JP2002097414A - Film forming composition and insulating film forming material - Google Patents

Abstract

(57) Abstract: A film capable of forming a silica-based film having a small relative permittivity of a coating film, a small residual stress of the coating film, and an excellent mechanical strength as an interlayer insulating film material in a semiconductor element or the like. A composition for forming and an insulating film forming material are obtained. A silicon polymer obtained by reacting (A) a silane compound with metallic lithium and/or metallic magnesium, and (B) a silane compound are hydrolyzed to contain a condensed hydrolyzed condensate. A film forming composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a silicon polymer and a film-forming composition, and more specifically, as an interlayer insulating film material for a semiconductor device or the like, the coating film has a small relative dielectric constant and Little residual stress,
The present invention relates to a film-forming composition and an insulating film-forming material capable of forming a silica-based film having excellent mechanical strength.

[0002]

2. Description of the Related Art Conventionally, as an interlayer insulating film in a semiconductor element or the like, a CVD (Chemical Vapor De) has been used.
A silica (SiO ₂ ) film formed by a vacuum process such as a position method is often used. In recent years, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used for the purpose of forming a more uniform interlayer insulating film. It has become. In addition, with the high integration of semiconductor elements and the like, an interlayer insulating film called organic SOG having a low relative dielectric constant containing polyorganosiloxane as a main component has been developed. In particular, due to higher integration and multi-layering of semiconductor elements and the like, better electrical insulation between conductors is required. Therefore, the relative dielectric constant is smaller, the residual stress of the coating film is smaller, and the mechanical strength is smaller. There has been a demand for an excellent interlayer insulating film material.

As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensing an alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of the alkoxysilane (JP-A-5-263045, Same as 5-315
319) or a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-340219 and JP-A-11-34022).
0) has been proposed, the materials obtained by these methods are not stable in the properties of the reaction product, and the relative permittivity of the coating film,
Since there are large variations such as residual stress and excellent mechanical strength, they were not suitable for industrial production.

[0004]

The present invention relates to a method for producing a silicon polymer and a film-forming composition for solving the above-mentioned problems, and more specifically, to a coating film as an interlayer insulating film in a semiconductor device or the like. An object of the present invention is to provide a film-forming composition having a small relative dielectric constant, a small residual stress in a coating film, and excellent mechanical strength, and an insulating film-forming material obtained from the composition.

[0005]

[In the formula, R ^{11 to} R ¹³ are the same or different, each is a monovalent organic group, f to g are the same or different, an integer of 0 to 2, R ¹³ is an oxygen atom, a phenylene group or -(CH ₂ ) _n A group represented by-(where n is an integer of 1 to 6), X is a halogen atom, and h is 0 or 1. ]

Component (A) In the present invention, the silicon polymer which is the component (A) is
It can be obtained by reacting at least one compound selected from the group of compounds represented by the general formulas (1) to (3) with metallic lithium and/or metallic magnesium. The compound represented by the general formula (1) includes a compound represented by the general formula (1)
In, R ¹⁰ is a monovalent organic group. Specific examples thereof include a linear or branched aliphatic group having 1 to 10 carbon atoms such as an alkyl group, an alkenyl group and an alkynyl group; a cycloalkyl group, a cycloalkenyl group, a bicycloalkyl group having a carbon number of 3 and the like. To 20 alicyclic group; 6 to 20 carbon atoms
And an aralkyl group having 6 to 20 carbon atoms. Specific examples of the alkyl group include:
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-
Examples thereof include a pentyl group, an isopentyl group, a neopentyl group and a thexyl group. Examples of the alkenyl group include a propenyl group, 3-butenyl group, 3-pentenyl group, 3
A hexenyl group may be mentioned. Examples of the alkynyl group include a propargyl group, a 3-methylpropargyl group, a 3-ethylpropargyl group and the like. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a norbornyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, an α-naphthyl group, a β-naphthyl group, an α-thiophene group, and a β-thiophene group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group and a phenylbutyl group. Specific examples of the compound represented by the general formula (1) include trichlorosilane, tribromosilane, triiodosilane, fluorotrichlorosilane, fluorotribromosilane, fluorotriiodosilane and the like;

Methyltrichlorosilane, methyltribromosilane, methyltriiodosilane, ethyltrichlorosisilane, ethyltribromosilane, ethyltriiodosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltriiodosilane, n-propyltrisilane. Chlorosilane, n-propyltribromosilane, n-propyltriiodosilane, i-propyltrichlorosilane,
i-propyltribromosilane, i-propyltriiodosilane, n-butyltrichlorosilane, n-butyltribromosilane, n-butyltriiodosilane, sec
-Butyltrichlorosilane, sec-butyltribromosilane, sec-butyltriiodosilane, t-butyltrichlorosilane, t-butyltribromosilane, t-
Butyltriiodosilane, phenyltrichlorosilane,
Phenyltribromosilane, phenyltriiodosilane, γ-aminopropyltrichlorosilane, γ-aminopropyltribromosilane, γ-aminopropyltriiodosilane, γ-glycidoxypropyltrichlorosilane, γ-glycidoxypropylbromosilane Silane, γ-glycidoxypropyliodosisilane, γ-trifluoropropyltrichlorosilane, γ-trifluoropropyltribromosilane, γ-trifluoropropyltriiodosilane, cyclohexyltrichlorosilane, cyclohexyltribromosilane, cyclohexyltriiodo Silane,
Phenethyltrichlorosilane, phenethyltribromosilane, phenethyltriiodosilane, 2-norbornyltrichlorosilane, 2-norbornyltribromosilane, 2-norbornyltriiodosilane, etc.;

Dimethyldichlorosilane, dimethyldibromosilane, dimethyldiiodosilane, diethyldichlorosilane, diethyldibromosilane, diethyldiiodosilane, di-n-propyldichlorosilane, di-n-propyldibromosilane, di-n-propyl Diiodosilane, di-iso-propyldichlorosilane, di-iso
-Propyldibromosilane, di-iso-propyldiiodosilane, di-n-butyldichlorosilane, di-n-
Butyldibromosilane, di-n-butyldiiodosilane, di-sec-butyldichlorosilane, di-sec-
Butyldibromosilane, di-sec-butyldiiodosilane, di-tert-butyldichlorosilane, di-te
Examples thereof include rt-butyldibromosilane, di-tert-butyldiiodosilane, diphenyldichlorosilane, diphenyldibromosilane, and diphenyldiiodosilane. These may be used either individually or in combination of two or more.

Compound Represented by General Formula (2) Specific examples of the compound represented by the above general formula (2) include
For example, tetrachlorosilane, tetrabromosilane, and tetraiodosilane can be mentioned. These may be used either individually or in combination of two or more.

