JP2010100591A - Halogen-substituted aromatic ring-containing polysiloxane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrolyzable silane having a brominated or chlorinated benzene exhibiting high refractive index as an organic group and using the high transparency and high heat resistance caused by an Si-O bond of a polysiloxane. <P>SOLUTION: The hydrolyzable silane is represented by general formula (1): R<SP>1</SP><SB>a</SB>R<SP>2</SP><SB>b</SB>R<SP>3</SP><SB>[4-(a+b)]</SB>[wherein, R<SP>1</SP>is formula (2) (wherein, R<SP>4</SP>to R<SP>8</SP>are each a bromine atom, a chlorine atom, a hydrogen atom or a monovalent organic group); R<SP>2</SP>is a monovalent organic group; each of R<SP>1</SP>and R<SP>2</SP>are bonded to a silicon atom by an Si-C bond; R<SP>3</SP>is an alkoxy group, an acyloxy group or a halogen atom; (a) is an integer of 1-2; b is an integer of 0-1; and a+b is an integer of 1-2]. The hydrolyzed product thereof and the hydrolysis-condensation product thereof are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a silicon compound having a high refractive index, and more particularly to a high refractive index silicon compound containing an aromatic ring containing bromine or chlorine.

Photodiode embedding materials and microlens materials used for solid-state imaging devices are required to have heat resistance to a device manufacturing process and high transparency for use as a device.
Recently, there is a trend to increase the number of pixels in order to achieve higher definition of devices. However, as the number of pixels increases, the amount of light incident on the photodiode decreases due to the reduction in area per pixel. Therefore, in order to increase the light capturing efficiency, the microlens material and the embedding material for the photodiode are required to have a high refractive index in addition to the above characteristics.
A photosensitive material using brominated benzene as a high refractive index material is described (see Patent Document 1).
Polysiloxane has been researched and developed for use as an electronic device, particularly as a member of a solid-state imaging device, utilizing the high transparency and high heat resistance resulting from the Si—O bond. When polysiloxane is incorporated in a device, it is necessary to form a polysiloxane varnish because it undergoes a step of coating on an arbitrary substrate by a wet process such as a spin coating method. However, the refractive index derived from the siloxane bond is about n = 1.4, and polysiloxanes having a high refractive index are very limited at present.
A photosensitive resin composition using a polysiloxane having a halogenated aromatic group is described (see Patent Document 2).
JP2005-239925 JP 2002-308990 A

The present invention provides a hydrolyzable silane having a brominated or chlorinated benzene having an organic group as an organic group, making use of high transparency and high heat resistance resulting from the Si—O bond.

As a first aspect of the present invention, the following general formula (1):

[In Formula (1), R ¹ is Formula (2):

(In the formula (2), R ^{4 to} R ⁸ are a bromine atom, a chlorine atom, a hydrogen atom, or a monovalent organic group, and the organic group is an alkyl group, a halogenated alkyl group, an alkenyl group, or an epoxy group. , An acryloyl group, a methacryloyl group, a mercapto group, an amino group, a carboxyl group, a phosphoric acid group, an amide group, a nitro group, an acyl group, a sulfone group, or a monovalent organic group having a cyano group, or a combination thereof, ⁹ is an alkylene group having 3 to 10 carbon atoms which may have a branch, and at least three of R ^{4 to} R ⁸ are a bromine atom or a chlorine atom.), R ² is an alkyl group , Aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, carboxyl group Group, a phosphate group, an amide group, a nitro group, an acyl group, a sulfonic group, or a monovalent organic group, or a combination thereof, having a cyano group. R ¹ and R ² are each bonded to a silicon atom by a Si—C bond. R ³ represents an alkoxy group, an acyloxy group, or a halogen group. a represents an integer of 1 to 2, b represents an integer of 0 to 1, and a + b represents an integer of 1 to 2. ] A hydrolyzable silane represented by
As a second aspect, the hydrolyzable silane according to the first aspect, in which at least three of R ^{4 to} R ⁸ are bromine atoms and R ⁹ is a propylene group or an isopropylene group in the above formula (1),
As a 3rd viewpoint, the hydrolyzate obtained from the compound described in the 1st viewpoint or the 2nd viewpoint, or its hydrolysis condensate,
As a fourth aspect, the above formula (1) and the following formula (3):

(Wherein R ¹⁰ is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, phosphoric acid group, amide group, nitro group. , An organic group having an acyl group, a sulfone group, a cyano group, or a combination thereof, and bonded to a silicon atom by a Si—C bond, and R ¹¹ represents an alkoxy group, an acyloxy group, or a halogen group. , A represents an integer of 0 to 3) and formula (4):

