JP2014232249A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition whose cured product has an excellent curing shrinkage property and a high refractive index.SOLUTION: A photosensitive composition comprises an adduct of an epoxy compound represented by formula (I) and an unsaturated monobasic acid, an inorganic compound, a crosslinking agent, a photopolymerization initiator and a solvent, where M represents one of formulas (II-1)-(II-4).

Description

  The present invention relates to a photosensitive composition containing an inorganic compound and a crosslinking agent, and a cured product thereof.

  Photosensitive compositions containing inorganic compounds are used in various applications. For example, Patent Document 1 discloses a conductive hard coat resin composition for a film comprising a compound having a fluorene skeleton, an acrylate not having a fluorene skeleton, a particulate metal oxide, and a photopolymerization initiator. Is disclosed. Patent Document 2 discloses a hard coat having a refractive index of 1.54 or more formed by curing a composition containing a fluorene derivative, a polyfunctional acrylate, and metal oxide fine particles having an average particle diameter of 1 to 300 nm by ultraviolet irradiation. A membrane is disclosed. Further, Patent Document 3 discloses a composite resin composition comprising inorganic fine particles and a polyvalent carboxylic acid resin.

  However, in these patent documents, in a photosensitive composition containing an inorganic compound, the curing shrinkage is increased by using a crosslinking agent, and the refractive index is increased because the inorganic compound is more closely packed. Is neither described nor suggested.

JP-A-5-164903 JP 2007-291217 A JP 2011-116943 A

  The objective of this invention is providing the photosensitive composition which the cured | curing material obtained when it hardens | cures is excellent in cure shrinkage, and has a high refractive index.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a cured product of a photosensitive composition containing a compound having a specific structure, an inorganic compound, and a crosslinking agent is excellent in curing shrinkage and high. It has been found that it has a refractive index and has reached the present invention.

  That is, the photosensitive composition of the present invention includes an adduct (A) and an inorganic compound (B) of a bifunctional epoxy compound (α) represented by the following general formula (I) and an unsaturated monobasic acid (β). And a crosslinking agent (C) (excluding those corresponding to the component (A)), a photopolymerization initiator (D) and a solvent (E).

（式中、Ｍは下記式（ＩＩ−１）〜（ＩＩ−４）で表される構造から選ばれる連結基を表し、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立に、ハロゲン原子で置換された若しくは無置換の炭素原子数１〜１０のアルキル基、ハロゲン原子で置換された若しくは無置換の炭素原子数１〜１０のアルコキシ基またはハロゲン原子を表し、ａ、ｂ、ｃ、およびｄは、それぞれ独立に、０〜４の数を表し、ｎは０または１〜１０の数を表し、ａ、ｂ、ｃ、およびｄが２〜４のとき、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ同一でも異なっていてもよい。）

(In the formula, M represents a linking group selected from the structures represented by the following formulas (II-1) to (II-4), and R ¹ , R ² , R ³ and R ⁴ are each independently a halogen atom. A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms or a halogen atom, a, b, c, and d each independently represent a number of 0 to 4, n represents the number 0 or 1 to 10, when a, b, c, and d is ^{2~4, R 1, R 2,} R 3 And R ⁴ may be the same or different.

（式中、Ｒ^５、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立に、ハロゲン原子で置換された若しくは無置換の炭素原子数１〜１０のアルキル基、ハロゲン原子で置換された若しくは無置換の炭素原子数１〜１０のアルコキシ基、ハロゲン原子で置換された若しくは無置換の炭素原子数６〜２０のアリール基、ハロゲン原子で置換された若しくは無置換の炭素原子数６〜２０のアリールオキシ基、ハロゲン原子で置換された若しくは無置換の炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換された若しくは無置換の炭素原子数７〜２０のアリールアルコキシ基、または、ハロゲン原子を表し、Ｒ^６は、炭素原子数１〜３のアルキル基を表し、ｅおよびｆは、それぞれ独立に、０〜５の数を表し、ｇおよびｈは、それぞれ独立に、０〜４の数を表す。）

(In the formula, R ⁵ , R ⁷ , R ⁸ and R ⁹ are each independently a halogen atom-substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a halogen atom-substituted or unsubstituted atom. An alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with a halogen atom, or an aryloxy having 6 to 20 carbon atoms substituted or unsubstituted with a halogen atom A group, a halogen atom-substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a halogen atom-substituted or unsubstituted arylalkoxy group having 7 to 20 carbon atoms, or a halogen atom , R ⁶ represents an alkyl group having 1 to 3 carbon atoms, e and f each independently represent a number of 0 to 5, g and h each independently represent Represents a number from 0 to 4.)

  According to the present invention, it is possible to realize a photosensitive composition in which a cured product obtained upon curing has excellent curing shrinkage and a high refractive index.

Hereinafter, the photosensitive composition of this invention is demonstrated based on preferable embodiment.
The photosensitive composition of the present invention comprises an adduct (A), an inorganic compound (B), a crosslinked product of a bifunctional epoxy compound (α) represented by the above general formula (I) and an unsaturated monobasic acid (β). An agent (C), a photoinitiator (D), and a solvent (E) are contained. Hereinafter, each component will be described in order.

<Adduct (A) of bifunctional epoxy compound (α) represented by general formula (I) and unsaturated monobasic acid (β)>
The adduct (A) of the bifunctional epoxy compound (α) represented by the general formula (I) and the unsaturated monobasic acid (β) is a bifunctional epoxy compound represented by the general formula (I) ( It is obtained by adding 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid (β) to one epoxy group of α).

In the general formula (I), examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, Secondary butyl, tertiary butyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, methylcyclohexyl, heptyl, cycloheptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, etc. Can be mentioned.

In the general formula (I), examples of the alkoxy group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include methoxy, ethoxy, propyloxy, butyloxy, methoxyethyl, ethoxyethyl, Examples include propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl and the like.

In the general formula (I), the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ and the halogen atom which may be substituted with the alkoxy group, and R ¹ , R ² , R ³ and R Examples of the halogen atom represented by ⁴ include fluorine, chlorine, bromine and iodine.

In the general formula (I), M is a linking group selected from the structures represented by the above formulas (II-1) to (II-4).
Among the linking groups represented by the above formulas (II-1) to (II-4), an alkyl group having 1 to 10 carbon atoms represented by R ⁵ , R ⁷ , R ⁸ and R ⁹ and R ⁵ , R Examples of the alkoxy group having 1 to 10 carbon atoms represented by ⁷ , R ⁸ and R ⁹ include an alkyl group having 1 to 10 carbon atoms and carbon represented by the above R ¹ , R ² , R ³ and R ^4. What was illustrated as a C1-C10 alkoxy group is mentioned.

Among the linking groups represented by the above formulas (II-1) to (II-4), examples of the aryl group having 6 to 20 carbon atoms represented by R ⁵ , R ⁷ , R ⁸ and R ⁹ include: Examples include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.

Among the linking groups represented by the above formulas (II-1) to (II-4), examples of the aryloxy group having 6 to 20 carbon atoms represented by R ⁵ , R ⁷ , R ⁸ and R ⁹ include Phenoxy, tolyloxy, xylyloxy, ethylphenoxy, chlorophenoxy, naphthyloxy, anthryloxy, phenanthrenyloxy and the like.

Among the linking groups represented by the above formulas (II-1) to (II-4), examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ⁵ , R ⁷ , R ⁸ and R ⁹ include , Benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

Among the linking groups represented by the above formulas (II-1) to (II-4), examples of the arylalkoxy group having 7 to 20 carbon atoms represented by R ⁵ , R ⁷ , R ⁸ and R ⁹ include , Benzyloxy, chlorobenzyloxy, α-methylbenzyloxy, α, α-dimethylbenzyloxy, phenylethyloxy and the like.

In the linking groups represented by the above formulas (II-1) to (II-4), halogen atoms represented by R ⁵ , R ⁷ , R ⁸ and R ⁹ , and R ⁵ , R ⁷ , R ⁸ and Examples of the halogen atom on which the alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group and arylalkoxy group represented by R ⁹ may be substituted include the above R ¹ , R ² , R ³ and R ^4. And those exemplified as the halogen atom which may be substituted for the alkyl group and alkoxy group represented by R ¹ , and the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ .

Among the linking groups represented by the above formulas (II-1) to (II-4), the alkyl group having 1 to 3 carbon atoms represented by R ⁶ includes methyl, ethyl, propyl, isopropyl and cyclopropyl. Can be mentioned.

  Examples of the unsaturated monobasic acid (β) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate. , Dicyclopentadiene malate and the like.

  Instead of the adduct (A) of the bifunctional epoxy compound (α) represented by the general formula (I) and the unsaturated monobasic acid (β), the bifunctional epoxy represented by the general formula (I) Using the reaction product (A ′) obtained by esterifying the polybasic acid anhydride (Y) with the adduct (A) of the compound (α) and the unsaturated monobasic acid (β). You can also. In this case, in the adduct (A) of the bifunctional epoxy compound (α) represented by the general formula (I) and the unsaturated monobasic acid (β), one hydroxyl group of the adduct (A) is used. The polybasic acid anhydride (Y) preferably has a ratio of 0.1 to 1.0 acid anhydride structures.

  Examples of the polybasic acid anhydride (Y) include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2′- 3,3′-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, nadic anhydride, methyl nadic anhydride , Trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride Maleic anhydride adduct, dodecenyl anhydride Acid, anhydride methylhymic Mick acid.

<Inorganic compound (B)>
Examples of the inorganic compound (B) include nickel oxide, iron oxide, iridium oxide, indium oxide, tin oxide, titanium oxide, zinc oxide, zirconium oxide, cerium oxide, tungsten oxide, yttrium oxide, niobium oxide, molybdenum oxide, Tantalum oxide, bismuth oxide, germanium oxide, iron oxide, copper oxide, magnesium oxide, calcium oxide, potassium oxide, chromium oxide, hafnium oxide, silica, alumina, antimony pentoxide, zinc antimonate, aluminum complex, titanium complex, tin complex Metal oxides such as those described above: Surface treatment of the above metal oxide; tin oxide-aluminum oxide composite particles, silicon oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles, tin oxide-silicon oxide composite particles, zirconium oxide − Metal oxide composite particles such as silicon hydride composite particles and zirconium oxide-tin oxide composite particles; barium titanate, lead titanate, strontium titanate, phosphorus-doped tin oxide, antimony-doped tin oxide (ATO), tin-doped indium oxide, ATO coating Complex oxides such as titanium oxide; nitrides such as boron nitride, silicon nitride, gallium nitride, titanium nitride, lithium nitride, sodium nitride, potassium nitride, beryllium, phosphorus nitride, iron nitride, zinc nitride, copper nitride; europium oxide Rare earth oxides such as yttrium oxide, scandium oxide, lanthanum oxide, neodymium oxide; layered clay minerals, miloli blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder, mica, talc, kaolin, ferrocyanide, various Metal sulfate, sulfide , Selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper and the like. Among these, titanium oxide, zirconium oxide, barium titanate is preferred. In particular, among the inorganic compounds, those having a refractive index of 1.6 to 2.7 are preferable because the refractive index of the obtained cured product is increased.

  The average particle size of the inorganic compound (B) is 1 to 100 nm, preferably 10 to 50 nm. When the average particle diameter is less than 1 nm, it is difficult to aggregate and disperse, and when it exceeds 100 nm, there is a possibility that transparency, refractive index and the like cannot be obtained sufficiently. The average particle size is, for example, a transmission electron microscope (TEM), a scanning electron microscope (SEM), a dynamic light scattering particle size distribution measuring device, a laser diffraction / scattering particle size distribution measuring device, or a DMA (Differential Mobility Analyzer). Etc. can be measured.

  Content of the said inorganic compound (B) is 0.1-95 mass% in solid content of the photosensitive composition of this invention, Preferably it is 50-90 mass%, These inorganic compounds are 1 Species or two or more can be used. If the content of the inorganic compound (B) is less than 0.1% by mass, the adhesion may be inferior. If it exceeds 95% by mass, the transparency and refractive index may not be sufficiently obtained.

  The inorganic compound (B) is an adduct (A) of the bifunctional epoxy compound (α) represented by the general formula (I) and an unsaturated monobasic acid (β), or this adduct ( 50-500 parts by mass, preferably 100-300 parts by mass with respect to 100 parts by mass of the reaction product (A ′) obtained by further esterifying the polybasic acid anhydride (Y) with respect to A). Used in proportions.

  Even if the said inorganic compound (B) is mixed and prepared with a dispersing agent, the target effect will be acquired. As a mixing method, a mechanical mixing method using a kneader, a roll, an attritor, a super mill, a dry pulverizer, or a method of depositing a dispersant on the surface of an inorganic compound (B) in a suspension system using an organic solvent or water. And so on.

<Crosslinking agent (C)>
Examples of the crosslinking agent (C) include an adduct (A) or a reaction product (A) of a bifunctional epoxy compound (α) represented by the general formula (I) and an unsaturated monobasic acid (β). It may be any of those that copolymerize with ') to crosslink main chains, or those that react with side chain substituents to crosslink main chains. Examples of the crosslinking agent include polyfunctional acrylates, polyisocyanates, polyols, polycarboxylic acids, polyfunctional epoxy compounds, divinyl compounds, styrene-maleic acid copolymers, dialdehydes, polyfunctional acrylamides, polyfunctional oxetane compounds, and polyalkylols. Melamine, polyalkylolated glycoluril, polyalkylolated hydroxyethylene urea, polyalkylolated urea, polyalkylolated benzoguanamine, polyalkylolated spiroguanamine, polyalkylolated acrylamide, polyalkylolated phenol / formaldehyde Adduct, urethane acrylate, polyester acrylate oligomer, urethane methacrylate, polyester methacrylate oligomer, acetoacetate, carbodi De, alkylene carbonate, polyhydric aziridine compounds, polyhydric amine compound, a silane coupling agent and the like, which may be used by mixing one kind alone or a plurality. Among these, polyfunctional acrylates are preferable from the viewpoint of reactivity.

  Examples of the polyfunctional acrylate include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6-hexanediol diacrylate. Acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate, tri [acryloylethyl] isocyan Nurate, polystyrylethyl acrylate, (2, , 6-tetramethylpiperidinyl) acrylate, bisphenol A diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, tricyclodecane dimethylol dimethacrylate , Tori [methacryl Ilethyl] isocyanurate, polystyrylethyl methacrylate, (2,6,6-tetramethylpiperidinyl) methacrylate, bisphenol A dimethacrylate, and the like. Among them, bifunctional to tetrafunctional (meth) acrylates are cured and contracted. Is preferable because the refractive index of the cured product is high.

  Examples of the polyisocyanate include 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4. , 4, -trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, aliphatic diisocyanates such as ω, ω'-diisocyanate dipropyl ether; cyclobutane-1,3-diisocyanate, cyclohexane-1 , 3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,2-diisocyanate-1-methyl-cyclohexane, -2,6-diisocyanate-1-methyl-cyclohexane, isophorodiisocyanate, 2,5- Screw -(Isocyanatomethyl) -8-methyl-1,4-methano-decahydronaphthalene, 3,5-bis- (isocyanatomethyl) -8-methyl-1,4-methano-decahydronaphthalene, 1,5 -Bis (isocyanatomethyl) -4,7-methano-hexahydroindane, 2,5-bis (isocyanatomethyl) -4,7-methano-hexahydroindane, 1,6-bis (isocyanatomethyl)- 4,7-methano-hexahydroindane, 2,6-bis (isocyanatomethyl) -4,7-methano-hexahydroindane, 1,5-, 2,5-, 1,6- and 2,6- Bis (isocyanate) -4,7-methano-hexahydroindane, dicyclohexyl-2,4'- and 4,4'-diisocyanate, 2,4- and 2,6-hexa Drotolylene diisocyanate, perhydro-2,4′-diphenylmethane diisocyanate, perhydro-4,4′-diphenylmethane diisocyanate, 4,4′-di (isocyanatocyclohexyl) -methane, 3-isocyanato-methyl-3,5 Cycloaliphatic diisocyanates such as 5-trimethylcyclohexyl isocyanate; ω, ω′-diisocyanate-1,4-diethyl-benzene, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diis Isocyanate-diphenyl, 4,4′-diisocyanate-3,3′-dichlorodiphenyl, 4,4′-diisocyanate-3,3′-dimethoxy-diphenyl, 4,4′-diisocyanate-3 , 3′-dimethyl-diphenyl, 4,4 ′ Diisocyanate-3,3′-diphenyl-diphenyl, 2,4′- and 4,4′-diisocyanate-diphenylmethane, naphthalene-1,5-diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene-diisocyanate, N, N ′-(4,4-dimethyl-3,3′-diisocyanatodiphenyl) -uretodione, m-xylylene-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4 ′ -Aromatic diisocyanates such as diisocyanate, 2,4,4'-triisocyanate-diphenyl ether, 4,4 ', 4 "-triisocyanate triphenylmethane, tris (4-isocyanatophenyl) -thiophosphate Carbodiimide modification, isocyania Rate modification may be used in the form of modified products such as biuret may be used in the form of blocked blocked isocyanate by a variety of blocking agents.

  Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2-butyl-2-ethyl-1. , 3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5- Pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1, 8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1, Aliphatic diols such as 0-decanediol; Alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; Low molecular diols such as aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and ethylene oxides such as triethylene glycol Adducts; propylene oxide adducts such as dipropylene glycol and tripropylene glycol; ethylene oxide and / or propylene oxide adducts of low molecular polyols, polyether diols such as polytetramethylene glycol, diols such as low molecular polyols; Less than the stoichiometric amount of the divalent carboxylic acid or its ester, anhydride, halide or other ester-forming derivative, and / or lactone or its hydrolyzate Polyester diol, poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene, etc. obtained by direct esterification reaction and / or transesterification reaction with hydroxycarboxylic acid obtained by ring opening ) Polycarbonate diols such as carbonates, polyolefin diols such as polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol.

  Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, dodecanedioic acid, and 2-methylsuccinic acid. 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, Aliphatic dicarboxylic acids such as dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

  The polyfunctional epoxy compound can be obtained, for example, by epoxidizing a diglycidyl ether of a dihydric alcohol or an alkylene oxide adduct thereof, a diglycidyl ester of a dibasic acid, a cyclohexene ring or a cyclopentene ring-containing compound with an oxidizing agent. Cyclohexene oxide or cyclopentene oxide-containing compounds can be used, and specific examples include the following compounds.

  That is, it is obtained by hydrogenating a bisphenol diglycidyl ether type epoxy resin such as a bisphenol M type epoxy resin, a bisphenol P type epoxy resin, an epoxy resin represented by the above formula (I); Hydrogenated bisphenol type diglycidyl ether; ethylene glycol diglycidyl ether, 1,3-propylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethyl Glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, glycidyl ether of aliphatic dihydric alcohols such as 1,4-cyclohexanedimethanol diglycidyl ether; phenol novolac Type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds and the like novolac type epoxy compounds; 3,4-epoxy-3-methylcyclohexylmethyl-3 , 4-Epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4- Epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, bis (3,4-epoxycyclohexylmethyl) adipate, methylenebis (3,4-epoxycyclohexane), isopropylidenebis (3,4-epoxycyclohexane) , Cycloaliphatic epoxy compounds such as dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), 1,2-epoxy-2-epoxyethylcyclohexane; diglycidyl phthalate Diglycidyl esters of dibasic acids such as terephthalate, tetrahydrophthalic acid diglycidyl ester and dimer acid glycidyl ester; glycidyl amines such as N, N-diglycidylaniline; complex such as 1,3-diglycidyl-5,5-dimethylhydantoin Cyclic epoxy compounds; dioxide compounds such as dicyclopentadiene dioxide; naphthalene-type epoxy compounds, triphenylmethane-type epoxy compounds, dicyclopentadiene-type epoxy compounds, and the like.

  As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, isocyanate groups such as KBE-9007, KBM-502, and KBE-403, methacryloyl groups, A silane coupling agent having an epoxy group is preferably used.

Polyalkylolated melamine, polyalkylolated glycoluril, polyalkylolated hydroxyethylene urea, polyalkylolated urea, polyalkylolated benzoguanamine, polyalkylolated spiroguanamine, polyalkylolated acrylamide, polyalkylol Examples of the phenol / formaldehyde adduct include compounds in which all or part (at least two) of active methylol groups (CH ₂ OH groups) in each nitrogen compound are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.

  In the photosensitive composition of the present invention, the crosslinking agent (C) is an adduct (A) of a bifunctional epoxy compound (α) represented by the general formula (I) and an unsaturated monobasic acid (β). Or 0.1 to 200 parts by mass with respect to 100 parts by mass of the reaction product (A ′) obtained by esterifying the polybasic acid anhydride (Y) with respect to the adduct (A). In particular, 1 to 100 parts by mass is preferable. When the content of the crosslinking agent (C) is less than 0.1 parts by mass, the refractive index may not be sufficiently obtained, and when it exceeds 200 parts by mass, the photolithography performance may not be sufficiently obtained. is there.

<Photopolymerization initiator (D)>
As the photopolymerization initiator (D), conventionally known compounds can be used. For example, acetophenone compounds, benzophenone compounds, benzoin compounds, benzyl compounds, benzyl ketal compounds, oxime ester compounds, acylphosphine compounds, triazines. Compounds, xanthone compounds, thioxanthone compounds, benzoquinone compounds, anthraquinone compounds, disulfide compounds, biimidazole compounds, 4,4-azobisisobutyronitrile, camphorquinone, benzoyl peroxide, and the like. 1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE369, IRGACURE907, IRGACURE OXE 01, IR ACURE OXE 02 (manufactured by BASF), and the like.

  Content of the said photoinitiator (D) is 0.1-30 mass% in solid content of the photosensitive composition of this invention, Especially 0.5-10 mass% is preferable. When the content of the photopolymerization initiator (D) is less than 0.1% by mass, curing by exposure may be insufficient. When the content is more than 30% by mass, the photopolymerization initiator is contained in the photosensitive composition. (D) may precipitate.

<Solvent (E)>
A solvent (E) can be further added to the photosensitive composition of the present invention. As the solvent, the above-mentioned components (addition product of the bifunctional epoxy compound (α) represented by the general formula (I) and the unsaturated monobasic acid (β) of the present invention) A) etc.) in which the solvent can be dissolved or dispersed, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, diacetone alcohol; ethyl ether, Ether solvents such as dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Cyclohexyl, ethyl lactate, dimethyl succinate, texano Ester solvents such as ethylene; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; ethylene Ether ester solvents such as glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; turpentine oil, D-li Terpene hydrocarbon oils such as nene and pinene; paraffinic solvents such as mineral spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like can be mentioned, and these solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, dimethylacetamide, methyl ethyl ketone, diacetone alcohol, etc., start photopolymerization with the resist in the photosensitive composition. It is preferable because the compatibility of the agent is good.

  In the photosensitive composition of the present invention, the amount of the solvent (E) used is preferably such that the concentration of the composition other than the solvent (E) is 5 to 30% by mass, and less than 5% by mass. It is difficult to increase the film thickness and the desired refractive index is not obtained, which is not preferable. When it exceeds 30% by mass, the storage stability of the composition due to the precipitation of the composition is reduced, and the viscosity is improved. It is not preferable because handling is reduced.

  In addition, the photosensitive composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Add conventional additives such as foaming agent, leveling agent, surface conditioner, antioxidant, ultraviolet absorber, dispersant, dispersion aid, aggregation inhibitor, catalyst, curing accelerator, crosslinking agent, thickener, etc. Can do.

  In the photosensitive composition of the present invention, an adduct (A) or a reaction product (A ′) of the bifunctional epoxy compound (α) represented by the general formula (I) and the unsaturated monobasic acid (β). The content of optional components other than the inorganic compound (B), the crosslinking agent (C) and the photopolymerization initiator (D) (excluding the solvent (E)) is appropriately selected according to the purpose of use, and in particular Although it does not restrict | limit, Preferably containing of the adduct (A) thru | or reaction product (A ') of bifunctional epoxy compound ((alpha)) represented by the said general formula (I) and unsaturated monobasic acid ((beta)) is preferable. The total amount is 50 parts by mass or less with respect to 100 parts by mass.

  In addition to the adduct (A) or reaction product (A ′) of the bifunctional epoxy compound (α) represented by the above general formula (I) and the unsaturated monobasic acid (β), other organic polymers By using this, the properties of the cured product comprising the photosensitive composition of the present invention can be improved. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate, polyvinyl butyral, cellulose ester, polyacrylamide, Saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, etc. are mentioned, among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin Preferred.

  In the photosensitive composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, melamine and the like can be further used in combination.

  As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-Mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercapto Phenol, 2- Lucaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing this mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Iodinated alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, -Dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropioate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, the following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko K.K.

Compound No. C1

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  The photosensitive composition of the present invention is a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, ink jet, various printing, dipping, etc., soda glass, quartz glass, semiconductor substrate, metal, paper It can be applied on a supporting substrate such as plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method. Also, after forming a coating film of the photosensitive composition on the substrate and irradiating the coating film with active light through a mask having a predetermined pattern shape, the exposed coating film is developed with a developer (especially an alkali developer). It is also possible to carry out patterning by a step of developing the film and heating the film after development.

  Moreover, as the light source of the active light used when curing the photosensitive composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, carbon An arc, a xenon arc, or the like can be used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but argon ion laser, helium neon laser, YAG laser, semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  The photosensitive composition (or cured product thereof) of the present invention is used for glasses, optical materials represented by imaging lenses, prism lens sheets used for backlights of liquid crystal display devices, screens for projection televisions, and the like. Lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, photocurable paints or varnishes, Color filters for color display liquid crystal display panels such as photo-curing adhesives, printed circuit boards, color televisions, PC monitors, personal digital assistants, digital cameras, etc., color filters or infrared absorption filters for CCD image sensors, for plasma display panels Electrode material, powder coating, mark Inks, printing plates, adhesives, dental compositions, stereolithography resins, gel coats, photoresists for electronics, electroplating resists, etching resists, both liquid and dry films, solder resists, for various display applications A resist for forming a structure in a manufacturing process of a color filter or a plasma display panel, an electroluminescent display device, and an LCD, a composition for encapsulating electrical and electronic components, a solder resist, a magnetic recording material, Micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, holographic recording materials, Image recording materials, fine electronic circuits, bleaching materials, paintings Decolorizing materials for recording materials, decoloring materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, dielectrics in sequential lamination of printed circuit boards It can be used for various applications such as a photoresist material or a protective film used for body layer formation, and the application is not particularly limited.

  The cured product of the photosensitive composition of the present invention preferably has a refractive index of 1.73 or more because it is useful for optical applications.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these Examples.

[Production Example 1]
(Obtained by esterification of polybasic acid anhydride (Y) to adduct (A) of bifunctional epoxy compound (α) and unsaturated monobasic acid (β) (A′-1) Preparation)
Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane 89.9 g, acrylic acid 23.5 g, 2,6-di-tert-butyl-p-cresol 0.457 g, benzyl The triethylammonium chloride 0.534g and PGMEA75.6g were prepared, and it stirred at 120 degreeC for 16 hours. This was cooled to room temperature, charged with 12.0 g of 2,4-pentanedione and 1.0 g of triethylamine, and stirred at 92 ° C. for 17 hours. This was cooled to room temperature, 25.6 g of succinic anhydride, 1.39 g of tetra-n-butylammonium bromide, and 40.42 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. This was cooled to room temperature, 46.7g of PGMEA was added, and the adduct (A'-1) which is a target object was obtained as a PGMEA solution.

[Production Example 2]
(Obtained by further esterifying a polybasic acid anhydride (Y) with an adduct (A) of a bifunctional epoxy compound (α) and an unsaturated monobasic acid (β) (A′-2) Preparation)
9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g, and 65.9 g of PGMEA was charged and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. This was cooled to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 30.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol, and 1.50 g of PGMEA were added thereto, and 90 ° C. Minutes, stirring at 120 ° C. for 4 hours, 93.4 g of PGMEA was added to obtain an adduct (A′-2) as a target product as a PGMEA solution.

[Production Example 3]
(Obtained by further esterification of polybasic acid anhydride (Y) to adduct (A) of bifunctional epoxy compound (α) and unsaturated monobasic acid (β) (A′-3) Preparation)
1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane 30.0 g, acrylic acid 7.52 g, 2,6-di-t-butyl-p-cresol 0.080 g, tetrabutylammonium 0.183 g of chloride and 11.0 g of PGMEA were charged and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour and 120 ° C. for 17 hours. This was cooled to room temperature, 8.11 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 11.1 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 12.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 0.080 g of 2,6-di-t-butyl-p-cresol and 0.600 g of PGMEA were added thereto. After stirring at 90 ° C. for 90 minutes and at 120 ° C. for 5 hours, 24.0 g of PGMEA was added to obtain an adduct (A′-3) as a PGMEA solution.

[Production Example 4]
(Preparation of adduct (A-4) of bifunctional epoxy compound (α) and unsaturated monobasic acid (β))
9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g, and 65.9 g of PGMEA was charged, and stirred at 90 ° C. for 1 hour, at 100 ° C. for 1 hour, at 110 ° C. for 1 hour and at 120 ° C. for 14 hours to obtain an addition product (A-4) as a target product as a PGMEA solution.

[Production Example 5]
(Obtained by further esterifying polybasic acid anhydride (Y) to adduct (A) of bifunctional epoxy compound (α) and unsaturated monobasic acid (β) (A′-5) Preparation)
1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane 30.0 g, acrylic acid 7.52 g, 2,6-di-t-butyl-p-cresol 0.104 g, tetrabutylammonium 0.183 g of chloride and 11.0 g of PGMEA were charged and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour and 120 ° C. for 17 hours. This was cooled to room temperature, 9.24 g of 3,3′-4,4′-biphenyltetracarboxylic dianhydride, 0.154 g of 1,2,3,6-tetrahydrophthalic anhydride, tetrabutylammonium chloride 0 .427 g and 12.1 g of PGMEA were added, and after stirring at 120 ° C. for 5 hours, 90 ° C. for 1 hour, 60 ° C. for 2 hours and 40 ° C. for 3 hours, 17.5 g of PGMEA was added, and the adduct (A '-5) was obtained.

[Comparative Production Example 1]
(Adjustment of comparative additive (A ''-1))
40 parts by mass of acrylic acid and 50 parts by mass of butyl methacrylate are dissolved in propylene glycol-1-monomethyl ether-2-acetate (PGMEA), and 4 parts by mass of azobisisobutyronitrile is used as a radical polymerization initiator. For 2 hours. Subsequently, 10 parts by mass of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin) was added thereto, followed by stirring at 120 ° C. for 3 hours to obtain a comparative adduct (A ″ -1).

[Examples 1 to 10 and Comparative Examples 1 to 3]
(Preparation of photosensitive compositions No. 1 to No. 10 of Examples 1 to 10 and Comparative photosensitive compositions No. 1 to No. 3 of Comparative Examples 1 to 3)
Each component was mixed by the mixing | blending shown in following Table 1 and Table 2, and photosensitive composition No. of Examples 1-10. 1-No. 10 and Comparative Photosensitive Composition Nos. 1 to 3 of Comparative Examples 1-3. 1-No. 3 was obtained. In addition, the compounding quantity in the following table | surface shows a mass part.

[Evaluation Examples 1 to 10 and Comparative Evaluation Examples 1 to 3]
(Evaluation of photosensitive composition No. 1 to No. 10 and comparative photosensitive composition No. 1 to No. 3)
On the glass substrate, photosensitive composition No. obtained in Examples 1-10 and Comparative Examples 1-3. 1-No. 10 and comparative photosensitive composition no. 1-No. 2.5 mL of No. 3 was dropped and spin-coated under the conditions of 500 rpm × 7 seconds, followed by drying at 90 ° C. for 60 seconds and then at 22 ° C. for 60 seconds, using a high pressure mercury lamp with a predetermined mask. The film was exposed at 100 mJ / cm ² , developed by being immersed in a 2.5% by mass sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 30 minutes. The following evaluation was performed about the obtained pattern. The results are shown in Tables 1 and 2 below.

(Refractive index)
The refractive index of the D line was measured at 25 ° C. using a digital Abbe refractometer DR-A1 manufactured by Atago Co., Ltd. The cured resin film having a size of 1.0 × 50 × 50 mm was used.

(Curing shrinkage)
The curing shrinkage was measured according to the method described in JIS K6911.

＊１）ＮＣＩ−９３０：（株）ＡＤＥＫＡ製 ラジカル開始剤
＊２）ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート

* 1) NCI-930: ADEKA Corporation radical initiator * 2) PGMEA: Propylene glycol monomethyl ether acetate

  From the results of Table 1 and Table 2, the cured product of the photosensitive composition of each Example according to the present invention has a high refractive index and curing shrinkage. On the other hand, the comparative photosensitive composition has no structure represented by the general formula (I) (Comparative Example 1), does not contain the inorganic compound (B) (Comparative Example 2), and a crosslinking agent (C ) Did not contain (Comparative Example 3), the refractive index and cure shrinkage were low.

  From the above, the cured product of the photosensitive composition of the present invention is useful for optical applications and the like because the curing shrinkage is large, and the inorganic compound is more densely packed and the refractive index is high.

Claims (5)

Addition product (A) of bifunctional epoxy compound (α) and unsaturated monobasic acid (β) represented by the following general formula (I), inorganic compound (B), crosslinking agent (C) (provided that (A ), A photopolymerization initiator (D), and a solvent (E).

(In the formula, M represents a linking group selected from the structures represented by the following formulas (II-1) to (II-4), and R ¹ , R ² , R ³ and R ⁴ are each independently a halogen atom. A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms or a halogen atom, a, b, c, and d each independently represent a number of 0 to 4, n represents the number 0 or 1 to 10, when a, b, c, and d is ^{2~4, R 1, R 2,} R 3 And R ⁴ may be the same or different.

(In the formula, R ⁵ , R ⁷ , R ⁸ and R ⁹ are each independently a halogen atom-substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a halogen atom-substituted or unsubstituted atom. An alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with a halogen atom, or an aryloxy having 6 to 20 carbon atoms substituted or unsubstituted with a halogen atom A group, a halogen atom-substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a halogen atom-substituted or unsubstituted arylalkoxy group having 7 to 20 carbon atoms, or a halogen atom , R ⁶ represents an alkyl group having 1 to 3 carbon atoms, e and f each independently represent a number of 0 to 5, g and h each independently represent Represents a number from 0 to 4.)   The polybasic acid anhydride (Y) is further esterified to the adduct (A) of the bifunctional epoxy compound (α) represented by the general formula (I) and the unsaturated monobasic acid (β). The photosensitive composition of Claim 1 containing the obtained reaction product (A '), an inorganic compound (B), a crosslinking agent (C), a photoinitiator (D), and a solvent (E).   The photosensitive composition according to claim 1, wherein the inorganic compound (B) is zirconium oxide, titanium oxide, or barium titanate.   The cross-linking agent (C) is at least one selected from the group consisting of difunctional acrylates, difunctional methacrylates, trifunctional acrylates, trifunctional methacrylates, tetrafunctional acrylates and tetrafunctional methacrylates. The photosensitive composition as described in any one of them.   A cured product of the photosensitive composition according to any one of claims 1 to 4, wherein the cured product has a refractive index of 1.73 or more.