WO2015029940A1 - Photosensitive composition, cured substance, and image display device - Google Patents

Photosensitive composition, cured substance, and image display device Download PDF

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Publication number
WO2015029940A1
WO2015029940A1 PCT/JP2014/072138 JP2014072138W WO2015029940A1 WO 2015029940 A1 WO2015029940 A1 WO 2015029940A1 JP 2014072138 W JP2014072138 W JP 2014072138W WO 2015029940 A1 WO2015029940 A1 WO 2015029940A1
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group
acid
meth
acrylate
derivative
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PCT/JP2014/072138
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French (fr)
Japanese (ja)
Inventor
田代　貴之
和樹 尾形
真奈 山下
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三洋化成工業株式会社
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Priority to JP2015534198A priority Critical patent/JPWO2015029940A1/en
Publication of WO2015029940A1 publication Critical patent/WO2015029940A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Definitions

  • the present invention is cured by irradiation with actinic rays, and is suitably used for flat panel displays, touch panels, coating agents, inks, paints, adhesives, resist pattern formation or ceramic electronic component production, etc.
  • the present invention relates to a photosensitive composition useful for an adhesive and a cured product obtained by curing the photosensitive composition.
  • FPDs flat panel displays
  • LCDs liquid crystal displays
  • organic EL displays are indispensable for many electronic devices such as televisions, tablet terminals, and mobile phones represented by smartphones.
  • the demand for a large number of optical materials that make up is also growing greatly.
  • smartphones and tablet terminals are equipped with touch panels in most models, and materials used in electronic devices include light resistance, weather resistance, heat resistance, moisture resistance, and other reliability, adhesion, and adhesion.
  • materials used in electronic devices include light resistance, weather resistance, heat resistance, moisture resistance, and other reliability, adhesion, and adhesion.
  • properties and transparency there is a demand for a highly reliable resin especially during heat and humidity resistance tests.
  • cover glasses used for flat panels have become thinner.
  • the cover glass becomes thin, when the cover glass and the LCD are bonded together with a resin that is cured by actinic ray irradiation, the LCD tends to bend and deform due to the stress generated at the time of curing.
  • the cover glass is broken due to the change or the brightness is uneven when the LCD is turned on.
  • a bonding method using a photosensitive composition containing a rubber component having an alicyclic structure but the adhesive surface may be peeled off during a heat and humidity resistance test. (For example, refer to Patent Document 1). Therefore, development of a photosensitive composition having high adhesive strength and little dimensional change is strongly demanded.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive material that can form a cured product having high adhesive strength (particularly heat-resistant adhesive and moisture-resistant adhesive) and little dimensional change. It is to provide a sex composition.
  • the present invention comprises a radical initiator (A), a polymerizable substance (D) containing a monofunctional radically polymerizable substance (D1), and a non-radically polymerizable polymer (E). It is a photosensitive composition satisfying (3).
  • the weight ratio of (D) to the total weight of (D) and (E) is 40 to 95% by weight.
  • the weight ratio of the (D1) to the weight of the (D) is 50 to 99.9% by weight.
  • the (D1) contains a monofunctional alkyl (meth) acrylate (D111) having 6 to 35 carbon atoms.
  • the photosensitive composition of the present invention By using the photosensitive composition of the present invention, it is possible to produce a cured product having high adhesive strength (particularly heat-resistant adhesiveness and moisture-resistant adhesiveness), flexibility, low dielectric property, and little dimensional change.
  • the cured product of the photosensitive composition is excellent in flexibility, for example, when used as an adhesive, shock absorption is good, and when it is excellent in low dielectric properties, for example, as a touch panel adhesive, the response speed of the touch panel And sensitivity is improved.
  • the photosensitive composition of the present invention contains a radical initiator (A), a polymerizable substance (D), and a non-radically polymerizable polymer (E).
  • the radical initiator (A) means a compound that generates radicals by at least one of actinic rays, acids, and bases, radical initiator (A1) that generates radicals by actinic rays, and acids.
  • a known compound such as a radical initiator (A2) that generates radicals with a base can be used.
  • acylphosphine oxide derivative polymerization initiator (A121), ⁇ -aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), ⁇ -hydroxyacetophenone derivative polymerization initiator (A124)
  • the benzoin derivative polymerization initiator (A125), the oxime ester derivative polymerization initiator (A126), the titanocene derivative polymerization initiator (A127), etc. can generate radicals by any of actinic rays, acids and bases. Any of (A1) and (A2) can be preferably used.
  • the organic peroxide polymerization initiator (A21), the azo compound polymerization initiator (A22), the other radical initiator (A23), and the like can generate radicals with an acid and / or a base. .
  • (A) may be used independently and may use 2 or more types together.
  • (A121) shows that it is the 1st example of the compound (A12) applicable as both (A1) and (A2).
  • acylphosphine oxide derivative polymerization initiator (A121) examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [manufactured by BASF Japan Ltd. (LUCIRIN (registered trademark) TPO, etc.)] and bis (2,4 , 6-trimethylbenzoyl) -phenylphosphine oxide [manufactured by BASF Japan Ltd. (IRGACURE (registered trademark) 819)] and the like.
  • ⁇ -aminoacetophenone derivative-based polymerization initiator A122
  • 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF Japan (IRGACURE 907), etc.]
  • 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF Japan Ltd. (IRGACURE 369) etc.]
  • 1,2- (dimethylamino) -2-[(4-methyl Phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF Japan Ltd. (IRGACURE 379)] and the like.
  • Examples of the benzyl ketal derivative polymerization initiator (A123) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF Japan Ltd. (IRGACURE 651)] and the like.
  • Examples of the ⁇ -hydroxyacetophenone derivative-based polymerization initiator (A124) include 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF Japan Ltd. (IRGACURE 184), etc.], 2-hydroxy-2-methyl-1-phenyl- Propan-1-one [manufactured by BASF Japan Ltd. (DAROCUR (registered trademark) 1173), etc.], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-one [manufactured by BASF Japan Ltd.
  • benzoin derivative polymerization initiator (A125) examples include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • the titanocene derivative polymerization initiator (A127) includes bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl). Titanium [BASF Japan Ltd. (IRGACURE 784) etc.] etc. are mentioned.
  • organic peroxide polymerization initiator (A21) examples include benzoyl peroxide (BPO), tert-butyl peroxyacetate, 2,2-di- (tert-butylperoxy) butane, tert-butyl peroxybenzoate, n-butyl 4,4-di- (tert-butylperoxy) valerate, di- (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, di-tert-hexyl peroxide, 2,5,- Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3 , 3-Tetramethylbutyl hydride Peroxide, cumene hydroperoxide, tert- butyl
  • azo compound polymerization initiator (A22) 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 Examples include '-azobis (N-cyclohexyl-2-methylpropionamide) and 2,2'-azobis (2,4,4-trimethylpentane).
  • polymerization initiators (A23) include 2,3-dimethyl-2,3-diphenylbutane.
  • radical initiator (A1) for generating radicals by actinic rays from the viewpoint of photocurability, acylphosphine oxide derivative polymerization initiator (A121), ⁇ -aminoacetophenone derivative polymerization initiator (A122), benzyl ketal Derivative polymerization initiator (A123), ⁇ -hydroxyacetophenone derivative polymerization initiator (A124), benzoin derivative polymerization initiator (A125), oxime ester derivative polymerization initiator (A126), and titanocene derivative polymerization initiator ( At least one radical initiator selected from the group consisting of A127) is preferred.
  • At least one radical initiator selected from the group consisting of an initiator (A127), an organic peroxide polymerization initiator (A21) and an azo compound polymerization initiator (A22) is preferred.
  • radical initiators (A) from the viewpoint of storage stability of the photosensitive composition, radical initiators (A1) [including (A12)] that generate radicals by actinic rays are preferable.
  • radical initiators (A1) [including (A12)] that generate radicals by actinic rays are preferable.
  • the photosensitive composition contains a base generator (C1) that generates a base by actinic rays, radical generation by the base generated from (C1) is further promoted, and therefore (A12) is used. preferable.
  • the content of the radical initiator (A) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight based on the weight of the polymerizable substance (D) from the viewpoint of photocurability, and further Preferably, the content is 0.1 to 25% by weight.
  • the polymerizable substance (D) in the present invention a known compound such as a monofunctional radical polymerizable substance (D1), a bifunctional radical polymerizable substance (D2), or a trifunctional or higher functional radical polymerizable substance (D3) is used.
  • (D) contains the monofunctional radically polymerizable substance (D1) as an essential component.
  • (D) may be used individually by 1 type, or may use 2 or more types together.
  • the “monofunctional radically polymerizable substance (D1)” means a radically polymerizable substance having one polymerizable functional group
  • the “bifunctional radically polymerizable substance (D2)” means a polymerization.
  • a radically polymerizable substance having two functional groups Means a radically polymerizable substance having two functional groups
  • a radically polymerizable substance having three or more functions (D3) means a radically polymerizable substance having three or more polymerizable functional groups.
  • Examples of the monofunctional radical polymerizable substance (D1) include (meth) acrylic acid, a monofunctional (meth) acrylate compound having 4 to 35 carbon atoms (D11), and a monofunctional (meth) acrylamide compound having 3 to 35 carbon atoms (D12 ), Monofunctional aromatic vinyl compounds having 6 to 35 carbon atoms (D13), monofunctional vinyl ether compounds having 3 to 20 carbon atoms (D14), and other monofunctional radical polymerizable substances (D15). (D1) may be used alone or in combination of two or more.
  • Examples of the monofunctional (meth) acrylate compound (D11) having 4 to 35 carbon atoms include monofunctional alkyl (meth) acrylate (D111) having 6 to 35 carbon atoms and monofunctional (meta) having an aromatic ring having 9 to 40 carbon atoms. ) Acrylate (D112), monofunctional (meth) acrylate (D113) having a hydroxyl group having 4 to 35 carbon atoms, and other monofunctional (meth) acrylate (D114). Monofunctional alkyl having 6 to 35 carbon atoms (Meth) acrylate (D111) is contained as an essential component.
  • Examples of the monofunctional alkyl (meth) acrylate having 6 to 35 carbon atoms (D111) include butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) ) Acrylate, tert-octyl (meth) acrylate, 2,3-dimethylhexyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) Examples include acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and 2-decyltetradecanyl (meth) acrylate.
  • (D111) is preferably a monofunctional alkyl (meth) acrylate having 11 to 35 carbon atoms from the viewpoint of adhesive strength and low dielectric constant, and 2,3-dimethylhexyl acrylate, stearyl acrylate, isooctyl acrylate, lauryl acrylate, More preferred is stearyl acrylate.
  • Monofunctional (meth) acrylate (D112) having an aromatic ring having 9 to 40 carbon atoms includes benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (Meth) acrylate, phenyldiethylene glycol (meth) acrylate, phenyltriethylene glycol (meth) acrylate, and the like.
  • the monofunctional (meth) acrylate (D113) having a hydroxyl group having 4 to 35 carbon atoms includes 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Examples thereof include hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • (D113) is preferably 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate from the viewpoint of compatibility with the polymerizable substance (D).
  • Other monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, Isobornyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, butoxymethyl (meth) Acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate , Alk
  • Monofunctional (meth) acrylamide compounds (D12) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide and N, N-diethyl (meth) acrylamide.
  • Monofunctional aromatic vinyl compound having 6 to 35 carbon atoms (D13) [not including vinyl ether compound (D14) described later. ]
  • vinyl thiophene vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid.
  • Methyl ester 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4- Hexyl styrene, 3-octyl styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, Kute alkenyl styrene, 4-tert-butoxycarbonyl styrene, 4-methoxystyrene and 4-tert-butoxystyren
  • Examples of the monofunctional vinyl ether compound (D14) having 3 to 20 carbon atoms include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether , Cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl Vinyl ether, methoxypo Ethylene glycol vinyl ether, tetrahydrofurfuryl vinyl
  • Other monofunctional radically polymerizable substances (D15) include acrylonitrile, aliphatic vinyl ester compounds (such as vinyl acetate, vinyl propionate and vinyl versatate), aliphatic allyl ester compounds (such as allyl acetate), halogen-containing single quantities Examples thereof include vinylidene chloride and vinyl chloride, and olefin compounds (ethylene and propylene, etc.).
  • the weight ratio of the monofunctional radically polymerizable substance (D1) to the weight of the polymerizable substance (D) is 50 to 99.9% by weight, and it is contained from 75 to 99.9% by weight from the viewpoint of substrate adhesion. From the viewpoint of flexibility, it is preferably 80 to 99.9% by weight, and more preferably 90 to 99.9% by weight.
  • the weight ratio of (D1) is less than 50% by weight, the substrate adhesion decreases, and in the case of only (D1), the photocurability is insufficient.
  • the weight ratio of the monofunctional alkyl (meth) acrylate (C111) having 6 to 35 carbon atoms to the weight of the polymerizable substance (D) is 20 to 99.9% by weight from the viewpoint of adhesive strength and low dielectric property. Is preferable, and more preferably 60 to 99.9% by weight.
  • the monofunctional (meth) acrylate (D112) having an aromatic ring having 9 to 40 carbon atoms is preferably less than 50 mol% based on the polymerizable substance (D) from the viewpoint of low dielectric properties of the cured product.
  • Examples of the bifunctional radically polymerizable substance (D2) include a bifunctional (meth) acrylate compound (D22) having 8 to 35 carbon atoms and a bifunctional vinyl ether compound (D24) having 6 to 20 carbon atoms. (D2) may be used alone or in combination of two or more.
  • Examples of the bifunctional (meth) acrylate compound (D22) having 8 to 35 carbon atoms include 1,6-hexanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol di (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, neopentyl hydroxypivalate Recall di (me
  • Examples of the bifunctional vinyl ether compound (D24) having 6 to 20 carbon atoms include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, and alkylene oxide modified. Examples thereof include bisphenol A divinyl ether and alkylene oxide-modified bisphenol F divinyl ether.
  • the tri- or higher functional radical polymerizable substance (D3) includes a tri- to hexa-functional alcohol tri-functional (meth) acrylate compound (D31) and a tri- to hexa-functional alcohol tri-functional vinyl ether compound (D32). And other trifunctional or higher functional radical polymerizable substances (D33). (D3) may be used alone or in combination of two or more.
  • tri- to hexa-functional (meth) acrylate compound (D31) of trivalent to hexavalent alcohol examples include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and trimethylolpropane alkylene oxide-modified tri (meta).
  • tri- to hexa-functional alcohol ether compound (D32) of tri- to hexavalent alcohol examples include trimethylol ethane trivinyl ether, trimethylol propane trivinyl ether, glycerin trivinyl ether EO-added trimethylol propane trivinyl ether, PO-added trimethylol propane trivinyl ether, Ditrimethylolpropane tetravinyl ether, pentaerythritol tetravinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythri
  • tri- or higher functional radical polymerizable substances include isocyanuric acid alkylene oxide modified tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri (meta). ) And acrylate and phosphazene alkylene oxide modified hexa (meth) acrylates.
  • bifunctional radical polymerizable substance (D2) and the trifunctional or higher functional radical polymerizable substance (D3) are bifunctional (meth) acrylate compounds (D22) having 8 to 35 carbon atoms, and 2 having 6 to 20 carbon atoms.
  • a vinyl polymer (E1) containing the monofunctional radical polymerizable substance (D1) as a structural unit, a divalent alcohol (e21) and a divalent carboxylic acid ( a known compound such as a polyester resin (E2) containing e22) as a structural unit and a polyurethane resin (E3) containing divalent alcohol (e21) and divalent isocyanate (e31) as structural units Can do.
  • Each of the structural units may be one type or two or more types.
  • the vinyl polymer (E1) containing the monofunctional radical polymerizable substance (D1) as a structural unit can be obtained by polymerizing a monomer composition containing the monofunctional radical polymerizable substance (D1).
  • the non-radically polymerizable polymer (E) means a compound having a weight average molecular weight (hereinafter abbreviated as Mw) of 10,000 or more that does not substantially have a radical polymerizable functional group. (E) may be used alone or in combination of two or more.
  • Examples of the divalent alcohol (e21) that is a structural unit of the polyester resin (E2) and the polyurethane resin (E3) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butanedio.
  • -Alkylene glycols such as diol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly Alkylene ether glycols such as tetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; bisphenol A, bisphenol F, bisphenol S, etc. Scan phenols, alkylene oxide bisphenol [EO, PO and butylene oxide, and the like] 2-8 moles adducts.
  • Examples of the divalent carboxylic acid (e22) that is a structural unit of the polyester resin (E2) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, Adipic acid, sevantinic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid, Examples include isooctyl succinic acid and the like, and anhydrides or lower alkyl esters of these acids.
  • divalent isocyanate (e31) that is a structural unit of the polyurethane resin (E3)
  • examples of the divalent isocyanate (e31) that is a structural unit of the polyurethane resin (E3) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4, 4'- or 2,4'-diphenylmethane diisocyanate (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Natobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, ethylene di
  • the non-radical polymerizable polymer (E) is preferably a vinyl polymer (E1) containing a monofunctional radical polymerizable substance (D1) as a structural unit from the viewpoint of compatibility, and more preferably a carbon number of 6 to A vinyl polymer containing 35 monofunctional branched alkyl (meth) acrylates as a structural unit, particularly preferably a vinyl polymer containing 50 mol% or more of 2-ethylhexyl (meth) acrylate as a structural unit.
  • the acid value of the non-radically polymerizable polymer (E) is usually from 0 to 100 mgKOH / g, preferably from 0 to 80 mgKOH / g, more preferably from 0 to 45 mgKOH / g from the viewpoint of compatibility with the polymerizable substance (D). g.
  • the acid value exceeds 100, compatibility with other components is deteriorated.
  • Mw of non-radically polymerizable polymer (E) [Measurement is based on the following gel permeation chromatography (GPC) method. ] Is usually 10,000 or more, preferably 12,000 to 1,000,000, more preferably 100,000 to 900,000. When Mw is less than 10,000, the adhesion to the substrate is deteriorated.
  • the weight ratio of the polymerizable substance (D) to the total weight of the polymerizable substance (D) and the non-radical polymerizable polymer (E) in the photosensitive composition of the present invention is 40 to 95% by weight, preferably 42 to 92% by weight, more preferably 60 to 90% by weight.
  • the content of the polymerizable substance (D) with respect to the total weight of the polymerizable substance (D) and the non-radically polymerizable polymer (E) is less than 40% by weight, the curability is poor because the polymerizable functional group is insufficient. If it exceeds 95% by weight, the adhesive strength decreases.
  • the photosensitive composition of the present invention preferably contains an acid generator (B) and / or a base generator (C) because adhesion to various substrates becomes better. Even if it uses any of an acid generator (B) and a base generator (C), the adhesiveness to various base materials is more excellent, and transparent hardened
  • the acid generator (B) means a compound that generates an acid by at least one of actinic rays, radicals, acids, and bases, and an acid generator (B1) that generates an acid by actinic rays, And known compounds such as an acid generator (B2) that generates an acid with at least one selected from the group consisting of radicals, acids and bases.
  • the photosensitive composition is highly sensitive and the reaction proceeds uniformly, so that the cured product of the present invention obtained by curing the photosensitive composition of the present invention has a high hardness. ⁇ It is estimated that high scratch resistance and high transparency can be realized.
  • the sulfonium salt derivative (B121) and the iodonium salt derivative (B122) can generate an acid by actinic rays or radicals, and can be applied as (B1) or (B2).
  • the sulfonic acid ester derivative (B21), the acetic acid ester derivative (B22), the phosphonic acid ester (B23), and the like can generate an acid with an acid and / or a base, and can be applied as (B2).
  • (B) may be used alone or in combination of two or more.
  • (B121) shows that it is the 1st example of the compound (B12) applicable as both (B1) and (B2).
  • Examples of the sulfonium salt derivative (B121) in the present invention include compounds represented by the following general formula (1) or the following general formula (2).
  • a 1 is represented by any of the following formula (3), formula (4), general formulas (5) to (8), formula (9), and formula (10).
  • Each of Ar 1 to Ar 7 independently has at least one benzene ring skeleton, and is a halogen atom, an acyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.
  • An aromatic hydrocarbon group or a heterocyclic group optionally substituted with at least one atom or substituent selected from the group consisting of a group, a phenoxy group and a phenylthio group, Ar 1 to Ar 4 , Ar 6 and Ar 7 is a monovalent group
  • Ar 5 is a divalent group
  • (X 1 ) ⁇ and (X 2 ) ⁇ each independently represents an anion
  • a is an integer of 0 to 2
  • b is an integer of 1 to 3
  • a + b is 2 Or it is the same integer as the valence of A 1 at 3.
  • R 1 to R 7 in the general formulas (5) to (8) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom, an acyl group having 1 to 20 carbon atoms, or 1 to 20 alkyl group, an amino group, a cyano group, a phenyl group, a naphthyl group, at least one atom or optionally substituted phenyl group which is substituted with a group selected from the group consisting of a phenoxy group and a phenylthio group, R 1 And R 2 , R 4 and R 5 , and R 6 and R 7 may be bonded to each other to form a ring structure.
  • any one of the general formula (5), the general formula (7), the general formula (8), the formula (9), and the formula (10) is preferable from the viewpoint of acid generation efficiency. And a group represented by any one of the general formula (5), general formula (8), formula (9) and formula (10) is more preferable.
  • Ar 1 to Ar 7 in the general formula (1) and the general formula (2) are groups in which the compound represented by the general formula (1) or the general formula (2) has absorption in the ultraviolet to visible light region. is there.
  • the number of benzene ring skeletons in Ar 1 to Ar 7 is preferably 1 to 5, and more preferably 1 to 4. Examples of the case of having one benzene ring skeleton include residues obtained by removing one or two hydrogen atoms from benzene or a heterocyclic compound such as benzofuran, benzothiophene, indole, quinoline and coumarin.
  • Examples of the case of having two benzene ring skeletons include one or two hydrogen atoms from heterocyclic compounds such as naphthalene, biphenyl, fluorene, or dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, acridine, phenothiazine, and thianthrene. Residues excluded are listed.
  • Examples of having three benzene ring skeletons include, for example, removing one or two hydrogen atoms from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthyl mercapto) benzene, and naphthobenzothiophene. Residue.
  • a residue obtained by removing one or two hydrogen atoms from naphthacene, pyrene, benzoanthracene, triphenylene and the like can be mentioned.
  • halogen atom examples include fluorine, chlorine, bromine and iodine, with fluorine and chlorine being preferred.
  • acyl group having 1 to 20 carbon atoms examples include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.
  • alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, n- or iso-propyl group, n-, sec- or tert-butyl group, n-, iso- or neo-pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned.
  • alkoxy group having 1 to 20 carbon atoms examples include methoxy group, ethoxy group, n- or iso-propoxy group, n-, sec- or tert-butoxy group, n-, iso- or neo-pentyloxy group, A hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.
  • alkylthio group having 1 to 20 carbon atoms examples include methylthio group, ethylthio group, n- or iso-propylthio group, n-, sec- or tert-butylthio group, n-, iso- or neo-pentylthio group, and hexylthio group. , Heptylthio group, octylthio group and the like.
  • alkylsilyl group having 1 to 20 carbon atoms examples include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group.
  • the alkyl may be a linear structure or a branched structure.
  • a halogen atom As the atom or substituent to be substituted in Ar 1 to Ar 7 , a halogen atom, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, a phenylthio group, an alkyl group having 1 to 20 carbon atoms is preferable from the viewpoint of acid generation efficiency.
  • An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an acyl group having 1 to 20 carbon atoms more preferably a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, An alkylthio group having 1 to 10 carbon atoms and an acyl group having 1 to 10 carbon atoms.
  • the alkyl moiety in the above substituent may be linear, branched or cyclic.
  • Ar 1 to Ar 4 , Ar 6 and Ar 7 are preferably a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group, a p-tert-butylphenyl group, 2,4, from the viewpoint of acid generation efficiency. 6-trimethylphenyl group, p- (thioxanthylmercapto) phenyl group and m-chlorophenyl group.
  • Ar 5 is preferably a phenylene group, a 2- or 3-methylphenylene group, a 2- or 3-methoxyphenylene group, a 2- or 3-butylphenylene group, and a 2- or 3-chloro group from the viewpoint of acid generation efficiency.
