JP2001240802A - Composition for film formation and material for insulating film formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for film formation capable of forming a coating film having uniform thickness, excellent in mechanical strength, clack resistance, resistance to CMP(chemical Mechanical Polishing) and low in dielectric constant as a layer insulation material of a semiconductor element. SOLUTION: This composition for film formation includes (A) a hydrolyzate and/or a condensate of one or more kind of compounds selected from (A-1) R1aSi(OR2)4-a, (e.g. phenyltrimethoxy silane or the like), (A-2) R3bSi(OR4)4-b, (e.g. tetramethoxy silane or the like), (A-3) R5c(R6O)3-cSi-(R9)e-Si(OR7)3-dR8d, (e.g. hexamethoxydisiloxane or the like), and (B) a radical generator and/or a triazene compound having two or more -N=N-NR10R11 groups (e.g. bis(3,3- dimethyl-triazenylphenyl) ether or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition, and more particularly, to a film-forming composition capable of forming a film having an appropriate uniform thickness as an interlayer insulating film material in a semiconductor device or the like. Mechanical strength, crack resistance and CMP (C
chemical Mechanical Polish
ng) The present invention relates to a film-forming composition having excellent resistance and capable of obtaining a coating film having a low relative 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. Further, with the increase in integration of semiconductor elements and the like, an interlayer insulating film having a low relative dielectric constant and mainly containing polyorganosiloxane called organic SOG has been developed. However, with higher integration and multi-layering of semiconductor devices and the like, better electrical insulation between conductors is required. Therefore, interlayer insulating film materials with lower relative permittivity and excellent surface hardness characteristics are required. It is supposed to be.

[0003] Japanese Patent Application Laid-Open No. 6-181201 discloses a coating composition for forming an insulating film having a lower relative 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. WO96 / 00758 also discloses that a thick film coating made of an alkoxysilane, a metal alkoxide other than silane, an organic solvent, and the like, which is used for forming an interlayer insulating film of a multilayer wiring board, is possible, and is resistant to oxygen. A silica-based coating-type insulating film forming material having excellent plasma properties is disclosed. Further, JP-A-3-20377 discloses a coating liquid for forming an oxide film, which is useful for flattening the surface of electronic components and the like, insulating between layers, and the like. 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 the silane compound as described above, the coating film does not have a well-balanced mechanical strength, crack resistance, CMP resistance, low relative dielectric constant, and the like.

[0004]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly, to a low dielectric constant characteristic, a crack resistance, and an interlayer insulating film in a semiconductor device or the like. It is another object of the present invention to provide a material for an interlayer insulating film which is excellent in balance between mechanical strength, CMP resistance and the like. The present _{^{invention, R 1 a Si (OR 2}} ) 4-a ····· (1) (R 1 represents a monovalent organic group containing a phenyl group, R ²
Represents a monovalent organic group, and a represents an integer of 1 to 2. ) (A-2) a compound represented by the following general formula _{^{(2) R 3 b Si (}} OR 4) 4-b ····· (2) (R 3 represents a monovalent alkyl group, R ⁴ Represents a monovalent organic group, b represents an integer of 0 to 2.) and (A-3) a compound represented by the following formula (3): R ⁵ _c (R ⁶ O) _3-c Si— (R ⁹ ) _e -Si (OR ⁷ ) _3-d R ⁸ _d ··· (3) (R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each is monovalent And c and d may be the same or different and each represents a number of 0 to 2, R ⁹ represents an oxygen atom or a group represented by — (CH ₂ ) _m —,
Represents 1 to 6, and e represents 0 or 1. And (B) a radical generator and a triazene compound having two or more groups represented by the following general formula (4), or a hydrolyzate and / or condensate of at least one compound selected from the group consisting of: either one ^{-N = N-NR 10 R 11} ····· (4) (R 10, R 11 are identical or different, a hydrogen atom, a carbon number 1
~ 20 alkyl groups or aryl groups. ), And a material for forming an insulating film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) Component (A-1) In the above formula (1), examples of the monovalent organic group for R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. be able to. 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), examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane,
Phenyltri-iso-propoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltri-n-propoxysilane, benzyltri-is
o-propoxysilane, chlorophenyltrimethoxysilane, chlorophenyltriethoxysilane, chlorophenyltri-n-propoxysilane, chlorophenyltri-iso-propoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n
-Propoxysilane, diphenyldi-iso-propoxysilane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, dibenzyldi-n-propoxysilane, dibenzyldi-iso-propoxysilane, bis (chlorophenyl) dimethoxysilane, bis (chlorophenyl) diethoxy Silane, bis (chlorophenyl) di-n-propoxysilane, bis (chlorophenyl) di-
iso-propoxysilane, and the like,
Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-iso-propoxysilane Is particularly preferred. These may be used alone or in combination of two or more.

