JP2001055554A - Film-forming composition and insulating film-forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film-forming composition which excels in the mechanical properties of a coated film and can effect firing of the coated film in a short period of time and exhibits a very low dielectric constant as the interlaminar insulating film material in semiconductor elements and the like. SOLUTION: A film-forming composition contains (A) a hydrolyzate and/or a condensate of at least one compound selected from (A-1) compounds represented by formula I: R1aSi(OR2)4-a (wherein R1 is hydrogen, fluorine or a monovalent organic group; R2 is a monovalent organic group; and (a) is an integer of 0-2) and (A-2) compounds represented by formula II: R3b(R4 O)3-bSi-(R7)d-Si(OR5)3-cR6c (wherein R3, R4, R5 and R6 are the same or different and each is a monovalent organic group; (b) and (c) are the same or different and each is a number of 0-2; R7 is an oxygen atom or -(CH2)n-; (n) is 1-6; and (d) is 0 or 1), (B) a latent acid catalyst and/or a latent base catalyst, and (C) a solvent having a boiling point at normal pressures of not lower than 180 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for forming a film, and more particularly, as a material for an interlayer insulating film in a semiconductor device or the like, which has excellent mechanical properties of a coating film and can bake the coating film in a short time. And a film-forming composition exhibiting a very low dielectric constant.

[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. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating-type insulating film mainly composed of a hydrolysis product of tetraalkoxylan, which is called an SOG (Spin on Glass) film, may be used. It has become. Also, with the high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant and mainly containing polyorganosiloxane called organic SOG has been developed. However, with higher integration and multilayering of semiconductor devices and the like, more excellent electrical insulation between conductors is required, and therefore,
There is a demand for an interlayer insulating film material having a lower dielectric constant and excellent mechanical strength.

[0003] Japanese Patent Application Laid-Open No. 6-181201 discloses a coating composition for forming an insulating film having a lower dielectric constant as an interlayer insulating film material. The coating type composition has a low water absorption and is intended to provide an insulating film of a semiconductor device having excellent crack resistance.
Titanium, zirconium, niobium and tantalum; an organometallic compound containing at least one element selected from the group consisting of polycondensation of an organosilicon compound having at least one alkoxy group in the molecule; This is a coating composition for forming an insulating film, which is mainly composed of an oligomer.

[0004] WO96 / 00758 also discloses that
A silica-based coating-type insulating film that is used for forming an interlayer insulating film of a multilayer wiring board and that is made of an alkoxysilane, a metal alkoxide other than silane, and an organic solvent, and that can be applied in a thick film and has excellent oxygen plasma resistance. A forming material is disclosed.

Further, Japanese Patent Application Laid-Open No. Hei 3-20377 discloses a coating liquid for forming an oxide film, which is useful for flattening the surface of electronic parts and the like and for interlayer insulation. The coating solution for forming an oxide film provides a uniform coating solution without generation of a gel-like substance. Further, by using this coating solution, curing at a high temperature and treatment by oxygen plasma are performed. Even so, the purpose is to obtain a good oxide film without cracks. The composition is a coating solution for forming an oxide film obtained by hydrolyzing and polymerizing a predetermined silane compound and a predetermined chelate compound in the presence of an organic solvent.

However, when a metal chelate compound such as titanium or zirconium is combined with a silane compound as described above, the mechanical properties of the coating film, baking of the coating film in a short time, and a very low dielectric constant are well balanced. Not something.

[0007]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly, to a film having excellent mechanical properties as an interlayer insulating film in a semiconductor device or the like. Baking of the coating film is possible in a short time,
An object of the present invention is to provide a material for an interlayer insulating film having a very low dielectric constant.

The present invention relates to (A) (A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) wherein R ¹ is hydrogen An atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) represented by the following general formula (2) Compound R ³ _b (R ⁴ O) _3-b Si— (R ⁷ ) _d —Si (OR ⁵ ) _3-c R ⁶ _c (2) (R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a monovalent organic group, b and c may be the same or different and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or-( CH2) _n- represents a group represented by n-
Represents 1 to 6, and d represents 0 or 1. Or at least one of a hydrolyzate and a condensate of at least one compound selected from the group consisting of (B) a latent acid catalyst and / or a latent base catalyst, and (C) a boiling point at normal pressure of 180 ° C. or higher. An object of the present invention is to provide a film-forming composition and a material for forming an insulating film, characterized by containing a solvent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

