００Ｌ（ビスフェノールＡエポキシ：ＡＤＥＫＡ社製）
化合物１Ａ－７：アデカレジンＥＰ－４９０１Ｌ
化合物１Ａ－８：アデカレジンＥＰ－４０００Ｌ
化合物１Ａ－９：ＴＥＣＨＭＯＲＥ　ＶＧ－３１０１Ｌ
化合物１Ａ－１０：アデカグリシロールＥＤ－５０９Ｓ（ＡＤＥＫＡ社製）
化合物１Ａ－１１：アデカグリシロールＥＤ－５０１（ＡＤＥＫＡ社製）
化合物１Ａ－１２：アデカグリシロールＥＤ－５２９（ＡＤＥＫＡ社製）
化合物１Ｂ－１：ネオペンチルグリコールジグリシジルエーテル
化合物１Ｂ－２：トリグリシジルトリス（２－ヒドロキシエチル）イソシアヌレート
化合物１Ｂ－３： ２－エチルヘキシルグリシジルエーテル
化合物１Ｂ－４：１，４－ブタンジオールジグリシジルエーテル
化合物１Ｃ－１：セロキサイド２０２１Ｐ（脂環式エポキシ；ダイセル社製）
化合物１Ｃ－２：メチル　３，４－エポキシシクロヘキサンカルボキシレート
化合物１Ｃ－３：セロキサイド３０００（脂環式エポキシ；ダイセル社製）
化合物１Ｄ－１：ＧＭＡ／ＭＭＡ＝３／７の共重合体（Ｍｗ：８０００）
化合物１Ｄ－２：ＧＭＡ／ＭＭＡ＝３／７の共重合体（Ｍｗ：１５０００）
化合物１Ｅ－１：アロンオキセタンＯＸＴ－１０１（東亞合成社製）
化合物１Ｅ－２：アロンオキセタンＯＸＴ－２１１（東亞合成社製）
化合物１Ｅ－３：ヒドロキシブチルビニルエーテル
化合物１Ｅ－４：１，４－ブタンジオールジビニルエーテル (1) As cationically polymerizable organic substances, the following compounds (1A-1) to (1A-12), (1B-1) to (1B-4), (1C-1) to (1C-3), ( 1D-1) to (1D-2) and (1E-1) to (1E-4) were used. These epoxy equivalents are shown together in [Table 1] to [Table 5].
Compound 1A-1: Resorcinol diglycidyl ether compound 1A-2: Diglycidyl o-phthalate compound 1A-3: Divinylbenzene oxide compound 1A-4: Phenyl glycidyl ether compound 1A-5: Styrene oxide compound 1A-6: EP-4100L ( Bisphenol A epoxy: manufactured by ADEKA)
Compound 1A-7: Adeka Resin EP-4901L
Compound 1A-8: Adeka Resin EP-4000L
Compound 1A-9: TECHMORE VG-3101L
Compound 1A-10: Adekaglycil ED-509S (manufactured by ADEKA)
Compound 1A-11: Adekaglycilol ED-501 (manufactured by ADEKA)
Compound 1A-12: Adekaglycil ED-529 (manufactured by ADEKA)
Compound 1B-1: Neopentyl glycol diglycidyl ether compound 1B-2: Triglycidyl tris (2-hydroxyethyl) isocyanurate compound 1B-3: 2-ethylhexyl glycidyl ether compound 1B-4: 1,4-butanediol diglycidyl Ether compound 1C-1: Celoxide 2021P (alicyclic epoxy; manufactured by Daicel)
Compound 1C-2: Methyl 3,4-epoxycyclohexanecarboxylate Compound 1C-3: Celoxide 3000 (alicyclic epoxy; manufactured by Daicel)
Compound 1D-1: Copolymer of GMA / MMA = 3/7 (Mw: 8000)
Compound 1D-2: Copolymer of GMA / MMA = 3/7 (Mw: 15000)
Compound 1E-1: Aron oxetane OXT-101 (manufactured by Toagosei Co., Ltd.)
Compound 1E-2: Aron oxetane OXT-211 (manufactured by Toagosei Co., Ltd.)
Compound 1E-3: Hydroxybutyl vinyl ether Compound 1E-4: 1,4-butanediol divinyl ether
　（２）エネルギー線感受性カチオン重合開始剤としては下記の化合物下記の化合物（２－１）を用いた。
化合物２－１：ＣＰＩ－１００Ｐ（サンアプロ社製） (2) The following compound (2-1) was used as the energy ray-sensitive cationic polymerization initiator.
Compound 2-1: CPI-100P (manufactured by San Apro)
Figure JPOXMLDOC01-appb-T000004
  