(Wherein R ¹² is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, phosphoric acid group, amide group, nitro group. , An organic group having an acyl group, a sulfone group, a cyano group, or a combination thereof, and bonded to a silicon atom by a Si—C bond, and R ¹³ represents an alkoxy group, an acyloxy group, or a halogen group. Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, and c represents an integer of 0 or 1.) A combination with at least one hydrolyzable silane selected from the group consisting of , Hydrolyzates of hydrolyzable silanes combined with them, or hydrolytic condensates combined with them
As a fifth aspect, the above formula (1) and the above formula (3) [provided that at least three of R ^{4 to} R ^{8 in} the formula (1) are bromine atoms, and R ⁹ is a propylene group or an isopropylene group. is there. A combination with at least one hydrolyzable silane selected from the group consisting of: a hydrolyzate of these combined hydrolyzable silanes, or a combined hydrolytic condensate thereof,
As a sixth aspect, an electronic device comprising a film made from the hydrolyzable silane according to any one of the first aspect to the fifth aspect, a hydrolyzate thereof, a hydrolysis condensate thereof, or a combination thereof,
As a seventh aspect, a charge bond comprising a film formed from the hydrolyzable silane according to any one of the first aspect to the fifth aspect, a hydrolyzate thereof, a hydrolysis condensate thereof, or a combination thereof A solid-state imaging device comprising a device (CCD) or a complementary metal oxide semiconductor (CMOS),
As an eighth aspect, a film formed from the hydrolyzable silane according to any one of the first aspect to the fifth aspect, a hydrolyzate thereof, a hydrolysis condensate thereof, or a combination thereof is provided on a color filter. A solid-state imaging device provided as a planarization layer, and, as a ninth aspect, the hydrolyzable silane according to any one of the first aspect to the fifth aspect, a hydrolyzate thereof, a hydrolyzate condensate thereof, or their It is a solid-state imaging device provided with a film formed from the combination as a planarizing layer or a conformal layer on a microlens.

  The present invention is a hydrolyzable silane, an hydrolyzate thereof, or a hydrolyzate condensate thereof containing an organic group having at least one aromatic ring substituted with at least three bromine atoms or chlorine atoms. The film-forming composition containing the polysiloxane composition obtained from them can form a film having a high refractive index while maintaining high transparency and high heat resistance.

  A substituent of a halogen atom on an aromatic ring such as a benzene ring has a higher refractive index in the order of fluorine, chlorine, bromine and iodine. On the other hand, the stability of carbon atoms and halogen atoms to light decreases in the order of carbon-fluorine, carbon-chlorine, carbon-bromine, and carbon-iodine. Therefore, in the present invention, it is preferable to use a polysiloxane material containing an organic group having a bond of benzene-bromine and benzene-chlorine, particularly a bond of benzene-bromine, as a material having high light resistance and a high refractive index. A hydrolyzable silane having such an organic group is provided, and the film formed by the film forming composition containing the hydrolyzable condensate of the hydrolyzable silane is a film having high transparency, high heat resistance, and high refractive index. It is possible.

  This invention is a hydrolysable silane shown by Formula (1), It can be set as the hydrolyzate or its hydrolysis condensate. The hydrolysis condensate is a polysiloxane.

In formula (1), R ¹ is an organic group represented by formula (2).
R ^{4 to} R ^{8 in the} formula (2) are a bromine atom, a chlorine atom, a hydrogen atom, or a monovalent organic group, and the organic group is an alkyl group, a halogenated alkyl group, an alkenyl group, an epoxy group, or acryloyl. R ⁹ is a monovalent organic group having a group, a methacryloyl group, a mercapto group, an amino group, a carboxyl group, a phosphoric acid group, an amide group, a nitro group, an acyl group, a sulfone group, or a cyano group, or a combination thereof. It is a C3-C10 alkylene group which may have a branch, and at least 3 is a bromine atom or a chlorine atom among R < ⁴ > -R < ⁸ >.
R ^{2 in} formula (1) is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, alkoxy group or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, carboxyl group, A monovalent organic group having a phosphoric acid group, an amide group, a nitro group, an acyl group, a sulfone group, or a cyano group, or a combination thereof. R ¹ and R ² are each bonded to a silicon atom by a Si—C bond.

  Examples of the alkyl group include alkyl having 1 to 10 carbon atoms. For example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclo Propyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2 -Dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl -Cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hex 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n -Butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2 -Methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl -Cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclo Propyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2 , 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclo And propyl.

  Examples of the alkylene group include alkylene groups having 3 to 10 carbon atoms, such as n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, s-butylene, t-butylene, cyclobutylene, 1-methylbutylene, 1 -Methyl-cyclopropylene, 2-methyl-cyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene, cyclopentylene, 1-methyl-cyclobutylene, 2-methyl-cyclobutylene, 3-methyl -Cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl -Cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1 -Dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3 -Dimethyl-n-butylene, 1-ethyl-n-butylene, 2-ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl -1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentylene, 2-methyl-cyclopentylene, 3-methyl-cyclo N-ylene, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4-dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclo Propylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl- Cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cycl Propylene and 2-ethyl-3-methyl - cyclopropylene and the like. As the alkylene group, an alkylene group having 3 to 5 carbon atoms can be preferably selected.

  Examples of the aryl group include aryl groups having 6 to 40 carbon atoms, such as a phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl Group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group Group, 9-phenanthryl group and the like.