(A-2) Component In the general formula (2), examples of the monovalent organic group represented by R ³ and R ⁴ include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Further, in the general formula (2), R ³ 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 (2), 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 (2) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri- sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, 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. Of these, preferred are 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, triethylmonomethoxysilane,
Triethyl monoethoxy silane, triphenyl monomethoxy silane, triphenyl mono ethoxy silane are mentioned, and particularly preferred examples are tetramethoxy silane, tetra ethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane Silane can be mentioned. These may be used alone or in combination of two or more.

(A-3) Component In the above general formula (3), 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 ⁹ in the general formula (3) include a methylene group and an alkylene group having 2 to 6 carbon atoms. In the general formula (3), examples of the compound in which R ⁹ is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldimethyldisiloxane. 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. In the general formula (3), examples of the compound in which e is 0 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 ⁹ in the general formula (3) is-(CH ₂ ) _m-
Examples of the compound having 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-
Using the component (2) and / or the component (A-3), the component (A-
Each of the component 1), the component (A-2) and the component (A-3) may be used in combination of two or more.

(B) Component The radical generator used in the present invention is not particularly limited, and examples thereof include a so-called radical polymerization initiator and a peroxide used for peroxide crosslinking.
Specifically, isobutyryl peroxide, α, α'bis (neodecanylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, 1, 1,3,3-tetramethylbutyl peroxy neodecanoate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2-ethoxy Ethyl peroxy dicarbonate, di (2-ethylhexyl peroxy) dicarbonate, t-hexyl peroxy neodecanoate, dimethoxybutyl peroxy dicarbonate, di (3-methyl-
3-methoxybutylperoxy) dicarbonate, t-
Butyl peroxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 3,5
5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5- Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-
Cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluoyl and benzoyl peroxide, benzoylper Oxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-
Methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane,
1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,3
5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4
4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy- 3,3,5-trimethylhexanoate, t
-Butyl peroxylaurate, 2,5-dimethyl-
2,5-di (m-toluoylperoxy) hexane, t
-Butyl peroxyisopropyl monocarbonate, t
-Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t- Butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′bis (t-butyl Peroxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthanehydro Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 Diisopropylbenzene hydroperoxide, t- butyl trimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t
-Hexyl hydroperoxide, t-butyl hydroperoxide and the like.

In the triazene compound having two or more groups represented by the following general formula (4) used in the present invention, -N = N-NR ¹⁰ R ¹¹ ... (4) (R ¹⁰ , R ¹¹ Are the same or different, and represent a hydrogen atom,
~ 20 alkyl groups or aryl groups. Here, as the alkyl group having 1 to 20 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-
Butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group,
and n-dodecyl group. Examples of the aryl group include a phenyl group.