Component (A) Component (A-1) In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Can be. Further, in the general formula (1), R ¹ 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, preferably having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), as the aryl group,
Examples 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, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane,
Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, etc .; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltrimethylsilane -N-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane,
Methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-s
ec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri- sec-butoxysilane, vinyl tri-tert
-Butoxysilane, vinyltriphenoxysilane, n-
Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane,
n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-
sec-butoxysilane, n-propyltri-tert
-Butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri- n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri- n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-te
rt-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-
n-propoxysilane, sec-butyl-tri-iso
-Propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxy Silane, 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, phenyltrisilane -Iso-
Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, 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-
tert-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-i
so-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-
Propoxysilane, di-iso-propyl-di-iso
-Propoxysilane, di-iso-propyl-di-n-
Butoxysilane, 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-sec-butyl-di-iso-propoxysilane,
Di-sec-butyl-di-n-butoxysilane, di-s
ec-butyl-di-sec-butoxysilane, di-se
c-butyl-di-tert-butoxysilane, di-se
c-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxy Silane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxy Silane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-s
ec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, and the like. Preferably, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-
Propoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmono Methoxysilane, triethylmonoethoxysilane, triphenylmonomethoxysilane, triphenylmonoethoxysila It is. These may be used alone or in combination of two or more.

(A-2) Component In the above general formula (2), examples of the monovalent organic group include the same organic groups as those in the above general formula (1).
Examples of the divalent organic group represented by R ⁷ in the general formula (2) include a methylene group and an alkylene group having 2 to 6 carbon atoms. In the general formula (2), as the compound in which R ⁷ is an oxygen atom, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldimethyl Siloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,
3,3-pentaethoxy-3-phenyldisiloxane,
1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3
-Dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,
3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triethoxy-1,3,3
3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,
3-triethoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,
3-tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraphenyldisiloxane, 1,3
-Diethoxy-1,1,3,3-tetraphenyldisiloxane and the like. 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, 1,3-dimethoxy-1,1,3,3
Preferred examples include 3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane. Compounds in which d is 0 in the general formula (2) include hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,1,2,2-pentamethoxy-2
-Methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2
-Pentaethoxy-2-phenyldisilane, 1,1,
2,2-tetramethoxy-1,2-dimethyldisilane,
1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-
1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,
1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane or the like, wherein R ⁷ in the general formula (2) is-(CH ₂ ) _n-
Examples of the compound of the group represented by are bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (hexaphenoxysilyl) methane, bis (dimethoxymethylsilyl) methane, and bis (diethoxymethylsilyl) methane , Bis (dimethoxyphenylsilyl)
Methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, bis (ethoxydiphenylsilyl) methane, bis (hexamethoxysilyl) ethane , Bis (hexaethoxysilyl) ethane, bis (hexaphenoxysilyl) ethane, bis (dimethoxymethylsilyl) ethane, bis (diethoxymethylsilyl) ethane, bis (dimethoxyphenylsilyl) ethane, bis (diethoxyphenylsilyl) ethane , Bis (methoxydimethylsilyl) ethane, bis (ethoxydimethylsilyl) ethane,
Bis (methoxydiphenylsilyl) ethane, bis (ethoxydiphenylsilyl) ethane, 1,3-bis (hexamethoxysilyl) propane, 1,3-bis (hexaethoxysilyl) propane, 1,3-bis (hexaphenoxysilyl) Propane, 1,3-bis (dimethoxymethylsilyl) propane, 1,3-bis (diethoxymethylsilyl) propane, 1,3-bis (dimethoxyphenylsilyl) propane, 1,3-bis (diethoxyphenylsilyl) Propane, 1,3-bis (methoxydimethylsilyl) propane, 1,3-bis (ethoxydimethylsilyl) propane, 1,3-bis (methoxydiphenylsilyl) propane, 1,3-bis (ethoxydiphenylsilyl) propane, etc. Can be mentioned. Among them, hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2
2-tetraethoxy-1,2-dimethyldisilane, 1,
1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis ( Preferred examples include dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, and bis (ethoxydiphenylsilyl) methane. It can be mentioned as. In the present invention,
As the component (A), the components (A-1) and (A-
2) Component or any one of them can be used, and two or more of each of the component (A-1) and the component (A-2) can be used.

In the present invention, the term “hydrolysis” refers to R ² O—, R ⁴ O—, and R ² O—
^It is not necessary that all the ⁵ O-groups be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof. In the present invention, condensation refers to condensation of a silanol group of the hydrolyzate of the component (A) to form a Si—O—Si bond. In the present invention, however, it is not necessary that all of the silanol groups are condensed. The concept encompasses the formation of a mixture of a small amount of silanol groups and a mixture of those having different degrees of condensation.
In addition, the weight average molecular weight of the hydrolysis-condensation product of the component (A) is usually about 1,000 to 120,000, preferably about 1,200 to 100,000.