The alkenyl group is an alkenyl group having 2 to 10 carbon atoms such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl- 1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1- n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl- 2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl Tyl-2-propenyl, 1-isopropylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1 -N-butylethenyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl -1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl- -Butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl -3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-s 1-butylethenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylethenyl, 2,2-dimethyl-3-butenyl, 2 1,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl -1-Buteni 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2 -Butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-t-butylethenyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1 -Propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2 -Methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl- -Cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl- 5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl and the like.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, and benzoyl group.
Examples of the organic group having an epoxy group include glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, and epoxycyclohexyl.
Examples of the organic group having an acryloyl group include acryloylmethyl, acryloylethyl, acryloylpropyl, and the like.
Examples of the organic group having a methacryloyl group include methacryloylmethyl, methacryloylethyl, methacryloylpropyl, and the like.
Examples of the organic group having a mercapto group include ethyl mercapto, butyl mercapto, hexyl mercapto, octyl mercapto and the like.
Examples of the organic group having a cyano group include cyanoethyl and cyanopropyl.
R ^{3 in the} formula (1) is an alkoxy group, an acyloxy group, or a halogen group.

  Examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms, and examples thereof include an alkoxy group having a linear, branched, or cyclic alkyl moiety, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy. , S-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2 -Dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3- Methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-buto 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2, -trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl- 2-methyl-n-propoxy and the like.

  Examples of the acyloxy group include C2-C20 acyloxy groups such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, s-butylcarbonyloxy. , T-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n -Propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2,2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n − N-methylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2 -Dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl -N-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n -Propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl 2-methyl -n- propyl carbonyloxy, and phenylcarbonyloxy, and tosyl carbonyloxy and the like.

Examples of the halogen group as the hydrolyzable group include fluorine, chlorine, bromine and iodine.
The formula (1) having the formula (2) in which at least three of R ^{4 to} R ⁸ are bromine atoms and R ⁹ is a propylene group or an isopropylene group can be used.
In the formula (1), a represents an integer of 1 to 2, b represents an integer of 0 to 1, and a + b represents an integer of 1 to 2.

The hydrolyzable silane of the above formula (1) can be prepared, for example, by the steps shown below.
First, formula (5):

(Wherein R ^{14 to} R ¹⁸ are the same as R ^{4 to} R ⁸ defined in formula (2)) and formula (6):

(In the formula, X represents chlorine or bromine, and R ¹⁹ represents an alkylene group having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms) to obtain the following formula (7). Although the solvent at this time is not specifically limited, For example, it can carry out at the temperature of -70 to 200 degreeC, for example, the reflux temperature of a solvent, in alcohol-type solvents, such as ethanol and methanol. The reaction temperature is 1 to 100 hours. The reaction can be promoted by using a catalyst such as potassium carbonate.

The alkylene group having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms, used for R ¹⁹ is an alkylene group such as methylene or ethylene in addition to the alkylene group having 3 to 10 carbon atoms represented by R ⁹ described above. It can be illustrated.
The structure of this reactant formula (7) is shown below.

(In the formula, R ^{14 to} R ¹⁸ are the same as R ^{4 to} R ⁸ defined in formula (2), and R ¹⁹ is the same as above).
The above formula (7) and the following formula (8):

(Wherein R ²⁰ represents an alkoxy group, an acyloxy group, or a halogen group, and is the same as defined in Formula (1). D represents an integer of 1 or 2) and a catalyst. It can be obtained by reaction. In this reaction, the silane of formula (8) undergoes addition reaction with the vinyl group of formula (7). A silicon atom reacts with the α-position or β-position of the vinyl group to form an α-form or a β-form. In the present invention, an α-form, a beta-form, or a mixture of both can be used.
The catalyst is not particularly limited. For example, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex, (bicyclo [2,2,1] hepta-2,5-diene) rhodium Examples include chloride dimer, tris (triphenylphosphine) rhodium chloride, benzenedichlororuthenium dimer, and the like. Although it does not specifically limit as a solvent, It can be made to react at the temperature of -70 to 200 degreeC, for example, room temperature (about 20 degreeC) using solvents, such as diethyl ether and tetrahydrofuran. The reaction time is 1 to 100 hours.

When R ²⁰ is a halogen in the formula (8), the obtained compound (ie, the halide of the formula (1)) is reacted in methanol in the presence of a pyridine catalyst at room temperature. A methoxy form can be obtained.

In the formula (3), R ¹⁰ is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, phosphoric acid group, amide group. , A nitro group, an acyl group, a sulfone group, a cyano group, or an organic group having a combination thereof, and bonded to a silicon atom by a Si—C bond, and R ¹¹ is an alkoxy group, an acyloxy group, or a halogen atom. A represents an integer of 0 to 3; These organic groups can be the same as those exemplified above.

In the formula (4), R ¹² is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, phosphate group, An organic group having an amide group, a nitro group, an acyl group, a sulfone group, a cyano group, or a combination thereof, and bonded to a silicon atom by a Si—C bond, and R ¹¹ is an alkoxy group, an acyloxy group, Or a halogen group, Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, and c represents an integer of 0 or 1. These organic groups can be the same as those exemplified above.
Examples of the arylene group include a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, and anthrylene group. As the substituent, the above organic group can be used.

