JP2001200203A - Film-forming composition and insulating film-forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain film-forming compositions which excel in long-term storage stability of the solutions and, simultaneously, can obtain coating films having low hygroscopicity and a low dielectric constant. SOLUTION: The film-forming compositions contain either a hydrolyzate or a condensate of (A) at least one compound selected from a compound represented by formula (1): R1aSi(OR2)4-a, wherein R1 is H, F or a monovalent organic group; R2 is a monovalent organic group; and a is an integer of 0-2 and a compound represented by formula (2): R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c wherein R3-R6 are each a monovalent organic group; b and c are each 0-2; R7 is an oxygen atom or a group represented by -(CH2)n-; n is 1-6; and d is 0 or 1) with (B) a compound represented by formula (3): HO-(SiR8R9O)eH wherein R8 and R9 are each a monovalent organic group; and e is an integer of 2-100.

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 long-term solution of a solution capable of forming a coating film having an appropriate uniform thickness as a material for an interlayer insulating film in a semiconductor device or the like. The present invention relates to a film-forming composition which is excellent in storage stability and can provide a coating film having a low dielectric constant and a low moisture absorption.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is often used as an interlayer insulating film in a semiconductor device or the like. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating-type insulating film mainly composed of a hydrolysis product of tetraalkoxylan, which is called an SOG (Spin on Glass) film, may be used. It has become. Also, with the high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant and mainly containing polyorganosiloxane called organic SOG has been developed. However, with higher integration and multilayering of semiconductor devices and the like, more excellent electrical insulation between conductors is required, and therefore,
There is a demand for an interlayer insulating film material having a lower dielectric constant and excellent surface hardness characteristics.

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

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

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

However, when a metal chelate compound such as titanium or zirconium is combined with a silane compound as described above, the uniformity of the coating film and the long-term storage stability of the solution are not excellent, and the dielectric constant, hygroscopicity and the like are not balanced. I don't have much.

[0007]

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 an object of the present invention to provide a material for an interlayer insulating film that is excellent in balance of adhesion to a substrate and the like.

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- represents a group represented by the formula: n
Represents 1 to 6, and d represents 0 or 1. And at least one compound selected from the group consisting of: (B) a compound represented by the following general formula (3): HO- (SiR ⁸ R ⁹ O) _e H (3) (R ⁸ and R ⁹ may be the same or different and each represents a monovalent organic group, and e represents an integer of 2 to 100). And a material for forming an insulating film.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

Component (A) Component (A-1) In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Can be. Further, in the general formula (1), R ¹ is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like, preferably having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), as the aryl group,
Examples include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane and tri-silane. sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane,
Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, etc .; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltrimethylsilane -N-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane,
Methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-s
ec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri- sec-butoxysilane, vinyl tri-tert
-Butoxysilane, vinyltriphenoxysilane, n-
Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane,
n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-
sec-butoxysilane, n-propyltri-tert
-Butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri- n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri- n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-te
rt-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-
n-propoxysilane, sec-butyl-tri-iso
-Propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxy Silane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-
n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisilane -Iso-
Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, etc .; dimethyldimethoxysilane , Dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec
-Butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n -Butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-
tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso- Propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-di- Phenoxysilane, di-i
so-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-
Propoxysilane, di-iso-propyl-di-iso
-Propoxysilane, di-iso-propyl-di-n-
Butoxysilane, di-iso-propyl-di-sec-
Butoxysilane, di-iso-propyl-di-tert
-Butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n
-Butyldiethoxysilane, di-n-butyl-di-n-
Propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di- tert-butoxysilane, di-n
-Butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane,
Di-sec-butyl-di-iso-propoxysilane,
Di-sec-butyl-di-n-butoxysilane, di-s
ec-butyl-di-sec-butoxysilane, di-se
c-butyl-di-tert-butoxysilane, di-se
c-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxy Silane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxy Silane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-s
ec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, and the like. 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-2) Component In the above general formula (2), examples of the monovalent organic group include the same organic groups as those in the above general formula (1).
Examples of the divalent organic group represented by R ⁷ in the general formula (2) include a methylene group and an alkylene group having 2 to 6 carbon atoms. In the general formula (2), as the compound in which R ⁷ is an oxygen atom, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldimethyl Siloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,
3,3-pentaethoxy-3-phenyldisiloxane,
1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3
-Dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,
3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triethoxy-1,3,3
3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,
3-triethoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,
3-tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraphenyldisiloxane, 1,3
-Diethoxy-1,1,3,3-tetraphenyldisiloxane and the like. Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-
1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3
Dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3
Preferred examples include 3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane. Compounds in which d is 0 in the general formula (2) include hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,1,2,2-pentamethoxy-2
-Methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2
-Pentaethoxy-2-phenyldisilane, 1,1,
2,2-tetramethoxy-1,2-dimethyldisilane,
1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-
1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,
1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane or the like, wherein R ⁷ in the general formula (2) is-(CH ₂ ) _n-
Examples of the compound 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-
2) Component or any one of them can be used, and two or more of each of the component (A-1) and the component (A-2) can be used.

