JP2003027001A - Composition for film formation, method for film formation, and silica-based film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for film formation capable of obtaining a coating film low in relative dielectric constant and high in elastic modulus usable as an interlayer insulation film material for semiconductor devices, or the like, and even when a varnish is used together therewith, generating less foreign material even after long term storage. SOLUTION: The composition for film formation is characterized in that it contains (A) a hydrolytic condensate obtained when an alkoxysilane undergoes hydrolysis and condensation in the presence of a metal chelate compound and/or an acid catalyst and water, (B) a hydrolytic condensate obtained when an alkoxysilane undergoes hydrolysis and condensation in the presence of an alkali catalyst and water, (C) an organic solvent, and (D) water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition, and more specifically, as a material for an interlayer insulating film in a semiconductor device or the like, a coating film having a low relative dielectric constant and a high elastic modulus can be obtained, and a varnish is used. The present invention relates to a film-forming composition that generates little foreign matter even after long-term storage.

[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, which contains a hydrolysis product of tetraalkoxylane as a main component, is also used. Further, with the high integration of semiconductor elements and the like, an interlayer insulating film called organic SOG, which has a low relative dielectric constant and whose main component is polyorganosiloxane, has been developed. In particular, with higher integration and multi-layering of semiconductor elements and the like, better electrical insulation between conductors is required, and therefore, interlayer insulating film materials with lower relative dielectric constant are 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, Same as 5-315
319) or a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-340219 and JP-A-11-34022).
0) has been proposed, the materials obtained by these methods are not stable in the properties of the reaction products, and it is difficult to obtain a coating film having a low dielectric constant and a high elastic modulus, and foreign materials are stored during the storage of the material. Was not suitable for industrial production.

[0004]

The present invention relates to a film-forming composition for solving the above problems, and more specifically, it has a low relative dielectric constant and a high elastic modulus as an interlayer insulating film in a semiconductor device or the like. An object of the present invention is to provide a film-forming composition in which a coating film can be obtained and less foreign matter is generated even when the varnish is stored for a long period of time, and a silica-based film obtained from the composition.

[0005]

[In the formula, R ^{4 to} R ⁷ 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 ⁸ is an oxygen atom, a phenylene group or — (CH ₂ ) _n A group represented by-(wherein n is an integer of 1 to 6), and d represents 0 or 1. ]

Next, the present invention applies the above film-forming composition to a substrate,
The present invention relates to a method for forming a film, which comprises heating. Next, the present invention relates to a silica-based film obtained by the above method for forming a film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the hydrolysis-condensation product of the component (A) and the component (B) means the compound (1) above.
To at least one hydrolyzate and / or condensate selected from the group of (3) to (3). here,
The hydrolyzate in the component (A) and the component (B) means
R ² O— group contained in the compounds (1) to (3) constituting the hydrolysis-condensation product of the component (A) and the component (B), R
^It is not necessary that all ³ O-groups, R ⁵ O-groups and R ⁶ O-groups are hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed. It may be one or a mixture thereof. Also,
The condensate in the component (A) and the component (B) is (A)
Compounds (1) to (3) constituting the component and the component (B)
The silanol groups of the hydrolyzate of Si are condensed to form Si-O-Si.
Although a bond is formed, in the present invention, it is not necessary that all the silanol groups are condensed, and a small part of the silanol groups is condensed, and a mixture of those having different degrees of condensation is also included. It is a concept.

Component (A) and component (B)

Compound (1): In the above general formula (1), examples of the monovalent organic group of R and R ² include an alkyl group, an aryl group, 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, as the alkyl group, a methyl group,
Examples thereof include an ethyl group, a propyl group and a butyl group, preferably having 1 to 5 carbon atoms, and these alkyl groups may be linear or branched, and further have a hydrogen atom substituted with a fluorine atom or the like. May be. 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 fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane,
Fluorotri-iso-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, etc .; 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-sec-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-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane , Sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-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-s
ec-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-trifluoropropyltriethoxysilane 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, 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 (1), examples of the monovalent organic group represented by R ³ include the same organic groups as in the above general formula (1). Specific examples of the compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxylan and tetra-sec-butoxysilane. , Tetra-tert-butoxysilane, tetraphenoxysilane and the like.

