JP2010254927A - Photo-polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysiloxane-based photo-polymerizable composition which has photo-polymerization and lithography capabilities, and an excellent insulation, and gives a cured product useful for a passivation film and a gate insulation film for a thin-film transistor. <P>SOLUTION: The polysiloxane-based photo-polymerizable composition involves a polysiloxane-based compound having a photo-polymerizable functional group and an SiH group in the same molecule and a polysiloxane structure having a polyhedronal skeleton formed of 6-24 Si elements, a compound having an alkenyl group, a photo-polymerization initiator, and a hydrosilylation catalyst. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photocurable curable composition having excellent heat resistance and light resistance.

  Epoxy group-containing siloxanes and methacryloyl group-containing siloxane compounds have long been known as photopolymerizable polysiloxanes, and are applied as various electronic device members such as coating agents and adhesives. Also, among polysiloxane structures, silsesquioxane compounds having a polyhedral structure are known as materials that are particularly excellent in thermal decomposition resistance and insulation, and those having various polymerizable functional groups are already known. ing.

  For example, one having an epoxy group (Patent Document 1), one having a (meth) acryloyl group (Patent Document 2), one having a hydrolyzable silyl group (Patent Document 3), one having an oxetanyl group (Patent Document 1) 4) etc. have been reported, and these compounds are crosslinked by heat or light in the presence of various curing initiators to give a cured product. However, in the cured epoxy resin and sol-gel crosslinked products, the cross-linking point is weak, and it becomes a starting point of thermal decomposition or a decrease in insulation during the reliability test of electronic devices. There is a demand for a proposal of a crosslinking method and a composition that do not deteriorate the excellent characteristics of the body.

JP 2004-359933 A JP 2004-143449 A JP 2006-269402 A Japanese Patent Laid-Open No. 2005-23256

  An object of the present invention is to provide a polysiloxane compound having photocurability and lithographic properties, in which the above-mentioned problems have been solved, and further excellent in insulating properties, and a composition using the compound.

As a result of intensive studies to solve the above problems, the present inventor has the following configuration.

  1). A polysiloxane compound containing a polysiloxane structure having a photopolymerizable functional group and a SiH group in the same molecule and having a polyhedral skeleton formed from 6 to 24 Si atoms, a compound having an alkenyl group, A photocurable composition comprising a photopolymerization initiator and a hydrosilylation catalyst.

  2). It contains at least one alkenyl group and a photopolymerizable functional group in the same molecule, and contains a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms. The composition according to 1).

3). The composition according to 1) or 2), wherein the photopolymerizable functional group of the polysiloxane compound is selected from an alicyclic epoxy group, a glycidyl group, and a hydrolyzable silicon group.

  4). The polysiloxane compound includes a reaction product obtained by hydrosilylation reaction of a cyclic siloxane compound having a SiH group and a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms having an alkenyl group. The composition according to any one of 1) to 3), characterized in that

  5). The polysiloxane compound has the following general formula

(Wherein R ^{9 to} R ³² are non-crosslinkable organic groups having 1 to 10 carbon atoms, and at least one of these R ^{9 to} R ³² is an alkenyl group or a hydrogen atom (SiH group)). A polysiloxane compound having a polyhedral skeleton and the following general formula:

Wherein R ¹ and R ² are non-crosslinkable organic groups having 1 to 6 carbon atoms, X is a hydrogen atom (SiH group) or an alkenyl group, n is 1 to 10, and m is a number from 0 to 10. 1) to 4), which are obtained by a hydrosilylation reaction with a cyclic siloxane compound represented by (II) and a compound having at least one photopolymerizable functional group and an alkenyl group in the same molecule. The composition according to any one of the above.

  6). The composition according to any one of 1) to 5), wherein the photopolymerization initiator is an onium salt.

  7). 6. The composition according to 6), which contains a sensitizer.

  According to the present invention, it is possible to provide a polysiloxane compound having photocurability, and further being excellent in insulation and heat and light resistance, and a composition using the compound.

The present invention is described in detail below.
The composition of the present invention is a composition containing a polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms, and is capable of proceeding with two crosslinking reactions, a photopolymerization reaction and a hydrosilylation reaction. The composition is not particularly limited as long as it can be cured. Compared with a general photocurable material, the composition of the present invention is a composition in which a photopolymerization reaction as a crosslinking reaction and a hydrosilylation reaction that forms a structurally stable Si—C bond after the reaction proceed. Therefore, a cured product that is cured by light and has excellent insulation reliability and heat resistance can be obtained.

  The cured product obtained by the composition of the present invention is suitable for an electronic component that requires photocurability and photolithography and requires high insulation properties. For example, it requires fine patterning and is high in a thin film. The present invention can be applied to a gate insulating film such as an insulating film for a TFT, a passivation film, or the like that requires insulating properties. When an electric device such as a thin film transistor is formed, if there is a leakage current or the like in the insulating layer, it leads to signal response delay, malfunction, and device failure, so that the insulating film is required to have high insulating properties.

  However, in general, an insulating film formed from a photosensitive resin composition that can be formed by solution coating cannot be used because the amount of leakage current when a voltage is applied to the thin film is too large, whereas the composition of the present invention The obtained thin film has a small amount of leakage current, and can be suitably used for the application.

(Polysiloxane structure with polyhedral skeleton)
The composition of the present invention is characterized by containing a polysiloxane compound having a polyhedral skeleton having a structure excellent in thermal decomposition resistance and insulation. The polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms mentioned here is specifically exemplified by, for example, silsesquioxane having a polyhedral structure represented by the following structure (here Then, the number of Si atoms = 8 is exemplified as a representative example).

In the above formula, R ^{1 to} R ⁸ are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, organic group containing amino group, hydrogen atom, methyl group An alkyl group such as an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups. The same or different, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms unsubstituted selected from a halogen atom, a chloromethyl group substituted with a cyano group, a trifluoropropyl group, a cyanoethyl group, or the like This is a substituted monovalent hydrocarbon group.

However, at least one of R ^{1 to} R ⁸ is an organic group containing a reactive group involved in either a photopolymerization reaction or a hydrosilylation reaction that is a crosslinking reaction of the present composition.