Compound Represented by General Formula (3) In the above general formula (3), the monovalent organic group represented by R ^{11 to} R ¹² is the same organic group as the above general formula (1). Can be mentioned. In the general formula (3), as the compound in which R ¹³ is an oxygen atom, hexachlorodisiloxane, hexabromodisiloxane, hexaiododisiloxane,
1,1,1,3,3-pentachloro-3-methyldisiloxane, 1,1,1,3,3-pentabromo-3-methyldisiloxane, 1,1,1,3,3-pentaiodo-
3-methyldisiloxane, 1,1,1,3,3-pentachloro-3-ethyldisiloxane, 1,1,1,3,3
-Pentabromo-3-ethyldisiloxane, 1,1,
1,3,3-pentaiodo-3-ethyldisiloxane,
1,1,1,3,3-pentachloro-3-phenyldisiloxane, 1,1,1,3,3-pentabromo-3-phenyldisiloxane, 1,1,1,3,3-pentaiodo-3- Phenyldisiloxane, 1,1,3,3-tetrachloro-1,3-dimethyldisiloxane, 1,1,
3,3-tetrabromo-1,3-dimethyldisiloxane, 1,1,3,3-tetraiodo-1,3-dimethyldisiloxane, 1,1,3,3-tetrachloro-1,3
-Diethyldisiloxane, 1,1,3,3-tetrabromo-1,3-diethyldisiloxane, 1,1,3,3-
Tetraiodo-1,3-diethyldisiloxane, 1,
1,3,3-tetrachloro-1,3-diphenyldisiloxane, 1,1,3,3-tetrabromo-1,3-diphenyldisiloxane, 1,1,3,3-tetraiodo-
1,3-diphenyldisiloxane, 1,1,3-trichloro-1,3,3-trimethyldisiloxane, 1,1,
3-tribromo-1,3,3-trimethyldisiloxane, 1,1,3-triiodo-1,3,3-trimethyldisiloxane, 1,1,3-trichloro-1,3,3-
Triethyldisiloxane, 1,1,3-tribromo-
1,3,3-triethyldisiloxane, 1,1,3-triiodo-1,3,3-triethyldisiloxane, 1,
1,3-trichloro-1,3,3-triphenyldisiloxane, 1,1,3-tribromo-1,3,3-triphenyldisiloxane, 1,1,3-triiodo-1,
3,3-triphenyldisiloxane, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane, 1,3
-Dibromo-1,1,3,3-tetramethyldisiloxane, 1,3-diiodo-1,1,3,3-tetramethyldisiloxane, 1,3-dichloro-1,1,3,3-tetraethyl Disiloxane, 1,3-dibromo-1,1,
3,3-tetraethyldisiloxane, 1,3-diiodo-1,1,3,3-tetraethyldisiloxane, 1,3
-Dichloro-1,1,3,3-tetraphenyldisiloxane, 1,3-dibromo-1,1,3,3-tetraphenyldisiloxane, 1,3-diiodo-1,1,3,3
-Tetraphenyldisiloxane etc. can be mentioned.

Further, in the general formula (3), as the compound in which h is 0, hexachlorodisilane, hexabromodisilane, hexaiododisilane, 1,1,1,2,2-
Pentachloro-2-methyldisilane, 1,1,1,2,
2-pentabromo-2-methyldisilane, 1,1,1,
2,2-Pentaiodo-2-methyldisilane, 1,1,
1,2,2-pentachloro-2-ethyldisilane, 1,
1,1,2,2-pentabromo-2-ethyldisilane,
1,1,1,2,2-Pentaiodo-2-ethyldisilane, 1,1,1,2,2-pentachloro-2-phenyldisilane, 1,1,1,2,2-pentabromo-2-phenyldisilane , 1,1,1,2,2-Pentaiodo-
2-phenyldisilane, 1,1,2,2-tetrachloro-1,2-dimethyldisilane, 1,1,2,2-tetrabromo-1,2-dimethyldisilane, 1,1,2,2-
Tetraiodo-1,2-dimethyldisilane, 1,1,
2,2-tetrachloro-1,2-diethyldisilane,
1,1,2,2-tetrabromo-1,2-diethyldisilane, 1,1,2,2-tetraiodo-1,2-diethyldisilane, 1,1,2,2-tetrachloro-1,2-
Diphenyldisilane, 1,1,2,2-tetrabromo-
1,2-diphenyldisilane, 1,1,2,2-tetraiodo-1,2-diphenyldisilane, 1,1,2-trichloro-1,2,2-trimethyldisilane, 1,1,
2-tribromo-1,2,2-trimethyldisilane,
1,1,2-triiodo-1,2,2-trimethyldisilane, 1,1,2-trichloro-1,2,2-triethyldisilane, 1,1,2-tribromo-1,2,2-triethyldisilane , 1,1,2-triiodo-1,2,
2-triethyldisilane, 1,1,2-trichloro-
1,2,2-triphenyldisilane, 1,1,2-tribromo-1,2,2-triphenyldisilane, 1,1,
2-triiodo-1,2,2-triphenyldisilane,
1,2-dichloro-1,1,2,2-tetramethyldisilane, 1,2-dibromo-1,1,2,2-tetramethyldisilane, 1,2-diiodo-1,1,2,2- Tetramethyldisilane, 1,2-dichloro-1,1,2,2
-Tetraethyldisilane, 1,2-dibromo-1,1,
2,2-tetraethyldisilane, 1,2-diiodo-
1,1,2,2-tetraethyldisilane, 1,2-dichloro-1,1,2,2-tetraphenyldisilane, 1,
Examples thereof include 2-dibromo-1,1,2,2-tetraphenyldisilane and 1,2-diiodo-1,1,2,2-tetraphenyldisilane.

Further, in the general formula (3), R ¹³ is-
(CH _{2) n} - in a compound of the group represented, bis (trichlorosilyl) methane, bis (tri-bromo) methane, bis (tri-iodo silyl) methane, 1,2
-Bis(trichlorosilyl)ethane, 1,2-bis(tribromosilyl)ethane, 1,2-bis(triiodosilyl)ethane, 1-(dichloromethylsilyl)-1-
(Trichlorosilyl)methane, 1-(dibromomethylsilyl)-1-(tribromosilyl)methane, 1-(diiodomethylsilyl)-1-(triiodosilyl)methane, 1-(dichloromethylsilyl)-2 -(Trichlorosilyl)ethane, 1-(dibromomethylsilyl)-2-
(Tribromosilyl)ethane, 1-(diiodomethylsilyl)-2-(triiodosilyl)ethane, bis(dichloromethylsilyl)methane, bis(dibromomethylsilyl)methane, bis(diiodomethylsilyl)methane,
1,2-bis(dichloromethylsilyl)ethane, 1,2
-Bis(dibromomethylsilyl)ethane, 1,2-bis(diiodomethylsilyl)ethane, 1,2-bis(trichlorosilyl)benzene, 1,2-bis(tribromosilyl)benzene, 1,2-bis (Triiodosilyl)benzene, 1,3-bis(trichlorosilyl)benzene,
1,3-bis(tribromosilyl)benzene, 1,3-
Bis(triiodosilyl)benzene, 1,4-bis(trichlorosilyl)benzene, 1,4-bis(tribromosilyl)benzene, 1,4-bis(triiodosilyl)
Examples include benzene. These may be used either individually or in combination of two or more.

In the silicon polymer of the present invention, at least one compound selected from the group of compounds represented by the general formulas (1) to (3) is reacted with metallic lithium and/or metallic magnesium. By this, a silicon polymer can be obtained. The metallic lithium and metallic magnesium to be reacted at this time are those used to reductively detach the halogen atom from the compounds represented by the general formulas (1) to (3) to form lithium halide or magnesium halide. The amount used is preferably equivalent to the total amount of the compounds represented by the general formulas (1) to (3).