Figure JPOXMLDOC01-appb-T000004
  
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000006
  
Figure JPOXMLDOC01-appb-T000006
  
Figure JPOXMLDOC01-appb-T000007
  
Figure JPOXMLDOC01-appb-T000007
  
Figure JPOXMLDOC01-appb-T000008
  
Figure JPOXMLDOC01-appb-T000008
  
[評価例１～３０、比較評価例１～２]
　上記実施例１～３０で得られた実施組成物及び比較例１～２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５]に示す。
（粘度）
　得られた実施組成物の１～３０、比較組成物の１～２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５］に示す。
（硬化性）
　得られた実施組成物１～３０、比較組成物の１～２のそれぞれをＰＥＴフィルム上にバーコーターで３～６μｍの厚さに塗布し、無電極紫外光ランプを用いて１０００ｍＪ／ｃｍ2のエネルギーを照射した。照射５分後に塗布面がタックフリーになっているものを◎、１５分後にタックフリーになっているものを○、１５分後でもタックが残っているものを×として評価した。結果を上記［表１］～［表５］に示す。
（耐温水試験）
　得られた実施組成物１～３０、比較組成物の１～２のそれぞれをＴＡＣ（トリアセチルセルロース）フィルムに塗布した後、ラミネーターを用いてＣＯＰ（シクロオレフィンポリマー）フィルムと貼り合わせ、ＣＯＰフィルム側から無電極紫外光ランプを用いて１０００ｍＪ／ｃｍ2のエネルギーを照射して接着して試験片を得た。４８時間後、２ｃｍ×４ｃｍに試験片を切り出し、６０℃の温水につけて経過を観察した。１２、２４時間後に試験片の状態を観察し、開始前と変化が見られないものを〇、端面にハガレが見られるものを△、フィルムの貼り合わせが剥がれて完全に脱落したものを×として評価した。結果を上記［表１］～［表５］に示す。
（接着性）
　得られた実施組成物１～３０、比較組成物の１～２のそれぞれを、一枚のコロナ放電処理を施したＣＯＰ（シクロオレフィンポリマー）フィルムに塗布した後、該フィルムを、ラミネーターを用いてコロナ放電処理を施したもう一枚のＣＯＰ（シクロオレフィンポリマー）フィルムと貼り合わせ、無電極紫外光ランプを用いて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度ピール試験を行い、強度が２．０Ｎ／ｃｍ以上あるものを◎、１．０～２．０Ｎ／ｃｍであるものを〇、１．０Ｎ／ｃｍ以下であるものを×として評価した。結果を［表１］～［表５］に示す。
（水分量）
　得られた実施組成物の１～３０、比較組成物の１～２のそれぞれについて、カールフィッシャー法に従い水分量を測定した。結果を上記［表１］～［表５］に示す。 [Evaluation Examples 1-30, Comparative Evaluation Examples 1-2]
The following evaluations were performed on the working compositions obtained in Examples 1 to 30 and the comparative compositions obtained in Comparative Examples 1 and 2. The results are shown in the above [Table 1] to [Table 5].
(viscosity)
The viscosity of each of the obtained practical compositions 1-30 and the comparative compositions 1-2 was measured at 25 ° C. with an E-type viscometer. The results are shown in [Table 1] to [Table 5].
(Curable)
Each of the obtained Example Compositions 1 to 30 and Comparative Compositions 1 to 2 was applied onto a PET film with a bar coater to a thickness of 3 to 6 μm, and 1000 mJ / cm 2 using an electrodeless ultraviolet lamp. Irradiated with energy. Evaluation was made with ◎ indicating that the coated surface was tack-free after 5 minutes of irradiation, ◯ indicating that the surface was tack-free after 15 minutes, and × indicating that the tack remained after 15 minutes. The results are shown in the above [Table 1] to [Table 5].
(Hot water resistance test)
Each of the obtained working compositions 1 to 30 and the comparative compositions 1 to 2 was applied to a TAC (triacetylcellulose) film, and then bonded to a COP (cycloolefin polymer) film using a laminator, and the COP film side Then, an electrodeless ultraviolet light lamp was used to irradiate with an energy of 1000 mJ / cm 2 and adhere to obtain a test piece. After 48 hours, a test piece was cut out to 2 cm × 4 cm, and was put on 60 ° C. warm water and the progress was observed. Observe the condition of the test piece after 12 and 24 hours, ◯ if there is no change from before the start, △ if there is peeling on the end face, × if the film is peeled off and completely dropped evaluated. The results are shown in the above [Table 1] to [Table 5].
(Adhesiveness)
Each of the obtained Example Compositions 1 to 30 and Comparative Compositions 1 to 2 was applied to a COP (cycloolefin polymer) film that had been subjected to corona discharge treatment, and then the film was laminated using a laminator. A test piece was obtained by bonding to another COP (cycloolefin polymer) film that had been subjected to corona discharge treatment, and using an electrodeless ultraviolet lamp to irradiate with 1000 mJ / cm 2 of energy. A 90 degree peel test is performed on the obtained test piece. A specimen having a strength of 2.0 N / cm or more is indicated by ◎, a specimen having a strength of 1.0 to 2.0 N / cm is ○, and a specimen having a strength of 1.0 N / cm or less. Was evaluated as x. The results are shown in [Table 1] to [Table 5].
(amount of water)
The water content of each of the obtained practical compositions 1-30 and the comparative compositions 1-2 was measured according to the Karl Fischer method. The results are shown in the above [Table 1] to [Table 5].
　[表１]～[表５]より、本発明のカチオン重合性組成物は、硬化性、耐温水性、及び接着性に優れることが明らかである。
  From [Table 1] to [Table 5], it is clear that the cationically polymerizable composition of the present invention is excellent in curability, hot water resistance and adhesiveness.