Specific examples of the compound represented by the above formula (4) include, for example, 1,2-bis (3,3-dimethyltriazenyl) benzene and 1,3-bis (3,3-dimethyltriazene). B) benzene, 1,4-bis (3,3-dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis (3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3-
Dimethyltriazenylphenyl) sulfide, 2,2-
Bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3,3-dimethyltriazene) Ruphenoxy) phenyl] propane, 1,
3,5-tris (3,3-dimethyltriazenyl) benzene, 2,7-bis (3,3-dimethyltriazenyl)
-9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-methyl-4
-(3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl)
-9,9-bis [3-phenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3
-Propenyl-4- (3,3-dimethyltriazenyl)
Phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro-4-
(3,3-Dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl)-
9,9-bis [3,5-difluoro-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene;

The ratio of the component (B) to the component (A) is 0.1 to 20 parts by weight of the component (B) in terms of 100 parts by weight of the component (A) (in terms of a complete hydrolysis condensate). Component (B) is 0.1 to 10 parts by weight. When the content of the component (B) is less than 0.1 part by weight, the crack resistance of the coating film becomes poor, and when it exceeds 20 parts by weight, the coating property of the coating film may be poor. These may be used alone or in combination of two or more.

In the present invention, the term “hydrolysis” refers to the R ² O—, R ⁴ O—, R ⁶ O—
It is not necessary that all of the groups and R ⁷ O— groups be hydrolyzed, for example, only one is hydrolyzed,
One or more of them are hydrolyzed or a mixture thereof is formed. The weight average molecular weight of the hydrolyzed condensate is usually 1,000 to 12,000.
0, preferably about 1,200 to 100,000.

In the present invention, when the component (A) is hydrolyzed, it is preferable to use a catalyst, such as a metal chelate compound represented by the general formula (4), an acidic catalyst or a basic catalyst. Can be mentioned. Examples of metal chelate compounds include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, tri-n
-Butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate)
Titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetate) Natto) titanium, di-n-butoxybis (acetylacetonato) titanium, di-sec-butoxy.
Bis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n
-Propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxytris (acetylacetonato) 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) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl) Acetoace Over G) titanium, diethoxy-bis (ethylacetoacetate) titanium, di -n- propoxy bis (ethylacetoacetate) titanium, di -i-
Propoxy bis (ethyl acetoacetate) titanium,
Di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetoacetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) ) 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 (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, Titanium chelate compounds such as mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxymono (Acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri-i-propoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono ( Acetylacetonate) zirconium, tri -sec- butoxy mono (acetylacetonate) zirconium, tri -t- butoxy mono (acetylacetonate) zirconium, diethoxy ·
Bis (acetylacetonate) zirconium, di-n-
Propoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di-n-butoxybis (acetylacetonate) zirconium, di-sec-butoxy.
Bis (acetylacetonate) zirconium, di-t-
Butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonato) zirconium, mono-i-propoxy.
Tris (acetylacetonate) zirconium, mono-
n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy. Mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) 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 the acidic catalyst include organic acids and inorganic acids. As the organic acid, for example, acetic acid,
Propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, melitic acid, arachidonic acid , Shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid Acetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like can be mentioned. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

The basic catalyst includes an organic base and an inorganic base. As the organic base, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, monobutylamine,
Dibutylamine, tributylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, etc. Can be. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Among these catalysts, metal chelate compounds,
Organic acids, inorganic acids, and organic bases are preferred, and more preferred are titanium chelate compounds, aluminum chelate compounds, organic acids, and organic bases. These may be used alone or in combination of two or more. The amount of the catalyst used is 100 parts (in terms of a complete hydrolysis condensate) of the component (A).
It is usually in the range of 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight, based on 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.

The film-forming composition of the present invention is obtained by dissolving or dispersing either the hydrolyzate or the condensate obtained by reacting the component (A) with a catalyst in the presence of water or the component (B) in an organic solvent. Do it. As the organic solvent used in the present invention, for example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,
Aliphatic hydrocarbon solvents such as 2,4-trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene,
Aromatic hydrocarbon solvents such as ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, and trimethylbenzene Methanol, ethanol, n-propanol, i
-Propanol, n-butanol, i-butanol, s
ec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec
-Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol,
sec-hexanol, 2-ethylbutanol, sec
-Heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol,
n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, Monoalcohol solvents such as 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol
2,4,2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2-
Polyhydric alcohol solvents such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; 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- Butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomer Ether solvents such as diether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate; Acetic acid i-
Propyl, n-butyl acetate, i-butyl acetate, acetic acid se
c-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, propylene glycol monoethyl acetate Ether, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropyl acetate Glycol monomethyl ether acetate, dipropylene glycol monoethyl ether,
Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactic acid n Ester solvents such as amyl, diethyl malonate, dimethyl phthalate and diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Nitrogen-containing solvents such as dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone; Can be listed That. Among these, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether can be mentioned, and particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl Ethers and propylene glycol monopropyl ether are particularly preferred. These organic solvents can be used alone or in combination of two or more.

