JP2001335652A - Film manufacturing method and insulating film - Google Patents

Abstract

(57) Abstract: A silica-based film excellent in mechanical strength and having a small temperature dependence of a relative dielectric constant is obtained as an interlayer insulating film in a semiconductor element or the like. SOLUTION: A method for producing a film, comprising treating the surface of a silica-based film with a silicon compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a film-forming composition, and more particularly, to an interlayer insulating film for a semiconductor device or the like, which is a silica excellent in mechanical strength and having a small temperature dependence of relative permittivity. The present invention relates to a method for producing a base film.

2. Description of the Related Art Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method has been frequently 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 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, as semiconductor devices and the like have become more highly integrated and multilayered, an interlayer insulating film material having a lower relative dielectric constant has been required.

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, 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 have problems in that the properties of the reaction products are not stable, the dielectric constant increases due to moisture absorption of the coating film, and the mechanical strength is small. And was not suitable for industrial production.

[0003]

The present invention relates to a method for producing a silica-based film for solving the above-mentioned problems and an insulating film using the same. It is an object of the present invention to provide a silica-based film having a small temperature dependence of a dielectric constant and excellent mechanical strength.

[0004]

SUMMARY OF THE INVENTION The present invention provides a method for producing a film, which comprises treating the surface of a silica-based film with a silicon compound, and an insulating film obtained by the method.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a silica-based film is a film comprising a cured product of a hydrolyzed condensate obtained by hydrolyzing and condensing a hydrolyzable silane compound (A). In the present invention, (A) a compound represented by the following general formula (1) (hereinafter, referred to as (A-1))
R _a Si (OR ¹ ) _4-a (1) wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, and R ¹ is a monovalent A represents an integer of 1 to 2.) (A-2) A compound represented by the following general formula (2)
(Hereinafter referred to as “compound (2)”) and Si (OR ² ) ₄ ... (2) (wherein, R ² represents a monovalent organic group.) (A-3) The following general formula (3) Compound represented by the following (hereinafter,
_{^{4 O) 3-b Si- (}} R 7) d -Si (OR 5) 3-c R 6 c ·· ··· (3) wherein "Compound (3)" hereinafter) R ³ _b (R, 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. At least one selected from the group of
Species of compound. Here, the hydrolyzate in the component (A) refers to the compound (1) to the compound (1) constituting the component (A).
Not all of the R ¹ O—, R ² O—, R ⁴ O— and R ⁵ O— groups contained in (3) need be hydrolyzed, for example, only one is hydrolyzed. What
One or more of them may be hydrolyzed, or a mixture thereof. The condensate in the component (A) is a product in which the silanol groups of the hydrolyzates of the compounds (1) to (3) constituting the component (A) are condensed to form a Si—O—Si bond. In the present invention, it is not necessary that all of the silanol groups are condensed, and the concept includes a mixture of a small amount of condensed silanol groups and a mixture of those having different degrees of condensation.

(A) The hydrolysis-condensation product is obtained by hydrolyzing and condensing at least one silane compound selected from the above-mentioned compounds (1) to (3), usually in the presence of a catalyst. . 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. 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, and a butyl group, and preferably have 1 to 1 carbon atoms.
5, these alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted by 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, tri- sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane and the like;

[0008] 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, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltrimethoxysilane 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 triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 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.

Of these, 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 represented by the 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, as the compounds (1) to (3) constituting the component (A), one or more of the above compounds (1), (2) and (3) can be used.

When hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3), 20 moles per mole of the total of the compounds (1) to (3) is used. It is preferable to use more than 150 mol of water, more preferably more than 20 mol and 130 mol of water. If the amount of water to be added is less than 20 mol, the crack resistance of the coating film may be inferior, and if it exceeds 150 mol, polymer precipitation or gelation during the hydrolysis and condensation reaction may occur.

In producing the hydrolyzed condensate (A) of the present invention, a catalyst is used for hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3). It is preferable to use Examples of the catalyst used here include a metal chelate compound, an acid catalyst, and an alkali catalyst.