The above-mentioned silsesquioxane having a polyhedral structure is, for example, RSiX ₃ (wherein R represents R ^{1 to} R ⁸ described above, and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by hydrolytic condensation reaction of the silane compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by the hydrolysis condensation reaction of RSiX ₃ , the ring is closed by reacting the same or different trifunctional silane compounds to form a polyhedral skeleton. A method for synthesizing silsesquioxane is also known.

  A more preferable example is a silylated silicic acid having a polyhedral structure as shown by the following structure (here, the number of Si atoms = 8 is exemplified as a representative example). In the compound, a Si atom forming a polyhedral skeleton and an organic group containing a reactive group involved in either a photopolymerization reaction or a hydrosilylation reaction that is a crosslinking reaction of the present composition are bonded via a siloxane bond. Therefore, the cured product obtained is not too rigid and a good molded product can be obtained.

In the above structure, R ^{9 to} R ³² are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom A methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part of hydrogen atoms bonded to carbon atoms of these groups Alternatively, they are the same or different organic groups selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like, all of which are substituted with a halogen atom, a cyano group or the like. However, at least one of these R ^{9 to} R ³² is an organic group containing a reactive group involved in either a photopolymerization reaction or a hydrosilylation reaction which is a crosslinking reaction of the present composition.

  It does not specifically limit as a synthesis method of the silicate which has a polyhedral structure, It can synthesize | combine using a well-known method. Specific examples of the synthesis method include a method in which tetraalkoxysilane is hydrolytically condensed in the presence of a base such as quaternary ammonium hydroxide. Examples of tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. Examples of the quaternary ammonium hydroxide include 2-hydroxyethyltrimethylammonium hydroxide and tetramethylammonium hydroxide. In the present invention, a silicate having a similar polyhedral structure can be obtained from a silica-containing substance such as silica or rice husk instead of tetraalkoxylane.

  In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. In addition, it is possible to obtain a polysiloxane in which Si atoms forming a polyhedral structure and an organic group having a crosslinking reaction group are bonded via a siloxane bond.

  In the present invention, the number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, more preferably 6 to 10. Further, it may be a mixture of polysiloxanes having polyhedral skeletons having different numbers of Si atoms.

(Photopolymerization reaction, photopolymerizable functional group)
Next, the photopolymerization reaction and photopolymerizable functional group referred to in the present invention will be described.

  The photopolymerization reaction here means a functional group that is polymerized and crosslinked by radicals or cationic species generated from a photopolymerization initiator when light energy is applied from the outside, and the reaction / crosslinking type is not particularly limited. Absent. In particular, from the viewpoint of high sensitivity due to light energy, a photoradical polymerization reaction of a (meth) acryloyl group, a photocationic polymerization reaction of an epoxy group, an oxetanyl group or a vinyloxy group, a photoacid condensation reaction of a hydrolyzable silicon group, or the like is preferable.

  Moreover, photolithographic property can also be expressed using a photopolymerization reaction. In a thin film using the present composition, fine patterning can be formed by exposing and developing through a photomask. Compared to a patterning step obtained by dry etching or the like, this is superior from the viewpoint of simplifying the process. The developer used here is not particularly limited as long as it is a solvent type in which the composition dissolves, and is generally used as a ketone, alcohol, aromatic, hydrocarbon, or ether type. And organic solvents such as

  The photopolymerizable functional group is preferably an epoxy group, a hydrolyzable silicon group, a (meth) acryloyl group, or a vinyloxy group, particularly from the viewpoint of reactivity and compound stability. Among the epoxy groups, an alicyclic epoxy group and a glycidyl group are preferable from the viewpoint of stability, and an alicyclic epoxy group is particularly preferable from the viewpoint of excellent cationic polymerization by light and heat.

  Examples of hydrolyzable silicon groups include hydrolyzable silicon groups such as alkoxysilyl groups, acetoxysilyl groups, phenoxysilyl groups, silanol groups, chlorosilyl groups, and particularly availability and stability of compounds. From this point, an alkoxysilyl group is particularly preferable. Examples of the alkoxysilyl group include those in which the functional group bonded to silicon is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, or a tert-butoxy group, A methoxy group and an ethoxy group are particularly preferable from the viewpoint that residual components after curing hardly remain.

  Among these, an epoxy group and an alkoxysilyl group are preferable from the viewpoint of high stability of polysiloxane, and an epoxy group is more preferable from the viewpoint that a thick film cured product can be formed. It suffices to have at least one photopolymerizable functional group, and each photopolymerizable functional group may be the same or may have two or more different functional groups. Further, it is sufficient that at least one photopolymerizable functional group is contained in one molecule, but it is preferably 2 or more, more preferably 3 or more. If it is three or more, there exists an advantage that the hardened | cured material with a high crosslinking density is obtained and it is excellent in heat resistance.

(Photopolymerization initiator)
In the present invention, the photopolymerization reaction can be initiated by adding a photopolymerization initiator. The photopolymerization initiator is a compound that generates a polymerization active species by irradiating active energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays, and i rays. It selects and uses suitably according to the kind of photopolymerizable functional group contained in a polysiloxane compound.

  When the polymerizable functional group is an epoxy group or a hydrolyzable silyl group, a photoacid generator is used as a polymerization initiator, but it can be used without any particular limitation. The pKa of the acid generated by the photoacid generator is not limited, but is preferably less than 3, more preferably less than 1.

  As the photoacid generator that can be used in the composition of the present invention, a known photoacid generator can be used. For example, various compounds which are considered suitable in JP 2000-1648 A, JP 2001-515533 A, and WO 2002-83764 can be mentioned, but the present invention is not particularly limited thereto. Examples of the photoacid generator that can be preferably used in the present invention include sulfonate esters, carboxylic acid esters, and onium salts, and onium salts are preferably used.

  In the present invention, various sulfonic acid derivatives can be used as a photoacid generator for sulfonate esters. For example, disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonyl benzoylmethanes, imide sulfonates such as trifluoromethyl sulfonates, benzoin sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol , Pyrogallol trisulfonates, and benzyl sulfonates.