Compound (3): In the above general formula (3), examples of the monovalent organic group represented by R ^{4 to} R ⁷ include the same organic groups as in the above general formula (2). . In the general formula (3), as a compound in which R ⁸ 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,
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 ⁸ 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) and the component (B), one or more compounds (1), (2) and (3) are used. You can

When at least one silane compound selected from the group consisting of the compounds (1) to (3) constituting the components (A) and (B) is hydrolyzed and condensed,
More than 0.5 mol and 1 per mol of the compounds (1) to (3)
It is preferable to use 50 mol or less of water, and it is particularly preferable to add 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 hydrolysis-condensation product of the components (A) and (B) of the present invention, the compounds (1) to (1) to
A feature is that a catalyst is used when hydrolyzing and condensing at least one silane compound selected from the group (3). When the hydrolysis-condensation product of the component (A) is produced,
An alkali catalyst is used in the production of the metal chelate compound and / or the acid catalyst and the hydrolysis-condensation product of the component (B).

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tritium. -N-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy.
Bis (acetylacetonato) titanium, di-n-propoxy bis (acetylacetonato) 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 (ethylacetoacetate) 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 (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 chelate compounds such as titanium, mono (acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy・ Mono (acetylacetonato) zirconium, tri-
n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylaceto) Nart) 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 (acetyl) Acetonato) zirconium, mono-t-butoxy tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxy mono (ethylacetoacetate) zirconium Tri -n- propoxy mono (ethylacetoacetate) zirconium, tri -i
-Propoxy mono (ethylacetoacetate) zirconium, tri-n-butoxy mono (ethylacetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) 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-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 (ethyl acetoacetate)
Zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate). Zirconium, a zirconium chelate compound such as tris (acetylacetonato) mono (ethylacetoacetate) zirconium; an aluminum chelate compound such as tris (acetylacetonato) aluminum, 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 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, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid hydrolysates, maleic anhydride hydrolysates, phthalic anhydride hydrolysates, and the like organic acids. Can be mentioned as a more preferable example. These compounds are 1 type or 2 types.
More than one species may be used simultaneously.

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 and the like can be mentioned, more preferably an organic amine, ammonia, alkylamine and tetramethyl. Ammonium hydroxide is particularly preferable from the viewpoint of adhesion of the silica film to the substrate. These alkali catalysts may be used either individually or in combination of two or more.

The amount of the above catalysts used is from compound (1) to
R in (3)² O-group, R³ O-group, R ^Five O-group and
R⁶ Normally, based on 1 mol of the total amount of the groups represented by O-groups,
0.00001 to 10 mol, preferably 0.00005
~ 5 moles. If the amount of the catalyst used is within the above range,
There is little risk of polymer precipitation or gelation during the reaction.

In the present invention, in the components (A) and (B), when each component is converted into a complete hydrolysis-condensation product,
The compound (2) is 5 to 5 in the total amount of the compounds (1) to (3).
It is 75% by weight, preferably 10 to 70% by weight, more preferably 15 to 70% by weight. Further, the compound (1) and / or (3) is contained in an amount of 95 to 25% by weight, preferably 90 to 30% by weight, in the total amount of the compounds (1) to (3).
More preferably, it is 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. Here, in the present invention, the complete hydrolysis-condensation product means R ² O in compounds (1) to (3).
- group, R ³ O-group, R ⁵ O-group, and R ⁶ O-group 10
It means that it is 0% hydrolyzed to be a SiOH group, and is completely condensed to have a siloxane structure. Also, (A)
The components and the component (B) are preferably hydrolysis-condensation products of the compound (1) and the compound (2) because the resulting composition has more excellent storage stability.

