JP2003163209A - Manufacturing method of composition for film formation, the composition for the film formation, forming method for film and silica-based film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for film formation capable of forming a silica-based film having good filtering of a solution and a small number of foreign matters in the solution as an inter-layer insulation film material in a semiconductor element or the like. <P>SOLUTION: The solution containing polysiloxane and an organic solvent is concentrated by a thin film vacuum evaporation method in a manufacturing method of the composition for the film formation. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a film-forming composition and a film-forming composition obtained by the method, and more specifically, as a material for an interlayer insulating film in a semiconductor device, etc. The present invention relates to a film-forming composition which is good and can form a silica-based film with a small number of foreign substances in a solution.

[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
For the purpose of forming a more uniform interlayer insulating film, S
A coating type insulating film called a OG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has also been used. In addition, with the high integration of semiconductor elements and the like, an interlayer insulating film called organic SOG having a low relative dielectric constant containing polyorganosiloxane as a main component has been developed. In particular, with higher integration and multi-layering of semiconductor elements, there has been a demand for an interlayer insulating film material that has a lower dielectric constant and a smaller number of foreign substances in the coating film to prevent short circuits between wirings. There is. As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensing an alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of the alkoxysilane (JP-A-5-263045, 315319) or a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-
340219 and 11-340220) have been proposed, but the materials obtained by these methods are purified by a general evaporative concentration operation, and the concentration increases the number of foreign substances in the solution. There was a problem of reducing the reliability of the.

[0003]

The present invention relates to a method for producing a film-forming composition and a film-forming composition using the same for solving the above problems, and more specifically, to an interlayer in a semiconductor device or the like. It is an object of the present invention to provide a film-forming composition capable of forming a silica-based film having good solution filterability and a small number of foreign substances in the solution as an insulating film.

[0004]

The present invention relates to a method for producing a film-forming composition, characterized in that a solution containing (A) polysiloxane and (B) an organic solvent is concentrated by a thin film vacuum evaporation method. . Next, the present invention relates to the film-forming composition produced by the above production method. Next, the present invention relates to a method for forming a film, which comprises applying the film forming composition onto a substrate and heating the substrate. Next, the present invention relates to a silica-based film obtained by the above method for forming a film.

[0005]

[In the formula, R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, b and c are the same or different, and represent a number of 0 to 2, and R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) A group represented by _n- (where n is an integer of 1 to 6), and d represents 0 or 1. ]

Here, the hydrolyzate in the component (A) means the R ¹ O-group, R ² O-group and R ⁴ O-group contained in the compounds (1) to (3) constituting the component (A). and all R ⁵ O-group need not be hydrolyzed, for example, 1
Only one may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. Further, the condensate in the component (A) is a condensate of silanol groups of the hydrolysates of the compounds (1) to (3) constituting the component (A) to form a Si-O-Si bond. In the present invention, it is not necessary that all silanol groups are condensed, and the concept includes a compound in which a small amount of silanol groups is condensed, a mixture of compounds having different degrees of condensation, and the like.

(A) Polysiloxane (A) Polysiloxane is obtained by hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3) in the presence of a catalyst. To be Compound (1); R and R in the general formula (1)
The ¹ monovalent organic group, an alkyl group, an aryl group,
Examples thereof include an allyl group and a glycidyl group. Further, 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, a butyl group, and the like, and preferably a carbon number of 1 to 1.
5, these alkyl groups may be linear or branched, and the hydrogen atom may be substituted with a fluorine atom or the like. Examples of the aryl group in the general formula (1) 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 (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane and tri-n.
-Butoxysilane, tri-sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane, fluorotri −
n-butoxysilane, fluorotri-sec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane and the like;

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

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

Preferred compounds as the compound (1) are methyltrimethoxysilane, methyltriethoxysilane,
Methyltri-n-propoxysilane, methyltri-is
o-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Examples thereof include vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. These may be used either individually or in combination of two or more.

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

Compound (3): In the above general formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as in the above general formula (1). . Among the compounds (3), examples of compounds in which R ⁷ in the general formula (3) is an oxygen atom include 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-phenyldisiloxane, 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, 1,3-diphenoxy-
1,1,3,3-tetraphenyldisiloxane etc. can be mentioned.