The film-forming composition of the present invention can be produced as follows. Specifically, water is intermittently or continuously added to an organic solvent in which the component (A) is dissolved. At this time, the catalyst may be added in advance to the organic solvent, or may be dissolved or dispersed in water at the time of adding water. The reaction temperature at this time is usually 0 to 1
00 ° C, preferably 15 to 80 ° C.

In constituting the film-forming composition, the content of the alcohol having a boiling point of 100 ° C. or less in the composition is preferably 20% by weight or less, particularly preferably 5% by weight or less. Alcohols having a boiling point of 100 ° C. or less can be obtained from the above (A-
It may occur during hydrolysis and / or condensation of component (1), component (A-2) and / or component (A-3). It is preferable to remove by distillation or the like.

The film-forming composition obtained by the present invention further comprises β-diketone, an organic polymer at 250 to 450 ° C.,
Surfactant, colloidal silica, colloidal alumina,
Components such as a silane coupling agent may be added. β
-As the diketone, 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).

As the compound having a boiling point or decomposition temperature at 250 to 450 ° C., an organic polymer can be mentioned. Examples of the organic polymer include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylate polymer, an aromatic vinyl compound, a dendrimer, a polyimide,
Examples thereof include polyamic acid, polyarylene, polyamide, polyquinoxaline, polyoxadiazole, and fluoropolymer. Examples of the compound having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, a polybutylene oxide structure, and the like. In particular,
Polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyoxypropylene block copolymer, Ether type compounds such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate and other ether ester type compounds, Polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester Fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures. - a (A) o- (B) p- (A) q- ( wherein, A is a group represented by -CH ₂ CH ₂ O-, the B - (A) o- (B ) p- -
A group represented by CH ₂ CH (CH ₃ ) O—;
90, p represents a number of 10 to 99, and q represents a number of 0 to 90. Among them, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene Ether-type compounds such as glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitol fatty acid ester can be mentioned as more preferable examples. These may be used alone or in combination of two or more.

The (meth) acrylic polymer is a (meth) acrylic polymer having at least one selected from the group consisting of a polyoxyethyl group, a polyoxypropyl group, an amide group, a hydroxyl group and a carboxyl group. No. The (meth) acrylic polymer includes acrylic acid, methacrylic acid, an acrylic acid derivative having the above functional group, a methacrylic acid derivative having the above functional group, an acrylate ester having no above functional group, and having the above functional group. Methacrylic acid ester. Specific examples of the acrylic acid derivative having the above functional group include 2-hydroxyethyl acrylate, diethylene glycol acrylate, polyethylene glycol acrylate, methoxy diethylene glycol acrylate, methoxy polyethylene glycol acrylate, ethoxy diethylene glycol acrylate, ethoxy polyethylene glycol acrylate, and 2-hydroxypropyl acrylate. ,
Dipropylene glycol acrylate, polypropylene glycol acrylate, methoxy dipropylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxydipropylene glycol acrylate, ethoxy polypropylene glycol acrylate, 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, N-vinylpyrrolidone, vinyl Monoacrylates such as pyridine, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide and glycidyl acrylate; and diacrylates such as diethylene glycol diacrylate and polyethylene glycol diacrylate. These may be used alone or in combination of two or more.