Examples of the metal chelate compound 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, diethoxy.
Bis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-
Propoxy bis (acetylacetonate) titanium, di-n-butoxybis (acetylacetonate) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonate) Titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy.
Tris (acetylacetonate) titanium, mono-n-butoxytris (acetylacetonate) titanium, mono-sec-butoxytris (acetylacetonate)
Titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate)
Titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) Acetate) titanium, tri-s
ec-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) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t
-Butoxy bis (ethyl acetoacetate) titanium,
Monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) ) Titanium, mono-sec
-Butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxytris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate)
Titanium chelate compounds such as titanium, mono (acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy・ Mono (acetylacetonate) zirconium, tri-
n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonate) Nart) zirconium,
Tri-t-butoxy mono (acetylacetonate) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxy.
Bis (acetylacetonate) zirconium, di-n-
Butoxy bis (acetylacetonate) zirconium, di-sec-butoxy bis (acetylacetonate) zirconium, di-t-butoxybis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono -N-propoxy tris (acetylacetonate) zirconium, mono-i-propoxy tris (acetylacetonate) zirconium, mono-n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetyl) (Acetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium Tri -n- propoxy mono (ethylacetoacetate) zirconium, tri -i
-Propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-
Butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di- n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium , Mono-n
-Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) 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; aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; Is a chelate compound of titanium and / or aluminum. Particularly preferred is a chelate compound of titanium. These metal chelate compounds may be used alone 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, melitic 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 And organic acids such as succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, a hydrolyzate of glutaric acid, a hydrolyzate of maleic anhydride, and a hydrolyzate of phthalic anhydride. And organic acids can be mentioned as more preferred examples. These compounds may be used alone or in combination of two or more.

Examples of the alkali catalyst include, for example,
Thorium, potassium hydroxide, lithium hydroxide, pyridi
, Pyrrole, piperazine, pyrrolidine, piperidine,
Picoline, monoethanolamine, diethanolamine
Dimethyl monoethanolamine, monomethyldiethanol
Nolamine, triethanolamine, diazabicyclo
Octane, diazabicyclononane, diazabicycloun
Decene, tetramethyl ammonium hydroxide
, Ammonia, methylamine, ethylamine, propyl
Ruamine, butylamine, pentylamine, hexylurea
Min, pentylamine, octylamine, nonylamine
, Decylamine, N, N-dimethylamine, N, N-
Diethylamine, N, N-dipropylamine, N, N-
Dibutylamine, trimethylamine, triethylamine
, Tripropylamine, tributylamine, cyclohexane
Xylamine, trimethylimidine, 1-amino-3-
Methylbutane, dimethylglycine, 3-amino-3-meth
Tylamine and the like, and more preferably
Amines, ammonia, alkylamines and
Tramethylammonium hydroxide is silica-based
It is particularly preferable from the viewpoint of the adhesion of the film to the substrate. These
Even if one or two or more lukari catalysts are used at the same time,
good. The amount of the catalyst used is determined by the amount of the compound (1) to (3).
R¹ O-group, R^Two O-group, R ^Four O-group and R^Five O-group
Is usually 0.000 to 1 mol of the total amount of the group represented by
01 to 10 mol, preferably 0.00005 to 5 mol
is there. If the amount of catalyst used is within the above range, po
Low risk of limer precipitation and gelation.

When the compounds (1) to (3) are converted to 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. 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 the compounds (1) to (3)
0% by weight. Compound (2) is a 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 completely hydrolyzed condensate is defined as R ¹ O— group, R ^{2 in} compounds (1) to (3).
O-group, R ⁴ O-group and R ⁵ O-group are hydrolyzed by 100% to form SiOH groups, which are further completely condensed to form siloxane structures. Further, the component (A) is preferably a hydrolyzed condensate of the compound (1) and the compound (2) because the obtained coating solution for forming a silica-based film has better storage stability.

In the present invention, the component (A) is usually dissolved or dispersed in an organic solvent to form a coating liquid for forming a silica film, and the coating liquid is applied to a substrate, dried if necessary, and then cured. Thereby, a silica-based film is formed. Examples of the organic solvent used at this time include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents, and aprotic solvents.

