JP2011219583A - Light curable composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light curable composition having light curability, usable for lithography, exhibiting good sensitivity and scarcely developing problems such as a pattern form defect after development and corrosion, and to provide a cured product.SOLUTION: The problems are solved by the light curable composition containing (a) a cationically polymerizable compound, (b) a cationic polymerization initiator and (c) a cure accelerator having an epoxy group or oxetanyl group, and an alkoxysilyl group; and the cured product obtained by curing the light curable composition with light irradiation.

Description

  The present invention relates to a photocurable composition excellent in sensitivity and optical transparency and a cured product thereof.

  About a photocurable composition containing a compound having a cationic polymerizable functional group and a cationic polymerization initiator, it is known to function as a UV curable resin having a good surface curability, and in particular, the cationic polymerizable functional group. The polyorganosiloxane compound having an excellent reliability and transparency at high temperatures. However, regarding these compositions, there is room for improvement in activity against photocationic polymerization, and problems such as poor curing may occur in applications that require particularly high sensitivity. On the other hand, measures such as increasing the amount of the cationic polymerization initiator and using a more active cationic polymerization initiator are possible, but problems such as corrosion tend to occur.

  In addition, for the purpose of accelerating the curing of the epoxy resin contained in the photo / thermosetting composition, a method of adding a basic compound such as an amine compound or an imidazole compound is known. It is intended to accelerate the thermosetting reaction to be performed, and cannot be used for the purpose of improving pattern shape defects after the development process in applications requiring lithography. (See Patent Document 2)

JP 2009-62490 A JP 2007-316545 A

  In view of the above circumstances, an object of the present invention is to provide a photocurable composition and a cured product that are photocurable, capable of lithography, have good sensitivity, and are less susceptible to problems such as shape defects after development and corrosion. Is to provide.

  In view of the above circumstances, as a result of intensive studies by the present inventors, a cationically polymerizable compound (a), a cationic polymerization initiator (b), an epoxy group, or an oxetanyl group, and a curing accelerator having an alkoxysilyl group (c The above-mentioned problems can be solved by a photo-curable composition comprising), and the present invention has been completed. That is, the present invention has the following configuration.

  1). A photocurable composition comprising a cationically polymerizable compound (a), a cationic polymerization initiator (b), an epoxy group or oxetanyl group, and a curing accelerator (c) having an alkoxysilyl group.

  2). The photocurable composition according to 1), wherein the cationically polymerizable compound (a) is a polyorganosiloxane compound.

  3). The photocurable composition according to 1) or 2), wherein the cationic polymerizable compound (a) is an epoxy group-containing compound.

  4). Any one of 1) to 3), wherein the cationically polymerizable compound (a) is a compound having a cationically polymerizable functional group and a SiH group in the same molecule, and (d) a compound having a carbon-carbon double bond. The photocurable composition as described in 2. above.

  5). The component (a) is a compound having in the same molecule at least one selected from the group consisting of each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group 1) -4) The photocurable composition in any one of.

  6). Component (d) is represented by the following general formula (I)

(In the formula, R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ represents reactivity with a SiH group. The photocurable composition according to 4) or 5), which is a compound represented by (including a carbon-carbon double bond having).

7). The photocurable composition according to any one of 4) to 6), wherein the component (d) is a compound having a Si—CH═CH ₂ group.

8). The photocurable composition according to any one of 1) to 7), wherein the component (a) uses a hydrosilylation reaction product of the following compounds (α) to (γ).
(Α) Organic compound having one or more carbon-carbon double bonds having reactivity with SiH group in one molecule (β) Organosiloxane compound (γ) 1 having at least two SiH groups in one molecule Compound having at least one cationically polymerizable functional group and one or more carbon-carbon double bond having reactivity with SiH group in the molecule 9). 8) The compound (α) described above has one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, and the following general formula (I)

(In the formula, R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ represents reactivity with a SiH group. The photocurable composition according to 8), which is a compound represented by (including a carbon-carbon double bond having).

10). 8) The photocurable composition according to any one of 8) or 9), wherein the compound (α) is a compound having a Si—CH═CH ₂ group.

  11). 8) The compound (α) described above has one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, and is represented by the following formulas (X1) to (X3). The photocurable composition according to any one of 8) to 10), which is an organic compound having at least one selected from the group consisting of each structure, a phenolic hydroxyl group, and a carboxyl group in the same molecule.

  12). Compound (β) is represented by the following general formula (III)

(Wherein R ⁴ and R ⁵ represent an organic group having 1 to 10 carbon atoms, and may be the same or different, n represents 1 to 10, and m represents a number of 0 to 10)
The photocurable composition according to any one of 8) to 11), which is a cyclic polyorganosiloxane compound having a SiH group represented by:

  13). Compound (γ) is represented by the following general formula (IV)

(Wherein R ⁶ and R ⁷ represent an organic group having 1 to 6 carbon atoms, n represents 1 to 3, m represents a number of 0 to 10), and 8) to 12) The photocurable composition in any one.

14). Hardened | cured material formed by hardening | curing the photocurable composition in any one of 1) -13).
The cured product of the present invention is obtained by curing the above photocurable composition.

  According to the present invention, a photocurable composition having photocurability and excellent sensitivity and a cured product having no defective shape can be provided.

