JP2002060691A - Film-forming composition and insulating film-forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film-forming composition and an insulating film-forming material useful as interlayer insulating film materials for semiconductor elements, etc., each of which yields a coated film having a relative dielectric constant showing little temperature dependence and a silica film having an excellent crack resistance and mechanical properties. SOLUTION: The film-forming composition contains a condensate obtained by hydrolyzing and condensing at least one compound chosen from the group consisting of compounds of the formula: RaSi(OR1)4-a, the formula: Si(OR2)4 and the formula: R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c (wherein R is H, F or a monovalent organic group; R1-R6 are each a monovalent organic group; R7 is O, a phenylene group or -(CH2)n-; (a) is 1-2; (b) and (c) are each an integer of 0-2; (d) is 0 or 1; and (n) is 1-6) (A) in the presence of a nitrogen-containing onium salt compound and (B) in the presence of a metal chelate catalyst and/or an acid catalyst, and (C) an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a film-forming composition, and more particularly, as a material for an interlayer insulating film in a semiconductor device or the like, the temperature dependence of the relative dielectric constant of a coating film is small.
The present invention relates to a film-forming composition and a material for forming an insulating film capable of forming a silica-based film having excellent crack resistance and mechanical strength.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is often used as an interlayer insulating film in a semiconductor device or the like. And in recent years,
In order to form a more uniform interlayer insulating film, S
A coating-type insulating film called a OG (Spin on Glass) film, which is mainly composed of a hydrolysis product of tetraalkoxylan, has also been used. Further, with the increase in integration of semiconductor elements and the like, an interlayer insulating film having a low relative dielectric constant and mainly containing polyorganosiloxane called organic SOG has been developed. In particular, with higher integration and multilayering of semiconductor devices and the like, better electrical insulation between conductors is required, and therefore, the relative dielectric constant of the coating is lower and the relative dielectric constant of the coating film is less dependent on temperature. Therefore, an interlayer insulating film material having excellent crack resistance and mechanical strength has been required.

As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensing alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (Japanese Patent Application Laid-Open No. H5-263045; 5-315
319) and a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-340219, JP-A-11-34022).
0) has been proposed, but the materials obtained by these methods are not stable in the nature of the reaction product, the temperature dependence of the relative dielectric constant of the coating film is large, and there are variations in crack resistance and mechanical strength. Therefore, it was not suitable for industrial production.

[0004]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly to a temperature-dependent dielectric constant of a coating film as an interlayer insulating film in a semiconductor device or the like. It is an object of the present invention to provide a film-forming composition which is low in crack resistance and excellent in mechanical strength and an insulating film-forming material obtained from the composition.

[0005]

The present invention relates to (A) a compound represented by the following general formula (1) (hereinafter referred to as "compound (1)").
), A compound represented by the following general formula (2) (hereinafter, referred to as
At least one silane compound selected from the group consisting of “compound (2)”) and a compound represented by the following general formula (3) (hereinafter, referred to as “compound (3)”) in the presence of an alkali catalyst Hydrolyzed and condensed hydrolyzed condensate,
(B) at least one silane compound 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) Is hydrolyzed and condensed in the presence of a metal chelate catalyst and / or an acid catalyst, and a condensed hydrolysis product R _a Si (OR ¹ ) _4-a ... (1) (where R is hydrogen An atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is an integer of 1 to 2.) Si (OR ² ) ₄ (2) ² represents a monovalent organic group.) R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR ⁵ ) _3-c R ⁶ _c (3) [ In the formula, R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, b to c are the same or different, and an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
(Where n is an integer of 1 to 6), d
Represents 0 or 1. ] (C) A film-forming composition comprising an organic solvent. Next, the present invention relates to a material for forming an insulating film comprising the above-described composition for forming a film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the hydrolyzed condensate of the components (A) and (B) refers to the above compounds (1) to (1).
It is a hydrolyzate or condensate of at least one silane compound selected from the group (3). Here, in the hydrolysis,
Compounds (1) to (C) constituting the above components (A) and (B)
Not all of the R ¹ O—, R ² O—, R ⁴ O— and R ⁵ O— groups contained in (3) need to be hydrolyzed, for example, only one is hydrolyzed. What 2
One or more of them may be hydrolyzed, or a mixture thereof. The condensation in the components (A) and (B) means that the silanol groups of the hydrolyzates of the compounds (1) to (3) constituting the components (A) and (B) condense to form Si—O—Si In the present invention, it is not necessary that all of the silanol groups are condensed, and the present invention also includes a mixture of a small number of silanol groups condensed and a mixture of those having different degrees of condensation. This is the concept.

[0007] (A) and (B) hydrolysis condensate (A) and (B) hydrolysis condensate are formed by catalyzing at least one silane compound selected from the group of compounds (1) to (3). Is obtained by hydrolysis and condensation in the presence of Compound (1): In the above general formula (1), R and R
The ¹ monovalent organic group, an alkyl group, an aryl group,
Examples include an allyl group and a glycidyl group. In the general formula (1), R is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and preferably have 1 to 1 carbon atoms.
5, and these alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), examples of the aryl group 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 (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane and tri-silane. 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;

[0009] 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,
Ethyl triphenoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-n-propoxy silane, vinyl tri-iso-propoxy silane, vinyl tri-n-butoxy silane, vinyl tri-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-
Butyl tri-tert-butoxy silane, t-butyl triphenoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tri-n-propoxy silane, phenyl tri-iso-propoxy silane, phenyl tri-n-butoxy silane, phenyl tri -Sec-butoxysilane, phenyltri-tert-
Butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ
-Aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-trifluoropropyltrimethoxysilane, gamma-trifluoropropyltrimethylsilane Ethoxysilane and the like;

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, Di-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 compound (1) are methyltrimethoxysilane, methyltriethoxysilane,
Methyltri-n-propoxysilane, methyltri-is
o-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Vinyl triethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, and the like. These may be used alone or in combination of two or more.

Compound (2): In the above formula (2), examples of the monovalent organic group represented by R ² include the same organic groups as in the above formula (1). Specific examples of the compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxysilane. , Tetra-tert-butoxysilane, tetraphenoxysilane and the like.

Compound (3) In the above formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as in the above formula (1). . In the general formula (3), 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-1,1,3,3-tetraphenyldisiloxane, 1,
Examples thereof include 3-diphenoxy-1,1,3,3-tetraphenyldisiloxane.

Among them, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane,
1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,1
3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,
Preferred examples include 3-dimethoxy-1,1,3,3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane.

In the general formula (3), the compound in which d is 0 includes hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,1
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-1,1,1
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, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1,1
2,2-tetraphenyldisilane and the like can be mentioned.

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-1,1,1,
Preferred examples include 2,2-tetraphenyldisilane and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane.

Further, in the general formula (3), R ⁷ is-
Examples of the compound having a group represented by (CH ₂ ) _n — include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, and 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-tert-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,
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 (1)
As (1) to (3), one or more kinds can be used.

When hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3), 0.1 mol / mol of the compounds (1) to (3) is used.
It is preferred to use more than 5 mol and up to 150 mol of water, particularly preferred to add more than 0.5 mol and 130 mol of water.

In producing the hydrolyzed condensates (A) and (B) of the present invention, at least one silane compound selected from the group of the compounds (1) to (3) is hydrolyzed and condensed. In this case, a specific catalyst is used.