The ratio of the component (B) to the component (A) is 5 to 95 parts by weight of the component (B) (completely hydrolyzed condensate) based on 100 parts by weight of the component (A) (calculated as complete hydrolysis and condensation product). Conversion), more preferably 6 to 94 parts by weight.
The proportions of the component (A) and the component (B) used can be changed depending on the target relative permittivity, but the components (A) and (B)
By containing both of the components, a very high elastic modulus of the coating film can be obtained.

Component (C) The film-forming composition of the present invention contains the component (A), the component (B), the component (D) described below, and the component (C). Examples of the organic solvent (C) include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents and aprotic solvents. Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl are used. Butanol, 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-ethylbutyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether,
Examples thereof include polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether. These alcohol solvents may be used alone or in combination.
More than one species may be used simultaneously.

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

As the amide solvent, formamide, N
-Methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N,
N-dimethylacetamide, N-ethylacetamide,
Examples include N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. To be 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, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoacetate
n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxytriglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents are 1
One kind or two or more kinds may be used at the same time. As the aprotic solvent, acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N −
Methyl-Δ3-pyrroline, N-methylpiperidine, N-
Ethylpiperidine, N, N-dimethylpiperazine, N-
Methylimidazole, N-methyl-4-piperidone, N
-Methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3
-Dimethyltetrahydro-2 (1H) -pyrimidinone and the like can be mentioned.

Among these organic solvents, the organic solvent represented by the following general formula (5) is particularly preferable. ^{R 9 O (R 11 0)} e R 10 ····· (5) (R 9 and R ¹⁰ are each independently a hydrogen atom, selected from alkyl or CH ₃ CO- 1 to 4 carbon atoms It represents a monovalent organic group, R ¹¹ represents an alkylene group, and e represents an integer of 1 to 2.) The above (C) organic solvent may be used alone or in combination of two or more. it can. The film-forming composition of the present invention can use the same solvent when hydrolyzing and / or condensing the compounds (1) to (3) constituting the component (A) and the component (B). .

Specifically, water or water diluted with a solvent is intermittently or continuously added to the solvent in which the compounds (1) to (3) are dissolved. At this time, the catalyst may be added to the solvent in advance, or may be dissolved or dispersed in water when water is added. As the reaction temperature at this time,
Usually, it is 0 to 100 ° C, preferably 15 to 90 ° C.

Component (D) The film-forming composition of the present invention is characterized by containing (D) water. By containing a certain amount of water, it is possible to obtain a film-forming composition with less generation of foreign matter even after long-term storage. The ratio of the component (D) to the component (C) is such that the component (D) is 2 to 1 with respect to 100 parts by weight of the component (C).
5 parts by weight, more preferably 2.5 to 12 parts by weight.
When the content of the component (D) is less than 2 parts by weight, the effect of suppressing the generation of foreign matter during long-term storage of the film-forming composition is small, and when it exceeds 15 parts by weight, the coating uniformity of the coating film may be poor.

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 acid anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle diameter of 5 to 30 nm, preferably 10 to 10.
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 component (A) (completely hydrolyzed condensate). These may be used either individually or in combination of two or more.

As the silane coupling agent, for example, 3
-Glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-
(2-Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethylenetriamine, 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 and diisopropylperoxy. Dicarbonate,
1,1,3,3-tetramethylbutylperoxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxy neodecanoate, dimethoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butyl peroxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl 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 content 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 adjustment of the total solid content concentration is carried out, if necessary, by concentration and dilution with the organic solvent (B). The composition of the present invention was applied to a silicon wafer, a SiO ₂ wafer, a SiN
When applying to a base material such as a wafer, a coating means such as spin coating, dipping, roll coating or spraying is used.