(Cationically polymerizable compound)
The cationically polymerizable compound used in the photocurable composition of the present invention is not particularly limited as long as it is a polymerizable compound having at least one cationically polymerizable functional group in the molecule. Examples of the cationic polymerizable functional group include an epoxy group, an oxetanyl group, a crosslinkable silicon group, a vinyl ether group, an episulfide group, and an ethyleneimine group. Of these, compounds having an epoxy group are preferably used.

  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.

  The compound having at least one epoxy group in the molecule (hereinafter also simply referred to as “epoxy compound”) is not particularly limited. For example, an epoxy group-containing polyorganosiloxane compound, an epoxy group-containing polyester compound, and an epoxy group-containing compound Polyurethane compounds, epoxy group-containing acrylic compounds, bisphenol type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds and other novolak type epoxy compounds, naphthalene type epoxy compounds, biphenyl type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, etc. Alcohol-type epoxy compounds, halogenated epoxy compounds such as brominated epoxy compounds, rubber-modified epoxy compounds, urethane-modified epoxy compounds, epoxidized polybutadiene, epoxidized steel Down - butadiene - styrene block copolymer and the like. Of these, an epoxy group-containing polyorganosiloxane compound is preferably used because of its excellent reliability and transparency at high temperatures. These epoxy compounds may be used independently and 2 or more types may be used together.

Here, the polyorganosiloxane compound refers to a compound or polymer composed of a siloxane unit (Si—O—Si) and an organic group X composed of C, H, N, O, and S as constituent elements, The structure is not particularly limited. Among the siloxane units in these compounds, the hardened product obtained with a higher content of T unit (XSiO _3/2 ) or Q unit (SiO _4/2 ) in the constituent component has higher hardness and more heat resistance reliability. The cured product is more flexible and has lower stress as it is more excellent and has a higher content of M units (X ₃ SiO _1/2 ) or D units (X ₂ SiO _2/2 ).

  A commercial product of the compound having at least one epoxy group in the molecule is not particularly limited. For example, “Epicoat” such as “Epicoat 807”, “Epicoat 828”, and “Epicoat 1001” manufactured by Japan Epoxy Resin Co., Ltd. ”Series,“ Epicron ”series such as“ Epiclon HP-4032 ”manufactured by DIC, and“ Celoxide ”series such as“ Celoxide 2021 ”manufactured by Daicel Chemical Industries.

  Moreover, in the cationically polymerizable compound (a) contained in the photocurable composition of the present invention, each structure represented by the following formulas (X1) to (X3);

  At least one selected from the group consisting of a phenolic hydroxyl group and a carboxyl group (hereinafter, “each structure represented by the above formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group” is referred to as an “acidic group”). In the same molecule, and by having this structure, it can be dissolved in an aqueous alkali solution and can be an industrially useful curable composition having lithographic properties.

  Among these organic structures, (X1) to (X3), a carboxyl group, and a structure represented by the following formula from the viewpoint that the obtained cured product is less colored at high temperatures.

From the viewpoint of obtaining a cured product having low thermal decomposability at high temperatures, those having each structure represented by the following formula are preferred.

(Cationic polymerization initiator)
The cationic polymerization initiator in the photocurable composition of the present invention is an active energy ray cationic polymerization initiator that generates a cationic species or Lewis acid by active energy rays, or a thermal cationic polymerization that generates a cationic species or Lewis acid by heat. Any initiator can be used without particular limitation.

Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653; bis (perfluoroalkyls) as described in US Pat. No. 3,586,616. Sulfonyl) methane metal salts; aryldiazonium compounds as described in US Pat. No. 3,708,296; aromatic onium salts of group VIa elements as described in US Pat. No. 4,058,400; described in US Pat. Aromatic onium salts of Group Va elements such as: dicarbonyl chelates of Group IIIa to Va elements as described in US Pat. No. 4068091; thiopyrylium salts as described in US Pat. No. 4,139,655; US Pat. No. 4,161,478 as described in JP MF6 ^- anions (here Element VIa in the form of M selected from phosphorus, antimony and arsenic; arylsulfonium complex salts as described in US Pat. No. 4,231,951; aromatic iodonium complex salts and fragrances as described in US Pat. No. 4,256,828 Group sulfonium complex salts; R. Bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluoro as described by Watt et al. In “Journal of Polymer Science, Polymer Chemistry Edition”, Vol. 22, page 1789 (1984). Metal salts (for example, phosphates, arsenates, antimonates, etc.); one or more aromatic iodonium complex salts and aromatic sulfonium complex salts whose anions are B (C ₆ F ₅ ) ₄ ^— are included.

  Preferred cationic active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, Group V and Group VI elements. Some of these salts are BBI-103 (Midori Chemical), FX-512 (3M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric). ), KI-85 (Degussa), SP-152 and SP-172 (Asahi Denka) and Sun-Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Industry), WPI113 and WPI116 (Wako Jun) Yakuhin Kogyo Co., Ltd.) and RHODORSIL PI2074 (Rhodia).