Specific examples of the methacrylic acid derivative having the above functional group include 2-hydroxyethyl methacrylate, diethylene glycol methacrylate, polyethylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, Hydroxypropyl methacrylate, dipropylene glycol methacrylate, polypropylene glycol methacrylate, methoxy dipropylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxy dipropylene glycol methacrylate, ethoxy polypropylene glycol methacrylate, 2-di Monomethacrylates such as tylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, methacrylamide, N-methyl methacrylamide, N, N-dimethyl methacrylamide, N-methylol methacrylamide, glycidyl methacrylate; diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate And dimethacrylates such as dipropylene glycol dimethacrylate and polypropylene glycol dimethacrylate. These may be used alone or in combination of two or more.

Specific examples of the acrylate having no functional group include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, and the like. ter
-Butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxypropyl acrylate, 2-ethoxypropyl acrylate, benzyl acrylate, phenylcarbitol acrylate, nonylphenyl acrylate, nonylphenylcarbitol acrylate, dicyclopentenyloxyethyl acrylate, tetrahydrofurfuryl acrylate, isovol Nil access relay Monoacrylate such as, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, neopentyl glycol diacrylate,
1,6-hexane glycol diacrylate, 2,2-
Diacrylates such as bis (4-acryloxypropoxyoxyphenyl) propane and 2,2-bis (4-acryloxydiethoxyphenyl) propane; trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and the like Triacrylates; and tetraacrylates such as pentaerythritol tetraacrylate. These may be used alone or in combination of two or more.

Specific examples of the methacrylic acid ester having no functional group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-
Propyl methacrylate, n-butyl methacrylate,
iso-butyl methacrylate, sec-butyl methacrylate, ter-butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-methoxypropyl methacrylate, 2-ethoxypropyl methacrylate, benzyl methacrylate, phenyl carbitol methacrylate, nonylphenyl methacrylate, nonylphenyl carbitol methacrylate DOO, dicyclopentenyl oxyethyl methacrylate, tetrahydrofurfuryl methacrylate, monomethacrylate such as isobornyl methacrylate, ethylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,4
-Dimethacrylates such as butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, 2,2-bis (4-methacryloxydiethoxyphenyl) propane; trimethylolethanetriethacrylate, trimethylol And trimethacrylates such as methylolpropane trimethacrylate. These may be used alone or in combination of two or more.

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

Examples of the silicone-based surfactant include SH7PA, SH21PA, SH30PA, and ST94P.
A (All are Dow Corning Toray Silicone Co., Ltd.)
And the like can be used. Among them, the above S
The following general formula (5) corresponding to H28PA, SH30PA
The polymer represented by is particularly preferable.

[0030]

Embedded image (In the formula (5), R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, z is an integer of 1 to 20, and x and y are each independently an integer of 2 to 100.)

The composition of the present invention may further contain colloidal silica or colloidal alumina. The 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 nm, preferably 10 to 20 n.
m, and a solid concentration of about 10 to 40% 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 and 100 manufactured by Nissan Chemical Industries, Ltd.
No. 200; alumina clear sol, alumina sol 10, and 132, available from Kawaken Fine Chemicals Co., Ltd.

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

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. When applying the composition of the present invention to a substrate such as a silicon wafer, SiO ₂ wafer, or 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 the coating film, relative dielectric constant, and low hygroscopicity of the coating film.
Interlayer insulating films for semiconductor devices such as RAM, SDRAM, RDRAM, D-RDRAM, etc., etching stoppers for interlayer insulating films, protective films such as surface coat films for semiconductor devices, interlayer insulating films for multilayer wiring boards, protection for liquid crystal display devices It is useful for applications such as films and insulation prevention films.

[0036]

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 was applied on a silicon wafer having a relative dielectric constant of 8 inches by a spin coating method, and the substrate was dried on a hot plate at 80 ° C. for 1 minute and at 200 ° C. for 1 minute. The substrate was baked on a hot plate in a nitrogen atmosphere for 25 minutes. Aluminum was vapor-deposited on the obtained substrate to produce a substrate for relative dielectric constant evaluation. Relative permittivity is measured using an HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd.
Using a P4284A precision LCR meter, 10
It was calculated from the capacitance value at kHz.