In the present invention, the reaction can be promoted by irradiating ultrasonic waves from the outside, if necessary, during the production of the silicon polymer. The frequency of the ultrasonic waves used here is preferably about 10 to 70 KHz. As a solvent to be used in the production of the silicon polymer, an ether solvent can be preferably used. The yield of the target soluble polysilane oligomer tends to be low in the hydrocarbon solvent used in the ordinary Kipping reaction. As an ether solvent,
For example, diethyl ether, di-n-propyl ether,
Di-isopropyl ether, dibutyl ether, ethyl propyl ether, anisole, phenetole, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether , Dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether,
Propylene glycol methyl ethyl ether, tetrahydrofuran, dioxane and the like can be mentioned. Of these, from the viewpoint of solubility of the component (C), diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Diethylene glycol dimethyl ether and diethylene glycol diethyl ether are preferred.

It is desirable to remove water from these ether solvents in advance. As a method for removing water, a deaeration distillation method in the presence of sodium-benzophenone ketyl is preferable. The amount of these solvents used is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight with respect to the total amount of the compounds represented by the general formulas (1) to (3). Is. The reaction temperature at this time is preferably −78° C. to +100° C. When the reaction temperature is −78° C. or lower, the reaction rate is slow and the productivity does not increase,
Further, when the reaction temperature is higher than +100° C., the reaction becomes complicated and the solubility of the obtained silicon polymer is likely to decrease. Furthermore, the reaction is usually preferably carried out in an inert gas such as argon or nitrogen.

In the present invention, unreacted addition is added to the end of the molecule.
Reduction of silicon polymers containing water-decomposable halogen atoms
The hydrolyzable halogen atom is reduced to stable water by reducing with an agent.
It may be replaced with elementary atoms. As such a reducing agent,
For example LiAlH_Four, NaH, LiBu₃BH, (C_FiveH
₁₁)₂BH, B₂H₆, NaBH_Four, Zn(BH_Four)₂, Na
BH₃CN, Bu₂AlH, Li(OBu)₃AlH, etc.
LiAlH_Four, NaH, B ₂H₆,
NaBH_FourCan be mentioned as a more preferable example
It The amount of reducing agent used is such that hydrogen atoms in the reducing agent remain
At least equivalent to the halogen atom, preferably
Is required to be 1.0 to 4.0 times equivalent. Also used at this time
As the solvent to be used, particularly a solvent that does not react with the reducing agent
Although not limited, usually ether solvents are preferable, and
It is possible to use the same ether solvent as the example.
Wear. These can be used alone or in admixture of two or more.
can do. The reaction temperature at this time is preferably −
It is 78°C to +60°C. The reaction is slow below -78°C
Reacts when productivity does not increase and is higher than +60°C
Formation of the silicon polymer of the present invention with reduced solubility of the product
Yield tends to decrease. In addition, the reaction is usually argon or nitrogen.
It is preferably carried out in an inert gas such as nitrogen.

Component (B) In the present invention, the component (B) is a compound represented by the following general formula (4) (hereinafter referred to as “compound (4)”) or a compound represented by the following general formula (5). (Hereinafter, "compound (5)"
And a compound represented by the following general formula (6) (hereinafter referred to as “compound (6)”) is a hydrolyzed condensate obtained by hydrolyzing and condensing at least one silane compound selected from the group consisting of: .. R _a Si(OR ¹ ) _4-a (4) (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is 1 to 2). Si(OR ² ) ₄ (5) (In the formula, R ² represents a monovalent organic group.) R ³ _b (R ⁴ ) _3-b Si-(R ⁷ ) _d- Si(OR ⁵ ) _3-c R ⁶ _c (6) [wherein, R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, and b to c are the same or different, An integer from 0 to 2,
R ⁷ represents an oxygen atom, a phenylene group or - (CH _{2) m} -
A group represented by (where m is an integer of 1 to 6), d
Represents 0 or 1. ]

Compound (4): In the above general formula (4), examples of the monovalent organic group of R and R ¹ include an alkyl group, an aryl group, an allyl group and a glycidyl group. Further, in the general formula (4), R is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, as the alkyl group, a methyl group,
Examples thereof include an ethyl group, a propyl group and a butyl group, preferably having 1 to 5 carbon atoms, and these alkyl groups may be linear or branched, and further, a hydrogen atom is substituted with a fluorine atom or the like. You may. Examples of the aryl group in the general formula (4) include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group and a fluorophenyl group.

Specific examples of the compound represented by the general formula (4) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane and tri-. sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane and the like;

Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n
-Butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n -Butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane,
Ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-s.
ec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane , N-propyltri-n-butoxysilane, n-propyltri-sec
-Butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-
Propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane,
i-Propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-
sec-butoxysilane, i-propyltri-tert
-Butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-
Butyltri-n-butoxysilane, n-butyltri-s
ec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, se
c-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, s
ec-butyl-tri-sec-butoxysilane, sec
-Butyl-tri-tert-butoxysilane, sec-
Butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso.
-Propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-
Butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri -Sec-butoxysilane, phenyltri-tert-
Butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltrisilane Ethoxysilane etc.;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane,
Dimethyl-di-iso-propoxysilane, dimethyl-
Di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n
-Propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-te
rt-butoxysilane, diethyldiphenoxysilane,
Di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di -N-butoxysilane, di-n-propyl-di-sec-butoxysilane,
Di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-
Propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxy. Silane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n -Butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl -Di-sec-butoxysilane, di-n-
Butyl-di-tert-butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, J-s
ec-butyl-di-iso-propoxysilane, di-s
ec-butyl-di-n-butoxysilane, di-sec-
Butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, Di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxy Silane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane,
Diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-
Butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane and the like;

Preferred compounds as the compound (4) are methyltrimethoxysilane, methyltriethoxysilane,
Methyltri-n-propoxysilane, methyltri-is
o-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Examples thereof include vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. These may be used either individually or in combination of two or more.

Compound (5): In the above general formula (5), the monovalent organic group represented by R ² includes the same organic groups as in the above general formula (4). Specific examples of the compound represented by the general formula (5) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxylan and tetra-sec-butoxysilane. , Tetra-tert-butoxysilane, tetraphenoxysilane and the like.

Compound (6): In the above general formula (6), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as in the above general formula (4). .. In the general formula (6), as a compound in which R ⁷ is an oxygen atom,
Hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,
3,3-pentamethoxy-3-methyldisiloxane,
1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3
-Methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3
-Pentaethoxy-3-ethyldisiloxane, 1,1,
1,3,3-Pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyl Disiloxane, 1,1,1,3,3-pentaphenoxy-3-phenyldisiloxane, 1,1,
3,3-Tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraphenoxy-
1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,
3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-
1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,
1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-
Trimethyldisiloxane, 1,1,3-triethoxy-
1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane,
1,1,3-trimethoxy-1,3,3-triethyldisiloxane, 1,1,3-triethoxy-1,3,3-
Triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,1,3-
Trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,
3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,
3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,
3,3-tetraethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraethyldisiloxane, 1,
3-diphenoxy-1,1,3,3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,
Examples include 1,3,3-tetraphenyldisiloxane and 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane.

Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,
1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,
3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,
Preferred examples include 3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane and the like.