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

Further, in the general formula (3), as the compound in which d is 0, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,
2,2-pentamethoxy-2-methyldisilane, 1,
1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2
-Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2
-Pentamethoxy-2-phenyldisilane, 1,1,
1,2,2-pentaethoxy-2-phenyldisilane,
1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-
Dimethyldisilane, 1,1,2,2-tetraethoxy-
1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2
-Tetramethoxy-1,2-diethyldisilane, 1,
1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1,
2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-
Tetraphenoxy-1,2-diphenyldisilane, 1,
1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2
-Trimethyldisilane, 1,1,2-trimethoxy-
1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,
1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,
2,2-triphenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, 1,2
-Dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-
Tetramethyldisilane, 1,2-dimethoxy-1,1,
2,2-tetraethyldisilane, 1,2-diethoxy-
1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane,
1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1,
2,2-tetraphenyldisilane etc. 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,
Preferred examples include 2,2-tetraphenyldisilane and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane.

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

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

When at least one silane compound selected from the group of the compounds (1) to (3) is hydrolyzed and condensed, the amount of the compounds (1) to (3) is 0.1% per 1 mol. It is preferable to use more than 5 mol and not more than 150 mol of water, particularly preferably more than 0.5 mol and 130 mol of water. If the amount of water added is 0.5 mol or less, the crack resistance of the coating film may be poor, and if it exceeds 150 mol, precipitation or gelation of the polymer may occur during the hydrolysis and condensation reaction.

In producing the organosilicon polymer of the present invention, a catalyst is used when hydrolyzing and condensing at least one silane compound selected from the group of the compounds (1) to (3). It is a feature. Examples of the catalyst that can be used in this case include a metal chelate compound, an acid catalyst, and an alkali catalyst. Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonate) titanium, tri-sec
-Butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di- -I-propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (acetylacetonate) titanium, di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy.
Bis (acetylacetonate) titanium, monoethoxy
Tris (acetylacetonate) titanium, mono-n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris (acetylacetonate)
Titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) Titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-
Propoxy mono (ethylacetoacetate) titanium,
Tri-n-butoxy mono (ethyl acetoacetate)
Titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (ethylacetoacetate) titanium, di-n-propoxy bis (ethylacetoacetate) Acetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-n
-Butoxy bis (ethylacetoacetate) titanium,
Di-sec-butoxy bis (ethylacetoacetate) titanium, di-t-butoxy bis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate). ) Titanium, mono-i-propoxy tris (ethylacetoacetate) titanium, mono-n-butoxy tris (ethylacetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy. -Tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (a) Titanium chelate compounds such as tylacetonato) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetyl). Acetonate) zirconium, tri-n-
Butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxy bis (acetylacetonato) zirconium, di- n-propoxy bis (acetylacetonato) zirconium,
Di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis ( Acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxy tris (acetylacetonato) zirconium, mono-i-propoxy tris (acetylacetonato) zirconium, mono-n-butoxy. -Tris (acetylacetonato) zirconium, mono-sec-butoxy tris (acetylacetonato) zirconium, mono-t-butoxy tris (acetylacetonato) zirconium, tetrakis (acetylacetonate) Ruconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) zirconium, tri-n-butoxy mono (ethylacetoacetate) Acetate) zirconium, tri-s
ec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate) zirconium, diethoxy bis (ethylacetoacetate) zirconium, di-n-propoxy.
Bis (ethylacetoacetate) zirconium, di-i
-Propoxy bis (ethylacetoacetate) zirconium, di-n-butoxy bis (ethylacetoacetate) zirconium, di-sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) ) Zirconium, monoethoxy tris (ethylacetoacetate) zirconium, mono-n-propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-
n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris (ethylacetoacetate) zirconium, mono-t-butoxy.
Tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonate) Zirconium chelate compounds such as mono (ethylacetoacetate) zirconium;
Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum; and the like can be mentioned, and titanium and / or aluminum chelate compounds are preferable.
Particularly preferred is a chelate compound of titanium. These metal chelate compounds may be used either individually or in combination of two or more.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid and oxalic acid;
Acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, meritic acid, Arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid,
Benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid , Succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid hydrolysates, maleic anhydride hydrolysates, phthalic anhydride hydrolysates and the like organic acids. , And organic acids can be mentioned as more preferable examples. These compounds may be used either individually or in combination of two or more.