When the component (A) is hydrolyzed and partially condensed, a catalyst is used. Examples of the catalyst used at this time include a metal chelate compound, an organic acid, an inorganic acid, an organic base, and an inorganic base. 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-propoxybis (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 ( Acetylacetonate) 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 (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) zirconium, tri-n-butoxy mono (ethylacetate) (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. Examples of organic acids 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, and gallic acid , Butyric acid, melitic acid, arachidonic acid, mykimic 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 the like. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine,
Monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane,
Examples thereof include diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide. As the inorganic base, for example, ammonia,
Sodium hydroxide, potassium hydroxide, barium hydroxide,
Calcium hydroxide and the like can be mentioned. Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable. These may be used alone or in combination of two or more.

The amount of the catalyst used is usually 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the component (A) (in terms of complete hydrolysis condensate).
The range is 0 parts by weight. Further, the catalyst may be previously added to the solvent, or may be dissolved or dispersed in water at the time of adding water.

(B) Component The film-forming composition of the present invention contains a latent acid catalyst and / or a latent base catalyst. Examples of the latent acid catalyst include a thermal acid generator and a photoacid generator. Thermal acid generator is usually 50 to 450
It is a compound which generates an acid by heating to 200C, preferably 200 to 350C, and an onium salt such as a sulfonium salt, a benzothiazolium salt, an ammonium salt, and a phosphonium salt is used.

A specific example of the above sulfonium salt is 4
-Acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-
4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-
Alkylsulfonium salts such as 4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate; benzyl -4-Hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl -2-methyl-4-hydroxyphenylmethylsulfonium hexafluoro Nchimoneto, benzyl-3-chloro-4-hydroxyphenyl methyl sulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl methyl sulfonium hexafluorophosphate, benzoin tosylate, 2
Benzylsulfonium salts such as -nitrobenzyl tosylate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, Dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-
tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-
Dibenzylsulfonium salts such as 4-hydroxyphenylsulfonium hexafluorophosphate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chloro Benzyl-4
-Hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-
4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4
Substituted benzylsulfonium salts such as -hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate;

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, and 3-benzylbenzothiazolium tetrafluoroborate. (P-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5
Benzylbenzothiazolium salts such as -chlorobenzothiazolium hexafluoroantimonate. Furthermore, as thermal acid generators other than the above, 2, 4,
4,6-tetrabromocyclohexadienone can be exemplified.

Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium
Hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate Nates and the like are preferably used. These commercial products include Sun-Aid SI-L85,
I-L110, SI-L145, SI-L150,
And SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.). These compounds can be used alone or in combination of two or more.

The latent photoacid generator used in the present invention comprises:
It is a compound which generates an acid upon irradiation with ultraviolet light of usually 1 to 100 mJ, preferably 10 to 50 mJ. Examples of the photoacid generator include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, and diphenyliodonium nonafluoro n-.
Butanesulfonate, bis (4-t-butylphenyl)
Iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium naphthalene sulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4 -T-butylphenyl) iodonium nonafluoro n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl (4- Methylphenyl) sulfonium trifluoromethanesulfonate, diphenyl (4-methoxyphenyl) sulfate Trifluoromethanesulfonate, (hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfoniumtrifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfoniumtrifluoromethanesulfonate, dimethyl (2-oxocyclohexyl) sulfoniumtrifluoromethane Sulfonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfone 4-cyano 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyl-diethylsulfonium Trifluoromethanesulfonate, 4
-Nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfoniumtrifluoromethanesulfonate,
4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-ethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1-methoxyethoxy) -1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-methoxyethoxy) -1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbenyloxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- n-butoxycarbyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1- Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-
(2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1-
Onium salt-based photoacid generators such as (naphthyl acetomethyl) tetrahydrothiophenium trifluoromethanesulfonate; phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl- Halogen-containing compound-based photoacid generators such as bis (trichloromethyl) -s-triazine; 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,3,4 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,4'-tetrabenzophenone or 1,2-naphthoquinonediazide-5
Diazoketone compound-based photoacid generators such as sulfonic acid esters; sulfonic acid compound-based photoacid generators such as 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane; benzoin tosylate, pyrogallol Trinitrotrifluoromethanesulfonate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3-
Examples thereof include sulfonic acid compound-based photoacid generators such as dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate. These compounds can be used alone or in combination of two or more.