Further, in the general formula (6), as the compound in which d is 0, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,
2,2-pentamethoxy-2-methyldisilane, 1,
1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2
-Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2
-Pentamethoxy-2-phenyldisilane, 1,1,
1,2,2-pentaethoxy-2-phenyldisilane,
1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-
Dimethyldisilane, 1,1,2,2-tetraethoxy-
1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2
-Tetramethoxy-1,2-diethyldisilane, 1,
1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1,
2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-
Tetraphenoxy-1,2-diphenyldisilane, 1,
1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2
-Trimethyldisilane, 1,1,2-trimethoxy-
1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2
-Triphenoxy-1,2,2-triethyldisilane,
1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-
1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-
Diethoxy-1,1,2,2-tetramethyldisilane,
1,2-diphenoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,
2-tetraethyldisilane, 1,2-diphenoxy-
1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane,
Examples thereof include 1,2-diethoxy-1,1,2,2-tetraphenyldisilane and 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane.

Of these, hexamethoxydisilane,
Hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,
2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,
Preferred examples include 2,2-tetraphenyldisilane and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane.

Further, in the general formula (6), R ⁷ is -.
Examples of the compound represented by (CH ₂ ) _m − include bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(tri-n-propoxysilyl)methane, bis(tri-i-propoxy). Silyl)methane, bis(tri-n-butoxysilyl)methane, bis(tri-
sec-butoxysilyl)methane, bis(tri-t-butoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,2-bis(tri- n-propoxysilyl)ethane, 1,2-bis(tri-i-propoxysilyl)ethane, 1,2-bis(tri-n-butoxysilyl)ethane, 1,2-bis(tri-sec-butoxysilyl) Ethane, 1,2-bis(tri-t-butoxysilyl)ethane, 1-(dimethoxymethylsilyl)-1-(trimethoxysilyl)methane, 1-(diethoxymethylsilyl)
-1-(triethoxysilyl)methane, 1-(di-n-
Propoxymethylsilyl)-1-(tri-n-propoxysilyl)methane, 1-(di-i-propoxymethylsilyl)-1-(tri-i-propoxysilyl)methane,
1-(di-n-butoxymethylsilyl)-1-(tri-
n-butoxysilyl)methane, 1-(di-sec-butoxymethylsilyl)-1-(tri-sec-butoxysilyl)methane, 1-(di-t-butoxymethylsilyl)
-1-(tri-t-butoxysilyl)methane, 1-(dimethoxymethylsilyl)-2-(trimethoxysilyl)
Ethane, 1-(diethoxymethylsilyl)-2-(triethoxysilyl)ethane, 1-(di-n-propoxymethylsilyl)-2-(tri-n-propoxysilyl)ethane, 1-(di-i -Propoxymethylsilyl)-2-
(Tri-i-propoxysilyl)ethane, 1-(di-n
-Butoxymethylsilyl)-2-(tri-n-butoxysilyl)ethane, 1-(di-sec-butoxymethylsilyl)-2-(tri-sec-butoxysilyl)ethane, 1-(di-t-butoxy) Methylsilyl)-2-(tri-t-butoxysilyl)ethane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)
Methane, bis(di-n-propoxymethylsilyl)methane, bis(di-i-propoxymethylsilyl)methane,
Bis(di-n-butoxymethylsilyl)methane, bis(di-sec-butoxymethylsilyl)methane, bis(di-t-butoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1, 2-bis(diethoxymethylsilyl)ethane, 1,2-bis(di-n-propoxymethylsilyl)ethane, 1,2-bis(di-i-propoxymethylsilyl)ethane, 1,2-
Bis(di-n-butoxymethylsilyl)ethane, 1,2
-Bis(di-sec-butoxymethylsilyl)ethane,
1,2-bis(di-t-butoxymethylsilyl)ethane, 1,2-bis(trimethoxysilyl)benzene,
1,2-bis(triethoxysilyl)benzene, 1,2
-Bis(tri-n-propoxysilyl)benzene, 1,
2-bis(tri-i-propoxysilyl)benzene,
1,2-bis(tri-n-butoxysilyl)benzene,
1,2-bis(tri-sec-butoxysilyl)benzene, 1,2-bis(tri-t-butoxysilyl)benzene, 1,3-bis(trimethoxysilyl)benzene,
1,3-bis(triethoxysilyl)benzene, 1,3
-Bis(tri-n-propoxysilyl)benzene, 1,
3-bis(tri-i-propoxysilyl)benzene,
1,3-bis(tri-n-butoxysilyl)benzene,
1,3-bis(tri-sec-butoxysilyl)benzene, 1,3-bis(tri-t-butoxysilyl)benzene, 1,4-bis(trimethoxysilyl)benzene,
1,4-bis(triethoxysilyl)benzene, 1,4
-Bis(tri-n-propoxysilyl)benzene, 1,
4-bis(tri-i-propoxysilyl)benzene,
1,4-bis(tri-n-butoxysilyl)benzene,
Examples thereof include 1,4-bis(tri-sec-butoxysilyl)benzene and 1,4-bis(tri-t-butoxysilyl)benzene.

Of these, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, 1,
2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1-(dimethoxymethylsilyl)-1-(trimethoxysilyl)methane, 1-
(Diethoxymethylsilyl)-1-(triethoxysilyl)methane, 1-(dimethoxymethylsilyl)-2-
(Trimethoxysilyl)ethane, 1-(diethoxymethylsilyl)-2-(triethoxysilyl)ethane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane, 1,2-bis(dimethoxymethyl) (Silyl)ethane, 1,2-bis(diethoxymethylsilyl)ethane, 1,2-bis(trimethoxysilyl)benzene, 1,2-bis(triethoxysilyl)benzene, 1,3-bis(trimethoxysilyl) )benzene,
1,3-bis(triethoxysilyl)benzene, 1,4
Preferred examples include -bis(trimethoxysilyl)benzene and 1,4-bis(triethoxysilyl)benzene. In the present invention, compound (4)
As (1) to (6), one kind or two or more kinds can be used.

When at least one silane compound selected from the group consisting of the compounds (4) to (6) is hydrolyzed and condensed, the amount of the compound (4) to (6) per mole of the compound is 0.4.
It is preferable to use more than 5 mol and less than 150 mol of water, and it is particularly preferable to add more than 0.5 mol and 130 mol of water. In producing the (B) hydrolysis-condensation product of the present invention, a specific catalyst is used when hydrolyzing and condensing at least one silane compound selected from the group of the compounds (4) to (6). It is characterized in that it is used, and at least one selected from the group consisting of an alkali catalyst, a metal chelate catalyst and an acid catalyst is used.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine,
Picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, ammonia,
Methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, pentylamine, octylamine, nonylamine, decylamine,
N,N-dimethylamine, N,N-diethylamine,
N,N-dipropylamine, N,N-dibutylamine,
Trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine and the like can be mentioned, and amine or amine salt is preferable. ,
Organic amines or organic amine salts are particularly preferable, and alkylamines and tetraalkylammonium hydroxides are most preferable. These alkali catalysts may be used either individually or in combination of two or more.