Here, the alcohol solvent includes 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,
Monoalcohol solvents 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-ethyl butyl 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,
Polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether; and the like. One or two of these alcohol solvents are used.
More than one species may be used simultaneously.

Examples of the ketone solvent include 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
-In addition to pentanedione, acetonylacetone, acetophenone, fenchone, etc., 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,
Β-diketones such as 1,1,1,5,5,5-hexafluoro-2,4-heptanedione and the like can be mentioned.
These ketone solvents may be used alone or in combination of two or more.

As amide solvents, formamide, N
-Methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide,
N-dimethylacetamide, N-ethylacetamide,
N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. Can be One or two or more of these amide solvents may be used simultaneously.

As ester solvents, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ
-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-acetate
n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxy 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, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents include 1
Species or two or more species may be used simultaneously. Examples of aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, −
Methyl-Δ3-pyrroline, N-methylpiperidine, N-
Ethyl piperidine, N, N-dimethylpiperazine, N-
Methylimidazole, N-methyl-4-piperidone, N
-Methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3
-Dimethyltetrahydro-2 (1H) -pyrimidinone.

Among these organic solvents, an organic solvent represented by the following general formula (4) is particularly preferred. R ⁸ O (CHCH ₃ CH ₂ O) _e R ⁹ (4) (R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—. 1 to be chosen
Represents a valent organic group, and e represents an integer of 1 to 2. The organic solvent (C) can be used alone or in combination of two or more. In the present invention, when the above compounds (1) to (3) are hydrolyzed and / or condensed, the same solvent can be used. Specifically, water or water diluted with a solvent is added intermittently or continuously to a solvent in which the compounds (1) to (3) are dissolved. At this time, the catalyst may be previously added to the solvent, or may be dissolved or dispersed in water at the time of adding water. The reaction temperature at this time is usually from 0 to 100.
° C, preferably 15 to 90 ° C.

Other Additives The coating liquid for forming a silica-based film used in the present invention further comprises a compound having a boiling point or a decomposition temperature of 250 to 450 ° C.
Components such as β-diketone, colloidal silica, colloidal alumina, surfactant, silane coupling agent, radical generator, and triazene compound may be added.

Examples of the compound having a boiling point or a decomposition temperature of 250 to 450 ° C. include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure,
Examples include vinylamide polymers, (meth) acrylate polymers, aromatic vinyl polymers, dendrimers, lipophilic compounds and dispersants, and ultrafine particles. In the present invention, the boiling point and the decomposition temperature refer to the temperature at 1 atm.

Compound having a polyalkylene oxide structure Here, examples of the polyalkylene oxide structure include a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene block copolymer Ether-type compounds such as oxyethylene polyoxypropylene alkyl ether, ether-type compounds such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, polyethylene Glycol fatty acid esters, ethylene glycol fatty acid esters, fatty acid monoglycerides, It can be mentioned Li glycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, ether-ester type compounds such as sucrose fatty acid esters and the like.

Compounds having a sugar chain structure As the compounds having a sugar chain structure, cyclodextrin,
Sucrose ester, oligosaccharide, glucose, fructose, mannitol, starch sugar, D-sorbitol, dextran, xanthan gum, curdlan, pullulan, cycloamylose, isomerized sugar, maltitol, cellulose acetate, cellulose, carboxymethylcellulose, hydroxyethylcellulose , Hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, chitin, chitosan and the like. The cyclodextrin is represented by the following formula, wherein n is 6 (α-cyclodextrin), 7 (β-cyclodextrin) or 8 (γ-cyclodextrin).