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

Among the above catalysts, an alkali catalyst is preferable in that a coating film having a lower relative dielectric constant can be obtained, and monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane. , Diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine are particularly preferable examples. Can be listed as

The amount of the above catalyst used is from compound (1) to
R in (3)¹ O-group, R² O-group, R ^Four O-group and
R^Five Normally, based on 1 mol of the total amount of the groups represented by O-groups,
0.00001 to 10 mol, preferably 0.00005
-5 mol, more preferably 0.001-0.5 mol
It If the amount of the catalyst used is within the above range, the poly
There is little risk of precipitation of gel and gelation.

In the compounds (1) to (3), when each component is converted into a complete hydrolysis-condensation product, the compound (2) is obtained.
Is 5 to 75% by weight in the total amount of the compounds (1) to (3),
Preferably 10-70% by weight, more preferably 15-
It is 70% by weight. Further, the compound (1) and / or (3) is 95 to 25 in the total amount of the compounds (1) to (3).
%, Preferably 90 to 30% by weight, more preferably 85 to 30% by weight. When the amount of the compound (2) is 5 to 75% by weight in the total amount of the compounds (1) to (3), the resulting coating film has a high elastic modulus and is particularly excellent in low dielectric property. In addition, a hydrolyzed condensate of the compound (1) and the compound (2) is preferable in that the obtained composition is more excellent in storage stability. Here, the term “hydrolysis” means R ¹ O— groups and R ² O— contained in the compounds (1) to (3).
It is not necessary that all groups, R ⁴ O-groups and R ⁵ O-groups, be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or , Or a mixture thereof. Further, the condensate is one in which silanol groups of the hydrolyzates of the compounds (1) to (3) are condensed to form a Si-O-Si bond, but in the present invention, all the silanol groups are condensed. It is not necessary, and it is a concept including a thing in which a small amount of silanol groups are condensed, a mixture of things with different degrees of condensation, and the like. In the present invention, the complete hydrolysis-condensation product means the R ¹ O-group, R ² O-group and R ^{4 in the} compounds (1) to (3).
SiO O-group and R ⁵ O-group, 100% hydrolyzed
It is an H group and is completely condensed to have a siloxane structure.

The reaction solvent for synthesizing the (A) hydrolysis-condensation product may be at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents and ester solvents.

Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-
Hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol -4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, s
ec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-
Trimethylcyclohexanol, benzyl alcohol,
A monoalcohol solvent such as diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , Ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,
Ethylene glycol mono-2-ethylbutyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether,
And a polyhydric alcohol partial ether solvent such as dipropylene glycol monopropyl ether; These alcohol solvents may be used either individually or in combination of two or more.

Among these alcohol solvents, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl. Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-
Hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and the like are preferable.

As the ketone solvent, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n
-Butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone,
2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone,
In addition to fencing, acetylacetone, 2,4-
Hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4 -Hexanedione, 2,2
6,6-Tetramethyl-3,5-heptanedione, 1,
Examples include β-diketones such as 1,1,5,5,5-hexafluoro-2,4-heptanedione. These ketone solvents may be used either individually or in combination of two or more.

As the amide solvent, formamide, N-
Methylformamide, N, N-dimethylformamide,
N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-
Dimethylacetamide, N-ethylacetamide, N,
N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine,
N-formylpiperidine, N-formylpyrrolidine, N
-Acetylmorpholine, N-acetylpiperidine, N-
Acetylpyrrolidine etc. are mentioned. These amide solvents may be used either individually or in combination of two or more.

As the ester solvent, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate,
Methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate,
N-Butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, acetic acid 3
-Methoxybutyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n acetate
-Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n acetate
-Butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy acetate Triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate , Dimethyl phthalate, diethyl phthalate and the like. These ester solvents may be used either individually or in combination of two or more. The above reaction solvents can be used alone or in combination of two or more.

The concentration of the (A) hydrolyzed condensate in the reaction solvent is 1 to 20% by weight (completely hydrolyzed condensate),
It is preferably 1.5 to 18% by weight. The reaction temperature is usually 0 to 100 ° C., preferably 15 to 90.
℃.