The film thickness at this time is a dry film thickness of about 0.05 to 2.5 μm for a single coating, and a film thickness of about 0.1 to 5.0 μm for a second coating. be able to. Then, it is dried at room temperature or 80 ~ 600
A glassy or giant polymer insulating film can be formed by heating at a temperature of about C for about 5 to 240 minutes and drying. As a heating method at this time, a hot plate, an oven, a furnace or the like can be used, and a heating atmosphere is under air, a nitrogen atmosphere,
It can be performed in an argon atmosphere, under vacuum, under reduced pressure with controlled oxygen concentration, and the like. The coating film can also be formed by irradiating with an electron beam or 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 1.2.
It is 2.0.

The interlayer insulating film thus obtained exhibits a low relative dielectric constant and is excellent in embedding in a step, so that it can be used as an LSI, a system LSI, a DRAM, an SDR.
Interlayer insulating film for semiconductor elements such as AM, RDRAM and D-RDRAM, etching stopper film, 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 It is useful for applications such as a protective film or an insulating film for a liquid crystal display element, a protective film or an insulating film for an electroluminescent display element, and the like.

[0047]

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

The composition sample was applied onto a silicon wafer having a relative dielectric constant of 8 inches by a spin coating method, and the substrate was dried on a hot plate at 80 ° C. for 1 minute and in a nitrogen atmosphere at 200 ° C. for 1 minute. Then, the substrate was baked on a hot plate in a vacuum atmosphere of 380 ° C. for 28 minutes. An aluminum electrode pattern was formed on the obtained substrate by a vapor deposition method to prepare a sample for measuring relative permittivity. HP16451 manufactured by Yokogawa-Hewlett-Packard Co., Ltd. at a frequency of 100 kHz.
The relative dielectric constant of the coating film was measured by the CV method using a B electrode and an HP4284A precision LCR meter.

Coefficient of elasticity of coating film A composition sample was applied onto a silicon wafer having an elasticity of 8 inches by a spin coating method, and the substrate was dried on a hot plate at 80 ° C. for 1 minute and in a nitrogen atmosphere at 200 ° C. for 1 minute. Further, the substrate was baked on a hot plate in a vacuum atmosphere of 380 ° C. for 28 minutes. The elastic modulus of the obtained coating film was measured by a continuous rigidity measuring method using Nanoindenter XP (manufactured by Nano Instruments).

Measurement of Foreign Material in Varnish The varnish for film formation was filtered using a Teflon (registered trademark) cartridge filter having a pore size of 0.1 μm. The number of foreign matters of 0.2 μm or more present in 1 cc of this solution is determined by RI.
It was measured using a particle counter KL-20A manufactured by ON Co., Ltd., and judged according to the following criteria. : (Number of foreign substances after storing varnish at 35 ° C x 2 months) /
(Initial number of foreign matter) ≤ 2 ×: (Number of foreign matter after storing the varnish at 35 ° C × 2 months) /
(Initial number of foreign matter)> 2

Synthesis Example 1 77.04 g of distilled methyltrimethoxysilane and 2 of distilled tetramethoxysilane were placed in a quartz separable flask.
4.05g and distilled tetrakis (acetylacetonate)
0.48 g of titanium was dissolved in 290 g of distilled propylene glycol monoethyl ether and then 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, and the reaction was further continued for 30 minutes, and the reaction solution was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain 149 g of a reaction solution. The weight average molecular weight of the thus obtained condensate and the like was 8,900.

Synthesis Example 2 205.50 g of distilled methyltrimethoxysilane and 8 parts of distilled tetramethoxysilane were placed in a quartz separable flask.
5.51 g was dissolved in 426 g of distilled propylene glycol monomethyl ether and then stirred with a three-one motor to stabilize the solution temperature at 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
A solution containing methanol was removed from the reaction solution at 0 ° C. by evaporation in an amount of 360 g to obtain a reaction solution. The condensate and the like thus obtained had a weight average molecular weight of 1,000.