[0036]

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It is preferable that the compound having a sugar chain structure used in the present invention is modified in part or all of a hydroxyl group or an amino group. Examples of the chemical modification of the hydroxyl group include modification including etherification, esterification, trialkylsilyl bond, and urethane bond. Examples of the chemical modification of the amino group include introduction of an amide bond, a urea bond, and an imide bond. Among the compounds having a sugar chain structure, cyclodextrin is preferable because the pore size after decomposition is small and the control becomes possible, and as the chemical modification, trialkylsilyl modification or urethanization is preferable, and trimethylsilyl modification is particularly preferable. In order to modify a compound having a sugar chain structure with a trimethylsil group, a compound having a sugar chain structure may be reacted with a trimethylsilylating agent such as trimethylchlorosilane or trimethylchlorosilylacetamide. 5 of the hydroxyl group of
-100% may be substituted. In order to modify a compound having a sugar chain structure with a urethane group, a compound having a sugar chain structure may be reacted with a urethane agent such as phenyl isocyanate or hexyl isocyanate. What is necessary is just to substitute 5-100% of a hydroxyl group.

Vinylamide Polymer Examples of the vinylamide polymer include poly (N-vinylacetamide), poly (N-vinylpyrrolidone, poly (2-methyl-2-oxazoline), and poly (N, N-dimethylacrylamide). No.

(Meth) acrylate-based polymers Examples of (meth) acrylate-based polymers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylate. )
Polymer of radical polymerizable monomer mainly composed of (meth) acrylate such as tetrahydrofurfuryl acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamidohydroxypropyl (meth) acrylate Can be mentioned.

Aromatic vinyl polymer Examples of the aromatic vinyl polymer include polystyrene, polymethylstyrene, and poly-α-methylstyrene.

Dendrimer Examples of the dendrimer include benzyl ether type, phenylacetylene, polyamine type and polyamide type, and polyamine type is preferable from the viewpoint of thermal decomposition.

Lipophilic compound and dispersant The lipophilic compound and dispersant are not compatible with component (A) in a wide composition range by using the lipophilic compound alone. It is compatible in the composition range. As the lipophilic compound, polycarboxylic acid esters such as didecyl phthalate, diundecyl phthalate, didodecyl phthalate, ditridecyl phthalate,
Tris (2-ethylhexyl) trimellitate, tridecyl trimellitate, tridodecyl trimellitate, tetrabutyl pyromellitate, tetrahexyl trimellitate, tetraoctyl pyromellitate, bis (2-ethylhexyl) dodecandioate, bisdecyl Dodecandioate and the like can be mentioned. Examples of dispersants that make these lipophilic compounds compatible include higher alcohols such as octanol, lauryl alcohol, decyl alcohol, and undecyl alcohol. The amount of the higher alcohol used as the dispersant can be used in the range of 0.1 to 10 times (weight) the lipophilic compound.

Ultra-fine particles Ultra-fine particles are polymer particles having a particle size of 100 nm or less, the particle size of which is controlled by the type of emulsifier, the concentration of the emulsifier, the stirring speed, and the like by ordinary emulsion polymerization. It is prepared from a monomer of a vinyl group compound or a (meth) acrylate compound using a crosslinkable monomer for controlling the particle size.

As the β-diketone, acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- 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 surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like.
Examples thereof include a fluorine-based surfactant, a silicone-based surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant. Preferably, a fluorine-based surfactant and a silicone-based surfactant are used. Can be mentioned. Examples of the fluorinated surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2
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- Hexafluoropentyl)
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.

Examples of the silicone-based surfactant include SH7PA, SH21PA, SH30PA, and 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 used is usually 0.0001 to 10 parts by weight based on 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.

Examples of the radical generator include, for example, isobutyryl peroxide, α, α'bis (neodecanoylperoxy) 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-tert-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 compounding amount of the radical generator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the compounds (1) to (3) in total (in terms of complete hydrolysis and condensate). 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.