Examples of the metal chelate catalyst include triethoxy mono(acetylacetonato)titanium, tri-n-propoxy mono(acetylacetonato)titanium, tri-i-propoxy mono(acetylacetonato)titanium, tritium. -N-butoxy mono(acetylacetonate) titanium, tri-sec-butoxy mono(acetylacetonate) titanium, tri-t-butoxy mono(acetylacetonate) titanium, diethoxy bis(acetylacetonate) titanium , Di-n-propoxy bis(acetylacetonato)titanium, di-i-propoxy bis(acetylacetonato)titanium, di-n
-Butoxy bis(acetylacetonate) titanium, di-sec-butoxy bis(acetylacetonate) titanium, di-t-butoxy bis(acetylacetonate) titanium, monoethoxy tris(acetylacetonate) titanium, Mono-n-propoxy tris(acetylacetonato)titanium, mono-i-propoxy tris(acetylacetonato)titanium, mono-n-butoxy tris(acetylacetonato)titanium, mono-s
ec-Butoxy tris(acetylacetonate) titanium, mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy. Mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, Tri-t-butoxy mono(ethyl acetoacetate) titanium, diethoxy bis(ethyl acetoacetate) titanium, di-n-propoxy bis(ethyl acetoacetate) titanium, di-i-propoxy bis(ethyl acetoacetate). Titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethyl). Acetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate)
Titanium, mono-i-propoxy tris(ethylacetoacetate) titanium, mono-n-butoxy tris(ethylacetoacetate) titanium, mono-sec-butoxy tris(ethylacetoacetate) titanium, mono-
t-Butoxy tris(ethylacetoacetate) titanium, tetrakis(ethylacetoacetate) titanium, mono(acetylacetonato) tris(ethylacetoacetate) titanium, bis(acetylacetonato)bis(ethylacetoacetate) titanium, tris( Acetylacetonato)mono(ethylacetoacetate)titanium chelate compounds such as titanium; triethoxy mono(acetylacetonato)zirconium, tri-n-propoxy mono(acetylacetonato)zirconium, tri-i-propoxy mono(acetyl) Acetonato)zirconium, tri-n-butoxy mono(acetylacetonato)zirconium, tri-sec-butoxy mono(acetylacetonato)zirconium, tri-t-
Butoxy mono(acetylacetonato) zirconium, diethoxy bis(acetylacetonato) zirconium, di-n-propoxy bis(acetylacetonato) zirconium, di-i-propoxy bis(acetylacetonato) zirconium, di- n-butoxy
Bis(acetylacetonato)zirconium, di-se
c-Butoxy bis(acetylacetonato)zirconium, di-t-butoxy bis(acetylacetonato)zirconium, monoethoxy tris(acetylacetonato)zirconium, mono-n-propoxy tris(acetylacetonato)zirconium , Mono-i
-Propoxy tris(acetylacetonato) zirconium, mono-n-butoxy tris(acetylacetonato) zirconium, mono-sec-butoxy tris(acetylacetonato) zirconium, mono-t-
Butoxy tris(acetylacetonate) zirconium, tetrakis(acetylacetonato) zirconium, triethoxy mono(ethylacetoacetate) zirconium, tri-n-propoxy mono(ethylacetoacetate) zirconium, tri-i-propoxy.
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, The-
n-propoxy bis(ethyl acetoacetate) zirconium, di-i-propoxy bis(ethyl acetoacetate) zirconium, di-n-butoxy bis(ethyl acetoacetate) zirconium, di-sec-butoxy bis(ethyl acetoacetate) Acetate) zirconium, di-t-butoxy bis(ethylacetoacetate) zirconium, monoethoxy tris(ethylacetoacetate) zirconium, mono-n-propoxy.
Tris(ethylacetoacetate) zirconium, mono-i-propoxy tris(ethylacetoacetate)
Zirconium, mono-n-butoxy tris(ethylacetoacetate) zirconium, mono-sec-butoxy tris(ethylacetoacetate) zirconium,
Mono-t-butoxy tris(ethylacetoacetate) zirconium, tetrakis(ethylacetoacetate) zirconium, mono(acetylacetonato) tris(ethylacetoacetate) zirconium, bis(acetylacetonato)bis(ethylacetoacetate)
Zirconium, zirconium chelate compounds such as tris(acetylacetonato)mono(ethylacetoacetate)zirconium; tris(acetylacetonato)aluminum, tris(ethylacetoacetate)
Aluminum chelate compounds such as aluminum; and the like can be mentioned, preferably titanium or aluminum chelate compounds, and particularly preferably titanium chelate compounds. These metal chelate catalysts may be used either individually or in combination of two or more.

As the acid catalyst, for example, hydrochloric acid,
Inorganic acids such as nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, oxalic acid; 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, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid , Oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid,
Malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid hydrolyzate, maleic anhydride hydrolyzate, An organic acid such as a hydrolyzate of phthalic anhydride can be mentioned, and an organic carboxylic acid can be mentioned as a more preferable example. These acid catalysts may be used either individually or in combination of two or more.

The amount of the above catalyst used is from compound (4) to
R in (6)¹ O-group, R² O-group, R ^Four O-group and
R^Five Normally, based on 1 mol of the total amount of the groups represented by O-groups,
0.00001 to 10 mol, preferably 0.00005
~ 5 moles. If the amount of the catalyst used is within the above range,
There is little risk of polymer precipitation or gelation during the reaction. Well
Further, in the present invention, the compounds (4) to (6) are hydrolyzed.
The temperature at this time is usually 0 to 100° C., preferably 15 to
It is 80°C.

When the compounds (4) to (6) are converted into complete hydrolysis-condensation products, the compound (5) is contained in the total amount of the compounds (4) to (6) in an amount of 5 to 75% by weight, preferably Is 10 to 70% by weight, more preferably 15 to 70% by weight
Is. Further, the compound (4) and/or (6) is
In the total amount of the compounds (4) to (6), 95 to 25% by weight, preferably 90 to 30% by weight, more preferably 85 to 3% by weight.
It is 0% by weight. Compound (5) is compound (4)-
When the total amount of (6) is 5 to 75% by weight, the resulting coating film has a high elastic modulus and is particularly excellent in low dielectric properties. Here, in the present invention, the complete hydrolysis-condensation product means the R ¹ O-group, R ² O-group and R ⁴ O in the compounds (4) to (6).
- group and R ⁵ O-group 100% hydrolyzed to the SiOH
It is a base and is further condensed completely to form a siloxane structure. Further, the component (B) is preferably a hydrolysis-condensation product of the compound (4) and the compound (5), since the obtained composition has more excellent storage stability.

In the present invention, the amount of the component (B) used with respect to the silicon polymer is 0 to 4000 parts by weight, more preferably 0 to 3000 parts by weight, relative to 100 parts by weight of the silicon polymer.

In the present invention, the above component (A) alone,
Alternatively, the component (A) and the component (B) may be combined to form a film-forming composition, in which case β-diketone, colloidal silica, colloidal alumina, organic polymer, surfactant, silane cup. You may add components, such as a ring agent and a radical generator. As β-diketone, acetylacetone, 2,4-hexanedione, 2,
4-heptanedione, 3,5-heptanedione, 2,4
-Octanedione, 3,5-octanedione, 2,4-
Nonanedione, 3,5-nonanedione, 5-methyl-
2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5
-Hexafluoro-2,4-heptanedione and the like, and more preferably acetylacetone, 2,
4-hexanedione, 2,4-heptanedione, 3,5
-Heptandione. These may be used either individually or in combination of two or more.