Specifically, (A) Production of hydrolysis condensate
And (B) a hydrolyzed condensate.
Of metal chelate and acid catalysts
Use one or the other. As a nitrogen-containing onium salt compound
Are ammonium hydroxide, ammonium chloride, ammonium bromide
Monium, ammonium iodide, ammonium fluoride, nitrate
Ammonium sulfate, ammonium sulfate, ammonium hydrogen sulfate
, Ammonium phosphate, ammonium carbonate, pheno
Ammonium, ammonium acetate, and adipic acid
Monium, ammonium alginate, ammonium benzoate
, Ammonium sulfate, ammonium citrate, formic acid
Ammonium, ammonium bicarbonate, ammonium phthalate
, Ammonium salicylate, ammonium succinate
, Ammonium maleate, ammonium propionate
, Ammonium butanoate, ammonium pentanate,
Ammonium hexanoate, ammonium heptanoate,
Ammonium butanoate, ammonium nonanoate, decane
Ammonium oxalate, ammonium oxalate, methylmalon
Ammonium, ammonium sebacate, gallic acid
Ammonium, ammonium butyrate, ammonium nitrate
Ammonium, arachidonic acid, ammonium shikimate
System, ammonium 2-ethylhexanoate, ammonium oleate
Ammonium, ammonium stearate, linoleic acid
Ammonium, ammonium linoleate, p-amino ammonium
Ammonium benzoate, p-toluenesulfonic acid ammonium
, Ammonium benzenesulfonate, monochloro vinegar
Ammonium, ammonium dichloroacetate, trichloro
Ammonium acetate, ammonium trifluoroacetate,
Ammonium malonate, ammonium sulfonate, fuma
Ammonium luate, ammonium tartrate, itaconic acid
Ammonium, ammonium mesaconate, citraconate
Ammonium, ammonium malate, ammonium glutarate
Nium: methyl ammonium hydroxide, methyl ammonium chloride
Ammonium, methyl ammonium bromide, methyl ammonium iodide
Ammonium, methyl ammonium fluoride, methyl ammonium nitrate
Ammonium, methyl ammonium sulfate, methyl ammonium sulfate
, Methyl ammonium phosphate, methyl ammonium carbonate
, Phenol methyl ammonium, methyl acetate
Ammonium, methylammonium adipate, algin
Ammonium methylate, methylammonium benzoate,
Methyl ammonium sulfate, methyl ammonium citrate
, Methyl ammonium formate, methyl ammonium bicarbonate
, Ammonium ammonium phthalate, methyl salicylate
Ammonium, methyl ammonium succinate, maleic
Ammonium methylate, methyl ammonium propionate
System, methyl ammonium butanoate, methyl ammonium pentanate
Ammonium, methyl ammonium hexanoate, heptane
Ammonium methylate, methyl ammonium octoate
Methyl, ammonium ammonium nonanoate, methyl ammonium decanoate
Monium, methyl ammonium oxalate, methyl malon
Ammonium, methyl ammonium sebacate
, Methyl ammonium gallate, methyl ammonium butyrate
Ammonium, methylammonium melitate, arachidonic acid
Tyl ammonium, methyl ammonium shikimate, 2-
Methyl ammonium hexanoate, methyl oleate
Ammonium, methyl ammonium stearate,
Methyl ammonium oleate, methyl linoleate
Monium, methyl ammonium p-aminobenzoate, p
-Methyl ammonium toluenesulfonate, benzenes
Methyl ammonium sulfonate, methyl monoacetate
Ammonium, methylammonium dichloroacetate, tric
Methyl ammonium roloacetate, methyl trifluoroacetate
Ammonium, methyl ammonium malonate, sulfone
Ammonium methylate, methylammonium fumarate,
Methyl ammonium tartrate, methyl ammonium itaconate
Ium, methylammonium mesaconate, citraconate
Tyl ammonium, methyl ammonium malate, glue
Methyl ammonium tallate; dimethyl ammonium hydroxide
Dimethyl ammonium chloride, dimethyl ammonium bromide
, Dimethyl ammonium iodide, dimethyl ammonium fluoride
Monium, dimethyl ammonium nitrate, dimethyl ammonium sulfate
Ammonium, dimethyl ammonium hydrogen sulfate, diphosphate
Methyl ammonium, dimethyl ammonium carbonate,
Nordimethylammonium, dimethylammonium acetate
Dimethylammonium adipate, dimethyl ammonium alginate
Tyl ammonium, dimethyl ammonium benzoate, sulfuric acid
Ammonium citrate, dimethyl ammonium citrate
Dimethyl ammonium formate, dimethyl ammonium bicarbonate
Monium, dimethyl ammonium phthalate, salicylic acid
Dimethyl ammonium, dimethyl ammonium succinate
Dimethyl ammonium maleate, dipropionate
Methyl ammonium, dimethyl ammonium butanoate,
Dimethyl ammonium pentanoate, dimethyl hexanoate
Ammonium, dimethyl ammonium heptanoate, octane
Dimethyl ammonium tannate, dimethyl ammonium nonanoate
, Dimethyl ammonium decanoate, dimethyl oxalate
Thilammonium, dimethylammonium methylmalonate
Dimethylammonium sebacate, dimethic gallate
Luammonium, dimethyl ammonium butyrate, benefits
Dimethyl ammonium, arachidonic acid dimethyl ammonium
, Dimethyl ammonium shikimate, 2-ethyl
Dimethyl ammonium oxalate, dimethyl oleate
Ammonium, dimethyl ammonium stearate, reno
Dimethyl ammonium oleate, dimethyl linoleate
Ammonium, dimethylammonium p-aminobenzoate
Dimethyl ammonium p-toluenesulfonate,
Dimethylammonium sulfonate, monochloro vinegar
Ammonium dimethylammonium salt
, Dimethyl ammonium trichloroacetate, torif
Dimethyl ammonium fluoroacetate, Dimethyl malonate
Ammonium, dimethyl ammonium sulfonate, fumar
Dimethylammonium, dimethylammonium tartrate
Dimethyl ammonium itaconate, dimesameconate
Thilammonium, dimethyl ammonium citraconic acid
Dimethyl ammonium malate, glutaric acid dimethyl
Ammonium, trimethylammonium hydroxide, chloride
Trimethylammonium, trimethylammonium bromide
System, trimethyl ammonium iodide, trimethyl ammonium fluoride
Ammonium, trimethylammonium nitrate, trime sulfate
Tyl ammonium, trimethyl ammonium hydrogen sulfate,
Trimethylammonium phosphate, trimethylammonium carbonate
, Phenoltrimethylammonium, triacetate
Methyl ammonium, trimethylammonium adipate
Trimethylammonium alginate, tribenzoic acid
Methyl ammonium, trimethyl ammonium sulfate,
Trimethylammonium formate, trimethylammonium formate
, Trimethyl ammonium bicarbonate, phthalic acid
Limethyl ammonium, trimethyl ammonium salicylate
And trimethylammonium succinate, maleate
Limethylammonium, trimethylammonium propionate
, Trimethylammonium butanoate, pentanoic acid
Trimethylammonium, trimethylammonium hexanoate
, Trimethylammonium heptanoate, octane
Ammonium trimethylammonate, trimethylammonium nonanoate
, Trimethylammonium decanoate, oxalate
Limethylammonium, trimethylan methyl malonate
Monium, trimethylammonium sebacate, gallic
Trimethylammonium, trimethylammonium butyrate
System, trimethylammonium melitate, arachidonic acid
Trimethyl ammonium, trimethyl ammonium shikimate
, Trimethylammonium 2-ethylhexanoate,
Trimethylammonium oleate, Tristearate
Methyl ammonium, trimethylammonium linoleate
Trimethylammonium linoleate, p-amino
Trimethylammonium benzoate, p-toluenesulfo
Trimethylammonium phosphate, tribenzenesulfonate
Methyl ammonium, trimethylammonium monochloroacetate
, Trimethylammonium dichloroacetate, Trik
Trimethylammonium loloacetate, trifluoroacetic acid
Limethylammonium, trimethylammonium malonate
Trimethylammonium sulfonate, trimethyl fumarate
Methyl ammonium, trimethyl ammonium tartrate,
Trimethylammonium itaconate, trime mesaconate
Thilammonium, trimethylammonium citraconic acid
, Trimethylammonium malate, triglutarate
Methyl ammonium; ethyl ammonium hydroxide, chloride
Ethyl ammonium, ethyl ammonium bromide, ethyl iodide
Tillammonium, ethylammonium fluoride, nitric acid
Tilammonium, ethylammonium sulfate, hydrogen sulfate
Ethyl ammonium, ethyl ammonium phosphate, carbonic acid
Ethyl ammonium, phenol ethyl ammonium,
Ethyl ammonium acetate, ethyl ammonium adipate
, Ethyl ammonium alginate, ethyl benzoate
Ammonium, ethyl ammonium sulfate, ethyl citrate
Ammonium, ethyl ammonium formate, hydrogen bicarbonate
Ammonium, ethyl ammonium phthalate, salicy
Ethyl ammonium oxalate, ethyl ammonium succinate
, Ethyl ammonium maleate, ethyl propionate
Ammonium, ethyl ammonium butanoate, penta
Ethyl ammonium phosphate, ethyl ammonium hexanoate
System, ethyl ammonium heptanoate, ethyl octanoate
Ammonium, ethyl ammonium nonanoate, decanoic acid
Ethyl ammonium, ethyl ammonium oxalate,
Ethyl ammonium tilmaronate, ethyl acetate sebacate
Ammonium, ethyl ammonium gallate, ethyl butyrate
Ammonium, ethyl ammonium melitate, arachi
Ethyl ammonium donate, ethyl ammonium shikimate
System, ethyl ammonium 2-ethylhexanoate, Olay
Ethyl ammonium, ethyl ammonium stearate
, Ethyl ammonium linoleate, linoleate
Tylammonium, ethyl ammonium p-aminobenzoate
, Ethyl ammonium p-toluenesulfonate,
Ethylammonium sulfonate, monochloroacetic acid
Ethyl ammonium, ethyl ammonium dichloroacetate
System, ethyl ammonium trichloroacetate, trifluoro
Ethyl ammonium acetate, ethyl ammonium malonate
System, ethyl ammonium sulfonate, ethyl ammonium fumarate
Ammonium, ethyl ammonium tartrate, itaconic acid
Tyl ammonium, ethyl ammonium mesaconate,
Ethyl ammonium traconic acid, ethyl ammonium malate
, Ethylammonium glutarate; diethyl hydroxide
Ammonium, diethylammonium chloride, diem bromide
Tilammonium, diethylammonium iodide, fluoride
Diethyl ammonium, diethyl ammonium nitrate, sulfuric acid
Ammonium diethyl sulfate, diethyl ammonium hydrogen sulfate
, Diethylammonium phosphate, diethylammonium carbonate
Phenol, diethylammonium, diethyl acetate
Ammonium, diethylammonium adipate,
Diethyl ammonium luginate, diethyl benzoate
Monium, diethylammonium sulfate, diethyl citrate
Luammonium, diethylammonium formate, hydrogen carbonate
Diethylammonium, diethylammonium phthalate
System, diethylammonium salicylate, diethyl succinate
Ammonium, diethylammonium maleate,
Diethylammonium lopionate, diethylabutanoate
Ammonium, diethyl ammonium pentanate, hexa
Diethyl ammonium phosphate, diethyl heptanoate
Ammonium, diethyl ammonium octoate, nonanoic acid di
Ethyl ammonium, diethyl ammonium decanoate,
Diethyl ammonium oxalate, methyl malonate
Ammonium, diethylammonium sebacate,
Diethylammonium succinate, diethylammonium butyrate
System, diethylammonium melitate, diarachidonic acid
Ethyl ammonium, diethyl ammonium shikimate,
Diethyl ammonium 2-ethylhexanoate, olein
Ammonium diethylate, diethylammonium stearate
, Diethylammonium linoleate, linolein
Ammonium diethylate, diethyl p-aminobenzoate
Ammonium, diethyl ammonium p-toluenesulfonate
Ammonium, diethylammonium benzenesulfonate,
Diethylammonium dichloroacetate
Thilammonium, diethylammonium trichloroacetate
System, diethylammonium trifluoroacetate, malonic acid
Diethyl ammonium, diethyl ammonium sulfonate
System, diethyl ammonium fumarate, diethyl ammonium tartrate
Ammonium, diethylammonium itaconate, mesaco
Ammonium diethylate, diethylanthrate citraconic acid
Monium, diethylammonium malate, glutaric acid
Diethylammonium; triethylammonium hydroxide
Triethylammonium chloride, triethylammonium bromide
Monium, triethylammonium iodide, trifluoride
Tyl ammonium, triethyl ammonium nitrate, sulfuric acid
Triethylammonium, triethylammonium hydrogen sulfate
, Triethylammonium phosphate, triethyl carbonate
Ammonium, phenol triethyl ammonium, vinegar
Triethylammonium, triethylammonium adipate
Monium, triethylammonium alginate, benzoic
Triethylammonium, triethylammonium sulfate
System, triethylammonium citrate, triethyl formate
Ammonium, triethylammonium bicarbonate, lid
Triethylammonium luate, triethyl ammonium salicylate
Ammonium, triethylammonium succinate, male
Triethylammonium, Triethylpropionate
Ammonium, triethylammonium butanoate, pen
Triethylammonium titanate, triethylhexanoate
Ammonium, triethylammonium heptanoate,
Triethylammonium butanoate, triethyl nonanoate
Ammonium, triethylammonium decanoate,
Triethylammonium oxalate, triethyl methylmalonate
Ammonium, triethylammonium sebacate,
Triethylammonium gallate, triethylanbutyrate
Monium, triethylammonium melitate, arachi
Triethyl ammonium donate, triethyl ammonium shikimate
Ammonium, triethylammonium 2-ethylhexanoate
, Triethylammonium oleate, stearin
Triethylammonium linoleate
Monium, triethylammonium linoleate, p-
Triethylammonium aminobenzoate, p-toluene
Triethylammonium sulfonate, benzene sulfone
Ammonium triethylate, triethyl monochloroacetate
Ammonium, triethylammonium dichloroacetate,
Triethylammonium trichloroacetate, trifluoro
Triethyl ammonium acetate, triethyl ammonium malonate
Monium, triethylammonium sulfonate, fumar
Ammonium triethylate, triethylammonium tartrate
, Triethylammonium itaconate, mesaconic acid
Triethyl ammonium, triethyl citrate
Monium, triethylammonium malate, glutar
Triethylammonium acid; tripropylammonium hydroxide
, Tripropylammonium chloride, Triprobromide
Pyrammonium, tripropylammonium iodide,
Tripropylammonium nitride, tripropylan nitrate
Monium, tripropylammonium sulfate, hydrogen sulfate
Lipropyl ammonium, tripropyl ammonium phosphate
, Tripropyl ammonium carbonate, phenol tri
Propyl ammonium, tripropyl ammonium acetate
, Tripropyl ammonium adipate, alginic acid
Tripropyl ammonium, tripropyl benzoate
Monium, tripropylammonium sulfate, citric acid
Lipropylammonium, tripropylammonium formate
Tripropyl ammonium bicarbonate, triphthalic phthalate
Propyl ammonium, tripropyl ammonium salicylate
, Tripropylammonium succinate, maleic
Ammonium tripropylate, tripropionate propionate
Ammonium, tripropylammonium butanoate,
Tripropylammonium pentanoate, trihexanoate
Propyl ammonium, tripropyl heptanoate
, Tripropylammonium octoate, nonane
