JP2003041191A - Composition for film formation, method of forming film and silica film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film-forming composition that shows excellent storage stability of the composition and can form silica films giving a small difference in specific inductive capacity caused by firing conditions. SOLUTION: The film-forming composition includes (A) a hydrolyzed and condensed product obtained by hydrolyzing and condensing alkoxysilane in the presence of an alkaline catalyst and water, (B) at least one selected from the group consisting of ammonium salt and first through quaternary alkylammonium salts in an amount of 0.005-0.5 pt.wt. per 100 pts.wt. of the component (A), calculated as completely hydrolyzed and condensed product and (C) an organic solvent and the pH is kept at 2-4.

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 an interlayer insulating film material for a semiconductor device or the like, the composition has excellent storage stability and a difference in relative dielectric constant depending on firing conditions. The present invention relates to a film-forming composition capable of forming a small silica-based film, a method for producing the composition, and a silica-based film.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is often used as an interlayer insulating film in a semiconductor device or the like. And in recent years
For the purpose of forming a more uniform interlayer insulating film, S
A coating type insulating film called a OG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has also been used. 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, but the materials obtained by these methods are not stable in the properties of the reaction product, the storage stability of the composition is poor, and the difference in the relative dielectric constant depending on the firing conditions is large. , 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 excellent storage stability as an interlayer insulating film in a semiconductor device, An object of the present invention is to provide a film-forming composition having a small difference in relative dielectric constant depending on firing conditions and a silica-based film obtained from the composition.

[0005]

The present invention provides (A) a compound represented by the following general formula (1) (hereinafter referred to as "compound (1)").
R _a Si (OR ¹ ) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, a Represents an integer of 1 to 2.) A compound represented by the following general formula (2) (hereinafter, also referred to as “compound (2)”) and Si (OR ² ) ₄ (2) (formula) In the formula, R ² represents a monovalent organic group.) A compound represented by the following general formula (3) (hereinafter, also referred to as “compound (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 and each represents a monovalent organic group, b-c is the same Or differently, an integer from 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
A group represented by (where n is an integer of 1 to 6), d
Represents 0 or 1. ] At least 1 selected from the group
With respect to a hydrolysis-condensation product obtained by hydrolyzing and condensing a seed compound in the presence of an alkali catalyst and water, and 100 parts by weight of component (B) (A) (in terms of complete hydrolysis-condensation product),
At least 1 selected from the group of 0.005 to 0.5 parts by weight of ammonium salt and primary to quaternary alkyl ammonium salt
Containing a seed, and (C) an organic solvent, and having a pH of 2 to 4
And a film-forming composition. Next, the present invention relates to a method for forming a film, which comprises applying the film forming composition to a substrate and heating the substrate. next,
The present invention relates to a silica-based film obtained by the above film forming method.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the hydrolytic condensate is at least one hydrolyzate and / or condensate selected from the group of the compounds (1) to (3). Here, the hydrolyzate in the component (A) means the R ¹ O-group contained in the compounds (1) to (3),
It is not necessary that all R ² O-groups, R ⁴ O-groups and R ⁵ O-groups are hydrolyzed, for example, only one is hydrolyzed and two or more are hydrolyzed. Existing or a mixture thereof. Also,
The hydrolyzed condensate is one in which the silanol groups of the hydrolyzates of the compounds (1) to (3) are condensed to form a Si-O-Si bond, but in the present invention, all the silanol groups are condensed. It does not need to be present, and is a concept that also includes a mixture of a small amount of silanol groups, a mixture of those having different degrees of condensation, and the like.

Component (A) Component (A) is at least one silane compound selected from the group consisting of the above compounds (1) to (3). Compound (1); R and R in the general formula (1)
The ¹ monovalent organic group, an alkyl group, an aryl group,
Examples thereof include an allyl group and a glycidyl group. Further, in the general formula (1), R is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like, and preferably a carbon number of 1 to 1.
5, these alkyl groups may be linear or branched, and the hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane and tri-. sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane and the like;

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

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

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

Compound (2): In the above general formula (2), examples of the monovalent organic group represented by R ² include the same organic groups as in the above general formula (1). Specific examples of the compound 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 ^{3 to} R ⁶ include the same organic groups as in the above general formula (1). . In the general formula (3), as the 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,
1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,
3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,
Preferred examples include 3-dimethoxy-1,1,3,3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane.

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

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

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

Of these, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,
2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1-
(Diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2-
(Trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethyl) (Silyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) )benzene,
1,3-bis (triethoxysilyl) benzene, 1,4
Preferred examples include -bis (trimethoxysilyl) benzene and 1,4-bis (triethoxysilyl) benzene.

In the present invention, as the compounds (1) to (3) constituting the component (A), the above compound (1),
One or more of (2) and (3) can be used.

When the component (A) is hydrolyzed and condensed, it is preferable to use more than 20 mol and not more than 150 mol of water per mol of the total amount of the component (A), preferably more than 20 mol and 130 mol. It is particularly preferred to add water.
If the amount of water added is 20 mol or less, the crack resistance of the coating film may be inferior, and if it exceeds 150 mol, polymer precipitation or gelation may occur during the hydrolysis and condensation reactions.

In the present invention, the compounds (1) to
It is particularly preferable to use an alkali catalyst when hydrolyzing and condensing at least one silane compound selected from the group (3). By using an alkaline catalyst,
A silica-based film having a low relative dielectric constant can be obtained. Examples of the alkali catalyst that can be used in the present invention include:
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydro Oxide, tetraethylammonium hydroxide,
Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, pentylamine, octylamine, nonylamine, decylamine, N, N-dimethylamine, N, N -Diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine,
Trimethylimidine, 1-amino-3-methylbutane,
Dimethylglycine, 3-amino-3-methylamine and the like can be mentioned, and preferred examples are ammonia, 1
To tertiary alkylamine, tetraalkylammonium hydroxide, sodium hydroxide, potassium hydroxide, particularly preferably primary to tertiary alkylamine and tetraalkylammonium hydroxide are particularly preferable from the viewpoint of adhesion of the silica-based film to the substrate. . These alkali catalysts may be used either individually or in combination of two or more.

The amount of the above-mentioned alkali catalyst used is such that R ¹ O-group, R ² O-group and R ⁴ O-in the compounds (1) to (3).
The total amount to 1 mole of the group represented by group and R ⁵ O-group, typically, 0.00001 mol, preferably 0.
It is from 00005 to 5 mol. When the amount of the alkali catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction.

The radius of gyration of the hydrolyzed condensate thus obtained is a radius of gyration by GPC (refractive index, viscosity, light scattering measurement) method, preferably 5 to 50 nm, more preferably 8 to 40 nm, and particularly preferably. Is 9 to 20 nm. When the radius of gyration of the hydrolyzed condensate is 5 to 50 nm, the obtained silica-based film can have particularly excellent relative permittivity, elastic modulus, and film uniformity. Further, the hydrolyzed condensate thus obtained is characterized in that it is not in the form of particles and thus has excellent coatability on a substrate. The fact that it does not have a particulate form is confirmed by, for example, transmission electron microscope observation (TEM).