  The amount of the cationic polymerization initiator used is 100 parts by weight of the cationic polymerizable compound from the viewpoints of curing time, remaining cationic polymerization initiator in the cured product, surface properties of the cured product, colorability, heat and light resistance, etc. In general, the amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

(Curing accelerator)
The curing accelerator having an epoxy group or oxetanyl group and an alkoxysilyl group in the photocurable composition of the present invention is particularly limited as long as it is a compound having an epoxy group or oxetanyl group and an alkoxysilyl group in the same molecule. It is not a thing. By adding the curing accelerator of the present invention, the photocuring of the photocurable composition of the present invention can be promoted without changing the initiator amount or the curing conditions. In particular, when patterning is performed, it is effective in preventing a reduction in film thickness after the development process and surface roughness.

  Specific examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-ethyl (triethoxysilylpropoxymethyl) oxetane, an epoxy group or an oxetanyl group, and a cyclic siloxane compound having an alkoxysilyl group can be used. The usage-amount of a hardening accelerator shall be 0.1-30 weight part with respect to 100 weight part of cationically polymerizable compounds from points, such as surface property of hardened | cured material, a pattern shape, and the viscosity of a photocurable composition. Is preferable, and it is more preferable that it is 0.1-20 weight part.

  When the cationically polymerizable compound contains a SiH group, the photocurable composition of the present invention contains a compound having at least one carbon-carbon double bond in one molecule, thereby providing thermosetting properties. Can be granted. The compound having at least one carbon-carbon double bond in one molecule is not particularly limited as long as it has at least one carbon-carbon double bond in one molecule. Regardless of a compound and an organic compound, it can be used without particular limitation.

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

  Examples of the alkenyl group-containing organic compound do not include a siloxane unit (Si—O—Si), but are composed of atoms selected from the group consisting of C, H, N, O, S and halogen as constituent elements. The compound is not particularly limited as long as it is an organic compound having one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule. Further, the bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

  The organic compounds can be classified into organic polymer compounds and organic monomer compounds. Examples of the organic polymer compounds include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based compounds. Hydrogen-based, polyacrylic acid ester-based, polyamide-based, phenol-formaldehyde-based (phenolic resin-based), and polyimide-based 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,
Other examples include those in which all of the glycidyl groups of conventionally known epoxy resins are replaced with allyl groups.

  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 (II) and derivatives thereof are particularly preferable from the viewpoint of high transparency, heat resistance, and light resistance.

(In the formula, R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ represents reactivity with a SiH group. The compound represented by the carbon-carbon double bond which has) is preferable.

As R < ³ > of the said general formula (II), 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-C1 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are 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.

  When a modified polyorganosiloxane compound is used as the cationically polymerizable compound used in the photocurable composition of the present invention, the approximate compound is obtained by various techniques such as condensation reaction, addition reaction and ring-opening polymerization by hydrolysis. However, there is no particular limitation on the method for introducing these specific organic structures into the polysiloxane compound structure, but Si-C is a chemically stable bond that can be introduced regioselectively. Preference is given to using hydrosilylation which can be introduced by bonding. The following embodiments are preferable as the modified polyorganosiloxane compound used as the cationically polymerizable compound of the present invention.

Hydrosilylation reaction products of the following compounds (α) to (γ):
(Α) An organic compound having one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule.
(Β) An organosiloxane compound having at least two SiH groups in one molecule.
(Γ) A compound having at least one photopolymerizable functional group and one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule.
Hereinafter, preferred embodiments of the modified polyorganosiloxane compound will be described.

(Compound (α))
The compound (α) will be described.

The compound (α) is not limited as long as it is a compound having one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, and in particular, the same compound as the component (B). Can be used. Among them, from the viewpoint of excellent insulation of the obtained cured product,
The following general formula (I)

(In the formula, R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ represents reactivity with a SiH group. Having a carbon-carbon double bond).
Further, from the viewpoint of availability, triallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monopropyl isocyanurate can be mentioned.

Moreover, the polysiloxane which has an alkenyl group can apply preferably from the transparency and sclerosis | hardenability viewpoint of the hardened | cured material obtained. 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-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5, 7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 1,3,5,7, -Pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane, etc. Compounds.

  In the component (α), each structure represented by the following formulas (X1) to (X3);

  At least one selected from the group consisting of a phenolic hydroxyl group and a carboxyl group (hereinafter, “each structure represented by the above formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group” is referred to as an “acidic group”). In the same molecule, and by having this structure, it can be dissolved in an aqueous alkali solution and can be an industrially useful curable composition having lithographic properties.

  Among these compounds, those having an isocyanuric acid structure are preferable from the viewpoint of excellent heat resistance, and diallyl isocyanuric acid, monoallyl isocyanuric acid and the like are specifically mentioned from the viewpoint of availability.

  It can also be used in combination with an alkenyl compound having no acidic group, and in particular from the viewpoint of heat resistance, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanate having an isocyanuric ring structure. Combination with nurate or the like is preferred.

  Further, from the viewpoint that the obtained cured product is excellent in transparency, it is preferably used in combination with a polysiloxane compound having an alkenyl group, and in particular, from the viewpoint of availability, a poly or oligosiloxane whose end is blocked with a dimethylvinylsilyl group, specifically 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane 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-hex Cyclic siloxane compounds such as methyl cyclosiloxane is preferred.

(Compound (β))
The compound (β) will be described.
The compound (β) is not particularly limited as long as it is an organopolysiloxane compound having at least two SiH groups in one molecule. For example, the compound described in International Publication WO96 / 15194 is at least two in one molecule. Those having a SiH group can be used.