In the method for producing the film-forming composition of the present invention,
The solution obtained by the above reaction may be directly concentrated by a thin film vacuum evaporation method, or thin film vacuum evaporation concentration may be performed by further adding an organic solvent. As an apparatus used for the thin film vacuum evaporation method, for example, Evapole (registered trademark) manufactured by Okawara Seisakusho Co., Ltd. or a concentrating apparatus equipped with a falling film external heat exchanger manufactured by Nisso Engineering Co., Ltd.
Kanto Chemical Machinery Manufacturing Co., Ltd., Hitachi Ltd.
An evaporative concentrator equipped with a wall wetter can be mentioned. The degree of vacuum in concentrating the reaction solution of the (A) hydrolysis-condensation product is 0.5 to 8 kPa, preferably 1 to 7 kPa, and the temperature in concentrating is 30 to 80 ° C., preferably 35 to 70.
℃. By combining the thin-film vacuum evaporation method and the above-described degree of vacuum and temperature at the time of concentration, a film-forming composition having a good solution filterability and a small number of foreign substances in the solution can be obtained.

Other Additives The film-forming composition obtained in the present invention further includes β-diketone, colloidal silica, colloidal alumina, organic polymers, surfactants, silane coupling agents, radical generators, triazenes. Ingredients such as compounds may be added.

As the β-diketone, acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- Nonangion,
3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro- 2,4-heptanedione and the like can be mentioned, and more preferred are acetylacetone, 2,4-hexanedione, 2,4-heptanedione and 3,5-heptanedione. These may be used either individually or in combination of two or more.

Colloidal silica is, for example, a dispersion liquid in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 nm, preferably 10 to 30 nm.
It has a thickness of 20 nm and a solid content concentration of about 10 to 40% by weight. Examples of such colloidal silica include, for example, Nissan Chemical Industry Co., Ltd., methanol silica sol and isopropanol silica sol; Catalyst Chemical Industry Co., Ltd.
Manufactured, Oscar and the like. As the colloidal alumina, alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.,
No. 100 and No. 200; Alumina Clear Sol, Alumina Sol 10 and No. 132 manufactured by Kawaken Fine Chemicals Co., Ltd. As the organic polymer, for example, a compound having a sugar chain structure, a vinylamide polymer, (meth)
Acrylic polymer, aromatic vinyl compound, dendrimer, polyimide, polyamic acid, polyarylene, polyamide, polyquinoxaline, polyoxadiazole,
Examples thereof include a fluorine-based polymer and a compound having a polyalkylene oxide structure.

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

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

Examples of the fluorinated surfactant include 1,
1,2,2-Tetrafluorooctyl (1,1,2,2-
Tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl)
Ether, hexaethylene glycol (1, 1, 2,
2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro) Pentyl) ether, sodium perfluorododecyl sulfonate,
1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctane sulfone Amido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt,
At least one of the terminal, main chain and side chain of perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate ester, etc. A fluorosurfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the site can be mentioned. Also, as commercially available products, Megafac F142D, F172, F173, F1
83 (above, manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC-430, FC-431.
(Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, same SC-103, same SC-104, same SC-1
05, the same SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-10
00, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15
(Neos Co., Ltd.) and other commercially available fluorine-based surfactants can be mentioned. Among these, the Megafac F172, BM-1000, BM-11
00, NBX-15 are particularly preferred. Examples of silicone-based surfactants include SH7PA, SH21PA, S
H30PA and ST94PA (both manufactured by Toray Dow Corning Silicone Co., Ltd., etc. can be used.
Among these, SH28PA and SH30PA are particularly preferable. The amount of the surfactant used is usually 0.0001 to 10 parts by weight based on the specific organic solvent (completely hydrolyzed condensate). These may be used either individually or in combination of two or more.

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

Examples of the radical generator include isobutyryl peroxide, α, α'bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, di-npropylperoxydicarbonate, diisopropylperoxy. Dicarbonate,
1,1,3,3-tetramethylbutylperoxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxy neodecanoate, dimethoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butyl peroxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl per Cide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) ) Hexane, 1-cyclohexyl-
1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,
m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy)-
3,3,5-Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-)
Butyl peroxycyclohexyl) propane, 1,1-
Bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-
3,3,5-Trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t -Butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis ( t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like can be mentioned. The blending amount of the radical generator is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer. These may be used either individually or in combination of two or more.

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 either individually or in combination of two or more.

The total solid concentration 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 concentration of the composition is 2 to 30% by weight, the film thickness of the coating film is in an appropriate range and the storage stability is further excellent. The total solid content concentration is adjusted, if necessary, by concentration and dilution with the (D) organic solvent.