The latent base catalyst can generate a base by an external stimulus. As the external stimulus, ultraviolet rays and heat are preferable, and orthonitrobenzyl carbamates, α, α-dimethyl-3,5- Examples include dimethoxybenzyl carbamates and acyloxyiminos. Further, as a base generated by light, hydrazine, tetramethylenediamine, toluenediamine, diaminodiphenylmethane, hexamethyltetraamine, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, cetylamine, piperidine, And piperazine. More specifically, [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy] carbonyl] hexylamine, [[(2-Nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl]
Aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, [[(2-nitrobenzyl) oxy] carbonyl] hexamethylenediamine, [[(2-
[Nitrobenzyl) oxy] carbonyl] phenylenediamine, [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, [[(2-nitrobenzyl) oxy] carbonyl] diaminodiphenylmethane,
[[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] propylamine,
[[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine,
[[(2,6-dinitrobenzyl) oxy] carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] phenylenediamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine,
[[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine,
[[(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonylmethylamine, [[(α, α-
Dimethyl-3,5-dimethoxybenzyl) oxy] carbonylpropylamine, [[(α, α-dimethyl-3,
5- [dimethoxybenzyl) oxy] carbonylhexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonylcyclohexylamine,
[[(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonylaniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonylpiperidine, [[(α, α-dimethyl -3,5-dimethoxybenzyl) oxy] carbonylhexamethylenediamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonylphenylenediamine,
[[(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyltoluenediamine, [[(α,
α-dimethyl-3,5-dimethoxybenzyl) oxy]
Carbonyldiaminodiphenylmethane, [[(α, α-
Dimethyl-3,5-dimethoxybenzyl) oxy] carbonylpiperazine, propionylacetophenone oxime, propionylbenzophenone oxime, propionylacetone oxime, butyrylacetophenone oxime, butyrylbenzophenone oxime, butyrylacetone oxime, adipoylacetophenone oxime, adipoyl Benzophenone oxime, adipoylacetone oxime, acroylacetophenone oxime, acroylbenzophenone oxime, acroylacetone oxime and the like. [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine,
[[(2-nitrobenzyl) oxy] carbonyl] hexamethylenediamine, [(α, α-dimethyl-3,5-
Dimethoxybenzyl) oxy] carbonylhexamethylenediamine. These compounds can be used alone or in combination of two or more.

The proportion of the component (B) in the composition of the present invention is 0.001 to 10 parts by weight, more preferably 0 to 10 parts by weight, based on 100 parts by weight of the component (A) (in terms of a completely hydrolyzed condensate). 0.01 to 10 parts by weight. When the amount of the component (B) is less than 0.001 part by weight, the dielectric constant of the coating film does not become a sufficiently low value, and when the amount of the component (B) exceeds 10 parts by weight, the storage stability of the solution becomes poor. It may deteriorate.

Component (C) The component (C) used in the present invention has a boiling point at normal pressure of 180.
It is a solvent at a temperature of not lower than ° C, and examples thereof include polyhydric alcohols, glycol solvents, glycol monoalkyl ether solvents, glycol dialkyl ether solvents, glycol monoalkyl ether ester solvents, and glycol diester solvents. Specific examples of these solvents include, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5 -Pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3- Hexanediol, 1,2-hexanediol, 1,7-heptanediol, 1,2-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-
Nonanediol, 1,2-nonanediol, 1,10-
Decanediol, 1,2-decanediol, 1,12-
Dodecanediol, 1,2-dodecanediol, 1,1
4-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, 1,18-octadecanediol,
1,2-octadecanediol, cyclohexanediol, adamantanediol, dicyclopentanediol, glycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, diglycerin,
Polyhydric alcohols such as sorbitol; glycol solvents such as diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, pentaethylene glycol and pentapropylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether Ter, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol Glycol monoalkyl ethers such as monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, and tetrapropylene glycol monobutyl ether Le solvents diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol diethyl ether,
Dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene Glycol dipropyl ether, tripropylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether Glycol dialkyl ether based solvents such as toluene, tetrapropylene glycol dipropyl ether and tetrapropylene glycol dibutyl ether; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate , Dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol Coal monopropyl ether acetate, triethylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monopropyl ether acetate, tripropylene glycol monobutyl ether acetate, tetraethylene glycol monomethyl ether acetate, Tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monopropyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol monoethyl ether acetate, tetrapropylene glycol Glycol monoalkyl ether ester solvents such as propyl ether acetate and tetrapropylene glycol monobutyl ether acetate; ethylene glycol diacetate, propylene glycol diacetate, diethylene glycol diacetate, dipropylene glycol diacetate, triethylene glycol diacetate, tripropylene glycol Diacetate,
Examples thereof include glycol diester solvents such as tetraethylene glycol diacetate and tetrapropylene glycol diacetate. Among them, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, glycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, diglycerin, sorbitol, diethylene glycol, diethylene glycol Propylene glycol,
Triethylene glycol, tripropylene glycol,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobu Diether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol Monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monopropyl ether acetate, triethylene glycol monobutyl ether acetate, tripropylene glycol monomer Ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monopropyl ether acetate, tripropylene glycol monobutyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, diethylene glycol diacetate, dipropylene glycol diacetate, triethylene glycol diacetate Acetate and tripropylene glycol diacetate can be mentioned as particularly preferred examples. These can be used alone or in combination of two or more.

