JP2001040283A - Production of composition for forming film, composition for forming film and material for forming insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful as an interlayer dielectric in a semiconductor element, etc., having a low dielectric constant and mechanical strength of coating film and long-term preservability of solution by hydrolyzing a specific compound and a specified metal chelate compound in the presence of an acid catalyst in a fixed solvent. SOLUTION: (A) One or more compounds selected from the group consisting of (i) a compound of formula I (R1 is H, F or a monofunctional organic group; R2 is a monofunctional organic group; (a) is 0-2) such as trimethoxysilane, etc., and (ii) a compound of formula II [R3 to R6 are each a monofunctional organic group; b and c are each 0-2; R7 is O, (CH2)n (n is 1-6); d is 0 or 1] such as hexamethoxydisiloxane, etc., and (B) a chelate compound of formula III (R8 is a chelating agent; M is metal atom; R9 is a 2-5C alkyl or a 6-20C aryl; f is a valence of M; e is an integer of 1-f) such as triethoxy.mono(acetylacetonato) titanium, etc., are hydrolyzed in the presence of an acid catalyst in a solvent of formula IV (R10 and R11 are each H or a 1-4C alkyl; R12 is an alkylene; g is 1 or 2) to give the objective composition for forming a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a film-forming composition, and more particularly, as a material for an interlayer insulating film in a semiconductor device or the like, such as a low dielectric constant or mechanical strength of a coating film and long-term storage stability of a solution. The present invention relates to a film-forming composition having excellent properties.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO2) film formed by a vacuum process such as a CVD method has been frequently used as an interlayer insulating film in a semiconductor element 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, excellent CMP resistance, and excellent storage stability.

[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, a film having a well-balanced low dielectric constant and mechanical strength of a coating film and long-term storage stability of a solution. is not.

[0007]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly, to a film having a low dielectric constant or mechanical properties as an interlayer insulating film in a semiconductor device or the like. It is an object of the present invention to provide a material for an interlayer insulating film having excellent strength and long-term storage stability of a solution.

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 represent a number of 0 to 2, and R ⁷ represents an oxygen atom or-( CH ₂ ) _n- , d is 0 or 1
And n represents a number of 1 to 6. )) (At least one compound selected from the group consisting of
(B) a metal chelate compound represented by the following general formula (3) R ⁸ _e M (OR ⁹ ) _fe (3) (R ⁸ is a chelating agent, M is a metal atom, and R ⁹ is 2-5 carbon atoms
Represents an alkyl group or an aryl group having 6 to 20 carbon atoms, f represents the valence of the metal M, and e represents an integer of 1 to f. )
And (C) a method for producing a film-forming composition, which is hydrolyzed in the presence of an acid catalyst, and a film-forming composition and an insulating film-forming material produced by the method. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

[0010](A) component  In the above general formula (1), R¹And R^TwoMonovalent organic
Examples of the group include an alkyl group, an aryl group, an allyl group,
Sidyl groups and the like can be mentioned. Also, the general formula
In (1), R¹Is a monovalent organic group, especially an alkyl group
Alternatively, it is preferably a phenyl group. Where al
As a kill group, a methyl group, an ethyl group, a propyl group,
And a butyl group.
These alkyl groups may be chain-like or branched.
And the hydrogen atom is replaced by a fluorine atom, etc.
Is also good. In the general formula (1), as the aryl group,
Phenyl, naphthyl, methylphenyl, ethyl
Phenyl, chlorophenyl, bromophenyl, full
Orophenyl groups and the like can be mentioned.

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.

In the general formula (2), examples of the monovalent organic group include the same organic groups as those in the general formula (1). In the general formula (2), examples of the compound in which R ⁷ is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane,
1,1,1,3,3-pentamethoxy-3-methyldisiloxane, 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-
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 compounds of the formula are bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (hexaphenoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, and bis (dimethoxyphenyl) (Silyl) 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 (ethoxy-butyldiphenylsilyl) propane and the like. 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,
Each of the components (A) may be used in combination of two or more.