The composition of the present invention was prepared by using silicon wafer, Si
When applied to a base material such as an O ₂ wafer or SiN wafer, a coating means such as spin coating, dipping, roll coating or spraying is used. The film thickness at this time can be a dry film thickness of about 0.05 to 2.5 μm by one coating, and a coating film of about 0.1 to 5.0 μm by two coating. . Then, it is dried at room temperature, or at a temperature of about 80 to 600 ° C, usually 5 to 240
By heating for about a minute and drying, a glassy or giant polymer 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, and a heating atmosphere is performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. You can The coating film can also be formed by irradiating with an electron beam or ultraviolet rays. In addition, in order to control the curing speed of the coating film, it is possible to heat stepwise or select an atmosphere such as nitrogen, air, oxygen, or reduced pressure, if necessary. Furthermore, the relative dielectric constant of the silica-based film of the present invention is usually 3.0 to 1.2, preferably 3.0 to 1.8, and more preferably 3.0 to 2.0.

The inter-layer insulating film thus obtained has a small number of foreign substances in the solution, so that the LSI and system LS
I, DRAM, SDRAM, RDRAM, D-RDRA
Interlayer insulating film for semiconductor elements such as M, etching stopper and chemical mechanical polishing stopper, protective film such as surface coating film of semiconductor element, intermediate layer of semiconductor manufacturing process using multilayer resist, interlayer insulating film of multilayer wiring board, liquid crystal It is useful for applications such as protective films and insulating films for display elements and electroluminescence display elements.

[0046]

EXAMPLES The present invention will be described more specifically below with reference to examples. However, the following description is a general description of example embodiments of the present invention, and the present invention is not limited to the description without particular reason. In addition, unless otherwise indicated, the part and% in an Example and a comparative example have shown that it is a weight part and weight%, respectively. Also,
Various evaluations were performed as follows.

Weight average molecular weight (Mw) It was measured by gel permeation chromatography (GPC) (refractive index, viscosity, light scattering measurement) method under the following conditions. Sample solution: A hydrolyzed condensate of a silane compound was diluted with methanol containing 10 mM LiBr so that the solid content concentration became 0.25%, and used as a sample solution for GPC (refractive index, viscosity, light scattering measurement). did. Equipment: Tosoh Corp., GPC system model GP
C-8020 Tosoh Corp. column, Alpha 5000/300
0 Viscotech, viscosity detector and light scattering detector model T-60 Dual meter Carrier solution: Methanol carrier containing 10 mM LiBr Feed rate: 1 ml / min Column temperature: 40 ° C

A composition sample was applied onto a silicon wafer having a relative dielectric constant of 8 inches by a spin coating method, and the composition sample was heated at 100 ° C. for 3 hours on a hot plate.
The substrate was dried for 3 minutes in a nitrogen atmosphere at 200 ° C. for 3 minutes, and then the substrate was baked for 20 minutes on a nitrogen atmosphere hot plate at 425 ° C. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for measuring relative permittivity. The sample at a frequency of 100 kHz,
HP1645 manufactured by Yokogawa / Hewlett-Packard Co., Ltd.
The relative dielectric constant of the coating film was measured by the CV method using a 1B electrode and an HP4284A precision LCR meter.

Filterability of Solution Using a polyfluorinated ethylene filter having a diameter of 0.2 μm and a diameter of 10 cm, 1 L of the solution was filtered at a pressure of 1 Kg / cm ² and the filterability was evaluated according to the following criteria. ◯: The filtration rate of the solution was 20 g / min or more. ×: The filtration rate of the solution was less than 20 g / min. The filtration was performed at a pressure of 1 Kg / cm ² using a polyfluoroethylene filter having a diameter of 10 μm and a foreign matter number of 0.2 μm. Concerning the solution, RION's automatic submerged particle counter KL-20A
The number of foreign matters per 1 ml in the solution (0.3 μm
The above was measured and judged according to the following criteria. ◯: The number of foreign matter is 10 pieces / ml or less ×: The number of foreign matter exceeds 10 pieces / ml

Synthesis Example 1 77.04 kg of distilled methyltrimethoxysilane, 24.05 kg of distilled tetramethoxysilane and 4800 g of distilled tetrakis (acetylacetonato) titanium were dissolved in 290 kg of distilled propylene glycol monopropyl ether in a 700 L reactor made of zirconium. Then, stir with a three-one motor, and the solution temperature is 60 ° C.
Stabilized to. Next, 84 kg of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, 25 kg of distilled acetylacetone was added to obtain a reaction solution. The polysiloxane thus obtained had a weight average molecular weight of 8,400.