The crack-resistant 8-inch silicon on the wafer is coated with a composition sample by spin coating, 1 minute at 80 ° C. on a hot plate, and dried for 1 minute substrate at 200 ° C., further 425 ° C. in a nitrogen The substrate was baked for 25 minutes on a hot plate in an atmosphere. At this time, the final coating film thickness was 1.7 μm.
The obtained substrate with a coating film was immersed in warm water at 60 ° C. for 30 minutes, and the appearance of the coating film was observed with a 350,000 lux surface observation lamp, and evaluated according to the following criteria. ；: No crack is observed on the coating film surface. C: Cracks are observed on the coating film surface.

[0040] On the elastic modulus 8-inch silicon wafer coating, and applying the composition sample by spin coating, 1 minute at 80 ° C. on a hot plate, and dried for 1 minute substrate at 200 ° C., further 425 The substrate was baked on a hot plate in a nitrogen atmosphere at 25 ° C. for 25 minutes. The elastic modulus of this substrate was measured by a continuous rigid body measurement method using a nanoindenter XP (manufactured by Nano Instruments).

A sample of the composition was coated on an 8-inch silicon wafer by CMP using a spin coating method, and the substrate was dried on a hot plate at 80 ° C. for 1 minute and at 200 ° C. for 1 minute. The substrate was baked on a hot plate in a nitrogen atmosphere at 25 ° C. for 25 minutes. The obtained coating film was polished under the following conditions. Slurry: silica-hydrogen peroxide polishing pressure: 300 g / cm ² polishing time: 60 seconds The appearance of the coating film after CMP was observed with a 350,000 lux surface observation lamp and evaluated according to the following criteria. ：: No change ×: Scratch or peeling is confirmed in the coating film

Synthesis Example 1 In a quartz separable flask, 231.13 g of methyltrimethoxysilane and phenyltrimethoxysilane 4
After dissolving 3.70 g and 1.44 g of tetrakis (acetylacetonato) titanium in 224 g of propylene glycol monopropyl ether, the solution was stirred with a three-one motor to stabilize the solution temperature at 60 ° C. Next, a mixed solution of 207.28 g of ion-exchanged water and 207 g of propylene glycol monopropyl ether was added to the solution over 1 hour. Thereafter, the mixture was reacted at 60 ° C. for 4 hours, and 50.00 g of acetylacetone was added thereto.
After reacting for 0 minutes, the reaction solution was cooled to room temperature. 368 g of propylene glycol monopropyl ether was added to this solution.
Was added, and 368 g of a solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 6,500.

Synthesis Example 2 In a quartz separable flask, 241.11 g of methyltrimethoxysilane and 100.3 g of tetramethoxysilane
After dissolving 3 g and 60.78 g of phenyltrimethoxysilane in 356 g of propylene glycol monoethyl ether, the mixture was stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, maleic anhydride 2.00
239.65 g of ion-exchanged water in which g was dissolved was added to the solution over 1 hour. Then, after reacting at 55 ° C. for 4 hours, the reaction solution was cooled to room temperature. To this solution was added 443 g of propylene glycol monoethyl ether,
At 50 ° C., a solution containing methanol and water was separated from the reaction solution by 443.
g The mixture was removed by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained is 1,2.
It was 40.

Comparative Synthesis Example In a quartz separable flask, 200.92 g of methyltrimethoxysilane and 250.8
3 g of propylene glycol monoethyl ether 24
After dissolving in 9 g, the mixture was stirred with a three-one motor, and the solution temperature was stabilized at 55 ° C. Next, 297.77 of ion-exchanged water in which 2.00 g of maleic anhydride was dissolved.
g was added to the solution over 1 hour. Then, at 55 ° C, 4
After reacting for an hour, the reaction solution was cooled to room temperature. To this solution was added propylene glycol monoethyl ether 551.
g was added thereto, and a solution containing methanol and water was removed from the reaction solution at 50 ° C. by 551 g of evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 2,640.