In the component (A), when each component is converted into a complete hydrolysis-condensation product, the compound (2) is contained in the total amount of the compounds (1) to (3), preferably 5 to 75% by weight. Is 10 to 70% by weight, more preferably 15 to 70% by weight
Is. Further, the compound (1) and / or (3) is
In the total amount of the compounds (1) to (3), 95 to 25% by weight, preferably 90 to 30% by weight, more preferably 85 to 3% by weight.
It is 0% by weight. Compound (2) is compound (1)-
When it is 5 to 75% by weight in the total amount of (3), the elastic modulus of the obtained coating film is high and the low dielectric property is particularly excellent. Here, in the present invention, the complete hydrolysis-condensation product means the R ¹ O— group, R ² O— group and R ⁴ O— in the compounds (1) to (3).
Group and R ⁵ O-group is 100% hydrolyzed to SiOH groups, more fully condensed it refers to became siloxane structure. Further, the component (A) is preferably a hydrolysis-condensation product of the compound (1) and the compound (2), because the storage stability of the obtained composition is more excellent.

Further, in the hydrolysis-condensation product, at least one selected from the group of compounds (1) to (3) is hydrolyzed and condensed in the presence of an alkali catalyst to give a hydrolysis-condensation product, preferably Has a radius of gyration of 5 to 50 nm, and then the pH of the composition is preferably adjusted to 7 or less. As a method of adjusting the pH, a method of adding a pH adjuster, a method of distilling an alkali catalyst from the composition under normal pressure or a reduced pressure, and a method of bubbling a gas such as nitrogen or argon in the composition And the like, a method of removing the alkali catalyst from the composition with an ion exchange resin, a method of removing the alkali catalyst from the system by extraction or washing, and the like. Each of these methods may be used in combination.

Here, examples of the pH adjusting agent include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, oxalic acid and the like. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid. , Gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, Benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid,
Malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid, maleic anhydride hydrolyzate, phthalic anhydride Hydrolyzate and the like can be mentioned. These compounds are 1 type or 2 types.
More than one species may be used simultaneously.

The pH of the composition prepared by the above pH adjusting agent is 7
Hereinafter, it is preferably adjusted to 1 to 6. In this way, the storage stability of the obtained composition is improved by adjusting the pH of the hydrolysis-condensation product to 50,000 to 10,000,000 and then adjusting the pH within the above range with the above pH adjusting agent. The effect of doing is obtained. The pH adjuster is used in such an amount that the pH of the composition falls within the above range, and the amount used is appropriately selected.

Component (B) The component (B) used in the present invention is an ammonium salt, 1 to
It is at least one selected from the group of quaternary alkyl ammonium salts. By containing the component (B) in a specific amount in the composition, the storage stability of the composition is improved.

As the component (B), ammonia organic acid salt, ammonium hydroxide, ammonia nitrate, primary to quaternary alkylamine organic acid salt, primary to quaternary alkylammonium hydroxide, and primary to quaternary alkylamine nitrate are used. I can name it.