Synthesis Example 2 In a 700 L reactor made of zirconium, 102.8 kg of distilled methyltrimethoxysilane and 42.8 kg of distilled tetramethoxysilane were dissolved in 213 kg of distilled propylene glycol monoethyl ether, and then stirred with a three-one motor. The solution temperature was stabilized at 60 ° C.
Next, 91 kg of ion-exchanged water in which 6.5 g of maleic anhydride was dissolved was added to the solution over 1 hour. Then 6
After reacting at 0 ° C. for 2 hours, the reaction solution was cooled to room temperature to obtain a reaction solution. The weight average molecular weight of the polysiloxane thus obtained was 950.

Synthesis Example 3 In a 700-liter reactor made of zirconium, 103 kg of distilled ethanol, 93 kg of ion-exchanged water and 6.8 kg of 25% tetramethylammonium hydroxide aqueous solution were put and stirred uniformly. Methyltrimethoxysilane 1 in this solution
A mixture of 7.7 kg, 27 kg of tetraethoxysilane and 82 kg of distilled ethanol was slowly added over 2 hours. The reaction was carried out for 2 hours while keeping the solution at 58 ° C. To this solution, 200 kg of distilled propylene glycol monopropyl ether and an aqueous nitric acid solution were added to adjust the pH of the solution.
Was set to 3.5 to obtain a reaction solution. The weight average molecular weight of the polysiloxane thus obtained was measured and found to be 1050,000.

Example 1 30 kg of the reaction solution obtained in Synthesis Example 1 was used using Evapol (registered trademark) CEP-1 manufactured by Okawara Seisakusho Co., Ltd.
While the reaction solution was circulated at a concentration of reduced pressure of 2 kPa and a concentration temperature of 50 ° C., the reaction solution was concentrated until the solid content concentration became 25% (in terms of complete hydrolysis condensate). When the weight average molecular weight of the obtained solution was measured, it was 8,500.
The change in molecular weight before and after the concentration was very small. Moreover, when the obtained solution was filtered through a 0.2 μm polyfluorinated ethylene filter, the filtration rate was 35 g / min, and the filterability was excellent. Further, the number of foreign matters in the solution was measured, and it was a very small number of foreign matters of 3 pieces / ml.
The above solution was applied onto an 8-inch silicon wafer by a spin coating method, dried on a hot plate at 100 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes, and further on a nitrogen atmosphere hot plate at 425 ° C. The substrate was baked for 20 minutes. The relative dielectric constant of this coating film was a low value of 2.73.

Example 2 30 kg of the reaction solution obtained in Synthesis Example 2 was used using Evapol (registered trademark) CEP-1 manufactured by Okawara Seisakusho Co., Ltd.
While the reaction solution was circulated at a concentration of reduced pressure of 2 kPa and a concentration temperature of 50 ° C., the reaction solution was concentrated until the solid content concentration became 30% (in terms of complete hydrolysis-condensation product). When the weight average molecular weight of the obtained solution was measured, it was 970, and the change in the molecular weight before and after the concentration was small. Moreover, when the obtained solution was filtered through a 0.2 μm polyfluorinated ethylene filter, the filtration rate was 44 g / min, and the filterability was excellent. When the number of foreign substances in the solution was measured,
The number of foreign substances was 4 / ml, which was extremely small. The above solution was applied onto an 8-inch silicon wafer by a spin coating method, dried on a hot plate at 100 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes, and further on a nitrogen atmosphere hot plate at 425 ° C. The substrate was baked for 20 minutes. The relative permittivity of this coating film was as low as 2.82.