  Specifically, diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, bis (cyclohexylsulfonyl) methane, 1,8 -Naphthalenedicarboxylic acid imidomethyl sulfonate, 1,8-naphthalenedicarboxylic acid imidotosyl sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate, 1,8-naphthalenedicarboxylic acid imide camphor sulfonate, succinimide phenyl sulfonate Acid imidotosyl sulfonate, succinimide trifluoromethyl sulfonate, succinimide camphor sulfonate, phthalic acid Midtrifluorosulfonate, cis-5-norbornene-endo-2,3-dicarboxylic acid imide trifluoromethylsulfonate, benzoin tosylate, 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di (4- Methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosylate, ortho-nitrophenyl methyl tosylate, para-nitrophenyl tosylate, etc. .

  These can be used alone or in combination of two or more. In the present invention, carboxylic acid esters can be used as well.

  In general, sulfonic acid esters and carboxylic acid esters may require a heating step (50 ° C. to 100 ° C.) to liberate the acid.

Examples of onium salts that can be used in the present invention include tetrafluoroborate (BF ₄ −), hexafluorophosphate (PF ₆ −), hexafluoroantimonate (SbF ₆ −), hexafluoroarsenate (AsF ₆ −), and hexachloro. antimonate (SbCl ₆ -), tetraphenyl borate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluorophenyl methylphenyl) borate, perchlorate ion _(ClO 4 -), trifluoromethanesulfonate ion _(CF 3 SO ₃ -), fluoro sulfonic acid ion (FSO 3 _-), toluenesulfonic acid ion, trinitrobenzene sulfonic acid anion, a sulfonium salt or Yodoniu having an anion such as trinitrotoluene sulfonate anion It is possible to use the salt.

  Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylate, triphenylsulfonium hexahexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, methyldiphenyl. Sulfonium tetrakis (pentafluorobenzyl) borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenylsulfate Honium hexahexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-butoxyphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) Sulfonium hexafluorophosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4-acetylphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, tris (4-thiomethoxyphenyl) ) Sulfonium hexafluorophosphate, di (methoxysulfonylphenyl) methylsulfate Nium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrakis (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, (4-octyloxyphenyl) ) Diphenylsulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, 4-acetamidophenyldiphenylsulfonium tetrafluoroborate, 4 -Acetamidophenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, dimethylnaphthylsulfonium hexafluorophosphine , Trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxathinium hexafluorophosphate, 5-methylthiantrenium Hexafluorophosphate, 10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium xanthenium tetrafluoroborate, 10-phenyl-9-oxothioxanthenium tetrakis (Pentafluorobenzyl) borate, 5-methyl-10-oxothiatrenium tetrafluoroborate, 5-methyl-10-oxothiatrenium tet Tetrakis (pentafluoro benzyl) borate, and 5-methyl-10,10-and di-oxo-thia tray hexafluorophosphate and the like. These can be used alone or in combination of two or more.

Examples of the iodonium salt that can be used in the present invention include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, [ 4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy -N-tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) io Donium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluorosulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) ) Iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium triflate, diphenyl Iodonium bisulphate, 4,4'-dichlorodiphenyl iodonium bisulphate, 4,4'-dibromodiphenyl Iodonium bisulphate, 3,3′-dinitrodiphenyliodonium bisulphate, 4,4′-dimethyldiphenyliodonium bisulphate, 4,4′-bissuccinimide diphenyliodonium bisulphate, 3-nitrodiphenyliodonium bisulphate, 4,4 ′ Dimethoxydiphenyl iodonium bisulphate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, US Pat. disclosed in EP 554,664 (Torirukumiru) iodonium tetrakis (pentafluorophenyl) borate _{(CH 3 C 6 H 4)} 2 I- (SO 2 CF 3 ₃ , (C ₆ H ₅ ) 2 IB (C ₆ F ₅ ) ₄ disclosed in US Pat. No. 5,514,728, and those disclosed in US Pat. No. 5,340,898 Etc. These can be used alone or in combination of two or more.

  As other onium salts, aromatic diazonium salts can be used. For example, p-methoxybenzenediazonium hexafluoroantimonate can be used.

  Commercially available onium salts that can be used in the present invention include Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI. -L160, SI-L110, SI-L147 (above, manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, manufactured by Union Carbide), Adeka optomer SP-150, SP-151, SP-170, SP-171, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2639, CI-2064 (above, manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-101 CD-1012 (manufactured by Sartomer), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI- 105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB -101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI -022T (Nippon Kayaku Co., Ltd.), IBPF, IBCF (Sanwa Chemical ( )) CD1012 (Sartomer), IBPF, IBCF (above, manufactured by Sanwa Chemical Co., Ltd.), BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured by Midori Chemical Co., Ltd.) UVE1014 (manufactured by General Electronics), RHODORSIL-PI2074 (manufactured by Rhodia), and the like.

  In addition, J.H. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1473-1482 (1993), J. MoI. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1483-1491 (1993) can also be used diaryl iodonium salts which can be prepared.

  The content of the photoacid generator in the composition of the present invention is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane compound from the viewpoint of curability. Further, from the viewpoint of balance of physical properties of the cured product, it is further preferably 0.1 to 10.0 parts by weight, and particularly preferably 0.2 to 8 parts by weight. If the amount of the photoacid generator is small, it may take a long time to cure or a cured product that is sufficiently cured may not be obtained. Moreover, if there are many photo-acid generators, there exists a possibility that a color may remain in hardened | cured material or coloring for rapid hardening, or heat resistance and light resistance may be impaired, and is not preferable.

  When the photopolymerizable functional group is a (meth) acryloyl group, a radical polymerization initiator is preferably used as the polymerization initiator, but can be used without any particular limitation.

  As radical polymerization initiators, acetophenone compounds, benzophenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzoin compounds, biimidazole compounds, α-diketone compounds, titanocene compounds, polynuclear quinone compounds , Xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, etc. Can do.

  Specific examples of acetophenone compounds include 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- (4′-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2′-hydroxyethoxy) phenyl (2-hydroxy-2) -Propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- (4'-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4′-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2 -Dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one Etc.

  Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  Specific examples of oxime ester compounds include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl 2-benzoylbenzoate and the like.

  Specific examples of the benzophenone compounds include benzyl dimethyl ketone, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.

  Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2 , 2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4 , 6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1, 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bi (2,4,6-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

  Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone and the like.