Claims (9)

  1. 　（１）カチオン重合性有機物質として、芳香族エポキシ化合物（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）又は脂環式エポキシ化合物（１Ｃ）の少なくとも一方を含有するカチオン重合性有機物質混合物、及び（２）エネルギー線感受性カチオン重合開始剤を含有することを特徴とするカチオン重合性組成物。 (1) Cationic polymerizable organic substance containing an aromatic epoxy compound (1A) as a main component and further containing at least one of an aliphatic epoxy compound (1B) or an alicyclic epoxy compound (1C) A cationically polymerizable composition comprising an organic substance mixture and (2) an energy ray-sensitive cationic polymerization initiator.
  2. 　上記脂肪族エポキシ化合物（１Ｂ）又は脂環式エポキシ化合物（１Ｃ）として、多官能エポキシ化合物を少なくとも一種含有することを特徴とする請求項１記載のカチオン重合性組成物。 The cationic polymerizable composition according to claim 1, wherein the aliphatic epoxy compound (1B) or the alicyclic epoxy compound (1C) contains at least one polyfunctional epoxy compound.
  3. 　上記芳香族エポキシ化合物（１Ａ）として、フェノール類のグリシジルエーテル、アルコール性水酸基を２ 個以上有する芳香族化合物のグリシジルエーテル化物、多価フェノール類のグリシジルエーテル化物、安息香酸類のグリシジルエステル、多塩基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の群から選ばれる少なくとも一種含有することを特徴とする請求項１又は２に記載のカチオン重合性組成物。 Examples of the aromatic epoxy compound (1A) include glycidyl ethers of phenols, glycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, glycidyl ethers of polyhydric phenols, glycidyl esters of benzoic acids, polybasic acids The cationic polymerizable composition according to claim 1, comprising at least one selected from the group of epoxidized products of glycidyl ester, styrene oxide, or divinylbenzene.
  4. 　上記芳香族エポキシ化合物（１Ａ）として、多官能エポキシ化合物を少なくとも一種含有することを特徴とする請求項１～３のいずれか一項に記載のカチオン重合性組成物。 4. The cationically polymerizable composition according to claim 1, wherein the aromatic epoxy compound (1A) contains at least one polyfunctional epoxy compound.
  5. 　上記芳香族エポキシ化合物（１Ａ）のエポキシ当量が８０～５００であることを特徴とする請求項１～４のいずれか一項に記載のカチオン重合性組成物。 5. The cationically polymerizable composition according to claim 1, wherein the aromatic epoxy compound (1A) has an epoxy equivalent of 80 to 500.
  6. （１）カチオン重合性有機物質として、さらにエポキシ基を有する重量平均分子量１０００～１００００００の高分子量体（１Ｄ）、ビニルエーテル化合物又はオキセタン化合物（１Ｅ）の少なくとも一方を含む請求項１～５のいずれか一項に記載のカチオン重合性組成物。 (1) The cationically polymerizable organic substance further comprises at least one of a high molecular weight substance (1D) having an epoxy group and a weight average molecular weight of 1,000 to 1,000,000, a vinyl ether compound or an oxetane compound (1E). The cationically polymerizable composition according to one item.
  7. 　（２）エネルギー線感受性カチオン重合開始剤が、［Ａ］r+［Ｂ］r-（式中、Ａは陽イオン種を表し、Ｂは陰イオン種を表し、ｒは価数を表す。）で表される陽イオンと陰イオンの塩である請求項１～６のいずれか一項に記載のカチオン重合性組成物。 (2) The energy ray sensitive cationic polymerization initiator is [A] r + [B] r− (wherein A represents a cationic species, B represents an anionic species, and r represents a valence). The cationically polymerizable composition according to any one of claims 1 to 6, which is a cation and anion salt represented.
  8. 　水分量が５質量％以下であることを特徴とする請求項１～７のいずれか一項に記載のカチオン重合性組成物。 The cationically polymerizable composition according to any one of claims 1 to 7, wherein the water content is 5% by mass or less.
  9. 　請求項１～８のいずれか一項に記載のカチオン重合性組成物からなることを特徴とする接着剤。
          An adhesive comprising the cationically polymerizable composition according to any one of claims 1 to 8.
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