Examples of the hydrolyzable silane of the above formula (3) are shown below.
Tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane , Methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxy Silane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β- Lysidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidyl Sidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycyl Sidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycyl Sidoxybutyl trie Xysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4 Epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltri Ethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycyl Sidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α- Glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane Silane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxy Propylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane , Vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, phenyltriacetoxysila , Γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldi Ethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxy Silane, .gamma.-methacryloxypropyl methyl diethoxy silane, .gamma.-mercaptopropyl methyl dimethoxy silane, .gamma.-mercapto methyl diethoxy silane, methyl vinyl dimethoxy silane, methyl vinyl diethoxy silane.

  The hydrolyzable silane of the formula (4) is, for example, methylene bistrimethoxysilane, methylene bistrichlorosilane, methylene bistriacetoxy silane, ethylene bistriethoxysilane, ethylene bistrichlorosilane, ethylene bistriacetoxy silane, propylene bistriethoxysilane, butylene bistrimethoxysilane, Examples include phenylenebistrimethoxysilane, phenylenebistriethoxysilane, phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane, naphthylenebistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, bismethyldimethoxydisilane, etc. It is done.

When the hydrolyzable silane of the formula (1) is used in combination with at least one hydrolyzable silane selected from the group consisting of the formula (3) and the formula (4), the mixing ratio is represented by the formula ( Use at least one hydrolyzable silane selected from the group consisting of the formula (3) and the formula (4) at a ratio of 0.01 to 10 mol with respect to 1 mol of the hydrolyzable silane of 1). Is preferred.
Among the hydrolyzable silanes, a combination of the formula (1) and the formula (3) can be selected. The hydrolyzable silane in which a in the formula (1) is 1 and b is 0; A combination with a hydrolyzable silane in which a is an integer of 0 to 2 is preferred.

Commercially available products can be used as the hydrolyzable silane represented by the formulas (3) and (4).
Hydrolyzing the hydrolyzable silane of formula (1) or a combination of formula (1) and at least one hydrolyzable silane selected from the group consisting of formula (3) and formula (4) The hydrolysis condensate (polysiloxane) obtained by condensing the decomposition product can obtain a condensate having a weight average molecular weight of 1,000 to 1,000,000, or 1,000 to 100,000. These molecular weights are molecular weights obtained in terms of polystyrene by GPC analysis.

Examples of the catalyst used when synthesizing the polysiloxane include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
Examples of the metal chelate compound as the hydrolysis catalyst include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-isopropoxy mono (acetylacetonato) titanium, tri- n-butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, Di-n-propoxy bis (acetylacetonato) titanium, di-isopropoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetyl) Acetonato) titanium, di-t- Toxi-bis (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-isopropoxy-tris (acetylacetonato) titanium, mono- n-butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy. Mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-isopropoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium Tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) Titanium, di-isopropoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-isopropoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy・ Tris Tylacetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris ( Titanium chelates such as ethyl acetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonato) zirconium, Tri-n-propoxy mono (acetylacetonato) zirconium, tri-isopropoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconi Tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxymono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-isopropoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy・ Bis (acetylacetonato) zirconium, monoethoxy-tris (acetylacetonato) zirconium, mono-n-propoxy-tris (acetylacetonato) zirconium, mono-isopropoxy-tris (acetylacetona) G) Zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetylacetate) Natto zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-isopropoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl) Acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis ( Ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-isopropoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec -Butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, Mono-isopropoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) ) Zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethyl) Zirconium chelate compounds such as acetoacetate) zirconium and tris (acetylacetonato) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum; Can do.

Organic acids as hydrolysis catalysts are, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacin Acid, gallic acid, butyric acid, merit acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.
Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazine. Examples thereof include zabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, 1,8-diazabicyclo [5,4,0] -7-undecene and the like.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.

  For hydrolysis of an alkoxysilyl group, an acyloxysilyl group, or a halogenated silyl group, 0.1 to 100 mol, or 0.1 to 10 mol, or 1 to 5 mol, or 1 mol per mol of the hydrolyzable group, or Use 2 to 3.5 moles of water.

  Further, 0.0001 to 10 mol, preferably 0.001 to 2 mol of hydrolysis catalyst can be used per mol of the hydrolyzable group.

  The reaction temperature for carrying out the hydrolysis and condensation is usually in the range of 20 ° C. (room temperature) to the reflux temperature under normal pressure of the solvent used for the hydrolysis.

Hydrolysis may be complete hydrolysis or partial hydrolysis. That is, a hydrolyzate or a monomer may remain in the hydrolysis condensate.
Although it does not specifically limit as a method to obtain polysiloxane, For example, the method of heating the mixture of a silicon compound, a solvent, and nitric acid is mentioned. Specifically, nitric acid is previously added to alcohol to form an alcohol solution of nitric acid, and then the solution and the silicon compound are mixed and heated. In that case, the amount of nitric acid is generally 0.2 to 2 mol relative to 1 mol of all alkoxy groups of the silicon compound. The heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and is preferably performed, for example, for several tens of minutes to several tens of hours under reflux in a sealed container so that the liquid does not evaporate or volatilize. Is called. The synthesis of polysiloxane may be in the order of reacting a mixture of solvent and oxalic acid in a silicon compound, or in the order of reacting by adding the silicon compound in the mixture of solvent and oxalic acid.