  Specific examples of the xanthone compound include xanthone, thioxanthone, 2-chlorothioxanthone and the like.

  Specific examples of the triazine compound include 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-methoxyphenyl) -s-triazine, 1,3-bis (Trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (2′-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine, 2- (4′-methoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( '-Methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-bromo-4'-methylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2'-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine and the like.

  In particular, from the viewpoint of excellent thin film curability, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- [4- [ 4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime) )], Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  In particular, from the viewpoint that the cured product is excellent in transparency, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4′-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2′-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone preferable.

(Hydrosilylation reaction)
The composition of the present invention is characterized in that a hydrosilylation reaction proceeds as another crosslinking reaction separately from the photopolymerization reaction. This hydrosilylation reaction is a generally known addition reaction between a SiH group and an alkenyl group, and is not particularly limited by a crosslinking reaction that proceeds when heat or light energy is applied to the composition in the presence of a hydrosilylation catalyst. Absent. The hydrosilylation reaction may proceed simultaneously with the photopolymerization reaction, or may proceed before or after the photopolymerization reaction.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 50-160 degreeC.

(Hydrosilylation catalyst)
Moreover, as a hydrosilylation catalyst used by this invention, what is normally used as a hydrosilylation catalyst can be used, there is no restriction | limiting in particular, Arbitrary things can be used. Specifically, for example, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum; a platinum-vinylsiloxane complex, for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, such as Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer) , Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Patent Platinum is described in the 3220972 Pat Arcola - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

The addition amount of the hydrosilylation catalyst is not particularly limited, but it is preferably used in the range of 10 ⁻¹ to 10 ⁻¹⁰ mol with respect to ¹ mol of the alkenyl group in the compound. Preferably, it is used in the range of 10 ⁻³ to 10 ⁻⁸ mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas may be generated and the cured product may foam, so it is better not to use 10 ⁻¹ mol or more.

(Suitable polysiloxane compound)
SiH group and photopolymerizable functional group-containing polysiloxane compound As a suitable polysiloxane compound that can be used in the present invention, each molecule has at least one SiH group and a photopolymerizable functional group, and 6 And a polysiloxane compound having a polyhedral skeleton formed of ˜24 Si atoms.

  It has one or more photopolymerizable functional groups and SiH groups in the same molecule, and contains a polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms. The synthesis method for obtaining the polysiloxane compound is not particularly limited, and examples thereof include a synthesis method by hydrosilylation in which a reaction that is easy to control and a stable Si—C bond is formed after the reaction.

  As a synthesis method, 1) one or more alkenyl groups and photopolymerizable functional groups in the same molecule as a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms having two or more SiH groups 2) Polysiloxane compound having 2 or more SiH groups and a polysiloxane compound having 1 or more alkenyl groups and a polyhedral skeleton formed from 6 to 24 Si atoms And a method obtained by a hydrosilylation reaction with a compound having at least one alkenyl group and photopolymerizable functional group in the same molecule.

  First, the polyhedral polysiloxane containing SiH groups used in the method 1) preferably has 6 to 24 Si atoms contained in the polyhedral skeleton. Illustrated are silsesquioxanes having the polyhedral structure shown (here, the number of Si atoms = 8 is exemplified as a representative example).

In the above formula, R ^{1 to} R ⁸ are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, organic group containing amino group, hydrogen atom, methyl group An alkyl group such as an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups. The same or different, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms unsubstituted selected from a halogen atom, a chloromethyl group substituted with a cyano group, a trifluoropropyl group, a cyanoethyl group, or the like This is a substituted monovalent hydrocarbon group. However, at least two of R ^{1 to} R ⁸ are SiH groups that are reactive groups for the hydrosilylation reaction.

The above-mentioned silsesquioxane having a polyhedral structure is, for example, RSiX ₃ (wherein R represents R ^{1 to} R ⁸ described above, and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by hydrolytic condensation reaction of the silane compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by the hydrolysis condensation reaction of RSiX ₃ , the ring is closed by reacting the same or different trifunctional silane compounds to form a polyhedral skeleton. A method for synthesizing silsesquioxane is also known.

  A more preferable example is a silylated silicic acid having a polyhedral structure as shown by the following structure (here, the number of Si atoms = 8 is exemplified as a representative example). In this compound, since the Si atom forming the polyhedral skeleton and the reactive group are bonded via a siloxane bond, the obtained cured product is not too rigid, and a good molded body can be obtained. it can.

In the above structure, R ^{9 to} R ³² are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom A methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part of hydrogen atoms bonded to carbon atoms of these groups Alternatively, they are the same or different organic groups selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like, all of which are substituted with a halogen atom, a cyano group or the like. However, at least two of these R ^{9 to} R ³² are SiH groups that are reactive groups for the hydrosilylation reaction.

  It does not specifically limit as a synthesis method of the silicate which has a polyhedral structure, It can synthesize | combine using a well-known method. Specific examples of the synthesis method include a method in which tetraalkoxysilane is hydrolytically condensed in the presence of a base such as quaternary ammonium hydroxide. Examples of tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. Examples of the quaternary ammonium hydroxide include 2-hydroxyethyltrimethylammonium hydroxide and tetramethylammonium hydroxide. In the present invention, a silicate having a similar polyhedral structure can be obtained from a silica-containing substance such as silica or rice husk instead of tetraalkoxylane.

  In this synthesis method, a silicate having a polyhedral structure is obtained by hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as SiH group-containing silyl chloride. In addition, it is possible to obtain a polysiloxane in which Si atoms forming a polyhedral structure and SiH groups that are reactive groups are bonded via a siloxane bond.

  In the present invention, the number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, more preferably 6 to 10. Further, it may be a mixture of polysiloxanes having polyhedral skeletons having different numbers of Si atoms. In the present invention, the number of SiH groups contained in one molecule is preferably at least 2, more preferably at least 3, and further preferably at least 4. In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom and a methyl group.

  Next, a compound having one or more alkenyl groups and photopolymerizable functional groups used in the method 1) in the same molecule will be described.

  The compound mentioned here has at least one photopolymerizable functional group selected from the above-mentioned epoxy group, crosslinkable silicon group, (meth) acryloyl group, vinyloxy group and the like in the same molecule. Any compound can be used without particular limitation.