  Among these, from the viewpoint that flexibility is imparted to the cured product,

(In formula, R < ¹³ >, R < ¹⁴ > represents a C1-C6 organic group, and may be same or different, l is 0-50, n is 2-50, m is the number of 0-10. Represents.)
A linear organopolysiloxane having at least two SiH groups in one molecule represented by R ¹³ and R ¹⁴ are preferably methyl groups from the viewpoints of availability and heat resistance, and are preferably phenyl groups from the viewpoint of increasing the strength of the cured product.

  Further, from the viewpoint of high heat resistance and light resistance of the cured product, organopolysiloxane having a T unit or a Q unit in the molecule is preferable, and specific examples include the following compounds.

(Wherein, R ^15, R ¹⁶ represents an organic group having 1 to 6 carbon atoms, n represents a number from 0 to 50.)
An organopolysiloxane having at least two SiH groups in one molecule and having a T or Q structure in the molecule is preferred. R ¹⁵ and R ¹⁶ are particularly methyl from the viewpoints of availability and heat resistance. What is group is preferable.

  Among these, from the viewpoint of availability and reactivity with the compounds (α) and (γ), the following general formula (III)

(Wherein R ⁴ and R ⁵ represent an organic group having 1 to 6 carbon atoms and may be the same or different, n represents 3 to 10, and m represents a number of 0 to 10). Cyclic organopolysiloxanes having at least 3 SiH groups per molecule are preferred.

The substituents R ⁴ and R ⁵ in the compound represented by the general formula (III) are preferably selected from the group consisting of C, H and O, and are preferably hydrocarbon groups. More preferably, it is a methyl group. The compound represented by the general formula (III) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of availability and reactivity. The various compounds (β) described above can be used alone or in combination of two or more.

(Compound (γ))
The compound (γ) will be described.

  The compound (γ) is not particularly limited as long as it is a compound having at least one photopolymerizable functional group and one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule. In addition, the photopolymerizable functional group here is the same as the photopolymerizable functional group which the above-mentioned modified polyorganosiloxane compound has, and a preferable aspect is also preferable.

  In particular, as a photopolymerizable functional group, at least one of the photopolymerizable functional groups is an epoxy group, a crosslinkable silicon group, a (meth) acryloyl group, an oxetanyl group, or a vinyloxy group from the viewpoint of reactivity and stability of the compound. preferable.

  Specific examples of the compound (γ) having an epoxy group as a photopolymerizable functional group include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and the like. From the viewpoint of superiority, vinylcyclohexene oxide, which is a compound having an alicyclic epoxy group, is particularly preferable.

  Specific examples of the compound (γ) having an oxetanyl group include allyl oxetanyl ether and vinyl oxetanyl ether. When using the compound which has an oxetanyl group, it is preferable from a viewpoint that the toughness of hardened | cured material improves.

  Specific examples of the compound (γ) having a crosslinkable silicon group as a photopolymerizable functional group include those represented by the following general formula (IV) from the viewpoint of availability and heat resistance.

(Wherein R ⁶ and R ⁷ represent an organic group having 1 to 6 carbon atoms, n represents 1 to 3, and m represents a number of 0 to 10) and have a crosslinkable silicon group. In view of easy removal of by-products after the reaction, trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, methoxydimethylvinylsilane, and ethoxydimethylvinylsilane are particularly preferable.

  Examples of the compound (γ) having an acryloyl group or a methacryloyl group as a photopolymerizable functional group include allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth). Acrylate, (meth) acrylic acid-modified allyl glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol acrylate DA111), and vinyl group or allyl group and the following general formula (IX)

(In the formula, R ¹⁷ represents a hydrogen atom or a methyl group.) A compound having one or more organic groups each in the same molecule, for example, in the above general formula (II), R in the formula ³ is a group represented by the above general formula (IX), and at least one of R ³ is a carbon-carbon double bond having reactivity with a SiH group such as a vinyl group or an allyl group. The compound which is a group to have is mentioned. Further, from the viewpoint of high selectivity for hydrosilylation, a compound in which a methacryloyl group coexists with an allyl or vinyl group 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 ((gamma)) can also be used together regardless of the kind of photopolymerizable functional group.

(Hydrosilylation catalyst)
As a catalyst for the hydrosilylation reaction of the compound (α), the compound (β) and the compound (γ), for example, the following can be used. Platinum simple substance, alumina, silica, carbon black or the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone or the like, platinum-olefin complex (for example, Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ]) _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄₎ (in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, n, m is an integer.), dicarbonyl dichloroplatinum, Karushuteto Karstedt catalyst, as well as the platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux US Pat. No. 3,220,972. And platinum alcoholate catalysts. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient for the SiH group of the compound (α) and the compound (γ) to have sufficient curability and keep the cost of the curable composition relatively low. The carbon-carbon double bond (hereinafter sometimes simply referred to as “alkenyl group”) having a reactivity with 1 mol, or 10 mol with respect to 1 mol of the alkenyl group of the compound (α) and the compound (γ) ^-8 mol, more preferably 10 ^-6 mol, and the upper limit of the preferable addition amount is 10 ^-1 mol, more preferably 10 ^-2 mol, relative to 1 mol of the alkenyl group of the above compound.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 Examples include acetylene alcohol compounds such as butyne and 1-ethynyl-1-cyclohexanol, and sulfur compounds such as simple sulfur. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

(Reaction of compound (α), compound (β) and compound (γ))
As described above, the modified polyorganosiloxane compound that can be used in the photocurable composition of the present invention is a reaction of the compound (α), the compound (β), and the compound (γ) in the presence of a hydrosilylation catalyst. The compound obtained by is mentioned.