(B) 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).
Specific examples of the compound represented by the general formula (3) include terminal hydroxypolydimethylsiloxane, terminal hydroxypolydiethylsiloxane, terminal hydroxypolydivinylsiloxane, terminal hydroxypolydiphenylsiloxane,
Examples thereof include a terminal hydroxypolydimethylsiloxane-polydiphenylsiloxane copolymer, and preferred are terminal hydroxypolydimethylsiloxane, terminal hydroxypolydiphenylsiloxane, and terminal hydroxypolydimethylsiloxane-polydiphenylsiloxane copolymer. As for the number of repetitions of the polymer, n in the general formula (3) is 2 to 100, preferably 2 to 50. One or more of these components (C) may be used in the same manner.

In the present invention, the use ratio of the component (B) to the component (A) is from 0.2 to 20 parts by weight of the component (B) in 100 parts by weight of the component (A) (in terms of a complete hydrolysis condensate). . When the use ratio of the component (B) exceeds 20 parts by weight, the heat resistance of the coating film deteriorates.

In the present invention, the term “hydrolysis” refers to R ² O—, R ⁴ O—, and R ² O—
^It is not necessary that all the ⁵ O-groups be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof. In the present invention, condensation refers to condensation of a silanol group of a hydrolyzate of the component (A) and a silanol group of the component (B) to form a Si—O—Si bond. It is not necessary that they are all condensed, and the concept includes the production of a mixture of a small amount of silanol groups and a mixture of those having different degrees of condensation. The weight-average molecular weight of the hydrolysis-condensation product is usually 1,000 to 120,0.
00, preferably about 1,200 to 100,000.

In the present invention, when hydrolyzing the components (A) and (B), it is preferable to use a catalyst, such as a metal chelate compound represented by the general formula (4) or an acidic catalyst. And a basic catalyst. 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 (acetylacetonate) titanium, diethoxy bis (acetylacetonate) Nato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n
-Butoxybis (acetylacetonato) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, Mono-n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris (acetylacetonate) titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-s
ec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy. Mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, Tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di-i-propoxy bis (ethyl acetoacetate) Chita , Di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetoacetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) Acetate) 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 (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris ( Titanium chelate compounds such as acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonato) zirconium, tri-n-propoxymono (acetylacetonato) zirconium, tri-i-propoxymono (acetyl) (Acetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-
Butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxybis (acetylacetonato) zirconium, di- n-butoxy
Bis (acetylacetonate) zirconium, di-se
c-butoxybis (acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium , Mono-i
-Propoxy tris (acetylacetonato) zirconium, mono-n-butoxy tris (acetylacetonato) zirconium, mono-sec-butoxy tris (acetylacetonato) 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 (ethylacetoacetate) zirconium, tri-
n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, Jee
n-propoxybis (ethylacetoacetate) zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetate) Acetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, mono-n-propoxy.
Tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate)
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; tris (acetylacetonate) aluminum, tris (ethylacetoacetate)
Aluminum chelate compounds such as 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 usually 0.1 part by weight based on 100 parts by weight of the total amount of the component (A) (in terms of the complete hydrolysis condensate) and the component (B).
001 to 10 parts by weight, preferably 0.01 to 10 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 a hydrolyzate and / or a condensate obtained by reacting the components (A) and (B) with a catalyst in the presence of water 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,
2,2,4-trimethylpentane, n-octane, i-
Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, diethylbenzene Aromatic hydrocarbon solvents such as i-propyl benzene, n-amylnaphthalene, trimethylbenzene; methanol, ethanol, n-propanol,
i-propanol, n-butanol, i-butanol,
sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec
-Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol,
sec-hexanol, 2-ethylbutanol, sec
-Heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol,
n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-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 components (A) and (B) are 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 100 ° 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 the component (A) and the component (A-2).
It is preferable to remove it by distillation or the like so as to be at most 5% by weight, preferably at most 5% by weight.

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,
You may add components, such as. As β-diketone,
Acetylacetone, 2,4-hexanedione, 2,4-
Heptanedione, 3,5-heptanedion, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4
-Hexanedione, 2,2,6,6-tetramethyl-
One or more kinds such as 3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione. In the present invention, the content of β-diketone in the composition for forming a film is usually from 0.1 to 100 parts by weight based on 100 parts by weight of the total amount of the component (A) (in terms of complete hydrolysis and condensate).
100 parts by weight, preferably in the range of 0.2 to 80 parts by weight. If the β-diketone is added in such a range, a certain storage stability can be obtained, and characteristics such as uniformity of the coating film of the film forming composition are less likely to be deteriorated. 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.