  From the viewpoint of availability, specific examples of the compound having an epoxy group include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, etc., which are excellent in photopolymerization reactivity. From the viewpoint, vinylcyclohexene oxide, which is a compound having an alicyclic epoxy group, is particularly preferable.

  Examples of the compound having an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group, and residual components after curing remain. From the viewpoint of difficulty, a methoxy group and an ethoxy group are preferable. Specific examples of the compound are preferably trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, methoxydimethylvinylsilane, and ethoxydimethylvinylsilane from the viewpoints of availability and heat resistance.

  Examples of compounds having an acryloyl group or a methacryloyl group include allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and (meth) acrylic acid-modified allyl. Examples thereof include glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol Acrylate DA111). Further, from the viewpoint of high hydrosilylation selectivity, a compound in which a methacryloyl group and an allyl or vinyl group coexist in the same molecule is preferable, and allyl methacrylate, vinyl methacrylate, and the like are particularly preferable in terms of availability. .

  Moreover, in the case of hydrosilylation reaction, 2 or more types of compounds can also be used together regardless of the kind of photopolymerizable functional group.

  Next, a polysiloxane compound having two or more SiH groups used in the method 2) will be described.

  As for the compound mentioned here, for example, it is possible to use a SiH group-containing polysiloxane having a linear structure, a polysiloxane having a SiH group at the molecular end, and a cyclic siloxane compound containing a SiH group. Although not limited, in view of heat resistance, light resistance, chemical stability, and the like, polysiloxane having a polyhedral skeleton containing SiH groups is preferable. Moreover, the polysiloxane to be used may be used independently and may use 2 or more types together.

  Specific examples of the SiH group-containing polysiloxane having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units. And a copolymer of a methylphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a polysiloxane having a terminal blocked with a dimethylhydrogensilyl group, and the like.

Specific examples of polysiloxanes having SiH groups at the molecular ends include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups exemplified above, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units And a polysiloxane composed of at least one siloxane unit selected from the group consisting of SiO ₂ units, SiO _3/2 units, and SiO units.

  As the cyclic siloxane compound containing SiH group, the following general formula

(Wherein R ¹ and R ² are non-crosslinkable organic groups having 1 to 6 carbon atoms, X is a hydrogen atom (SiH group), n is 1 to 10, and m is a number from 0 to 10). Cyclic siloxane. A compound having 3 to 12, more preferably 3 to 6 silicon atoms in the cyclic structure is preferred.

  Specifically, 1,3,5,7-hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7 -Tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5 -Trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen- Examples include 1,3,5,7,9,11-hexamethylcyclosiloxane.

  In the case of hydrosilylating these siloxane compounds having SiH groups, those using cyclic siloxane compounds are particularly preferred from the viewpoint of improving the strength of the resulting cured product, and from the viewpoint of availability, 1, 3, 5, 7-hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1, 3,5,7,9,11-Hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane is preferably used. Furthermore, after the hydrosilylation reaction, 1,3,5,7-hydrogen-1,3,5,7- from the viewpoint of improving the strength of a cured product that can be easily removed by removing the unreacted siloxane compound by devolatilization under reduced pressure. It is preferable to use tetramethylcyclotetrasiloxane.

(Alkenyl group-containing component)
In the present invention, by using a compound having one or more alkenyl groups in the molecule together with the polysiloxane compound having the SiH group and the photopolymerizable functional group, a crosslinking reaction by a hydrosilylation reaction proceeds.

  The compound is not particularly limited as long as it is a compound having at least one alkenyl group in one molecule, and can be used without particular limitation regardless of a polysiloxane compound or an organic compound.

In particular, polysiloxane having an alkenyl group can be preferably applied from the viewpoint of transparency and curability of the cured product. Among these, from the viewpoint of compound availability, a polysiloxane compound having a vinyl group (Si—CH═CH ₂ group) bonded to a silicon group is preferable.

  Specific examples include poly or oligosiloxanes end-capped with dimethylvinylsilyl groups, poly or oligosiloxanes having vinyl groups in the side chains, tetramethyldivinyldisiloxane, hexamethyltrivinyltrisiloxane, SiH groups Examples of the cyclic siloxane include those in which the hydrogen atom of the SiH group is substituted with an alkenyl group such as a vinyl group or an allyl group.

  Specifically, 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclo Tetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 1,3,5,7,9 -Pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane, etc. Compounds.

  Further, from the viewpoint that a cured product having particularly excellent heat resistance can be obtained, polysiloxane having an alkenyl group and having a polyhedral structure can be preferably used. The number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24. Specifically, for example, silsesquioxane having a polyhedral structure represented by the following structure is exemplified (here, Si atoms) Number = 8 is exemplified as a representative example).

In the above formula, R ^{1 to} R ⁸ are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, organic group containing amino group, hydrogen atom, methyl group An alkyl group such as an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups. The same or different, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms unsubstituted selected from a halogen atom, a chloromethyl group substituted with a cyano group, a trifluoropropyl group, a cyanoethyl group, or the like This is a substituted monovalent hydrocarbon group.

However, at least one of R ^{1 to} R ⁸ is an alkenyl group. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance.

The above-mentioned silsesquioxane having a polyhedral structure is, for example, RSiX ₃ (wherein R represents R ^{1 to} R ⁸ described above, and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by hydrolytic condensation reaction of the silane compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by the hydrolysis condensation reaction of RSiX ₃ , the ring is closed by reacting the same or different trifunctional silane compounds to form a polyhedral skeleton. A method for synthesizing silsesquioxane is also known.

  A more preferable example is a silylated silicic acid having a polyhedral structure as shown by the following structure (here, the number of Si atoms = 8 is exemplified as a representative example). In this compound, since the Si atom forming the polyhedral skeleton and the alkenyl group which is a reactive group are bonded via a siloxane bond, the resulting cured product is not too rigid, and a good molded product Can be obtained.

In the above structure, R ^{9 to} R ³² are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom A methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part of hydrogen atoms bonded to carbon atoms of these groups Alternatively, they are the same or different organic groups selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like, all of which are substituted with a halogen atom, a cyano group or the like. However, at least one of these R ^{9 to} R ³² is an alkenyl group. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance.