Example 3 30 kg of the reaction solution obtained in Synthesis Example 3 was used with Evapol (registered trademark) CEP-1 manufactured by Okawara Corporation.
While the reaction solution was circulated at a concentration of reduced pressure of 2 kPa and a concentration temperature of 50 ° C., the reaction solution was concentrated until the solid content concentration became 13% (completely hydrolyzed condensate equivalent). When the weight average molecular weight of the obtained solution was measured, it was 1050,000.
The molecular weight did not change before and after the concentration. Moreover, when the obtained solution was filtered through a 0.2 μm polyfluorinated ethylene filter, the filtration rate was 24 g / min, and the filterability was excellent. Further, the number of foreign matters in the solution was measured, and it was a very small number of foreign matters of 7 pieces / ml.
The above solution was applied onto an 8-inch silicon wafer by a spin coating method, dried on a hot plate at 100 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes, and further on a nitrogen atmosphere hot plate at 425 ° C. The substrate was baked for 20 minutes. The relative permittivity of this coating film was a low value of 2.25.

Example 4 30 kg of the reaction solution obtained in Synthesis Example 3 was concentrated by using a concentrator equipped with a falling film type external heat exchanger manufactured by Nisso Engineering Co., Ltd. to a concentration degree of reduced pressure of 2 kPa and a concentration temperature of 50. While circulating the reaction solution at 0 ° C., concentration was carried out until the solid content concentration of the reaction solution reached 13% (completely hydrolyzed condensate). When the weight average molecular weight of the obtained solution was measured, it was 1050,000, and there was no change in the molecular weight before and after the concentration. In addition, the obtained solution is 0.2 μm
When filtered with a polyfluoroethylene filter of
The filtration rate was 22 g / min and the filterability was excellent.
Further, the number of foreign matters in the solution was measured, and it was a very small number of foreign matters of 8 pieces / ml. The above solution was applied onto an 8-inch silicon wafer by spin coating, and then on a hot plate at 100 ° C for 3 minutes in a nitrogen atmosphere of 200 ° C.
The substrate was dried for 3 minutes and further baked for 20 minutes on a nitrogen atmosphere hot plate at 425 ° C. The relative permittivity of this coating film was a low value of 2.25.

Example 5 30 kg of the reaction solution obtained in Synthesis Example 3 was used as a solid of the reaction solution while circulating the reaction solution at a concentration of reduced pressure of 2 kPa and a concentration temperature of 50 ° C. using a controller manufactured by Hitachi, Ltd. Concentration was performed until the partial concentration reached 13% (completely hydrolyzed condensate conversion). When the weight average molecular weight of the obtained solution was measured, it was 1050,000, and there was no change in the molecular weight before and after the concentration. Moreover, when the obtained solution was filtered through a 0.2 μm polyfluorinated ethylene filter, the filtration rate was 24 g / min, and the filterability was excellent. Moreover, the number of foreign matters in the solution was measured, and it was a very small number of 10 foreign matters / ml. The above solution was applied onto an 8-inch silicon wafer by spin coating, and then on a hot plate at 100 ° C for 3 minutes in a nitrogen atmosphere of 200 ° C.
The substrate was dried for 3 minutes and further baked for 20 minutes on a nitrogen atmosphere hot plate at 425 ° C. The relative permittivity of this coating film was a low value of 2.25.

Example 6 30 kg of the reaction solution obtained in Synthesis Example 3 was reacted at an evaporating and concentrating apparatus equipped with a wall wetter manufactured by Kansai Kagaku Kikai K.K. While stirring the liquid, the reaction liquid was concentrated until the solid content concentration became 13% (in terms of complete hydrolysis-condensation product). The weight average molecular weight of the obtained solution was measured and found to be 1,05
It was 10,000, and there was no change in the molecular weight before and after the concentration. Moreover, when the obtained solution was filtered through a 0.2 μm polyfluorinated ethylene filter, the filtration rate was 23 g.
/ Min and the filterability was excellent. Further, the number of foreign matters in the solution was measured, and it was a very small number of foreign matters of 9 pieces / ml. The above solution was placed on an 8-inch silicon wafer,
Apply using the spin coat method, and 1 on the hot plate.
The substrate was dried at 00 ° C. for 3 minutes, nitrogen atmosphere at 200 ° C. for 3 minutes, and further dried at 425 ° C. in a nitrogen atmosphere hot plate for 2 minutes.
The substrate was baked for 0 minutes. The relative permittivity of this coating film was a low value of 2.25.