  • Examples of the anion represented by (X 1 ) ⁇ or (X 2 ) ⁇ in the general formula (1) or (2) include a halide anion, a hydroxide anion, a thiocyanate anion, and those having 1 to 4 carbon atoms.
  • hexafluorophosphate anion More preferred are hexafluorophosphate anion, trifluoro [tris (perfluoroethyl)] phosphate anion and tetrakis (perfluorophenyl) borate anion, and particularly preferred is trifluoro [tris (perfluoroethyl)] phosphate anion and Tetrakis (perfluorophenyl) borate anion.
  • sulfonium salt derivative (B121) a compound having a triphenylsulfonium cation, a tri-p-tolylsulfonium cation, or a [p- (phenylmercapto) phenyl] diphenylsulfonium cation as a cation skeleton is preferable from the viewpoint of acid generation efficiency.
  • Compounds represented by the following general formulas (11) to (14) are preferable, and compounds represented by the following general formulas (11) to (14) are more preferable.
  • (X 3 ) ⁇ to (X 6 ) ⁇ in the general formulas (11) to (14) each independently represents an anion, and specifically, (X 1 ) ⁇ in the general formula (1) or (2) or (X 2) - include the same ones as exemplified as, preferable ones are also same.
  • Examples of the iodonium salt derivative (B122) in the present invention include compounds represented by the following general formula (15) or the following general formula (16).
  • a 2 is a divalent or trivalent group represented by any one of the above formula (3), formula (4), general formulas (5) to (8), formula (9) and formula (10).
  • Each of Ar 8 to Ar 12 independently has at least one benzene ring skeleton, and is a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • alkylthio group having 1 to 20 carbon atoms alkylsilyl group having 1 to 20 carbon atoms, nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, phenoxy group and phenylthio group
  • An aromatic hydrocarbon group or a heterocyclic group which may be substituted with at least one substituent selected from the group consisting of Ar 8 to Ar 10 and Ar 12 are monovalent groups, and Ar 11 is divalent.
  • (X 7) - Beauty (X 8) - each independently represent an anion
  • c is an integer of 0 to 2
  • d is 1 to 3 as an integer
  • c + d are the same integer as the valence of A 2 in 2 or 3 .
  • a halogen atom an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an alkylsilyl group having 1 to 20 carbon atoms; The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.
  • the general formula (5), the general formula (7), the general formula (8), the formula (9), and the formula (10) are preferable. And a group represented by any one of formulas (5), (8), (9), and (10) is more preferred.
  • Ar 8 to Ar 12 in the general formula (15) or the general formula (16) are groups that allow the compound represented by the general formula (15) or the general formula (16) to absorb in the ultraviolet to visible light region. is there.
  • the number of benzene ring skeletons in Ar 8 to Ar 12 is preferably 1 to 5, and more preferably 1 to 4.
  • Specific examples of Ar 8 to Ar 12 include those represented by general formula (1) or general formula (2).
  • Examples of Ar 1 to Ar 7 are the same as those exemplified above, and preferable examples are also the same.
  • iodonium salt derivative (B122) (4-methylphenyl) ⁇ 4- (2-methylpropyl) phenyl ⁇ iodonium cation, [bis (4-tert-butylphenyl)] iodonium are preferable from the viewpoint of acid generation efficiency.
  • the compounds represented by the following general formulas (17) to (20) are more preferred, and the compounds represented by the following general formulas (17) to (20) (including the exemplified compounds) are more preferable.
  • R 8 to R 13 are each independently a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms.
  • a halogen atom an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an alkylsilyl group having 1 to 20 carbon atoms; The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.
  • R 8 to R 13 are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. More preferred are a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, and particularly preferred are those having 1 to 10 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
  • the above alkyl moiety may be linear, branched or cyclic.
  • a photopolymerization initiator that can be used for curing in the visible light region (360 nm to 830 nm; see JIS-Z8120) absorbs visible light, and the initiator itself is colored, which adversely affects the hue of the cured film.
  • the compound represented by the general formula (2) or the general formula (16) an adverse effect on the hue of the cured film can be suppressed.
  • Examples of the sulfonic acid ester derivative (B21) include methanesulfonic acid cyclohexyl ester, ethanesulfonic acid isopropyl ester, benzenesulfonic acid-tert-butyl ester, p-toluenesulfonic acid cyclohexyl ester, and naphthalenesulfonic acid cyclohexyl ester.
  • Examples of the acetic acid ester derivative (B22) include dichloroacetic acid cyclohexyl ester and trichloroacetic acid isopropyl ester.
  • Examples of the phosphonic acid ester (B23) include triphenylphosphonic acid cyclohexyl ester.
  • At least one acid generator selected from is preferred.
  • at least one acid generator selected from the group consisting of a sulfonium salt derivative (B121) and an iodonium salt derivative (B122) is more preferable.
  • the base generator (C) means a compound that generates a base with at least one of actinic rays, radicals, acids and bases, and a base generator (C1) that generates a base with actinic rays,
  • a known compound such as a base generator (C2) that generates a base by at least one selected from the group consisting of radicals, acids and bases can be used.
  • the oxime derivative (C121), the quaternary ammonium salt derivative (C122), the quaternary amidine salt derivative (C123) and the like can generate a base by actinic rays or radicals, and are applied as (C1) or (C2). it can. Further, the carbamate derivative (C21) can generate a base with a base and can be applied as (C2). (C) may be used alone or in combination of two or more. In addition, (C121) shows that it is the 1st example of the compound (C12) applicable as both (C1) and (C2).
  • Examples of the oxime derivative (C121) include O-acyloxime.
  • Examples of the quaternary ammonium salt derivative (C122) and the quaternary amidine salt derivative (C123) include compounds represented by any of the following general formulas (21) to (23).
  • R 14 to R 41 in the general formulas (21) to (23) are each independently a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.
  • R 42 to R 45 in the general formulas (24) and (25) are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 46 to R 48 are each independently substituted with a hydroxyl group. Or an alkyl group having 1 to 20 carbon atoms, (X 13 ) — and (X 14 ) — each independently represents an anion, and e is an integer of 2 to 4.
  • a halogen atom an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon
  • alkylsilyl group of 1 to 20 are the same as those described in the description of the general formula (1) and the general formula (2).
  • the compound represented by the general formula (21) is an anthracene skeleton
  • the compound represented by the general formula (22) is a thioxanthone skeleton
  • the compound represented by the general formula (23) is a compound having a benzophenone skeleton, i-line (365 nm). It is an example of a compound having a maximum absorption wavelength in the vicinity.
  • R 14 to R 23 are appropriately selected in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity, decomposability, etc., and include a hydrogen atom, a halogen atom, and an alkoxy having 1 to 20 carbon atoms.
  • any one of R 14 to R 23 is a substituent represented by the general formula (24) or the general formula (25).
  • R 14 to R 23 are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. More preferred are a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, and particularly preferred are those having 1 to 10 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
  • the above alkyl moiety may be linear, branched or cyclic.
  • R 14 to R 23 include atoms and substituents described in the description of R 8 to R 13 in the general formulas (17) to (19).
  • the substituent represented by the general formula (24) is a substituent having a cationized amidine skeleton, and e is an integer of 2 to 4.
  • Examples of the substituent include a substituent having a structure in which 1,8-diazabicyclo [5.4.0] -7-undecene in which e is 4 and a 1,5-diazabicyclo [4. 3.0] -5-Nonene is preferably a substituent having a cationized structure.
  • R 42 and R 43 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom and an alkyl group having 1 to carbon atoms. 5 alkyl groups.
  • Formula (25) has a quaternary ammonium structure, and R 44 and R 45 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or 1 to 10 carbon atoms. More preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 46 to R 48 each independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, and may be linear, branched or cyclic.
  • R 46 to R 48 are preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms.
  • (X 13 ) ⁇ and (X 14 ) ⁇ in the general formulas (24) and (25) each independently represent an anion, specifically, (X 1 ) ⁇ in the general formula (1) or (2). or (X 2) - it includes the same as those exemplified as. Of these, aliphatic or aromatic carboxy anions and borate anions are preferred from the viewpoint of photodegradability.
  • the compound represented by the general formula (24) generates a basic compound having an amidine skeleton by cleaving the bond between carbon and nitrogen to which R 42 and R 43 are bonded by irradiation with actinic rays.
  • irradiation with actinic rays ruptures the bond between carbon and nitrogen to which R 44 and R 45 are bonded to produce a tertiary amine.
  • base generators (C1) that generate a base by actinic rays a group consisting of an oxime derivative (C121), a quaternary ammonium salt derivative (C122) and a quaternary amidine salt derivative (C123) from the viewpoint of photocurability.
  • at least one base generator selected from the group consisting of the compounds represented by formula (26) is more preferable from the viewpoint of photodegradability.
  • (X 15 ) ⁇ in the general formula (26) represents an anion, specifically, the same as those exemplified as (X 1 ) ⁇ or (X 2 ) ⁇ in the general formula (1) or (2) Things.
  • aliphatic or aromatic carboxy anions and borate anions are preferred from the viewpoint of photodegradability.
  • Examples of the carbamate derivative (C21) include 1-Z-4-piperidone, 1-Fmoc-4-piperidone and o-nitrobenzoyl carbamate.
  • (C) in the present invention is more preferably at least one base generator selected from the group consisting of a quaternary ammonium salt derivative (C122) and a quaternary amidine salt derivative (C123).
  • the content of the acid generator (B) and / or the base generator (C) [total of (B) and (C)] in the photosensitive composition of the present invention is a polymerizable substance from the viewpoint of photocurability.
  • the content is preferably 0.01 to 30% by weight, more preferably 0.01 to 25% by weight, based on the weight of (D).
  • the radical initiator (A), the acid generator (B) and the base generator (C) generates an active species (H) by irradiation with actinic rays
  • the active species (H) reacts with the radical initiator (A), the acid generator (B) and / or the base generator (C) to produce a new active species (I), and the new active species
  • the polymerization reaction of the polymerizable compound (D) by (I) proceeds.
  • the active species (H) and (I) include a radical, an acid, and a base.
  • the active species (H) or (I) is preferably an acid or a base.
  • Curing is further promoted by the diffusion of the active species (H), and the curability of the photosensitive composition including the shadowed portion of the wiring is improved. Moreover, the adhesiveness to the base material of the hardened
  • a radical initiator (A) that does not react with the active species (H).
  • (A1), (A2), (B1), (B2), (C1), or (C2) may be contained in any combination of the following (1) to (4) preferable.
  • (1) Contains (A1) and (B2) and / or (C2).
  • (2) Contains (B1), (A2) and (C2) as necessary.
  • (3) Contains (C1), (A2) and (B2) if necessary.
  • (4) A combination of two or more of (1) to (3) above.
  • radicals are generated as active species (H) upon irradiation with actinic rays, and acids and / or bases are generated as active species (I).
  • an acid is generated as the active species (H) by irradiation with actinic rays
  • a radical is generated as the active species (I)
  • a base is generated when further containing (C2).
  • irradiation with actinic rays generates a base as the active species (H), generates a radical as the active species (I), and further generates an acid when it contains (B2).
  • more preferred are those containing (A1) and (B2) of (1), (B1) and (A2) of (2), (A1) and (A2).
  • Particularly preferred are those containing (A1) and (B2), and those containing (B1) and (A12).
  • examples of (A1) and (B2) include an ⁇ -aminoacetophenone derivative polymerization initiator (A122) and an iodonium salt derivative (B122). Is preferably used.
  • a sulfonium salt derivative (B121) and an acylphosphine oxide derivative polymerization initiator (A121) are used as (B1) and (A12). It is preferable.
  • the photosensitive composition of the present invention contains (C1) and (A12), as (C1) and (A12), for example, a quaternary ammonium salt derivative (C122) or a quaternary amidine salt derivative (C123), and It is preferable to use an ⁇ -aminoacetophenone derivative polymerization initiator (A122).
  • the photosensitive composition of the present invention can contain a polymerization inhibitor (hydroquinones and the like), a solvent, a sensitizer and the like, if necessary.
  • Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether).
  • glycol ethers ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.
  • ketones acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • esters ethyl acetate, butyl acetate, ethylene glycol alkyl ether.
  • the photosensitive composition contains a solvent, the content thereof is preferably 0.01 to 99% by weight, more preferably 0.01 to 90% by weight, based on the weight of the photosensitive composition. .
  • Sensitizers include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and their derivatives, perylene, and substituted anthracene.
  • the content of the sensitizer is preferably from 0.01 to 20% by weight, more preferably from 0.01 to 15% by weight, particularly preferably from 0.01 to 10% by weight, based on the photosensitive composition.
  • the photosensitive composition of the present invention further comprises an adhesion-imparting agent (such as a silane coupling agent), a tackifier, a dispersant, an antifoaming agent, a leveling agent, a thixotropy imparting agent, a slip according to the purpose of use.
  • an adhesion-imparting agent such as a silane coupling agent
  • a tackifier such as a silane coupling agent
  • a dispersant such as a silane coupling agent
  • an antifoaming agent such as sodium bicarbonate
  • leveling agent such as sodium bicarbonate
  • a thixotropy imparting agent such as sodium bicarbonate
  • a slip such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
  • the photosensitive composition of the present invention comprises a radical initiator (A), a polymerizable substance (D) containing a monofunctional radically polymerizable substance (D1), a non-radically polymerizable polymer (E) and, if necessary, an acid generator ( B), the base generator (C) and other components can be obtained by kneading with a rotation / revolution stirrer, a ball mill or a three-roll mill.
  • the kneading temperature is preferably 10 ° C to 40 ° C, more preferably 20 ° C to 30 ° C.
  • Examples of the method for applying the photosensitive composition of the present invention to a substrate include known coating methods such as spin coating, roll coating, and spray coating, and nanoimprint processes, lithographic printing, carton printing, metal printing, offset printing, screen printing, and the like. Printing methods such as gravure printing can be applied. Further, the present invention can also be applied to coating using an ink jet method or a liquid fixed quantity discharge device that discharges fine droplets continuously.
  • Examples of the active light used for curing the photosensitive composition of the present invention include visible light and ultraviolet light. Since the photosensitive composition of the present invention can be photocured by irradiation with actinic rays of 360 to 830 nm, in addition to commonly used high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, high-power metal halide lamps, etc. (UV The latest trends in EB curing technology, edited by Radtech Research Association, CMC Publishing, 138, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently. Furthermore, sunlight, a low-pressure mercury lamp, a semiconductor laser, or the like can be used.
  • Heating may be performed for the purpose of diffusing and accelerating curing of the acid and / or base generated from the acid generator (B) and / or the base generator (C) during and / or after irradiation with actinic rays.
  • the heating temperature is preferably 30 ° C. to 200 ° C., more preferably 35 ° C. to 150 ° C., and particularly preferably 40 ° C. to 120 ° C.
  • a cured product obtained by curing the photosensitive composition of the present invention by irradiation with actinic rays is also included in the present invention.
  • the photosensitive composition of the present invention preferably has a durometer E hardness of a cured product obtained by curing the resin composition by irradiation with actinic rays of less than 20, preferably less than 15. More preferably, it is particularly preferably less than 10.
  • the durometer E hardness of the cured product By setting the durometer E hardness of the cured product to less than 20, the flexibility is improved, so that the impact absorption of the cured product is improved.
  • the durometer E hardness in this invention can be measured by the method mentioned later.
  • the relative dielectric constant at 1 MHz of a cured product obtained by curing the resin composition by irradiation with actinic rays is preferably 5.0 or less from the viewpoint of low dielectric properties. Is more preferably 0.0 or less, and particularly preferably 3.0 or less.
  • the relative dielectric constant in the present invention can be measured by the method described later.
  • the photosensitive composition of the present invention is suitably used, for example, as a photosensitive composition for coating agents, inks, paints, adhesives, resist patterns, or ceramic electronic parts. Among these, it is preferably used as an adhesive.
  • Use of the photosensitive composition of the present invention as a photosensitive composition for an adhesive is one of the preferred embodiments of the present invention.
  • the photosensitive composition of the present invention is suitably used as an adhesive for bonding a substrate such as an optical substrate in the production of an image display device, for example.
  • An image display device including an optical substrate bonded using the photosensitive composition of the present invention is also included in the present invention.
  • an image display apparatus in which the photosensitive composition of the present invention is used for example, a flat panel display, a touch panel and the like are suitable.
  • the photosensitive composition of the present invention is particularly suitable for bonding optical substrates such as transparent substrates, transparent plates, decorative plates, touch panels, icon sheets, and image display members in the production of such image display devices. Used for.
  • E1-Ew vinyl polymer
  • Examples 1 to 19 and Comparative Examples 1 to 5 The number of polymerizable substances (D), non-radically polymerizable polymer (E), radical initiator (A), and acid generator (B) or base generator (C), as required, shown in Tables 1 and 2 are shown. 1 to 2 are blended and mixed at 25 ° C. for 10 minutes using a rotating and rotating stirrer, and compared with the photosensitive compositions (Q-1) to (Q-19) of the present invention. Sex compositions (Q′-1) to (Q′-5) were produced.
  • the photosensitive compositions (Q-1) to (Q-19) and the comparative photosensitive compositions (Q′-1) to (Q′-5) were evaluated by the following methods.
  • the exposure amount was 1500 mJ / cm 2 at 365 nm.
  • the adhesive strength of the cured round test piece was evaluated using a tensile tester [Product name: Autograph AG-IS, manufactured by Shimadzu Corporation, the same applies below] according to JIS K-6849.
  • Each photosensitive composition obtained in Examples 1 to 19 and Comparative Examples 1 to 5 was measured for liquid specific gravity [ ⁇ 1 ] in accordance with JIS Z-8804 using a 25 mL specific gravity bottle. Further, the photosensitive compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 5 were placed on a 25 ⁇ m-thick PP (polypropylene) film [manufactured by Nippon Polypro Co., Ltd., Wintech (registered trademark) WFX4TA]. Using a gauge [thickness 1.00 mm, manufactured by Nagai Gauge Manufacturing Co., Ltd.], the film was molded so as to have a film thickness of 1.0 mm with another PP film prepared.
  • Exposure was carried out using a belt conveyor type UV irradiation device.
  • the exposure amount was 1500 mJ / cm 2 at 365 nm.
  • the specific gravity [ ⁇ 2 ] of the cured product was measured by an underwater substitution method according to JIS K-7112.
  • Comparative Example 1 could not be evaluated because the resin was not cured. Further, Comparative Examples 2 and 5 had a high cure shrinkage, and the glass was not cracked at the time of exposure, and the bond strength could not be evaluated.
  • the photosensitive composition of the present invention is excellent in adhesiveness, heat resistance, moisture resistance and flexibility, and has a low curing shrinkage and low dielectric property, it is used for adhesives (for example, for manufacturing flat panel displays or touch panels).
  • adhesives for example, for manufacturing flat panel displays or touch panels.
  • coating agents, inks, paints, resist patterns and ceramic electronic parts, and particularly useful as adhesives are particularly useful as adhesives.

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Abstract

The photosenstive composition of the present invention contains a radical initiator (A), a polymerizable substance (D) containing monofunctional radical polymerizable substance (D1), and a nonradical polymerizable polymer (E), and satisfies the following (1) to (3). (1) The weight ratio of (D) with respect to the total weight of (D) and (E) is 40 to 90 wt%. (2) The weight ratio of (D1) with respect to the weight of (D) is 50 to 99.9 wt%. (3) (D1) contains a C6-C35 monofunctional alkyl(meth)acrylate (D111).

Description

感光性組成物、硬化物及び画像表示装置Photosensitive composition, cured product, and image display device
　本発明は、活性光線照射で硬化し、フラットパネルディスプレイ用、タッチパネル用、コーティング剤用、インキ用、塗料用、接着剤用、レジストパターン形成用又はセラミック電子部品製造用等として好適に用いられ、特に接着剤用として有用な感光性組成物及び感光性組成物が硬化されてなる硬化物に関する。 The present invention is cured by irradiation with actinic rays, and is suitably used for flat panel displays, touch panels, coating agents, inks, paints, adhesives, resist pattern formation or ceramic electronic component production, etc. In particular, the present invention relates to a photosensitive composition useful for an adhesive and a cured product obtained by curing the photosensitive composition.
　現在、液晶ディスプレイ（ＬＣＤ）や有機ＥＬディスプレイに代表されるフラットパネルディスプレイ（ＦＰＤ）は、テレビやタブレット端末、スマートフォンに代表される携帯電話まで多くの電子機器に不可欠なものとなっており、ＦＰＤを構成する数多くの光学用材料の需要も大きく伸びている。また、近年のスマートフォンやタブレット端末にはタッチパネルがほとんどの機種で搭載されており、電子機器に用いられる材料には、耐光性、耐候性、耐熱性、耐湿性等の信頼性、密着性、接着性、透明性等の様々な要求項目があり、特に耐熱・耐湿試験時の信頼性の高い樹脂が求められている。 At present, flat panel displays (FPDs) represented by liquid crystal displays (LCDs) and organic EL displays are indispensable for many electronic devices such as televisions, tablet terminals, and mobile phones represented by smartphones. The demand for a large number of optical materials that make up is also growing greatly. In addition, most smartphones and tablet terminals are equipped with touch panels in most models, and materials used in electronic devices include light resistance, weather resistance, heat resistance, moisture resistance, and other reliability, adhesion, and adhesion. There are various requirements such as properties and transparency, and there is a demand for a highly reliable resin especially during heat and humidity resistance tests.
　近年フラットパネルに用いられるカバーガラスが薄くなってきている。カバーガラスが薄くなると、活性光線照射で硬化する樹脂でカバーガラスとＬＣＤを貼り合わせた際、硬化時に発生する応力でＬＣＤがたわみ変形しやすくなり、従来の感光性組成物では、硬化時の寸法変化によりカバーガラスが割れたり、ＬＣＤ点灯表示時に明るさにムラが生じるという問題があった。カバーガラスの割れやムラの発生を改良する方法としては、例えば、脂環構造を有するゴム成分を含有した感光性組成物を用いる貼り合わせ方法があるが、耐熱・耐湿試験時に接着面が剥がれたりする等の懸念がある（例えば特許文献１参照）。
　したがって、接着強度が高く、寸法変化の少ない感光性組成物の開発が強く求められている。 In recent years, cover glasses used for flat panels have become thinner. When the cover glass becomes thin, when the cover glass and the LCD are bonded together with a resin that is cured by actinic ray irradiation, the LCD tends to bend and deform due to the stress generated at the time of curing. There has been a problem that the cover glass is broken due to the change or the brightness is uneven when the LCD is turned on. As a method for improving the generation of cracks and unevenness in the cover glass, for example, there is a bonding method using a photosensitive composition containing a rubber component having an alicyclic structure, but the adhesive surface may be peeled off during a heat and humidity resistance test. (For example, refer to Patent Document 1).
Therefore, development of a photosensitive composition having high adhesive strength and little dimensional change is strongly demanded.
特開２０１３－０２０２５８号公報JP 2013-020258 A
　本発明は、上記問題点に鑑みてなされたものであり、本発明の目的は、接着強度（特に耐熱接着性及び耐湿接着性）が高く、寸法変化の少ない硬化物を形成することができる感光性組成物を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive material that can form a cured product having high adhesive strength (particularly heat-resistant adhesive and moisture-resistant adhesive) and little dimensional change. It is to provide a sex composition.
　本発明者らは、上記の目的を達成すべく鋭意検討を行った結果、本発明に到達した。即ち、本発明は、ラジカル開始剤（Ａ）、単官能ラジカル重合性物質（Ｄ１）を含有する重合性物質（Ｄ）及び非ラジカル重合性ポリマー（Ｅ）を含有し、以下の（１）～（３）を満たす感光性組成物である。
（１）前記（Ｄ）と前記（Ｅ）との合計重量に対する前記（Ｄ）の重量割合が、４０～９５重量％である。
（２）前記（Ｄ）の重量に対する前記（Ｄ１）の重量割合が、５０～９９．９重量％である。
（３）前記（Ｄ１）が、炭素数６～３５の単官能アルキル（メタ）アクリレート（Ｄ１１１）を含有する。 As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention comprises a radical initiator (A), a polymerizable substance (D) containing a monofunctional radically polymerizable substance (D1), and a non-radically polymerizable polymer (E). It is a photosensitive composition satisfying (3).