Compounds having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure,
Examples include a polytetramethylene oxide structure and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyether Oxypropylene block copolymers, ether compounds such as polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid alkanolamide sulfates and the like Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures. - 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 is a number from 10 to 99, and q is a number from 0 to 90) Among these, polyoxyethylene alkyl ether,
Polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
And ether-type compounds such as those described above as more preferable examples. These may be used alone or in combination of two or more.

Examples of the (meth) acrylic polymer include 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, methoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate, ethoxydiethylene glycol acrylate, ethoxy polyethylene glycol acrylate, Hydroxypropyl acrylate, dipropylene glycol acrylate, polypropylene glycol acrylate,
Methoxy dipropylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy dipropylene glycol acrylate, ethoxy polypropylene glycol acrylate, 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, N-vinylpyrrolidone, vinylpyridine, acrylamide, N-methylacrylamide, Monoacrylates such as N, N-dimethylacrylamide, N-methylolacrylamide and glycidyl acrylate; 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 acrylic acid ester having no functional group include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, 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 methacrylates having no functional group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate and iso-methacrylate.
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.

[0034]

Embedded image General formula (5) General formula

The composition of the present invention may further contain colloidal silica or colloidal alumina. 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 μm, preferably 10 to 20 m.
μ, the solid content of which is 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.

The total solid content of the film-forming composition of the present invention is preferably 2 to 30% by weight, and is appropriately adjusted according to 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 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, and low hygroscopicity of coating film.
Interlayer insulating films for semiconductor devices such as AM, 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.

[0040]

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 dielectric constant of 8 inches by using a spin coating method.
The substrate is dried at 200 ° C. for 2 minutes, and further dried at 450 ° C.
The substrate was baked for 30 minutes on a hot plate in a nitrogen atmosphere. Aluminum was vapor-deposited on the obtained substrate to produce a substrate for permittivity evaluation. Dielectric constant is measured using an HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd.
10 kHz using a 284A precision LCR meter
It was calculated from the capacitance value at z.

A composition sample was applied on a crack-resistant 8-inch silicon wafer by a spin coating method, and was applied on a hot plate at 100 ° C. for 2 hours.
The substrate is dried at 200 ° C. for 2 minutes, and further dried at 450 ° C.
The substrate was baked for 30 minutes on a hot plate in a nitrogen atmosphere. At this time, the final thickness of the coating film was 1.5 μm.
The obtained substrate with a coating film was immersed in warm water at 60 ° C. for 1 hour, 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.

Adhesion of Coating Film A composition sample was applied on an 8-inch silicon wafer by a spin coating method, and was applied on a hot plate at 100 ° C. for 2 hours.
The substrate is dried at 200 ° C. for 2 minutes, and further dried at 450 ° C.
The substrate was baked for 30 minutes on a hot plate in a nitrogen atmosphere. This substrate was subjected to a heat treatment at 100 ° C. for 2 hours. Ten stud pins were fixed on the obtained substrate using an epoxy resin, and dried at 150 ° C. for 1 hour. This stud pin was subjected to a pull-out test using the Sebastian method, and the adhesion was evaluated according to the following criteria. ：: No peeling occurred at the interface between the silicon wafer and the coating film for all 10 stud pins.

Synthesis Example 1 In a quartz separable flask, 77.04 g of methyltrimethoxysilane and 24.05 of tetramethoxysilane were used.
g, 5.21 g of terminal hydroxypolydimethylsiloxane having a weight average molecular weight of about 700 and 0.48 g of titanium tetrakis (acetylacetonate) were dissolved in 290 g of propylene glycol monopropyl ether, and the mixture was stirred with a three-one motor to reduce the solution temperature. Stabilized at 65 ° C. Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 65 ° C. for 2 hours, 25 g of acetylacetone was added, the reaction was further performed for 30 minutes, and the reaction solution was cooled to room temperature. At 50 ° C., 149 g of a solution containing methanol and water was removed from the reaction solution by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 10,900.

Synthesis Example 2 In a quartz separable flask, 77.04 g of methyltrimethoxysilane and 24.05 g of tetramethoxysilane
After dissolving 5.21 g of terminal hydroxypolydimethylsiloxane having a weight average molecular weight of about 1,400 in 290 g of propylene glycol monomethyl ether, the solution was stirred with a three-one motor to stabilize the solution temperature at 65 ° C. Next, 84 g of ion-exchanged water in which 1.5 g of maleic anhydride was dissolved was added to the solution over 1 hour. afterwards,
After reacting at 65 ° C. for 2 hours, the reaction solution was cooled to room temperature. At 50 ° C., 149 g of a solution containing methanol and water was removed from the reaction solution by evaporation to obtain a reaction solution.
The weight average molecular weight of the condensate and the like thus obtained is
2,200.