Ammonium tripropylate, tripropyl ammonium decanoate
Ammonium, tripropylammonium oxalate, methyl
Tripropyl ammonium lumaronate, tri sebacate
Propyl ammonium, tripropyl ammonium gallate
, Tripropylammonium butyrate, trimeritate
Propyl ammonium, tripropyl arachidonic acid
Monium, tripropylammonium shikimate, 2-d
Tripropylammonium tylhexanoate, oleic acid
Tripropyl ammonium, tripropyl stearate
Ammonium, tripropylammonium linoleate,
Tripropyl ammonium linoleate, p-amino ammonium
Tripropyl ammonium benzoate, p-toluene sulfo
Ammonium tripropylate, benzenesulfonic acid
Lipropyl ammonium, tripropyl monochloroacetate
Ammonium, tripropylammonium dichloroacetate
System, tripropylammonium trichloroacetate, torif
Tripropylammonium fluoroacetate, triplon malonate
Ropylammonium, tripropylammonium sulfonate
, Tripropylammonium fumarate, tritartrate
Propyl ammonium, tripropylammonate itaconate
, Tripropylammonium mesaconate, citrus
Tripropyl ammonium conate, tripropyl malate
Luammonium, tripropylammonium glutarate
Tributyl ammonium hydroxide, tributyl ammonium chloride
Ammonium, tributylammonium bromide, trib iodide
Tyl ammonium, tributyl ammonium fluoride, nitrate
Ammonium tributylate, ammonium tributyl sulfate
System, tributylammonium hydrogen sulfate, tributyl phosphate
Ammonium, tributylammonium carbonate, pheno
Tributylammonium, tributylammonium acetate
, Tributylammonium adipate, alginic acid
Tributyl ammonium, tributyl ammonium benzoate
, Tributylammonium sulfate, Tributyl citrate
Luammonium, tributylammonium formate, carbonated water
Tributyl ammonium hydrogen, tributyl ammonium phthalate
, Tributylammonium salicylate, succinic acid
Tributyl ammonium, tributyl ammonium maleate
, Tributylammonium propionate, butane
Ammonium tributylate, tributyl ammonium pentanate
Monium, tributylammonium hexanoate, hepta
Tributyl ammonium octoate, tributyl ammonium octoate
Ammonium, tributylammonium nonanoate, decane
Tributyl ammonium oxalate, tributyl ammonium oxalate
, Tributylammonium methylmalonate, SEVA
Tributyl ammonium succinate, tributyl ammonium gallate
Ammonium, tributylammonium butyrate, melitic acid
Tributylammonium, tributylan arachidonic acid
Monium, tributylammonium shikimate, 2-ethyl
Tributylammonium hexanoate, trioleate
Butyl ammonium, tributyl ammonium stearate
, Tributylammonium linoleate, linolein
Ammonium tributyl, tri-p-aminobenzoate
Tyl ammonium, tributyl p-toluenesulfonate
Ammonium, tributylammonium benzenesulfonate
, Tributyl ammonium monochloroacetate, dichloromethane
Tributylammonium roacetate, Trib trichloroacetate
Thilammonium, tributylammonium trifluoroacetate
, Tributylammonium malonate, sulfonic acid
Tributyl ammonium, tributyl ammonium fumarate
, Tributylammonium tartrate, triitaconate
Butyl ammonium, tributyl ammonium mesaconate
System, tributylammonium citraconic acid, malic acid
Libutyl ammonium, tributyl ammonium glutarate
Um; tetramethylammonium hydroxide, tetramethyl chloride
Tyl ammonium, tetramethyl ammonium bromide, iodine
Tetramethylammonium fluoride, tetramethylammonium fluoride
Monium, tetramethylammonium nitrate, tetrasulfate
Methyl ammonium, tetramethylammonium hydrogen sulfate
System, tetramethylammonium phosphate, tetramethyl carbonate
Luammonium, phenol tetramethylammonium
System, tetramethylammonium acetate, tetraadipate
Methyl ammonium, tetramethylammonium alginate
, Tetramethylammonium benzoate, tetrasulfate
Methyl ammonium, tetramethyl ammonium citrate
Tetramethylammonium formate, hydrogen carbonate
Tylammonium, tetramethylammonium phthalate
Tetramethylammonium salicylate,
Tramethylammonium, tetramethylan maleate
Monium, tetramethylammonium propionate,
Tetramethylammonium tannate, tetramepentanoate
Thilammonium, tetramethylammonium hexanoate
System, tetramethylammonium heptanoate, octanoic acid
Tetramethyl ammonium, tetramethyl ammonium nonanoate
Monium, Tetramethylammonium decanoate, Shu
Ammonium tetramethylammonate, tetramethyl methylmalonate
Thilammonium, tetramethylammonium sebacate
Tetramethylammonium gallate, tetrame butyrate
Thilammonium, tetramethylammonium melitate
System, tetramethylammonium arachidonic acid, shikimic acid
Tetramethylammonium, 2-ethylhexanoic acid tet
Lamethylammonium, tetramethylammonium oleate
, Tetramethylammonium stearate, Reno
Tetramethylammonium oleate, Tetralinoleate
Methyl ammonium, tetramethyl p-aminobenzoate
Ammonium, tetramethyl ammonium p-toluenesulfonate
Ammonium, benzenesulfonic acid tetramethylammonium
Ium, tetramethylammonium monochloroacetate, dik
Tetramethyl ammonium roloacetate, trichloroacetic acid
Tramethylammonium, tetramethyl trifluoroacetate
Ammonium, tetramethylammonium malonate,
Tetramethyl ammonium sulfonate, tetra fumarate
Methyl ammonium, tetramethylammonium tartrate
, Tetramethylammonium itaconate, mesaconic acid
Tetramethyl ammonium, tetramethyl citraconic acid
Ammonium, tetramethylammonium malate,
Tetramethylammonium rutharate; Tetraethyl hydroxide
Ammonium, tetraethylammonium chloride, bromide
Tetraethylammonium, tetraethylammonium iodide
, Tetraethylammonium fluoride, tetraethyl nitrate
Tillammonium, tetraethylammonium sulfate, sulfuric acid
Tetraethylammonium hydrogen acid, tetraethyl phosphate
Ammonium, tetraethylammonium carbonate, pheno
Tetraethylammonium, tetraethylammonium acetate
Monium, tetraethylammonium adipate, aluminum
Tetraethylammonium formate, tetraethyl benzoate
Ammonium, tetraethylammonium sulfate, que
Tetraethylammonium formate, tetraethylammonium formate
Monium, tetraethylammonium bicarbonate, phthalate
Ammonium tetraethyl salicylate
Ammonium, tetraethylammonium succinate,
Tetraethylammonium oleate, Tetopropionate
Laethyl ammonium, tetraethyl ammonium butanoate
, Tetraethylammonium pentanoate, hexane
Ammonium tetraethyl, tetraethyl heptanoate
Ammonium, tetraethylammonium octoate,
Tetraethylammonium nonanoate, Tetraethyl decanoate
Tylammonium, tetraethylammonium oxalate
System, tetraethylammonium methylmalonate, SEBASHI
Tetraethylammonium acid, tetraethyl gallate
Ammonium, tetraethylammonium butyrate,
Tetraethylammonium tomate, arachidonic acid tetraet
Thilammonium, tetraethylammonium shikimate
Tetraethylammonium 2-ethylhexanoate,
Tetraethylammonium oleate, Te stearate
Traethylammonium, tetraethylanole linoleate
Monium, tetraethylammonium linoleate, p
Tetraethylammonium aminobenzoate, p-toluene
Tetraethylammonium enesulfonate, benzenes
Tetraethylammonium sulfonate, monochloroacetic acid
Traethylammonium, tetraethyl acetate dichloroacetate
Ammonium, tetraethylammonium trichloroacetate
System, tetraethylammonium trifluoroacetate, malo
Ammonium tetraethylammonium, sulfonic acid tetraethyl
Ammonium, tetraethylammonium fumarate,
Tetraethylammonium tartrate, tetraethyl itaconate
Thilammonium, tetraethylammonium mesaconate
System, tetraethylammonium citraconic acid, malic acid
Tetraethyl ammonium, tetraethyl glutarate
Ammonium; tetrapropylammonium hydroxide, chloride
Tetrapropylammonium, tetrapropylanbromide
Monium, tetrapropylammonium iodide,
Trapropylammonium, tetrapropylammonium nitrate
Ammonium, tetrapropylammonium sulfate, hydrogen sulfate
Trapropylammonium, tetrapropylan phosphate
Monium, tetrapropylammonium carbonate, phenol
Tetrapropyl ammonium, tetrapropyl ammonium acetate
Ammonium, tetrapropylammonium adipate,
Tetrapropylammonium alginate, Tetobenzoate
Lapropyl ammonium, tetrapropyl ammonium sulfate
, Tetrapropyl ammonium citrate, tet
Lapropylammonium, tetrapropylan bicarbonate
Monium, tetrapropylammonium phthalate, sari
Tetrapropyl ammonium citrate, tetrap succinate
Ropylammonium, tetrapropylammonate maleate
, Tetrapropylammonium propionate,
Tetrapropylammonium tannate, tetrapentanoate
Propyl ammonium, tetrapropylan hexanoate
Monium, tetrapropylammonium heptanoate,
Tetrapropylammonium butanoate, tetranonanoate
Propyl ammonium, tetrapropyl ammonium decanoate
Ium, tetrapropylammonium oxalate, methyl
Tetrapropylammonium malonate, tetose sebacate
Lapropylammonium, tetrapropylan gallate
Monium, tetrapropyl ammonium butyrate, benefits
Ammonium tetraacrylate, tetrap arachidonic acid
Ropylammonium, tetrapropylammonium shikimate
Um, tetrapropylammonium 2-ethylhexanoate
System, tetrapropylammonium oleate, stearyl
Ammonium tetrapropylate, tetrap linoleate
Ropylammonium, tetrapropyl linoleate
Monium, tetrapropylammonium p-aminobenzoate
And p-toluenesulfonic acid tetrapropyl ammonium
Ium, tetrapropylammonium benzenesulfonate
System, tetrapropylammonium monochloroacetate, dik
Tetrapropylammonium loroacetate, trichloroacetic acid
Tetrapropylammonium, tetratrifluoroacetate
Propylammonium, tetrapropylammonate malonate
, Tetrapropylammonium sulfonate, Fuma
Tetrapropylammonium luate, tetrapropyl tartrate
Luammonium, tetrapropylammonium itaconate
, Tetrapropylammonium mesaconate, citraco
Ammonium tetrapropylate, tetrapromalate
Pyrammonium, tetrapropylammonium glutarate
: Tetrabutylammonium hydroxide, Tetrabu chloride
Tyl ammonium, tetrabutyl ammonium bromide, iodine
Tetrabutylammonium fluoride, tetrabutylammonium fluoride
Monium, tetrabutylammonium nitrate, tetrasulfate
Butyl ammonium, tetrabutylammonium hydrogen sulfate
System, tetrabutylammonium phosphate, tetrabutyl carbonate
Luammonium, phenol tetrabutylammonium
Tetrabutylammonium acetate, tetraadipate
Butylammonium, tetrabutylammonium alginate
, Tetrabutylammonium benzoate, tetrasulfate
Butyl ammonium, tetrabutyl ammonium citrate
, Tetrabutylammonium formate, tetrabu bicarbonate
Tylammonium, tetrabutylammonium phthalate
Tetrabutylammonium salicylate,
Trabutylammonium, tetrabutylan maleate
Monium, tetrabutylammonium propionate,
Tetrabutylammonium tannate, tetrabupentanoate
Thilammonium, tetrabutylammonium hexanoate
System, tetrabutylammonium heptanoate, octanoic acid
Tetrabutylammonium, tetrabutylannonate
Monium, Tetrabutylammonium decanoate, Shu
Ammonium tetrabutylate, tetramale methyl malonate
Tylammonium, tetrabutylammonium sebacate
Tetrabutylammonium gallate, tetrabutyrate
Thilammonium, tetrabutylammonium melitate
System, tetrabutylammonium arachidonic acid, shikimic acid
Tetrabutylammonium, 2-ethylhexanoic acid tet
Labutylammonium, tetrabutylammonium oleate
, Tetrabutylammonium stearate, Reno
Tetrabutylammonium oleate, tetralinoleate
Butyl ammonium, tetrabutyl p-aminobenzoate
Ammonium, tetrabutyl toluene p-toluenesulfonate
Nummonium, tetrabutylammonium benzenesulfonate
Ium, tetrabutylammonium monochloroacetate, dik
Tetrabutylammonium roloacetate, tetrachloroacetate
Trabutylammonium, tetrabutyl acetate trifluoroacetate
Ammonium, tetrabutylammonium malonate,
Tetrabutyl ammonium sulfonate, tetra fumarate
Butyl ammonium, tetrabutylammonium tartrate
System, tetrabutyl ammonium itaconate, mesaconic acid
Tetrabutylammonium, tetrabutyl citrate
Ammonium, tetrabutylammonium malate,
Tetrabutylammonium rutalate; trimethyl hydroxide
Benzyl ammonium, trimethylbenzylammonium chloride
, Trimethylbenzylammonium bromide, iodide
Limethylbenzylammonium, trimethylbenfluoride
Zylammonium, trimethylbenzylammonium nitrate
System, trimethylbenzyl ammonium sulfate, hydrogen sulfate
Limethylbenzylammonium, trimethylbenphosphate
Zylammonium, trimethylbenzylammonium carbonate
Phenol, trimethylbenzylammonium, acetic acid
Trimethylbenzylammonium, trimethyl adipate
Rubenzyl ammonium, trimethyl benzyl alginate
Luammonium, trimethylbenzylammonium benzoate
, Trimethylbenzylammonium sulfate, citric acid
Trimethylbenzylammonium, trimethylbenformate
Zylammonium, trimethylbenzylammonium bicarbonate
, Trimethylbenzylammonium phthalate
Trimethylbenzylammonium lithate, succinate
Limethylbenzyl ammonium, trimethyl maleate
Benzyl ammonium, trimethylbenzene propionate
Luammonium, trimethylbenzyl ammonium butanoate
And trimethylbenzylammonium pentanoate,
Trimethylbenzyl ammonium xanate, heptanoic acid
Trimethylbenzyl ammonium, trimethyl octanoate
Rubenzyl ammonium, trimethylbenzyl nonanoate
Ammonium, trimethylbenzylammonium decanoate
Trimethylbenzyl ammonium oxalate, methyl
Trimethylbenzyl ammonium malonate, sebacic acid
Trimethylbenzyl ammonium, trimethyl gallate
Benzyl ammonium, trimethylbenzyl ammonium butyrate
, Trimethylbenzylammonium melitate,
Trimethylbenzyl ammonium arachidonic acid, shikimi
Trimethylbenzylammonium acid, 2-ethylhexa
Trimethylbenzylammonium phosphate, trioleate
Methylbenzylammonium, trimethyl stearate
Benzyl ammonium, trimethylbenzyl linoleate
Ammonium, trimethylbenzylammonium linoleate
Ium, trimethylbenzylammonium p-aminobenzoate
And p-toluenesulfonate trimethylbenzyl acetate
Ammonium, trimethylbenzyl benzenesulfonate
Nmonium, trimethylbenzylammonium monochloroacetate
And trimethylbenzylammonium dichloroacetate
Trimethylbenzylammonium trichloroacetate,
Trimethylbenzylammonium trifluoroacetate
Trimethylbenzylammonium lonate, sulfonate
Limethylbenzylammonium, trimethylbefumarate
Ammonium diammonium, trimethylbenzylammonium tartrate
, Trimethylbenzylammonium itaconate,
Trimethylbenzyl ammonium mesaconate, Citraco
Trimethylbenzyl ammonium phosphate, Trime malate
Tylbenzyl ammonium, trimethylben glutarate
Diammonium;