(1) The weight ratio of (D) to the total weight of (D) and (E) is 40 to 95% by weight.
(2) The weight ratio of the (D1) to the weight of the (D) is 50 to 99.9% by weight.
(3) The (D1) contains a monofunctional alkyl (meth) acrylate (D111) having 6 to 35 carbon atoms.
　本発明の感光性組成物を使用することにより、接着強度（特に耐熱接着性及び耐湿接着性）が高く、柔軟性、低誘電性及び寸法変化の少ない硬化物が製造可能となる。
　感光性組成物の硬化物が柔軟性に優れると、例えば接着剤用として用いた場合に衝撃吸収性が良好となり、低誘電性に優れると例えばタッチパネル用接着剤として用いた場合にタッチパネルの応答速度や感度が向上する。 By using the photosensitive composition of the present invention, it is possible to produce a cured product having high adhesive strength (particularly heat-resistant adhesiveness and moisture-resistant adhesiveness), flexibility, low dielectric property, and little dimensional change.
When the cured product of the photosensitive composition is excellent in flexibility, for example, when used as an adhesive, shock absorption is good, and when it is excellent in low dielectric properties, for example, as a touch panel adhesive, the response speed of the touch panel And sensitivity is improved.
　本発明の感光性組成物は、ラジカル開始剤（Ａ）、重合性物質（Ｄ）及び非ラジカル重合性ポリマー（Ｅ）を含有する。 The photosensitive composition of the present invention contains a radical initiator (A), a polymerizable substance (D), and a non-radically polymerizable polymer (E).
　以下に、本発明の感光性組成物の必須構成成分である（Ａ）、（Ｄ）及び（Ｅ）について、順に説明する。 Hereinafter, (A), (D) and (E) which are essential components of the photosensitive composition of the present invention will be described in order.
　本発明においてラジカル開始剤（Ａ）とは、活性光線、酸及び塩基のうちの少なくとも１種によりラジカルを発生する化合物を意味し、活性光線によりラジカルを発生するラジカル開始剤（Ａ１）、並びに酸及び／若しくは塩基によりラジカルを発生するラジカル開始剤（Ａ２）等の公知の化合物を用いることができる。
　例えば、アシルホスフィンオキサイド誘導体系重合開始剤（Ａ１２１）、α－アミノアセトフェノン誘導体系重合開始剤（Ａ１２２）、ベンジルケタール誘導体系重合開始剤（Ａ１２３）、α－ヒドロキシアセトフェノン誘導体系重合開始剤（Ａ１２４）、ベンゾイン誘導体系重合開始剤（Ａ１２５）、オキシムエステル誘導体系重合開始剤（Ａ１２６）及びチタノセン誘導体系重合開始剤（Ａ１２７）等は活性光線、酸及び塩基いずれによってもラジカルを発生させることが可能で（Ａ１）、及び（Ａ２）のいずれとしても好ましく用いることができる。
　また、有機過酸化物系重合開始剤（Ａ２１）、アゾ化合物系重合開始剤（Ａ２２）、その他のラジカル開始剤（Ａ２３）等は、酸及び／又は塩基によってラジカルを発生させることが可能である。
　（Ａ）は単独で用いてもよいし、２種以上を併用してもよい。
　尚、（Ａ１２１）は、（Ａ１）、及び（Ａ２）のいずれとしても適用できる化合物（Ａ１２）の１番目の例であることを示す。 In the present invention, the radical initiator (A) means a compound that generates radicals by at least one of actinic rays, acids, and bases, radical initiator (A1) that generates radicals by actinic rays, and acids. In addition, a known compound such as a radical initiator (A2) that generates radicals with a base can be used.
For example, acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124) The benzoin derivative polymerization initiator (A125), the oxime ester derivative polymerization initiator (A126), the titanocene derivative polymerization initiator (A127), etc. can generate radicals by any of actinic rays, acids and bases. Any of (A1) and (A2) can be preferably used.
The organic peroxide polymerization initiator (A21), the azo compound polymerization initiator (A22), the other radical initiator (A23), and the like can generate radicals with an acid and / or a base. .
(A) may be used independently and may use 2 or more types together.
In addition, (A121) shows that it is the 1st example of the compound (A12) applicable as both (A1) and (A2).
　アシルホスフィンオキサイド誘導体系重合開始剤（Ａ１２１）としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド［ＢＡＳＦジャパン（株）製（ＬＵＣＩＲＩＮ（登録商標）　ＴＰＯ）等］及びビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ（登録商標）　８１９）等］等が挙げられる。 Examples of the acylphosphine oxide derivative polymerization initiator (A121) include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [manufactured by BASF Japan Ltd. (LUCIRIN (registered trademark) TPO, etc.)] and bis (2,4 , 6-trimethylbenzoyl) -phenylphosphine oxide [manufactured by BASF Japan Ltd. (IRGACURE (registered trademark) 819)] and the like.
　α－アミノアセトフェノン誘導体系重合開始剤（Ａ１２２）としては、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン［ＢＡＳＦ（株）ジャパン製（ＩＲＧＡＣＵＲＥ　９０７）等］、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　３６９）等］及び１，２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　３７９）等］等が挙げられる。 As the α-aminoacetophenone derivative-based polymerization initiator (A122), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF Japan (IRGACURE 907), etc.] 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF Japan Ltd. (IRGACURE 369) etc.] and 1,2- (dimethylamino) -2-[(4-methyl Phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF Japan Ltd. (IRGACURE 379)] and the like.
　ベンジルケタール誘導体系重合開始剤（Ａ１２３）としては、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　６５１）等］等が挙げられる。 Examples of the benzyl ketal derivative polymerization initiator (A123) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF Japan Ltd. (IRGACURE 651)] and the like.
　α－ヒドロキシアセトフェノン誘導体系重合開始剤（Ａ１２４）としては、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　１８４）等］、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン［ＢＡＳＦジャパン（株）製（ＤＡＲＯＣＵＲ（登録商標）　１１７３）等］、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　２９５９）等］及び２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　１２７）等］等が挙げられる。 Examples of the α-hydroxyacetophenone derivative-based polymerization initiator (A124) include 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF Japan Ltd. (IRGACURE 184), etc.], 2-hydroxy-2-methyl-1-phenyl- Propan-1-one [manufactured by BASF Japan Ltd. (DAROCUR (registered trademark) 1173), etc.], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-one [manufactured by BASF Japan Ltd. (IRGACURE 2959), etc.] and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl- Propan-1-one [manufactured by BASF Japan Ltd. (IRGACURE 127) etc.] etc. It is below.
　ベンゾイン誘導体系重合開始剤（Ａ１２５）としては、ベンゾインメチルエーテル、ベンゾインエチルエーテル及びベンゾインイソプロピルエーテル等が挙げられる。 Examples of the benzoin derivative polymerization initiator (A125) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
　オキシムエステル誘導体系重合開始剤（Ａ１２６）としては、１，２－オクタンジオン－１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１）等］及びエタノン－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２）等］等が挙げられる。 As the oxime ester derivative polymerization initiator (A126), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] [manufactured by BASF Japan Ltd. (IRGACURE OXE 01) Etc.] and ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) [manufactured by BASF Japan Ltd. (IRGACURE OXE 02) Etc.].
　チタノセン誘導体系重合開始剤（Ａ１２７）としては、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウム［ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ　７８４）等］等が挙げられる。 The titanocene derivative polymerization initiator (A127) includes bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl). Titanium [BASF Japan Ltd. (IRGACURE 784) etc.] etc. are mentioned.
　有機過酸化物系重合開始剤（Ａ２１）としては、ベンゾイルパーオキサイド（ＢＰＯ）、ｔｅｒｔ－ブチルパーオキシアセテート、２，２－ジ－（ｔｅｒｔ－ブチルパーオキシ）ブタン、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｎ－ブチル４，４－ジ－（ｔｅｒｔ－ブチルパーオキシ）バレレート、ジ－（２－ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン、ジクミルパーオキサイド、ジ－ｔｅｒｔ－ヘキシルパーオキサイド、２，５，－ジメチル－２，５，－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキサン、ｔｅｒｔ－ブチルクミルパーオキサイド、ジ－ｔｅｒｔ－ブチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、ｐ－メンタンハイドロパーオキサイド、１，１，３，３，－テトラメチルブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイド及びｔｅｒｔ－ブチルトリメチルシリルパーオキサイド等が挙げられる。 Examples of the organic peroxide polymerization initiator (A21) include benzoyl peroxide (BPO), tert-butyl peroxyacetate, 2,2-di- (tert-butylperoxy) butane, tert-butyl peroxybenzoate, n-butyl 4,4-di- (tert-butylperoxy) valerate, di- (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, di-tert-hexyl peroxide, 2,5,- Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3 , 3-Tetramethylbutyl hydride Peroxide, cumene hydroperoxide, tert- butyl hydroperoxide and tert- butyl trimethylsilyl peroxide.
　アゾ化合物系重合開始剤（Ａ２２）としては、１－［（１－シアノ－１－メチルエチル）アゾ］ホルムアミド、２，２’－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド）、２，２’－アゾビス（Ｎ－シクロヘキシル－２－メチルプロピオンアミド）及び２，２’－アゾビス（２，４，４－トリメチルペンタン）等が挙げられる。 As the azo compound polymerization initiator (A22), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 Examples include '-azobis (N-cyclohexyl-2-methylpropionamide) and 2,2'-azobis (2,4,4-trimethylpentane).
　その他の重合開始剤（Ａ２３）としては、２，３－ジメチル－２，３－ジフェニルブタン等が挙げられる。 Other polymerization initiators (A23) include 2,3-dimethyl-2,3-diphenylbutane.
　活性光線によりラジカルを発生するラジカル開始剤（Ａ１）としては、光硬化性の観点から、アシルホスフィンオキサイド誘導体系重合開始剤（Ａ１２１）、α－アミノアセトフェノン誘導体系重合開始剤（Ａ１２２）、ベンジルケタール誘導体系重合開始剤（Ａ１２３）、α－ヒドロキシアセトフェノン誘導体系重合開始剤（Ａ１２４）、ベンゾイン誘導体系重合開始剤（Ａ１２５）、オキシムエステル誘導体系重合開始剤（Ａ１２６）及びチタノセン誘導体系重合開始剤（Ａ１２７）からなる群から選ばれる少なくとも１種のラジカル開始剤が好ましい。 As the radical initiator (A1) for generating radicals by actinic rays, from the viewpoint of photocurability, acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal Derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124), benzoin derivative polymerization initiator (A125), oxime ester derivative polymerization initiator (A126), and titanocene derivative polymerization initiator ( At least one radical initiator selected from the group consisting of A127) is preferred.
　酸及び／又は塩基によりラジカルを発生するラジカル開始剤（Ａ２）としては、光硬化性の観点から、アシルホスフィンオキサイド誘導体系重合開始剤（Ａ１２１）、α－アミノアセトフェノン誘導体系重合開始剤（Ａ１２２）、ベンジルケタール誘導体系重合開始剤（Ａ１２３）、α－ヒドロキシアセトフェノン誘導体系重合開始剤（Ａ１２４）、ベンゾイン誘導体系重合開始剤（Ａ１２５）、オキシムエステル誘導体系重合開始剤（Ａ１２６）、チタノセン誘導体系重合開始剤（Ａ１２７）、有機過酸化物系重合開始剤（Ａ２１）及びアゾ化合物系重合開始剤（Ａ２２）からなる群から選ばれる少なくとも１種のラジカル開始剤が好ましい。 As the radical initiator (A2) that generates a radical by an acid and / or a base, from the viewpoint of photocurability, an acylphosphine oxide derivative polymerization initiator (A121), an α-aminoacetophenone derivative polymerization initiator (A122) , Benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124), benzoin derivative polymerization initiator (A125), oxime ester derivative polymerization initiator (A126), titanocene derivative polymerization At least one radical initiator selected from the group consisting of an initiator (A127), an organic peroxide polymerization initiator (A21) and an azo compound polymerization initiator (A22) is preferred.
　これらのラジカル開始剤（Ａ）の中では、感光性組成物の貯蔵安定性の観点から、活性光線によりラジカルを発生するラジカル開始剤（Ａ１）〔（Ａ１２）を含む〕が好ましい。特に感光性組成物中に活性光線により塩基を発生する塩基発生剤（Ｃ１）を含む場合は、（Ｃ１）から発生した塩基によるラジカル発生がより促進されることから、（Ａ１２）を用いるのが好ましい。 Among these radical initiators (A), from the viewpoint of storage stability of the photosensitive composition, radical initiators (A1) [including (A12)] that generate radicals by actinic rays are preferable. In particular, when the photosensitive composition contains a base generator (C1) that generates a base by actinic rays, radical generation by the base generated from (C1) is further promoted, and therefore (A12) is used. preferable.
　本発明の感光性組成物中のラジカル開始剤（Ａ）の含有量は、光硬化性の観点から、重合性物質（Ｄ）の重量に対して、好ましくは０．０５～３０重量％、更に好ましくは０．１～２５重量％である。 The content of the radical initiator (A) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight based on the weight of the polymerizable substance (D) from the viewpoint of photocurability, and further Preferably, the content is 0.1 to 25% by weight.
　本発明における重合性物質（Ｄ）としては、単官能ラジカル重合性物質（Ｄ１）、２官能ラジカル重合性物質（Ｄ２）及び３官能以上のラジカル重合性物質（Ｄ３）等の公知の化合物を用いることができ、（Ｄ）は単官能ラジカル重合性物質（Ｄ１）を必須成分として含有する。
　（Ｄ）は１種を単独で用いても、２種以上を併用してもよい。
　尚、上記「単官能ラジカル重合性物質（Ｄ１）」とは、重合性官能基の数が１個のラジカル重合性物質を意味し、「２官能ラジカル重合性物質（Ｄ２）」とは、重合性官能基の数が２個のラジカル重合性物質を意味し、「３官能以上のラジカル重合性物質（Ｄ３）」とは、重合性官能基の数が３個以上のラジカル重合性物質を意味する。以下同様の記載法を用いる。 As the polymerizable substance (D) in the present invention, a known compound such as a monofunctional radical polymerizable substance (D1), a bifunctional radical polymerizable substance (D2), or a trifunctional or higher functional radical polymerizable substance (D3) is used. (D) contains the monofunctional radically polymerizable substance (D1) as an essential component.
(D) may be used individually by 1 type, or may use 2 or more types together.
The “monofunctional radically polymerizable substance (D1)” means a radically polymerizable substance having one polymerizable functional group, and the “bifunctional radically polymerizable substance (D2)” means a polymerization. Means a radically polymerizable substance having two functional groups, and “a radically polymerizable substance having three or more functions (D3)” means a radically polymerizable substance having three or more polymerizable functional groups. To do. Hereinafter, the same description method is used.
　単官能ラジカル重合性物質（Ｄ１）としては、（メタ）アクリル酸、炭素数４～３５の単官能（メタ）アクリレート化合物（Ｄ１１）、炭素数３～３５の単官能（メタ）アクリルアミド化合物（Ｄ１２）、炭素数６～３５の単官能芳香族ビニル化合物（Ｄ１３）、炭素数３～２０の単官能ビニルエーテル化合物（Ｄ１４）及びその他の単官能ラジカル重合性物質（Ｄ１５）等が挙げられる。
　（Ｄ１）は１種を単独で用いても、２種以上を併用してもよい。 Examples of the monofunctional radical polymerizable substance (D1) include (meth) acrylic acid, a monofunctional (meth) acrylate compound having 4 to 35 carbon atoms (D11), and a monofunctional (meth) acrylamide compound having 3 to 35 carbon atoms (D12 ), Monofunctional aromatic vinyl compounds having 6 to 35 carbon atoms (D13), monofunctional vinyl ether compounds having 3 to 20 carbon atoms (D14), and other monofunctional radical polymerizable substances (D15).
(D1) may be used alone or in combination of two or more.
　尚、上記及び以下において、「アクリレート」、「メタクリレート」の双方又はいずれかを指す場合「（メタ）アクリレート」と、「アクリル」、「メタクリル」の双方又はいずれかを指す場合「（メタ）アクリル」と、それぞれ記載することがある。 In the above and the following, when referring to both and / or “acrylate” and “methacrylate”, when referring to “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” May be described respectively.
　炭素数４～３５の単官能（メタ）アクリレート化合物（Ｄ１１）としては、炭素数６～３５の単官能アルキル（メタ）アクリレート（Ｄ１１１）、炭素数９～４０の芳香環を有する単官能（メタ）アクリレート（Ｄ１１２）、炭素数４～３５の水酸基を有する単官能（メタ）アクリレート（Ｄ１１３）、その他の単官能（メタ）アクリレート（Ｄ１１４）等が挙げられ、炭素数６～３５の単官能アルキル（メタ）アクリレート（Ｄ１１１）を必須成分として含有する。 Examples of the monofunctional (meth) acrylate compound (D11) having 4 to 35 carbon atoms include monofunctional alkyl (meth) acrylate (D111) having 6 to 35 carbon atoms and monofunctional (meta) having an aromatic ring having 9 to 40 carbon atoms. ) Acrylate (D112), monofunctional (meth) acrylate (D113) having a hydroxyl group having 4 to 35 carbon atoms, and other monofunctional (meth) acrylate (D114). Monofunctional alkyl having 6 to 35 carbon atoms (Meth) acrylate (D111) is contained as an essential component.
　炭素数６～３５の単官能アルキル（メタ）アクリレート（Ｄ１１１）としては、ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｔｅｒｔ－オクチル（メタ）アクリレート、２，３－ジメチルヘキシル（メタ）アクリレート、イソアミル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、２－デシルテトラデカニル（メタ）アクリレート等が挙げられる。
　（Ｄ１１１）としては、接着強度及び低誘電性の観点から炭素数１１～３５の単官能アルキル（メタ）アクリレートが好ましく、２，３－ジメチルヘキシルアクリレート、ステアリルアクリレート、イソオクチルアクリレート、ラウリルアクリレート及びイソステアリルアクリレートが更に好ましい。 Examples of the monofunctional alkyl (meth) acrylate having 6 to 35 carbon atoms (D111) include butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) ) Acrylate, tert-octyl (meth) acrylate, 2,3-dimethylhexyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) Examples include acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and 2-decyltetradecanyl (meth) acrylate.
(D111) is preferably a monofunctional alkyl (meth) acrylate having 11 to 35 carbon atoms from the viewpoint of adhesive strength and low dielectric constant, and 2,3-dimethylhexyl acrylate, stearyl acrylate, isooctyl acrylate, lauryl acrylate, More preferred is stearyl acrylate.
　炭素数９～４０の芳香環を有する単官能（メタ）アクリレート（Ｄ１１２）としては、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシメチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシプロピル（メタ）アクリレート、フェニルジエチレングリコール（メタ）アクリレート及びフェニルトリエチレングリコール（メタ）アクリレート等が挙げられる。 Monofunctional (meth) acrylate (D112) having an aromatic ring having 9 to 40 carbon atoms includes benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (Meth) acrylate, phenyldiethylene glycol (meth) acrylate, phenyltriethylene glycol (meth) acrylate, and the like.
　炭素数４～３５の水酸基を有する単官能（メタ）アクリレート（Ｄ１１３）としては、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート及び４－ヒドロキシブチル（メタ）アクリレート等が挙げられる。
　（Ｄ１１３）としては、重合性物質（Ｄ）との相溶性の観点から、２－ヒドロキシプロピル（メタ）アクリレート及び４－ヒドロキシブチル（メタ）アクリレートが好ましい。 The monofunctional (meth) acrylate (D113) having a hydroxyl group having 4 to 35 carbon atoms includes 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Examples thereof include hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
(D113) is preferably 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate from the viewpoint of compatibility with the polymerizable substance (D).
　その他の単官能（メタ）アクリレート（Ｄ１１４）としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、４－ｎ－ブチルシクロへキシル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、２－エチルヘキシルジグリコール（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、２－クロロエチル（メタ）アクリレート、４－ブロモブチル（メタ）アクリレート、シアノエチル（メタ）アクリレート、ブトキシメチル（メタ）アクリレート、メトキシプロピレンモノ（メタ）アクリレート、３－メトキシブチル（メタ）アクリレート、アルコキシメチル（メタ）アクリレート、２－エチルへキシルカルビトール（メタ）アクリレート、アルコキシエチル（メタ）アクリレート、２－（２－メトキシエトキシ）エチル（メタ）アクリレート、２－（２－ブトキシエトキシ）エチル（メタ）アクリレート、２，２，２－テトラフルオロエチル（メタ）アクリレート、１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロデシル（メタ）アクリレート、４－ブチルフェニル（メタ）アクリレート、フェニル（メタ）アクリレート、グリシジル（メタ）アクリレート、グリシジロキシブチル（メタ）アクリレート、グリシジロキシエチル（メタ）アクリレート、グリシジロキシプロピル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、ジエチルアミノプロピル（メタ）アクリレート、トリメトキシシリルプロピル（メタ）アクリレート、トリメチルシリルプロピル（メタ）アクリレート、ポリエチレンオキサイドモノメチルエーテル（メタ）アクリレート、オリゴエチレンオキサイドモノメチルエーテル（メタ）アクリレート、ポリエチレンオキサイド（メタ）アクリレート、オリゴエチレンオキサイド（メタ）アクリレート、オリゴエチレンオキサイドモノアルキルエーテル（メタ）アクリレート、ポリエチレンオキサイドモノアルキルエーテル（メタ）アクリレート、ジプロピレングリコール（メタ）アクリレート、ポリプロピレンオキサイドモノアルキルエーテル（メタ）アクリレート、オリゴプロピレンオキサイドモノアルキルエーテル（メタ）アクリレート、２－メタクリロイロキシエチルコハク酸、２－メタクリロイロキシヘキサヒドロフタル酸、ブトキシジエチレングリコール（メタ）アクリレート、トリフロロエチル（メタ）アクリレート、パーフロロオクチルエチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、エチレンオキサイド（以下、ＥＯと記載）変性フェノール（メタ）アクリレート、ＥＯ変性クレゾール（メタ）アクリレート、ＥＯ変性ノニルフェノール（メタ）アクリレート、プロピレンオキサイド（以下、ＰＯと記載）変性ノニルフェノール（メタ）アクリレート及びＥＯ変性－２－エチルヘキシル（メタ）アクリレート等のビニルエーテル基及び／又はアリルエーテル基を有しないもの等が挙げられる。 Other monofunctional (meth) acrylates (D114) include methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, Isobornyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, butoxymethyl (meth) Acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate , Alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxy Ethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate Rate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate , Oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene Oxide monoalkyl ether (meth) acrylate 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl (meth) acrylate, ethylene oxide (hereinafter referred to as EO) modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, propylene oxide (hereinafter referred to as PO) modification Examples thereof include those having no vinyl ether group and / or allyl ether group, such as nonylphenol (meth) acrylate and EO-modified-2-ethylhexyl (meth) acrylate.
　炭素数３～３５の単官能（メタ）アクリルアミド化合物（Ｄ１２）としては、（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－プロピル（メタ）アクリルアミド、Ｎ－ｎ－ブチル（メタ）アクリルアミド、Ｎ－ｔｅｒｔ－ブチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド及びＮ，Ｎ－ジエチル（メタ）アクリルアミド等が挙げられる。 Monofunctional (meth) acrylamide compounds (D12) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide and N, N-diethyl (meth) acrylamide.