The thus obtained coating solution for forming a silica-based film used in the present invention has a total solid content concentration of preferably 2 to 30% by weight, which is appropriately adjusted according to the purpose of use. When the total solid content of the composition is 2 to 30% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. In addition, the adjustment of the total solid content concentration is as follows.
If necessary, this is performed by concentration and dilution with the above organic solvent. In the present invention, a coating solution for forming a silica-based film,
When applying to a substrate such as a silicon wafer, SiO ₂ wafer, or SiN wafer, a coating method such as spin coating, dipping, roll coating, or spraying is used. In this case, the film thickness was 0.0
About 5 to 2.5 μm, thickness of 0.1 to 5.0 when applied twice
A coating film of about μm can be formed. Then, dry at room temperature, or at a temperature of about 80 to 600 ° C,
Usually, by heating and drying for about 5 to 240 minutes,
A vitreous or macromolecular silica-based 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 can be performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like. Further, the silica-based film can be formed by irradiating an electron beam or an ultraviolet ray.
Further, in order to control the curing speed of the silica-based film, if necessary, heating may be performed stepwise, or an atmosphere such as nitrogen, air, oxygen, or reduced pressure may be selected. Further, in the present invention, the relative permittivity of the silica-based film is usually 3.0 to 3.0.
1.2, preferably 3.0 to 1.8, and more preferably 3.0 to 2.0.

(C) Silicon Compound In the method for producing a film of the present invention, the surface of the silica-based film formed as described above is treated with the (C) silicon compound. As the (C) silicon compound used here, a compound containing an alkyl group or a phenyl group and having reactivity with a Si—OH group is preferable. Examples of the silicon compound (C) include allyloxytrimethylsilane,
N, O-bis (trimethylsilyl) acetamide, N,
O-bis (triphenylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, bis (trimethylsilyl) urea, bis (triphenylsilyl) urea, trimethylchlorosilane, N- (trimethylsilyl) acetamide, N- (triphenylsilyl) acetamide , Trimethylsilyl azide, triphenylsilyl azide, trimethylsilyl cyananide, triphenylsilyl cyananide, N- (trimethylsilyl) imidazole, N- (triphenylsilyl) imidazole, 3
-Trimethylsilyl-2-oxazolidinone, 3-triphenylsilyl-2-oxazolidinone, trimethylsilyltrifluoromethanesulfonate, triphenylsilyltrifluoromethanesulfonate, hexamethyldisilazane, hexaphenyldisilazane, heptamethyldisilazane, hexamethyl Disiloxane, hexaphenyldisiloxane, N-methyl-N-trimethylsilyltrifluoroacetamide, N-methyl-N-triphenylsilyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-dimethylamino ) Triphenylsilane, nonamethyltrisilazane,
1,1,3,3-tetramethyldisilazane, 1,1,
3,3-tetraphenyldisilazane, trimethyliodosilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triethyl Methoxysilane,
Triethylethoxysilane and the like can be mentioned.
These may be used alone or in combination of two or more.

As a method of surface treatment of the silica-based film,
The method can be performed by a method of dipping a silica-based film in a silicon compound, a method of spin-coating the silicon-based film on the silica-based film, or a method of exposing the silica-based film to a vapor atmosphere of the silicon compound. In the present invention, in the above method, the silicon compound may be a solution or a mixture thereof as it is. During the surface treatment with the silicon compound, the silica-based film may be subjected to a heat treatment, a vacuum treatment, or a reduction treatment with a gas containing hydrogen gas before and / or after the treatment. The heating conditions at this time are 80 to 600 ° C.
Preferably it is 100-500 degreeC. In particular, it is preferable to remove the unreacted silicon compound by heating the silica-based film after the surface treatment with the silicon compound.
Since the interlayer insulating film thus obtained has a small temperature dependence of the dielectric constant and is excellent in mechanical strength, the
System L, DRAM, SDRAM, RDRAM, D
-Interlayer insulating films and etching stopper films for semiconductor devices such as RDRAMs, protective films such as surface coating films for semiconductor devices, intermediate layers in semiconductor manufacturing processes using multilayer resists, interlayer insulating films for multilayer wiring boards, and liquid crystal display devices It is useful for applications such as protective films and insulating films.

[0053]

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 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: 1 cc / min

A composition sample is applied on an 8-inch silicon wafer by temperature dependence of relative permittivity by using a spin coat method, and the substrate is dried on a hot plate at 80 ° C. for 2 minutes and in a nitrogen atmosphere at 200 ° C. for 2 minutes. Then, the substrate was baked on a hot plate in a vacuum atmosphere at 420 ° C. for 25 minutes. This film was subjected to a surface treatment with the silicon compound described in the example. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for relative dielectric constant measurement. After leaving the sample in a clean room at a sample temperature of 23 ° C. and a humidity of 50% for 2 weeks, an HP16451B electrode and HP428 manufactured by Yokogawa-Hewlett-Packard Co., Ltd. were used at a frequency of 100 kHz.
The relative dielectric constant of the coating film at 23 ° C. and 200 ° C. was measured by a CV method using a 4A precision LCR meter.