Synthesis Example 3 A reaction solution was obtained in the same manner as in Synthesis Example 2 except that the amount of hydroxypolydimethylsiloxane used was changed to 2.22 g. The weight average molecular weight of the condensate and the like thus obtained was 2,100. Synthesis Example 4 In a quartz separable flask, 570 g of ethanol was added.
160 g of ion exchange water and 90% aqueous solution of methylamine 90
g was added, and the liquid temperature was stabilized at 50 ° C. Next, a mixed solution of 14.5 g of methyltrimethoxysilane and 20.0 g of tetraethoxysilane and 1.4 g of terminal hydroxypolydiphenylsiloxane having a weight average molecular weight of about 700 was added to the solution over 1 minute. Then, after reacting at 60 ° C. for 2 hours, the reaction solution was cooled to room temperature. 200 g of propylene glycol monopropyl ether was added to this solution, and methanol, ethanol,
930 g of a solution containing water, methylamine and propylene glycol monopropyl ether was removed by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 134,800.

Comparative Synthesis Example 1 A reaction solution was obtained in the same manner as in Synthesis Example 1, except that the terminal hydroxypolydimethylsiloxane having a weight average molecular weight of about 700 was not added. The weight average molecular weight of the condensate and the like thus obtained is 9,30.
It was 0.

Example 1 NBX-15 was added to 100 g of the reaction solution obtained in Synthesis Example 1.
0.006 g was added, 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,
The value was as low as 2.59. When the crack resistance of the coating film was evaluated, no crack was observed on the surface. When the adhesion of the coating film was evaluated, the stud pin 10
No peeling at the interface between the silicon wafer and the coating film was observed.

Examples 2 to 6 Evaluations were made in the same manner as in Example 1 with the compositions shown in Table 1.
Table 1 shows the evaluation results.

[0051]

[Table 1]

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. When the relative permittivity of the obtained coating film was evaluated, it was as low as 2.63, but cracks were observed on the surface of the coating film. Also,
When the adhesion of the coating film was evaluated, peeling at the interface between the silicon wafer and the coating film was recognized with three stud pins.

[0053]

According to the present invention, by reacting an alkoxysilane with a terminal hydroxypolysiloxane in the presence of a catalyst and water, a film having excellent balance among low dielectric constant, crack resistance and adhesion can be obtained. It is possible to provide a composition (material for an interlayer insulating film).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/06 C09D 183/06 183/08 183/08 183/14 183/14 H01B 3/46 H01B 3 / 46 E H01L 21/312 H01L 21/312 C (72) Inventor Kinji Yamada 2-11-24 Tsukiji 2-chome, Chuo-ku, Tokyo FSR term in JSR Corporation (reference) 4J002 BG042 BG132 CH022 CH052 CP031 CP032 CP191 DD016 DE056 DE086 DF006 DF036 DG036 DH026 EB067 EC076 EE046 EE047 EF036 EF066 EF086 EN026 EN106 EU026 EU046 EU076 EU136 EV287 EW047 GQ01 4J038 DL021 DL052 DL071 DL161 JA34 JC38 KA04 KA09 LA02 A07 NA01 A01 NA02 BJ02 5G305 AA07 AA11 AB10 AB26 AB36 BA09 CA26 CB27 CD07 CD12 CD18

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 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 ) _n - represents a group represented by, n
Represents 1 to 6, and d represents 0 or 1. And at least one compound selected from the group consisting of: (B) a compound represented by the following general formula (3): HO- (SiR ⁸ R ⁹ O) _e H (3) (R ⁸ and R ⁹ may be the same or different and each represents a monovalent organic group, and e represents an integer of 2 to 100). A film forming composition to be used. 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. 3. The metal chelate compound wherein the component (A) and the component (B) are represented by the following general formula (4): R ¹⁰ _f M (OR ¹¹ ) _gf (4) (R) ¹⁰ is a chelating agent, M is a metal atom, R ¹¹ has 2 to 2 carbon atoms.
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. )
The film forming composition according to claim 1, wherein the composition is hydrolyzed in the presence of at least one selected from the group consisting of an acidic catalyst and a basic catalyst. 4. The use ratio of the component (B) with respect to the component (A) is 100 to 100 parts by weight of the component (A) (in terms of a completely hydrolyzed condensate) and 0.2 to 20 parts by weight of the component (B). 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.