Ethanol ammonium hydroxide, ethanol ammonium chloride, ethanol ammonium bromide, ethanol ammonium iodide, ethanol ammonium fluoride, ethanol ammonium nitrate, ethanol ammonium sulfate, ethanol ammonium hydrogen sulfate, ethanol ammonium phosphate, ethanol ammonium carbonate, phenol Ethanol ammonium, ethanol ammonium acetate, ethanol ammonium adipate,
Ethanolammonium alginate, ethanolammonium benzoate, ethanolammonium sulfate, ethanolammonium citrate, ethanolammonium formate, ethanolammonium hydrogen carbonate, ethanolammonium phthalate, ethanolammonium salicylate, ethanolammonium succinate, ethanolammonium maleate, ethanolammonium propionate Ethanolammonium butanoate, ethanolammonium pentanoate, ethanolammonium hexanoate, ethanolammonium heptanoate, ethanolammonium octoate, ethanolammonium nonanoate, ethanolammonium decanoate, ethanolammonium oxalate, ethanolammonium methylmalonate, sebacic acid Ethanol ammonium, ethanol ammonium gallic acid, butyric acid ethanol ammonium, mellitic acid ethanol ammonium, ethanol ammonium arachidonic acid, ethanol ammonium shikimic acid, 2-ethylhexanoic acid in ethanol ammonium,
Ethanolammonium oleate, ethanolammonium stearate, ethanolammonium linoleate, ethanolammonium linoleate, ethanolammonium p-aminobenzoate, ethanolammonium p-toluenesulfonate, ethanolammonium benzenesulfonate, ethanolammonium monochloroacetate, ethanol dichloroacetate Ammonium, ethanol ammonium trichloroacetate, ethanol ammonium trifluoroacetate, ethanol ammonium malonate, ethanol ammonium sulfonate, ethanol ammonium fumarate, ethanol ammonium tartrate,
Ethanolammonium itaconic acid, ethanolammonate mesaconate, ethanolammonium citraconic acid, ethanolammonium malate, ethanolammonium glutarate; diethanolammonium hydroxide, diethanolammonium chloride, diethanolammonium bromide, diethanolammonium iodide, diethanolammonium fluoride, nitric acid nitrate Diethanol ammonium, diethanol ammonium sulfate, diethanol ammonium hydrogen sulfate, diethanol ammonium phosphate, diethanol ammonium carbonate, phenol diethanol ammonium, diethanol ammonium acetate,
Diethanol ammonium adipate, diethanol ammonium alginate, diethanol ammonium benzoate, diethanol ammonium sulfate, diethanol ammonium citrate, diethanol ammonium formate,
Diethanol ammonium bicarbonate, diethanol ammonium phthalate, diethanol ammonium salicylate, diethanol ammonium succinate, diethanol ammonium maleate, diethanol ammonium propionate, diethanol ammonium butanoate, diethanol ammonium pentanoate, diethanol ammonium hexanoate, diethanol ammonium heptanoate, octane Ammonium diethanolate, diethanolammonium nonanoate, diethanolammonium decanoate, diethanolammonium oxalate, diethanolammonium methylmalonate, diethanolammonium sebacate, diethanolammonium gallate, diethanolammonium butyrate, diethanolammonium melitate Diethanol ammonium arachidonic acid, diethanol ammonium shikimate, diethanol ammonium 2-ethylhexanoate, diethanol ammonium oleate, diethanol ammonium stearate, diethanol ammonium linoleate, diethanol ammonium linoleate, diethanol ammonium p-aminobenzoate, p-toluene sulfone Ammonium diethanolate, diethanolammonium benzenesulfonate, diethanolammonium monochloroacetate, diethanolammonium dichloroacetate,
Diethanolammonium trichloroacetate, diethanolammonium trifluoroacetate, diethanolammonium malonate, diethanolammonium sulfonate, diethanolammonium fumarate, diethanolammonium tartrate, diethanolammonium itaconate, diethanolammonium mesaconate, diethanolammonium citraconic acid, diethanolammonium malate, Diethanol ammonium glutarate;
Triethanol ammonium hydroxide, triethanol ammonium chloride, triethanol ammonium bromide, triethanol ammonium iodide, triethanol ammonium fluoride, triethanol ammonium nitrate, triethanol ammonium sulfate, triethanol ammonium hydrogen sulfate, triethanol ammonium phosphate , Triethanol ammonium carbonate, phenol triethanol ammonium, triethanol ammonium acetate,
Triethanol ammonium adipate, triethanol ammonium alginate, triethanol ammonium benzoate, triethanol ammonium sulfate, triethanol ammonium citrate, triethanol ammonium formate, triethanol ammonium bicarbonate, triethanol ammonium phthalate, triethanol ammonium salicylate, Triethanol ammonium succinate, triethanol ammonium maleate, triethanol ammonium propionate, triethanol ammonium butanoate, triethanol ammonium pentanoate, triethanol ammonium hexanoate, triethanol ammonium heptanoate, triethanol ammonium octanoate, nonanoic acid Triethanol ammonium, decane Triethanol ammonium, triethanol ammonium oxalate, triethanol ammonium methyl malonate, triethanol ammonium sebacate, triethanol ammonium gallate, triethanol ammonium butyrate, triethanol ammonium melitate, triethanol ammonium arachidonic acid, triethanol shikimate Ammonium, triethanolammonium 2-ethylhexanoate, triethanolammonium oleate, triethanolammonium stearate, triethanolammonium linoleate, triethanolammonium linoleate, p
-Triethanolammonium aminobenzoate, triethanolammonium p-toluenesulfonate, triethanolammonium benzenesulfonate, triethanolammonium monochloroacetate, triethanolammonium dichloroacetate, triethanolammonium trichloroacetate, triethanolammonium trifluoroacetate, malon Triethanol ammonium sulfonic acid, triethanol ammonium sulfonic acid, triethanol ammonium fumarate, triethanol ammonium tartrate, triethanol ammonium itaconate, triethanol ammonium mesaconate, triethanol ammonium citraconic acid, triethanol ammonium malate, triethanol glutarate Ammonium and the like. Tetraalkyl ammonium hydroxide is most preferred. These may be used alone or in combination of two or more.