Comparative Example 1 In a 700 L reactor made of zirconium, 300 kg of the reaction solution obtained in Synthesis Example 1 was stirred at 50 rpm while the concentration of reduced pressure was 2 kPa and the concentration temperature was 50 ° C., and the solid content concentration of the reaction solution was 25%. Evaporation and concentration were performed until (complete hydrolysis hydrolysis condensate conversion) was reached. When the weight average molecular weight of the obtained solution was measured, it was 10,500, and an increase in the molecular weight was observed after concentration. In addition, the obtained solution is 0.2μ
When it was filtered through a polyfluoroethylene filter of m, the filtration rate was 17 g / min and the filterability was poor. Moreover, when the number of foreign matters in the solution was measured, it was 2
The number was 2 pieces / ml, which was inferior to the number of foreign matters.

Comparative Example 2 In a 700 L reactor made of zirconium, 300 kg of the reaction solution obtained in Synthesis Example 2 was stirred at 50 rpm, the concentration of reduced pressure was 2 kPa, the concentration temperature was 50 ° C., and the solid content concentration of the reaction solution was 30%. Evaporation and concentration were performed until (complete hydrolysis hydrolysis condensate conversion) was reached. When the weight average molecular weight of the obtained solution was measured, it was 2,500, and an increase in the molecular weight was observed after the concentration. In addition, the obtained solution is 0.2 μm
When filtered with a polyfluoroethylene filter of
The filtration rate was 19 g / min and the filterability was poor. Further, the number of foreign matters in the solution was measured, and it was 28 pieces / ml, which was inferior to the number of foreign matters.

Comparative Example 3 In a 700 L reactor made of zirconium, while stirring 300 kg of the reaction solution obtained in Synthesis Example 3 at 50 rpm, the concentration of reduced pressure was 2 kPa, the concentration temperature was 50 ° C., and the solid content concentration of the reaction solution was 13%. Evaporation and concentration were performed until (complete hydrolysis hydrolysis condensate conversion) was reached. The weight average molecular weight of the obtained solution was measured and found to be 1,800,000, showing an increase in the molecular weight after concentration. Moreover, when the obtained solution was filtered through a 0.2 μm polyfluorinated ethylene filter, the filtration rate was 8 g / min and the filterability was poor. Further, the number of foreign matters in the solution was measured, and it was 31 pieces / ml, which was inferior to the number of foreign matters.

[0062]

According to the present invention, by concentrating the alkoxysilane polymer solution by the thin film vacuum evaporation method, it is possible to form a silica-based film having excellent solution filterability and a small number of foreign substances in the solution. It is possible to provide a film-forming composition (material for an interlayer insulating film).

Continued front page    (72) Inventor Kinji Yamada             2-11-21 Tsukiji, Chuo-ku, Tokyo JAE             Within Suar Co., Ltd. F-term (reference) 4J038 DL021 DL031 DL161 HA306                       JA19 JA37 JB01 JB11 JC38                       KA04 KA06 LA05 MA07 MA09                       NA21 NA23 PA19                 5F058 AA10 AC03 AF04 AG01 AH02                       AH03 BA20 BC05 BF46 BH01                       BJ02 BJ03

Claims (8)

[Claims] 1. A method for producing a film-forming composition, which comprises concentrating a solution containing polysiloxane and an organic solvent by a thin film vacuum evaporation method. 2. The manufacturing method according to claim 1, wherein the thin film vacuum evaporation method is based on forming a liquid film on the inner wall of the evaporative concentrator and the heat exchanger or on the heat transfer surface of one of them and heating. . 3. The polysiloxane is selected from the group consisting of (A) 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). At least one silane compound is condensed and hydrolyzed in the presence of a catalyst, and condensed and condensed, R _a Si (OR ¹ ) _4-a (1) (wherein R is hydrogen. 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) (wherein, R 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) wherein, R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, b and c are the same or different and each represents a number of 0 to 2, and R ⁷ is an oxygen atom, a phenylene group or — (CH 2
₂ ) A group represented by _n − (where n is an integer of 1 to 6), and d represents 0 or 1. ] The manufacturing method of the film-forming composition of Claim 1 characterized by these. 4. The method for producing a film-forming composition according to claim 1, wherein the organic solvent (B) is an alcohol solvent. 5. The method for producing a film-forming composition according to claim 3, wherein the catalyst is at least one selected from an acid catalyst, a metal chelate catalyst and an alkali catalyst. 6. A film-forming composition obtained by the production method according to claim 1. 7. A method for forming a film, which comprises applying the composition for forming a film according to claim 1 to a substrate and heating the substrate. 8. A silica-based film obtained by the method for forming a film according to claim 7.