Synthesis Example 3 In a quartz separable flask, distilled ethanol 470.
9 g, ion-exchanged water 226.5 g and 25% tetramethylammonium hydroxide aqueous solution 17.2 g were added and stirred uniformly. Methyltrimethoxysilane 44.9 was added to this solution.
and a mixture of 68.6 g of tetraethoxysilane were added over 2 hours. The reaction was carried out for 6 hours while keeping the solution at 58 ° C. 80g of 20% maleic acid solution in this solution
Was added, and the mixture was sufficiently stirred and then cooled to room temperature. Add propylene glycol monopropyl ether 400 to this solution.
g, and then the solution was concentrated to 10% (completely hydrolyzed condensate equivalent) using an evaporator at 50 ° C., and then 10 g of a 10% propylene glycol monopropyl ether solution of maleic acid was added to react. A liquid was obtained. The weight average molecular weight of the thus obtained condensate and the like was 990,000.

Synthesis Example 4 570 g of distilled ethanol was placed in a quartz separable flask.
Deionized water 160 g and 10% methylamine aqueous solution 50
g, and stirred at 57 ° C. A mixture of 15.6 g of methyltriethoxysilane and 20.9 g of tetraethoxysilane was added to this mixed solution at a constant rate over 1 hour. This solution was reacted at 57 ° C. for another 3 hours. Add propylene glycol monopropyl ether 300 to this solution.
g was added, and then the solution was concentrated using an evaporator at 50 ° C. until it became 10% (completely hydrolyzed condensate). A propylene glycol solution of 10% maleic acid was added to this solution to adjust the pH of the solution to 4 to obtain a reaction solution. The weight average molecular weight of the thus obtained condensate and the like was 10,050,000.

Example 1 45 g of the reaction solution obtained in Synthesis Example 1, 40 g of the reaction solution obtained in Synthesis Example 3 and 2.9 g of ion-exchanged water were added and sufficiently stirred. This solution was filtered through a Teflon filter having a pore size of 0.1 μm to obtain a film forming composition of the present invention. The obtained composition was applied onto a silicon wafer by spin coating. The coating film had a low relative dielectric constant of 2.64, and the elastic modulus of the coating film was 8.9 GPa, which was excellent in mechanical strength. In addition, the increase in foreign substances after storing the varnish was 1.
It was 3 times and was excellent in storage stability.

Examples 2-5 In Example 1, instead of the reaction solution and the reaction solution, Table 1 was used.
Evaluation was performed in the same manner as in Example 1 except that the reaction solution shown in 1 was used. The evaluation results are also shown in Table 1.

[0058]

[Table 1]

Comparative Example 1 A coating film was evaluated in the same manner as in Example 1 except that only the reaction liquid obtained in Synthesis Example 1 was used. The relative permittivity of the coating film was a low value of 2.89, but the elastic modulus of the coating film was 3.7.
The value was inferior to GPa and the example. In addition, the storage stability was inferior because the increase in the amount of foreign substances after storing the varnish was 5.1 times.

Comparative Example 2 The coating film was evaluated in the same manner as in Example 1 except that only 45 g of the reaction solution obtained in Synthesis Example 1 and 40 g of the reaction solution obtained in Synthesis Example 3 were used. The relative permittivity of the coating film is 2.67.
Although the elastic modulus of the coating film was as high as 8.2 GPa, the increase of foreign substances after storing the varnish was 6.3.
It was twice as inferior in storage stability.

Comparative Example 3 A coating film was evaluated in the same manner as in Example 1 except that only the reaction liquid obtained in Synthesis Example 4 was used. The relative permittivity of the coating film was as low as 2.23, and the increase of foreign substances after storing the varnish was 1.9 times, but the elastic modulus of the coating film was 4.0 G.
Pa was inferior to that of the example.