Specific examples of the component (B) include, for example,
Monia acetate, ammonia propionate, ammonia
Butanoate, ammonia pentatanate, ammonia hex
Sanate, ammonia heptanoate, ammonia octa
Phosphate, ammonia nonanoate, ammonia decanoic acid
Salt, ammonia oxalate, ammonia maleate,
Ammonia methyl malonate, ammonia adipic acid
Salt, ammonia sebacate, ammonia gallate,
Ammonia butyrate, Ammonia meritate, Ammonium
Aarachidonate, ammonia shikimate, ammonia
2-ethylhexanoate, ammonia oleate, a
Ammonia stearate, ammonia linoleate,
Ammonia linoleinate, ammonia salicylate,
Ammonia benzoate, ammonia p-aminobenzoic acid
Salt, ammonia p-toluenesulfonate, ammonia
Benzene sulfonate, ammonia monochloroacetate,
Ammonia dichloroacetate, Ammonia trichloroacetic acid
Salt, ammonia trifluoroacetate, ammonia formic acid
Salt, ammonia malonate, ammonia sulfonate,
Ammonia phthalate, Ammonia fumarate, Ammonia
Near citrate, ammonia tartrate, ammonia
Citrate, ammonia fumarate, ammonia itaconic acid
Salt, ammonia mesaconate, ammonia citraconic acid
Salt, ammonia malate, ammonia glutarate,
Ammonium hydroxide, ammonia nitrate,
(Mono, di, tri) methylamine acetate, (mono, di,
(Tri) methylamine propionate, (mono, di,
Li) methylamine butanoate, (mono, di, tri) methyl
Lumine pentatanate, (mono, di, tri) methylami
Hexanoate, (mono, di, tri) methylamine hep
Tantalate, (mono, di, tri) methylamine octanoic acid
Salt, (mono-, di-, tri) methylamine nonanoate, (mo
No, di, tri) methylamine decanoate, (mono, di,
Tri) methylamine oxalate, (mono, di, tri)
Cylamine maleate, (mono, di, tri) methyl
Minmethyl malonate, (mono, di, tri) methylami
Acid adipate, (mono, di, tri) methylamine seba
Phosphate, (mono-, di-, tri) methylamine gallic acid
Salt, (mono, di, tri) methylamine butyrate, (mono,
Di, tri) methylamine mellitate, (mono, di, tho
Li) methylamine arachidonate, (mono, di, tri)
Methylamine shikimate, (mono-, di-, tri) methyl
Min 2-ethylhexanoate, (mono, di, tri) meth
Ruamine oleate, (mono, di, tri) methylami
Stearate, (mono, di, tri) methylamine
Nolate, (mono-, di-, tri) methylamine linolei
Phosphate, (mono-, di-, tri) methylamine salicylic acid
Salt, (mono-, di-, tri) methylamine benzoate, (molybdenum
No, di, tri) methylamine p-aminobenzoate,
(Mono-, di-, tri-) methylamine p-toluene sulfone
Acid salt, (mono-, di-, tri) methylamine benzenesulfo
Phosphate, (mono, di, tri) methylamine monochloro vinegar
Acid salt, (mono-, di-, tri) methylamine dichloroacetic acid
Salt, (mono, di, tri) methylamine trichloroacetic acid
Salt, (mono-, di-, tri) methylamine trifluoroacetic acid
Salt, (mono, di, tri) methylamine formate, (mono,
Di, tri) methylamine malonate, (mono, di, tho
Li) methylamine sulfonate, (mono, di, tri)
Cylamine phthalate, (mono, di, tri) methylami
Fumarate, (mono, di, tri) methylamine quench
Acid salt, (mono-, di-, tri) methylamine tartrate, (molybdenum
No, di, tri) methylamine succinate, (mono, di,
Tri) methylamine fumarate, (mono, di, tri)
Cylamine itaconic acid salt, (mono, di, tri) methyl
Minmesaconate, (mono-, di-, tri) methylamine
Traconate, (mono, di, tri) methylamine apple
Acid salt, (mono-, di-, tri) methylamine glutarate,
(Mono-, di-, tri-) methyl ammonium hydroxide
Id, (mono, di, tri) methylamine nitrate, (mo
No, di, tri) ethylamine acetate, (mono, di, tri)
Li) ethylamine propionate, (mono, di, tri)
Ethylamine butanoate, (mono, di, tri) ethyl acetate
Minpentanate, (mono, di, tri) ethylamine
Xanthate, (mono-, di-, tri) ethylamine heptane
Acid salt, (mono-, di-, tri) ethylamine octanoate,
(Mono, di, tri) ethylamine nonanoate, (mono,
Di, tri) ethylamine decanoate, (mono, di, tho
Li) ethylamine oxalate, (mono, di, tri) ethyl
Ruamine maleate, (mono, di, tri) ethylami
Methyl malonate, (mono-, di-, tri) ethylamine
Adipate, (mono, di, tri) ethylamine sebac
Phosphate, (mono-, di-, tri) ethylamine gallate,
(Mono, di, tri) ethylamine butyrate, (mono, di,
Tri) ethylamine mellitic acid salt, (mono, di, tri)
Ethylamine arachidonate, (mono, di, tri) ethyl
Lumine shikimate, (mono-, di-, tri) ethylamine
2-ethylhexanoate, (mono, di, tri) ethyl
Minoleate, (mono, di, tri) ethylamines
Thearate, (mono, di, tri) ethylamine linole
Phosphate, (mono, di, tri) ethylamine linoleic acid
Salt, (mono, di, tri) ethylamine salicylate,
(Mono, di, tri) ethylamine benzoate, (mono,
Di, tri) ethylamine p-aminobenzoate, (mo
No, di, tri) ethylamine p-toluenesulfonic acid
Salt, (mono, di, tri) ethylamine benzene sulfone
Acid salt, (mono-, di-, tri) ethylamine monochloroacetic acid
Salt, (mono-, di-, tri) ethylamine dichloroacetate,
(Mono, di, tri) ethylamine trichloroacetate,
(Mono, di, tri) ethylamine trifluoroacetate,
(Mono, di, tri) ethylamine formate, (mono, di,
Tri) ethylamine malonate, (mono-, di-, tri) -e
Cylamine sulfonate, (mono-, di-, tri) ethyl acetate
Minphthalate, (mono-, di-, tri) ethylamine fuma
Phosphate, (mono-, di-, tri) ethylamine citrate,
(Mono, di, tri) ethylamine tartrate, (mono,
Di, tri) ethylamine succinate, (mono, di, tho
Li) ethylamine fumarate, (mono, di, tri) ethyl
Ruamine itaconate, (mono, di, tri) ethylami
Nmesaconate, (mono-, di-, tri) ethylamine cit
Laconate, (mono, di, tri) ethylamine malic acid
Salt, (mono, di, tri) ethylamine glutarate,
(Mono-, di-, tri-) ethylammonium hydroxa
Id, (mono, di, tri) ethylamine nitrate, (mo
No, di, tri) propylamine acetate, (mono, di,
Li) propylamine propionate, (mono, di,
Li) Propylamine butanoate, (mono, di, tri) pu
Ropylamine pentanoate, (mono, di, tri) propyi
Ruamine hexanoate, (mono-, di-, tri) propylate
Minheptanoate, (mono, di, tri) propylamine
Octanoate, (mono-, di-, tri) propylamine nona
Phosphate, (mono, di, tri) propylamine decanoic acid
Salt, (mono-, di-, tri) propylamine oxalate,
(Mono, di, tri) propylamine maleate, (mo
No, di, tri) propylamine methylmalonate, (mo
No, di, tri) propylamine adipate, (mono,
Di, tri) propylamine sebacate, (mono, di,
Tri) propylamine gallate, (mono, di, tri)
Propylamine butyrate, (mono, di, tri) propyl
Minmellitic acid salt, (mono-, di-, tri) propylamine
Arachidonate, (mono, di, tri) propylamine
Chimate, (mono-, di-, tri) propylamine 2-ethyl
Ruhexanoate, (mono-, di-, tri) propylamine
Leanate, (mono-, di-, tri) propylamine steer
Phosphate, (mono-, di-, tri) propylamine linole
Acid salt, (mono-, di-, tri) propylamine linoleic acid
Salt, (mono-, di-, tri) propylamine salicylate,
(Mono, di, tri) propylamine benzoate, (mo
No, di, tri) propylamine p-aminobenzoate,
(Mono-, di-, tri) propylamine p-toluenesulfo
Phosphate, (mono-, di-, tri) propylamine benzene
Ruphonate, (mono, di, tri) propylamine monoc
Loroacetate, (mono, di, tri) propylamine dichloro
Roacetate, (mono, di, tri) propylamine trichloro
Roacetate, (mono, di, tri) propylamine triflu
Oroacetate, (mono, di, tri) propylamine formic acid
Salt, (mono-, di-, tri) propylamine malonate,
(Mono, di, tri) propylamine sulfonate, (mo
No, di, tri) propylamine phthalate, (mono,
Di, tri) propylamine fumarate, (mono, di, tho
Li) propylamine citrate, (mono, di, tri)