  There are various reaction sequences and methods, but from the viewpoint that the synthesis process is simple, the compound (α), the compound (β), and the compound (γ) are hydrosilylated in one pot and finally unreacted. A method of removing the compound of the reaction is preferable, and from the viewpoint that it is difficult to contain a low molecular weight substance, an excess of the compound (α) and the compound (β), or an excess of the compound (β) and the compound (α) After the hydrosilylation reaction, an unreacted compound (α) or compound (β) is once removed, and the obtained reaction product and the compound (γ) are subjected to a hydrosilylation reaction.

  The proportion of each compound to be modified is not particularly limited, but when the total alkenyl group amount of the compounds (α) and (γ) is A and the total SiH group amount of the compound (β) is B, 1 ≦ B / A ≦ 30 It is preferable that 1 ≦ B / A ≦ 10. In the case of 1> B / A, unreacted alkenyl groups remain in the composition, which causes coloring. In the case of 30 <B / A, a large amount of (β) component is used. It is not preferable from the viewpoint of increasing.

  Regarding the modification ratio of the compound (α) and the compound (γ), when the alkenyl group of the compound (α) is A1, and the alkenyl group of the compound (γ) is A2, A1 + A2 = 1 and 0.01 ≦ A1 ≦ 0.99 and 0.01 ≦ A2 <0.99 can be appropriately selected and modified.

  The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Various reaction times and pressures during the reaction can be set as required.

  Oxygen can be used during the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase portion of the reaction vessel. From the point of setting the amount of oxygen to be below the lower limit of explosion limit, the oxygen volume concentration in the gas phase must be controlled to 3% or less. In view of promoting the hydrosilylation reaction effect by the addition of oxygen, the oxygen volume concentration in the gas phase is preferably at least 0.1%, more preferably at least 1%.

  A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

  After the compound (α), the compound (β) and the compound (γ) are hydrosilylated, the solvent and / or the unreacted compound can be removed. By removing these volatile components, the reaction product obtained does not have volatile components. Therefore, when creating a cured product using the reaction product, problems of voids and cracks due to volatilization of volatile components are unlikely to occur. . Examples of the removal method include vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 80 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

  In the production method of the modified organopolysiloxane compound as the cationic polymerizable compound of the present invention, various additives can be used depending on the purpose.

(Method for adjusting photocurable composition and curing method)
The preparation method of a photocurable composition is not specifically limited, It can prepare by various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance.

  The usage method of the photocurable composition of this invention is not specifically limited, It can use using the coating by spin coat, slit coat, potting by dispensing, etc. Further, viscosity adjustment with a solvent and surface tension adjustment with a surfactant may be appropriately performed according to the state of the substrate.

  Moreover, the photocurable composition of this invention makes a hardened | cured material by making a crosslinking reaction advance by light irradiation. According to the present invention, it is possible to provide a protective film or pattern excellent in film thickness uniformity and uniform cross-sectional shape even when formed with a low light quantity. As a light source for photocuring, a light source that emits an absorption wavelength of a polymerization initiator or a sensitizer to be used may be used, and a light source usually containing a wavelength in the range of 200 to 450 nm, such as a high-pressure mercury lamp, High pressure mercury lamp, metal halide lamp, high power metal halide lamp, xenon lamp, carbon arc lamp, light emitting diode, etc. can be used.

The exposure amount is not particularly limited, but a preferable exposure amount range is 1 to 500 mJ / cm ² , more preferably 1 to 100 mJ / cm ² , and further preferably 1 to 60 mJ / cm ² . If the exposure amount is small, the surface becomes rough, the film thickness decreases, and the pattern edge portion is chipped. If the exposure amount is large, the color may change due to rapid curing. A preferred curing time range is 1 to 120 seconds, more preferably 1 to 60 seconds. When the curing time is long, productivity is lowered and the characteristics of rapid curing of photocuring are not utilized.

  Although the heating temperature after film formation is not particularly limited, it is preferably 200 ° C. or less from the viewpoint that the influence on the surrounding low heat-resistant member is small, particularly when a resin substrate or the like is used. Considering dimensional stability and the like, the temperature is preferably 180 ° C. or lower.

(About photolithography)
The photocurable composition of the present invention can be finely patterned by alkali development. The patterning formation is not particularly limited, and a desired pattern can be formed by dissolving / removing the unexposed portion by a commonly used developing method such as an immersion method or a spray method.

  In addition, the developer at this time can be used without particular limitation as long as it is generally used. Specific examples thereof include an aqueous organic alkali solution such as an aqueous tetramethylammonium hydroxide solution and an aqueous choline solution, and an aqueous potassium hydroxide solution. Inorganic alkali aqueous solutions such as sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution, and those obtained by adding alcohol or surfactant to these aqueous solutions for adjusting the dissolution rate, etc. .