Example 1 1 g of isobutyryl peroxide was added to 100 g of the reaction solution obtained in Synthesis Example 1, and the mixture 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. When the relative permittivity of the obtained coating film was evaluated, it was a low value of 2.69. When the crack resistance of the coating film was evaluated, no crack was observed on the surface.
When the elastic modulus of the coating film was evaluated, it was a high value of 5.2 GPa. In addition, when the CMP resistance of the coating film was evaluated, no scratch was observed on the surface.

Examples 2 to 5 Evaluations were made in the same manner as in Example 1 with the compositions shown in Table 1.
Table 1 shows the evaluation results.

[0047]

[Table 1]

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 relative permittivity of the obtained coating film was evaluated, it was a low value of 2.67,
Coating cracks occurred after immersion in warm water.

Comparative Example 2 Evaluation was carried out in the same manner as in Example 1 except that isoptyl peroxide was added to 100 g of the reaction solution obtained in Comparative Synthesis Example. When the relative permittivity of the obtained coating film was evaluated, it was a high value of 3.02. In addition, cracks in the coating film occurred after immersion in warm water.

[0050]

According to the present invention, a hydrolyzate and / or a condensate of an alkoxysilane containing a phenyl group is combined with a radical generator and / or two
By using a solution containing a compound having three or more triazene groups, low dielectric constant, crack resistance, elastic modulus, C
It is possible to provide a film-forming composition (material for an interlayer insulating film) excellent in balance such as MP resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/04 C08L 83/04 H01L 21/312 H01L 21/312 C 21/316 21/316 G (72) Inventor Kinji Yamada 2-11 Tsukiji 2-chome, Chuo-ku, Tokyo F-term in JSR Co., Ltd. DJ022 DL031 JA34 JA66 JB16 JC38 KA03 KA04 KA09 NA21 5F058 AA02 AC03 AD05 AD07 AF04 AH02

Claims (5)

[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 phenyl group R ² represents a monovalent organic group contained therein;
Represents a monovalent organic group, and a represents an integer of 1 to 2. ) (A-2) a compound represented by the following general formula _{^{(2) R 3 b Si (}} OR 4) 4-b ····· (2) (R 3 represents a monovalent alkyl group, R ⁴ Represents a monovalent organic group, b represents an integer of 0 to 2.) and (A-3) a compound represented by the following formula (3): R ⁵ _c (R ⁶ O) _3-c Si— (R ⁹ ) _e -Si (OR ⁷ ) _3-d R ⁸ _d ··· (3) (R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each is monovalent And c and d may be the same or different and each represents a number of 0 to 2, R ⁹ represents an oxygen atom or a group represented by — (CH ₂ ) _m —,
Represents 1 to 6, and e represents 0 or 1. And (B) a radical generator and a triazene compound having two or more groups represented by the following general formula (4), or a hydrolyzate and / or condensate of at least one compound selected from the group consisting of: either one ^{-N = N-NR 10 R 11} ····· (4) (R 10, R 11 are identical or different, a hydrogen atom, a carbon number 1
~ 20 alkyl groups or aryl groups. ). A film-forming composition comprising: 2. The film forming method according to claim 1, further comprising at least one selected from the group consisting of β-diketone, a compound having a boiling point or decomposition temperature at 250 to 450 ° C., and a surfactant. Composition. The component (A) is a metal chelate compound represented by the following general formula (5): R ¹² _f M (OR ¹³ ) _gf (5) (R ¹² is a chelating agent , M is a metal atom, and R ¹³ has 2 to 2 carbon atoms.
5 represents an alkyl group or an aryl group having 6 to 20 carbon atoms, g represents the valence of the metal M, and f represents an integer of 0 to g. The film forming composition according to claim 1, wherein the composition is hydrolyzed in the presence of at least one member selected from the group consisting of an acidic catalyst and a basic catalyst. 4. The use ratio of the component (B) to the component (A) is 0.1 to 20 parts by weight of the component (B) in 100 parts by weight of the component (A) (in terms of a completely hydrolyzed condensate). The composition for forming a film according to claim 1, wherein: 5. An insulating film forming material comprising the film forming composition according to claim 1.