In the present invention, the component (A) is hydrolyzed in the presence of a compound represented by the following general formula (4). R ¹⁰ O (CHCH ₃ CH ₂ O) _g R ¹¹ ... (4) (R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—. Represents a selected monovalent organic group, and g represents an integer of 1 or 2.) Examples of the compound represented by the general formula (4) include propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl. Ether, propylene glycol monobutyl ether,
Propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether , Dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyrate Ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol diacetate, propylene glycol and the like. In particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate are preferable. These can be used alone or in combination of two or more.

When the component (A) is hydrolyzed and condensed,
R ² O-which the component (A) has, R ⁴ O-and R ⁵ O-per 1 mole of the group represented by, it is preferable to use 0.25 to 3 moles of water, 0.3 to 2.5 It is particularly preferred to add molar water. When the amount of water to be added falls within the range of 0.25 to 3 mol, there is no possibility that the uniformity of the coating film is reduced, and the storage stability of the film-forming composition is less likely to be reduced. That's why. Further, the water is preferably added intermittently or continuously.

In the present invention, the component (A) is hydrolyzed,
At the time of condensation, a metal chelate compound (B) represented by the general formula (3) and an acid catalyst (D) are used.

Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, -N-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy.
Bis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-
Propoxy bis (acetylacetonate) titanium, di-n-butoxybis (acetylacetonate) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonate) Titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy.
Tris (acetylacetonate) titanium, mono-n-butoxytris (acetylacetonate) titanium, mono-sec-butoxytris (acetylacetonate)
Titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate)
Titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) Acetate) titanium, tri-s
ec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t
-Butoxy bis (ethyl acetoacetate) titanium,
Monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) ) Titanium, mono-sec
-Butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxytris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate)
Titanium chelating compounds such as titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxy・ Mono (acetylacetonate) zirconium, tri-
n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonate) Nart) zirconium,
Tri-t-butoxy mono (acetylacetonate) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxy.
Bis (acetylacetonate) zirconium, di-n-
Butoxy bis (acetylacetonate) zirconium, di-sec-butoxy bis (acetylacetonate) zirconium, di-t-butoxybis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono -N-propoxy tris (acetylacetonate) zirconium, mono-i-propoxy tris (acetylacetonate) zirconium, mono-n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetyl) (Acetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium Tri -n- propoxy mono (ethylacetoacetate) zirconium, tri -i
-Propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-
Butoxy mono (ethylacetoacetate) zirconium, diethoxybis (ethylacetoacetate) zirconium, di-n-propoxybis (ethylacetoacetate) zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di- n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium , Mono-n
-Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-
sec-butoxy tris (ethyl acetoacetate)
Zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium; aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; and titanium. A particularly preferred example is a metal chelate compound containing

Examples of the acid catalyst include organic acids and inorganic acids. Examples of the organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, and decane acid. 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, benzene Examples thereof include sulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. Among these, organic acids can be mentioned as preferred examples, acetic acid, propionic acid, oxalic acid, maleic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid,
Tartaric acid is particularly preferred.

The total amount of the metal chelate compound and the acid catalyst used is usually 0.001 to 10 parts by weight, preferably 100 to 10 parts by weight, based on 100 parts by weight of the total amount of the component (A) (in terms of complete hydrolysis condensate). Ranges from 0.01 to 10 parts by weight.
Further, the metal chelate compound and the acid catalyst may be previously added to the solvent, or may be dissolved or dispersed in water at the time of adding water. In the present invention, the term “hydrolysis” refers to the R ² O— group, R ⁴ O—
It is not necessary that all of the groups and R ⁵ O— groups be hydrolyzed, for example, only one is hydrolyzed,
One or more of them are hydrolyzed or a mixture thereof is formed. In the production method of the present invention, the component (A) may be condensed after hydrolysis.
In the present invention, condensation refers to condensation of a silanol group of a hydrolyzate of the component (A) to form a Si-O-Si bond. However, in the present invention, it is not necessary that all 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 the present invention,
The temperature for hydrolyzing the component (A) is usually from 0 to 100.
° C, preferably 15 to 80 ° C.