  The aqueous solution concentration is preferably 25% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less from the viewpoint that the contrast between the exposed part and the unexposed part is easily obtained. preferable.

(About additives)
(Sensitizer)
In the photocurable composition of the present invention, when cured with light energy, the light sensitivity is improved and high wavelengths such as g-line (436 nm), h-line (405 nm) and i-line (365 nm) are called. In order to give sensitivity to the light, a sensitizer can be appropriately added. These sensitizers can be used in combination with the cationic polymerization initiator to adjust the curability. Examples of the compound to be added include anthracene compounds and thioxanthone compounds.

  Specific examples of the anthracene compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-di. Ethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di- tert-butylanthracene and the like can be mentioned, and from the viewpoint of easy availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like preferable.

  Anthracene is preferable from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxy from the viewpoint of excellent compatibility with the curable composition. Anthracene and the like are preferable.

  Specific examples of the thioxanthone series include thioxanthone, 2-chlorothioxanthone, 2,5-diethyldioxanthone and the like.

  These sensitizers may be used alone or in combination of two or more. The addition amount of the sensitizer is approximately 0.1 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane compound from the viewpoints of curing time, sensitizer remaining in the cured product, and colorability. Is preferably 0.1 to 5 parts by weight.

(Phosphorus compound)
When the photocurable composition of the present invention is cured by light or heat, and is used in applications requiring transparency, a phosphorus compound is used to improve the hue after curing by light or heat. Is preferred. Specific examples of phosphorus compounds include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, tris (2,4-di-t-butyl). Phenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentane tetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis (2, Phosphites such as 6-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite An antioxidant selected from the group 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa- Coloring agents selected from oxaphosphaphenanthrene oxides such as 10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are preferably used. Is done.

  The amount of the phosphorus compound used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the modified polyorganosiloxane compound. When the amount of the phosphorus compound used is less than 0.01 parts by weight, the effect of improving the hue is reduced. If the amount used exceeds 10 parts by weight, the curability and the physical properties of the cured product may be adversely affected.

(Thermoplastic resin)
Various thermoplastic resins can be added to the photocurable composition of the present invention for the purpose of modifying the properties. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as fat, norbornene derivative ring-opening metathesis polymer, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as maleimide copolymers (eg TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids and aliphatic dicarboxylic acids such as terephthalic acid and isophthalic acid (eg O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene resin Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  As a thermoplastic resin, you may have the carbon-carbon double bond and / or SiH group which have a reactivity with SiH group in a molecule | numerator. In the point that the obtained cured product tends to be tougher, the molecule has one or more carbon-carbon double bonds and / or SiH groups having reactivity with SiH groups in the molecule on average. It is preferable.

  The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product tends to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10000 or less, and preferably 5000 or less in that the compatibility with the modified organosiloxane compound is likely to be good. More preferred. On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.

  Although there is no limitation in particular as a compounding quantity of a thermoplastic resin, the range of the preferable usage-amount is 5 to 50 weight% of the whole curable composition, More preferably, it is 10 to 30 weight%. If the amount added is small, the resulting cured product tends to be brittle. If the amount added is large, the heat resistance (elastic modulus at high temperature) tends to be low.

  A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the modified polyorganosiloxane compound and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed to be in a dispersed state. Good. From the viewpoint that the resulting cured product tends to be more transparent, it is preferable to dissolve in the modified polyorganosiloxane compound and mix in a uniform state. In this case as well, the thermoplastic resin may be directly dissolved in the modified polyorganosiloxane compound, or may be mixed uniformly using a solvent, etc., and then the solvent is removed to obtain a uniform dispersed state and / or mixture. It is good also as a state.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle sizes, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good, The diameter variation coefficient is preferably 10% or less.

(Filler)
You may add a filler to the photocurable composition of this invention as needed.
Various fillers are used. For example, silica-based fillers such as quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, silicon nitride, silver powder, etc. Inorganic fillers such as alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloon As a filler for a conventional sealing material such as an epoxy type, a filler that is generally used or / and proposed can be used.

(Anti-aging agent)
An anti-aging agent may be added to the photocurable composition of the present invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
These anti-aging agents may be used alone or in combination of two or more.

(Radical inhibitor)
A radical inhibitor may be added to the photocurable composition of the present invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.
These radical inhibitors may be used alone or in combination of two or more.

(UV absorber)
You may add a ultraviolet absorber to the photocurable composition of this invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.
These ultraviolet absorbers may be used alone or in combination of two or more.

(solvent)
When the cationically polymerizable compound used in the photocurable composition of the present invention has a high viscosity, it can be used by dissolving in a solvent. Solvents that can be used are not particularly limited. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, chloroform, methylene chloride, A halogen-based solvent such as 1,2-dichloroethane can be preferably used.

  As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, propylene glycol-1-monomethyl ether-2-acetate, and chloroform are preferable.

  Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferred amount of use with respect to 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. It is disadvantageous and the industrial utility value decreases.

  These solvents may be used alone or as a mixed solvent of two or more.

(Other additives)
The photocurable composition of the present invention includes other colorants, mold release agents, flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, antimony-bismuth and the like. Ion trap agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity The purpose and effect of the present invention include a property imparting agent, an antistatic agent, a radiation shielding agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent, and a physical property modifier. Can be added within a range that does not impair.