Mechanical strength (elastic modulus) A composition sample is applied on an 8-inch silicon wafer by spin coating, and the substrate is dried on a hot plate at 80 ° C. for 2 minutes and in a nitrogen atmosphere at 200 ° C. for 2 minutes. Then, the substrate was baked on a hot plate in a vacuum atmosphere at 420 ° C. for 25 minutes. This film was subjected to a surface treatment with the silicon compound described in the example. The modulus of the resulting film is
It was measured by a continuous stiffness measurement method using a nanoindenter XP (manufactured by Nano Instruments).

Synthesis Example 1 77.04 g of distilled methyltrimethoxysilane and distilled tetramethoxysilane 2 were placed in a quartz separable flask.
4.05 g and distilled tetrakis (acetylacetonate)
After dissolving 0.48 g of titanium in 290 g of distilled propylene glycol monopropyl ether, the solution was stirred with a three-one motor to stabilize the solution temperature at 60 ° C.
Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, 25 g of distilled acetylacetone was added, the reaction was further performed for 30 minutes, and the reaction solution was cooled to room temperature. At 50 ° C., 149 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 8,900.

Synthesis Example 2 In a quartz separable flask, 205.50 g of distilled methyltrimethoxysilane and distilled tetramethoxysilane 8 were added.
After dissolving 5.51 g in 426 g of distilled propylene glycol monoethyl ether, the solution was stirred with a three-one motor and stabilized at a solution temperature of 60 ° C. Next, ion-exchanged water 18 in which 0.013 g of maleic anhydride was dissolved.
2 g was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, the reaction solution was cooled to room temperature. 5
At 0 ° 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 1,000.

Synthesis Example 3 Distilled ethanol 570 was placed in a quartz separable flask.
g, 160 g of ion-exchanged water and 90 g of a 10% distilled dimethylamine ion-exchange aqueous solution were added, and the mixture was stirred uniformly. 13.6 of distilled methyltrimethoxysilane was added to this solution.
g of distilled tetraethoxysilane and 20.9 g of distilled tetraethoxysilane.
Added over 0 minutes. While keeping the solution at 65 ° C.,
A time reaction was performed. To this solution was added 3000 g of distilled propylene glycol monopropyl ether, and then 5 g
Using a 0 ° C. evaporator, the solution was concentrated to 10% (complete hydrolyzed condensate conversion). 10% of this solution
Add a solution of maleic acid in distilled propylene glycol,
The reaction solution was obtained by adjusting the pH of the solution to 4. The weight average molecular weight of the condensate and the like thus obtained is 993,
000.

Example 1 100 g of the reaction solution obtained in Synthesis Example 1 was mixed with a polyoxyethylene-polyoxypropylene-polyethylene block polymer (Newpole PE61, manufactured by Sanyo Chemical Industries, Ltd.).
7 g of Teflon (registered trademark) having a pore size of 0.2 μm.
The mixture was filtered through a filter made of silica gel to obtain a coating liquid for forming a silica film used in the present invention. After applying the obtained coating solution on a silicon wafer by a spin coating method, the coating film was baked on a hot plate under a nitrogen atmosphere at 400 ° C. for 30 minutes to form a film having a thickness of 0.7 μm.
m of the silica-based film was obtained. After exposing this silica-based film to a container filled with hexamethyldisilazane vapor for 10 minutes, the silica-based film was baked on a hot plate under a nitrogen atmosphere at 400 ° C. for 5 minutes. When the relative dielectric constant of this film was measured, it was 2.25 at 23 ° C. and 2.25 at 200 ° C.
22 and the temperature dependence of the relative dielectric constant was very small. The elastic modulus of the coating film was 4.0 GPa, which was excellent in mechanical strength.