Component (D) The component (D) used in the present invention has a boiling point of 160 at normal pressure.
C. or less, for example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-pentane
Aliphatic hydrocarbon solvents such as heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene; methanol; Ethanol, n-propanol, i-
Propanol, n-butanol, i-butanol, se
c-butanol, t-butanol, n-pentanol,
Monoalcohol solvents such as i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n- Butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone,
Ketone solvents such as ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione; ethyl ether, i-propyl ether, n- Butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-
Ethers such as methyl dioxolan, dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran System solvent: methyl acetate, ethyl acetate, -n-propyl acetate, -i-propyl acetate, -n-butyl acetate, -i-acetic acid
-Butyl, -sec-butyl acetate, -n-pentyl acetate, -sec-pentyl acetate, -3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl acetate Ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate acetate, propylene glycol monoethyl acetate ethyl propionate, n-butyl propionate,
Ester solvents such as i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, diethyl malonate, 3-methoxymethyl propionate, and 3-ethoxyethyl propionate; N-
Methylformamide, N, N-dimethylformamide,
And the like. Among them, methanol, ethanol, n-propanol, i-
Propanol, n-butanol, i-butanol, se
c-butanol, t-butanol, 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, cyclohexanone, methylcyclohexanone, 2,
4-pentanedione, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl acetate, n-propyl acetate, acetic acid-i -Propyl, n-butyl acetate, i-butyl acetate, s-acetic acid
ec-butyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate acetate,
Propylene glycol monoethyl ether ethyl acetate propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, diethyl malonate, 3
-Methoxymethyl propionate and 3-ethoxyethyl propionate can be mentioned as particularly preferred examples. These can be used alone or in combination of two or more.

The proportion of the components (C) and (D) used in the composition is (C) :( D) = 5: 95 to 50:50 (weight ratio), and more preferably (C) :( D) = 8: 92
45:55 (weight ratio). When the amount of the component (C) is less than 5%, the dielectric constant of the coating film does not become a sufficiently low value.
If the component amount exceeds 50%, the coatability of the solution may deteriorate.

The hydrolysis of the component (A) can be carried out in the above-mentioned component (C) and / or the organic solvent of either one of the components (C) and (C).
The component and / or the component (D) may be added.

In the present invention, the content of alcohol having a boiling point of 100 ° C. or less in the film-forming composition is 20% by weight or less,
In particular, it is preferably at most 5% by weight. Boiling point 100 ° C
The following alcohols are used as the component (A-1) and the component (A).
-2) It may occur during hydrolysis and condensation of the component, and it is preferable to remove the component by distillation or the like so that the content is 20% by weight or less, preferably 5% by weight or less.

The film forming composition of the present invention may further contain the following components. β-diketones β-diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- Nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2
6,6-tetramethyl-3,5-heptanedione, 1,
One or more kinds such as 1,1,5,5,5-hexafluoro-2,4-heptanedione. In the present invention, the β-diketone content in the film-forming composition,
Total amount of component (A) (in terms of complete hydrolysis condensate) 100
It is usually in the range of 0.1 to 100 parts by weight, preferably 0.2 to 80 parts by weight based on parts by weight. Β in such a range
Addition of a diketone can provide a certain storage stability and reduce the risk of deterioration of properties such as coating uniformity of the film-forming composition. This β-diketone is preferably added after the hydrolysis and condensation reaction of the component (A).