The film-forming composition of the present invention is a composition obtained by the above-mentioned production method, and the content of alcohol having a boiling point of 100 ° C. or less in the composition is 20% by weight or less, particularly 5% by weight or less. Preferably, there is. The alcohol having a boiling point of 100 ° C. or lower may be generated during hydrolysis and / or condensation of the component (A), and the content thereof is 20% by weight.
Hereafter, it is preferable to remove by distillation or the like so as to be preferably 5% by weight or less.

The film-forming composition of the present invention may further contain the following organic solvents. As the organic solvent used in the present invention, for example, n-pentane, i-pentane,
aliphatic hydrocarbon solvents such as n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane; benzene, toluene, Xylene, ethylbenzene, trimethylbenzene,
Methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene,
aromatic hydrocarbon solvents such as n-amylnaphthalene and trimethylbenzene; 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,
Ketone solvents such as trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-butyl ether; n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide,
Dioxolan, 4-methyldioxolan, dioxane,
Dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-
n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n- Ether solvents such as butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate; γ-butyrolactone, γ-valerola Kuton, n-propyl acetate, i-acetate
-Propyl, n-butyl acetate, i-butyl acetate, s-acetic acid
ec-butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, acetoacetate Methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl acetate, methoxytriglycol acetate,
Ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-oxalate
-Butyl, methyl lactate, ethyl lactate, n-butyl lactate,
Ester solvents such as n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide,
Nitrogen-containing solvents such as N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide;
Examples thereof include sulfur-containing solvents such as sulfolane and 1,3-propane sultone. These can be used alone or in combination of two or more.

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. In the present invention, the completely hydrolyzed condensate refers to a group represented by —OR ² and —OR ³ in the compound (1) and the compound (2) of 100.
% Hydrolyzed to form OH groups, which are completely condensed. If β-diketone is added in such a range,
A certain storage stability can be obtained, and there is little possibility that properties such as uniformity of a coating film of the film-forming composition are deteriorated. 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 surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether, polyoxyethylene n- Polyoxyethylene alkyl phenyl ethers such as nonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.)
Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (Sumitomo 3M Limited)
Asahi Guard, Surflon (above, Asahi Glass Co., Ltd.)
), Disperbyk (manufactured by BYK Japan KK), Solsperse (manufactured by Zeneca Corporation), and the like. These surfactants can be used alone or
More than one species can be used in combination.

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 weight average molecular weight of all the polyorganosiloxane components [the hydrolyzed condensate of the component (A)] in the composition thus obtained is as follows:
Usually 1,000 to 120,000, preferably 1,2
It is about 100 to 100,000.

[0024] The composition of the present invention is applied to 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
-It is useful for applications such as interlayer insulating films for semiconductor devices such as RDRAMs, protective films such as surface coat films for semiconductor devices, interlayer insulating films for multilayer wiring boards, protective films for liquid crystal display devices, and insulating films.

[0027]

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 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 composition sample is applied on a silicon wafer having a dielectric constant of 8 inches by a spin coating method, and is coated on a hot plate at 100 ° C. for 4 hours.
For 4 minutes at 250 ° C.
The substrate was baked in a vacuum oven for 120 minutes. Aluminum was vapor-deposited on the obtained substrate to produce a substrate for permittivity evaluation. Dielectric constants were measured using an HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd. and an HP4284A.
Calculated from the capacitance value at 10 kHz using a precision LCR meter

[0030] mechanical strength 8-inch silicon on the wafer is coated with a composition sample by spin coating, at 100 ° C. on a hot plate 4
For 4 minutes at 250 ° C.
The substrate was baked in a vacuum oven for 120 minutes. The obtained film was measured by a continuous stiffness measuring method using a nanoindenter XP (manufactured by Nano Instruments) to measure the elastic modulus.

Long-term storage stability The film-forming composition stored at 25 ° C. for 3 months was applied on an 8-inch silicon wafer using a spin coater under the conditions of a rotation speed of 2,000 rpm and 17 seconds. Then, using a hot plate maintained at a temperature of 85 ° C,
The silicon wafer coated with the film-forming composition was heated for 4 minutes to disperse the organic solvent. Next, using a hot plate maintained at a temperature of 200 ° C., the silicon wafer coated with the film-forming composition was heated for 4 minutes to form a coating film on the silicon wafer. The film thickness of the coating film thus obtained is measured using an optical film thickness meter (Rudolph Techno).
Spectra Laser20 manufactured by logies
Using 0), 50 points were measured in the coating film surface. The thickness of the obtained film thickness was measured, and the film thickness increase rate determined by the following equation was used to calculate the film thickness.
The storage stability was evaluated. Film thickness increase rate (%) = ((film thickness after storage) − (film thickness before storage)) ÷ (film thickness before storage) × 100 〇: film thickness change rate ≦ 10% △: 10% <film Thickness change rate ≦ 20% ×: 20% <Thickness change rate

Synthesis Example 1 In a quartz separable flask, 154.1 g of methyltrimethoxysilane, 48.1 g of tetramethoxysilane, 0.96 g of diisopropoxytitanium bisethylacetyl acetate and 1 g of maleic acid were added to 200 g of propylene glycol monomethyl ether. After the dissolution, the solution was stirred with a three-one motor to stabilize the solution temperature at 65 ° C. Next, 92 g of ion-exchanged water was added to the solution over 2 hours. Then, after reacting at 65 ° C. for 4 hours, the reaction solution was cooled to room temperature. 299 g of propylene glycol monomethyl ether was added to this reaction solution, and at 50 ° C., 299 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 in the reaction solution thus obtained is 7,600.
Met.

Synthesis Example 2 In a quartz separable flask, 154.1 g of methyltrimethoxysilane, 48.1 g of tetramethoxysilane, 0.96 g of diisopropoxytitanium bisethylacetyl acetate and 1 g of oxalic acid were mixed with 200 g of propylene glycol monopropyl ether. , And stirred with a three-one motor to stabilize the solution temperature at 65 ° C. Next, 92 g of ion-exchanged water was added to the solution over 2 hours. Then, after reacting at 65 ° C. for 4 hours, the reaction solution was cooled to room temperature. 299 g of propylene glycol monopropyl ether was added to this reaction solution, and at 50 ° C., 299 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 in the reaction solution thus obtained is 8,90.
It was 0.

Comparative Synthesis Example 1 → Deleted A reaction was performed in the same manner as in Synthesis Example 1 except that maleic acid was not added.
400 reaction liquids were obtained.

Comparative Synthesis Example 2 → Deleted A reaction was performed in the same manner as in Synthesis Example 1 except that diisopropoxytitanium bisethylacetyl acetate was not added, to obtain a reaction solution having a weight average molecular weight of 3,100. Was.

Example 1 The reaction solution obtained in Synthesis Example 1 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 dielectric constant of the obtained coating film was as low as 2.59, and the elastic modulus of the coating film was 7.8 MPa, which was excellent in mechanical strength. When the storage stability of the solution was evaluated, the film growth rate after 3 months was 8.4%, indicating excellent storage stability.

Example 2 Example 1 was repeated except that the reaction solution obtained in Synthesis Example 2 was used.
The evaluation was performed in the same manner as described above. The dielectric constant of the obtained coating film was as low as 2.61, and the elastic modulus of the coating film was 7.5 MPa.
And the mechanical strength was excellent. Further, when the storage stability of the solution was evaluated, the film increase rate after 3 months was 8.7%, showing excellent storage stability.

Example 3 Evaluation was carried out in the same manner as in Example 1 except that a solution obtained by adding 2 g of acetylacetone to 100 g of the reaction solution obtained in Synthesis Example 1 was used. The dielectric constant of the obtained coating film is 2.60.
And the elastic modulus of the coating film was 7.5 MPa, which was excellent in mechanical strength. In addition, when the storage stability of the solution was evaluated, the film increase rate after three months was 4.9%, showing excellent storage stability.

Example 4 Evaluation was performed in the same manner as in Example 1 except that a solution obtained by adding 10 g of polyisopropyl methacrylate having a weight molecular weight of about 4,000 to 100 g of the reaction solution obtained in Synthesis Example 1 was used. The dielectric constant of the obtained coating film was as low as 2.30, and the elastic modulus of the coating film was excellent in mechanical strength instead of a very low dielectric constant of 4.0 MPa. When the storage stability of the solution was evaluated, the rate of film increase after 3 months was 8.
It exhibited excellent storage stability of 7%.