The colloidal silica is, for example, a dispersion liquid in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle diameter of 5 to 30 nm, preferably 10 to 30 nm.
It has a thickness of 20 nm and a solid content concentration of about 10 to 40% by weight. Examples of such colloidal silica include, for example, Nissan Chemical Industry Co., Ltd., methanol silica sol and isopropanol silica sol; Catalyst Chemical Industry Co., Ltd.
Manufactured, Oscar and the like. As the colloidal alumina, alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.,
Said 100, 200; Kawaken Fine Chemical Co., Ltd.'s alumina clear sol, alumina sol 10, and 132, etc. are mentioned. As the organic polymer, for example, a compound having a sugar chain structure, a vinylamide polymer, (meth)
Acrylic polymer, aromatic vinyl compound, dendrimer, polyimide, polyamic acid, polyarylene, polyamide, polyquinoxaline, polyoxadiazole,
Examples thereof include a fluoropolymer and a compound having a polyalkylene oxide structure.

As the compound having a polyalkylene oxide structure, a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure,
Examples thereof include a polytetramethylene oxide structure and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene ethylene phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, alkylphenol formalin condensate ethylene oxide derivative, polyoxyethylene polyether Oxypropylene block copolymer, ether type compounds such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. Examples thereof include ether ester type compounds, polyethylene glycol fatty acid esters, ethylene glycol fatty acid esters, fatty acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and sucrose fatty acid esters. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures. - (X) j- (Y) k- - (X) j- (Y) k- (X) l- ( wherein, X is a group represented by -CH ₂ CH ₂ O-, Y is -
Represents a group represented by CH ₂ CH(CH ₃ )O-, and j is 1 to
90, k are 10 to 99, 1 is a number of 0 to 90) Among these, polyoxyethylene alkyl ether,
Polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
More preferred examples include ether type compounds such as These may be used either individually or in combination of two or more.

Examples of the surface active agent include nonionic surface active agents, anionic surface active agents, cationic surface active agents, amphoteric surface active agents, and the like. Further, fluorine surface active agents and silicone surface active agents. Activators, polyalkylene oxide-based surfactants, poly(meth)acrylate-based surfactants and the like can be mentioned, and preferably fluorine-based surfactants and silicone-based surfactants can be mentioned.

Examples of the fluorinated surfactant include 1,
1,2,2-Tetrafluorooctyl (1,1,2,2-
Tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl)
Ether, hexaethylene glycol (1, 1, 2,
2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoro) Pentyl) ether, sodium perfluorododecyl sulfonate,
1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3-(perfluorooctane sulfone Amido)propyl]-N,N′-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamidopropyl trimethyl ammonium salt,
At least one of the terminal, main chain and side chain of perfluoroalkyl-N-ethylsulfonylglycine salt, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, etc. A fluorosurfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the site can be mentioned. Commercially available products are MegaFac F142D, F172, F173, and F1.
83 (above, manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC-430, FC-431.
(Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, same SC-103, same SC-104, same SC-1
05, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-10
00, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15
(Neos Co., Ltd.) and other commercially available fluorine-based surfactants can be mentioned. Among these, the Megafac F172, BM-1000, BM-11
00, NBX-15 are particularly preferred.

Examples of silicone-based surfactants include SH7PA, SH21PA, SH30PA, ST94P.
A (all are Toray Dow Corning Silicone Co., Ltd.)
It can be manufactured. Among these, the above S
H28PA and SH30PA are particularly preferable. The amount of the surfactant used is usually 0.0001 to 10 parts by weight based on the component (A) (completely hydrolyzed condensate). These may be used either individually or in combination of two or more.

As the silane coupling agent, for example, 3
-Glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-
(2-Aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- 1,4,7-Triazadecane, 10-
Triethoxysilyl-1,4,7-triazadecane, 9
-Trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriamine Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-
Examples thereof include aminopropyltrimethoxysilane and N-bis(oxyethylene)-3-aminopropyltriethoxysilane. These may be used either individually or in combination of two or more.

Examples of the radical generator include isobutyryl peroxide, α,α′ bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxy neodecanoate, di-npropylperoxydicarbonate and diisopropylperoxy. Dicarbonate,
1,1,3,3-tetramethylbutylperoxyneodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, t-hexylperoxy neodecanoate, dimethoxybutyl peroxydicarbonate, di(3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butyl peroxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di( 2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-
1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,
m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-
3,3,5-Trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-
Bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-)
Butyl peroxycyclohexyl)propane, 1,1-
Bis(t-butylperoxy)cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-
3,3,5-Trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t -Butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-
2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis( t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α′bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di( t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butylperoxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like can be mentioned. The blending amount of the radical generator is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer. These may be used either individually or in combination of two or more. The film-forming composition of the present invention comprises the above components (A) or (A) and (B) and, if necessary, the above additives dissolved or dispersed in a solvent.

Examples of the solvent that can be used in this case include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents and aprotic solvents. Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-
Propanol, n-butanol, i-butanol, se
c-butanol, t-butanol, n-pentanol,
i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, se
c-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,
Monoalcoholic solvents such as 3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,
Ethylene glycol mono-2-ethylbutyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl 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,
Examples thereof include polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether. These alcohol solvents are used alone or in combination.
More than one species may be used simultaneously.

As the ketone solvent, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-
n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-
Butyl ketone, methyl-n-hexyl ketone, di-i-
Butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4
-Pentanedione, acetonylacetone, acetophenone, fenchon, etc., as well as acetylacetone, 2,
4-hexanedione, 2,4-heptanedione, 3,5
-Heptanedione, 2,4-octanedione, 3,5-
Octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,
2,6,6-tetramethyl-3,5-heptanedione,
Examples include β-diketones such as 1,1,1,5,5,5-hexafluoro-2,4-heptanedione.
These ketone solvents may be used either individually or in combination of two or more.

As the amide solvent, formamide, N
-Methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,
N-dimethylacetamide, N-ethylacetamide,
Examples include N,N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. Be done. These amide solvents may be used either individually or in combination of two or more.

Ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ.
-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoacetate
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 glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxytriglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents are 1
One kind or two or more kinds may be used at the same time.

As the aprotic solvent, acetonitrile, dimethylsulfoxide, N,N,N',N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-
Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N −
Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2(1
H)-pyrimidinone and the like. These aprotic solvents may be used either individually or in combination of two or more.

The total solid concentration of the film-forming composition of the present invention thus obtained is preferably 2 to 30% by weight.
And is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 2 to 30% by weight, the film thickness of the coating film is in an appropriate range and the storage stability is further excellent.
The total solid content concentration is adjusted, if necessary, by concentration and dilution with the above organic solvent. The composition of the present invention was applied to a silicon wafer, SiO ₂ wafer, Si
When applying to a substrate such as N wafer, spin coating,
A coating method such as a dipping method, a roll coating method, or a spraying method is used.