Other Additives Components such as colloidal silica, colloidal alumina, organic polymer and surfactant may be further added to the film-forming composition obtained in the present invention. Colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 m.
μ, preferably 10-20 μm, solid content concentration of 10-4
It is about 0% by weight. Examples of such colloidal silica include methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industry Co., Ltd .; and Oscar manufactured by Catalyst Chemicals Co., Ltd. Examples of the colloidal alumina include alumina sols 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; and alumina clear sol, alumina sol 10, and 132 manufactured by Kawaken Fine Chemicals Co., Ltd. As the organic polymer, for example, a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound,
Examples include dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, polyquinoxalines, polyoxadiazoles, and fluoropolymers.
Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a silicone surfactant, a polyalkylene oxide surfactant And fluorinated surfactants and acrylic surfactants. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether, and polyoxyethylene. Polyoxyethylene alkyl phenyl ethers such as n-nonyl phenyl ether; and polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate. As a specific example of the fluorine-based surfactant, a compound having a fluoroalkyl or fluoroalkylene group at at least one of terminal, main chain, and side chain can be suitably used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether,
1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,
1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3, 3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,
2,2,8,8,9,9,10,10-decafluorododecane,
1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, fluoroalkyloxyethylene ether, diglycerin tetrakisfluoroalkylammonium iodide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol , Perfluoroalkyl alkoxylates, fluorine-based alkyl esters and the like. Moreover, as these commercially available products, BM-100
0, BM-1100 (above, manufactured by BM Chemie), MegaFac F142D, F172, F17
3, F183, F178, F191, F47
1, (the above are manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC-170C, FC-171, FC-430, F
C-431 (above, Sumitomo 3M Limited) and the like. Specific examples of the silicone-based surfactant include, for example, Toray silicone DC3PA, DC7
PA, SH11PA, SH21PA, SH28P
A, SH29PA and SH30PA (all manufactured by Toray Silicone Co., Ltd.), TSF-4440, TSF-43
00, TSF-4445, TSF-4446, TSF-
4460 and TSF-4452 (both manufactured by Toshiba Silicone Co., Ltd.). Other surfactants include, for example, sorbitan fatty acid esters; fatty acid-modified polyesters;
Tertiary amine-modified polyurethanes; polyethylene imines and the like. These surfactants can be used alone or in combination of two or more.

The total solid content of the film-forming composition of the present invention is preferably 2 to 30% by weight, and is appropriately adjusted depending on the purpose of use. When the total solid content of the composition is 2 to 30
When it is% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent.

The composition of the present invention is prepared by using a silicon wafer, Si
When applying to a substrate such as an O2 wafer or a SiN wafer, a coating method such as spin coating, dipping, roll coating, or spraying is used.

In this case, the film thickness may be about 0.05 to 1.5 μm in a single coating, and about 0.1 to 3 μm in a double coating. it can. Thereafter, by drying at room temperature or by heating at a temperature of about 80 to 600 ° C., usually 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. As a heating atmosphere, the heating is performed in the atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like. Can be.

The interlayer insulating film thus obtained is excellent in insulation, uniformity of coating film, dielectric constant, crack resistance of coating film, and surface hardness of coating film.
System L, DRAM, SDRAM, RDRAM, D
-An interlayer insulating film for semiconductor devices such as RDRAM, a protective film such as a surface coat film of a semiconductor device, an intermediate layer of a semiconductor manufacturing process using a multilayer resist, an interlayer insulating film of a multilayer wiring board,
It is useful for applications such as protective films and insulating films for liquid crystal display elements.

[0035]

The present invention will now be described more specifically with reference to examples. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, respectively, unless otherwise specified. Further, the evaluation of the film-forming composition in the examples was measured as follows.

The weight average molecular weight (Mw) was measured by a gel permeation chromatography (GPC) method 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

The composition for forming a mechanical strength (elastic modulus) coating film was applied on an 8-inch silicon wafer using a spin coater under the conditions of a rotation speed of 1,500 rpm and 30 seconds. 3 on a hot plate at 70 ° C
For 3 minutes at 200 ° C.
The substrate was baked on a hot plate in a nitrogen atmosphere for 30 minutes. The modulus of elasticity of the obtained coating film was measured by a continuous stiffness measuring method using Nanoindenter XP (manufactured by Nano Instruments).

Short-time baking (measurement of desorbed gas amount) The composition for forming a coating film was applied on an 8-inch silicon wafer by using a spin coater under the conditions of a rotation speed of 1,500 rpm and 30 seconds. 3 on a hot plate at 70 ° C
For 3 minutes at 200 ° C.
The substrate was baked on a hot plate in a nitrogen atmosphere for 10 minutes. The obtained substrate was heated up to 400 ° C. using a temperature rising gas analyzer EMD-WA1000S manufactured by Electronic Science Co., Ltd., and the desorbed gas was measured. The amount of desorbed gas was compared with the SiO ₂ film formed by CVD, and evaluated based on the following criteria. ；: Desorption gas amount is equal to or less than the SiO ₂ film formed by CVD ×: Desorption gas amount exceeds the SiO ₂ film formed by CVD