(Use)
The curable composition or cured product of the present invention can be used for various applications. It can be applied to various uses where conventional acrylic resin and epoxy resin adhesives are used.

  For example, transparent materials, optical materials, optical lenses, optical films, optical sheets, optical component adhesives, optical waveguide coupling optical adhesives, optical waveguide peripheral member fixing adhesives, DVD bonding adhesives, adhesives, Dicing tape, electronic materials, insulating materials (including printed circuit boards, wire coatings, etc.), high-voltage insulating materials, interlayer insulating films, TFT passivation films, TFT gate insulating films, TFT interlayer insulating films, TFT transparent flattening Membrane, insulating packing, insulation coating material, adhesive, high heat resistant adhesive, high heat dissipation adhesive, optical adhesive, LED element adhesive, various substrate adhesive, heat sink adhesive, paint, UV powder Body paint, ink, colored ink, UV inkjet ink, coating material (hard coat, sheet, film, release paper coat, optical disc coat, optical fabric ), Molding materials (including sheets, films, FRP, etc.), sealing materials, potting materials, sealing materials, light-emitting diode sealing materials, optical semiconductor sealing materials, liquid crystal sealing agents, display devices Sealing material, sealing material for electrical materials, sealing material for various solar cells, high heat resistant sealing material, resist material, liquid resist material, colored resist, dry film resist material, solder resist material, binder resin for color filter, color Transparent flattening material for filter, binder resin for black matrix, photo spacer material for liquid crystal cell, transparent sealing material for OLED element, stereolithography, solar cell material, fuel cell material, display material, recording material, vibration proof material , Waterproof materials, moisture-proof materials, heat-shrinkable rubber tubes, O-rings, photoconductor drums for copying machines, battery fixing The electrolyte can be applied to a gas separation membrane. Further, concrete protective materials, linings, soil injection agents, cold storage heat materials, sealing materials for sterilization treatment devices, contact lenses, oxygen permeable membranes, additives to other resins, and the like can be mentioned.

  Among these, the curable composition of the present invention is a material that can be used as an alkali-developable transparent resist, and is particularly suitable as an FPD material. More specifically, a passivation film for TFT, a gate insulating film for TFT, an interlayer insulating film for TFT, a transparent planarizing film for TFT, a binder resin for color filter, a transparent planarizing material for color filter, a binder resin for black matrix, Examples thereof include a photospacer material for liquid crystal cells and a transparent sealing material for OLED elements.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Examples 1-2, Comparative Examples 1-5)
The curable compositions obtained in Examples 1-2 and Comparative Examples 1-5 were evaluated using the following methods. The results are shown in Table 1.

  The hardened | cured material obtained by hardening | curing the curable composition of this invention functions as a photocurable material which has the sensitivity with respect to the photocuring reaction outstanding compared with the composition of the comparative example.

(Patternability evaluation)
The following patterning evaluation samples were prepared using the resin compositions obtained in Examples and Comparative Examples. A glass plate with a resin composition spin-coated (rotation speed 1500 rpm, 10 seconds) is heated on a hot plate heated to 65 ° C. for 2 minutes, and an exposure apparatus (high-pressure mercury lamp, mask alignment apparatus MA-10) is installed. Used, exposed with various integrated light quantities through a pattern mask (proximity exposure, gap 12 μm), heated on a hot plate heated to 65 ° C. for 2 minutes, and immersed in an alkaline developer (TMAH 2.38% aqueous solution) for 60 seconds Washed with water to form a pattern. Thereafter, the sample was heated for 1 hour on a hot plate heated to 150 ° C. to obtain an evaluation sample. The obtained evaluation sample was observed for a pattern shape using a white interference microscope (NewView 5030), and the degree of film thickness reduction (film reduction) was evaluated according to the following criteria as compared to before development.

<Evaluation criteria>
○: A uniform pattern can be formed without film loss. Δ: Film loss occurs locally. ×: Film loss occurs over a wide area.

(Example 1)
A 500 mL four-necked flask was charged with 100 g of toluene and 57.49 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed solution of 3.8 g of triallyl isocyanurate, 5.0 g of diallyl isocyanuric acid, 70.0 g of 1,4-dioxane, and 0.0186 g of a platinum vinylsiloxane complex in xylene (containing 3 wt% as platinum) is dropped over 30 minutes. did. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl 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 B”.

A 100 mL four-necked flask was charged with 20 g of toluene and 10 g of “Reactant B”, the gas phase was replaced with nitrogen, and then heated at an internal temperature of 105 ° C. A mixed solution of 3.0 g of vinylcyclohexene oxide and 3.0 g of toluene. 3 hours after the addition, it was confirmed by ¹ H-NMR that the reaction rate of the vinyl group was 95% or more. The reaction solution was cooled to obtain “Reaction product 1”. 1H-NMR measurement shows an epoxy group equivalent to 2.0 mmol / g, SiH group 4.0 mmol / g, and a structure represented by the following formula (X1) in terms of equivalent when the standard substance is dibromoethane. It was confirmed that it was a polyorganosiloxane compound.