[0062]

INDUSTRIAL APPLICABILITY According to the present invention, (A) an alkoxysilane hydrolysis polymer synthesized in the presence of a metal chelate compound and / or an acid catalyst and water, and (B) a catalyst synthesized in the presence of an alkali catalyst and water. Alkoxysilane hydrolysis polymer,
By using the film-forming composition containing (C) an organic solvent and (D) water, a coating film having a low relative dielectric constant and a high elastic modulus can be obtained, and even if the varnish is stored for a long period of time, it is It is possible to provide a film-forming composition (interlayer insulating film material) that is less likely to occur.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) C09D 183/14 C09D 183/14 H01L 21/312 H01L 21/312 C 21/316 21/316 G (72) Inventor Atsushi Shiota 2-11-24 Tsukiji, Chuo-ku, Tokyo J-SR Co., Ltd. (72) Inventor Toshinori Nishikawa 2--11-21 Tsukiji, Chuo-ku, Tokyo J-S Co., Ltd. (72) Kinji Yamada 2-11-24 Tsukiji, Chuo-ku, Tokyo J-SR Co., Ltd. F-term (reference) 4D075 BB26Z CA03 CA23 DA06 DB14 DC19 DC22 EA06 EA07 EB16 EB33 EB43 EB47 EB56 EC01 EC07 EC08 EC30 EC54 4J002 CP031 CP032 CP081 GQ05 HA07 4J038 DL02 DL031 DL032 DL051 DL052 DL071 DL072 DL081 DL082 DL111 HA156 JA17 JA26 JA33 JA34 JA53 JB13 KA06 NA17 NA21 NA26 PA18 PA19 PB07 5F058 AC03 BC02 BF46 BH01 BJ02

Claims (6)

[Claims] 1. A compound 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). A hydrolysis-condensation product obtained by hydrolyzing and condensing at least one compound with a metal chelate compound and / or an acid catalyst in the presence of water, (B) the following general formula (1)
In the presence of an alkali catalyst and water, at least one compound selected from the group consisting of a compound represented by the following formula, a compound represented by the following general formula (2) and a compound represented by the following general formula (3): A film-forming composition comprising a hydrolysis-condensation product obtained by hydrolysis and condensation, (C) an organic solvent, and (D) water. R _a Si (OR ² ) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ² is a monovalent organic group, and a is 1 to 2). Si (OR ³ ) ₄ (2) (In the formula, R ³ represents a monovalent organic group.) R ⁴ _b (R ⁵ O) _3-b Si- ( ^{_{R 8) d -Si (oR 6}} ) 3-c R 7 c ·· (3) wherein, R ⁴ to R ⁷ are the same or different and each represents a monovalent organic group, b-c are identical or different, R is an integer from 0 to 2
⁸ represents an oxygen atom, a phenylene group or - (CH _{2) n} - group represented by (wherein, n represents an integer from 1 to 6), d is 0
Or 1 is shown. ] 2. The film-forming composition according to claim 1, wherein the component (D) is contained in an amount of 2 to 15 parts by weight based on 100 parts by weight of the component (C). 3. The use ratio of the component (B) to the component (A) is 5 to 95 parts by weight (complete hydrolysis) of the component (A) relative to 100 parts by weight of the component (A). The film forming composition according to claim 1, wherein the composition is a condensate. 4. The film-forming composition according to claim 1, wherein the component (C) is an organic solvent represented by the following general formula (4). ^{R 9 O (R 11 0)} e R 10 ····· (4) (R 9 and R ¹⁰ are each independently a hydrogen atom, selected from alkyl or CH ₃ CO- 1 to 4 carbon atoms Represents a monovalent organic group, R ¹¹ represents an alkylene group, and e represents an integer of 1 to 2.) 5. A method for forming a film, which comprises applying the film forming composition according to claim 1 on a substrate and heating the substrate. 6. A silica-based film obtained by the method for forming a film according to claim 5.