Examples of the metal chelate catalyst include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, -N-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxybis (acetylacetonate) titanium , Di-n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n
-Butoxybis (acetylacetonato) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, Mono-n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris (acetylacetonate) titanium, mono-n-butoxy tris (acetylacetonate) 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 (ethyl acetoacetate) titanium, tri-i-propoxy 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-i-propoxy bis (ethyl acetoacetate) Chita , Di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetoacetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) Acetate) titanium, mono-n-propoxy tris (ethyl acetoacetate)
Titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-
t-butoxy-tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris ( Titanium chelate compounds such as acetylacetonato) mono (ethylacetoacetate) 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, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxybis (acetylacetonato) zirconium, di- n-butoxy
Bis (acetylacetonate) zirconium, di-se
c-butoxybis (acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (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 (acetylacetonate) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy.
Mono (ethylacetoacetate) 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, Jee
n-propoxybis (ethylacetoacetate) zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetate) Acetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, mono-n-propoxy.
Tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate)
Zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium,
Mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate)
Zirconium chelate compounds such as zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium; tris (acetylacetonate) aluminum, tris (ethylacetoacetate)
An aluminum chelate compound such as aluminum; and the like, preferably a titanium or aluminum chelate compound, particularly preferably a titanium chelate compound. One or more of these metal chelate catalysts may be used at the same time.