　炭素数６～３５の単官能芳香族ビニル化合物（Ｄ１３）〔後述するビニルエーテル化合物（Ｄ１４）は含まない。〕としては、ビニルチオフェン、ビニルフラン、ビニルピリジン、スチレン、メチルスチレン、トリメチルスチレン、エチルスチレン、イソプロピルスチレン、クロルメチルスチレン、メトキシスチレン、アセトキシスチレン、クロルスチレン、ジクロルスチレン、ブロムスチレン、ビニル安息香酸メチルエステル、３－メチルスチレン、４－メチルスチレン、３－エチルスチレン、４－エチルスチレン、３－プロピルスチレン、４－プロピルスチレン、３－ブチルスチレン、４－ブチルスチレン、３－ヘキシルスチレン、４－ヘキシルスチレン、３－オクチルスチレン、４－オクチルスチレン、３－（２－エチルヘキシル）スチレン、４－（２－エチルヘキシル）スチレン、アリルスチレン、イソプロペニルスチレン、ブテニルスチレン、オクテニルスチレン、４－ｔｅｒｔ－ブトキシカルボニルスチレン、４－メトキシスチレン及び４－ｔｅｒｔ－ブトキシスチレン等が挙げられる。 Monofunctional aromatic vinyl compound having 6 to 35 carbon atoms (D13) [not including vinyl ether compound (D14) described later. ] Are vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid. Methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4- Hexyl styrene, 3-octyl styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, Kute alkenyl styrene, 4-tert-butoxycarbonyl styrene, 4-methoxystyrene and 4-tert-butoxystyrene, and the like.
　炭素数３～２０の単官能ビニルエーテル化合物（Ｄ１４）としては、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ｎ－ブチルビニルエーテル、ｔｅｒｔ－ブチルビニルエーテル、２－エチルヘキシルビニルエーテル、ｎ－ノニルビニルエーテル、ラウリルビニルエーテル、シクロヘキシルビニルエーテル、シクロヘキシルメチルビニルエーテル、４－メチルシクロヘキシルメチルビニルエーテル、ベンジルビニルエーテル、ジシクロペンテニルビニルエーテル、２－ジシクロペンテノキシエチルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、ブトキシエチルビニルエーテル、メトキシエトキシエチルビニルエーテル、エトキシエトキシエチルビニルエーテル、メトキシポリエチレングリコールビニルエーテル、テトラヒドロフルフリルビニルエーテル、２－ヒドロキシエチルビニルエーテル、２－ヒドロキシプロピルビニルエーテル、４－ヒドロキシブチルビニルエーテル、４－ヒドロキシメチルシクロヘキシルメ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、ポリエチレングリコールビニルエーテル、クロルエチルビニルエーテル、クロルブチルビニルエーテル、クロルエトキシエチルビニルエーテル、フェニルエチルビニルエーテル及びフェノキシポリエチレングリコールビニルエーテル等が挙げられる。 Examples of the monofunctional vinyl ether compound (D14) having 3 to 20 carbon atoms include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether , Cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl Vinyl ether, methoxypo Ethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether Chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxypolyethylene glycol vinyl ether, and the like.
　その他の単官能ラジカル重合性物質（Ｄ１５）としては、アクリロニトリル、脂肪族ビニルエステル化合物（酢酸ビニル、プロピオン酸ビニル及びバーサチック酸ビニル等）、脂肪族アリルエステル化合物（酢酸アリル等）、ハロゲン含有単量体（塩化ビニリデン及び塩化ビニル等）及びオレフィン化合物（エチレン及びプロピレン等）等が挙げられる。 Other monofunctional radically polymerizable substances (D15) include acrylonitrile, aliphatic vinyl ester compounds (such as vinyl acetate, vinyl propionate and vinyl versatate), aliphatic allyl ester compounds (such as allyl acetate), halogen-containing single quantities Examples thereof include vinylidene chloride and vinyl chloride, and olefin compounds (ethylene and propylene, etc.).
　重合性物質（Ｄ）の重量に対する単官能ラジカル重合性物質（Ｄ１）の重量割合は、５０～９９．９重量％であり、基材密着性の観点から７５～９９．９重量％含有するのが好ましく、柔軟性の観点から好ましくは８０～９９．９重量％であり、更に好ましくは９０～９９．９重量％である。（Ｄ１）の重量割合が５０重量％未満であると基材密着性が低下し、（Ｄ１）のみの場合は光硬化性が不足する。 The weight ratio of the monofunctional radically polymerizable substance (D1) to the weight of the polymerizable substance (D) is 50 to 99.9% by weight, and it is contained from 75 to 99.9% by weight from the viewpoint of substrate adhesion. From the viewpoint of flexibility, it is preferably 80 to 99.9% by weight, and more preferably 90 to 99.9% by weight. When the weight ratio of (D1) is less than 50% by weight, the substrate adhesion decreases, and in the case of only (D1), the photocurability is insufficient.
　重合性物質（Ｄ）の重量に対する炭素数６～３５の単官能アルキル（メタ）アクリレート（Ｄ１１１）の重量割合は、接着強度及び低誘電性の観点から、２０～９９．９重量％であることが好ましく、６０～９９．９重量％であることが更に好ましい。 The weight ratio of the monofunctional alkyl (meth) acrylate (C111) having 6 to 35 carbon atoms to the weight of the polymerizable substance (D) is 20 to 99.9% by weight from the viewpoint of adhesive strength and low dielectric property. Is preferable, and more preferably 60 to 99.9% by weight.
　炭素数９～４０の芳香環を有する単官能（メタ）アクリレート（Ｄ１１２）は、硬化物の低誘電性の観点から、重合性物質（Ｄ）に対して５０モル％未満であることが好ましい。 The monofunctional (meth) acrylate (D112) having an aromatic ring having 9 to 40 carbon atoms is preferably less than 50 mol% based on the polymerizable substance (D) from the viewpoint of low dielectric properties of the cured product.
　２官能ラジカル重合性物質（Ｄ２）としては、例えば、炭素数８～３５の２官能（メタ）アクリレート化合物（Ｄ２２）及び炭素数６～２０の２官能ビニルエーテル化合物（Ｄ２４）が挙げられる。（Ｄ２）は１種を単独で使用しても、２種以上を併用してもよい。 Examples of the bifunctional radically polymerizable substance (D2) include a bifunctional (meth) acrylate compound (D22) having 8 to 35 carbon atoms and a bifunctional vinyl ether compound (D24) having 6 to 20 carbon atoms. (D2) may be used alone or in combination of two or more.
　炭素数８～３５の２官能（メタ）アクリレート化合物（Ｄ２２）としては、１，６－ヘキサンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、２，４－ジメチル－１，５－ペンタンジオールジ（メタ）アクリレート、ブチルエチルプロパンジオールジ（メタ）アクリレート、エトキシ化シクロヘキサンメタノールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、オリゴエチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、２－エチル－２－ブチル－ブタンジオールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ＥＯ変性ビスフェノールＡジ（メタ）アクリレート、ＥＯ変性ビスフェノールＦジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、オリゴプロピレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、２－エチル－２－ブチル－プロパンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート及びプロポキシ化エトキシ化ビスフェノールＡジ（メタ）アクリレート等が挙げられる。 Examples of the bifunctional (meth) acrylate compound (D22) having 8 to 35 carbon atoms include 1,6-hexanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol di (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, neopentyl hydroxypivalate Recall di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate and the like.
　炭素数６～２０の２官能ビニルエーテル化合物（Ｄ２４）としては、例えば、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、ポリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ブチレングリコールジビニルエーテル、ヘキサンジオールジビニルエーテル、アルキレンオキサイド変性ビスフェノールＡジビニルエーテル、アルキレンオキサイド変性ビスフェノールＦジビニルエーテル等が挙げられる。 Examples of the bifunctional vinyl ether compound (D24) having 6 to 20 carbon atoms include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, and alkylene oxide modified. Examples thereof include bisphenol A divinyl ether and alkylene oxide-modified bisphenol F divinyl ether.
　３官能以上のラジカル重合性物質（Ｄ３）としては、３～６価のアルコールの３～６官能（メタ）アクリレート化合物（Ｄ３１）、３～６価のアルコールの３～６官能ビニルエーテル化合物（Ｄ３２）及び、その他の３官能以上のラジカル重合性物質（Ｄ３３）が挙げられる。（Ｄ３）は１種を単独で用いても、２種以上を併用してもよい。 The tri- or higher functional radical polymerizable substance (D3) includes a tri- to hexa-functional alcohol tri-functional (meth) acrylate compound (D31) and a tri- to hexa-functional alcohol tri-functional vinyl ether compound (D32). And other trifunctional or higher functional radical polymerizable substances (D33). (D3) may be used alone or in combination of two or more.
　３～６価のアルコールの３～６官能（メタ）アクリレート化合物（Ｄ３１）としては、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパンのアルキレンオキサイド変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスルトールトリ（メタ）アクリレート、トリメチロールプロパントリ（（メタ）アクリロイルオキシプロピル）エーテル、ソルビトールトリ（メタ）アクリレート、ペンタエリスリトールの炭素数２～４のアルキレンオキサイド１～３０モル付加物のトリ（メタ）アクリレート、エトキシ化グリセリントリ（メタ）アクリレート、プロピオン酸ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ソルビトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、プロピオン酸ジペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールの炭素数２～４のアルキレンオキサイド１～３０モル付加物のテトラ（メタ）アクリレート、ソルビトールペンタ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ソルビトールヘキサ（メタ）アクリレート及びカプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 Examples of tri- to hexa-functional (meth) acrylate compound (D31) of trivalent to hexavalent alcohol include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and trimethylolpropane alkylene oxide-modified tri (meta). ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, sorbitol tri (meth) acrylate, pentaerythritol 4 alkylene oxide 1-30 mol adduct tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, pen Carbon number of erythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, pentaerythritol Tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, and caprolactone Examples thereof include modified dipentaerythritol hexa (meth) acrylate.
　３～６価のアルコールの３～６官能ビニルエーテル化合物（Ｄ３２）としては、トリメチロールエタントリビニルエーテル、トリメチロールプロパントリビニルエーテル、グリセリントリビニルエーテルＥＯ付加トリメチロールプロパントリビニルエーテル、ＰＯ付加トリメチロールプロパントリビニルエーテル、ジトリメチロールプロパンテトラビニルエーテル、ペンタエリスリトールテトラビニルエーテル、ＥＯ付加ジトリメチロールプロパンテトラビニルエーテル、ＰＯ付加ジトリメチロールプロパンテトラビニルエーテル、ＥＯ付加ペンタエリスリトールテトラビニルエーテル、ＰＯ付加ペンタエリスリトールテトラビニルエーテル、ジペンタエリスリトールペンタビニルエーテル、ジペンタエリスリトールヘキサビニルエーテル、ＥＯ付加ジペンタエリスリトールヘキサビニルエーテル及びＰＯ付加ジペンタエリスリトールヘキサビニルエーテル等が挙げられる。 Examples of the tri- to hexa-functional alcohol ether compound (D32) of tri- to hexavalent alcohol include trimethylol ethane trivinyl ether, trimethylol propane trivinyl ether, glycerin trivinyl ether EO-added trimethylol propane trivinyl ether, PO-added trimethylol propane trivinyl ether, Ditrimethylolpropane tetravinyl ether, pentaerythritol tetravinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether EO adduct of dipentaerythritol hexa ether and PO adduct of dipentaerythritol hexavinyl ether.
　その他の３官能以上のラジカル重合性物質（Ｄ３３）としては、イソシアヌル酸アルキレンオキサイド変性トリ（メタ）アクリレート、トリ（（メタ）アクリロイルオキシエチル）イソシアヌレート、ヒドロキシピバルアルデヒド変性ジメチロールプロパントリ（メタ）アクリレート及びフォスファゼンのアルキレンオキサイド変性ヘキサ（メタ）アクリレート等が挙げられる。 Other tri- or higher functional radical polymerizable substances (D33) include isocyanuric acid alkylene oxide modified tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri (meta). ) And acrylate and phosphazene alkylene oxide modified hexa (meth) acrylates.
　２官能ラジカル重合性物質（Ｄ２）及び３官能以上のラジカル重合性物質（Ｄ３）として好ましいのは、炭素数８～３５の２官能（メタ）アクリレート化合物（Ｄ２２）、炭素数６～２０の２官能ビニルエーテル化合物（Ｄ２４）及び３～６価のアルコールの３～６官能（メタ）アクリレート化合物（Ｄ３１）である。 Preferred as the bifunctional radical polymerizable substance (D2) and the trifunctional or higher functional radical polymerizable substance (D3) are bifunctional (meth) acrylate compounds (D22) having 8 to 35 carbon atoms, and 2 having 6 to 20 carbon atoms. A functional vinyl ether compound (D24) and a tri- to hexa-functional (meth) acrylate compound (D31) of a tri- to hexavalent alcohol.
　本発明における非ラジカル重合性ポリマー（Ｅ）としては、前記単官能ラジカル重合性物質（Ｄ１）を構成単位として含有するビニルポリマー（Ｅ１）、２価のアルコール（ｅ２１）と２価のカルボン酸（ｅ２２）とを構成単位として含有するポリエステル樹脂（Ｅ２）、２価のアルコール（ｅ２１）と２価のイソシアネート（ｅ３１）とを構成単位として含有するポリウレタン樹脂（Ｅ３）等の公知の化合物を用いることができる。上記各構成単位は、１種であっても２種以上であってもよい。例えば、単官能ラジカル重合性物質（Ｄ１）を構成単位として含有するビニルポリマー（Ｅ１）は、単官能ラジカル重合性物質（Ｄ１）を含む単量体組成物を重合することにより得られる。
　尚、本発明における非ラジカル重合性ポリマー（Ｅ）とは、ラジカル重合性官能基を実質的に有さない重量平均分子量（以下、Ｍｗと略記）１万以上の化合物を意味する。（Ｅ）は１種を単独で用いても、２種以上を併用してもよい。 As the non-radically polymerizable polymer (E) in the present invention, a vinyl polymer (E1) containing the monofunctional radical polymerizable substance (D1) as a structural unit, a divalent alcohol (e21) and a divalent carboxylic acid ( a known compound such as a polyester resin (E2) containing e22) as a structural unit and a polyurethane resin (E3) containing divalent alcohol (e21) and divalent isocyanate (e31) as structural units Can do. Each of the structural units may be one type or two or more types. For example, the vinyl polymer (E1) containing the monofunctional radical polymerizable substance (D1) as a structural unit can be obtained by polymerizing a monomer composition containing the monofunctional radical polymerizable substance (D1).
In the present invention, the non-radically polymerizable polymer (E) means a compound having a weight average molecular weight (hereinafter abbreviated as Mw) of 10,000 or more that does not substantially have a radical polymerizable functional group. (E) may be used alone or in combination of two or more.
　ポリエステル樹脂（Ｅ２）及びポリウレタン樹脂（Ｅ３）の構成単位である２価のアルコール（ｅ２１）としては、例えば、エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，４－ブタンジオ－ル、ネオペンチルグリコール、１，４－ブテンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール等のアルキレングリコール類；ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のアルキレンエーテルグリコール類；１，４－シクロヘキサンジメタノール、水素添加ビスフェノールＡ等の脂環式ジオール類；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ等のビスフェノール類；ビスフェノール類のアルキレンオキサイド［ＥＯ、ＰＯ及びブチレンオキサイド等］２～８モル付加物等が挙げられる。 Examples of the divalent alcohol (e21) that is a structural unit of the polyester resin (E2) and the polyurethane resin (E3) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butanedio. -Alkylene glycols such as diol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly Alkylene ether glycols such as tetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; bisphenol A, bisphenol F, bisphenol S, etc. Scan phenols, alkylene oxide bisphenol [EO, PO and butylene oxide, and the like] 2-8 moles adducts.
　ポリエステル樹脂（Ｅ２）の構成単位である２価のカルボン酸（ｅ２２）としては、例えば、マレイン酸、フマール酸、シトラコン酸、イタコン酸、グルタコン酸、フタル酸、イソフタル酸、テレフタル酸、コハク酸、アジピン酸、セバンチン酸、アゼライン酸、マロン酸、ｎ－ドデセニルコハク酸、イソドデセニルコハク酸、ｎ－ドデシルコハク酸、イソドデシルコハク酸、ｎ－オクテニルコハク酸、イソオクテニルコハク酸、ｎ－オクチルコハク酸、イソオクチルコハク酸等及びこれらの酸の無水物又は低級アルキルエステル等が挙げられる。 Examples of the divalent carboxylic acid (e22) that is a structural unit of the polyester resin (E2) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, Adipic acid, sevantinic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid, Examples include isooctyl succinic acid and the like, and anhydrides or lower alkyl esters of these acids.
　ポリウレタン樹脂（Ｅ３）の構成単位である２価のイソシアネート（ｅ３１）としては、１，３－又は１，４－フェニレンジイソシアネート、２，４－又は２，６－トリレンジイソシアネート（ＴＤＩ）、４，４’－又は２，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、ｍ－又はｐ－イソシアナトフェニルスルホニルイソシアネート、４，４’－ジイソシアナトビフェニル、３，３’－ジメチル－４，４’－ジイソシアナトビフェニル、３，３’－ジメチル－４，４’－ジイソシアナトジフェニルメタン、１，５－ナフチレンジイソシアネート、ｍ－又はｐ－イソシアナトフェニルスルホニルイソシアネート、エチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、ヘプタメチレンジイソシアネート、オクタメチレンジイソシアネート、ノナメチレンジイソシアネート、デカメチレンジイソシアネート、ドデカメチレンジイソシアネート、２，２，４－又は２，４，４－トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２，６－ジイソシアナトメチルカプロエート、２，６－ジイソシアナトエチルカプロエート、ビス（２－イソシアナトエチル）フマレート、ビス（２－イソシアナトエチル）カーボネート、トリメチルヘキサメチレンジイソシアネート（ＴＭＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、２，４－又は２，６－メチルシクロヘキサンジイソシアネート（水添ＴＤＩ）、ジシクロヘキシルメタン－４，４’－ジイソシアネート（水添ＭＤＩ）、シクロヘキシレンジイソシアネート、メチルシクロヘキシレンジイソシアネート、ビス（２－イソシアナトエチル）－４－シクロヘキシレン－１，２－ジカルボキシレート、２，５－又は２，６－ノルボルナンジイソシアネート、ダイマー酸ジイソシアネート（ＤＤＩ）、ｍ－又はｐ－キシリレンジイソシアネート（ＸＤＩ）、ジエチルベンゼンジイソシアネート及びα，α，α’，α’－テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）等が挙げられる。 Examples of the divalent isocyanate (e31) that is a structural unit of the polyurethane resin (E3) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4, 4'- or 2,4'-diphenylmethane diisocyanate (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Natobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate ( HDI), hepta Tylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate 2,6-diisocyanatoethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, trimethylhexamethylene diisocyanate (TMDI), isophorone diisocyanate (IPDI), 2,4- Or 2,6-methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene dii Cyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, dimer acid diisocyanate (DDI), m- Alternatively, p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like can be mentioned.
　非ラジカル重合性ポリマー（Ｅ）として好ましいのは、相溶性の観点から、単官能ラジカル重合性物質（Ｄ１）を構成単位として含有するビニルポリマー（Ｅ１）であり、更に好ましくは、炭素数６～３５の単官能分岐アルキル（メタ）アクリレートを構成単位として含有するビニルポリマーであり、特に好ましくは、２－エチルヘキシル（メタ）アクリレートを構成単位として５０モル％以上含有するビニルポリマーである。
　非ラジカル重合性ポリマー（Ｅ）の酸価は、通常０～１００ｍｇＫＯＨ／ｇであり、重合性物質（Ｄ）との相溶性の観点から好ましくは０～８０ｍｇＫＯＨ／ｇ、更に好ましくは０～４５ｍｇＫＯＨ／ｇである。酸価が１００を超えると、他の成分との相溶性が悪くなる。 The non-radical polymerizable polymer (E) is preferably a vinyl polymer (E1) containing a monofunctional radical polymerizable substance (D1) as a structural unit from the viewpoint of compatibility, and more preferably a carbon number of 6 to A vinyl polymer containing 35 monofunctional branched alkyl (meth) acrylates as a structural unit, particularly preferably a vinyl polymer containing 50 mol% or more of 2-ethylhexyl (meth) acrylate as a structural unit.
The acid value of the non-radically polymerizable polymer (E) is usually from 0 to 100 mgKOH / g, preferably from 0 to 80 mgKOH / g, more preferably from 0 to 45 mgKOH / g from the viewpoint of compatibility with the polymerizable substance (D). g. When the acid value exceeds 100, compatibility with other components is deteriorated.
　非ラジカル重合性ポリマー（Ｅ）のＭｗ［測定は下記ゲルパーミエイションクロマトグラフィー（ＧＰＣ）法による。］は、通常１０，０００以上、好ましくは１２，０００～１，０００，０００、更に好ましくは１００，０００～９００，０００である。Ｍｗが１０，０００未満では基材に対する密着性が悪くなる。 Mw of non-radically polymerizable polymer (E) [Measurement is based on the following gel permeation chromatography (GPC) method. ] Is usually 10,000 or more, preferably 12,000 to 1,000,000, more preferably 100,000 to 900,000. When Mw is less than 10,000, the adhesion to the substrate is deteriorated.
　＜ＧＰＣ測定条件＞
［１］装置　　：ゲルパーミエイションクロマトグラフィー
　　　　　　　　型式「ＨＬＣ－８１２０ＧＰＣ」、東ソー（株）製
［２］カラム　：「ＴＳＫｇｅｌ　ＧＭＨＸＬ」２本＋「ＴＳＫｇｅｌ
　　　　　　　　Ｍｕｌｔｉｐｏｒｅ　ＨＸＬ－Ｍ」（いずれも製品名）、
　　　　　　　　東ソー（株）製
［３］溶離液　：テトラヒドロフラン
［４］基準物質：標準ポリスチレン
　　　　　　　（ＴＳＫｓｔａｎｄａｒｄ　ＰＯＬＹＳＴＹＲＥＮＥ）、
　　　　　　　　東ソー（株）製
［５］注入条件：サンプル濃度０．２５重量％、カラム温度４０℃ <GPC measurement conditions>
[1] Apparatus: Gel permeation chromatography Model “HLC-8120GPC”, manufactured by Tosoh Corporation [2] Column: “TSKgel GMHXL” x 2 + “TSKgel”
Multipore HXL-M "(all product names),
Tosoh Co., Ltd. [3] Eluent: Tetrahydrofuran [4] Reference material: Standard polystyrene (TSK standard POLYSTYRENE),
[5] Injection conditions manufactured by Tosoh Corporation: Sample concentration 0.25% by weight, column temperature 40 ° C.
　本発明の感光性組成物中の重合性物質（Ｄ）と非ラジカル重合性ポリマー（Ｅ）との合計重量に対する重合性物質（Ｄ）の重量割合は、４０～９５重量％であり、好ましくは４２～９２重量％、更に好ましくは、６０～９０重量％である。重合性物質（Ｄ）と非ラジカル重合性ポリマー（Ｅ）との合計重量に対する重合性物質（Ｄ）の含有量が４０重量％未満であると、重合性官能基が不足するため硬化性が悪くなり、９５重量％を超えると、接着強度が低下する。 The weight ratio of the polymerizable substance (D) to the total weight of the polymerizable substance (D) and the non-radical polymerizable polymer (E) in the photosensitive composition of the present invention is 40 to 95% by weight, preferably 42 to 92% by weight, more preferably 60 to 90% by weight. When the content of the polymerizable substance (D) with respect to the total weight of the polymerizable substance (D) and the non-radically polymerizable polymer (E) is less than 40% by weight, the curability is poor because the polymerizable functional group is insufficient. If it exceeds 95% by weight, the adhesive strength decreases.
　本発明の感光性組成物中は、各種基材への密着性がより良好となることから、酸発生剤（Ｂ）及び／又は塩基発生剤（Ｃ）を含有するのが好ましい。
　酸発生剤（Ｂ）と塩基発生剤（Ｃ）のいずれを用いても、各種基材への密着性がより優れ、かつ透明な硬化物が得られるが、硬化物の耐黄変性の観点からは、酸発生剤（Ｂ）を用いるのが更に好ましい。 The photosensitive composition of the present invention preferably contains an acid generator (B) and / or a base generator (C) because adhesion to various substrates becomes better.
Even if it uses any of an acid generator (B) and a base generator (C), the adhesiveness to various base materials is more excellent, and transparent hardened | cured material is obtained, but from a viewpoint of yellowing resistance of hardened | cured material. More preferably, the acid generator (B) is used.