  0.5 g of the obtained “reaction product 1”, 0.19 g of triallyl isocyanurate, 0.7 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), BBI-103 (manufactured by Midori Chemical, photocationic polymerization initiation Agent) A 40% PGMEA solution was prepared by adding 0.02 g, 0.01 g of 9,10-dipropoxyanthracene, and 0.025 g of 3-glycidoxypropyltrimethoxysilane.

(Example 2)
0.5 g of “Reactant 1” obtained in Example 1, 0.19 g of triallyl isocyanurate, 0.7 mg of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), BBI-103 (manufactured by Midori Chemical, A 40% PGMEA solution was prepared by adding 0.02 g of photocationic polymerization initiator), 0.01 g of 9,10-dipropoxyanthracene, and 0.050 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

(Comparative Example 1)
0.5 g of “Reactant 1” obtained in Example 1, 0.19 g of triallyl isocyanurate, 0.7 mg of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), BBI-103 (manufactured by Midori Chemical, Photocationic polymerization initiator) 0.02 g and 0.01 g of 9,10-dipropoxyanthracene were added to prepare a 40% PGMEA solution.

(Comparative Example 2)
0.5 g of “Reactant 1” obtained in Example 1, 0.19 g of triallyl isocyanurate, 0.7 mg of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), BBI-103 (manufactured by Midori Chemical, A 40% PGMEA solution was prepared by adding 0.02 g of a cationic photopolymerization initiator), 0.01 g of dibutylanthracene, and 0.050 g of vinyltrimethoxysilane.

(Comparative Example 3)
0.5 g of “Reactant 1” obtained in Example 1, 0.19 g of triallyl isocyanurate, 0.7 mg of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), BBI-103 (manufactured by Midori Chemical, Photocationic polymerization initiator) 0.02 g, 0.01 g of 9,10-dipropoxyanthracene, and 0.050 g of allyl glycidyl ether were added to prepare a 40% PGMEA solution.

(Comparative Example 4)
0.5 g of “Reactant 1” obtained in Example 1, 0.19 g of triallyl isocyanurate, 0.7 mg of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), BBI-103 (manufactured by Midori Chemical, Photocationic polymerization initiator) 0.02 g, 0.01 g of 9,10-dipropoxyanthracene, and 0.050 g of vinylcyclohexene oxide were added to prepare a 40% PGMEA solution.

Claims (14)

  A photocurable composition comprising a cationically polymerizable compound (a), a cationic polymerization initiator (b), an epoxy group or oxetanyl group, and a curing accelerator (c) having an alkoxysilyl group.   2. The photocurable composition according to claim 1, wherein the cationically polymerizable compound (a) is a polyorganosiloxane compound.   The photocurable composition according to claim 1 or 2, wherein the cationic polymerizable compound (a) is an epoxy group-containing compound.   The cation polymerizable compound (a) is a compound having a cation polymerizable functional group and a SiH group in the same molecule, and (d) a compound having a carbon-carbon double bond. The photocurable composition according to one item. The component (a) is a compound having in the same molecule at least one selected from the group consisting of each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. The photocurable composition as described in any one of 1-4.

Component (d) is represented by the following general formula (I)

(In the formula, R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ represents reactivity with a SiH group. The photocurable composition according to claim 4 or 5, which is a compound represented by (including a carbon-carbon double bond having). Component (d) is, the photocurable composition according to any one of claims 4 to 6 is a compound having a Si-CH = CH ₂ group. The photocurable composition according to any one of claims 1 to 7, wherein the component (a) uses a hydrosilylation reaction product of the following compounds (α) to (γ):
(Α) Organic compound having one or more carbon-carbon double bonds having reactivity with SiH group in one molecule (β) Organosiloxane compound (γ) 1 having at least two SiH groups in one molecule Compound having in the molecule at least one cationically polymerizable functional group and one or more carbon-carbon double bonds having reactivity with SiH group The compound (α) according to claim 8 has at least one carbon-carbon double bond having reactivity with a SiH group in one molecule, and the following general formula (I):

(In the formula, R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ represents reactivity with a SiH group. The photocurable composition of Claim 8 which is a compound represented by the carbon-carbon double bond which has). 8. The compound according (alpha) is, Si-CH = CH photocurable composition according to any one of claims 8 or 9, which is a compound having ₂ group. The compound (α) according to claim 8 has at least one carbon-carbon double bond having reactivity with a SiH group in one molecule, and is represented by the following formulas (X1) to (X3). The photocurable composition as described in any one of Claims 8-10 which is an organic compound which has at least 1 type chosen from the group which consists of each structure which consists of, a phenolic hydroxyl group, and a carboxyl group in the same molecule | numerator. .

Compound (β) is represented by the following general formula (III)

(Wherein R ⁴ and R ⁵ represent an organic group having 1 to 10 carbon atoms, and may be the same or different, n represents 1 to 10, and m represents a number of 0 to 10)
The photocurable composition as described in any one of Claims 8-11 which is a cyclic polyorganosiloxane compound which has SiH group represented by these. Compound (γ) is represented by the following general formula (IV)

(Wherein R ⁶ and R ⁷ represent an organic group having 1 to 6 carbon atoms, n represents 1 to 3, and m represents a number of 0 to 10). The photocurable composition as described in any one of Claims.   Hardened | cured material formed by hardening | curing the photocurable composition as described in any one of Claims 1-13.