Examples of the acid catalyst include, 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, heptanoic, octanoic, nonanoic, decanoic, oxalic, maleic, methylmalonic, adipic, sebacic, gallic, butyric, melitic, arachidonic, shikimic, 2-ethylhexanoic 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, Organic acids such as a hydrolyzate of phthalic anhydride can be mentioned, and organic carboxylic acids can be mentioned as more preferable examples. One or more of these acid catalysts may be used simultaneously.

The amount of the above-mentioned catalyst to be used is as follows:
R in (3)¹ O-group, R^Two O-group, R ^Four An O-group and
R^Five Usually, based on 1 mol of the total amount of the group represented by the O- group,
0.00001 to 10 mol, preferably 0.00005
５5 mol. If the amount of catalyst used is within the above range,
There is little risk of polymer precipitation or gelation during the reaction. Ma
In the present invention, the compounds (1) to (3) are hydrolyzed.
The temperature at the time is usually 0 to 100 ° C., preferably 15 to 100 ° C.
80 ° C.

When the compounds (1) to (3) are converted into a complete hydrolyzed condensate, the compound (2) is 5 to 75% by weight, preferably 5 to 75% by weight, based on the total amount of the compounds (1) to (3). Is 10 to 70% by weight, more preferably 15 to 70% by weight
It is. Further, the compounds (1) and / or (3)
95 to 25% by weight, preferably 90 to 30% by weight, more preferably 85 to 3% by weight, based on the total amount of compounds (1) to (3)
0% by weight. Compound (2) is the compound (1)-
When the amount is 5 to 75% by weight based on the total amount of (3), 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 condensate refers to R ¹ O—, R ² O—, R ⁴ O in compounds (1) to (3).
- group and R ⁵ O-group 100% hydrolyzed to the SiOH
It is a group that becomes a group and is further completely condensed to form a siloxane structure. Further, the components (A) and (B) are preferably hydrolyzed condensates of the compound (1) and the compound (2) because the resulting composition has better storage stability.