Example 2 100 g of the reaction solution obtained in Synthesis Example 2 was mixed with a polyoxyethylene-polyoxypropylene-polyethylene block polymer (Newpole PE61, manufactured by Sanyo Chemical Co., Ltd.).
After adding 7 g, the mixture was filtered through a Teflon filter having a pore size of 0.2 μm to obtain a coating liquid for forming a silica film used in the present invention. After the obtained coating solution was applied on a silicon wafer by a spin coating method, the coating film was baked on a hot plate at 400 ° C. in a nitrogen atmosphere for 30 minutes to obtain a silica-based film having a thickness of 0.9 μm. N, O-bis (trimethylsilyl) acetamide was dropped on the silica-based film, and 1 drop at 2000 rpm.
After spin coating for 0 seconds, the coating film was baked on a hot plate at 400 ° C. in a nitrogen atmosphere for 5 minutes. When the relative permittivity of the obtained silica-based film was measured, it was 2.22 at 23 ° C. and 2.20 at 200 ° C., and the temperature dependence of the relative permittivity was very small. Further, the elastic modulus of the silica-based film was 4.3 GPa, which was excellent in mechanical strength.

Example 3 The reaction solution obtained in Synthesis Example 3 was filtered through a Teflon filter having a pore size of 0.2 μm to obtain a coating solution for forming a silica film used in the present invention. After applying the obtained coating solution on a silicon wafer by a spin coating method, the coating film was baked on a hot plate under a nitrogen atmosphere at 400 ° C. for 30 minutes to obtain a film thickness of 1.1.
A silica-based film having a thickness of μm was obtained. After exposing this silica-based film to a container filled with trimethylmethoxysilane vapor for 10 minutes, it was baked on a hot plate under a nitrogen atmosphere at 400 ° C. for 5 minutes. The relative permittivity of the obtained silica-based film was measured to be 2.19 at 23 ° C. and 2.18 at 200 ° C., indicating that the temperature dependence of the relative permittivity was very small. The elastic modulus of the silica-based film was 4.8 GPa, which was excellent in mechanical strength.

Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that the treatment with the vapor of hexamethyldisilazane was not performed. When the relative dielectric constant of this silica-based film was measured,
The temperature dependence of the relative permittivity was very large, 2.49 at 23 ° C. and 2.19 at 200 ° C.

[0064]

According to the present invention, it is possible to provide a silica-based film suitable for an interlayer insulating film which has a small temperature dependence of the relative dielectric constant and excellent mechanical strength.

Continued on the front page F term (reference) 4F073 AA02 BA33 EA64 5F058 AA10 AC03 AF04 AG01 AH01 AH02 BA20 BC05 BF46 BH01 BJ01 BJ02

Claims (7)

[Claims] 1. A method for producing a film, comprising treating the surface of a silica-based film with a silicon compound. 2. The method for producing a film according to claim 1, wherein the silica-based film is a cured product of a hydrolyzed condensate obtained by hydrolyzing and condensing a hydrolyzable silane compound (A). 3. A film comprising a silica-based film containing (A) a hydrolyzed condensate obtained by hydrolyzing and condensing a hydrolyzable silane compound, and (B) a compound having a boiling point or decomposition temperature of 250 to 450 ° C. The method for producing a film according to claim 1, which is a cured product of the above. (A) a compound represented by the following general formula (1): R _a Si (OR ¹ ) _4-a (1) In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2.) (A-2) Table represented by the following general formula (2) compound and _{^{Si (OR 2) 4 ····· (}} 2) which is (wherein, R ² represents a monovalent organic group.) (a-3) a compound represented by the following general formula (3) ^{_{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. At least one selected from the group of
The method for producing a film according to claim 1, wherein the compound is a species compound. 5. The method according to claim 1, wherein the silicon compound is a compound containing an alkyl group or a phenyl group and having reactivity with a Si—OH group. 6. An insulating film produced by the method according to claim 1. Description: 7. The insulating film according to claim 7, wherein the dielectric constant of the film is 2.5 or less.