　本発明において酸発生剤（Ｂ）とは、活性光線、ラジカル、酸及び塩基のうちの少なくとも１種により酸を発生する化合物を意味し、活性光線により酸を発生する酸発生剤（Ｂ１）、並びにラジカル、酸及び塩基からなる群から選ばれる少なくとも１種により酸を発生する酸発生剤（Ｂ２）等の公知の化合物が挙げられる。
　酸発生剤（Ｂ）を含むことで、感光性組成物が高感度化され、反応が均一に進行する為、本発明の感光性組成物が硬化されてなる本発明の硬化物は、高硬度・高い耐擦傷性、高透明性が発現可能となると推定される。
　例えば、スルホニウム塩誘導体（Ｂ１２１）及びヨードニウム塩誘導体（Ｂ１２２）等は活性光線又はラジカルによって酸を発生させることが可能で、（Ｂ１）又は（Ｂ２）として適用できる。
　また、スルホン酸エステル誘導体（Ｂ２１）、酢酸エステル誘導体（Ｂ２２）及びホスホン酸エステル（Ｂ２３）等は酸及び／又は塩基によって酸を発生させることが可能で、（Ｂ２）として適用できる。
　（Ｂ）は単独で用いてもよいし、２種以上を併用してもよい。
　尚、（Ｂ１２１）は、（Ｂ１）及び（Ｂ２）のいずれとしても適用できる化合物（Ｂ１２）の１番目の例であることを示す。 In the present invention, the acid generator (B) means a compound that generates an acid by at least one of actinic rays, radicals, acids, and bases, and an acid generator (B1) that generates an acid by actinic rays, And known compounds such as an acid generator (B2) that generates an acid with at least one selected from the group consisting of radicals, acids and bases.
By containing the acid generator (B), the photosensitive composition is highly sensitive and the reaction proceeds uniformly, so that the cured product of the present invention obtained by curing the photosensitive composition of the present invention has a high hardness.・ It is estimated that high scratch resistance and high transparency can be realized.
For example, the sulfonium salt derivative (B121) and the iodonium salt derivative (B122) can generate an acid by actinic rays or radicals, and can be applied as (B1) or (B2).
In addition, the sulfonic acid ester derivative (B21), the acetic acid ester derivative (B22), the phosphonic acid ester (B23), and the like can generate an acid with an acid and / or a base, and can be applied as (B2).
(B) may be used alone or in combination of two or more.
In addition, (B121) shows that it is the 1st example of the compound (B12) applicable as both (B1) and (B2).
　本発明におけるスルホニウム塩誘導体（Ｂ１２１）としては、下記一般式（１）又は下記一般式（２）で示される化合物等が挙げられる。 Examples of the sulfonium salt derivative (B121) in the present invention include compounds represented by the following general formula (1) or the following general formula (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　一般式（１）又は（２）において、Ａ１は下記式（３）、式（４）、一般式（５）～（８）、式（９）及び式（１０）のいずれかで表される２価又は３価の基であり、Ａｒ１～Ａｒ７はそれぞれ独立にベンゼン環骨格を少なくとも１個有し、ハロゲン原子、炭素数１～２０のアシル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数１～２０のアルキルシリル基、ニトロ基、カルボキシル基、水酸基、メルカプト基、アミノ基、シアノ基、フェニル基、ナフチル基、フェノキシ基及びフェニルチオ基からなる群から選ばれる少なくとも１種の原子又は置換基で置換されていてもよい芳香族炭化水素基又は複素環基であってＡｒ１～Ａｒ４、Ａｒ６及びＡｒ７は１価の基、Ａｒ５は２価の基であり、（Ｘ１）－及び（Ｘ２）－はそれぞれ独立に陰イオンを表し、ａは０～２の整数、ｂは１～３の整数で、かつａ＋ｂは２又は３でＡ１の価数と同じ整数である。 In the general formula (1) or (2), A 1 is represented by any of the following formula (3), formula (4), general formulas (5) to (8), formula (9), and formula (10). Each of Ar 1 to Ar 7 independently has at least one benzene ring skeleton, and is a halogen atom, an acyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. , Alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, alkylsilyl groups having 1 to 20 carbon atoms, nitro groups, carboxyl groups, hydroxyl groups, mercapto groups, amino groups, cyano groups, phenyl groups, naphthyl groups An aromatic hydrocarbon group or a heterocyclic group optionally substituted with at least one atom or substituent selected from the group consisting of a group, a phenoxy group and a phenylthio group, Ar 1 to Ar 4 , Ar 6 and Ar 7 is a monovalent group, Ar 5 is a divalent group, (X 1 ) − and (X 2 ) − each independently represents an anion, a is an integer of 0 to 2, b is an integer of 1 to 3, and a + b is 2 Or it is the same integer as the valence of A 1 at 3.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（５）～（８）におけるＲ１～Ｒ７は、それぞれ独立に水素原子、炭素数１～２０のアルキル基、又は、ハロゲン原子、炭素数１～２０のアシル基、炭素数１～２０のアルキル基、アミノ基、シアノ基、フェニル基、ナフチル基、フェノキシ基及びフェニルチオ基からなる群から選ばれる少なくとも１種の原子又は置換基で置換されていてもよいフェニル基を表し、Ｒ１とＲ２、Ｒ４とＲ５、及びＲ６とＲ７は互いに結合して環構造を形成していてもよい。 R 1 to R 7 in the general formulas (5) to (8) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom, an acyl group having 1 to 20 carbon atoms, or 1 to 20 alkyl group, an amino group, a cyano group, a phenyl group, a naphthyl group, at least one atom or optionally substituted phenyl group which is substituted with a group selected from the group consisting of a phenoxy group and a phenylthio group, R 1 And R 2 , R 4 and R 5 , and R 6 and R 7 may be bonded to each other to form a ring structure.
　一般式（２）におけるＡ１として、酸発生効率の観点から好ましいのは、一般式（５）、一般式（７）、一般式（８）、式（９）及び式（１０）のいずれかで表される基であり、一般式（５）、一般式（８）、式（９）及び式（１０）のいずれかで表される基が更に好ましい。 As A 1 in the general formula (2), any one of the general formula (5), the general formula (7), the general formula (8), the formula (9), and the formula (10) is preferable from the viewpoint of acid generation efficiency. And a group represented by any one of the general formula (5), general formula (8), formula (9) and formula (10) is more preferable.
　一般式（１）及び一般式（２）におけるＡｒ１～Ａｒ７は、一般式（１）又は一般式（２）で表される化合物が紫外～可視光領域に吸収をもつようになる基である。
　Ａｒ１～Ａｒ７におけるベンゼン環骨格の数は、好ましくは１～５、更に好ましくは１～４である。
　ベンゼン環骨格を１個有する場合の例としては、例えばベンゼン、又はベンゾフラン、ベンゾチオフェン、インドール、キノリン及びクマリン等の複素環化合物から水素原子を１個又は２個除いた残基が挙げられる。
　ベンゼン環骨格を２個有する場合の例としては、例えばナフタレン、ビフェニル、フルオレン、又はジベンゾフラン、ジベンゾチオフェン、キサントン、キサンテン、チオキサントン、アクリジン、フェノチアジン及びチアントレン等の複素環化合物から水素原子を１個又は２個除いた残基が挙げられる。
　ベンゼン環骨格を３個有する場合の例としては、例えば、アントラセン、フェナントレン、ターフェニル、ｐ－（チオキサンチルメルカプト）ベンゼン及びナフトベンゾチオフェン等の複素環化合物から水素原子を１個又は２個除いた残基が挙げられる。
　ベンゼン環骨格を４個有する場合の例としては、例えばナフタセン、ピレン、ベンゾアントラセン及びトリフェニレン等から水素原子を１個又は２個除いた残基が挙げられる。 Ar 1 to Ar 7 in the general formula (1) and the general formula (2) are groups in which the compound represented by the general formula (1) or the general formula (2) has absorption in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar 1 to Ar 7 is preferably 1 to 5, and more preferably 1 to 4.
Examples of the case of having one benzene ring skeleton include residues obtained by removing one or two hydrogen atoms from benzene or a heterocyclic compound such as benzofuran, benzothiophene, indole, quinoline and coumarin.
Examples of the case of having two benzene ring skeletons include one or two hydrogen atoms from heterocyclic compounds such as naphthalene, biphenyl, fluorene, or dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, acridine, phenothiazine, and thianthrene. Residues excluded are listed.
Examples of having three benzene ring skeletons include, for example, removing one or two hydrogen atoms from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthyl mercapto) benzene, and naphthobenzothiophene. Residue.
As an example in the case of having four benzene ring skeletons, for example, a residue obtained by removing one or two hydrogen atoms from naphthacene, pyrene, benzoanthracene, triphenylene and the like can be mentioned.
　ハロゲン原子としては、フッ素、塩素、臭素及びヨウ素が挙げられ、フッ素及び塩素が好ましい。 Examples of the halogen atom include fluorine, chlorine, bromine and iodine, with fluorine and chlorine being preferred.
　炭素数１～２０のアシル基としては、例えばホルミル基、アセチル基、プロピオニル基、イソブチリル基、バレリル基及びシクロヘキシルカルボニル基等が挙げられる。 Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.
　炭素数１～２０のアルキル基としては、メチル基、エチル基、ｎ－又はｉｓｏ－プロピル基、ｎ－、ｓｅｃ－又はｔｅｒｔ－ブチル基、ｎ－、ｉｓｏ－又はｎｅｏ－ペンチル基、ヘキシル基、ヘプチル基及びオクチル基等が挙げられる。 Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n- or iso-propyl group, n-, sec- or tert-butyl group, n-, iso- or neo-pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned.
　炭素数１～２０のアルコキシ基としては、例えばメトキシ基、エトキシ基、ｎ－又はｉｓｏ－プロポキシ基、ｎ－、ｓｅｃ－又はｔｅｒｔ－ブトキシ基、ｎ－、ｉｓｏ－、又はｎｅｏ－ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基及びオクチルオキシ基等が挙げられる。 Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n- or iso-propoxy group, n-, sec- or tert-butoxy group, n-, iso- or neo-pentyloxy group, A hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.
　炭素数１～２０のアルキルチオ基としては、例えばメチルチオ基、エチルチオ基、ｎ－又はｉｓｏ－プロピルチオ基、ｎ－、ｓｅｃ－又はｔｅｒｔ－ブチルチオ基、ｎ－、ｉｓｏ－又はｎｅｏ－ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基及びオクチルチオ基等が挙げられる。 Examples of the alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n- or iso-propylthio group, n-, sec- or tert-butylthio group, n-, iso- or neo-pentylthio group, and hexylthio group. , Heptylthio group, octylthio group and the like.
　炭素数１～２０のアルキルシリル基としては、例えばトリメチルシリル基及びトリイソプロピルシリル基等のトリアルキルシリル基等が挙げられる。ここでアルキルは直鎖構造でも分岐構造でも構わない。 Examples of the alkylsilyl group having 1 to 20 carbon atoms include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.
　Ａｒ１～Ａｒ７における置換する原子又は置換基として、酸発生効率の観点から好ましいのは、ハロゲン原子、シアノ基、フェニル基、ナフチル基、フェノキシ基、フェニルチオ基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基及び炭素数１～２０のアシル基であり、更に好ましいのは、シアノ基、フェニル基、炭素数１～１５のアルキル基、炭素数１～１５のアルコキシ基、炭素数１～１５のアルキルチオ基及び炭素数１～１５のアシル基、特に好ましいのは、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基及び炭素数１～１０のアシル基である。尚、上記の置換基中のアルキル部分は直鎖でも分岐でも環状でもよい。 As the atom or substituent to be substituted in Ar 1 to Ar 7 , a halogen atom, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, a phenylthio group, an alkyl group having 1 to 20 carbon atoms is preferable from the viewpoint of acid generation efficiency. , An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an acyl group having 1 to 20 carbon atoms, more preferably a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, An alkylthio group having 1 to 10 carbon atoms and an acyl group having 1 to 10 carbon atoms. The alkyl moiety in the above substituent may be linear, branched or cyclic.
　Ａｒ１～Ａｒ４、Ａｒ６及びＡｒ７として、酸発生効率の観点から好ましいのは、フェニル基、ｐ－メチルフェニル基、ｐ－メトキシフェニル基、ｐ－ｔｅｒｔ－ブチルフェニル基、２，４，６－トリメチルフェニル基、ｐ－（チオキサンチルメルカプト）フェニル基及びｍ－クロロフェニル基である。 Ar 1 to Ar 4 , Ar 6 and Ar 7 are preferably a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group, a p-tert-butylphenyl group, 2,4, from the viewpoint of acid generation efficiency. 6-trimethylphenyl group, p- (thioxanthylmercapto) phenyl group and m-chlorophenyl group.
　Ａｒ５として、酸発生効率の観点から好ましいのは、フェニレン基、２－又は３－メチルフェニレン基、２－又は３－メトキシフェニレン基、２－又は３－ブチルフェニレン基及び２－又は３－クロロフェニレン基である。 Ar 5 is preferably a phenylene group, a 2- or 3-methylphenylene group, a 2- or 3-methoxyphenylene group, a 2- or 3-butylphenylene group, and a 2- or 3-chloro group from the viewpoint of acid generation efficiency. A phenylene group.
　一般式（１）又は（２）において（Ｘ１）－又は（Ｘ２）－で表される陰イオンとしては、ハロゲン化物アニオン、水酸化物アニオン、チオシアナートアニオン、炭素数１～４のジアルキルジチオカルバメートアニオン、炭酸アニオン、炭酸水素アニオン、ハロゲンで置換されていてもよい脂肪族又は芳香族カルボキシアニオン（安息香酸アニオン、トリフルオロ酢酸アニオン、パーフルオロアルキル酢酸アニオン、及びフェニルグリオキシル酸アニオン等）、ハロゲンで置換されていてもよい脂肪族又は芳香族スルホキシアニオン（トリフルオロメタンスルホン酸アニオン等）、６フッ化アンチモネートアニオン（ＳｂＦ６ －）、ホスフィンアニオン［ヘキサフルオロホスフェートアニオン（ＰＦ６ －）及びトリフルオロ［トリス（パーフルオロエチル）］ホスフェートアニオン（ＰＦ３（Ｃ２Ｆ５）３ －）等］及びボレートアニオン（テトラフェニルボレートアニオン、テトラキス（パーフルオロフェニル）ボレートアニオン及びブチルトリフェニルボレートアニオン等）等が挙げられ、酸発生効率の観点から、ホスフィンアニオン、ハロゲンで置換された脂肪族スルホキシアニオン及びボレートアニオンが好ましい。更に好ましくは、ヘキサフルオロホスフェートアニオン、トリフルオロ［トリス（パーフルオロエチル）］ホスフェートアニオン及びテトラキス（パーフルオロフェニル）ボレートアニオンであり、特に好ましくは、トリフルオロ［トリス（パーフルオロエチル）］ホスフェートアニオン及びテトラキス（パーフルオロフェニル）ボレートアニオンである。 Examples of the anion represented by (X 1 ) − or (X 2 ) − in the general formula (1) or (2) include a halide anion, a hydroxide anion, a thiocyanate anion, and those having 1 to 4 carbon atoms. Dialkyldithiocarbamate anion, carbonate anion, bicarbonate anion, aliphatic or aromatic carboxy anion optionally substituted with halogen (benzoate anion, trifluoroacetate anion, perfluoroalkylacetate anion, phenylglyoxylate anion, etc.) An aliphatic or aromatic sulfoxy anion (trifluoromethanesulfonic acid anion etc.) optionally substituted with halogen, hexafluoroantimonate anion (SbF 6 − ), phosphine anion [hexafluorophosphate anion (PF 6 − ) And trifluoro [Tris Perfluoroethyl) phosphate anion (PF 3 (C 2 F 5 ) 3 -) , etc.] and borate anion (tetraphenyl borate anion, tetrakis (perfluorophenyl) borate anion and butyl triphenyl borate anion), and the like From the viewpoint of acid generation efficiency, a phosphine anion, an aliphatic sulfoxy anion substituted with a halogen, and a borate anion are preferred. More preferred are hexafluorophosphate anion, trifluoro [tris (perfluoroethyl)] phosphate anion and tetrakis (perfluorophenyl) borate anion, and particularly preferred is trifluoro [tris (perfluoroethyl)] phosphate anion and Tetrakis (perfluorophenyl) borate anion.
　スルホニウム塩誘導体（Ｂ１２１）として、酸発生効率の観点から好ましいのは、トリフェニルスルホニウムカチオン、トリ－ｐ－トリルスルホニウムカチオン又は［ｐ－（フェニルメルカプト）フェニル］ジフェニルスルホニウムカチオンをカチオン骨格として有する化合物及び下記一般式（１１）～（１４）で示される化合物であり、更に好ましいのは下記一般式（１１）～（１４）で示される化合物である。 As the sulfonium salt derivative (B121), a compound having a triphenylsulfonium cation, a tri-p-tolylsulfonium cation, or a [p- (phenylmercapto) phenyl] diphenylsulfonium cation as a cation skeleton is preferable from the viewpoint of acid generation efficiency. Compounds represented by the following general formulas (11) to (14) are preferable, and compounds represented by the following general formulas (11) to (14) are more preferable.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　一般式（１１）～（１４）における（Ｘ３）－～（Ｘ６）－は、それぞれ独立に陰イオンを表し、具体的には一般式（１）又は（２）における（Ｘ１）－又は（Ｘ２）－として例示したものと同様のものが挙げられ、好ましいものも同様である。 (X 3 ) − to (X 6 ) − in the general formulas (11) to (14) each independently represents an anion, and specifically, (X 1 ) − in the general formula (1) or (2) or (X 2) - include the same ones as exemplified as, preferable ones are also same.
　本発明におけるヨードニウム塩誘導体（Ｂ１２２）としては、下記一般式（１５）又は下記一般式（１６）で示される化合物等が挙げられる。 Examples of the iodonium salt derivative (B122) in the present invention include compounds represented by the following general formula (15) or the following general formula (16).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式中、Ａ２は前記式（３）、式（４）、一般式（５）～（８）、式（９）及び式（１０）のいずれかで表される２価又は３価の基であり、Ａｒ８～Ａｒ１２はそれぞれ独立にベンゼン環骨格を少なくとも１個有し、ハロゲン原子、炭素数１～２０のアシル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数１～２０のアルキルシリル基、ニトロ基、カルボキシル基、水酸基、メルカプト基、アミノ基、シアノ基、フェニル基、ナフチル基、フェノキシ基及びフェニルチオ基からなる群から選ばれる少なくとも１種の置換基で置換されていてもよい芳香族炭化水素基又は複素環基であって、Ａｒ８～Ａｒ１０及びＡｒ１２は１価の基、Ａｒ１１は２価の基であり、（Ｘ７）－及び（Ｘ８）－は、それぞれ独立に陰イオンを表し、ｃは０～２の整数、ｄは１～３の整数で、かつｃ＋ｄは２又は３でＡ２の価数と同じ整数である。 In the formula, A 2 is a divalent or trivalent group represented by any one of the above formula (3), formula (4), general formulas (5) to (8), formula (9) and formula (10). Each of Ar 8 to Ar 12 independently has at least one benzene ring skeleton, and is a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Group, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, phenoxy group and phenylthio group An aromatic hydrocarbon group or a heterocyclic group which may be substituted with at least one substituent selected from the group consisting of Ar 8 to Ar 10 and Ar 12 are monovalent groups, and Ar 11 is divalent. a group, (X 7) - Beauty (X 8) - each independently represent an anion, c is is an integer of 0 to 2, d is 1 to 3 as an integer, and c + d are the same integer as the valence of A 2 in 2 or 3 .
　ハロゲン原子、炭素数１～２０のアシル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基及び炭素数１～２０のアルキルシリル基としては、一般式（１）及び一般式（２）の説明で記載したものと同様のものが例示される。 A halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an alkylsilyl group having 1 to 20 carbon atoms; The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.
　一般式（１６）におけるＡ２として、酸を発生する効率の観点から好ましいのは、前記一般式（５）、一般式（７）、一般式（８）、式（９）及び式（１０）のいずれかで表される基であり、一般式（５）、一般式（８）、式（９）及び式（１０）のいずれかで表される基が更に好ましい。 As A 2 in the general formula (16), from the viewpoint of the efficiency of generating an acid, the general formula (5), the general formula (7), the general formula (8), the formula (9), and the formula (10) are preferable. And a group represented by any one of formulas (5), (8), (9), and (10) is more preferred.
　一般式（１５）又は一般式（１６）におけるＡｒ８～Ａｒ１２は、一般式（１５）又は一般式（１６）で表される化合物が紫外～可視光領域に吸収をもつようになる基である。
　Ａｒ８～Ａｒ１２におけるベンゼン環骨格の数は、好ましくは１～５、更に好ましくは１～４であり、Ａｒ８～Ａｒ１２の具体例としては、一般式（１）又は一般式（２）のＡｒ１～Ａｒ７として例示したものと同様のものが挙げられ、好ましいものも同様である。 Ar 8 to Ar 12 in the general formula (15) or the general formula (16) are groups that allow the compound represented by the general formula (15) or the general formula (16) to absorb in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar 8 to Ar 12 is preferably 1 to 5, and more preferably 1 to 4. Specific examples of Ar 8 to Ar 12 include those represented by general formula (1) or general formula (2). Examples of Ar 1 to Ar 7 are the same as those exemplified above, and preferable examples are also the same.
　（Ｘ７）－及び（Ｘ８）－としては、一般式（１）又は（２）における（Ｘ１）－又は（Ｘ２）－として例示したものと同様のものが挙げられ、好ましいものも同様である。 (X 7) - and (X 8) - as is in the general formula (1) or (2) (X 1) - or (X 2) - the like can be mentioned and those exemplified as preferable ones also It is the same.
　ヨードニウム塩誘導体（Ｂ１２２）として、酸発生効率の観点から好ましいのは、（４－メチルフェニル）｛４－（２－メチルプロピル）フェニル｝ヨードニウムカチオン、［ビス（４－ｔｅｒｔ－ブチルフェニル）］ヨードニウムカチオン、［ビス（４－ｔｅｒｔ－ブチルフェニル）］トリフルオロ［トリス（パーフルオロエチル）］ヨードニウムカチオン及び［ビス（４－メトキシフェニル）］ヨードニウムカチオンのいずれかをカチオン骨格として有する化合物、並びにこれら以外の下記一般式（１７）～（２０）で示される化合物であり、更に好ましいのは下記一般式（１７）～（２０）で示される化合物（例示した化合物を含む）である。 As the iodonium salt derivative (B122), (4-methylphenyl) {4- (2-methylpropyl) phenyl} iodonium cation, [bis (4-tert-butylphenyl)] iodonium are preferable from the viewpoint of acid generation efficiency. A compound having either a cation, [bis (4-tert-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium cation or [bis (4-methoxyphenyl)] iodonium cation as a cation skeleton, and others The compounds represented by the following general formulas (17) to (20) are more preferred, and the compounds represented by the following general formulas (17) to (20) (including the exemplified compounds) are more preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　一般式（１７）～（２０）において、Ｒ８～Ｒ１３は、それぞれ独立に水素原子、ハロゲン原子、炭素数１～２０のアシル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数１～２０のアルキルシリル基、ニトロ基、カルボキシル基、水酸基、メルカプト基、アミノ基、シアノ基、フェニル基、及びナフチル基からなる群から選ばれる原子又は置換基であり、（Ｘ９）－～（Ｘ１２）－は、それぞれ独立に陰イオンを表す。 In the general formulas (17) to (20), R 8 to R 13 are each independently a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. An alkoxy group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, and a naphthyl group. Is an atom or substituent selected, and (X 9 ) − to (X 12 ) − each independently represents an anion.
　ハロゲン原子、炭素数１～２０のアシル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基及び炭素数１～２０のアルキルシリル基としては、一般式（１）及び一般式（２）の説明で記載したものと同様のものが例示される。 A halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an alkylsilyl group having 1 to 20 carbon atoms; The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.