The amount of component (B) used in the film-forming composition is 5 to 2,000 parts by weight, more preferably 7 to 2000 parts by weight, per 100 parts by weight of component (A) (in terms of complete hydrolysis and condensate). 1800 parts by weight. (B) The amount of the component added is 5
If the amount is less than parts by weight, the crack resistance of the coating film may be insufficient, and if it exceeds 2,000 parts by weight, the temperature dependency of the relative dielectric constant may be deteriorated.

(C) Solvent The film-forming composition of the present invention comprises the component (A) and the component (B), and usually comprises (C) a solvent represented by the following general formula (4): R ¹⁵ O (R ¹⁷ 0) _g R ¹⁶ (4) (R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a monovalent organic group selected from CH ₃ CO—. R ¹⁷ represents an alkylene group, and g represents an integer of 1 to 2.). In the general formula (4), the alkyl group of R ¹⁵ and R ¹⁶ is a methyl group, an ethyl group, an n-propyl group, an I-propyl group, a butyl group and the like, and the alkylene group of R ¹⁷ is an ethylene group, n- Examples thereof include a propylene group and an isopropylene group. Specific examples of the solvent represented by the general formula (4) include propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl 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, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene Glycol diacetate, dipropylene glycol diacetate, propylene glycol; ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol diacetate, ethylene glycol, etc. In particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate are preferable. These can be used alone or in combination of two or more.

The film-forming composition of the present invention may further contain the following organic solvent in addition to the solvent represented by the general formula (4).

As the organic solvent used in the present invention, for example, n-pentane, i-pentane, n-hexane, i-pentane
Hexane, n-heptane, i-heptane, 2,2,4-
Aliphatic hydrocarbon solvents such as trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene,
Aromatic hydrocarbon solvents such as n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene and trimethylbenzene; acetone, methylethylketone, 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, trimethyl nonanone, Ketone solvents such as cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-butyl Ether, n- hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-
Methyl dioxolane, dioxane, dimethyl dioxane, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethoxytriglycol, tetraethylene glycol di-n-
Ether solvents such as butyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; 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, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-oxalate Ester solvents such as -butyl, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide; N-diethylformamide,
Acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-
Nitrogen-containing solvents such as methylpyrrolidone; dimethyl sulfide,
Diethyl sulfide, thiophene, tetrahydrothiophene,
Examples thereof include sulfur-containing solvents such as dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These can be used alone or in combination of two or more.

Other Additives The film-forming composition obtained by the present invention further comprises β-diketone, colloidal silica, colloidal alumina, organic polymer, surfactant, silane coupling agent, radical generator, triazene Components such as compounds and nitrogen onium salt compounds may be added.

Examples of the β-diketone include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, and 2,4-hexane. Nonanion,
3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro- Examples thereof include 2,4-heptanedione, and more preferred are acetylacetone, 2,4-hexanedione, 2,4-heptanedione, and 3,5-heptanedione. These may be used alone or in combination of two or more.

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

Compounds having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure,
Examples include a polytetramethylene oxide structure and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene poly Oxypropylene block copolymers, ether compounds such as polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid alkanolamide sulfates and the like Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as 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 -
And represents a group represented by CH ₂ CH (CH ₃ ) O—, wherein j is 1 to
90, k is a number from 10 to 99, and l is a number from 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,
And ether-type compounds such as those described above as more preferable examples. These may be used alone or in combination of two or more.

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a fluorine-based surfactant, a silicone-based surfactant, and the like. Examples of the surfactant include a surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant, and preferably a fluorine-based surfactant and a silicone-based surfactant.

As the fluorine-based surfactant, for example, 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- (perfluorooctanesulfone Amido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt,
At least one of terminal, main chain and side chain of perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, etc. And a fluorine-based surfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the position (1). Commercially available products are MegaFac F142D, F172, F173, F1
83 (manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC-430, and FC-431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, SC-103, SC-104, 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 fluorosurfactants. Among them, the above MegaFac F172, BM-1000, BM-11
00, NBX-15 is particularly preferred.

As the silicone surfactant, for example, SH7PA, SH21PA, SH30PA, ST94P
A (All are Dow Corning Toray Silicone Co., Ltd.)
And the like can be used. Among them, the above S
H28PA and SH30PA are particularly preferred. The amount of the surfactant to be used is generally 0.0001 to 10 parts by weight relative to the component (A) (completely hydrolyzed condensate). These may be used alone 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-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-
Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

As the radical generator, for example, isobutyryl peroxide, α, α'bis (neodecanylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxy Dicarbonate,
1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl par Oxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy ) Hexane, 1-cyclohexyl-
1-methylethyl peroxy 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-
Butylperoxycyclohexyl) 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-hexylperoxybenzoate, 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-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like can be mentioned. The mixing amount of the radical generator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. These may be used alone or in combination of two or more.

As the triazene compound, for example, 1,
2-bis (3,3-dimethyltriazenyl) benzene,
1,3-bis (3,3-dimethyltriazenyl) benzene, 1,4-bis (3,3-dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis ( 3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3-dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3 ,
3-dimethyltriazenylphenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) benzene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl)- 9,9-bis [3-methyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3- Phenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-propenyl-4- (3,3 -Dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro-4- (3,3-dimethyltriazenyl) phenyl] Fluorene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3
-Dimethyltriazenyl) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl)
Phenyl] fluorene and the like. These may be used alone or in combination of two or more. Examples of the nitrogen onium salt compound include the same compounds as those used in the production of the above-mentioned component (A).

The total solid content of the composition of the present invention thus obtained is preferably 2 to 30% by weight,
It is appropriately adjusted according to the purpose of use. When the total solid content 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 more excellent. The adjustment of the total solid concentration is performed by concentration and dilution with the component (C), if necessary.

When the composition of the present invention is applied to a silicon wafer, Si
When coating on a substrate such as an O ₂ wafer or a SiN wafer, a coating method such as spin coating, dipping, roll coating, or spraying is used. The film thickness at this time is about 0.05 to 2.5 μm in a single coating as a dry film thickness, and a coating film with a thickness of about 0.1 to 5.0 μm in a double coating can be formed. . Then, it is dried at room temperature or at a temperature of about 80 to 600 ° C., usually for 5 to 240
By heating and drying for about a minute, a glassy or macromolecular insulating film can be formed. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used. As a heating atmosphere, the heating is performed in the atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like. Can be. Further, the coating film can be formed by irradiating an electron beam or an ultraviolet ray. Further, in order to control the curing speed of the coating film, if necessary, heating may be performed stepwise, or an atmosphere such as nitrogen, air, oxygen, or reduced pressure may be selected. Further, the relative dielectric constant of the silica-based film of the present invention is usually 3.2 to 1.2, preferably 3.1 to 1.8, and more preferably 3.0 to 2.0.

The interlayer insulating film thus obtained has low temperature dependence of the relative dielectric constant of the coating film and is excellent in crack resistance and mechanical strength.
Interlayer insulating films for semiconductor devices such as RAM, SDRAM, RDRAM, D-RDRAM, etc., protective films such as etching stopper films and CMP stopper films, surface coat films of semiconductor devices, intermediate layers and multilayers in semiconductor manufacturing processes using multilayer resists It is useful for applications such as interlayer insulating films for wiring boards, protective films and insulating films for liquid crystal display elements.

[0044]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the following description generally shows an embodiment of the present invention, and the present invention is not limited by the description without any particular reason. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, respectively, unless otherwise specified. Also,
Various evaluations were performed as follows.

The radius of inertia was measured by gel permeation chromatography (GPC) (refractive index, viscosity, light scattering measurement) under the following conditions. Sample solution: A hydrolyzed condensate of a silane compound is diluted with methanol containing 10 mM LiBr so as to have a solid concentration of 0.25%. did. Equipment: Tosoh Corporation, GPC system model GP
C-8020 Tosoh Corporation, column Alpha5000 / 300
0 Viscotec Co., Ltd., viscosity detector and light scattering detector Model T-60 dual meter Carrier solution: methanol containing 10 mM LiBr Carrier sending rate: 1 ml / min Column temperature: 40 ° C.