  It does not specifically limit as a synthesis method of the silicate which has a polyhedral structure, It can synthesize | combine using a well-known method. Specific examples of the synthesis method include a method in which tetraalkoxysilane is hydrolytically condensed in the presence of a base such as quaternary ammonium hydroxide. Examples of tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. Examples of the quaternary ammonium hydroxide include 2-hydroxyethyltrimethylammonium hydroxide and tetramethylammonium hydroxide. In the present invention, a silicate having a similar polyhedral structure can be obtained from a silica-containing substance such as silica or rice husk instead of tetraalkoxylane.

  In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polysiloxane in which Si atoms forming a polyhedral structure and an alkenyl group which is a reactive group are bonded via a siloxane bond.

  In the present invention, the number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, more preferably 6 to 10. Further, it may be a mixture of polysiloxanes having polyhedral skeletons having different numbers of Si atoms. In the present invention, the number of alkenyl groups contained in one molecule is preferably at least 1, more preferably at least 2, and further preferably at least 3.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of vinyl and methyl groups.

  Moreover, it is preferable to apply the organic compound containing an alkenyl group from a viewpoint of obtaining hardened | cured material with high adhesiveness and toughness with a base material.

  The organic compound is not particularly limited as long as it contains an alkenyl group, and an organic polymer compound or an organic monomer compound can be applied.

  Examples of organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (phenolic resin) ), Polyimide compounds can be used.

  Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds and their A mixture etc. are mentioned.

  Specific examples of the compound include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1, 1,2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4 -Cyclohexane dimethanol diallyl ether, triethylene glycol diallyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, vinyl Phenol S diallyl ether, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl Ethers, 2,5-diallylphenol allyl ether, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), novolak phenol Allyl ether Le polyphenylene oxide, and other like are replaced with an allyl group all glycidyl groups of a conventionally known epoxy resins.

  Further, as the compound, a low molecular weight compound that is difficult to express by dividing into a skeleton portion and an alkenyl group (a carbon-carbon double bond having reactivity with the SiH group) can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  In particular, triallyl isocyanurate represented by the following general formula (I) and derivatives thereof are particularly preferable from the viewpoint of high transparency, heat resistance, and light resistance.

(Wherein R represents a monovalent organic group having 1 to 50 carbon atoms, each R may be different or the same, and at least one R is a carbon having reactivity with a SiH group) A compound represented by (including a carbon double bond) is preferable.

As R of the said general formula (I), it is preferable that it is a C1-C20 monovalent organic group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and C1-C10. The monovalent organic group is more preferably, and the monovalent organic group having 1 to 4 carbon atoms is more preferable. Examples of these preferable R ³ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group and allyl group.

  Specific examples of these compounds include triallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monopropyl isocyanurate, and triallyl isocyanurate from the viewpoint of availability. It is done.

Alkenyl group and photopolymerizable functional group-containing polysiloxane compound As a suitable polysiloxane compound that can be used in the present invention, at least one alkenyl group and photopolymerizable functional group are contained in one molecule. Examples thereof include polysiloxane compounds having a polyhedral skeleton formed of 6 to 24 Si atoms.

  It has one or more of the photopolymerizable functional group and alkenyl group in the same molecule, and contains a polysiloxane structure having a polyhedral skeleton formed from 6 to 24 Si atoms. The synthesis method for obtaining the polysiloxane compound is not particularly limited, and examples thereof include a synthesis method by hydrosilylation in which a reaction that is easy to control and a stable Si—C bond is formed after the reaction.

  As a synthesis method, 1) one or more SiH groups and photopolymerizable functional groups in the same molecule as a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms having two or more alkenyl groups 2) A method obtained by hydrosilylation reaction with a compound having 2) a polysiloxane compound having 2 or more SiH groups and a polyhedral skeleton formed from 6 to 24 Si atoms, a compound having 2 or more alkenyl groups and the same Examples thereof include a method obtained by a hydrosilylation reaction with a compound having one or more alkenyl groups and photopolymerizable functional groups in the molecule.

  A compound having one or more SiH groups and photopolymerizable functional groups in the same molecule that can be used in the method 1) can be used without any particular limitation. Specifically, halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; alkoxy such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane Silanes; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; ketoximatesilanes such as bis (dimethylketoxymate) methylsilane and bis (cyclohexylketoximate) methylsilane However, it is not limited to these. Among these, alkoxysilanes can be preferably used.

  In addition, a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms having two or more alkenyl groups, and a polyhedron having two or more SiH groups and formed from 6 to 24 Si atoms. For polysiloxane compounds having a skeleton, compounds having two or more alkenyl groups, and compounds having one or more alkenyl groups and photopolymerizable functional groups in the same molecule, the above-described photopolymerization with SiH groups in one molecule The same compounds as those used for obtaining a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms each having at least one functional group are used without particular limitation. Can do.

<Sensitizer>
The composition in the present invention can achieve desired photosensitivity by blending a sensitizer.

  The sensitizer is not particularly limited and can be appropriately selected from known sensitizers. Specifically, for example, anthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 9,10-dimethylanthracene, 2,4-diethylthioxanthone, mihiraketone, bis- 4,4′-diethylaminobenzophenone, benzophenone, camphorquinone, benzyl, 4,4′-dimethylaminobenzyl, 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone, 3,5-bis (dimethylamino) Benzylidene) -N-methyl-4-piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 3,3′-carbonylbis (7-diethylamino) coumarin, riboflavin tetrabutyrate, 2- Methyl-1- [4- Methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethylthioxanthone, 3,5-diisopropylthioxanthone, 1-phenyl-2- (ethoxycarbonyl) oxyiminopropan-1-one, benzoin ether, benzoin isopropyl ether, benzanthrone, 5-nitroacenaphthene, 2-nitrofluorene, anthrone, 1,2-benzanthraquinone, 1- Phenyl-5-mercapto-1H-tetrazole, thioxanthen-9-one, 10-thioxanthenone, 3-acetylindole, 2,6-di (p-dimethylaminobenzal) -4-carboxycyclohexanone, 2, 6-di (p-dimethylaminobenzal) -4-hydroxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4- Hydroxycyclohexanone, 4,6-dimethyl-7-ethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 7-diethylamino-3- (1-methylbenzimidazolyl) coumarin, 3- (2-benzimidazolyl) -7-diethylaminocoumarin 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) quinoline, 2- (P-dimethylaminostyryl) ze Zochiazoru, 2-(p-dimethylamino styryl) -3,3-dimethyl -3H- indole and the like, but is not limited thereto. These sensitizers may be used alone or in combination of two or more.