Lopyramine tartrate, (mono-, di-, tri) propyla
Minsuccinate, (mono, di, tri) propylamine
Malate, (mono, di, tri) propylamine itacone
Acid salt, (mono-, di-, tri) propylamine mesaconic acid
Salt, (mono-, di-, tri) propylamine citraconic acid
Salt, (mono-, di-, tri) propylamine malate,
(Mono, di, tri) propylamine glutarate, (mo
No, di, tri) propyl ammonium hydroxide
De, (mono, di, tri) propylamine nitrate, (mo
No, di, tri) butylamine acetate, (mono, di,
Li) Butylamine propionate, (mono, di, tri)
Butylamine butanoate, (mono-, di-, tri) -butyla
Minpentanate, (mono, di, tri) butylamine
Xanthate, (mono, di, tri) butylamine heptane
Acid salt, (mono-, di-, tri) butylamine octanoate,
(Mono, di, tri) butylamine nonanoate, (mono,
Di, tri) butylamine decanoate, (mono, di, tho
Li) Butylamine oxalate, (mono, di, tri) butyrate
Ruamine maleate, (mono, di, tri) butylami
Methyl malonate, (mono-, di-, tri) butylamine
Adipate, (mono, di, tri) butylamine sebac
Phosphate, (mono-, di-, tri) butylamine gallate,
(Mono, di, tri) butylamine butyrate, (mono, di,
Tri) butylamine mellitic acid salt, (mono, di, tri)
Butylamine arachidonate, (mono, di, tri) butyrate
Ruamine shikimate, (mono-, di-, tri) butylamine
2-Ethylhexanoate, (mono, di, tri) butyrua
Minoleate, (mono, di, tri) butylamines
Thearate, (mono, di, tri) butylamine linole
Phosphate, (mono-, di-, tri) butylamine linoleic acid
Salt, (mono, di, tri) butylamine salicylate,
(Mono, di, tri) butylamine benzoate, (mono,
Di, tri) butylamine p-aminobenzoate, (mo
No, di, tri) butylamine p-toluenesulfonic acid
Salt, (mono-, di-, tri) butylamine benzene sulfone
Acid salt, (mono-, di-, tri) butylamine monochloroacetic acid
Salt, (mono, di, tri) butylamine dichloroacetate,
(Mono, di, tri) butylamine trichloroacetate,
(Mono, di, tri) butylamine trifluoroacetate,
(Mono, di, tri) butylamine formate, (mono, di,
Tri) butylamine malonate, (mono-, di-, tri) bu
Cylamine sulfonate, (mono-, di-, tri) -butyla
Minphthalate, (mono, di, tri) butylamine fumara
Phosphate, (mono-, di-, tri) butylamine citrate,
(Mono, di, tri) butylamine tartrate, (mono,
Di, tri) butylamine succinate, (mono, di, tho
Li) Butylamine fumarate, (mono, di, tri) butyrate
Ruamine itaconate, (mono, di, tri) butylami
Nmesaconate, (mono-, di-, tri) butylamine cit
Laconate, (mono, di, tri) butylamine malic acid
Salt, (mono, di, tri) butylamine glutarate,
(Mono-, di-, tri-) butylammonium hydroxa
Id, (mono, di, tri) butylamine nitrate, (mo
No, di, tri) ethanolamine acetate, (mono, di,
Tri) ethanolamine propionate, (mono, di,
Tri) ethanolamine butanoate, (mono, di,
Re) ethanolamine pentatanate, (mono, di,
Re) ethanolamine hexanoate, (mono, di,
Re) ethanolamine heptanoate, (mono, di,
Re) ethanolamine octanoate, (mono, di,
Li) ethanolamine nonanoate, (mono, di, tri)
Ethanolamine decanoate, (mono, di, tri) eta
Nolamine oxalate, (mono, di, tri) ethanol
Ruamine maleate, (mono, di, tri) ethanol
Amine methyl malonate, (mono, di, tri) ethanol
Luamine adipate, (mono, di, tri) ethanol
Amine sebacate, (mono, di, tri) ethanol
Mingal gallate, (mono, di, tri) ethanolamine
Butyrate, (mono, di, tri) ethanolamine benefits
Acid salt, (mono, di, tri) ethanolamine arachidone
Acid salt, (mono, di, tri) ethanolamine shikimic acid
Salt, (mono, di, tri) ethanolamine 2-ethyl
Xanthate, (mono, di, tri) ethanolamine ole
Inoate, (mono, di, tri) ethanolamine steer
Phosphate, (mono, di, tri) ethanolamine linole
Phosphate, (mono, di, tri) ethanolamine linolei
Phosphate, (mono, di, tri) ethanolamine salicyl
Acid salt, (mono, di, tri) ethanolamine benzoic acid
Salt, (mono, di, tri) ethanolamine p-aminoammonium
Benzoate, (mono, di, tri) ethanolamine p-to
Ruene sulfonate, (mono, di, tri) ethanol
Minbenzene sulfonate, (mono, di, tri) ethano
Oleamine monochloroacetate, (mono, di, tri) eta
Nolamine dichloroacetate, (mono, di, tri) eth
Nolamine trichloroacetate, (mono, di, tri)
Tanolamine trifluoroacetate, (mono, di,
Re) ethanolamine formate, (mono, di, tri) eta
Nolamine malonate, (mono, di, tri) ethanol
Ruamine sulfonate, (mono, di, tri) ethanol
Amine phthalate, (mono, di, tri) ethanolamine
N-fumarate, (mono, di, tri) ethanolamine
Enoate, (mono, di, tri) ethanolamine tartaric acid
Salt, (mono, di, tri) ethanolamine succinate,
(Mono, di, tri) ethanolamine fumarate, (mo
No, di, tri) ethanolamine itaconic acid salt, (mo
(No, di, tri) ethanolamine mesaconic acid salt, (mo
No, di, tri) ethanolamine citraconic acid salt, (mo
No, di, tri) ethanolamine malate, (mono,
Di, tri) ethanolamine glutarate, (mono,
Di, tri) ethanol ammonium hydroxide
De, (mono, di, tri) ethanolamine nitrate, tet
Lamethylammonium hydroxide acetate, tet
Lamethylammonium hydroxide propionic acid
Salt, tetramethylammonium hydroxide pig
Phosphate, tetramethylammonium hydroxide
Pentanoate, Tetramethylammonium Hydroxy
Side hexanoate, tetramethyl ammonium hydroxide
Rooxide heptanoate, tetramethylammonium
Hydroxide octanoate, tetramethylammo
Aluminum hydroxide nonanoate, tetramethyl
Ammonium hydroxide decanoate, tetramethy
Lumonium hydroxide oxalate, tetra
Methyl ammonium hydroxide maleate,
Tetramethylammonium hydroxide methylmer
Ronate, tetramethylammonium hydroxide
Doadipic acid salt, tetramethylammonium hydroo
Quiside sebacate, tetramethylammonium high
Drooxide gallate, tetramethylammonium
Hydroxide butyrate, tetramethylammonium
Hydroxide meritate, tetramethylammo
Aluminum hydroxide arachidonate, tetramethy
Lumonium hydroxide shikimate, tetra
Methyl ammonium hydroxide 2-ethylhexyl
Sanate, tetramethylammonium hydroxide
Doleate, Tetramethylammonium Hydro
Cide stearate, tetramethylammonium ha
Idrooxide linoleate, tetramethylammoni
Um hydroxide linoleinate, tetramethyl
Ammonium hydroxide salicylate, tetra
Methyl ammonium hydroxide benzoate, te
Tramethylammonium hydroxide p-amino
Benzoate, tetramethylammonium hydroxide
Id p-toluenesulfonate, tetramethylammonium
Um hydroxide benzene sulfonate, tetra
Methyl ammonium hydroxide monochloroacetic acid
Salt, tetramethylammonium hydroxide oxide
Loroacetate, tetramethylammonium hydroxide
Id trichloroacetate, tetramethyl ammonium high
Drooxide trifluoroacetate, tetramethylan
Monium hydroxide formate, tetramethylan
Monium hydroxide butylamine malonate,
Tetramethylammonium hydroxide sulfone
Acid salt, tetramethylammonium hydroxide
Tartrate, tetramethylammonium hydroxide
Dofumarate, Tetramethylammonium Hydroxy
Side citrate, tetramethylammonium hydro
Oxide Tartrate, Tetramethylammonium Hyde
Rooxide succinate, tetramethyl ammonium chloride
Idrooxide fumarate, tetramethylammonium
Mu-hydroxide itaconate, tetramethyl-an
Monium Hydroxide Mesaconate, Tetramethy
Lumonium hydroxide citraconate, te
Tramethylammonium hydroxide malic acid
Salt, tetramethylammonium hydroxide glu
Tartrate, tetramethylammonium hydroxide
Denitrate, tetramethylammonium hydroxide
And tetramethylammonium hydroxide nitric acid
Salt, tetraethylammonium hydroxide acetic acid
Salt, tetraethylammonium hydroxide pro
Pionate, tetraethylammonium hydroxa
Idbutanoate, tetraethylammonium hydro
Quiside pentatanate, tetraethylammonium high
Drooxide hexanoate, tetraethylammonium
Hydroxide heptanoate, tetraethylan
Monium hydroxide octanoate, tetraethyl
Lumonium hydroxide nonanoate, tetra
Ethyl ammonium hydroxide decanoate, te
Traethylammonium hydroxide oxalic acid
Salt, tetraethylammonium hydroxide male
Inoate, tetraethylammonium hydroxide
Demethyl malonate, tetraethyl ammonium hydroxide
Rooxide adipate, tetraethylammonium
Hydroxide sebacate, tetraethylammo
Aluminum hydroxide gallate, tetraethyl
Ammonium hydroxide butyrate, tetraethyl
Ammonium hydroxide meritate, tetrae
Chill ammonium hydroxide arachidonate,
Tetraethylammonium hydroxide shikimic acid
Salt, tetraethylammonium hydroxide 2-
Ethyl hexanoate, tetraethyl ammonium hydroxide
Looxide oleate, tetraethylammonium
Hydroxide stearate, tetraethylan
Monium hydroxide linoleate, tetraethyl
Lumonium hydroxide linoleinate, te
Traethylammonium hydroxide salicylic acid
Salt, tetraethylammonium hydroxide benzoate
Perfume salt, tetraethylammonium hydroxide
p-aminobenzoate, tetraethylammonium high
Drooxide p-toluenesulfonate, tetraethyl
Lumonium hydroxide benzene sulfonic acid
Salt, tetraethylammonium hydroxide mono
Chloroacetate, Tetraethylammonium Hydroxy
Side dichloroacetate, tetraethylammonium high
Drooxide trichloroacetate, tetraethylammo
Aluminum hydroxide trifluoroacetate, tetra
Ethyl ammonium hydroxide formate, tetra
Ethyl ammonium hydroxide butyl amine
Ronate, tetraethylammonium hydroxide
Dosulphonate, tetraethylammonium hydro
Quide phthalate, tetraethyl ammonium hydroxide
Roxoxide fumarate, tetraethyl ammonium
Idrooxide citrate, tetraethylammonium
Mu Hydroxide Tartrate, Tetraethylammonium
Umhydroxide succinate, tetraethylan
Monium hydroxide fumarate, tetraethyl
Ammonium hydroxide itaconate, tetra
Ethyl ammonium hydroxide mesaconate,
Tetraethylammonium hydroxide citraco
Phosphate, tetraethylammonium hydroxide
Malate, tetraethylammonium hydroxa
Idglutarate, tetraethylammonium hydro
Oxide nitrate, tetraethylammonium hydro
Oxide, tetraethylammonium hydroxa
Id nitrate, Tetrapropylammonium Hydroxy
Side acetate, tetrapropyl ammonium hydroo
Xydopropionate, Tetrapropylammonium
Hydroxide butanoate, tetrapropylammo
Nium hydroxide pentatanate, tetrapropy
Lumonium hydroxide hexanoate, tet
Lapropyl ammonium hydroxide heptanoic acid
Salt, tetrapropylammonium hydroxide
Octanoate, Tetrapropylammonium Hydroxy
Sidenonanoate, tetrapropylammonium hydroxide
Rooxide decanoate, tetrapropyl ammonium
Hydroxide oxalate, tetrapropylammo
Nium hydroxide maleate, tetrapropy
Lumonium hydroxide methyl malonate,
Tetrapropyl ammonium hydroxide adipi
Phosphate, tetrapropylammonium hydroxide
Docebacate, tetrapropylammonium hydro
Oxide gallate, tetrapropyl ammonium
Idrooxide butyrate, tetrapropylammonium
Hydroxide meritate, tetrapropylan
Monium hydroxide arachidonate, tetrap
Ropylammonium hydroxide shikimate, te
Trapropylammonium hydroxide 2-eth
Ruhexanoate, tetrapropylammonium hydro
Oxide oleate, tetrapropylammonium
Hydroxide stearate, tetrapropyl acetate
Ammonium hydroxide linoleate, tetrap
Ropyl ammonium hydroxide linoleic acid
Salt, tetrapropylammonium hydroxide
Licylate, Tetrapropylammonium Hydroxy
Side benzoate, tetrapropyl ammonium hydroxide
Rooxide p-aminobenzoate, tetrapropyl
Ammonium hydroxide p-toluenesulfonic acid
Salt, tetrapropylammonium hydroxide
Benzene sulfonate, tetrapropyl ammonium high
Drooxide monochloroacetate, tetrapropylan
Monium hydroxide dichloroacetate, tetrap
Ropyl ammonium hydroxide trichloroacetic acid
Salt, tetrapropylammonium hydroxide
Lifluoroacetate, tetrapropyl ammonium hydroxide
Rooxide formate, tetrapropyl ammonium high
Drooxide Butylamine Malonate, Tetrapropy
Lumonium hydroxide sulfonate, tet
Lapropyl ammonium hydroxide phthalic acid
Salt, tetrapropylammonium hydroxide
Malate, tetrapropylammonium hydroxa
Id citrate, tetrapropylammonium hydro
Oxide tartrate, tetrapropyl ammonium high
Drooxide succinate, tetrapropylammonium
Mu-hydroxide fumarate, tetrapropylan
Monium hydroxide itaconate, tetrapro
Pyrammonium hydroxide mesaconate, te
Trapropyl ammonium hydroxide citraco
Phosphate, tetrapropylammonium hydroxide
Domarate, tetrapropylammonium hydroo
Quiside glutarate, tetrapropyl ammonium
Idrooxide nitrate, tetrapropylammonium
Hydroxide, tetrapropyl ammonium high
Drooxide nitrate, tetrabutylammonium high
Drooxide acetate, tetrabutylammonium high
Drooxide propionate, tetrabutylammoni
Umium hydroxide butanoate, Tetrabutylan
Monium hydroxide pentatanate, tetrabutyl
Lumonium hydroxide hexanoate, tet
Labylammonium hydroxide heptanoic acid
Salt, tetrabutylammonium hydroxide octa
Tantalate, tetrabutylammonium hydroxide
Dononanoate, Tetrabutylammonium Hydroxy
Side decanoate, tetrabutylammonium hydro
Oxide oxalate, tetrabutylammonium high
Drooxide maleate, tetrabutylammonium
Mu-hydroxide methyl malonate, tetrabutyl
Ammonium hydroxide adipate, tetra
Butyl ammonium hydroxide sebacate,
Tetrabutylammonium hydroxide gallic acid
Salt, tetrabutylammonium hydroxide butyric acid
Salt, tetrabutylammonium hydroxide
Titanate, tetrabutylammonium hydroxide
Doarachidonate, Tetrabutylammonium Hydro
Oxide shikimate, tetrabutylammonium high
Drooxide 2-ethylhexanoate, tetrabutyl
Ammonium hydroxide oleate, tetra
Butyl ammonium hydroxide stearic acid
Salt, tetrabutylammonium hydroxide lino
Phosphate, tetrabutylammonium hydroxide
Dolinoleate, tetrabutylammonium hydro
Oxide salicylate, tetrabutyl ammonium
Idrooxide benzoate, tetrabutylammonium
Mu-hydroxide p-aminobenzoate, tetrabu
Tylammonium hydroxide p-toluene sulphate
Honate, tetrabutylammonium hydroxide
Debenzene sulfonate, tetrabutyl ammonium
Idrooxide monochloroacetate, tetrabutylan
Monium hydroxide dichloroacetate, tetrabu
Tylammonium hydroxide trichloroacetic acid
Salt, tetrabutylammonium hydroxide tri
Fluoroacetate, tetrabutylammonium hydro
Quide formate, tetrabutylammonium hydro
Quiside butyl amine malonate, tetrabutyl ammo
Aluminum hydroxide sulfonate, tetrabutyl
Ammonium hydroxide phthalate, tetrabu
Tylammonium hydroxide fumarate, tet
Labyl ammonium hydroxide citrate,
Tetrabutylammonium hydroxide tartaric acid
Salt, tetrabutylammonium hydroxide
Citrate, tetrabutylammonium hydroxide
Fumarate, tetrabutylammonium hydroxa
Idoitaconate, tetrabutylammonium hydro
Oxide mesaconate, tetrabutyl ammonium
Idrooxide citraconic acid salt, tetrabutylammo
Nium hydroxide malate, tetrabutyla
Ammonium hydroxide glutarate, tetrabu
Tylammonium hydroxide nitrate, tetrabu
Tylammonium hydroxide, tetrabutyla
Names such as ammonium hydroxide nitrate
Can be done. In the above compound name notation (mono,
Those that are described as "di, tri" correspond to each
It is a list of three types of compounds, for example,
Described as (mono-, di-, tri) methylamine acetate
Rumono is monomethylamine acetate, dimethylamine acetic acid
The three types of salt and trimethylamine acetate are collectively represented.
Of.

The ratio of the component (B) to the component (A) used is 0.005 to 0.05 part by weight of the component (B) based on 100 parts by weight of the component (A) (calculated as a complete hydrolyzed condensate). , And more preferably 0.007 to 0.03 parts by weight. If the proportion of the component (B) used is less than 0.0005 parts by weight, the storage stability of the composition may be poor.
If it exceeds the weight part, the coating uniformity of the coating film may be deteriorated.

The pH of the film-forming composition after the addition of the component (B) is 2 to 4, more preferably 2.2 to 3.8. When the pH of the film-forming composition is less than 2 or more than 4, the storage stability of the film-forming composition becomes poor.

(C) Organic Solvent The film-forming composition of the present invention is usually obtained by dissolving or dispersing (A) a hydrolytic condensate and (B) component in (C) an organic solvent. 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, examples of the alcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, and 2-methyl. 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-dimethylhepta Nol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol,
sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5
A monoalcoholic solvent such as trimethylcyclohexanol, benzyl alcohol, 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.

Ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ.
-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoacetate
n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxytriglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents are 1
One kind or two or more kinds may be used at the same time. As the aprotic solvent, acetonitrile, 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 (4) is particularly preferable. ^{_{R 8 O (CHCH 3 CH 2}} O) e R 9 ····· (4) (R 8 and ^{R 9} are each independently a hydrogen atom, alkyl group or CH ₃ CO- 1 to 4 carbon atoms The selected monovalent organic group is shown, and e represents an integer of 1 to 2.) The above (C) organic solvent can be used alone or in combination of two or more.

The film-forming composition of the present invention comprises the compound (1)
When hydrolyzing and condensing (3) to (3), the same solvent can be used.

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 alkali catalyst may be added to the solvent in advance, or may be dissolved or dispersed in water when water is added. The reaction temperature at this time is usually 0 to 100 ° C., preferably 15 to 90 ° C.
Is.

Other Additives The film-forming composition obtained in the present invention further contains components such as colloidal silica, colloidal alumina, organic polymers, surfactants, silane coupling agents, radical generators and triazene compounds. May be added. 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 size of 5 to 5.
30 nm, preferably 10 to 20 nm, solid content concentration is 1
It is about 0 to 40% by weight. Examples of such colloidal silica include those manufactured by Nissan Chemical Industries, Ltd.,
Methanol silica sol and isopropanol silica sol; manufactured by Catalyst Kasei Kogyo Co., Ltd., Oscar, and the like. As colloidal alumina, Nissan Chemical Industry Co., Ltd.
Alumina sol 520, 100 and 200 manufactured by Kawaken Fine Chemicals Co., Ltd .; As the organic polymer, for example, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, a polyquinoxaline,
Examples thereof include polyoxadiazoles, fluoropolymers, compounds having a polyalkylene oxide structure, and the like.

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, SH30PA, ST94P.
A (all are Toray Dow Corning Silicone Co., Ltd.)
It is possible to use manufactured products. Among these, the above S
H28PA and SH30PA are particularly preferable.

The amount of the surfactant used is usually 0.0001 to 10 parts by weight based on the component (A) (completely hydrolyzed condensate). These may be used either individually or in combination of two or more.

As the silane coupling agent, for example, 3
-Glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-
(2-Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- 1,4,7-Triazadecane, 10-
Triethoxysilyl-1,4,7-triazadecane, 9
-Trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-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 amount of the radical generator compounded is 100
0.1 to 10 parts by weight is preferable with respect to parts by weight. 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.

Method for Preparing Film-Forming Composition When preparing the film-forming composition of the present invention, for example, the compounds (1) to (3) are mixed in a solvent and water is continuously or intermittently added. There is no particular limitation as long as it is added, hydrolyzed and condensed.

Specific examples of the method for preparing the composition of the present invention include the following methods 1) to 11). 1) A method of performing a hydrolysis / condensation reaction by adding a predetermined amount of water to a mixture of the compounds (1) to (3), an alkali catalyst and an organic solvent. 2) A method of performing a hydrolysis or condensation reaction by continuously or intermittently adding a predetermined amount of water to a mixture of the compounds (1) to (3), an alkali catalyst and an organic solvent. 3) A method of adding a predetermined amount of water and an alkali catalyst to a mixture of the compounds (1) to (3) and an organic solvent to carry out a hydrolysis / condensation reaction. 4) A method in which a predetermined amount of water and an alkali catalyst are continuously or intermittently added to a mixture of the compounds (1) to (3) and an organic solvent to carry out hydrolysis and condensation reactions. 5) In a mixture consisting of organic solvent, water and alkali catalyst,
A method of adding a predetermined amount of compounds (1) to (3) and performing a hydrolysis / condensation reaction. 6) In a mixture of organic solvent, water and alkali catalyst,
A method of performing a hydrolysis / condensation reaction by continuously or intermittently adding a predetermined amount of compounds (1) to (3). 7) In a mixture consisting of organic solvent, water and alkali catalyst,
A method of adding a predetermined amount of compounds (1) to (3), performing a hydrolysis / condensation reaction, and adding a pH adjuster. 8) In a mixture of organic solvent, water and alkali catalyst,
A method of adding a predetermined amount of compounds (1) to (3), performing a hydrolysis / condensation reaction, concentrating the solution to a certain concentration, and then adding a pH adjuster. 9) A method of extracting the solution obtained by the above method 1) to 8) with another organic solvent. 10) A method of replacing the solution obtained by the method of 1) to 8) with another organic solvent. 11) A method of extracting the solution obtained by the above method 1) to 8) with another organic solvent and then substituting with another organic solvent.

