JP2002003783A - Composition for film formation, method for forming film and silica-based film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film-forming composition capable of burning in a short time as a interlaminar insulating film in semiconductor device, etc., and forming a silica-based film excellent in crack resistance after PCT(Pressure Cooker Test). SOLUTION: This composition for film formation comprises (A) a product of hydrolysis and condensation obtained by hydrolyzing and condensing at least one compound selected from the group consisting of compounds represented by formula (1): RaSi(OR1)4-a, compounds represented by formula (2): Si(OR2)4 and compounds represented by formula (3): R1bSi(OR1)3-b-R2-Si-(OR1)3-cR1c [wherein R is H, F or a monovalent organic group; R1s are the same or mutually different monovalent organic groups; R2s are each O, C6H4 or (CHd2)n; (a) is 1, (b) is 0, 1 or 2 and (c) is 0, 1 or 2], (B) at least one member selected from the group consisting of compounds of the metals in Groups IA and IIA of the periodic table; and (C) an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a film-forming composition, and more particularly, to a PCT (Pt) which can be fired in a short time as a material for an interlayer insulating film in a semiconductor device or the like.
The present invention relates to a film-forming composition capable of forming a silica-based film having excellent crack resistance after a stress cooker test.

[0002]

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

As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensing alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (JP-A-5-263045, 5-315
319) and a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-340219, JP-A-11-34022).
0) has been proposed, but the materials obtained by these methods do not have stable properties of reaction products, can be fired for a short time, and have large variations in film properties such as crack resistance after PCT. Therefore, it was not suitable for industrial production.

[0004]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly, to a film-forming composition which can be baked for a short time as an interlayer insulating film in a semiconductor device or the like. It is an object of the present invention to provide a film-forming composition having excellent crack resistance and a silica-based film obtained from the composition.

[0005]

The present invention provides (A) (A-
1) A compound represented by the following general formula (1) (hereinafter, referred to as “compound 1”): _Ra Si (OR ¹ ) _4-a (1) (where R is a hydrogen atom, fluorine An atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is an integer of 1 or 2.) (A-2) A compound represented by the following general formula (2)
(Referred to as “compound 2”) and Si (OR ² ) ₄ ... (2) (wherein, R ² represents a monovalent organic group.) (A-3) Table represented by the following general formula (3) Compound (hereinafter, referred to as
"Compound 3" ^{_{hereinafter) R 3 b (R 4 O}} ) 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ····· (3) wherein, R ³ To R ⁶ are the same or different, each is a monovalent organic group, b to c are the same or different, and an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
(Where n is an integer of 1 to 6), d
Represents 0 or 1. At least one selected from the group of
Hydrolyzed and condensed products obtained by hydrolyzing and condensing a compound of the type, (B) a Group IA metal compound in the periodic table of the elements, and
The present invention relates to a film-forming composition comprising a Group IIA metal compound and (C) an organic solvent. Next, the present invention relates to a method for forming a film, which comprises applying the composition for film formation to a substrate and heating the substrate. Next, the present invention relates to a silica-based film obtained by the method for forming a film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (A) a hydrolyzed condensate is at least one hydrolyzate and / or condensate selected from the group of the compounds (1) to (3). It is. Here, the hydrolyzate in the component (A) refers to the compound (1) to the compound (1) constituting the component (A).
Not all of the R ¹ O—, R ² O—, R ⁴ O— and R ⁵ O— groups contained in (3) need to be hydrolyzed, for example, only one is hydrolyzed. What
One or more of them may be hydrolyzed, or a mixture thereof. The condensate in the component (A) is a product in which the silanol groups of the hydrolyzates of the compounds (1) to (3) constituting the component (A) are condensed to form a Si—O—Si bond. In the present invention, it is not necessary that all of the silanol groups are condensed, but the concept encompasses a mixture of a small amount of silanol groups condensed and a mixture of those having different degrees of condensation.

(A) Hydrolytic condensate (A) The hydrolytic condensate comprises at least one silane compound selected from the group of compounds (1) to (3) above,
It is obtained by hydrolysis and condensation in the presence of components. Compound (1): In the above general formula (1), R and R
The ¹ monovalent organic group, an alkyl group, an aryl group,
Examples include an allyl group and a glycidyl group. In the general formula (1), R is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and preferably have 1 to 1 carbon atoms.
5, these alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted by a fluorine atom or the like. In the general formula (1), examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

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

[0009] Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n
-Butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n -Butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane,
Ethyl triphenoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-n-propoxy silane, vinyl tri-iso-propoxy silane, vinyl tri-n-butoxy silane, vinyl tri-s
ec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane , N-propyltri-n-butoxysilane, n-propyltri-sec
-Butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-
Propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane,
i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-
sec-butoxysilane, i-propyltri-tert
-Butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-
Butyltri-n-butoxysilane, n-butyltri-s
ec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, se
c-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, s
ec-butyl-tri-sec-butoxysilane, sec
-Butyl-tri-tert-butoxysilane, sec-
Butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso
-Propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-
Butyl tri-tert-butoxy silane, t-butyl triphenoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tri-n-propoxy silane, phenyl tri-iso-propoxy silane, phenyl tri-n-butoxy silane, phenyl tri -Sec-butoxysilane, phenyltri-tert-
Butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ
-Aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-trifluoropropyltrimethoxysilane, gamma-trifluoropropyltrimethylsilane Ethoxysilane and the like;

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

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

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

Compound (3): In the above formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as in the above formula (1). . In the general formula (3), as a compound in which R ⁷ is an oxygen atom,
Hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,
3,3-pentamethoxy-3-methyldisiloxane,
1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3
-Methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3
-Pentaethoxy-3-ethyldisiloxane, 1,1,
1,3,3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyl Disiloxane, 1,1,1,3,3-pentaphenoxy-3-phenyldisiloxane, 1,1,
3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraphenoxy-
1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,
3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-
1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,
1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-
Trimethyldisiloxane, 1,1,3-triethoxy-
1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane,
1,1,3-trimethoxy-1,3,3-triethyldisiloxane, 1,1,3-triethoxy-1,3,3
Triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,
1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3 -Triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy- 1,1,3
3-tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraethyldisiloxane, 1,3-
Diethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,3
3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 1,
Examples thereof include 3-diphenoxy-1,1,3,3-tetraphenyldisiloxane.

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

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

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

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

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

When hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3) constituting the component (A), 0% per mole of the component (A) is used. It is preferred to use more than 0.5 mol and up to 150 mol of water, particularly preferred to add more than 0.5 mol and 130 mol of water. When the amount of water to be added is 0.5 mol or less, the crack resistance of the coating film may be inferior.
If it exceeds 50 mol, precipitation and gelation of the polymer during the hydrolysis and condensation reactions may occur.

In producing the hydrolyzed condensate (A) of the present invention, a catalyst is used for hydrolyzing and condensing at least one silane compound selected from the group of the compounds (1) to (3). It is characterized by using. Examples of the catalyst that can be used at this time include a metal chelate compound, an acid catalyst, and an alkali catalyst. Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, and tri-n- Butoxy mono (acetylacetonate) titanium, tri-se
c-butoxy mono (acetylacetonate) titanium,
Tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetonate) Titanium, di-n-butoxybis (acetylacetonato) titanium, di-sec-butoxybis (acetylacetonato) 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 (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-
Propoxy mono (ethyl acetoacetate) titanium,
Tri-n-butoxy mono (ethyl acetoacetate)
Titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) Acetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-n
-Butoxy bis (ethyl acetoacetate) titanium,
Di-sec-butoxybis (ethylacetoacetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxytris (ethylacetoacetate) titanium, mono-n-propoxytris (ethylacetoacetate) ) Titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy・ Tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (a) Titanium chelate compounds such as tilacetonate) mono (ethylacetoacetate) titanium; triethoxymono (acetylacetonato) zirconium, tri-n-propoxymono (acetylacetonato) zirconium, tri-i-propoxymono (acetyl) Acetonate) zirconium, tri-n-
Butoxy mono (acetylacetonate) zirconium, tri-sec-butoxy mono (acetylacetonate) zirconium, tri-t-butoxy mono (acetylacetonate) zirconium, diethoxybis (acetylacetonate) zirconium, di- n-propoxy bis (acetylacetonate) zirconium,
Di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxybis (acetylacetonato) zirconium, di-sec-butoxybis (acetylacetonato) zirconium, di-t-butoxybis ( (Acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetylacetonato) zirconium, mono-n-butoxy Tris (acetylacetonate) zirconium, mono-sec-butoxytris (acetylacetonate) zirconium, mono-t-butoxytris (acetylacetonate) zirconium, tetrakis (acetylacetonate) Ruconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) (Acetate) zirconium, tri-s
ec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy.
Bis (ethylacetoacetate) zirconium, di-i
-Propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) ) Zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-
n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy.
Tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) zirconium, tris (acetylacetonate) Zirconium chelate compounds such as mono (ethylacetoacetate) zirconium;
Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; and the like, and preferably a chelate compound of titanium and / or aluminum.
Particularly preferred is a chelate compound of titanium. One or more of these metal chelate compounds may be used simultaneously.

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

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine,
Picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, ammonia, methylamine, ethylamine, propyl Amine, 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 organic amines are more preferable. Is particularly preferred. One or more of these alkali catalysts may be used simultaneously.

The amount of the above-mentioned catalyst to be used depends on compounds (1) to
R in (3)¹ O-group, R^Two O-group, R ^Four An O-group and
R^Five Usually, based on 1 mol of the total amount of the group represented by the O- group,
0.00001 to 10 mol, preferably 0.00005
５5 mol. If the amount of catalyst used is within the above range,
There is little risk of polymer precipitation or gelation during the reaction.

In the component (A), when each component is converted into a complete hydrolysis condensate, the compound (2) is 5 to 75% by weight, preferably 5 to 75% by weight, based on the total amount of the compounds (1) to (3). Is 10 to 70% by weight, more preferably 15 to 70% by weight
It is. Compounds (1) and / or (3)
95 to 25% by weight, preferably 90 to 30% by weight, more preferably 85 to 3% by weight, based on the total amount of the compounds (1) to (3)
0% by weight. Compound (2) is a compound (1)-
When the amount is 5 to 75% by weight based on the total amount of (3), the resulting coating film has a high elastic modulus and is particularly excellent in low dielectric properties. Here, in the present invention, the completely hydrolyzed condensate refers to R ¹ O—, R ² O—, R ⁴ O in compounds (1) to (3).
- group and R ⁵ O-group 100% hydrolyzed to the SiOH
It is a group that becomes a group and is completely condensed to form a siloxane structure. In addition, the component (A) is preferably a hydrolyzed condensate of the compound (1) and the compound (2) because the composition obtained is more excellent in storage stability.

Component (B) The component (B) used in the present invention is a compound of a Group IA metal and a Group IIA metal in the periodic table of the elements, more preferably potassium, rubidium, cesium, beryllium, magnesium, calcium, It is at least one metal compound selected from the group consisting of strontium and barium.

The component (B) includes, for example, potassium acetate, potassium aluminate, potassium aluminum sulfate, potassium gold cyanide, potassium benzoate, potassium bicarbonate, potassium biiodate, potassium bioxalate, and heavy phthalate. Potassium acid, potassium bisulfate, potassium bisulfite, potassium bitartrate, potassium borate, potassium borohydride, potassium oxalate, potassium oxalate, potassium-t-butoxide, potassium carbonate, potassium chlorate, potassium chloride, Potassium chloroplatinate, potassium chromate, potassium citrate, potassium cyanate, potassium cyclohexanebutyrate, potassium dichromate, potassium dicyano silver, potassium dihydrogen citrate, potassium dihydrogen phosphate, 2,5-dihydroxy-1 1,4-benzenesulfonic acid potassium salt Potassium disulfide, dithio carbonate -O
-Ethyl potassium, potassium ethyl xanthate, potassium ethyl xanthate, potassium ferricyanide, potassium ferrocyanide, potassium formate, potassium gluconate, potassium potassium cyanide, potassium hexachloroplatinate, potassium 2,4-hexadienoate, potassium hexafluorophosphate, Potassium hexafluorosilicate, potassium hexafluorozirconate, potassium hexahydroxoantimonate, potassium hydride, potassium hydrogen carbonate, dipotassium hydrogen citrate, potassium hydrogen iodate, potassium hydrogen oxalate, dipotassium hydrogen phosphate, phthalic acid Potassium hydrogen hydrogen, potassium hydrogen sulfate, potassium hydrogen sulfite, potassium hydrogen tartrate, hydroquinone-2,5-
Dipotassium disulfonate, potassium hydrosulfide, potassium hydroxide, potassium hypochlorite, potassium lactate, potassium laurate, potassium malate, potassium metaborate, potassium metaiodate, potassium metaphosphate, potassium methoxide, potassium nickel cyanide , Potassium nitrate, potassium nitrite, potassium nonafluoro-1-butanesulfonate, potassium oleate, potassium oxalate, potassium palladium chloride, potassium palmitate,
Potassium perchlorate, potassium periodate, potassium permanganate, potassium peroxodisulfate, potassium persulfate, dipotassium phosphate, tripotassium phosphate, dipotassium phosphite, dipotassium phosphonate, potassium phthalate,
Potassium phthalimide, potassium picrate, potassium platinum chloride, potassium pyrophosphate, potassium pyrosulfate, potassium pyrosulfite, dipotassium rhodizonate, potassium selenite, potassium silicate, potassium sodium carbonate,
Sodium potassium tartrate, potassium sorbate, potassium stannate, potassium stearate, potassium succinate, potassium sulfate, potassium sulfide, potassium sulfite, p
-Potassium sulfobenzoate, potassium tellurate, potassium tellurite, potassium tetraborate, potassium tetrachloropalladate, potassium tetrachloroplatinate, potassium tetracyanonickelate, potassium tetraiodomercury, potassium tetraoxalate, potassium thiocyanate , Potassium thiosulfate, potassium titanium fluoride, potassium potassium oxalate, potassium trichloro (ethylene) platinate,
Potassium compounds such as potassium 2,4,6-trinitrophanol, potassium xanthate and potassium zirconium fluoride; rubidium acetate, rubidium aluminate, aluminum rubidium sulfate, gold (Ru) dium cyanide, rubidium benzoate, rubidium bicarbonate , Rubidium biiodate, rubidium bioxalate, rubidium biphthalate, rubidium bisulfate, rubidium bisulfite,
Rubidium bitartrate, rubidium borate, rubidium borohydride, rubidium oxalate, rubidium oxalate, rubidium-t-butoxide, rubidium carbonate,
Rubidium chlorate, rubidium chloride, rubidium chloroplatinate, rubidium chromate, rubidium citrate, rubidium cyanate, rubidium cyclohexanebutyrate, rubidium dichromate, rubidium dicyano silver, rubidium dihydrogen citrate, rubidium dihydrogen phosphate, rubidium dihydrogen phosphate, Rubidium 2,5-dihydroxy-1,4-benzenesulfonate,
Rubidium disulfide, -O-ethyl rubidium dithiocarbonate, rubidium ethyl xanthate, rubidium ethyl xanthogenate, rubidium ferricyanide, rubidium ferrocyanide, rubidium formate, rubidium gluconate, rubidium gold cyanide, rubidium hexachloroplatinate, 2, 4-Rubidium hexadienoate, rubidium hexafluorophosphate, rubidium hexafluorosilicate, rubidium hexafluorozirconate, rubidium hexahydroxoantimonate, rubidium hydride, rubidium hydrogen carbonate, rubidium hydrogen citrate,
Rubidium hydrogen iodate, Rubidium hydrogen oxalate, Rubidium hydrogen phosphate, Rubidium hydrogen phthalate, Rubidium hydrogen sulfate, Rubidium hydrogen sulfite, Rubidium hydrogen tartrate, Rubidium hydroquinone-2,5-disulfonic acid, Rubidium hydrosulfide, Rubidium hydrosulfide, Hydroxide Rubidium, rubidium hypochlorite, rubidium lactate, rubidium laurate, rubidium malate, rubidium metaborate, rubidium metaiodate, rubidium metaphosphate, rubidium methoxide, rubidium nickel cyanide, rubidium nitrate, rubidium nitrite, nonafluoro -1-Rubidium butanesulfonate, Rubidium oleate, Rubidium oxalate, Rubidium palladium chloride, Rubidium palmitate, Rubidium perchlorate, Rubidium periodate, Permanate Phosphate rubidium, peroxydisulfate rubidium persulfate rubidium dihydrogen phosphate, rubidium,
Rubidium triphosphate, Rubidium phosphite, Rubidium phosphonate, Rubidium phthalate, Rubidium phthalimidium, Rubidium picrate, Rubidium chloride platinum, Rubidium pyrophosphate, Rubidium pyrosulfate, Rubidium pyrosulfite, Rubidium rhodizonate, Selenium selenium Rubidium acid, rubidium silicate, sodium rubidium carbonate, sodium rubidium tartrate, rubidium sorbate, rubidium stannate, rubidium stearate,
Rubidium succinate, rubidium sulfate, rubidium sulfide, rubidium sulfite, rubidium p-sulfobenzoate, rubidium tellurate, rubidium tellurite, rubidium tetraborate, rubidium tetrachloropalladate, rubidium tetrachloroplatinate, tetracyanonickelate Rubidium, rubidium tetraiodomercury, rubidium tetraoxalate, rubidium thiocyanate, rubidium thiosulfate, rubidium titanium titanate, rubidium titanate oxalate, rubidium trichloro (ethylene) platinate, 2,4,6-trinitrophanol rubidium, xanthogen Rubidium compounds such as rubidium acid and rubidium zirconium fluoride; cesium acetate, cesium aluminate, cesium aluminum sulfate, cesium cyanide, cesium benzoate , Cesium bicarbonate, cesium biiodate, cesium bioxalate, cesium biphthalate, cesium bisulfate, cesium bisulfite, cesium bitartrate, cesium borate, cesium borohydride, cesium oxalate, cesium oxalate , Cesium-t-butoxide, cesium carbonate, cesium chlorate, cesium chloride, cesium chloroplatinate, cesium chromate, cesium citrate, cesium cyanate, cesium cyclohexane butyrate, cesium dichromate, cesium dicyanosilver, cesium silver citrate Cesium dihydrogen, cesium dihydrogen phosphate, 2,5-
Cesium dihydroxy-1,4-benzenesulfonate,
Cesium disulfide, -O-ethyl cesium dithiocarbonate, cesium ethyl xanthate, cesium ethyl xanthate, cesium ferricyanide, cesium ferrocyanide, cesium formate, cesium gluconate, gold cesium cyanide, cesium hexachloroplatinate, 2, 4-cesium hexadienoate, cesium hexafluorophosphate, cesium hexafluorosilicate, cesium hexafluorozirconate, cesium hexahydroxoantimonate, cesium hydride, cesium hydrogen carbonate, dicesium hydrogen citrate, cesium hydrogen iodate, shu Cesium hydrogen oxyate, dicesium hydrogen phosphate, cesium hydrogen phthalate,
Cesium hydrogen sulfate, cesium hydrogen sulfite, cesium bitartrate, cesium hydroquinone-2,5-disulfonate, cesium hydrosulfide, cesium hydroxide, cesium hypochlorite, cesium lactate, cesium laurate, cesium malate, metaborate Cesium, cesium metaiodate, cesium metaphosphate, cesium methoxide, cesium nickel cyanide, cesium nitrate, cesium nitrite, cesium nonafluoro-1-butanesulfonate, cesium oleate, cesium oxalate, cesium chloride, palladium Cesium acid, cesium perchlorate,
Cesium periodate, cesium permanganate, cesium peroxodisulfate, cesium persulfate, dicesium phosphate, tricesium phosphate, dicesium phosphite, dicesium phosphonate, cesium phthalate, cesium phthalimido, cesium picrate , Cesium chloride, cesium pyrophosphate, cesium pyrosulfate, cesium pyrosulfite,
Cesium rhodizonate, cesium selenite, cesium silicate, cesium sodium carbonate, cesium sodium tartrate, cesium sorbate, cesium stannate, cesium stearate, cesium succinate, cesium sulfate, cesium sulfide, cesium sulfite, p-sulfo Cesium benzoate, cesium tellurate, cesium tellurite, cesium tetraborate, cesium tetrachloropalladium, cesium tetrachloroplatinate, cesium tetracyanonickelate, cesium tetraiodomercury, cesium tetraoxalate, cesium thiocyanate, thiosium Cesium sulfate, cesium fluoride titanium, cesium titanium oxalate, cesium trichloro (ethylene) platinate, cesium 2,4,6-trinitrophanol, cesium xanthate, cesium fluoride zirconium Cesium compounds such as magnesium acetate, magnesium ammonium phosphate, magnesium ammonium sulfate, magnesium benzoate, magnesium oxalate, magnesium hydroxide hydroxide, magnesium chloride, magnesium chromate, magnesium diethoxide, magnesium di (methoxyethoxide), Magnesium diethoxide, magnesium hexafluorosilicate, magnesium hydrogen phosphate, magnesium hydroxide, magnesium hydrogen hydroxide, magnesium lactate, magnesium methoxide methyl carbonate, magnesium methoxide ethoxide, methyl magnesium carbonate, magnesium nitrate, magnesium oleate , Magnesium oxalate, magnesium oxide, magnesium perchlorate, magnesium phosphate, magnesium fluorosilicate , Magnesium compounds such as magnesium stearate, magnesium succinate and magnesium sulfate; beryllium acetate, beryllium ammonium phosphate, beryllium ammonium sulfate, beryllium benzoate, beryllium oxalate, beryllium carbonate, beryllium chloride, beryllium chromate, beryllium di Ethoxide, beryllium di (methoxy ethoxide), beryllium diethoxide, beryllium hexafluorosilicate, beryllium hydrogen phosphate, beryllium hydroxide, beryllium hydrogen hydroxide, beryllium lactate, beryllium methoxide methyl carbonate, beryllium methoxide ethoxide , Methyl beryllium carbonate, beryllium nitrate, beryllium oleate, beryllium oxalate,
Beryllium oxide, beryllium perchlorate, beryllium phosphate, beryllium fluorosilicate, beryllium stearate,
Beryllium compounds such as beryllium succinate and beryllium sulfate; calcium acetate, calcium ammonium phosphate, calcium ammonium sulfate, calcium benzoate, calcium oxalate, calcium carbonate hydroxide, calcium chloride, calcium chromate, calcium diethoxide, calcium di (methoxy) Ethoxide), calcium diethoxide, calcium hexafluorosilicate, calcium hydrogen phosphate, calcium hydroxide, calcium hydrogen hydroxide, calcium lactate, calcium methoxide methyl carbonate, calcium methoxide ethoxide, methyl calcium carbonate, calcium nitrate , Calcium oleate, calcium oxalate, calcium oxide, calcium perchlorate, calcium phosphate, calcium fluorosilicate, calcium stearate Calcium compounds such as calcium, calcium succinate, and calcium sulfate; strontium acetate, strontium ammonium phosphate, strontium ammonium sulfate, strontium benzoate, strontium oxalate, strontium hydroxide, strontium hydroxide, strontium chromate, strontium chromate, strontium diethoxide, Strontium di (methoxy ethoxide), strontium diethoxide, strontium hexafluorosilicate, strontium hydrogen phosphate, strontium hydroxide, strontium hydrogen hydroxide, strontium lactate, strontium methoxide methyl carbonate, strontium methoxide ethoxide, methyl carbonate Strontium, strontium nitrate, strontium oleate, strontium oxalate Um, strontium oxide, perchlorate, strontium phosphate, fluorosilicate, strontium stearate, strontium succinate, strontium compounds such as strontium sulfate; barium acetate, barium ammonium phosphate, ammonium barium sulfate,
Barium benzoate, barium oxalate, barium carbonate hydroxide, barium chloride, barium chromate, barium diethoxide, barium di (methoxyethoxide), barium diethoxide, barium hexafluorosilicate, barium hydrogen phosphate, hydroxide Barium, barium hydrogen hydroxide, barium lactate, barium methoxide methyl carbonate, barium methoxide ethoxide, methyl barium carbonate, barium nitrate, barium oleate, barium oxalate, barium oxide, barium perchlorate, barium phosphate, silicon oxide Barium compounds such as barium chloride, barium stearate, barium succinate and barium sulfate can be exemplified. Among the above metal compounds, organic acid salts such as oxalate and lactate are particularly preferred.

The amount of the component (B) in the film-forming composition is as follows:
The amount is 0.0001 to 0.015 parts by weight, more preferably 0.0002 to 0.01 parts by weight, based on 100 parts by weight of the component (A) (in terms of a completely hydrolyzed condensate). (B)
If the component content is less than 0.0001 part by weight, it may be difficult to bake the coating film in a short time, and if it exceeds 0.015 part by weight, the coating uniformity of the solution may be poor. Two or more of these components (B) may be used simultaneously.

(C) Organic Solvent The film-forming composition of the present invention is usually obtained by dissolving or dispersing the component (A) and the component (B) in the organic solvent (C).
Examples of the (C) organic solvent 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-methylbutanol, sec-pentanol, t
-Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n -Nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec
-Monoalcohol solvents such as heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-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-ethyl butyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether,
Polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether; and the like. One or two of these alcohol solvents are used.
More than one species may be used simultaneously.

Examples of ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl
n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-
Butyl ketone, methyl-n-hexyl ketone, di-i-
Butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4
-In addition to pentanedione, acetonylacetone, acetophenone, fenchone, etc., acetylacetone, 2,
4-hexanedione, 2,4-heptanedione, 3,5
-Heptanedione, 2,4-octanedione, 3,5-
Octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,
2,6,6-tetramethyl-3,5-heptanedione,
Β-diketones such as 1,1,1,5,5,5-hexafluoro-2,4-heptanedione and the like can be mentioned.
These ketone solvents may be used alone or in combination of two or more.

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

Examples of the 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, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-acetate
n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxy triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents include 1
Species or two or more species may be used simultaneously. Examples of aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, −
Methyl-Δ3-pyrroline, N-methylpiperidine, N-
Ethyl piperidine, N, N-dimethylpiperazine, N-
Methylimidazole, N-methyl-4-piperidone, N
-Methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3
-Dimethyltetrahydro-2 (1H) -pyrimidinone.

Among these organic solvents, an organic solvent represented by the following general formula (4) is particularly preferred. R ⁸ O (CHCH ₃ CH ₂ O) _e R ⁹ (4) (R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—. 1 to be chosen
Represents a valent organic group, and e represents an integer of 1 to 2. The above (C) organic solvents can be used alone or in combination of two or more. The film-forming composition of the present invention includes:
When the compounds (1) to (3) constituting the component (A) are hydrolyzed and / or condensed, the same solvent can be used.

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

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

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

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

Compounds having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure,
Examples include a polytetramethylene oxide structure and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene poly Oxypropylene block copolymers, ether compounds such as polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid alkanolamide sulfates and the like Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures. - (X) j- (Y) k- - (X) j- (Y) k- (X) l- ( wherein, X is a group represented by -CH ₂ CH ₂ O-, Y is -
A group represented by CH ₂ CH (CH ₃ ) O—, wherein j is 1 to
90, k is a number from 10 to 99, and l is a number from 0 to 90).
Polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
And the like. More preferred examples include ether-type compounds such as These may be used alone or in combination of two or more.

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

As the fluorine-based surfactant, for example, 1,
1,2,2-tetrafluorooctyl (1,1,2,2-
Tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl)
Ether, hexaethylene glycol (1, 1, 2,
2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro) Pentyl) ether, sodium perfluorododecyl sulfonate,
1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctanesulfone Amido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt,
At least one of terminal, main chain and side chain of perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, etc. And a fluorine-based surfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the position (1). Commercially available products are MegaFac F142D, F172, F173, F1
83 (manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC-430, and FC-431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, SC-103, SC-104, SC-1
05, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-10
00, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15
(Neos Co., Ltd.) and other commercially available fluorosurfactants. Among them, the above MegaFac F172, BM-1000, BM-11
00, NBX-15 is particularly preferred. Examples of the silicone-based surfactant include SH7PA, SH21PA, and S7PA.
H30PA and ST94PA (both are available from Dow Corning Toray Silicone Co., Ltd.).
Among them, 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 alone or in combination of two or more.

As the silane coupling agent, for example, 3
-Glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- 1,4,7-triazadecane, 10-
Triethoxysilyl-1,4,7-triazadecane, 9
-Trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriacetate Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-
Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the radical generator include isobutyryl peroxide, α, α'bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate and diisopropylperoxy. Dicarbonate,
1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl par Oxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy ) Hexane, 1-cyclohexyl-
1-methylethyl peroxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,
m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-
Butylperoxycyclohexyl) propane, 1,1-
Bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-
3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t -Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis ( t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like can be mentioned. The mixing amount of the radical generator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. These may be used alone or in combination of two or more.

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

The total solid content of the composition of the present invention thus obtained is preferably 2 to 30% by weight,
It is adjusted appropriately according to the purpose of use. When the total solid content of the composition is 2 to 30% by weight, the film thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The adjustment of the total solid content concentration is performed, if necessary, by concentration and dilution with the above (D) organic solvent. The composition of the present invention is applied to a silicon wafer, SiO ₂ wafer, SiN
When applying to a substrate such as a wafer, coating means such as spin coating, dipping, roll coating, and spraying are used.

In this case, the film thickness is about 0.05 to 2.5 μm in a single application as a dry film thickness, and a 0.1 to 5.0 μm thickness in a second application. be able to. Then dry at room temperature or 80-600
By heating and drying at a temperature of about 5 ° C. for about 5 to 240 minutes, a glassy or macromolecular insulating film can be formed. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used.
The reaction can be performed in an argon atmosphere, under vacuum, under reduced pressure with controlled oxygen concentration, or the like. Further, the coating film can be formed by irradiating an electron beam or an ultraviolet ray. Further, in order to control the curing speed of the coating film, if necessary, heating may be performed stepwise, or an atmosphere such as nitrogen, air, oxygen, or reduced pressure may be selected. 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 1.8.
2.0.

The interlayer insulating film thus obtained can be fired for a short time and has excellent crack resistance after PCT.
Interlayer insulating films for semiconductor devices such as RAM, RDRAM, D-RDRAM, etc., etching stopper films, protective films such as surface coat films for semiconductor devices, intermediate layers in the semiconductor manufacturing process using a multilayer resist, interlayer insulating films for multilayer wiring boards This is useful for applications such as protective films and insulating films for liquid crystal display elements.

[0047]

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

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

A sample of the composition was applied to 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. The substrate was baked for 8 minutes on a hot plate in a nitrogen atmosphere at ℃. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for relative dielectric constant measurement. The sample was made at a frequency of 100 kHz, HP16451B manufactured by Yokogawa-Hewlett-Packard Co., Ltd.
The relative permittivity of the coating film was measured by a CV method using an electrode and an HP4284A precision LCR meter.

A composition sample is applied on a crack-resistant 8-inch silicon wafer after PCT using a spin coating method, and the substrate is dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes, The substrate was further baked on a hot plate at 420 ° C. in a nitrogen atmosphere for 8 minutes. At this time, the thickness of the coating film was 1.5 μm. The obtained film was subjected to PCT for 1 hour at 100 ° C., 100% RH and 2 atm. A part of the obtained coating film was scratched with a knife and immersed in pure water for 4 hours. A knife scar in the coating film was observed with a microscope, and evaluated according to the following criteria. ：: No crack propagation was observed. ×: Propagation of cracks observed

Synthesis Example 1 77.04 g of distilled methyltrimethoxysilane and distilled tetramethoxysilane 2 were placed in a quartz separable flask.
4.05 g and distilled tetrakis (acetylacetonate)
After dissolving 0.48 g of titanium in 290 g of distilled propylene glycol monopropyl ether, the solution was stirred with a three-one motor to stabilize the solution temperature at 60 ° C.
Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, 25 g of distilled acetylacetone was added, the reaction was further performed for 30 minutes, and the reaction solution was cooled to room temperature. At 50 ° C., 149 g of a solution containing methanol and water was removed from the reaction solution by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 8,900. The content of the Group IA metal compound and the Group IIA metal compound in the periodic table of the elements in this solution was measured by atomic absorption spectroscopy.
pb or less (below the detection limit in the atomic absorption method).

Synthesis Example 2 In a quartz separable flask, 205.50 g of distilled methyltrimethoxysilane and distilled tetramethoxysilane 8 were added.
After dissolving 5.51 g in 426 g of distilled propylene glycol monoethyl ether, the solution was stirred with a three-one motor and stabilized at a solution temperature of 60 ° C. Next, ion-exchanged water 18 in which 0.013 g of maleic anhydride was dissolved.
2 g was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, the reaction solution was cooled to room temperature. 5
At 0 ° C., 360 g of a solution containing methanol was removed from the reaction solution by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 1,000. The content of the Group IA metal compound and the Group IIA metal compound in the periodic table of the elements in this solution was measured by atomic absorption spectrometry and found to be 1 ppb or less (less than the detection limit in atomic absorption spectrometry).