The reaction temperature when synthesizing the polysiloxane may be reacted at a reaction temperature of 0 to 50 ° C. for 24 to 2000 hours for the purpose of stably synthesizing a uniform polymer.
Examples of the organic solvent used for the hydrolysis include n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane and the like. Aliphatic hydrocarbon solvents: benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, n-amylnaphthalene, trimethylbenzene, etc. Aromatic hydrocarbon solvents: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pe Tanol, isopentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol -3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol , Sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol Monoalcohol solvents such as cresol; ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2 , 4,2-ethylhexanediol-1,3, polyhydric alcohol solvents such as diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n -Butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methyl Ketone solvents such as clohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl Ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dib Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether Ether solvents such as ter, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate , Isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, acetic acid n-nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, acetic acid Ethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene acetate Glycol monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate Ester solvents such as n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, Nitrogen-containing solvents such as N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide And sulfur-containing solvents such as thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more.

  Generally, an alcohol is generated as the solvent by a condensation polymerization reaction with a hydrolyzate of hydrolyzable silane, and therefore, an organic solvent having good compatibility with alcohols or alcohols is used. Specific examples of such organic solvents include methanol, ethanol, propanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, n-propyl acetate, ethyl Preferred examples include lactate, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, cyclohexanone and the like.

Hydrolyzable silane is hydrolyzed in a solvent, and the hydrolyzate is subjected to a condensation reaction to obtain a condensate (polysiloxane), which is obtained as a polysiloxane varnish dissolved in the hydrolysis solvent. It is done.
When the hydrolyzable silane is polycondensed, it is generally heated at a SiO2 solid content concentration of the charged silane in the range of 1 to 50% by mass, particularly 20% by mass or less. Is effective. By selecting an arbitrary concentration within such a concentration range, it is possible to suppress the formation of a high-molecular weight substance having low solubility and obtain a homogeneous polysiloxane-containing solution.
The obtained polysiloxane varnish may be solvent-substituted. Specifically, when ethanol is selected as the solvent during hydrolysis and condensation (solvent during synthesis), after the polysiloxane is obtained in ethanol, the same amount of substitution solvent as that used during the synthesis is added, Ethanol may be distilled off azeotropically with an evaporator or the like. The solvent at the time of synthesis at the time of solvent substitution is preferably azeotropically distilled off, and therefore has a lower boiling point than the solvent for substitution. For example, methanol, ethanol, isopropanol, etc. are mentioned at the time of hydrolysis and condensation, and the solvent for substitution includes propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, and the like.

The solvent used for the dilution or substitution of the polysiloxane varnish may be the same as the solvent used for hydrolysis and polycondensation of the hydrolyzable silane, or another solvent.
Specific examples of such solvents include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether. , Ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether Diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy-2 -Butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyllactone , Acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl iso Butyl ketone, methyl normal butyl ketone, cyclohexanone, ethyl acetate, isopropyl ketone, normal propyl acetate, isobutyl acetate, normal butyl acetate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, normal propanol, 2-methyl-2-butanol , Isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1 -Methoxy-2-butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, isopropyl Ether, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2-pyrrolidinone In view of storage stability of polysiloxane varnish, methanol, ethanol, isopropanol, butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, propylene glycol, hexylene glycol, methyl cellosolve, Ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone, methyl acetate, ethyl acetate, and ethyl lactate ester and the like.

In the polysiloxane varnish obtained in the present invention, other components such as a leveling agent and a surfactant are included in addition to the polysiloxane, the photosensitizer, and the solvent as long as the effects of the present invention are not impaired. May be.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene, and the like. Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan trioleate Sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name EFTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, R-08, R-30 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431 (Sumitomo 3M) Manufactured by Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP3 1 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. These surfactants may be used alone or in combination of two or more. When a surfactant is used, the ratio is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 0. 0 parts by mass with respect to 100 parts by mass of the condensate (polysiloxane). 5 parts by mass.
In the present invention, at least one hydrolyzable silane selected from the group consisting of the hydrolyzable silane of formula (1) or the hydrolyzable silane of formula (1) and the formula (3) and formula (4); Is hydrolyzed to obtain a hydrolysis-condensation product (polysiloxane).

In the present invention, a desired coating film can be obtained by applying a polysiloxane varnish to a substrate and thermosetting it. A known or well-known method can be adopted as the coating method. For example, spin coating method, dip method, flow coating method, ink jet method, spray method, bar coating method, gravure coating method, roll coating method, transfer printing method, brush coating, blade coating method, air knife coating method, etc. Can be adopted. The base material used in that case can include a base material made of silicon, indium tin oxide (ITO), indium zinc oxide (IZO, plastic, glass, ceramics, or the like).
The baking equipment is not particularly limited, and may be fired in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like, using a hot plate, an oven, or a furnace, for example. Thereby, it is possible to obtain a film having a uniform film forming surface.
Although a calcination temperature is not specifically limited in order to evaporate a solvent, For example, it can carry out at 40-200 degreeC. Moreover, although it does not specifically limit in the objective which accelerates | stimulates polycondensation of polysiloxane with a heat | fever, For example, it can carry out at 200-400 degreeC. In these cases, the temperature may be changed in two or more steps for the purpose of expressing a higher uniform film forming property or allowing the reaction to proceed on the substrate.
The coating of the present invention thus obtained can be formed on any substrate, and gap fill planarization material on a photo diode for an electronic device, particularly a solid-state imaging device, planarization material on a color filter, micro Suitable as a planarizing or conformal material on the lens. The film thickness can be in the range of 10 nm to 10 μm, and can be used in the range of 50 nm to 1 μm for electronic device applications.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, each measuring apparatus used in the Example is as follows.
For the nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR), the product name Varian 400-MR manufactured by Varian Technologies Japan Limited was used.
The molecular weight measurement of the polymer (hereinafter abbreviated as GPC) was performed by Showa Denko Co., Ltd., trade name Shodex GPC-104 / 101 system.

Gas chromatographic measurement (hereinafter abbreviated as GC) was performed under the following conditions using Shimadzu Corporation's trade name Shimadzu GC-14B.
Column: Capillary column CBP1-W25-100 (25 mm × 0.53 mmφ × 1 μm)
The column temperature was raised from a starting temperature of 50 ° C. at 15 ° C./min to an ultimate temperature of 290 ° C. (3 minutes). The sample injection amount was 1 μL, the injection temperature was 240 ° C., the detector temperature was 290 ° C., the carrier gas was nitrogen (flow rate 30 mL / min), and the detection method was the FID method.

The refractive index was measured using a trade name n & k Analyzer 1512RT manufactured by n & k Technology. All refractive indexes were measured at 633 nm.
[Synthesis Example 1]
<Synthesis of 2,3,4,5-tetrabromo-6-methylphenylallyl ether>
After adding 212.86 g (0.5 mol) of tetrabromo-o-cresol (hereinafter referred to as TBC) and 1.8 L of ethanol to a 3 L four-necked flask and dissolving at room temperature, 69.065 g of potassium carbonate (0.5 mol) ) And heated in an oil bath to 50 ° C. in a nitrogen atmosphere. Then, allyl bromide 50.2067 g (0.415 mol)
Was added and refluxed for 15 hours. The obtained solution was filtered while hot to remove potassium carbonate, and the filtrate was recrystallized and then filtered again, followed by vacuum drying at room temperature to obtain 2,3,4,5- 55.44 g (yield: 28%) of tetrabromo-6-methylphenylallyl ether (hereinafter abbreviated as M-1) was obtained.
When the structure was identified from the IR and NMR spectra, it was confirmed to be M-1.
IR (cm ⁻¹ ): 3050 (Arom, ν _C—H ) 2970 (ν _C—H ), 1640 (ν _{C = C} ), 1467 (ν _C—H ), 1240 (ν _C—O—C )
1H-NMR (ppm / CHCl ₃ -d): 6.103 ppm (m, 1H), 5.475 ppm (dd, 1H), 5.312 ppm (dd, 1H), 4.395 ppm (d, 2H), 559ppm (s, 3H)

[Synthesis Example 2]
<Synthesis of 2,3,4,5-tetrabromo-6-methylphenyl-3-trimethoxysilylpropyl ether>
46.3 g (0.1 mol) of M-1 obtained in Synthesis Example 1 was added to a 1 L four-necked flask, and the atmosphere was replaced with nitrogen. Then, 661 ml of tetrahydrofuran (hereinafter abbreviated as THF) was added and dissolved at room temperature. . Thereto was added 0.2 ml of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex and 27.09 g (0.2 mol) of trichlorosilane (hereinafter abbreviated as TCS) at room temperature. After stirring for 24 hours, 2,3,4,5-tetrabromo-6-methylphenyl-3-trichlorosilylpropyl ether was obtained. Further, 28.836 g (0.9 mol) of methanol and 71.19 g of pyridine were added and stirred for 24 hours. The obtained solution was filtered, and the solvent of the filtrate was distilled off, followed by distillation under reduced pressure to obtain 2,3,4,5-tetrabromo-6-methylphenyl-3-trimethoxysilyl as a pale yellow transparent viscous liquid. 10.66 g (yield: 18.2%) of propyl ether (hereinafter abbreviated as M-2) was obtained.
When the structure was identified from the IR and NMR spectra, it was confirmed to be M-2.
IR (cm ⁻¹ ): 3050 (Arom, ν _C—H ), 2970 (ν _C—H ), 1467 (ν _C—H ), 1290 (ν _Si—C ), 1240 (ν _C—O—C ) , 900 (ν _Si-O )
1H-NMR (ppm / CHCl ₃ -d): 3.837 ppm (t, 2H), 3.590 ppm (s, 9H), 2.455 ppm (s, 3H), 1.859 ppm (tt, 2H), 0. 916 ppm (t, 2H)