The composition for forming a dielectric constant coating film was applied on an 8-inch silicon wafer using a spin coater under the conditions of a rotation speed of 1,500 rpm for 30 seconds. 3 on a hot plate at 70 ° C
For 3 minutes at 200 ° C.
The substrate was baked on a hot plate in a nitrogen atmosphere for 30 minutes. Aluminum was vapor-deposited on the obtained substrate to produce a substrate for permittivity evaluation. Dielectric constant is measured using an HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd.
10 kHz using a 284A precision LCR meter
It was calculated from the capacitance value at z.

Synthesis Example 1 In a quartz separable flask, 308.5 g of methyltrimethoxysilane, 96.5 g of tetramethoxysilane and 0.95 g of diisopropoxytitanium bisethylacetyl acetate were dissolved in 500 g of propylene glycol monomethyl ether. Thereafter, the solution was stirred by a three-one motor, and the solution temperature was stabilized at 60 ° C. Next, 84 g of ion-exchanged water was added to the solution over 2 hours. Then 6
After reacting at 0 ° C. for 2 hours, the reaction solution was cooled to room temperature. 595 g of propylene glycol monomethyl ether was added to this reaction solution, and a solution containing methanol was removed from the reaction solution at 50 ° C. by evaporation of 595 g to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 7,800.

Synthesis Example 2 In a quartz separable flask, 308.5 g of methyltrimethoxysilane and 96.5 g of tetramethoxysilane were dissolved in 545 g of propylene glycol monoethyl ether, and the mixture was stirred with a three-one motor to adjust the solution temperature. Stabilized at 60 ° C. Next, 10.0 g of maleic acid
Was dissolved in the solution over 2 hours. Then, after reacting at 60 ° C. for 2 hours, the reaction solution was cooled to room temperature. 595 g of propylene glycol monoethyl ether was added to the reaction solution,
595 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 3,200.

Example 1 To 100 g of the reaction solution obtained in Synthesis Example 1, 16 g of triethylene glycol monoethyl ether and 0.2 g of SI-L85 (manufactured by Sanshin Chemical Industry Co., Ltd.) were added, followed by sufficient stirring. The solution was filtered through a Teflon 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 resulting coating film had an elastic modulus of 5.4 GPa, which was excellent in mechanical strength. When the amount of desorbed gas of the coating film was measured, the amount of desorbed gas was as small as that of a SiO ₂ film formed by CVD or less even after baking for a short time. In addition, when the dielectric constant of the coating film was evaluated, it showed a very low dielectric constant of 2.43.

Examples 2 to 6 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.

[0044]

[Table 1]

Example 7 16 g of triethylene glycol monoethyl ether, 0.2 g of SI-L85 (manufactured by Sanshin Chemical Industry Co., Ltd.) and 4 g of acetylacetone were added to 100 g of the reaction solution obtained in Synthesis Example 1.
Was added and stirred sufficiently. The solution was filtered through a Teflon 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 elastic modulus of the obtained coating film was 5.3 GPa, which was excellent in mechanical strength. When the amount of desorbed gas of the coating film was measured, the amount of desorbed gas was as small as that of a SiO ₂ film formed by CVD or less even after baking for a short time. In addition, when the dielectric constant of the coating film was evaluated, it showed a very low dielectric constant of 2.42.

Example 8 To 100 g of the reaction solution obtained in Synthesis Example 1, 16 g of triethylene glycol monoethyl ether, 0.2 g of SI-L85 (manufactured by Sanshin Chemical Industry Co., Ltd.) and a molecular weight of about 2,000
0 g of polyethylene glycol was added and stirred sufficiently. The solution was filtered through a Teflon 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 obtained coating film had an elastic modulus of 5.1 GPa, which was excellent in mechanical strength. When the amount of desorbed gas of the coating film was measured, the amount of desorbed gas was as small as that of a SiO ₂ film formed by CVD or less even after baking for a short time. In addition, when the dielectric constant of the coating film was evaluated, it showed a very low dielectric constant of 2.12.

Example 9 To 100 g of the reaction solution obtained in Synthesis Example 1, 16 g of triethylene glycol monoethyl ether, 0.2 g of SI-L85 (manufactured by Sanshin Chemical Industry Co., Ltd.) and a weight molecular weight of about 4,000
Then, 10 g of polyisopropyl methacrylate of No. 0 was added and stirred sufficiently. The solution was filtered through a Teflon 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 resulting coating film had an elastic modulus of 5.0 GPa, which was excellent in mechanical strength. After measuring the amount of gas released from the coating film,
And the amount of desorbed gas was small even after baking for a short time, which was less than the SiO ₂ film formed. When the dielectric constant of the coating film was evaluated, it showed a very low dielectric constant of 2.15.

Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that only the reaction solution obtained in Synthesis Example 1 was used. When the dielectric constant of the coating film was measured, it was a relatively low dielectric constant of 2.65.
The resulting coating film had an elastic modulus of 2.9 GPa, which was poor in mechanical strength. Further, when the amount of desorbed gas of the coating film was measured, the amount of desorbed gas was larger than that of the SiO ₂ film formed by CVD.

Comparative Example 2 Evaluation was performed in the same manner as in Example 1 except that only 16 g of triethylene glycol monoethyl ether was added to the reaction solution obtained in Synthesis Example 1. When the dielectric constant of the coating film was measured, it was a relatively low dielectric constant of 2.67, but the elastic modulus of the obtained coating film was 2.7 GPa, which was poor in mechanical strength. Further, when the amount of desorbed gas of the coating film was measured, the amount of desorbed gas was larger than that of the SiO ₂ film formed by CVD.

Comparative Example 3 Example 1 was repeated except that only 0.2 g of SI-L85 (manufactured by Sanshin Chemical Industry Co., Ltd.) was added to the reaction solution obtained in Synthesis Example 1.
The evaluation was performed in the same manner as described above. The modulus of elasticity of the obtained coating film was as high as 5.1 Gpa, but the dielectric constant of the coating film was measured and found to be as high as 3.02. Further, when the amount of desorbed gas of the coating film was measured, the amount of desorbed gas was larger than that of the SiO ₂ film formed by CVD.

[0051]

According to the present invention, a hydrolyzate of an alkoxysilane and / or a condensate thereof, a solvent having a boiling point of 180 ° C. or more at normal pressure, a latent acid generation catalyst and / or a latent base generation Provides a film-forming composition (interlayer insulating film material) that contains a catalyst, has excellent mechanical properties of the coating film, enables baking of the coating film in a short time, and exhibits a very low dielectric constant. It is possible to

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Satoko Hakamuka 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. F term (reference) in the corporation 4J038 CG142 DF022 DL021 DL031 JA34 KA04 KA06 NA21 4J040 DF041 DF042 DF051 DF052 EE022 EK051 EK071 HB10 HB11 HB15 HB20 HB24 HB31 HD13 HD21 HD41 KA14 LA23F04 KA14 KA23 KA22 AA10 AC03 AF04 AG01 AH01 AH02

Claims (7)

[Claims] 1. A (A) (A-1) below compound represented by the general formula (1) and _{^{R 1 a Si (OR 2)}} 4-a ····· (1) (R 1 is a hydrogen atom , A fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 2.) (A-2) a compound represented by the following general formula (2) _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (oR 5) 3-c R 6 c ··· (2) (R 3, R 4, R 5 and R ^6, May be the same or different, each represents a monovalent organic group, b and c may be the same or different, each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or — (CH ₂ ) _n -Represents a group represented by -n
Represents 1 to 6, and d represents 0 or 1. Or at least one of a hydrolyzate and a condensate of at least one compound selected from the group consisting of: (B) a latent acid catalyst and / or a latent base catalyst; and (C) a boiling point at normal pressure of 180. A composition for forming a film, comprising a solvent having a temperature of not less than ° C. 2. The film-forming composition according to claim 1, further comprising (D) a solvent having a boiling point at normal pressure of 160 ° C. or lower. 3. The use ratio of the component (B) is (A) 1
0.0 parts by weight (equivalent to a complete hydrolysis condensate)
The composition for forming a film according to claim 1, wherein the amount is from 01 to 10 parts by weight. 4. The component (C) is selected from polyhydric alcohols, glycol solvents, glycol monoalkyl ether solvents, glycol dialkyl ether solvents, glycol monoalkyl ether ester solvents, and glycol diester solvents. The composition for forming a film according to claim 1, wherein 5. The composition according to claim 1, wherein the component (C) and the component (D) are used in a proportion of (C) :( D) = 5: 95 to 50:50 (weight ratio, (C) component + (D) component). = 100). The film-forming composition according to claim 1, wherein 6. The film according to claim 1, further comprising at least one compound selected from the group consisting of a β-diketone, a compound having a polyalkylene oxide structure, and a (meth) acrylic polymer. Forming composition. 7. A material for forming an insulating film, comprising the composition for forming a film according to claim 1. Description: