JP2001115028A - Composition for film forming, method for forming film and silica-based film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for film forming excellent in dielectric constant properties and mechanical properties as an interlayer insulating film in a semiconductor element, etc., and capable of forming a silica-based film. SOLUTION: The characteristic of this composition for film forming is to comprise (A) a hydrolytic condensate obtained by hydrolyzing and carrying out condensation at least one kind of a silane compound selected from the group of a compound represented by general formula (1): RaSi(OR1)4-a [R denotes H, F or a monovalent organic group; R1 denotes a monovalent organic group; and (a) denotes an integer of 1-2], a compound represented by general formula (2): Si(OR2)4 (R2 denotes a monovalent organic group) and a compound represented by general formula (3): R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c [R3 to R6 are same or different and denote each a monovalent organic group; b and c are same or different and denote each an integer of 0-2; R7 denotes O, phenylene group or a group represented by the following:-(CH2)n- (n is an integer of 1-6); and d denotes 0 or 1] in the presence of an alkaline compound in an amount of >=0.1 mol based on 1 mol of the silane compound and (B) an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a film-forming composition, and more particularly, to a method for forming a silica-based film having excellent relative dielectric constant and mechanical strength as an interlayer insulating film material for a semiconductor device or the like. The present invention relates to a composition for forming a film.

[0002]

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

As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensing alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (Japanese Patent Application Laid-Open No. H5-263045; 5-315
319) and a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-340219, JP-A-11-34022).
0) has been proposed, but the materials obtained by these methods all have relative dielectric constants exceeding 2.5, which are insufficient for high integration and multilayering of semiconductor elements and the like.

[0004]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly to an interlayer insulating film for a semiconductor device or the like, which has excellent low dielectric properties and high mechanical strength. It is an object of the present invention to provide a film-forming composition capable of obtaining a silica-based coating having improved properties, a method for producing the same, and a silica-based film obtained from the composition.

[0005]

The present invention relates to (A) a compound represented by the following general formula (1) (hereinafter also referred to as "compound (1)") and a compound represented by the following general formula (2) (Hereinafter also referred to as “compound (2)”) and at least one silane compound selected from the group of compounds represented by the following general formula (3) (hereinafter also referred to as “compound (3)”): is hydrolyzed in the presence of 0.1 mol or more alkaline compounds moles, (hereinafter also referred to as "(a) hydrolytic condensate") fused hydrolytic condensates ^{_{R a Si (oR 1) 4}} -a (1) (wherein, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2). Si (OR ² ) ) ₄ ..... (2) (wherein, R ² represents a monovalent organic _{^{group.) R 3 b (R 4}} O) 3-b Si- (R 7 ) _D -Si (OR ⁵ ) _{3 -c} R ⁶ _c (3) wherein R ^{3 to} R ⁶ are the same or different, and a monovalent organic group and b and c are the same or different. , 0 to 2, R ⁷ represents an oxygen atom, a phenylene group or — (CH
₂ ) a group represented by _n- (where n is an integer of 1 to 6), and d represents 0 or 1. And (B) a film-forming composition comprising an organic solvent. Next, the present invention relates to a method for forming a film, which comprises applying the composition for forming a film to a substrate and heating the substrate.
Next, the present invention relates to a silica-based film obtained by the method for forming a film.

[0006]

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

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

Specific examples of the compound (1) 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, fluorotrifluorosilane −
n-butoxysilane, fluorotri-sec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane and the like;

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

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

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

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

Compound (3): In the above formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as in the above formula (1). . Among the compounds (3), compounds in which R ⁷ in the general formula (3) is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy- 3-methyldisiloxane, 1,1,1,3,3-pentaethoxy-
3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-methyldisiloxane, 1,1,1,
3,3-pentamethoxy-3-ethyldisiloxane,
1,1,1,3,3-pentaethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3
-Ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,
3-pentaethoxy-3-phenyldisiloxane, 1,
1,1,3,3-pentaphenoxy-3-phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3-
Dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-
Tetraphenoxy-1,3-dimethyldisiloxane,
1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraethoxy-1,3
-Diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,
3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldisiloxane 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,
1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-
1,3,3-triethyldisiloxane, 1,1,3-
Triethoxy-1,3,3-triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,1,3-trimethoxy-
1,3,3-triphenyldisiloxane, 1,1,3-
Triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,1
3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,
3-diphenoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diethoxy-1,1,
3,3-tetraethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraethyldisiloxane,
1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-
Tetraphenyldisiloxane, 1,3-diphenoxy-
Examples thereof include 1,1,3,3-tetraphenyldisiloxane.

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

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

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

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

Of these, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane,
2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1-
(Diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2-
(Trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethyl) (Silyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) )benzene,
1,3-bis (triethoxysilyl) benzene, 1,4
Preferred examples include -bis (trimethoxysilyl) benzene and 1,4-bis (triethoxysilyl) benzene.

In the present invention, the compounds (1) to (3) constituting the component (A) include the above-mentioned compound (1),
One or more of (2) and (3) can be used.

When hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3) constituting the component (A), an R ¹ O— group,
It is preferable to use 5 to 50 mol of water per 1 mol of the total amount of ² O-, R ⁴ O- and R ⁵ O- groups,
It is particularly preferred to add 30 mol of water. When the amount of water to be added is less than 5 mol, sufficient relative dielectric constant and elastic modulus may not be obtained. On the other hand, when the amount is more than 50 mol, polymer precipitation or gelation during hydrolysis and condensation reactions may occur. May occur.

In producing the hydrolyzed condensate (A) of the present invention, when hydrolyzing and condensing at least one silane compound selected from the above-mentioned compounds (1) to (3), It is characterized in that an amount of alkaline compound is used. In the present invention, by using an alkaline compound in a specific amount or more, a silica-based film having a low relative dielectric constant and a high elastic modulus can be obtained. Examples of the alkaline compound that can be used in the present invention include ammonia (including an aqueous ammonia solution), an organic amine, and an alkaline inorganic compound. In the present invention, ammonia and an organic amine are preferable. In the present invention, examples of the organic amine include an alkylamine, an alkanolamine, and an arylamine. Alkylamines that can be used in the present invention include methylamine,
Ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine,
N, N-diethylamine, N, N-dipropylamine,
Compounds having an alkyl group having 1 to 4 carbon atoms such as N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxy Ethylamine, ethoxypropylamine,
Examples thereof include compounds having an alkoxy group such as ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, and butoxybutylamine. Alkanolamines include methanolamine, ethanolamine, propanolamine,
Butanolamine, N-methylmethanolamine, N-
Ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-
Methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-
Ethyl butanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine,
N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine, N, N
-Diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine, N, N -Dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-
Ethyl diethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine,
N-ethyldibutanolamine, N-propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl)
Ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) butanolamine, N-
(Aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine,
N- (aminopropyl) methanolamine, N- (aminopropyl) ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ) Ethanolamine, N- (aminobutyl) propanolamine, N- (aminobutyl) butanolamine and the like. As the arylamine, aniline and the like can be mentioned. Further, as an organic amine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine , Methylaminoethylamine, methylaminopropylamine,
Methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine,
Butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, morpholine, methylmorpholine,
Examples thereof include diazabicyclooctane, diazabicyclononane, and diazabicycloundecene.

These alkaline compounds may be used alone or in combination of two or more. In the present invention, it is more preferable to use an alkylamine as the alkaline compound from the viewpoint of the adhesion of the silica-based film to the substrate. In the present invention, the amount of the alkaline compound used is 0.1 mol or more based on 1 mol of the total of the compounds (1) to (3).
It is preferably at least 0.5 mol, particularly preferably at least 0.9 mol. In the present invention, the upper limit of the amount of the alkaline compound used is not particularly limited, but is usually less than 10 mol per 1 mol of the silane compound.

The radius of gyration of the hydrolyzed condensate (A) thus obtained is the radius of gyration according to the GPC (refractive index, viscosity, light scattering measurement) method, preferably 5 to 50 nm, more preferably 8 to 40 nm. And particularly preferably 9 to 20.
nm. The radius of gyration of the hydrolysis condensate is 5 to 50 nm
In this case, the obtained silica-based film can be particularly excellent in relative dielectric constant, elastic modulus, and film uniformity. Further, the (A) hydrolyzed condensate obtained in this manner has a feature that the coatability on a substrate is excellent because it is not in the form of particles. The absence of the particulate form is confirmed, for example, by transmission electron microscopy (TEM).

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

Further, in the hydrolysis condensate (A), at least one silane compound selected from the group of compounds (1) to (3) is hydrolyzed and condensed in the presence of an alkylamine to form a hydrolyzed condensate. It is a decomposed condensate, and preferably has an inertial radius of 5 to 50 nm. Thereafter, it is preferable to adjust the pH of the composition to 7 or less. Examples of the method of adjusting the pH include a method of adding a pH adjuster, a method of distilling an alkali catalyst from the composition under normal pressure or reduced pressure, and a method of bubbling a gas such as nitrogen or argon into the composition. A method of removing the alkali catalyst from the composition, a method of removing the alkali catalyst from the composition with an ion exchange resin, and the like. Each of these methods may be used in combination.

Here, examples of the pH adjuster include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, and oxalic acid. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, and sebacic acid. Gallic acid, butyric acid, melitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, Benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid,
Malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, malic acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, glutaric acid and the like can be mentioned.

The pH of the composition with the above pH adjuster is 7
Hereinafter, it is preferably adjusted to 1 to 6. Thus, after making the radius of gyration of the hydrolysis condensate 5 to 50 nm,
By adjusting the pH within the above range with the pH adjuster, the effect of improving the storage stability of the obtained composition can be obtained. The amount of the pH adjuster used depends on the pH of the composition.
Is within the above range, and the amount used is appropriately selected.

(B) Organic Solvent The film-forming composition of the present invention comprises the component (A)
(B) It is dissolved or dispersed in an organic solvent. This (B)
As organic solvents, alcohol solvents, ketone solvents,
At least one selected from the group consisting of amide solvents, ester solvents and aprotic solvents is exemplified. Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol,
-Methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, s
ec-octanol, n-nonyl alcohol, 2,6-
Dimethylheptanol-4, n-decanol, sec-
Undecyl alcohol, trimethyl nonyl alcohol,
mono-alcohol solvents such as sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,
Ethylene glycol mono-2-ethyl butyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether,
Polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether; and the like. One or two of these alcohol solvents are used.
More than one species may be used simultaneously.

Of these alcohols, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, s
ec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether And propylene glycol monobutyl ether.

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

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

Examples of the ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ
-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-acetate
n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxy triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents include 1
Species or two or more species may be used simultaneously. Examples of aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, −
Methyl-Δ3-pyrroline, N-methylpiperidine, N-
Ethyl piperidine, N, N-dimethylpiperazine, N-
Methylimidazole, N-methyl-4-piperidone, N
-Methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3
-Dimethyltetrahydro-2 (1H) -pyrimidinone. The above (B) organic solvent is 1
Species or a mixture of two or more can be used.

In the film-forming composition of the present invention, the same solvent can be used when the compounds (1) to (3) constituting the component (A) are hydrolyzed and / or condensed.

Specifically, water or water diluted with a solvent is intermittently or continuously added to a solvent in which the compounds (1) to (3) are dissolved. At this time, the alkaline compound may be added in advance to the solvent, or may be dissolved or dispersed in water at the time of adding water. The reaction temperature at this time is generally 0 to 100 ° C, preferably 15 to 9 ° C.
0 ° C.

Other Additives Surfactants and components such as colloidal silica and colloidal alumina may be added to the film-forming composition of the present invention.

The surfactant used in the present invention is not particularly limited. Examples thereof include silicone surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, Fluorinated surfactant,
Acrylic surfactants and the like can be mentioned, and these can be used alone or in combination of two or more. As the surfactant, a silicone-based, nonionic, fluorine-based, or acrylic-based surfactant is preferable. Among them, a silicone-based surfactant is particularly preferable because it has excellent film-forming properties and does not generate a metal corrosive gas.

Here, the silicone-based surfactant is not particularly limited, and examples thereof include a dimethylpolysiloxane-polyoxyalkylene copolymer. Commercially available silicone surfactants include organosiloxane polymer KP341 [Shin-Etsu Chemical Co., Ltd.]
SH7PA, SH21PA, SH28PA, SH
30PA, ST94PA (both made by Dow Corning Toray Silicone) and the like.

Examples of the cationic surfactant include an alkylamine salt, a quaternary ammonium salt and a polyoxyalkylamine. Further, as anionic surfactants, fatty acid salts, higher alcohol sulfates,
Examples thereof include an alkyl benzene sulfonate, a diphenyl ether disulfonate, a dialkyl disulfosuccinate, an alkyl phosphate salt, and a polyoxyethylene sulfate salt.

Further, nonionic surfactants include:
Although not particularly limited, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene dilaurate and polyoxyethylene distearate Oxyethylene dialkyl esters; sorbitan fatty acid esters; fatty acid-modified polyoxyethylenes; polyoxyethylene-polyoxypropylene block copolymers, and the like.

The amphoteric surfactant is not particularly limited, but has a structure in which two or more of the above-mentioned anionic surfactants, cationic surfactants, and nonionic surfactants are combined. Is mentioned.

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 such as 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 fluorine surfactants include Megafac F142D, F172, F173, F173
183 (above, manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC-430, FC-431
[Sumitomo 3M Ltd.], 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
Examples include a fluorine-based surfactant commercially available under a name such as [NEOS CORPORATION]. Among them, the above MegaFac F172, BM-1000, BM-11
00, NBX-15 is particularly preferred.

Examples of the acrylic surfactant that can be used in the present invention include (meth) acrylic acid copolymers and the like. Polyflow Nos. 57 and 95 [manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.] ] Which are commercially available.

The colloidal silica is, for example, a dispersion obtained by dispersing high-purity silicic anhydride in the above-mentioned hydrophilic organic solvent, and usually has an average particle size of 5 to 30 nm, preferably 10 to 30 nm.
It has a thickness of 20 nm and a solid concentration of about 10 to 40% by weight. Examples of such colloidal silica include, for example, methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industries, Ltd .;
And Oscar. Examples of the colloidal alumina include alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.
Examples 100 and 200 include alumina clear sol, alumina sol 10 and 132, manufactured by Kawaken Fine Chemicals Co., Ltd.

Method for Preparing Film-Forming Composition In preparing the film-forming composition of the present invention, for example, compounds (1) to (3) are mixed in a solvent and water is continuously or intermittently mixed. Add, hydrolyze, condense,
After the component (A) is prepared, the component (B) may be added thereto, and there is no particular limitation.

Specific examples of the method for preparing the composition of the present invention include the following methods. A method in which a predetermined amount of water is added to a mixture of the compounds (1) to (3) constituting the component (A), the alkaline compound, and the organic solvent (B) to perform a hydrolysis / condensation reaction. A predetermined amount of water is continuously or intermittently added to a mixture composed of the compounds (1) to (3), the alkaline compound and the organic solvent (B) constituting the component (A) to undergo hydrolysis and condensation reactions. Method. A method in which a predetermined amount of water and an alkaline compound are added to a mixture of the compounds (1) to (3) constituting the component (A) and the organic solvent (B), and a hydrolysis / condensation reaction is performed. A predetermined amount of water and an alkaline compound are continuously or intermittently added to a mixture of the compounds (1) to (3) and the component (B) constituting the component (A) to carry out hydrolysis and condensation reactions. Method.

The total solid content of the composition of the present invention thus obtained is preferably 2 to 30% by weight.
It is appropriately adjusted according to the purpose of use. When the total solid content of the composition is 2 to 30% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The adjustment of the total solid content concentration is performed, if necessary, by concentration and dilution with the above (B) organic solvent.

To form a film using the composition of the present invention, first, the composition of the present invention is applied to a substrate to form a coating film. Here, examples of the substrate on which the composition of the present invention can be applied include a semiconductor, glass, ceramics, and metal. In addition, examples of the coating method include spin coating, dipping, and a roller blade. The compositions of the present invention, in particular a silicon wafer, SiO ₂
It is applied on a wafer, a SiN wafer, or the like, and is suitable for forming an insulating film.

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. The thickness of the coating film to be formed is usually 0.2 to 20 μm.
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 under air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like. Can be. Further, in order to control the curing speed of the component (A), if necessary, the composition may be heated stepwise, or may be nitrogen,
An atmosphere such as air, oxygen, or reduced pressure can be selected. The thus obtained silica-based film of the present invention has a film density of usually 0.35 to 1.2 g / cm ³ , preferably 0.4 to 1.1 g / cm ³ , and more preferably 0.5 to 1.1 g / cm ³ .
１．０1.0 g / cm ³ . 0.35 g / cm film density
^If it is less than ³ , the mechanical strength of the coating film decreases, while 1.2
If it exceeds g / cm ³ , a low dielectric constant cannot be obtained. Also,
The silica-based film of the present invention has no pores of 10 nm or more in pore distribution measurement by the BJH method, and is preferable as an interlayer insulating film material between fine wirings. Further, the silica-based film of the present invention is characterized in that it has a low water absorption.
When the film is left for a long time, no water adsorption to the film is observed from the IR spectrum observation of the film after standing. This water absorption can be adjusted by adjusting the amount of the tetraalkoxysilane of the compound (1) used in the film-forming composition of the present invention. Further, the relative permittivity of the silica-based film of the present invention is a low relative permittivity, usually 2.5 to 1.2, preferably 2.4 to 1.2.

The low-density film of the present invention is excellent in insulating properties, uniformity of coating film, dielectric properties, crack resistance of coating film, and surface hardness of coating film.
Interlayer insulating films for semiconductor devices such as RAM, SDRAM, RDRAM, and D-RDRAM; protective films such as surface coat films for semiconductor devices; interlayer insulating films for multilayer wiring substrates; protective films and insulating films for liquid crystal display devices; Useful for applications.

[0052]

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

Inertia radius : Measured by gel permeation chromatography (GPC) (refractive index, viscosity, light scattering measurement) under the following conditions. Sample solution: hydrolyzed condensate of silane compound,
10 mM Li so that the solid concentration is 0.25%.
It was diluted with methanol containing Br to prepare a sample solution for GPC (refractive index, viscosity, light scattering measurement). Equipment: Tosoh Corporation, GPC system model GP
C-8020 Tosoh Corporation, Column Alpha5000 / 300
0 Viscotec Co., Ltd., viscosity detector and light scattering detector Model T-60 dual meter Carrier solution: methanol containing 10 mM LiBr Carrier feed rate: 1 ml / min Column temperature: 40 ° C. Relative dielectric constant On the other hand, an aluminum electrode pattern was formed by an evaporation method to prepare a sample for measuring a relative dielectric constant. The relative permittivity of the coating film of the sample was measured at a frequency of 100 kHz by a CV method using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. Elastic Modulus (Young's Modulus ) The obtained film was measured by a continuous stiffness measuring method using a nano indenter XP (manufactured by Nano Instruments).

Example 1 In a mixed solution of 6 g of a 40% aqueous solution of methylamine, 228 g of ultrapure water and 570 g of ethanol, 13.6 g of methyltrimethoxysilane (6.7% in terms of complete hydrolysis condensate).
g) and 20.9 g of tetraethoxysilane (6 g of completely hydrolyzed condensate) were added and reacted at 60 ° C. for 2 hours.
g, and then concentrated under reduced pressure to a total solution amount of 116 g. Thereafter, 10 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a composition solution having a solid content of 10%. The inertia of the hydrolyzed condensate in the obtained composition solution was 12 nm. Example 2 A composition solution having a solid content of 10% was obtained in the same manner as in Example 1 except that 98 g of a 25% aqueous ammonia solution was used instead of 6 g of a 40% aqueous methylamine solution. The inertia of the hydrolyzed condensate in the obtained composition solution is 1
4 nm. Example 3 In a mixed solution of 27 g of a 40% aqueous solution of methylamine, 137 g of ultrapure water and 342 g of ethanol, 13.6 g of methyltrimethoxysilane (6.7% in terms of complete hydrolysis condensate).
g) and 28.7 g of tetraethoxysilane (6 g of completely hydrolyzed condensate), and reacted at 60 ° C. for 2 hours.
g, and then concentrated under reduced pressure to a total solution amount of 116 g. Thereafter, 10 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a composition solution having a solid content of 10%. The inertia of the hydrolyzed condensate in the obtained composition solution was 26 nm.

Comparative Example 1 (1) The same operation as in Reference Example 1 was carried out except that 1 g of a 25% aqueous ammonia solution was used instead of 6 g of the 40% aqueous methylamine solution in Example 1 (1), and the solid content was changed. A 10% composition solution was obtained. The inertia of the hydrolyzed condensate in the obtained composition solution was 8 nm. Formation of Film The compositions obtained in Examples 1 to 3 and Comparative Example 1 were used,
An 8 inch silicon wafer is coated by a spin coating method, and is dried at 80 ° C. for 5 minutes in air and then at 200 ° C. under nitrogen.
After heating for more than one minute,
C. and 380.degree. C. in that order for 30 minutes each, and further heated under vacuum at 425.degree. C. for 1 hour to form a colorless and transparent silica-based film. The above-described evaluation was performed on the obtained silica-based film. Table 1 shows the results.

[0056]

[Table 1]

[0057]

According to the present invention, it is possible to provide a film-forming composition capable of forming a silica-based film having excellent low dielectric properties and improved mechanical strength.

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Claims (7)

[Claims] (A) at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2) and a compound represented by the following general formula (3) One type of silane compound is hydrolyzed and condensed in the presence of an alkali compound in an amount of 0.1 mol or more with respect to 1 mol of the silane compound, and a condensed hydrolyzed condensate R _a Si (OR ¹ ) _4-a ... (1) (wherein, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2.) Si (OR ² ) _4. (2) (wherein, R ² represents a monovalent organic ^{_{group.) R 3 b (R 4}} O) 3-b Si- (R 7) d -Si (OR 5) 3-c R ⁶ _c · · · · (3) wherein, R ³ to R ⁶ are the same or different and each represents a monovalent organic group, b and c individually represent integers of 0 to 2, R ⁷ is oxygen Child, a phenylene group or - (CH
₂ ) a group represented by _n- (where n is an integer of 1 to 6), and d represents 0 or 1. ] And (B) an organic solvent. 2. The film-forming composition according to claim 1, wherein the amount of the alkaline compound is 0.5 mol or more per 1 mol of the silane compound. 3. The film-forming composition according to claim 1, wherein the alkaline compound is selected from the group consisting of ammonia and an organic amine. 4. The composition according to claim 3, wherein the organic amine is an alkylamine, an alkanolamine or an arylamine. 5. An organic solvent selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3): A method for producing a film-forming composition, comprising hydrolyzing and condensing at least one silane compound in the presence of 0.1 mol or more of an alkaline compound per 1 mol of the silane compound. R _a Si (OR ¹ ) _4-a ... (1) (where R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is 1-2) of an _{^{integer.) Si (OR 2) 4}} ····· (2) ( wherein, R ² represents a monovalent organic ^{_{group.) R 3 b (R 4}} O) 3-b Si- ( R ⁷ ) _d -Si (OR ⁵ ) _{3 -c} R ⁶ _c (3) wherein R ^{3 to} R ⁶ are the same or different, and a monovalent organic group and b and c are the same. Or differently, a number of 0 to 2 is represented, and R ⁷ is an oxygen atom, a phenylene group or — (CH
₂ ) a group represented by _n- (where n is an integer of 1 to 6), and d represents 0 or 1. ] 6. A method for forming a film, comprising applying the composition for forming a film according to claim 1 to a substrate and heating the substrate. 7. A silica-based film obtained by the method for forming a film according to claim 6.