　Ｒ８～Ｒ１３として好ましいのは、ハロゲン原子、シアノ基、フェニル基、ナフチル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基及び炭素数１～２０のアシル基であり、更に好ましいのは、シアノ基、フェニル基、炭素数１～１５のアルキル基、炭素数１～１５のアルコキシ基及び炭素数１～１５のアシル基、特に好ましいのは、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基及び炭素数１～１０のアシル基である。尚、上記のアルキル部分は直鎖でも分岐でも環状でもよい。 R 8 to R 13 are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. More preferred are a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, and particularly preferred are those having 1 to 10 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.
　一般式（１７）～（２０）における（Ｘ９）－～（Ｘ１２）－としては一般式（１）又は（２）における（Ｘ１）－又は（Ｘ２）－として例示したものと同様のものが挙げられ、好ましいものも同様である。 (X 9 ) − to (X 12 ) − in the general formulas (17) to (20) are the same as those exemplified as (X 1 ) − or (X 2 ) − in the general formula (1) or (2). The preferable thing is also the same.
　一般に可視光領域（３６０ｎｍ～８３０ｎｍ；ＪＩＳ－Ｚ８１２０参照）での硬化に使用可能な光重合開始剤は、可視光を吸収するため開始剤自体が着色しており、硬化膜の色相に悪影響を与えるが、一般式（２）又は一般式（１６）で示される化合物を使用することにより硬化膜の色相への悪影響を抑止することができる。 Generally, a photopolymerization initiator that can be used for curing in the visible light region (360 nm to 830 nm; see JIS-Z8120) absorbs visible light, and the initiator itself is colored, which adversely affects the hue of the cured film. However, by using the compound represented by the general formula (2) or the general formula (16), an adverse effect on the hue of the cured film can be suppressed.
　スルホン酸エステル誘導体（Ｂ２１）としては、メタンスルホン酸シクロヘキシルエステル、エタンスルホン酸イソプロピルエステル、ベンゼンスルホン酸－ｔｅｒｔ－ブチルエステル、ｐ－トルエンスルホン酸シクロヘキシルエステル及びナフタレンスルホン酸シクロヘキシルエステル等が挙げられる。 Examples of the sulfonic acid ester derivative (B21) include methanesulfonic acid cyclohexyl ester, ethanesulfonic acid isopropyl ester, benzenesulfonic acid-tert-butyl ester, p-toluenesulfonic acid cyclohexyl ester, and naphthalenesulfonic acid cyclohexyl ester.
　酢酸エステル誘導体（Ｂ２２）としては、ジクロロ酢酸シクロヘキシルエステル及びトリクロロ酢酸イソプロピルエステル等が挙げられる。 Examples of the acetic acid ester derivative (B22) include dichloroacetic acid cyclohexyl ester and trichloroacetic acid isopropyl ester.
　ホスホン酸エステル（Ｂ２３）としては、トリフェニルホスホン酸シクロヘキシルエステル等が挙げられる。 Examples of the phosphonic acid ester (B23) include triphenylphosphonic acid cyclohexyl ester.
　（Ｂ）の内、光硬化性の観点からスルホニウム塩誘導体（Ｂ１２１）、ヨードニウム塩誘導体（Ｂ１２２）、スルホン酸エステル誘導体（Ｂ２１）、酢酸エステル誘導体（Ｂ２２）及びホスホン酸エステル（Ｂ２３）からなる群から選ばれる少なくとも１種の酸発生剤が好ましい。中でも、スルホニウム塩誘導体（Ｂ１２１）及びヨードニウム塩誘導体（Ｂ１２２）からなる群から選ばれる少なくとも１種の酸発生剤がより好ましい。 Among (B), from the viewpoint of photocurability, a group consisting of a sulfonium salt derivative (B121), an iodonium salt derivative (B122), a sulfonic acid ester derivative (B21), an acetic acid ester derivative (B22), and a phosphonic acid ester (B23). At least one acid generator selected from is preferred. Among these, at least one acid generator selected from the group consisting of a sulfonium salt derivative (B121) and an iodonium salt derivative (B122) is more preferable.
　本発明において塩基発生剤（Ｃ）とは、活性光線、ラジカル、酸及び塩基のうちの少なくとも１種により塩基を発生する化合物を意味し、活性光線により塩基を発生する塩基発生剤（Ｃ１）、並びにラジカル、酸及び塩基からなる群から選ばれる少なくとも１種により塩基を発生する塩基発生剤（Ｃ２）等の公知の化合物を用いることができる。
　塩基発生剤（Ｃ）を含むことで、感光性組成物が高感度化され、反応が均一に進行する為、本発明の感光性組成物が硬化されてなる本発明の硬化物は、高硬度・高い耐擦傷性、高透明性が発現可能となると推定される。
　例えば、オキシム誘導体（Ｃ１２１）、４級アンモニウム塩誘導体（Ｃ１２２）及び４級アミジン塩誘導体（Ｃ１２３）等は活性光線又はラジカルによって塩基を発生させることが可能で、（Ｃ１）又は（Ｃ２）として適用できる。
　また、カルバメート誘導体（Ｃ２１）は塩基によって塩基を発生させることが可能で、（Ｃ２）として適用できる。
　（Ｃ）は単独で用いてもよいし、２種以上を併用してもよい。
　尚、（Ｃ１２１）は、（Ｃ１）、（Ｃ２）のいずれとしても適用できる化合物（Ｃ１２）の１番目の例であることを示す。 In the present invention, the base generator (C) means a compound that generates a base with at least one of actinic rays, radicals, acids and bases, and a base generator (C1) that generates a base with actinic rays, In addition, a known compound such as a base generator (C2) that generates a base by at least one selected from the group consisting of radicals, acids and bases can be used.
By containing the base generator (C), the photosensitive composition is highly sensitive and the reaction proceeds uniformly, so the cured product of the present invention obtained by curing the photosensitive composition of the present invention has a high hardness.・ It is estimated that high scratch resistance and high transparency can be realized.
For example, the oxime derivative (C121), the quaternary ammonium salt derivative (C122), the quaternary amidine salt derivative (C123) and the like can generate a base by actinic rays or radicals, and are applied as (C1) or (C2). it can.
Further, the carbamate derivative (C21) can generate a base with a base and can be applied as (C2).
(C) may be used alone or in combination of two or more.
In addition, (C121) shows that it is the 1st example of the compound (C12) applicable as both (C1) and (C2).
　オキシム誘導体（Ｃ１２１）としては、例えばＯ－アシロキシム等が挙げられる。 Examples of the oxime derivative (C121) include O-acyloxime.
　４級アンモニウム塩誘導体（Ｃ１２２）及び４級アミジン塩誘導体（Ｃ１２３）としては、例えば下記一般式（２１）～（２３）のいずれかで示される化合物が挙げられる。 Examples of the quaternary ammonium salt derivative (C122) and the quaternary amidine salt derivative (C123) include compounds represented by any of the following general formulas (21) to (23).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　一般式（２１）～（２３）におけるＲ１４～Ｒ４１は、それぞれ独立に水素原子、ハロゲン原子、炭素数１～２０のアシル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数１～２０のアルキルシリル基、ニトロ基、カルボキシル基、水酸基、メルカプト基、アミノ基、シアノ基、フェニル基、ナフチル基、一般式（２４）で表される置換基及び一般式（２５）で表される置換基からなる群から選ばれる原子又は置換基であって、Ｒ１４～Ｒ２３のいずれか１つは一般式（２４）又は一般式（２５）で表される置換基であり、Ｒ２４～Ｒ３１のいずれか１つは一般式（２４）又は一般式（２５）で表される置換基であり、Ｒ３２～Ｒ４１のいずれか１つは一般式（２４）又は一般式（２５）で表される置換基である。 R 14 to R 41 in the general formulas (21) to (23) are each independently a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Alkoxy group, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, general formula (24) An atom or a substituent selected from the group consisting of a substituent represented by formula (25) and a substituent represented by formula (25), wherein any one of R 14 to R 23 represents formula (24) or formula wherein a substituent represented by (25), any one of R 24 ~ R 31 is a substituent represented by the general formula (24) or formula (25), the R 32 ~ R 41 One of them is the general formula (24) or It is a substituent represented by the general formula (25).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　一般式（２４）及び（２５）におけるＲ４２～Ｒ４５は、それぞれ独立に水素原子又は炭素数１～２０のアルキル基であり、Ｒ４６～Ｒ４８は、それぞれ独立に水酸基で置換されていてもよい炭素数１～２０のアルキル基であり、（Ｘ１３）－及び（Ｘ１４）－は、それぞれ独立に陰イオンを表し、ｅは２～４の整数である。 R 42 to R 45 in the general formulas (24) and (25) are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 46 to R 48 are each independently substituted with a hydroxyl group. Or an alkyl group having 1 to 20 carbon atoms, (X 13 ) — and (X 14 ) — each independently represents an anion, and e is an integer of 2 to 4.
　一般式（２１）～（２３）におけるハロゲン原子、炭素数１～２０のアシル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基及び炭素数１～２０のアルキルシリル基としては、一般式（１）及び一般式（２）の説明で記載したものと同様のものが例示される。 In general formulas (21) to (23), a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon Examples of the alkylsilyl group of 1 to 20 are the same as those described in the description of the general formula (1) and the general formula (2).
　一般式（２１）で示される化合物はアントラセン骨格、一般式（２２）で示される化合物はチオキサントン骨格、一般式（２３）で示される化合物はベンゾフェノン骨格を有する化合物であり、それぞれｉ線（３６５ｎｍ）付近に最大吸収波長を有する化合物の一例である。Ｒ１４～Ｒ２３は吸収波長の調整、感度の調整、熱安定性、反応性、分解性等を考慮して適宜選択されるものであり、水素原子、ハロゲン原子、炭素数１～２０のアルコキシ基、ニトロ基、カルボキシル基、水酸基、メルカプト基、炭素数１～２０のアルキルシリル基、炭素数１～２０のアシル基、アミノ基、シアノ基、炭素数１～２０のアルキル基、フェニル基、及びナフチル基からなる群から選ばれる原子又は置換基から目的に応じて選択される。但し、Ｒ１４～Ｒ２３のいずれか１つは一般式（２４）又は一般式（２５）で表される置換基である。 The compound represented by the general formula (21) is an anthracene skeleton, the compound represented by the general formula (22) is a thioxanthone skeleton, and the compound represented by the general formula (23) is a compound having a benzophenone skeleton, i-line (365 nm). It is an example of a compound having a maximum absorption wavelength in the vicinity. R 14 to R 23 are appropriately selected in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity, decomposability, etc., and include a hydrogen atom, a halogen atom, and an alkoxy having 1 to 20 carbon atoms. Group, nitro group, carboxyl group, hydroxyl group, mercapto group, alkylsilyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, alkyl group having 1 to 20 carbon atoms, phenyl group, And an atom or substituent selected from the group consisting of a naphthyl group, depending on the purpose. However, any one of R 14 to R 23 is a substituent represented by the general formula (24) or the general formula (25).
　Ｒ１４～Ｒ２３として好ましいのは、ハロゲン原子、シアノ基、フェニル基、ナフチル基、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基及び炭素数１～２０のアシル基であり、更に好ましいのは、シアノ基、フェニル基、炭素数１～１５のアルキル基、炭素数１～１５のアルコキシ基及び炭素数１～１５のアシル基、特に好ましいのは、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基及び炭素数１～１０のアシル基である。尚、上記のアルキル部分は直鎖でも分岐でも環状でもよい。 R 14 to R 23 are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. More preferred are a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, and particularly preferred are those having 1 to 10 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.
　上記のＲ１４～Ｒ２３の具体例としては、一般式（１７）～（１９）のＲ８～Ｒ１３の説明で記載した原子及び置換基が例示される。 Specific examples of R 14 to R 23 include atoms and substituents described in the description of R 8 to R 13 in the general formulas (17) to (19).
　一般式（２４）で示される置換基はカチオン化したアミジン骨格を有する置換基であり、ｅは２～４の整数である。この置換基としては、ｅが４である１，８－ジアザビシクロ［５．４．０］－７－ウンデセンがカチオン化した構造を有する置換基及びｅが２である１，５－ジアザビシクロ［４．３．０］－５－ノネンがカチオン化した構造を有する置換基が好ましい。Ｒ４２とＲ４３は、それぞれ独立に水素原子又は炭素数１～２０のアルキル基を表し、好ましいのは水素原子及び炭素数１～１０のアルキル基、更に好ましいのは水素原子及び炭素数１～５のアルキル基である。 The substituent represented by the general formula (24) is a substituent having a cationized amidine skeleton, and e is an integer of 2 to 4. Examples of the substituent include a substituent having a structure in which 1,8-diazabicyclo [5.4.0] -7-undecene in which e is 4 and a 1,5-diazabicyclo [4. 3.0] -5-Nonene is preferably a substituent having a cationized structure. R 42 and R 43 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom and an alkyl group having 1 to carbon atoms. 5 alkyl groups.
　一般式（２５）は４級アンモニウム構造を有しており、Ｒ４４とＲ４５は、それぞれ独立に水素原子又は炭素数１～２０のアルキル基を表し、好ましくは水素原子又は炭素数１～１０のアルキル基、更に好ましくは水素原子又は炭素数１～５のアルキル基である。また、Ｒ４６～Ｒ４８は、それぞれ独立に水酸基で置換されていてもよい炭素数１～２０のアルキル基を表し、直鎖でも分岐でも環状でもよい。Ｒ４６～Ｒ４８は好ましくは炭素数１～１０のアルキル基、特に好ましくは炭素数１～５のアルキル基である。 Formula (25) has a quaternary ammonium structure, and R 44 and R 45 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or 1 to 10 carbon atoms. More preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 46 to R 48 each independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, and may be linear, branched or cyclic. R 46 to R 48 are preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms.
　一般式（２４）及び（２５）における（Ｘ１３）－及び（Ｘ１４）－は、それぞれ独立に陰イオンを表し、具体的には一般式（１）又は（２）における（Ｘ１）－又は（Ｘ２）－として例示したものと同様のものが挙げられる。これらの内、光分解性の観点から、脂肪族又は芳香族カルボキシアニオン及びボレートアニオンが好ましい。 (X 13 ) − and (X 14 ) − in the general formulas (24) and (25) each independently represent an anion, specifically, (X 1 ) − in the general formula (1) or (2). or (X 2) - it includes the same as those exemplified as. Of these, aliphatic or aromatic carboxy anions and borate anions are preferred from the viewpoint of photodegradability.
　一般式（２４）で示される化合物は活性光線の照射により、Ｒ４２とＲ４３とが結合した炭素と窒素との間の結合が解裂してアミジン骨格を有する塩基性化合物を生成し、一般式（２５）で示される化合物は活性光線の照射により、Ｒ４４とＲ４５とが結合した炭素と窒素との間の結合が解裂して３級アミンが生成する。 The compound represented by the general formula (24) generates a basic compound having an amidine skeleton by cleaving the bond between carbon and nitrogen to which R 42 and R 43 are bonded by irradiation with actinic rays. In the compound represented by the formula (25), irradiation with actinic rays ruptures the bond between carbon and nitrogen to which R 44 and R 45 are bonded to produce a tertiary amine.
　これらの活性光線により塩基を発生する塩基発生剤（Ｃ１）の内、光硬化性の観点からオキシム誘導体（Ｃ１２１）、４級アンモニウム塩誘導体（Ｃ１２２）及び４級アミジン塩誘導体（Ｃ１２３）からなる群から選ばれる少なくとも１種の塩基発生剤が好ましく、光分解性の観点から、下記一般式（２６）で示される化合物が更に好ましい。 Among these base generators (C1) that generate a base by actinic rays, a group consisting of an oxime derivative (C121), a quaternary ammonium salt derivative (C122) and a quaternary amidine salt derivative (C123) from the viewpoint of photocurability. And at least one base generator selected from the group consisting of the compounds represented by formula (26) is more preferable from the viewpoint of photodegradability.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（２６）における（Ｘ１５）－は、陰イオンを表し、具体的には一般式（１）又は（２）における（Ｘ１）－又は（Ｘ２）－として例示したものと同様のものが挙げられる。これらの内、光分解性の観点から、脂肪族又は芳香族カルボキシアニオン及びボレートアニオンが好ましい。 (X 15 ) − in the general formula (26) represents an anion, specifically, the same as those exemplified as (X 1 ) − or (X 2 ) − in the general formula (1) or (2) Things. Of these, aliphatic or aromatic carboxy anions and borate anions are preferred from the viewpoint of photodegradability.
　カルバメート誘導体（Ｃ２１）としては、１－Ｚ－４－ピペリドン、１－Ｆｍｏｃ－４－ピペリドン及びｏ－ニトロベンゾイルカルバメート等が挙げられる。 Examples of the carbamate derivative (C21) include 1-Z-4-piperidone, 1-Fmoc-4-piperidone and o-nitrobenzoyl carbamate.
　ラジカル、酸及び塩基からなる群から選ばれる少なくとも１種により塩基を発生する塩基発生剤（Ｃ２）の内、光硬化性の観点から、オキシム誘導体（Ｃ１２１）、４級アンモニウム塩誘導体（Ｃ１２２）、４級アミジン塩誘導体（Ｃ１２３）及びカルバメート誘導体（Ｃ２１）からなる群から選ばれる少なくとも１種の塩基発生剤が好ましい。
　本発明における（Ｃ）として、４級アンモニウム塩誘導体（Ｃ１２２）及び４級アミジン塩誘導体（Ｃ１２３）からなる群より選択される少なくとも１種の塩基発生剤がより好ましい。 Of the base generator (C2) that generates a base by at least one selected from the group consisting of a radical, an acid and a base, from the viewpoint of photocurability, an oxime derivative (C121), a quaternary ammonium salt derivative (C122), At least one base generator selected from the group consisting of a quaternary amidine salt derivative (C123) and a carbamate derivative (C21) is preferred.
(C) in the present invention is more preferably at least one base generator selected from the group consisting of a quaternary ammonium salt derivative (C122) and a quaternary amidine salt derivative (C123).
　本発明の感光性組成物中の酸発生剤（Ｂ）及び／又は塩基発生剤（Ｃ）の含有量〔（Ｂ）と（Ｃ）の合計〕は、光硬化性の観点から、重合性物質（Ｄ）の重量に対して、好ましくは０．０１～３０重量％、更に好ましくは０．０１～２５重量％である。 The content of the acid generator (B) and / or the base generator (C) [total of (B) and (C)] in the photosensitive composition of the present invention is a polymerizable substance from the viewpoint of photocurability. The content is preferably 0.01 to 30% by weight, more preferably 0.01 to 25% by weight, based on the weight of (D).
　本発明の感光性組成物においては、ラジカル開始剤（Ａ）、酸発生剤（Ｂ）及び塩基発生剤（Ｃ）の内の少なくとも１つが活性光線の照射により活性種（Ｈ）を発生し、該活性種（Ｈ）がラジカル開始剤（Ａ）、酸発生剤（Ｂ）及び／又は塩基発生剤（Ｃ）と反応して新たな活性種（Ｉ）を生成して、該新たな活性種（Ｉ）による重合性化合物（Ｄ）の重合反応が進行するのが好ましい。ここで、活性種（Ｈ）及び（Ｉ）としては、ラジカル、酸及び塩基等が挙げられるが、上記反応において、活性種（Ｈ）又は（Ｉ）は酸又は塩基であることが好ましい。活性種（Ｈ）が拡散することにより硬化がより促進され、配線の影となる部分を含めて感光性組成物の硬化性が向上する。また、得られる硬化物の基材への密着性が向上する。活性種（Ｈ）が容易に拡散するためには、ラジカル開始剤（Ａ）として、活性種（Ｈ）と反応しないものを使用することが好ましい。 In the photosensitive composition of the present invention, at least one of the radical initiator (A), the acid generator (B) and the base generator (C) generates an active species (H) by irradiation with actinic rays, The active species (H) reacts with the radical initiator (A), the acid generator (B) and / or the base generator (C) to produce a new active species (I), and the new active species It is preferable that the polymerization reaction of the polymerizable compound (D) by (I) proceeds. Here, examples of the active species (H) and (I) include a radical, an acid, and a base. In the above reaction, the active species (H) or (I) is preferably an acid or a base. Curing is further promoted by the diffusion of the active species (H), and the curability of the photosensitive composition including the shadowed portion of the wiring is improved. Moreover, the adhesiveness to the base material of the hardened | cured material obtained improves. In order for the active species (H) to diffuse easily, it is preferable to use a radical initiator (A) that does not react with the active species (H).
　本発明においては、（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、又は（Ｃ２）を、以下の（１）～（４）のいずれかの組合せで含有することが好ましい。
　（１）（Ａ１）並びに（Ｂ２）及び／又は（Ｃ２）を含有する。
　（２）（Ｂ１）、（Ａ２）及び必要により（Ｃ２）を含有する。
　（３）（Ｃ１）、（Ａ２）及び必要により（Ｂ２）を含有する。
　（４）上記（１）～（３）の２種類以上の組合せ。 In the present invention, (A1), (A2), (B1), (B2), (C1), or (C2) may be contained in any combination of the following (1) to (4) preferable.
(1) Contains (A1) and (B2) and / or (C2).
(2) Contains (B1), (A2) and (C2) as necessary.
(3) Contains (C1), (A2) and (B2) if necessary.
(4) A combination of two or more of (1) to (3) above.
　上記（１）においては、活性光線の照射により活性種（Ｈ）としてラジカルが発生し、活性種（Ｉ）として酸及び／又は塩基が発生する。
　上記（２）においては、活性光線の照射により活性種（Ｈ）として酸が発生し、活性種（Ｉ）としてラジカルが発生し、更に（Ｃ２）を含有する場合には塩基が発生する。
　上記（３）においては、活性光線の照射により活性種（Ｈ）として塩基が発生し、活性種（Ｉ）としてラジカルが発生し、更に（Ｂ２）を含有する場合には酸が発生する。
　これらの組合せの中で更に好ましいものは、（１）の内（Ａ１）及び（Ｂ２）を含有するもの、（２）の内（Ｂ１）及び（Ａ２）の内前記（Ａ１）及び（Ａ２）のいずれとしても適用できる前記化合物（Ａ１２）を含有するもの、並びに（３）の内（Ｃ１）及び（Ａ２）の内前記（Ａ１）及び（Ａ２）のいずれとしても適用できる前記化合物（Ａ１２）を含有するものであり、特に好ましいものは、（Ａ１）及び（Ｂ２）を含有するもの、並びに（Ｂ１）及び（Ａ１２）を含有するものである。 In (1) above, radicals are generated as active species (H) upon irradiation with actinic rays, and acids and / or bases are generated as active species (I).
In the above (2), an acid is generated as the active species (H) by irradiation with actinic rays, a radical is generated as the active species (I), and a base is generated when further containing (C2).
In the above (3), irradiation with actinic rays generates a base as the active species (H), generates a radical as the active species (I), and further generates an acid when it contains (B2).
Among these combinations, more preferred are those containing (A1) and (B2) of (1), (B1) and (A2) of (2), (A1) and (A2). A compound containing the compound (A12) applicable as any of the above, and the compound (A12) applicable as any of the above (A1) and (A2) out of (C1) and (A2) in (3) Particularly preferred are those containing (A1) and (B2), and those containing (B1) and (A12).
　本発明の感光性組成物が（Ａ１）及び（Ｂ２）を含有する場合、（Ａ１）及び（Ｂ２）として、例えば、α－アミノアセトフェノン誘導体系重合開始剤（Ａ１２２）及びヨードニウム塩誘導体（Ｂ１２２）を用いることが好ましい。また、感光性組成物が（Ｂ１）及び（Ａ１２）を含有する場合、（Ｂ１）及び（Ａ１２）として、例えば、スルホニウム塩誘導体（Ｂ１２１）及びアシルホスフィンオキサイド誘導体系重合開始剤（Ａ１２１）を用いることが好ましい。
　本発明の感光性組成物が（Ｃ１）及び（Ａ１２）を含有する場合、（Ｃ１）及び（Ａ１２）として、例えば、４級アンモニウム塩誘導体（Ｃ１２２）又は４級アミジン塩誘導体（Ｃ１２３）、及びα－アミノアセトフェノン誘導体系重合開始剤（Ａ１２２）を用いることが好ましい。 When the photosensitive composition of the present invention contains (A1) and (B2), examples of (A1) and (B2) include an α-aminoacetophenone derivative polymerization initiator (A122) and an iodonium salt derivative (B122). Is preferably used. Further, when the photosensitive composition contains (B1) and (A12), for example, a sulfonium salt derivative (B121) and an acylphosphine oxide derivative polymerization initiator (A121) are used as (B1) and (A12). It is preferable.