The film thickness at this time is a dry film thickness of about 0.05 to 2.5 μm for a single coating, and a film thickness of about 0.1 to 5.0 μm for a second coating. be able to. Then, dry at room temperature or 80~600
A glassy or giant polymer insulating film can be formed by heating and drying at a temperature of about C for about 5 to 240 minutes. As a heating method at this time, a hot plate, an oven, a furnace or the like can be used, and a heating atmosphere is under air, a nitrogen atmosphere,
It can be performed in an argon atmosphere, under vacuum, under reduced pressure with controlled oxygen concentration, and the like. The coating film can also be formed by irradiating with an electron beam or an ultraviolet ray. Further, in order to control the curing speed of the coating film, it is possible to heat stepwise or select an atmosphere such as nitrogen, air, oxygen, or reduced pressure, if necessary. The silica-based film of the present invention thus obtained usually has a film density of 0.
35-1.2 g/cm ³ , preferably 0.4-1.1 g
/Cm ³ , more preferably 0.5 to 1.0 g/cm ^3.
Is. When the film density is less than 0.35 g/cm ³ , the mechanical strength of the coating film is lowered, while when it exceeds 1.2 g/cm ³ , a low relative dielectric constant cannot be obtained. Furthermore, the relative dielectric constant of the silica-based film of the present invention is usually 3.2 to 1.2, preferably 3.0 to 1.5, and more preferably 2.7 to 1.8.

The interlayer insulating film thus obtained has a small relative dielectric constant of the coating film and a small residual stress of the coating film.
LSI and system LS because of their excellent mechanical strength
I, DRAM, SDRAM, RDRAM, D-RDRA
An interlayer insulating film for a semiconductor element such as M and an etching stopper film, a protective film such as a surface coating film for a semiconductor element, an intermediate layer in a semiconductor manufacturing process using a multilayer resist, an interlayer insulating film for a multilayer wiring board, and a liquid crystal display element. It is useful for applications such as protective films and insulating films.

[0054]

EXAMPLES The present invention will be described more specifically below with reference to examples. However, the following description generally shows an example of the embodiment of the present invention, and the present invention is not limited to the description by no particular reason. In the examples and comparative examples, parts and% are parts by weight and% by weight, respectively, unless otherwise specified. Also,
Various evaluations were performed as follows.

Radius of inertia Measured by gel permeation chromatography (GPC) (refractive index, viscosity, light scattering measurement) method under the following conditions. Sample solution: A hydrolyzed condensate of a silane compound was diluted with methanol containing 10 mM LiBr so as to have a solid content concentration of 0.25% and used as a sample solution for GPC (refractive index, viscosity, light scattering measurement). did. Device: Tosoh Corp., GPC system model GPC-8020 Tosoh Corp., column Alpha5000/3000 Viscotech, viscosity detector and light scattering detector model T-60 dual meter Carrier solution: 10 mM LiBr Containing methanol Carrier delivery rate: 1 ml/min Column temperature: 40°C

Weight average molecular weight (Mw) It was measured by a gel permeation chromatography (GPC) method under the following conditions. Sample: Prepared by dissolving 1 g of the hydrolyzed condensate in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemicals was used. Device: High-temperature high-performance gel permeation chromatogram (Model 150-C ALC/GPC) manufactured by US Waters Co., Ltd. Column: SHODEX A-80M manufactured by Showa Denko KK
(Length 50 cm) Measurement temperature: 40° C. Flow rate: 1 cc/min

A composition sample was applied onto a silicon wafer having a relative dielectric constant of 8 inches by a spin coating method, dried on a hot plate at 90° C. for 3 minutes and at 200° C. for 3 minutes in a nitrogen atmosphere, and further 445. The substrate was baked for 25 minutes on a nitrogen atmosphere hot plate at ℃. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for measuring relative permittivity. The sample at a frequency of 100 kHz,
HP1645 manufactured by Yokogawa/Hewlett-Packard Co., Ltd.
The relative dielectric constant of the coating film at room temperature was measured by the CV method using a 1B electrode and an HP4284A precision LCR meter.

Residual stress A composition sample was applied onto an 8-inch silicon wafer by spin coating, dried on a hot plate at 90° C. for 3 minutes and in a nitrogen atmosphere at 200° C. for 3 minutes, and further at 445° C. The substrate was baked for 25 minutes on the nitrogen atmosphere hot plate of. The sample is FLX- manufactured by Tencor Co., Ltd.
The residual stress of the coating film was measured using a 2320 thin film stress measuring device and evaluated according to the following criteria. ◯: The residual stress of the coating film is less than 60 MPa ×: The residual stress of the coating film exceeds 60 MPa

Mechanical Strength (Elastic Modulus) A composition sample was applied onto an 8-inch silicon wafer by spin coating, and the substrate was dried on a hot plate at 90° C. for 3 minutes and nitrogen atmosphere at 200° C. for 3 minutes. Then, the substrate was baked on a nitrogen atmosphere hot plate at 445° C. for 25 minutes. The obtained film was measured by a continuous stiffness measurement method using Nanoindenter XP (manufactured by Nano Instruments).

Synthesis Example 1 273.01 g of methyltrimethoxysilane and 86.14 of tetramethoxysilane in a quartz separable flask.
g and tetrakis(acetylacetonato)titanium (0.0092 g) were dissolved in propylene glycol monoethyl ether (101 g) and stirred with a three-one motor to stabilize the solution temperature at 55°C. Next, a mixed solution of 225.52 g of ion-exchanged water and 263.00 g of propylene glycol monoethyl ether was added to the solution over 1 hour. Then, after reacting at 55° C. for 4 hours, 48.12 g of acetylacetone was added, the reaction was continued for 30 minutes, and the reaction solution was cooled to room temperature. 50°C
A solution containing methanol and water was removed from the reaction solution by 227 g by evaporation to obtain a reaction solution A. The weight average molecular weight of the thus obtained condensate and the like was 1,230.

Synthesis Example 2 205.50 g of methyltrimethoxysilane and 85.51 of tetramethoxysilane were placed in a quartz separable flask.
g, propylene glycol monoethyl ether 426
After dissolving in g, stir with a three-one motor,
The solution temperature was stabilized at 50°C. Then succinic acid 0.63
182 g of ion-exchanged water having g dissolved therein was added to the solution over 1 hour. Then, after reacting at 50° C. for 3 hours, the reaction solution was cooled to room temperature. A solution containing methanol was removed from the reaction solution at 50° C. by evaporation in an amount of 360 g to obtain a reaction solution B. The weight average molecular weight of the thus obtained condensate and the like was 1,400.

Synthesis Example 3 A quartz separable flask was charged with distilled ethanol 370.
g, distilled propylene glycol monopropyl ether 2
00 g, 160 g of ion-exchanged water, and 90 g of a 10% aqueous methylamine solution were added and uniformly stirred. 136 g of methyltrimethoxysilane and 2 parts of tetraethoxysilane were added to this solution.
09 g of the mixture was added. The reaction was carried out for 2 hours while keeping the solution at 55°C. 300 g of propylene glycol monopropyl ether was added to this solution, and then 5
The solution was concentrated to 10% (completely hydrolyzed condensate) using an evaporator at 0° C., and then 1% of acetic acid was added.
0% propylene glycol monopropyl ether solution 1
0 g was added to obtain a reaction liquid C. The radius of gyration of the condensate and the like thus obtained was 15.4 nm.