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

A composition sample is applied on an 8-inch silicon wafer using a temperature dependence of the relative dielectric constant by a spin coating method, and the substrate is dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was further baked on a hot plate at 440 ° C. in a nitrogen atmosphere for 25 minutes. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for relative dielectric constant measurement. The sample is taken 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 and 250 ° C. was measured by a CV method using a 1B electrode and an HP4284A precision LCR meter.

A composition sample was applied on an 8-inch silicon wafer by crack coating using a spin coating method, and the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was baked for 25 minutes in a nitrogen atmosphere hot plate. At this time, the thickness of the coating film was 1.2 μm. A part of the obtained coating film was scratched with a knife, and 100% in pure water.
Soaked for hours. A knife scar in the coating film was observed with a microscope, and evaluated according to the following criteria. ：: No crack propagation was observed. ×: Propagation of cracks observed

Mechanical Strength (Hardness) A composition sample was applied on an 8-inch silicon wafer by spin coating, and the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was baked on a hot plate at 440 ° C. for 25 minutes in a nitrogen atmosphere. The obtained film was measured by a continuous stiffness measuring method using a nano indenter XP (manufactured by Nano Instruments).

Synthesis Example 1 In a quartz separable flask, 276.01 g of methyltrimethoxysilane and 86.14 of tetramethoxysilane were used.
g and tetrakis (acetylacetonato) titanium 0.0092 g were dissolved in propylene glycol monoethyl ether 101 g, and then 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 further performed for 30 minutes, and the reaction solution was cooled to room temperature. 50 ℃
227 g of a solution containing methanol and water was removed from the reaction solution by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 1,230.

Synthesis Example 2 In a quartz separable flask, 205.50 g of methyltrimethoxysilane and 85.51 of tetramethoxysilane were used.
g of propylene glycol monoethyl ether 426
g, then stirred with a three-one motor,
The solution temperature was stabilized at 50 ° C. Next, succinic acid 0.63
182 g of ion-exchanged water in which g was dissolved 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. At 50 ° C., 360 g of a solution containing methanol was removed from the reaction solution by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 1,400.

Synthesis Example 3 Distilled ethanol 428 was placed in a quartz separable flask.
g, 215 g of ion-exchanged water and 15.6 g of a 25% aqueous solution of tetramethylammonium hydroxide were added and uniformly stirred. Add methyltrimethoxysilane 4 to this solution.
A mixture of 0.8 g and 61.4 g of tetraethoxysilane was added. The reaction was performed for 2 hours while maintaining 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% (complete hydrolyzed condensate) using an evaporator at 50 ° C., and then 10% propylene glycol monopropyl maleate was added. 20 g of an ether solution was added to obtain a reaction solution. The radius of inertia of the condensate and the like thus obtained was 20.4 nm.

Reference Synthesis Example 1 A reaction solution was obtained in the same manner as in Synthesis Example 1 except that diacetone alcohol was used instead of propylene glycol monoethyl ether. The weight average molecular weight of the condensate and the like thus obtained is 700
Met. Reference synthesis example 2 In synthesis example 3, except that diacetone alcohol was used instead of propylene glycol monoethyl ether, the same as in synthesis example 1,
A reaction solution was obtained. The radius of inertia of the condensate and the like thus obtained was 10.4 nm.

Example 1 20 g of the reaction solution was added to 50 g of the reaction solution obtained in Synthesis Example 1 and sufficiently stirred. This 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 on a silicon wafer by spin coating. The relative dielectric constant of the coating film at room temperature was 2.78, and the relative dielectric constant at 250 ° C. was 2.70, and the temperature dependence of the relative dielectric constant was small. No crack propagation was observed even when the coating film was immersed in water. Also, when the hardness of the coating film was measured, it was 1.7 GPa, which was excellent in mechanical strength.

Examples 2 to 8 Evaluations were made in the same manner as in Example 1 except that the reaction solutions shown in Table 1 were used. The evaluation results are also shown in Table 1.

[0056]

[Table 1]

Comparative Example 1 The coating film was evaluated in the same manner as in Example 1 except that only the reaction solution 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 obtained in Synthesis Example 2 was used. Table 2 shows the evaluation results.
Shown in Reference Example 4 50 g of the reaction solution obtained in Comparative Synthesis Example 1 and Comparative Synthesis Example 2
The coating film was evaluated in the same manner as in Example 1 except that 20 g of the reaction solution obtained in was used. Table 2 shows the evaluation results.

[0058]

[Table 2]

[0059]

According to the present invention, a hydrolyzed alkoxysilane polymer synthesized with a nitrogen onium salt compound, a hydrolyzed alkoxysilane polymer synthesized with a metal chelate catalyst and / or an acid catalyst, a specific glycol solvent The use of a film-forming composition containing: provides a film-forming composition (material for an interlayer insulating film) in which the temperature dependence of the relative dielectric constant of the coating film is small and crack resistance and mechanical strength are excellent. It is possible.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kinji Yamada 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 4J038 DL021 DL031 DL041 DL071 DL161 GA01 HA096 HA306 HA326 HA366 HA416 HA476 JA02 JA05 JA26 JA27 JA33 JA37 JA39 JA42 JA56 JB01 JB06 JB13 JB27 JC02 JC11 JC13 JC14 JC37 JC38 KA04 KA06 MA08 MA10 MA14 NA11 NA21 PA19 PB09 5F058 AA02 AB04 AB06 AC03 AF04 AG01 AH02

Claims (9)

[Claims] (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) One kind of silane compound is hydrolyzed and condensed in the presence of a nitrogen-containing onium salt compound, (B) a compound represented by the following general formula (1), and a compound represented by the following general formula (1) Hydrolysis and condensation of at least one silane compound selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (3) in the presence of a metal chelate catalyst and / or an acid catalyst: Compound R _a Si (OR ¹ ) _4-a (1) (where 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 shows two _{^{integers.) Si (OR 2) 4}} ····· (2) ( wherein, R ² is Indicating the valency of the organic ^{_{radical.) R 3 b (R 4}} O) 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ····· (3) wherein, R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, b to c are the same or different, an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
(Where n is an integer of 1 to 6), d
Represents 0 or 1. ] (C) A film-forming composition comprising an organic solvent. 2. The film-forming composition according to claim 1, wherein the hydrolytic condensate of the component (A) has a radius of gyration of 5 to 50 nm by a GPC method. 3. The film-forming composition according to claim 1, wherein the weight-average molecular weight of the hydrolyzed condensate of the component (B) by GPC is from 500 to 20,000. 4. The film forming composition according to claim 1, wherein the alkali catalyst is an amine and / or an amine salt. 5. The film forming composition according to claim 1, wherein the metal chelate catalyst is a titanium-containing chelate compound and the acid catalyst is an organic carboxylic acid. 6. The use ratio of the component (A) and the component (B) is as follows:
The membrane according to any one of claims 1 to 5, wherein the amount of the component (B) is 5 to 2,000 parts by weight (converted to a completely hydrolyzed condensate) based on 100 parts by weight of the component (A) (converted to a completely hydrolyzed condensate). Forming composition. 7. A solvent represented by the general formula (4): R ¹⁵ O (R ¹⁷⁰ ) _g R ¹⁶ ... (4) (R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, Wherein R ¹⁷ represents a monovalent organic group selected from alkyl groups of formulas 1 to 4 or CH ₃ CO—, R ¹⁷ represents an alkylene group, and g represents an integer of 1 to 2.) A composition for forming a film. 8. The composition according to claim 1, wherein the component (C) is ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate. , Dipropylene glycol monoalkyl ether,
A film-forming composition comprising at least one member selected from the group consisting of dipropylene glycol dialkyl ether and dipropylene glycol monoalkyl ether acetate. 9. An insulating film forming material comprising the film forming composition according to claim 1.