Synthesis Example 3 Distilled ethanol 570 was placed in a separable flask made of quartz.
g, 160 g of ion-exchanged water and 90 g of a 10% distilled dimethylamine ion-exchange aqueous solution were added, and the mixture was stirred uniformly. 13.6 of distilled methyltrimethoxysilane was added to this solution.
g of distilled tetraethoxysilane and 20.9 g of distilled tetraethoxysilane.
Added over 0 minutes. While keeping the solution at 65 ° C.,
A time reaction was performed. To this solution was added 3000 g of distilled propylene glycol monopropyl ether, and then 5 g
Using a 0 ° C. evaporator, the solution was concentrated to 10% (complete hydrolyzed condensate conversion). 10% of this solution
Add a solution of maleic acid in distilled propylene glycol,
The reaction solution was obtained by adjusting the pH of the solution to 4. The weight average molecular weight of the condensate and the like thus obtained is 993,
000. IA in the periodic table of the elements in this solution
The content of the Group II metal compound and the Group IIA metal compound was measured by atomic absorption spectrometry and found to be 1 ppb or less (below the detection limit in atomic absorption spectrometry).

Example 1 0.1 g of ion-exchanged water in which 0.0002 g of potassium lactate was dissolved was added to 100 g of the reaction solution obtained in Synthesis Example 1, and the mixture was sufficiently stirred. This solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a film-forming composition of the present invention. The obtained composition was applied on a silicon wafer by a spin coating method. The dielectric constant of the coating is 2.6
The value was as low as 2, and no crack propagation was observed even when the coating film after PCT was immersed in water.

Examples 2 to 9 In Example 1, the reaction solution shown in Table 1 was used instead of the reaction solution, and (B) shown in Table 1 was used instead of potassium lactate.
Evaluation was performed in the same manner as in Example 1 except that the components were used.
The evaluation results are also shown in Table 1.

[0056]

[Table 1]

Comparative Example 1 The coating film was evaluated in the same manner as in Example 1 except that only the reaction solution obtained in Synthesis Example 1 was used. The relative permittivity of the coating film was as high as 3.16. When the coating film after PCT was immersed in water, propagation of cracks was observed.

Comparative Example 2 The coating film was evaluated in the same manner as in Example 1 except that only the reaction solution obtained in Synthesis Example 1 was used. The relative permittivity of the coating film was as high as 3.34, and when the coating film after PCT was immersed in water, propagation of cracks was observed. Comparative Example 3 100 g of zinc acetate was added to 100 g obtained in Synthesis Example 1.
The coating film was evaluated in the same manner as in Example 1 except that g was added. The relative dielectric constant of the coating film was as high as 3.12, and when the coating film after PCT was immersed in water, propagation of cracks was observed.

[0059]

According to the present invention, by adding a specific metal compound to an alkoxysilane hydrolyzed polymer, it is possible to perform sintering for a short time, and to provide a film forming composition excellent in crack resistance after PCT ( (A material for an interlayer insulating film).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/316 H01L 21/316 G F-term (Reference) 4J038 DL011 DL021 DL041 DL051 DL071 DL081 DL111 HA076 HA096 HA126 HA176 HA246 HA256 HA336 HA376 HA426 HA476 JA17 JA27 JA33 JA35 JA43 JA48 JA53 JA65 JB01 JB12 JC04 JC14 JC38 KA04 KA06 LA03 MA09 5F058 AA02 AA10 AC03 AC06 AF04 AG01 AH02 BA04 BC05 BF46 BJ02

Claims (8)

[Claims] (A) (A-1) a compound represented by the following general formula (1): R _a Si (OR ¹ ) _4-a (1) wherein R is hydrogen An atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is an integer of 1 to 2.) (A-2) a compound represented by the following general formula (2); (OR ² ) ₄ (2) (wherein, R ² represents a monovalent organic group.) (A-3) 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 same or different and each represents a monovalent Organic groups, b to c are the same or different, an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
(Where n is an integer of 1 to 6), d
Represents 0 or 1. At least one selected from the group of
A hydrolyzed condensate obtained by hydrolyzing and condensing a kind of compound, (B) at least one selected from compounds of Group IA metals and Group IIA metals in the periodic table of the elements, and (C) an organic solvent. A composition for forming a film, characterized by: 2. Component (B) is potassium, rubidium,
2. A compound of at least one metal selected from the group consisting of cesium, beryllium, magnesium, calcium, strontium and barium.
The composition for forming a film according to the above. 3. The composition according to claim 2, wherein the compound is an organic acid salt. 4. The composition according to claim 1, wherein the content of the component (B) is 10%.
0.00 to 0 parts by weight (in terms of complete hydrolysis condensate)
The film forming composition according to any one of claims 1 to 3, wherein the amount is from 0.01 to 0.015 parts by weight. 5. The method according to claim 1, wherein the component (A) is hydrolyzed in the presence of at least one selected from the group consisting of a metal chelate compound, an acid catalyst and an alkali catalyst. A composition for forming a film according to any one of claims 1 to 4. 6. 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 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—. 1 to be chosen
Represents a valent organic group, and e represents an integer of 1 to 2. ) 7. A method for forming a film, comprising applying the composition for film formation according to claim 1 to a substrate and heating the substrate. 8. A silica-based film obtained by the method for forming a film according to claim 7.