Synthesis Example 4 A quartz separable flask was charged with distilled ethanol 428.
g, 215 g of ion-exchanged water and 15.6 g of a 25% tetramethylammonium hydroxide aqueous solution were added, and the mixture was stirred uniformly. Methyltrimethoxysilane 4 in this solution
A mixture of 0.8 g and tetraethoxysilane 61.4 g was added. The reaction was carried out for 2 hours while keeping the solution at 60°C. 300 g of propylene glycol monopropyl ether was added to this solution, and then the solution was concentrated to 10% (completely hydrolyzed condensate equivalent) using an evaporator at 50° C., and then 10% propylene glycol monopropyl maleic acid was added. 20 g of an ether solution was added to obtain a reaction solution D. The radius of gyration of the condensate and the like thus obtained was 20.4 nm.

Example 1 A 4-liter flask having a 3 L capacity equipped with a thermometer, a cooling condenser, a dropping funnel and a stirrer was replaced with argon gas and then dried with 1 L of tetrahydrofuran.
And 60 g of magnesium metal were charged, and bubbling was performed with argon gas. To this, 150 g of methyltrichlorosilane was slowly added from a dropping funnel while stirring at 20°C. After completion of dropping, stirring was continued at room temperature for another 3 hours. The polymer was precipitated by pouring into 15 L of ice water.
The polymer produced was thoroughly washed with water and vacuum dried to obtain 60 g of a polymer. The weight average molecular weight of the silicon polymer thus obtained was 700.

Example 2 20 g of the polymer obtained in Synthesis Example 1 was mixed with LiAlH ₄
10 g was added to a solution suspended in 300 ml of dry tetrahydrofuran, and the mixture was reacted at room temperature for 5 hours. next,
The reaction mixture was poured into 15 L of ice water to precipitate the produced polymer. The produced polymer was thoroughly washed with water and vacuum dried to obtain 12 g of a brown solid polymer. The weight average molecular weight of the silicon polymer thus obtained is
It was 680.

Example 3 A 4-liter flask having a capacity of 3 L equipped with a thermometer, a cooling condenser, a dropping funnel and a stirrer was replaced with argon gas and then dried with 1 L of tetrahydrofuran.
And 60 g of magnesium metal were charged, and bubbling was performed with argon gas. While stirring at 20° C., a mixed solution of 113 g of 2-norbornyltrichlorosilane and 85 g of tetrachlorosilane was slowly added from a dropping funnel. After completion of dropping, stirring was continued at room temperature for another 3 hours. Then, to this solution, 10 g of LiAlH ₄ was added to a solution obtained by suspending in 300 ml of dry tetrahydrofuran, and reacted at room temperature for 5 hours. Next, the reaction mixture was poured into 15 L of ice water to precipitate the produced polymer. The resulting polymer was thoroughly washed with water and vacuum dried to obtain 65 g of a brown solid polymer. The weight average molecular weight of the silicon polymer thus obtained was 1,100.

Example 4 0.5 g of the polymer obtained in Example 1 was dissolved in 9.5 g of tetrahydrofuran. Add the reaction solution A100 to this solution.
g and stirred well. The solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a film-forming composition of the present invention. The obtained composition was applied onto a silicon wafer by spin coating. The relative permittivity of the coating film at room temperature was 2.64, and when the residual stress of the coating film was evaluated, it was a low value of 45 MPa. The elastic modulus of the coating film was measured and found to be 7.3 GPa, which was excellent in mechanical strength.

Examples 5 to 9 Evaluations were performed in the same manner as in Example 4 except that the silicon polymer and the reaction solution shown in Table 1 were used. The evaluation results are also shown in Table 1.

[0069]

[Table 1]

Comparative Example 1 A coating film was evaluated in the same manner as in Example 1 except that only the reaction solution A obtained in Synthesis Example 1 was used. Table 2 shows the evaluation results
Shown in.

Comparative Example 2 The coating film was evaluated in the same manner as in Example 1 except that only the reaction solution B obtained in Synthesis Example 2 was used. Table 2 shows the evaluation results
Shown in.

[0072]

[Table 2]

[0073]

According to the present invention, by using a film forming composition containing a specific silicon polymer, the relative dielectric constant of the coating film is small, the residual stress of the coating film is small, and the mechanical strength is improved. It is possible to provide an excellent film-forming composition (interlayer insulating film material).

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 183/14 C09D 183/14 H01L 21/312 H01L 21/312 C 21/316 21/316 G F term (reference) 4J035 JA01 JB03 LA03 LB01 4J038 DL021 DL022 DL071 DL072 DL161 DL162 HA066 KA04 MA07 NA11 NA21 PA19 PB09 5F058 AA02 AC03 AF04 AH02 BA04 BC05 BF46 BH01 BJ02

Claims (3)

[Claims] 1. A compound represented by the following general formula (1):
A compound represented by the following general formula (2) and the following general
At least one selected from the group of compounds represented by formula (3)
One type of silane compound is used for metallic lithium and metallic magnesia.
Silicon obtained by reacting with either or both
Polymer R^Ten _eSiX_4-e (1) (In the formula, R^TenIs a hydrogen atom or a monovalent organic group, X is halo
The gen atom and e represent an integer of 1 to 2. ) SiX_Four (2) (In the formula, X represents a halogen atom.) R¹¹ _fX_3-fSi-(R¹³)_h-SiX_3-gR¹² _g (3) [wherein R¹¹~R¹³Are the same or different and each has a single
Organic groups, f to g are the same or different, an integer of 0 to 2,
R¹³Is an oxygen atom, a phenylene group or -(CH₂)_n-In
A group represented (where n is an integer of 1 to 6), X is
Halogen atom, h is 0 or 1. ] And (B) a compound represented by the following general formula (4):
The compound represented by the general formula (5) and the following general formula
At least 1 selected from the group of compounds represented by (6)
Hydrolysis and condensation of certain silane compounds
Thing R_a Si(OR¹ )_4-a (4) (In the formula, R is a hydrogen atom, a fluorine atom, or a monovalent organic compound.
Group, R¹ Represents a monovalent organic group, and a represents an integer of 1 to 2. ) Si(OR² )_Four (5) (In the formula, R² Represents a monovalent organic group. ) R³ _b(R^FourO)_3-bSi-(R⁷)_d-Si(OR^Five)_3-c R⁶ _c ...(6) [wherein R³ ~R⁶ Are the same or different and each has a single
Organic groups, b to c are the same or different, an integer of 0 to 2,
R⁷Is an oxygen atom, a phenylene group or -(CH₂) _m-In
The group represented (where m is an integer from 1 to 6), d is
Indicates 0 or 1. ] Membrane form characterized by containing
Composition for use. 2. An insulating film forming material comprising the film forming composition according to claim 1. 3. (A) At least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2) and a compound represented by the following general formula (3). An insulating film forming material comprising a silicon polymer obtained by reacting one kind of silane compound with metallic lithium and/or metallic magnesium. R ¹⁰ _e SiX _4-e (1) (In the formula, R ¹⁰ represents a hydrogen atom or a monovalent organic group, X represents a halogen atom, and e represents an integer of 1 to 2.) SiX ₄ · .... (2) (wherein, X represents a halogen _{^{atom.) R 11 f X 3-}} f Si- (R 13) h -SiX 3-g R 12 g ····· (3) [ In the formula, R ^{11 to} R ¹³ are the same or different, each is a monovalent organic group, and f to g are the same or different, an integer of 0 to 2,
R ¹³ is an oxygen atom, a phenylene group or a group represented by —(CH ₂ ) _n — (where n is an integer of 1 to 6), X is a halogen atom, and h is 0 or 1. ]