[Synthesis Example 3]
<Synthesis of 2,4,6-tribromophenyl allyl ether>
To a 3 L four-necked flask, 165.5 g (0.5 mol) of 2,4,6-tribromophenol and 1.8 L of ethanol were added and dissolved at room temperature, and then 69.065 g (0.5 mol) of potassium carbonate. And heated up to 50 ° C. in an oil bath in a nitrogen atmosphere. Then, allyl bromide 50.2067 g (0.415 mol)
Was added and refluxed for 15 hours. The obtained solution was filtered while hot to remove potassium carbonate, and the filtrate was recrystallized and then filtered again, followed by vacuum drying at room temperature to obtain 2,4,6-tribromo of white yellow needle crystals. 118.33 g of phenylallyl ether (hereinafter abbreviated as M-3) was obtained (yield: 48%).
When the structure was identified from the IR and NMR spectra, it was confirmed to be M-3.
IR (cm ⁻¹ ): 3055 (Arom, ν _C—H ), 2970 (ν _C—H ), 1640 (ν _{C = C} ), 1467 (ν _C—H ), 1240 (ν _C—O—C )
1H-NMR (ppm / CHCl ₃ -d): 7.634 ppm (s, 2H) 6.063 ppm (m, 1H), 5.425 ppm (dd, 1H), 5.282 ppm (dd, 1H), 4.685 ppm (D, 2H)

[Synthesis Example 4]
<Synthesis of 2,4,6-tribromophenyl-3-trimethoxysilylpropyl ether>
To a 1 L four-necked flask, 36.9 g (0.1 mol) of M-3 obtained in Synthesis Example 3 was added and purged with nitrogen. Then, 661 ml of tetrahydrofuran (hereinafter abbreviated as THF) was added and dissolved at room temperature. . Thereto was added 0.2 ml of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex and 27.09 g (0.2 mol) of trichlorosilane (hereinafter abbreviated as TCS) at room temperature. After stirring for 24 hours, 2,4,6-tribromophenyl-3-trichlorosilylpropyl ether was obtained. Further, 28.836 g (0.9 mol) of methanol and 71.19 g of pyridine were added and stirred for 24 hours. The obtained solution was filtered, and the solvent of the filtrate was distilled off, followed by distillation under reduced pressure to obtain 2,4,6-tribromophenyl-3-trimethoxysilylpropyl ether (hereinafter referred to as a light yellow transparent viscous liquid). 8.13 g (yield: 16.5%) was obtained.
When the structure was identified from the IR and NMR spectra, it was confirmed to be M-4.
IR (cm ⁻¹ ): 3050 (Arom, ν _C—H ), 2970 (ν _C—H ), 1467 (ν _C—H ), 1290 (ν _Si—C ), 1240 (ν _C—O—C ) , 900 (ν _Si-O )
1H-NMR (ppm / CHCl ₃ -d): 7.631 ppm (s, 2H), 3.953 ppm (t, 2H), 3.621 ppm (s, 9H), 1.911 ppm (tt, 2H), 0. 871 ppm (t, 2H)

<Production of polymer>
[Synthesis Example 5]
In a four-necked reaction flask equipped with a reflux tube, 4.4 g of M-2 (7.5 mmol) obtained in Synthesis Example 2, 17.6 g of dehydrated ethanol, 0.03 g (0.3 mmol) of nitric acid (65 wt. % Aqueous solution) and 0.47 g (27 mmol) of pure water were added, and the mixture was heated and stirred in an oil bath. After confirming reflux, the mixture was reacted for 4 hours. After completion of the reaction, the oil bath was removed and the mixture was allowed to cool to 23 ° C. to obtain polysiloxane varnish (PS-1). The molecular weight by GPC measurement was Mw 1550 and Mn 1431.
When PS-1 was measured by GC, no monomer of M-2 was detected.

[Synthesis Example 6]
In a four-necked reaction flask equipped with a reflux tube, 3.7 g of M-4 obtained in Synthesis Example 4 was added.
(7.5 mmol), 17.6 g of dehydrated ethanol, 0.03 g (0.3 mmol) of nitric acid (65 wt% aqueous solution), 0.47 g (27 mmol) of pure water were added, heated and stirred in an oil bath, and refluxed. After confirmation, the reaction was allowed to proceed for 4 hours. After completion of the reaction, the oil bath was removed and the mixture was allowed to cool to 23 ° C. to obtain polysiloxane varnish (PS-2). The molecular weight by GPC measurement was Mw of 1664 and Mn of 1471.
When PS-2 was measured by GC, no monomer of M-4 was detected.

[Comparative Synthesis Example 1]
In a four-necked reaction flask equipped with a reflux tube, 1.5 g of phenyltrimethoxysilane (7.5 mmol), 17.6 g of dehydrated ethanol, 0.03 g (0.3 mmol) of nitric acid (65 wt% aqueous solution), 0 .47 g (27 mmol) of pure water was added, and the mixture was heated and stirred in an oil bath. After confirming reflux, the mixture was reacted for 4 hours. After completion of the reaction, the oil bath was removed and the mixture was allowed to cool to 23 ° C. to obtain polysiloxane varnish (PS-3). The molecular weight determined by GPC was 917 for Mw and 850 for Mn.
When PS-3 was measured by GC, no phenyltrimethoxysilane monomer was detected.