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 total solid content concentration is adjusted, if necessary, by concentration and dilution with the organic solvent (C).

The composition of the present invention was prepared by using a silicon wafer, Si
When applied to a base material such as an O ₂ wafer or SiN wafer, a coating means such as spin coating, dipping, roll coating or spraying is used.

The film thickness at this time is a dry film thickness of about 0.02 to 2.5 μm for one coating, and about 0.04 to 5.0 μm for two coatings. 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. The silica-based film of the present invention thus obtained usually has a film density of 0.
35-1.2 g / cm ³ , preferably 0.4-1.1 g
/ Cm ³ , more preferably 0.5-1.0 g / cm ³
Is. When the film density is less than 0.35 g / cm ³ , the mechanical strength of the coating film is lowered, while when it exceeds 1.2 g / cm ³ , a low relative dielectric constant cannot be obtained. In addition, the silica-based film of the present invention is preferable as an interlayer insulating film material between fine wirings because voids having a diameter of 10 nm or more are not recognized in the pore distribution measurement by the BJH method. Furthermore, the silica-based film of the present invention is characterized in that it has a low water absorption property.
When left in an environment of 5 atm and 100% RH for 1 hour,
From the IR spectrum observation of the coating film after standing, adsorption of water to the coating film was not observed. This water absorption can be adjusted by the amount of the tetraalkoxysilanes of the compound (1) used in the film forming composition of the present invention. Furthermore, the relative dielectric constant of the silica-based film of the present invention is usually 2.6 to
It is 1.2, preferably 2.5 to 1.2, and more preferably 2.4 to 1.2.

The interlayer insulating film thus obtained has a small difference in relative dielectric constant depending on the firing conditions and exhibits excellent adhesion to the substrate.
I, DRAM, SDRAM, RDRAM, D-RDRA
An interlayer insulating film for a semiconductor element such as M and an etching stopper film, a protective film such as a surface coating film for a semiconductor element, an intermediate layer in a semiconductor manufacturing process using a multilayer resist, an interlayer insulating film for a multilayer wiring board, and a liquid crystal display element. It is useful for applications such as protective films and insulating films.

[0057]

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.

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

A 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 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes, and further 390. 30 in a nitrogen atmosphere furnace at ℃ and 415 ℃
The substrate was baked. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for measuring relative permittivity. The sample was manufactured by Yokogawa / Hewlett Packard Co., H at a frequency of 100 kHz.
The relative dielectric constant of the coating film was measured by the CV method using a P16451B electrode and HP4284A precision LCR meter.

PH of the Composition The film-forming composition was diluted 10 times with a solution of ethanol / ultra pure water = 3/1 (weight ratio), and the pH of the composition was measured.

Storage stability of the composition The composition for film formation, which was stored at 40 ° C. for 30 days, was applied as a composition sample by a spin coating method, and the composition sample was applied on a hot plate at 90 ° C. for 3 minutes in a nitrogen atmosphere of 200 ° C. The substrate was dried for 3 minutes and further baked for 30 minutes in a nitrogen atmosphere furnace at 390 ° C. The film thickness of the coating film thus obtained is measured by an optical film thickness meter (Rudolph Technology).
50 points were measured on the surface of the coating film using Spectra Laser 200 manufactured by Geies. The film thickness of the obtained film thickness was measured, and the storage stability was evaluated by the rate of film thickness increase obtained by the following formula. Film thickness increase rate (%) = ((film thickness after storage)-(film thickness before storage)) / (film thickness before storage) x 100 ◯: film thickness increase rate of 4% or less x: film thickness increase rate Over 4%

Synthesis Example 1 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. A mixture of 44.9 g of methyltrimethoxysilane and 68.6 g of tetraethoxysilane was added to this solution over 1 hour. The reaction was carried out for 2 hours while keeping the solution at 55 ° C. To this solution, 50 g of a 20% aqueous nitric acid solution was added, and after sufficiently stirring, it was cooled to room temperature.
700 g of distilled butyl acetate was added to this solution, and the mixture was thoroughly stirred and the upper layer alone was taken out from the layer-separated solution. Ion-exchanged water (500 g) was added to this solution and stirred sufficiently to remove the lower aqueous layer. After repeating this operation 10 times, distilled propylene glycol monopropyl ether 400 was added to the upper layer solution.
g and add 1 to the solution using an evaporator at 50 ° C.
The reaction solution was obtained by concentrating the solution to 3% (converted to a complete hydrolysis-condensation product). The radius of gyration of the thus obtained condensate and the like was 20.0 nm. Further, when the amount of tetramethylammonium hydroxide in the solution was measured by a flame photometer, it was 0.001 part by weight based on 100 parts by weight of the solid content (completely hydrolyzed condensate equivalent).

Synthesis Example 2 In a quartz separable flask, distilled ethanol 470.
9 g, ion-exchanged water 233.3 g and 25% potassium hydroxide aqueous solution 10.4 g were put and stirred uniformly. A mixture of 44.9 g of methyltrimethoxysilane and 68.6 g of tetraethoxysilane was added to this solution over 20 minutes. The reaction was carried out for 2 hours while keeping the solution at 50 ° C.
To this solution, 50 g of 20% maleic acid aqueous solution was added, and after sufficiently stirring, it was cooled to room temperature. Ion-exchanged water (500 g) was added to this solution and stirred sufficiently to remove the lower aqueous layer. After repeating this operation 10 times, 400 g of distilled propylene glycol monopropyl ether was added to the upper layer solution, and the solution was adjusted to 13% by using an evaporator at 50 ° C.
The reaction solution was obtained by concentrating until it became (completely hydrolyzed condensate equivalent). The radius of gyration of the condensate and the like thus obtained was 19.6 nm.

Synthesis Example 3 Distilled ethanol 570 was placed in a quartz separable flask.
g, 160 g of ion-exchanged water, and 90 g of an ion-exchange aqueous solution of 10% methylamine were added and uniformly stirred. A mixture of 13.6 g of distilled methyltrimethoxysilane and 20.9 g of distilled tetraethoxysilane was added to this solution over 30 minutes. The reaction was carried out for 2 hours while keeping the solution at 65 ° C. To this solution, 50 g of 20% maleic acid aqueous solution was added, and after sufficiently stirring, it was cooled to room temperature. Ion-exchanged water (500 g) was added to this solution and stirred sufficiently to remove the lower aqueous layer. After repeating this operation 10 times, 400 g of distilled propylene glycol monopropyl ether was added to the upper layer solution.
Was added, and the solution was adjusted to 13 using an evaporator at 50 ° C.
The reaction solution was obtained by concentrating the mixture until the concentration reached 100% (in terms of complete hydrolysis condensate). The radius of gyration of the condensate or the like thus obtained was 17.0 nm. The amount of methylamine maleate in the solution was measured with a flame photometer to find that it was 0.001 part by weight with respect to 100 parts by weight of solid content (completely hydrolyzed condensate).