When the photosensitive composition of the present invention contains (C1) and (A12), as (C1) and (A12), for example, a quaternary ammonium salt derivative (C122) or a quaternary amidine salt derivative (C123), and It is preferable to use an α-aminoacetophenone derivative polymerization initiator (A122).
　本発明の感光性組成物は、必要により、重合禁止剤（ハイドロキノン類等）、溶剤及び増感剤等を含有することができる。 The photosensitive composition of the present invention can contain a polymerization inhibitor (hydroquinones and the like), a solvent, a sensitizer and the like, if necessary.
　溶剤としては、グリコールエーテル類（エチレングリコールモノアルキルエーテル及びプロピレングリコールモノアルキルエーテル等）、ケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン及びシクロヘキサノン等）、エステル類（エチルアセテート、ブチルアセテート、エチレングリコールアルキルエーテルアセテート及びプロピレングリコールアルキルエーテルアセテート等）、芳香族炭化水素類（トルエン、キシレン及びメシチレン等）、アルコール類（メタノール、エタノール、ノルマルプロパノール、イソプロパノール、ブタノール、ゲラニオール、リナロール及びシトロネロール等）及びエーテル類（テトラヒドロフラン及び１，８－シネオール等）が挙げられる。これらは、単独で使用しても２種以上を併用してもよい。
　感光性組成物が溶剤を含有する場合、その含有量は感光性組成物の重量を基準として、０．０１～９９重量％であることが好ましく、更に好ましくは０．０１～９０重量％である。 Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether). Acetate and propylene glycol alkyl ether acetate), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (tetrahydrofuran) And 1,8-cineole). These may be used alone or in combination of two or more.
When the photosensitive composition contains a solvent, the content thereof is preferably 0.01 to 99% by weight, more preferably 0.01 to 90% by weight, based on the weight of the photosensitive composition. .
　増感剤としては、ケトクマリン、フルオレン、チオキサントン、アントラキノン、ナフチアゾリン、ビアセチル、ベンジル及びこれらの誘導体、ペリレン並びに置換アントラセン等が挙げられる。増感剤の含有量は、感光性組成物に対して０．０１～２０重量％が好ましく、更に好ましくは０．０１～１５重量％、特に好ましくは０．０１～１０重量％である。 Sensitizers include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and their derivatives, perylene, and substituted anthracene. The content of the sensitizer is preferably from 0.01 to 20% by weight, more preferably from 0.01 to 15% by weight, particularly preferably from 0.01 to 10% by weight, based on the photosensitive composition.
　本発明の感光性組成物は、更に、使用目的に合わせて、密着性付与剤（シランカップリング剤等）、粘着性付与剤、分散剤、消泡剤、レベリング剤、チクソトロピー性付与剤、スリップ剤、難燃剤、帯電防止剤、酸化防止剤及び紫外線吸収剤等を含有することができる。 The photosensitive composition of the present invention further comprises an adhesion-imparting agent (such as a silane coupling agent), a tackifier, a dispersant, an antifoaming agent, a leveling agent, a thixotropy imparting agent, a slip according to the purpose of use. Agents, flame retardants, antistatic agents, antioxidants, ultraviolet absorbers and the like.
　本発明の感光性組成物は、ラジカル開始剤（Ａ）、単官能ラジカル重合性物質（Ｄ１）を含む重合性物質（Ｄ）と、非ラジカル重合性ポリマー（Ｅ）と必要により酸発生剤（Ｂ）、塩基発生剤（Ｃ）及びその他の成分等とを自転公転式攪拌装置、ボールミル又は３本ロールミル等で混練することで得られる。混練温度は好ましくは１０℃～４０℃、更に好ましくは２０℃～３０℃である。 The photosensitive composition of the present invention comprises a radical initiator (A), a polymerizable substance (D) containing a monofunctional radically polymerizable substance (D1), a non-radically polymerizable polymer (E) and, if necessary, an acid generator ( B), the base generator (C) and other components can be obtained by kneading with a rotation / revolution stirrer, a ball mill or a three-roll mill. The kneading temperature is preferably 10 ° C to 40 ° C, more preferably 20 ° C to 30 ° C.
　本発明の感光性組成物の基材への塗布方法としては、スピンコート、ロールコート及びスプレーコート等の公知のコーティング法並びにナノインプリントプロセス、平版印刷、カルトン印刷、金属印刷、オフセット印刷、スクリーン印刷及びグラビア印刷といった印刷法を適用できる。また、微細液滴を連続して吐出するインクジェット方式や液体定量吐出装置を用いた塗布にも適用できる。 Examples of the method for applying the photosensitive composition of the present invention to a substrate include known coating methods such as spin coating, roll coating, and spray coating, and nanoimprint processes, lithographic printing, carton printing, metal printing, offset printing, screen printing, and the like. Printing methods such as gravure printing can be applied. Further, the present invention can also be applied to coating using an ink jet method or a liquid fixed quantity discharge device that discharges fine droplets continuously.
　本発明の感光性組成物を硬化するのに用いる活性光線としては、可視光線及び紫外線等が挙げられる。
　本発明の感光性組成物は、３６０ｎｍ～８３０ｎｍの活性光線の照射で光硬化できるため、一般的に使用されている高圧水銀灯の他、超高圧水銀灯、メタルハライドランプ及びハイパワーメタルハライドランプ等（ＵＶ・ＥＢ硬化技術の最新動向、ラドテック研究会編、シーエムシー出版、１３８頁、２００６）が使用できる。また、ＬＥＤ光源を使用した照射装置も好適に使用できる。更に、太陽光、低圧水銀灯及び半導体レーザー等も使用できる。活性光線の照射時及び／又は照射後に酸発生剤（Ｂ）及び／又は塩基発生剤（Ｃ）から発生した酸及び／又は塩基の拡散と硬化促進の目的で、加熱を行ってもよい。加熱温度は、好ましくは３０℃～２００℃であり、更に好ましくは３５℃～１５０℃、特に好ましくは４０℃～１２０℃である。
　本発明の感光性組成物が活性光線の照射により硬化されてなる硬化物も、本発明に包含される。 Examples of the active light used for curing the photosensitive composition of the present invention include visible light and ultraviolet light.
Since the photosensitive composition of the present invention can be photocured by irradiation with actinic rays of 360 to 830 nm, in addition to commonly used high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, high-power metal halide lamps, etc. (UV The latest trends in EB curing technology, edited by Radtech Research Association, CMC Publishing, 138, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently. Furthermore, sunlight, a low-pressure mercury lamp, a semiconductor laser, or the like can be used. Heating may be performed for the purpose of diffusing and accelerating curing of the acid and / or base generated from the acid generator (B) and / or the base generator (C) during and / or after irradiation with actinic rays. The heating temperature is preferably 30 ° C. to 200 ° C., more preferably 35 ° C. to 150 ° C., and particularly preferably 40 ° C. to 120 ° C.
A cured product obtained by curing the photosensitive composition of the present invention by irradiation with actinic rays is also included in the present invention.
　本発明の感光性組成物は、柔軟性の観点から、樹脂組成物が活性光線の照射により硬化されてなる硬化物のデュロメータＥ硬さが２０未満であることが好ましく、１５未満であることが更に好ましく、１０未満であることが特に好ましい。硬化物のデュロメータＥ硬さを２０未満にすることにより、柔軟性が向上することから、硬化物の衝撃吸収性が良好となる。尚、本発明におけるデュロメータＥ硬さは、後述の方法で測定することができる。 From the viewpoint of flexibility, the photosensitive composition of the present invention preferably has a durometer E hardness of a cured product obtained by curing the resin composition by irradiation with actinic rays of less than 20, preferably less than 15. More preferably, it is particularly preferably less than 10. By setting the durometer E hardness of the cured product to less than 20, the flexibility is improved, so that the impact absorption of the cured product is improved. In addition, the durometer E hardness in this invention can be measured by the method mentioned later.
　本発明の感光性組成物は、低誘電性の観点から、樹脂組成物が活性光線の照射により硬化されてなる硬化物の１ＭＨｚでの比誘電率が５．０以下であることが好ましく、４．０以下であることが更に好ましく、３．０以下であることが特に好ましい。硬化物の１ＭＨｚでの比誘電率が５．０以下であることにより、タッチパネル用接着剤として使用した場合に誤作動を起こしにくくなり、タッチパネルの応答速度や感度が向上する。
　尚、本発明における比誘電率は、後述の方法で測定することができる。 In the photosensitive composition of the present invention, the relative dielectric constant at 1 MHz of a cured product obtained by curing the resin composition by irradiation with actinic rays is preferably 5.0 or less from the viewpoint of low dielectric properties. Is more preferably 0.0 or less, and particularly preferably 3.0 or less. When the relative permittivity of the cured product at 1 MHz is 5.0 or less, malfunctions are less likely to occur when used as an adhesive for touch panels, and the response speed and sensitivity of the touch panel are improved.
The relative dielectric constant in the present invention can be measured by the method described later.
　本発明の感光性組成物は、例えば、コーティング剤用、インキ用、塗料用、接着剤用、レジストパターン形成用又はセラミック電子部品製造用等の感光性組成物として好適に用いられる。中でも、接着剤として好適に用いられる。本発明の感光性組成物を接着剤用感光性組成物として用いることは、本発明における好ましい実施態様の１つである。 The photosensitive composition of the present invention is suitably used, for example, as a photosensitive composition for coating agents, inks, paints, adhesives, resist patterns, or ceramic electronic parts. Among these, it is preferably used as an adhesive. Use of the photosensitive composition of the present invention as a photosensitive composition for an adhesive is one of the preferred embodiments of the present invention.
　本発明の感光性組成物は、例えば、画像表示装置の製造において、光学基材等の基材を貼り合わせる接着剤として好適に用いられる。本発明の感光性組成物を用いて貼り合わされた光学基材を含む画像表示装置も、本発明に包含される。
　本発明の感光性組成物が使用される画像表示装置としては、例えば、フラットパネルディスプレイ、タッチパネル等が好適である。本発明の感光性組成物は、このような画像表示装置の製造において、例えば、透明基板、透明板、化粧板、タッチパネル、アイコンシート及び画像表示部材等の光学基材を貼り合わせるために特に好適に使用される。 The photosensitive composition of the present invention is suitably used as an adhesive for bonding a substrate such as an optical substrate in the production of an image display device, for example. An image display device including an optical substrate bonded using the photosensitive composition of the present invention is also included in the present invention.
As an image display apparatus in which the photosensitive composition of the present invention is used, for example, a flat panel display, a touch panel and the like are suitable. The photosensitive composition of the present invention is particularly suitable for bonding optical substrates such as transparent substrates, transparent plates, decorative plates, touch panels, icon sheets, and image display members in the production of such image display devices. Used for.
　以下、実施例により本発明を更に説明するが、本発明はこれらに限定されるものではない。以下、特に規定しない限り、％は重量％、部は重量部を示す。 Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.
［酸発生剤（Ｂ）の製造］
製造例１
［活性光線により酸を発生するスルホニウム塩誘導体（Ｂ１２１－１）｛化学式（２７）で表される化合物｝の合成］ [Production of acid generator (B)]
Production Example 1
[Sulphonium Salt Derivative (B121-1) {Compound Represented by Chemical Formula (27)} that Generates Acid by Active Light]
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
（１）２－（フェニルチオ）チオキサントン［中間体（Ｂ１２１－１－１）］の合成：
　２－クロロチオキサントン１１．０部、チオフェノール４．９部、水酸化カリウム２．５部及びＮ，Ｎ－ジメチルホルムアミド１６２部を均一混合し、１３０℃で９時間反応させた後、反応溶液を室温（約２５℃）まで冷却し、蒸留水２００部中に投入し、生成物を析出させた。これをろ過し、残渣を水で濾液のｐＨが中性になるまで洗浄した後、残渣を減圧乾燥させ、黄色粉末状の生成物を得た。カラムクロマトグラフィー（溶離液：トルエン／ヘキサン＝１／１：容量比）で精製し、中間体（Ｂ１２１－１－１）（黄色固体）３．１部を得た。 (1) Synthesis of 2- (phenylthio) thioxanthone [intermediate (B121-1-1)]:
11.0 parts of 2-chlorothioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed and reacted at 130 ° C. for 9 hours. The product was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. Purification by column chromatography (eluent: toluene / hexane = 1/1: volume ratio) gave 3.1 parts of intermediate (B121-1-1) (yellow solid).
（２）２－［（フェニル）スルフィニル］チオキサントン［中間体（Ｂ１２１－１－２）］の合成：
　中間体（Ｂ１２１－１－１）１１．２部、アセトニトリル２１５部及び硫酸０．０２部を４０℃で撹拌しながら、これに３０％過酸化水素水溶液４．０部を徐々に滴下し、４０～４５℃で１４時間反応させた後、反応溶液を室温（約２５℃）まで冷却し、蒸留水２００部中に投入し、生成物を析出させた。これをろ過し、残渣を水で濾液のｐＨが中性になるまで洗浄した後、残渣を減圧乾燥させ、黄色粉末状の生成物を得た。カラムクロマトグラフィー（溶離液：酢酸エチル／トルエン＝１／３：容量比）にて生成物を精製して、中間体（Ｂ１２１－１－２）（黄色固体）１３．２部を得た。 (2) Synthesis of 2-[(phenyl) sulfinyl] thioxanthone [intermediate (B121-1-2)]:
While stirring 11.2 parts of the intermediate (B121-1-1), 215 parts of acetonitrile, and 0.02 part of sulfuric acid at 40 ° C., 4.0 parts of 30% aqueous hydrogen peroxide was gradually added dropwise thereto. After reacting at ˜45 ° C. for 14 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: ethyl acetate / toluene = 1/3: volume ratio) to obtain 13.2 parts of intermediate (B121-1-2) (yellow solid).
（３）スルホニウム塩誘導体（Ｂ１２１－１）の合成：
　中間体（Ｂ１２１－１－２）４．３部、無水酢酸４．１部及びアセトニトリル１１０部を４０℃で撹拌しながら、これにトリフルオロメタンスルホン酸２．４部を徐々に滴下し、４０～４５℃で１時間反応させた後、反応溶液を室温（約２５℃）まで冷却し、蒸留水１５０部中に投入し、クロロホルムで抽出し、水相のｐＨが中性になるまで水で洗浄した。クロロホルム相をロータリーエバポレーターに移して溶媒を留去した後、トルエン５０部を加えて超音波洗浄器でトルエン中に分散し約１５分間静置してから上澄みを除く操作を３回繰り返して、生成した固体を洗浄した後、残渣を減圧乾燥した。この残渣をジクロロメタン２１２部に溶かし、１０％カリウム｛トリフルオロ［トリス（パーフルオロエチル）］ホスフェート｝水溶液６５部中に投入してから、室温（約２５℃）で２時間撹拌し、ジクロロメタン層を分液操作にて水で３回洗浄した後、有機溶媒を減圧留去することにより、スルホニウム塩誘導体（Ｂ１２１－１）（黄色固体）５．５部を得た。 (3) Synthesis of sulfonium salt derivative (B121-1):
While stirring 4.3 parts of intermediate (B121-1-2), 4.1 parts of acetic anhydride and 110 parts of acetonitrile at 40 ° C., 2.4 parts of trifluoromethanesulfonic acid was gradually added dropwise to After reacting at 45 ° C. for 1 hour, the reaction solution is cooled to room temperature (about 25 ° C.), poured into 150 parts of distilled water, extracted with chloroform, and washed with water until the pH of the aqueous phase becomes neutral. did. After the chloroform phase was transferred to a rotary evaporator and the solvent was distilled off, 50 parts of toluene was added, dispersed in toluene with an ultrasonic cleaner, allowed to stand for about 15 minutes, and then the supernatant was removed three times to produce The washed solid was washed, and the residue was dried under reduced pressure. This residue was dissolved in 212 parts of dichloromethane, poured into 65 parts of 10% potassium {trifluoro [tris (perfluoroethyl)] phosphate} aqueous solution, and stirred at room temperature (about 25 ° C.) for 2 hours. After washing with water three times by a liquid separation operation, the organic solvent was distilled off under reduced pressure to obtain 5.5 parts of a sulfonium salt derivative (B121-1) (yellow solid).
製造例２
［活性光線により酸を発生するヨードニウム塩誘導体（Ｂ１２２－１）｛化学式（２８）で表される化合物｝の合成］ Production Example 2
[Synthesis of iodonium salt derivative (B122-1) {compound represented by chemical formula (28)} that generates an acid by actinic rays]
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　トルエン６．５部、イソプロピルベンゼン８．１部、ヨウ化カリウム５．３５部及び無水酢酸２０部を酢酸７０部に溶解させ、１０℃まで冷却し、温度を１０±２℃に保ちながら、濃硫酸１２部と酢酸１５部との混合溶液を１時間かけて滴下した。２５℃まで昇温し、２４時間攪拌した。その後、反応溶液にジエチルエーテル５０部を加え、水で３回洗浄し、ジエチルエーテルを減圧留去した。残渣にカリウム｛トリフルオロ［トリス（パーフルオロエチル）］ホスフェート｝１１８部を水１００部に溶解させた水溶液を加え、２５℃で２０時間攪拌した。その後、反応溶液に酢酸エチル５００部を加え、水で３回洗浄し、有機溶剤を減圧留去することで目的とするヨードニウム塩誘導体（Ｂ１２２－１）（淡黄色液体）１４．０部を得た。 6.5 parts of toluene, 8.1 parts of isopropylbenzene, 5.35 parts of potassium iodide and 20 parts of acetic anhydride are dissolved in 70 parts of acetic acid, cooled to 10 ° C., and kept at a temperature of 10 ± 2 ° C. A mixed solution of 12 parts of sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour. It heated up to 25 degreeC and stirred for 24 hours. Thereafter, 50 parts of diethyl ether was added to the reaction solution, washed with water three times, and diethyl ether was distilled off under reduced pressure. An aqueous solution in which 118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate} was dissolved in 100 parts of water was added to the residue, followed by stirring at 25 ° C. for 20 hours. Thereafter, 500 parts of ethyl acetate was added to the reaction solution, washed three times with water, and the organic solvent was distilled off under reduced pressure to obtain 14.0 parts of the desired iodonium salt derivative (B122-1) (light yellow liquid). It was.
［塩基発生剤（Ｃ）の製造］
製造例３
［塩基発生剤（Ｃ１２２－１）｛化学式（２９）で表される化合物｝の合成］ [Production of base generator (C)]
Production Example 3
[Synthesis of Base Generator (C122-1) {Compound Represented by Chemical Formula (29)}]
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　９－クロロメチルアントラセン２．０部をクロロホルムに溶解させ、そこへ、トリオクチルアミン３．１部を少量ずつ加え（添加後若干の発熱が見られた。）、このまま室温（約２５℃）で１時間攪拌して反応液を得た。ナトリウムテトラフェニルボレート塩４．０部及び水４０部からなる水溶液に、反応液を少しずつ滴下し、更に１時間室温（約２５℃）で攪拌した後、水層を分液操作により除き、有機層を水で３回洗浄した。有機溶剤を減圧留去することで、白色固体７．１部を得た。この白色固体をアセトニトリルで再結晶させて、塩基発生剤（Ｃ１２２－１）（白色固体）６．２部を得た。 2.0 parts of 9-chloromethylanthracene was dissolved in chloroform, and 3.1 parts of trioctylamine was added little by little (a slight exotherm was observed after the addition), and the temperature was kept at room temperature (about 25 ° C.). The reaction solution was obtained by stirring for 1 hour. The reaction solution is dropped little by little into an aqueous solution consisting of 4.0 parts of sodium tetraphenylborate salt and 40 parts of water, and the mixture is further stirred for 1 hour at room temperature (about 25 ° C.). The layer was washed 3 times with water. The organic solvent was distilled off under reduced pressure to obtain 7.1 parts of a white solid. This white solid was recrystallized from acetonitrile to obtain 6.2 parts of a base generator (C122-1) (white solid).
製造例４
［塩基発生剤（Ｃ１２３－１）｛化学式（３０）で表される化合物｝の合成］ Production Example 4
[Synthesis of Base Generator (C123-1) {Compound Represented by Chemical Formula (30)}]
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　「トリオクチルアミン３．１部」を「１，８－ジアザビシクロ［５．４．０］－７－ウンデセン１．３部」に変更したこと以外、製造例３と同様にして、塩基発生剤（Ｃ１２３－１）（白色固体）４．７部を得た。 In the same manner as in Production Example 3, except that “3.1 parts of trioctylamine” was changed to “1.3 parts of 1,8-diazabicyclo [5.4.0] -7-undecene” (base generator ( C123-1) (white solid) 4.7 parts was obtained.
［非ラジカル重合性ポリマー（Ｅ）の製造］
製造例５
［ビニルポリマー（Ｅ１－１）の製造］
　撹拌機、温度計、還流冷却管、滴下ロート及び窒素ガス導入管を備えた反応容器に、溶剤としての酢酸エチル１３０部を仕込み８０℃まで昇温した。溶剤還流下、２－エチルヘキシルアクリレート５００部を酢酸エチル２００部に溶解させたモノマー溶液と、２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．２４５部を酢酸エチル５０部に溶解させた開始剤溶液とを、反応容器内に窒素を吹き込みながら滴下ロートで４時間かけて連続的に滴下させた。続いて２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．４９０部を酢酸エチル３０部に溶解させた開始剤溶液を滴下ロートを用いて２時間かけて連続的に追加し、溶剤還流下で４時間反応させた。反応終了後、減圧下に１２０℃で２時間かけて酢酸エチルを留去することにより、Ｍｗ＝２５０，０００のポリ（２－エチルヘキシルアクリレート）であるビニルポリマー（Ｅ１－１）を得た。 [Production of non-radically polymerizable polymer (E)]
Production Example 5
[Production of vinyl polymer (E1-1)]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, 130 parts of ethyl acetate as a solvent was charged and the temperature was raised to 80 ° C. Under reflux of the solvent, a monomer solution in which 500 parts of 2-ethylhexyl acrylate was dissolved in 200 parts of ethyl acetate and 0.245 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were dissolved in 50 parts of ethyl acetate. The initiator solution was continuously dropped over 4 hours with a dropping funnel while nitrogen was blown into the reaction vessel. Subsequently, an initiator solution prepared by dissolving 0.490 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 30 parts of ethyl acetate was continuously added over 2 hours using a dropping funnel, The reaction was carried out for 4 hours under reflux. After completion of the reaction, ethyl acetate was distilled off under reduced pressure at 120 ° C. for 2 hours to obtain a vinyl polymer (E1-1) which is poly (2-ethylhexyl acrylate) having Mw = 250,000.
製造例６
［ビニルポリマー（Ｅ１－２）の製造］
　撹拌機、温度計、還流冷却管、滴下ロート及び窒素ガス導入管を備えた反応容器に、溶剤としての酢酸エチル１３０部を仕込み８０℃まで昇温した。溶剤還流下、アクリル酸５０部、２－エチルヘキシルアクリレート４００部、酢酸ビニル５０部及び酢酸エチル２００部を配合させたモノマー配合液と、２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．２４５部を酢酸エチル５０部に溶解させた開始剤溶液とを反応容器内に窒素を吹き込みながら、滴下ロートで４時間かけて連続的に滴下させた。続いて２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．４９０部を酢酸エチル３０部に溶解させた開始剤溶液を滴下ロートを用いて２時間かけて連続的に追加し、溶剤還流下で４時間反応させた。反応終了後、減圧下に１２０℃で２時間かけて酢酸エチルを留去することにより、Ｍｗ＝３００，０００のアクリル酸、２－エチルヘキシルアクリレート及び酢酸ビニルの共重合物であるビニルポリマー（Ｅ１－２）を得た。 Production Example 6
[Production of vinyl polymer (E1-2)]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, 130 parts of ethyl acetate as a solvent was charged and the temperature was raised to 80 ° C. Under reflux of the solvent, a monomer mixture containing 50 parts of acrylic acid, 400 parts of 2-ethylhexyl acrylate, 50 parts of vinyl acetate and 200 parts of ethyl acetate, and 2,2′-azobis (2,4-dimethylvaleronitrile) 0 The initiator solution in which 245 parts were dissolved in 50 parts of ethyl acetate was continuously dropped over 4 hours with a dropping funnel while nitrogen was blown into the reaction vessel. Subsequently, an initiator solution prepared by dissolving 0.490 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 30 parts of ethyl acetate was continuously added over 2 hours using a dropping funnel, The reaction was carried out for 4 hours under reflux. After completion of the reaction, ethyl acetate was distilled off at 120 ° C. under reduced pressure for 2 hours to remove a vinyl polymer (E1-Ew), which is a copolymer of acrylic acid, 2-ethylhexyl acrylate and vinyl acetate with Mw = 300,000. 2) was obtained.
製造例７
［ポリエステル樹脂（Ｅ２－１）の製造］
　攪拌機、温度計、還流冷却管、空気・窒素混合気体の導入管、及び分水器を備えた反応容器に、アジピン酸２９０部、ネオペンチルグリコール２６０部、トルエン７０部及びｐ－トルエンスルホン酸５部を仕込み、空気・窒素混合気体の気流下で攪拌しながら１２０℃まで昇温して、生成する水を分水器により連続的に系外へ除去しながら、反応液の酸価が５以下となるまで反応させた。反応終了後、減圧下に１２０℃で４時間かけてトルエンを留去することにより、Ｍｗ＝１２，０００のポリエステル樹脂（Ｅ２－３）を得た。 Production Example 7
[Production of polyester resin (E2-1)]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, air / nitrogen mixed gas inlet tube, and water separator, 290 parts of adipic acid, 260 parts of neopentyl glycol, 70 parts of toluene and 5 parts of p-toluenesulfonic acid The temperature of the reaction solution is raised to 120 ° C. while stirring under an air / nitrogen mixed gas stream, and the acid value of the reaction solution is 5 or less while continuously removing the generated water from the system using a water separator. The reaction was continued until After completion of the reaction, toluene was distilled off under reduced pressure at 120 ° C. for 4 hours to obtain a polyester resin (E2-3) having Mw = 12,000.
実施例１～１９及び比較例１～５
　表１～２に示す部数の重合性物質（Ｄ）、非ラジカル重合性ポリマー（Ｅ）、ラジカル開始剤（Ａ）と、必要により酸発生剤（Ｂ）又は塩基発生剤（Ｃ）とを表１～２に記載の部数配合し、自転公転式攪拌装置を用いて２５℃で１０分混合して、本発明の感光性組成物（Ｑ－１）～（Ｑ－１９）と比較用の感光性組成物（Ｑ’－１）～（Ｑ’－５）とを製造した。 Examples 1 to 19 and Comparative Examples 1 to 5
The number of polymerizable substances (D), non-radically polymerizable polymer (E), radical initiator (A), and acid generator (B) or base generator (C), as required, shown in Tables 1 and 2 are shown. 1 to 2 are blended and mixed at 25 ° C. for 10 minutes using a rotating and rotating stirrer, and compared with the photosensitive compositions (Q-1) to (Q-19) of the present invention. Sex compositions (Q′-1) to (Q′-5) were produced.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　感光性組成物（Ｑ－１）～（Ｑ－１９）と比較用の感光性組成物（Ｑ’－１）～（Ｑ’－５）の評価は、以下の方法により行った。 The photosensitive compositions (Q-1) to (Q-19) and the comparative photosensitive compositions (Q′-1) to (Q′-5) were evaluated by the following methods.
［接着強度］
　厚さ０．５ｍｍの薄板ガラス［セントラル硝子（株）製　以下同様］上に、実施例１～１９及び比較例１～５で得た各感光性組成物を約０．１ｍＬ塗布し、隙間ゲージ［（株）永井ゲージ製作所製　厚さ０．１０ｍｍ］を用いてもう一枚用意したスライドガラスとの間に膜厚１００μｍとなるように円形に成型した。ベルトコンベア式ＵＶ照射装置［アイグラフィックス株式会社、型式「ＥＣＳ－１５１Ｕ」、以下同様］を使用して露光を行った。露光量は３６５ｎｍとして１５００ｍＪ／ｃｍ２であった。
　硬化後の円形の試験片を、ＪＩＳ　Ｋ－６８４９に準拠し、引張試験機［製品名　オートグラフＡＧ－ＩＳ、（株）島津製作所製、以下同様］により接着強度を評価した。 [Adhesive strength]
About 0.1 mL of each photosensitive composition obtained in Examples 1 to 19 and Comparative Examples 1 to 5 was applied onto a thin glass sheet (manufactured by Central Glass Co., Ltd., the same applies below) having a thickness of 0.5 mm, and a gap gauge Using [manufactured by Nagai Gauge Mfg. Co., Ltd., thickness 0.10 mm], it was molded into a circular shape so as to have a film thickness of 100 μm with another slide glass prepared. Exposure was carried out using a belt conveyor type UV irradiation device [I Graphics Co., Ltd., model “ECS-151U”, the same applies hereinafter]. The exposure amount was 1500 mJ / cm 2 at 365 nm.
The adhesive strength of the cured round test piece was evaluated using a tensile tester [Product name: Autograph AG-IS, manufactured by Shimadzu Corporation, the same applies below] according to JIS K-6849.
［耐熱試験後の接着強度］
　実施例１～１９及び比較例１～５で得た各感光性組成物を用い、上記接着強度測定用の試験片を作製した。８５℃で１０００ｈｒ試験片を耐熱試験にかけた後、耐熱試験後の試験片について、ＪＩＳ　Ｋ－６８４９に準拠し、引張試験機により接着強度を評価した。
［耐湿試験後の接着強度］
　実施例１～１９及び比較例１～５で得た各感光性組成物を用い、上記接着強度測定用の試験片を作製した。６０℃、９０％ＲＨで１０００ｈｒ試験片を耐湿試験にかけた後、耐湿試験後の試験片について、ＪＩＳ　Ｋ－６８４９に準拠し、引張試験機により接着強度を評価した。 [Adhesive strength after heat test]
Using the photosensitive compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 5, the above test pieces for measuring adhesive strength were prepared. A 1000 hr test piece was subjected to a heat test at 85 ° C., and the test piece after the heat test was evaluated for adhesive strength with a tensile tester in accordance with JIS K-6849.
[Adhesive strength after moisture resistance test]
Using the photosensitive compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 5, the above test pieces for measuring adhesive strength were prepared. After a 1000 hr test piece was subjected to a moisture resistance test at 60 ° C. and 90% RH, the test piece after the moisture resistance test was evaluated for adhesive strength by a tensile tester in accordance with JIS K-6849.
［硬化収縮率］
　実施例１～１９及び比較例１～５で得た各感光性組成物について２５ｍＬ比重瓶を用い、ＪＩＳ　Ｚ－８８０４に準拠し液比重〔ρ１〕を測定した。
　また、実施例１～１９及び比較例１～５で得た各感光性組成物を厚さ２５μｍのＰＰ（ポリプロピレン）フィルム［日本ポリプロ（株）製、ウィンテック（登録商標）ＷＦＸ４ＴＡ］上に隙間ゲージ［（株）永井ゲージ製作所製　厚さ１．００ｍｍ］を用いてもう一枚用意した上記ＰＰフィルムとの間に膜厚１．０ｍｍとなるよう成型した。ベルトコンベア式ＵＶ照射装置を使用して露光を行った。露光量は３６５ｎｍとして１５００ｍＪ／ｃｍ２であった。硬化後の塗膜を用い、ＪＩＳ　Ｋ－７１１２に準拠し水中置換法により硬化物比重〔ρ２〕を測定した。
　硬化収縮率を下記式から計算し求めた。
　硬化収縮率（％）＝｛１－（ρ１／ρ２）｝×１００ [Curing shrinkage]
Each photosensitive composition obtained in Examples 1 to 19 and Comparative Examples 1 to 5 was measured for liquid specific gravity [ρ 1 ] in accordance with JIS Z-8804 using a 25 mL specific gravity bottle.
Further, the photosensitive compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 5 were placed on a 25 μm-thick PP (polypropylene) film [manufactured by Nippon Polypro Co., Ltd., Wintech (registered trademark) WFX4TA]. Using a gauge [thickness 1.00 mm, manufactured by Nagai Gauge Manufacturing Co., Ltd.], the film was molded so as to have a film thickness of 1.0 mm with another PP film prepared. Exposure was carried out using a belt conveyor type UV irradiation device. The exposure amount was 1500 mJ / cm 2 at 365 nm. Using the cured coating film, the specific gravity [ρ 2 ] of the cured product was measured by an underwater substitution method according to JIS K-7112.
The cure shrinkage was calculated from the following formula.
Curing shrinkage (%) = {1- (ρ 1 / ρ 2 )} × 100
［柔軟性］
　実施例１～１９及び比較例１～５で得た各感光性組成物を膜厚が１ｃｍとなるように円柱状の型に流しこみ、ベルトコンベア式ＵＶ照射装置を使用して露光を行い、柔軟性評価用の試験片を得た。露光量は３６５ｎｍとして３０００ｍＪ／ｃｍ２であった。この試験片を使用して、ＪＩＳ－Ｋ７２１５に準拠し、デュロメータ硬度計（タイプＥ）［製品名　アスカーゴム硬度計、高分子計器（株）社製］を用いてデュロメータＥ硬さを測定した。 [Flexibility]
Each photosensitive composition obtained in Examples 1 to 19 and Comparative Examples 1 to 5 was poured into a cylindrical mold so as to have a film thickness of 1 cm, and exposed using a belt conveyor type UV irradiation device. A test piece for flexibility evaluation was obtained. The exposure amount was 3000 mJ / cm 2 at 365 nm. Using this test piece, the durometer E hardness was measured using a durometer hardness meter (type E) [product name Asker rubber hardness meter, manufactured by Kobunshi Keiki Co., Ltd.] in accordance with JIS-K7215.
［比誘電率］
　実施例１～１９及び比較例１～５で得た各感光性組成物を膜厚が３ｍｍとなるように円柱状の型に流しこみ、ベルトコンベア式ＵＶ照射装置を使用して露光を行い、比誘電率測定用の試験片を得た。露光量は３６５ｎｍとして３０００ｍＪ／ｃｍ２であった。この試験片を使用して、ＪＩＳ－Ｋ６９１１に準拠し、誘電体損自動測定装置［安藤電気（株）製、型式ＴＲ－１１００］を用いて比誘電率を測定した。比誘電率は、測定値に応じて以下のように示した。
　◎：３．０未満
　○：３．０以上４．０未満
　×：４．０以上 [Relative permittivity]
Each photosensitive composition obtained in Examples 1 to 19 and Comparative Examples 1 to 5 was poured into a cylindrical mold so as to have a film thickness of 3 mm, and was exposed using a belt conveyor type UV irradiation device. A test piece for measuring the relative dielectric constant was obtained. The exposure amount was 3000 mJ / cm 2 at 365 nm. Using this test piece, the relative dielectric constant was measured using a dielectric loss automatic measuring device [manufactured by Ando Electric Co., Ltd., model TR-1100] in accordance with JIS-K6911. The relative dielectric constant was shown as follows according to the measured value.
◎: Less than 3.0 ○: 3.0 or more and less than 4.0 ×: 4.0 or more
　これらの評価結果を表１～２に示す。 These evaluation results are shown in Tables 1-2.
　比較例１は樹脂が硬化せず、評価できなかった。また、比較例２及び５は硬化収縮率が高く、露光時にガラスが割れ接着強度を評価できなかった。 Comparative Example 1 could not be evaluated because the resin was not cured. Further, Comparative Examples 2 and 5 had a high cure shrinkage, and the glass was not cracked at the time of exposure, and the bond strength could not be evaluated.
　本発明の感光性組成物は、接着性、耐熱性、耐湿性及び柔軟性に優れ、かつ、低硬化収縮率、低誘電性であるため、接着剤用（例えば、フラットパネルディスプレイ製造用又はタッチパネル製造用）、コーティング剤用、インキ用、塗料用、レジストパターン形成用及びセラミック電子部品製造用として好適であり、特に接着剤用として極めて有用である。 Since the photosensitive composition of the present invention is excellent in adhesiveness, heat resistance, moisture resistance and flexibility, and has a low curing shrinkage and low dielectric property, it is used for adhesives (for example, for manufacturing flat panel displays or touch panels). For production), coating agents, inks, paints, resist patterns and ceramic electronic parts, and particularly useful as adhesives.

Claims (14)

  1. 　ラジカル開始剤（Ａ）、単官能ラジカル重合性物質（Ｄ１）を含有する重合性物質（Ｄ）及び非ラジカル重合性ポリマー（Ｅ）を含有し、以下の（１）～（３）を満たす感光性組成物。
    （１）前記（Ｄ）と前記（Ｅ）との合計重量に対する前記（Ｄ）の重量割合が、４０～９５重量％である。
    （２）前記（Ｄ）の重量に対する前記（Ｄ１）の重量割合が、５０～９９．９重量％である。
    （３）前記（Ｄ１）が、炭素数６～３５の単官能アルキル（メタ）アクリレート（Ｄ１１１）を含有する。     Photosensitivity containing a radical initiator (A), a polymerizable substance (D) containing a monofunctional radical polymerizable substance (D1), and a non-radical polymerizable polymer (E) and satisfying the following (1) to (3) Sex composition.
    (1) The weight ratio of (D) to the total weight of (D) and (E) is 40 to 95% by weight.
    (2) The weight ratio of the (D1) to the weight of the (D) is 50 to 99.9% by weight.
    (3) The (D1) contains a monofunctional alkyl (meth) acrylate (D111) having 6 to 35 carbon atoms.
  2. 　前記非ラジカル重合性ポリマー（Ｅ）が、炭素数６～３５の単官能分岐アルキル（メタ）アクリレートを構成単位として含有するビニルポリマーである請求項１に記載の感光性組成物。 2. The photosensitive composition according to claim 1, wherein the non-radically polymerizable polymer (E) is a vinyl polymer containing a monofunctional branched alkyl (meth) acrylate having 6 to 35 carbon atoms as a structural unit.
  3. 　前記非ラジカル重合性ポリマー（Ｅ）が、２－エチルヘキシル（メタ）アクリレートを構成単位として５０モル％以上含有するビニルポリマーである請求項１又は２に記載の感光性組成物。 The photosensitive composition according to claim 1 or 2, wherein the non-radically polymerizable polymer (E) is a vinyl polymer containing 2-ethylhexyl (meth) acrylate as a structural unit in an amount of 50 mol% or more.
  4. 　更に酸発生剤（Ｂ）及び／又は塩基発生剤（Ｃ）を含有する請求項１～３のいずれか１項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 3, further comprising an acid generator (B) and / or a base generator (C).
  5. 　前記ラジカル開始剤（Ａ）、前記酸発生剤（Ｂ）及び前記塩基発生剤（Ｃ）の内の少なくとも１つが活性光線の照射により活性種（Ｈ）を発生し、前記活性種（Ｈ）が前記ラジカル開始剤（Ａ）、前記酸発生剤（Ｂ）又は前記塩基発生剤（Ｃ）と反応して新たな活性種（Ｉ）を生成して前記新たな活性種（Ｉ）による前記重合性物質（Ｄ）の重合反応が進行し、前記活性種（Ｈ）又は（Ｉ）が酸又は塩基である請求項４に記載の感光性組成物。 At least one of the radical initiator (A), the acid generator (B) and the base generator (C) generates an active species (H) by irradiation with actinic rays, and the active species (H) It reacts with the radical initiator (A), the acid generator (B) or the base generator (C) to generate a new active species (I) and the polymerizability by the new active species (I). The photosensitive composition according to claim 4, wherein the polymerization reaction of the substance (D) proceeds, and the active species (H) or (I) is an acid or a base.
  6. 　前記ラジカル開始剤（Ａ）が、活性光線によりラジカルを発生するラジカル開始剤（Ａ１）、又は酸及び／若しくは塩基によりラジカルを発生するラジカル開始剤（Ａ２）であり、前記酸発生剤（Ｂ）が、活性光線により酸を発生する酸発生剤（Ｂ１）、又はラジカル、酸及び塩基からなる群から選ばれる少なくとも１種により酸を発生する酸発生剤（Ｂ２）であり、前記塩基発生剤（Ｃ）が、活性光線により塩基を発生する塩基発生剤（Ｃ１）、又はラジカル、酸及び塩基からなる群から選ばれる少なくとも１種により塩基を発生する塩基発生剤（Ｃ２）であって、（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）又は（Ｃ２）を以下の（１）～（４）のいずれかの組合せで含有する請求項４又は５に記載の感光性組成物。
    　（１）（Ａ１）並びに（Ｂ２）及び／又は（Ｃ２）を含有する。
    　（２）（Ｂ１）、（Ａ２）及び必要により（Ｃ２）を含有する。
    　（３）（Ｃ１）、（Ａ２）及び必要により（Ｂ２）を含有する。
    　（４）上記（１）～（３）の２種類以上の組合せ。     The radical initiator (A) is a radical initiator (A1) that generates radicals with actinic rays, or a radical initiator (A2) that generates radicals with an acid and / or a base, and the acid generator (B) Is an acid generator (B1) that generates an acid by actinic rays, or an acid generator (B2) that generates an acid by at least one selected from the group consisting of radicals, acids and bases, and the base generator ( C) is a base generator (C1) that generates a base by actinic rays, or a base generator (C2) that generates a base by at least one selected from the group consisting of radicals, acids and bases, (A1 6. The photosensitive composition according to claim 4 or 5, which comprises (A2), (B1), (B2), (C1) or (C2) in any combination of the following (1) to (4): object.
    (1) Contains (A1) and (B2) and / or (C2).
    (2) Contains (B1), (A2) and (C2) as necessary.
    (3) Contains (C1), (A2) and (B2) if necessary.
    (4) A combination of two or more of (1) to (3) above.
  7. 　前記ラジカル開始剤（Ａ１）が、アシルホスフィンオキサイド誘導体系重合開始剤（Ａ１２１）、α－アミノアセトフェノン誘導体系重合開始剤（Ａ１２２）、ベンジルケタール誘導体系重合開始剤（Ａ１２３）、α－ヒドロキシアセトフェノン誘導体系重合開始剤（Ａ１２４）、ベンゾイン誘導体系重合開始剤（Ａ１２５）、オキシムエステル誘導体系重合開始剤（Ａ１２６）及びチタノセン誘導体系重合開始剤（Ａ１２７）からなる群から選ばれる少なくとも１種のラジカル開始剤であり、前記ラジカル開始剤（Ａ２）が、前記開始剤（Ａ１２１）、前記開始剤（Ａ１２２）、前記開始剤（Ａ１２３）、前記開始剤（Ａ１２４）、前記開始剤（Ａ１２５）、前記開始剤（Ａ１２６）、前記開始剤（Ａ１２７）、有機過酸化物系重合開始剤（Ａ２１）及びアゾ化合物系重合開始剤（Ａ２２）からなる群から選ばれる少なくとも１種のラジカル開始剤である請求項６に記載の感光性組成物。 The radical initiator (A1) is an acylphosphine oxide derivative polymerization initiator (A121), an α-aminoacetophenone derivative polymerization initiator (A122), a benzyl ketal derivative polymerization initiator (A123), an α-hydroxyacetophenone derivative. At least one radical initiation selected from the group consisting of a systemic polymerization initiator (A124), a benzoin derivative polymerization initiator (A125), an oxime ester derivative polymerization initiator (A126) and a titanocene derivative polymerization initiator (A127). The radical initiator (A2) is the initiator (A121), the initiator (A122), the initiator (A123), the initiator (A124), the initiator (A125), and the initiator. Agent (A126), initiator (A127), organic peroxide polymerization initiator The photosensitive composition according to claim 6, which is at least one radical initiator selected from the group consisting of (A21) and an azo compound-based polymerization initiator (A22).
  8. 　前記活性光線により酸を発生する酸発生剤（Ｂ１）、又は前記ラジカル、酸及び塩基からなる群から選ばれる少なくとも１種により酸を発生する酸発生剤（Ｂ２）が、スルホニウム塩誘導体（Ｂ１２１）、ヨードニウム塩誘導体（Ｂ１２２）、スルホン酸エステル誘導体（Ｂ２１）、酢酸エステル誘導体（Ｂ２２）及びホスホン酸エステル（Ｂ２３）からなる群から選ばれる少なくとも１種の酸発生剤である請求項６又は７に記載の感光性組成物。 The acid generator (B1) that generates an acid by the actinic ray or the acid generator (B2) that generates an acid by at least one selected from the group consisting of the radical, acid and base is a sulfonium salt derivative (B121). And at least one acid generator selected from the group consisting of an iodonium salt derivative (B122), a sulfonic acid ester derivative (B21), an acetic acid ester derivative (B22), and a phosphonic acid ester (B23). The photosensitive composition as described.
  9. 　前記活性光線により酸を発生する酸発生剤（Ｂ１）のアニオン部が、ヘキサフルオロホスフェートアニオン、トリフルオロ［トリス（パーフルオロエチル）］ホスフェートアニオン又はテトラキス（パーフルオロフェニル）ボレートアニオンである請求項６～８のいずれか１項に記載の感光性組成物。 The anion part of the acid generator (B1) that generates an acid by actinic rays is a hexafluorophosphate anion, a trifluoro [tris (perfluoroethyl)] phosphate anion, or a tetrakis (perfluorophenyl) borate anion. 9. The photosensitive composition according to any one of 1 to 8.
  10. 　前記活性光線により塩基を発生する塩基発生剤（Ｃ１）が、オキシム誘導体（Ｃ１２１）、４級アンモニウム塩誘導体（Ｃ１２２）及び４級アミジン塩誘導体（Ｃ１２３）からなる群から選ばれる少なくとも１種の塩基発生剤であり、前記ラジカル、酸及び塩基からなる群から選ばれる少なくとも１種により塩基を発生する塩基発生剤（Ｃ２）が、前記誘導体（Ｃ１２１）、前記誘導体（Ｃ１２２）、前記誘導体（Ｃ１２３）及びカルバメート誘導体（Ｃ２１）からなる群から選ばれる少なくとも１種の塩基発生剤である請求項６～９のいずれか１項に記載の感光性組成物。 The base generator (C1) that generates a base by actinic rays is at least one base selected from the group consisting of an oxime derivative (C121), a quaternary ammonium salt derivative (C122), and a quaternary amidine salt derivative (C123). A base generator (C2) that is a generator and generates a base with at least one selected from the group consisting of the radical, acid, and base is the derivative (C121), the derivative (C122), or the derivative (C123). The photosensitive composition according to any one of claims 6 to 9, which is at least one base generator selected from the group consisting of a carbamate derivative (C21).
  11. 　前記重合性物質（Ｄ）に対する前記ラジカル開始剤（Ａ）の含有量が０．０５～３０重量％であり、前記重合性物質（Ｄ）に対する前記酸発生剤（Ｂ）及び／又は前記塩基発生剤（Ｃ）の含有量〔（Ｂ）と（Ｃ）の合計〕が０．０１～３０重量％である請求項４～１０のいずれか１項に記載の感光性組成物。 The content of the radical initiator (A) relative to the polymerizable substance (D) is 0.05 to 30% by weight, and the acid generator (B) and / or the base generation relative to the polymerizable substance (D) The photosensitive composition according to any one of claims 4 to 10, wherein the content of the agent (C) [the sum of (B) and (C)] is 0.01 to 30% by weight.
  12. 　接着剤として用いられる請求項１～１１のいずれか１項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 11, which is used as an adhesive.
  13. 　請求項１～１２のいずれか１項に記載の感光性組成物が活性光線の照射により硬化されてなる硬化物。 A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 12 by irradiation with actinic rays.
  14. 　請求項１～１２のいずれか１項に記載の感光性組成物を用いて貼り合わされた光学基材を含む画像表示装置。 An image display device comprising an optical substrate bonded with the photosensitive composition according to any one of claims 1 to 12.
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