Example 5 Evaluation was performed in the same manner as in Example 1 except that a solution obtained by adding 10 g of polyethylene glycol having a weight molecular weight of about 2,000 to 100 g of the reaction solution obtained in Synthesis Example 2 was used. The obtained coating film had a very low dielectric constant of 2.25, and the elastic modulus of the coating film was 4.1 MPa, which was excellent in mechanical strength instead of a very low dielectric constant. Further, when the storage stability of the solution was evaluated, the film increase rate after 3 months was 8.6%, indicating excellent storage stability.

Comparative Example 1 Evaluation was carried out in the same manner as in Example 1 except that the reaction solution obtained in Comparative Synthesis Example 1 was used. The dielectric constant of the obtained coating film was as low as 2.59, but the elastic modulus of the coating film was 3.2M.
Pa and mechanical strength were inferior.

Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that the reaction solution obtained in Comparative Synthesis Example 1 was used. The elastic modulus of the coating film is 7.6M
Although Pa and mechanical strength were excellent, the dielectric constant of the obtained coating film was a high value of 3.03. When the storage stability of the solution was evaluated, the film increase rate after 3 months was 15.4%, which was inferior to the storage stability.

[0043]

According to the present invention, an alkoxysilane is hydrolyzed in the presence of a metal chelate compound and an acid catalyst to form a film having an excellent balance of dielectric constant, mechanical strength, long-term storage stability and the like. Composition (material for interlayer insulating film)
It is possible to provide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/312 H01L 21/312 C 21/316 21/316 G 21/768 C07F 7/04 Z // C07F 7/04 7/12 G 7/12 7/18 B 7/18 EF H01L 21/90 S (72) Inventor Satoko Hakamuka 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Kinji Yamada 2-11-24 Tsukiji 2-chome, Chuo-ku, Tokyo FSR in JSR Co., Ltd. (reference) 4H049 VN01 VP01 VP02 VQ02 VQ10 VQ16 VQ20 VQ21 VR11 VR21 VR31 VR41 VR42 VR43 VS02 VS10 VS20 VS20 V33 VW02 4J035 BA16 CA162 EA01 EB01 EB02 EB03 EB04 LB01 LB20 4J038 CG142 DL031 DL051 DL061 DL071 DL081 JA26 JA27 JA34 JC38 KA04 KA06 KA09 LA01 NA09 NA17 NA21 NA26 PB09 5F033 RR21 SS21A23A5 06 AA10 AC03 AD05 AF04 AG01 AH02 BA01 BA04 BA09 BA20 BC02 BD04 BF46 BH01 BJ02

Claims (6)

[Claims] (A) (A-1) a compound represented by the following general formula (1): 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, a represents an integer of 0 to 2) and (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 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 — (CH ₂ ) _{Represents n-} , d is 0 or 1
And n represents a number of 1 to 6. ) At least one compound selected from the group consisting of (B)
In metal chelate compound represented _{^{R 8 e M (OR 9)}} fe ····· (3) (R 8 chelating agent, M is a metal atom, R ⁹ is C2-5
Represents an alkyl group or an aryl group having 6 to 20 carbon atoms, f represents the valence of the metal M, and e represents an integer of 1 to f. )
And (C) hydrolyzing in a solvent represented by the following general formula (4) in the presence of an acid catalyst. R ¹⁰ O (R ¹² O) _g R ¹¹ ... (4) (R ¹⁰ and R ¹¹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—. Represents a monovalent organic group, R ¹² represents an alkylene group, and g represents an integer of 1 to 2.) 2. The method for producing a film-forming composition according to claim 1, wherein M in the general formula (3) is at least one selected from titanium, zirconium and aluminum. 3. The method for producing a film-forming composition according to claim 1, wherein the acid catalyst is an organic acid. 4. A film-forming composition obtained by the production method according to claim 1. 5. The film-forming composition according to claim 3, 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. A composition for forming a film, comprising: 6. An insulating film forming material comprising the film forming composition according to claim 5.