Comparative Synthesis Example 1 A reaction solution was obtained in the same manner as in Synthesis Example 1, except that 2.4 g of succinic acid was used instead of the 25% tetramethylammonium hydroxide aqueous solution.
The radius of gyration of the condensate or the like thus obtained is 0.2
was nm.

Example 1 Ammonia maleate was added in an amount of 0.007 parts by weight to 100 parts by weight of the solid content (calculated as a complete hydrolysis condensate) of the reaction solution obtained in Synthesis Example 1, and the mixture was sufficiently added. It was stirred. This solution is treated with Teflon (registered trademark) having a pore size of 0.2 μm.
The film-forming composition of the present invention was obtained by performing filtration with a filter. The pH of this composition was 3.3. The obtained composition was applied onto a silicon wafer by spin coating. Three
The relative permittivity of the coating film baked at 90 ° C. was 2.22, and the relative permittivity of the coating film baked at 415 ° C. was 2.21, showing that firing dependence of the relative dielectric constant was very small. Further, when the storage stability of the composition was evaluated, the film thickness increase rate was 2.3%, which was excellent in storage stability.

Examples 2 to 8 Film forming compositions having the compositions shown in Table 1 were prepared and evaluated in the same manner as in Example 1. The evaluation results are also shown in Table 1.

[0068]

[Table 1]

Comparative Example 1 A coating film was evaluated in the same manner as in Example 1 except that only the reaction solution obtained in Synthesis Example 3 was used. The pH of this composition was 4.1. The relative permittivity of the coating film baked at 390 ° C is 2.21, and the relative permittivity of the coating film baked at 415 ° C is 2.2.
3, the relative dielectric constant was very little dependent on firing, but when the storage stability of the composition was evaluated, the film thickness increase rate was 4.8%.
And it was inferior in storage stability.

Comparative Example 2 A coating film was evaluated in the same manner as in Example 1 except that only the reaction solution obtained in Synthesis Example 2 was used. The pH of this composition was 4.2. The relative dielectric constant of the coating film baked at 390 ° C is 2.03, and the relative dielectric constant of the coating film baked at 415 ° C is 2.0.
5 and the relative dielectric constant was very small, but when the storage stability of the composition was evaluated, the film thickness increase rate was 5.2%.
And it was inferior in storage stability.

Comparative Example 3 Ammonia maleate was added in an amount of 0.2 parts by weight based on 100 parts by weight of the solid content of the reaction solution obtained in Synthesis Example 3 (calculated as a complete hydrolysis condensate). The coating film was evaluated in the same manner as in Example 1. P of this composition
H was 2.1. The relative permittivity of the coating film baked at 390 ° C. was 2.18, and the relative permittivity of the coating film baked at 415 ° C. was 2.20, and the firing dependence of the relative dielectric constant was very small, but the storage stability of the composition was As a result of evaluation, the film thickness increase rate was 6.3%, which was inferior in storage stability.

Comparative Example 4 Example except that ammonia sulfate was added so as to be 1 part by weight with respect to 100 parts by weight of the solid content of the reaction solution obtained in Synthesis Example 3 (calculated as a complete hydrolysis condensate). The coating film was evaluated in the same manner as in 1. The pH of this composition is 1.9.
Met. The relative dielectric constant of the coating film baked at 390 ° C. is 2.18,
The relative dielectric constant of the coating film baked at 415 ° C. was 2.20, and the baking dependence of the relative dielectric constant was very small. However, when the storage stability of the composition was evaluated, the film thickness increase rate was 6.9%. It was inferior in stability.

Comparative Example 5 Ammonia maleate was added in an amount of 0.01 parts by weight to 100 parts by weight of the solid content of the reaction solution obtained in Comparative Synthesis Example 1 (calculated as a complete hydrolysis-condensation product). The coating film was evaluated in the same manner as in Example 1 except for the above. The pH of this composition was 3.7. The relative dielectric constant of the coating film baked at 390 ° C. is 3.24, and the relative dielectric constant of the coating film baked at 415 ° C. is 2.24.
The relative dielectric constant was 78 and the firing dependence was inferior.

[0074]

According to the present invention, (A) an alkoxysilane hydrolyzed polymer, (B) a specific amount of ammonium salt, 1
To at least one selected from the group of quaternary alkyl ammonium salts, and (C) an organic solvent, and having a pH of 2
It is possible to provide a film forming composition (material for an interlayer insulating film) which has a small difference in relative dielectric constant depending on firing conditions and has excellent storage stability of the composition.

Continued front page    (72) Inventor Mitsunori Nishikawa             2-11-21 Tsukiji, Chuo-ku, Tokyo JAE             Within Suar Co., Ltd. (72) Inventor Kinji Yamada             2-11-21 Tsukiji, Chuo-ku, Tokyo JAE             Within Suar Co., Ltd. F-term (reference) 4J038 DL021 DL031 DL071 DL161                       HA176 HA316 JA16 JA30                       JA53 JB01 JB11 JB12 KA04                       KA06 LA03 NA21 NA26 PA19                       PB09

Claims (7)

[Claims] 1. A compound represented by the following general formula (1), R _a Si (OR ¹ ) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom or Monovalent organic group, R ¹ is a monovalent organic group, and a is an integer of 1 to 2.) A compound represented by the following general formula (2) and Si (OR ² ) ₄ ( 2) (In the formula, R ² represents a monovalent organic group.) 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 and each represents a monovalent organic group, b-c are identical or different, represent an integer of 0 to 2 ,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
A group represented by (where n is an integer of 1 to 6), d
Represents 0 or 1. ] At least 1 selected from the group
Hydrolyzed condensate obtained by hydrolyzing and condensing a seed compound in the presence of an alkali catalyst and water, (B) (A) component 10
0.00 based on 0 parts by weight (completely hydrolyzed condensate equivalent)
5 to 0.5 parts by weight of at least one selected from the group consisting of ammonium salts and quaternary alkylammonium salts and (C) an organic solvent, and having a pH of 2 to 4 A film forming composition. 2. The film-forming composition according to claim 1, wherein the organic solvent (C) is a solvent represented by the following general formula (4). ^{_{R 8 O (CHCH 3 CH 2}} O) e R 9 ····· (4) (R 8 and ^{R 9} are each independently a hydrogen atom, alkyl group or CH ₃ CO- 1 to 4 carbon atoms Represents a monovalent organic group selected, and e represents an integer of 1 to 2.) 3. The film-forming composition according to claim 1, wherein the alkali catalyst is ammonia, a primary to tertiary alkylamine, a tetraalkylammonium hydroxide, sodium hydroxide or potassium hydroxide. 4. The component (B) is an ammonium organic acid salt, ammonium hydroxide, ammonia nitrate, 1 to
The film-forming composition according to claim 1, which is a quaternary alkylamine organic acid salt, a quaternary alkylammonium hydroxide, or a quaternary alkylamine nitrate. 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. 7. The silica-based film according to claim 6, which has a relative dielectric constant of 2.4 or less.