  The content of the sensitizer in the composition of the present invention is not particularly limited as long as it is an amount capable of exerting a sensitizing effect, but 0.01 to 300 mol of the sensitizer is added to 1 mol of the photopolymerization initiator. It is preferable that it is 0.1 mol-100 mol. If the amount of the sensitizer is small, the sensitization effect cannot be obtained, and it may take a long time for curing or unfavorably affect the developability. This is not preferable because coloring for curing, heat resistance and light resistance may be impaired.

<Solvent>
The composition in the present invention may be used after diluted with an arbitrary solvent. There is no restriction | limiting in particular as arbitrary solvent, A general organic solvent can be used.
Specific examples of the solvent used for diluting the polysiloxane composition include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, methyl isobutyl ketone, γ-butyrolactone, methyl ethyl ketone, methanol, ethanol, dimethyl imidazolide. Non, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), tetraethylene glycol Dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol Cole monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, isopropanol, ethylene carbonate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, diisopropylbenzene, toluene, xylene, mesitylene and the like can be mentioned. These solvents may be used alone or in combination of two or more. May be used.

<Filler>
To the composition used in the present invention, in addition to the above essential components, fillers such as silica, pulverized quartz, calcium carbonate, carbon and the like are added as a bulking agent as necessary as long as the effects of the present invention are not hindered. May be.

In addition, various additives such as a colorant and a heat resistance improver, a reaction control agent, a release agent, a filler dispersant, and the like can be optionally added to the composition of the present invention as necessary. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, the flame retardancy and fire resistance can be improved by adding titanium dioxide, manganese carbonate, Fe ₂ O ₃ , ferrite, mica, glass fiber, and glass flake to the composition of the present invention. In addition, it is preferable to stop these components to the minimum addition amount so that the effect of this invention may not be impaired.

  The composition used in the present invention is to uniformly mix the above components using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and heat-treat as necessary. Can be obtained.

  The cured product and the laminate on the substrate in the present invention can be obtained by curing the above composition.

  Specifically, the cured product in the present invention can be prepared, for example, by irradiating the composition with a predetermined container or film and then irradiating with an activation energy ray. Examples of the active energy ray source include ultraviolet rays and electron beams. As the light source, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, a medium pressure mercury lamp, or a low pressure mercury lamp, and a laser light source such as an argon ion laser, an excimer laser, or a nitrogen laser can be used. The intensity of the active energy ray and the irradiation time can be arbitrarily set according to the application and production process. Further, in the present invention, the curing rate is very fast and the heat history can be suppressed. If curing is insufficient only by irradiation with active energy rays, curing may be further advanced by subsequent annealing.

The laminate on the base material of the present invention can be specifically prepared by, for example, the following method.
The polysiloxane composition is formed on a base material by a spin coating method, a roll coating method, a printing method, a bar coating method or the like, and the film thickness is usually 0.05 to 100 μm, preferably 0.1 to 50 μm. More preferably, it is applied so as to be 0.5 to 20 μm. Examples of the base material include glass, polycarbonates, films, silicon wafers on which an image sensor is formed, patterned colored resin films for LCD or CCD color filters, printing paper, printing fibers, metal plates, etc. Is mentioned. Next, a laminate can be obtained by performing exposure with the active energy rays.

(Use)
The cured product and laminate obtained from the composition of the present invention can be used as a composition for optical materials. The optical material mentioned here refers to general materials used for the purpose of allowing light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material.

  Specifically, substrate materials in the field of liquid crystal displays, light guide plates, prism sheets, deflector plates, retardation plates, viewing angle correction films, adhesives, color filters, polarizer protective films, liquid crystal films such as passivation films, etc. The peripheral material of the liquid crystal display device is exemplified. PDP (plasma display) sealant, antireflection film, optical correction film, housing material, front glass protective film, front glass substitute material, adhesive, color filter, passivation film.

  Also, LED element molding materials used in LED display devices, front glass protective films, front glass substitute materials, adhesives, color filters, passivation films, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prisms Sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, color filters, polarizer protective films, passivation films. Also, front glass protective film, front glass substitute material, color filter, adhesive, passivation film in organic EL (electroluminescence) display.

  Further, various film substrates in a field emission display (FED), a front glass protective film, a front glass substitute material, an adhesive, a color filter, and a passivation film are exemplified.

  Among these, since the composition of the present invention has patterning properties, in particular, a passivation film for TFT, a gate insulating film for TFT, an interlayer insulating film for TFT, a transparent flattening film for TFT, a binder resin for color filter, and a transparent for color filter Examples thereof include a planarizing material, a binder resin for black matrix, a photo spacer material for liquid crystal cells, and a transparent sealing material for OLED elements.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives.

  In the field of optical equipment, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

  In the field of optical components, fiber materials, lenses, waveguides, element sealants, adhesives and the like around optical switches in optical communication systems are exemplified. Examples include optical fiber materials, ferrules, sealants, adhesives and the like around the optical connector. Examples of optical passive components and optical circuit components include lenses, waveguides, LED element sealants, adhesives, and the like. Examples include substrate materials, fiber materials, element sealants, adhesives, and the like around an optoelectronic integrated circuit (OEIC).

  In the field of optical fibers, examples include sensors for industrial use such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in the home.

  Examples of the semiconductor integrated circuit peripheral material include an interlayer insulating film, a passivation film, an LSI, and a resist material for microlithography for an LSI material.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Examples include rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, and glass substitutes.

Moreover, the multilayer glass for rail vehicles is illustrated. Further, examples thereof include a toughness imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating.
In the construction field, interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials are exemplified. In agriculture, a house covering film is exemplified.

  Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.

Table 1 shows the results of evaluating the characteristics of the compositions obtained in the examples and comparative examples.

As can be seen from the results, it can be seen that a thin film having lithographic properties and high electrical characteristics can be obtained by the present invention.

(Lithography evaluation)
The composition obtained in Examples and Comparative Examples was applied to a glass plate (50 × 100 × 0.7 mm) by spin coating, and the central portion of the coating surface was masked with an aluminum plate to convey the conveyor type. An integrated light amount of 200 mJ / cm ^{2 was} exposed using an apparatus (high pressure mercury lamp, LH6 manufactured by Fusion).
The exposure sample is immersed in acetone (organic developer) for 10 seconds, and has a development contrast (exposed portion of the resin remains and the unexposed portion of the mask is removed). Those not present were evaluated as x for alkali developability.

(Film thickness measurement)
The thin film formed on the glass / AL substrate was calculated by measuring the UV-vis spectrum. A thin film prepared using the resin composition of the present invention has excellent insulating properties and can be applied as a thin film insulating material that can be formed by solution coating.

(Electrical characteristics evaluation)
The following electrical property evaluation samples were prepared for dielectric breakdown voltage evaluation and leakage current measurement evaluation. The resin composition obtained in Examples and Comparative Examples was spin coated (rotation speed: 2000 rpm, 30 seconds) on a glass substrate on which a Mo film was formed as a lower electrode by sputtering to 2000 ° C., and 150 ° C. for 1 hour on a hot plate. Was baked to form a thin film. Further, an AL electrode (3 mmΦ) was formed as an upper electrode on the thin film to prepare a sample.

(Leakage current measurement)
The amount of leakage current was evaluated by measuring the amount of leakage current per electrode unit area when applying 30V between the electrodes (AL-Mo) of the above electrical property evaluation sample in steps of 0.5V from 0 to 50V. It was. For the measurement, a semiconductor parameter measurement device (Agilent 4156C) was used.

Example 1
A 500 mL four-necked flask was charged with 100 g of toluene and 40 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. Mixing 10.0 g of octa (vinyldimethylsiloxy) octasilsesquioxane, 10.0 g of toluene, and 2 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), which is a polyhedral polysiloxane containing vinyldimethylsiloxy groups The liquid was added dropwise.

Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the vinyl group was 95% or more, and the reaction was terminated by cooling. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a colorless and transparent liquid “Reactant A”.

A 100 mL four-necked flask was charged with 20 g of toluene and 10 g of “Reactant A”, the gas phase was replaced with nitrogen, and then heated at an internal temperature of 105 ° C. A mixed liquid of 3.0 g of vinylcyclohexene oxide and 3.0 g of toluene. And the reaction rate of the vinyl group was confirmed to be 95% or more by ¹ H-NMR. The reaction solution was cooled to obtain a polysiloxane compound.

  1 g of the above polysiloxane compound, 2 g of MQV7 (vinyl group-containing siloxane, manufactured by Clariant Japan), 1.5 mg of platinum vinylsiloxane complex (Pt-VTSC-3.0x, manufactured by NMCAT), RHODORSIL-PI2074 (photocation initiation) Agent, Rhodia) 0.06 g, anthracene 0.005 g, and MIBK 7 g were added to obtain a resin composition.

(Comparative Example 1)
A 500 mL four-necked flask was charged with 10 g of toluene and 4 g of 1,3,5,7-tetramethylcyclotetrasiloxane, heated at an internal temperature of 80 ° C., and stirred. A mixed liquid of 8.2 g of vinylcyclohexene oxide, 5 g of toluene, and a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise.

  After confirming that the reaction rate of the vinyl group was 95% or more by H-NMR, toluene was distilled off under reduced pressure, and a colorless and transparent liquid “reactant B” (1,3,5,7-tetramethylcyclotetrasiloxane was obtained. The product was reacted with vinylcyclohexene oxide, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 28, 479-503 (1990)).

  To 1 g of the above “Reactant B”, 0.01 g of RHODORSIL-PI2074 (photocation initiator, Rhodia) and 7 g of MIBK were added to obtain a resin composition.

(Comparative Example 2)
Add 0.5 g of oxetanyl group-containing silsesquioxane OX-SQ (manufactured by Toagosei Co., Ltd.) and add 4 g of methyl isobutyl ketone and 0.005 g of Adeka Opton CP-77 (a photoacid generator as an onium salt, manufactured by Adeka). It was set as the composition.

(Comparative Example 3)
To 1 g of ethyl silicate 40 (manufactured by Colcoat Co., Ltd.), 8 g of methyl isobutyl ketone and 0.01 g of RHODORSIL-PI2074 (photocation initiator, manufactured by Rhodia) were added to obtain a resin composition.

Claims (7)

A polysiloxane compound containing a polysiloxane structure having a photopolymerizable functional group and a SiH group in the same molecule and having a polyhedral skeleton formed from 6 to 24 Si atoms, a compound having an alkenyl group, A photocurable composition comprising a photopolymerization initiator and a hydrosilylation catalyst. It contains at least one alkenyl group and a photopolymerizable functional group in the same molecule, and contains a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms. The composition according to claim 1. The composition according to claim 1 or 2, wherein the photopolymerizable functional group of the polysiloxane compound is selected from an alicyclic epoxy group, a glycidyl group, and a hydrolyzable silicon group. The polysiloxane compound includes a reaction product obtained by hydrosilylation reaction of a cyclic siloxane compound having a SiH group and a polysiloxane compound having a polyhedral skeleton formed from 6 to 24 Si atoms having an alkenyl group. The composition according to claim 1, characterized in that it is characterized in that The polysiloxane compound has the following general formula

(Wherein R ^{9 to} R ³² are non-crosslinkable organic groups having 1 to 10 carbon atoms, and at least one of these R ^{9 to} R ³² is an alkenyl group or a hydrogen atom (SiH group)). A polysiloxane compound having a polyhedral skeleton and the following general formula:

Wherein R ¹ and R ² are non-crosslinkable organic groups having 1 to 6 carbon atoms, X is a hydrogen atom (SiH group) or an alkenyl group, n is 1 to 10, and m is a number from 0 to 10. 5) obtained by a hydrosilylation reaction with a cyclic siloxane compound represented by formula (1) and a compound having at least one photopolymerizable functional group and an alkenyl group in the same molecule. The composition according to any one of the above. The composition according to any one of claims 1 to 5, wherein the photopolymerization initiator is an onium salt. The composition according to claim 6, further comprising a sensitizer.