<Polysiloxane varnish film formation and refractive index measurement>
Film formation was performed by a spin coating method, and the film was formed under conditions where the film thickness was 500 nm by baking after spin coating. The baking apparatus used the hotplate and baked at 120 degreeC for 2 minute (s) in air | atmosphere. A 4-inch silicon wafer was used as the substrate.
[Example 1]
PS-1 obtained in Synthesis Example 5 was spin-coated and then baked at 120 ° C. for 2 minutes. When the refractive index of the obtained film was measured, it was n = 1.6001.
[Example 2]
PS-2 obtained in Synthesis Example 6 was spin-coated and then baked at 120 ° C. for 2 minutes. When the refractive index of the obtained film was measured, it was n = 1.5917.

[Comparative Example 1]
PS-3 obtained in Comparative Synthesis Example 1 was spin-coated and then baked at 120 ° C. for 2 minutes. When the refractive index of the obtained film was measured, it was n = 1.5611.

  The polysiloxane varnish obtained from the compound of the present invention sufficiently penetrates into the concavo-convex portions. Moreover, the coating film obtained has a high refractive index, and the light extraction efficiency can be improved by using it as an electronic device, particularly as a member of a solid-state imaging device.

Claims (9)

The following general formula (1):

[In Formula (1), R ¹ is Formula (2):

(In the formula (2), R ^{4 to} R ⁸ are a bromine atom, a chlorine atom, a hydrogen atom, or a monovalent organic group, and the organic group is an alkyl group, a halogenated alkyl group, an alkenyl group, or an epoxy group. , An acryloyl group, a methacryloyl group, a mercapto group, an amino group, a carboxyl group, a phosphoric acid group, an amide group, a nitro group, an acyl group, a sulfone group, or a monovalent organic group having a cyano group, or a combination thereof, ⁹ is an alkylene group having 3 to 10 carbon atoms which may have a branch, and at least three of R ^{4 to} R ⁸ are a bromine atom or a chlorine atom.), R ² is an alkyl group , Aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, carboxyl group Group, a phosphate group, an amide group, a nitro group, an acyl group, a sulfonic group, or a monovalent organic group, or a combination thereof, having a cyano group. R ¹ and R ² are each bonded to a silicon atom by a Si—C bond. R ³ represents an alkoxy group, an acyloxy group, or a halogen group. a represents an integer of 1 to 2, b represents an integer of 0 to 1, and a + b represents an integer of 1 to 2. ] Hydrolyzable silane shown by this. The hydrolyzable silane according to claim 1, wherein at least three of R ^{4 to} R ⁸ in the formula (1) are bromine atoms, and R ⁹ is a propylene group or an isopropylene group. A hydrolyzate obtained from the compound according to claim 1 or 2, or a hydrolyzed condensate thereof. The above formula (1) and the following formula (3):

(Wherein R ¹⁰ is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, phosphoric acid group, amide group, nitro group. , An organic group having an acyl group, a sulfone group, a cyano group, or a combination thereof, and bonded to a silicon atom by a Si—C bond, and R ¹¹ represents an alkoxy group, an acyloxy group, or a halogen group. , A represents an integer of 0 to 3) and formula (4):

(Wherein R ¹² is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, phosphoric acid group, amide group, nitro group. , An organic group having an acyl group, a sulfone group, a cyano group, or a combination thereof, and bonded to a silicon atom by a Si—C bond, and R ¹³ represents an alkoxy group, an acyloxy group, or a halogen group. Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, and c represents an integer of 0 or 1.) A combination with at least one hydrolyzable silane selected from the group consisting of , Hydrolyzates of hydrolyzable silanes combined with them, or hydrolyzed condensates combined with them. The above formula (1) and the above formula (3) [wherein at least three of R ^{4 to} R ^{8 in} the formula (1) are bromine atoms, and R ⁹ is a propylene group or an isopropylene group. ] A hydrolyzate of the hydrolyzable silane combined with at least one hydrolyzable silane selected from the group consisting of the above, or a hydrolytic condensate combined thereof. An electronic device comprising a film made from the hydrolyzable silane according to any one of claims 1 to 5, a hydrolyzate thereof, a hydrolyzate condensate thereof, or a combination thereof. A charge-coupled device (CCD) comprising a film prepared from the hydrolyzable silane according to any one of claims 1 to 5, a hydrolyzate thereof, a hydrolyzate condensate thereof, or a combination thereof. A solid-state imaging device made of a complementary metal oxide semiconductor (CMOS). A film formed from the hydrolyzable silane according to any one of claims 1 to 5, a hydrolyzate thereof, a hydrolyzate condensate thereof, or a combination thereof is provided as a planarizing layer on a color filter. Solid-state image sensor. A film formed from the hydrolyzable silane according to any one of claims 1 to 5, a hydrolyzate thereof, a hydrolyzate condensate thereof, or a combination thereof, A solid-state image sensor provided as a formal layer.