JP2002235037A - Method for producing composition for film formation, composition for film formation, method for forming film, and silica-based film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for film formation capable of forming a silica-based film exhibiting a very small dielectric constant as a material for an interlayer insulating film in a semiconductor element, and the like, and having few foreign matter in a solution. SOLUTION: Disclosed is a method for producing a composition for film formation and comprises the production of (A) a condensation product by hydrolyzing one kind or more compounds represented by general formulas 1 to 3 in the presence of an alkylamine or an onium salt to be condensed and (B) filtration of a solution containing an organic solvent through an ultrafiltration membrane. Ra(Si)(OR1)4-a...(1) Si(OR2)4...(2) R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c...(3) [R is H, F or a monovalent organic group; R1 to R6 is each a monovalent organic group; R7 is O, phenylene group or (CH2)n; (a) is an integer from 1 to 2; (b) and (c) are each an integer from 0 to 2; (d) is 0 or 1; (n) is an integer from 1 to 6].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a film-forming composition and a film-forming composition obtained by the method, and more particularly, to a material having an extremely low dielectric constant as an interlayer insulating film material in a semiconductor device or the like. And a film-forming composition capable of forming a silica-based film having a small number of foreign substances in a solution.

[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. In particular, with the further increase in integration and multilayering of semiconductor devices, etc., there is a need for an interlayer insulating film material having a lower dielectric constant and a smaller number of foreign substances in a coating film in order to prevent a short circuit between wirings. I have.

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 (JP-A-5-263045, 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 material obtained by these methods is purified by a concentration method which is usually performed, and the concentration increases the number of foreign substances in the solution,
There is a problem that the reliability of the device is reduced. Also,
In the materials obtained by these methods, the relative permittivity of the obtained coating film exceeds 2.5, and there is also a problem that a signal delay becomes remarkable in a semiconductor element aiming at a higher speed.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a film-forming composition for solving the above problems and a film-forming composition using the same. An object of the present invention is to provide a film-forming composition capable of forming a silica-based film having a very low dielectric constant and a small number of foreign substances in a solution as an insulating film.

[0005]

The present invention provides (A) 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 hydrolyzed condensate R _a Si (OR ¹ ) _4-a ... Obtained by hydrolyzing and condensing at least one silane compound selected from the group of compounds in the presence of an alkylamine or onium salt. (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, each is a monovalent organic group, b and c are the same or different, each represents 0 to 2, 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. And (B) a method for producing a film-forming composition, comprising concentrating a solution containing an organic solvent with an ultrafiltration membrane. Next, the present invention relates to a film-forming composition produced by the above production method. 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 above 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 of them 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 hydrolyzing at least one silane compound selected from the group of compounds (1) to (3) in the presence of a catalyst. Obtained by 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 represented by the general formula (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,
Fluorotri-n-butoxysilane, fluorotri-s
ec-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-butoxysilane, 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, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-trifluoropropyltrimethoxysilane, gamma-trifluoropropyltrimethylsilane 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 represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxysilane. , Tetra-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). . In the general formula (3), as a compound in which R ⁷ is an oxygen atom,
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-phenyl Disiloxane, 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-1,1,3,3-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
3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 1,
Examples thereof include 3-diphenoxy-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 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, as the compounds (1) to (3) constituting the component (A), one or more of the above compounds (1), (2) and (3) can be used.

When at least one silane compound selected from the group consisting of the compounds (1) to (3) is hydrolyzed and condensed, the silane compound is added in an amount of 0.1 to 1 mol per mol of the total amount of the compounds (1) to (3). It is preferred to use more than 5 mol and up to 150 mol of water, particularly preferred to add more than 0.5 mol and 130 mol of water. If the amount of water to be added is 0.5 mol or less, the crack resistance of the coating film may be poor, and if it exceeds 150 mol, precipitation or gelation of the polymer during the hydrolysis and condensation reaction may occur.

In the present invention, the compounds (1) to (4)
A feature is that a catalyst is used when hydrolyzing and condensing at least one silane compound selected from the group (3). The catalyst that can be used in the present invention is an alkylamine or an onium salt. Examples of the alkylamine include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine,
Pentylamine, octylamine, nonylamine, decylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexyl Examples include amines. Examples of the onium salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
One or two or more of these catalysts may be used simultaneously.

The amount of the above-mentioned catalyst to be used is as follows:
R in (3)¹ O-group, R^Two O-group, R ^Four An O-group and
R^Five Usually, based on 1 mol of the total amount of the group represented by the O- group,
0.00001 to 10 mol, preferably 0.00005
To 5 mol, more preferably 0.001 to 0.5 mol.
You. If the amount of the catalyst used is within the above range, the amount of
There is little danger of polymer precipitation and gelation.

In the compounds (1) to (3), when each component is converted into a complete hydrolysis condensate, the compound (2)
Represents 5 to 75% by weight of the total amount of the compounds (1) to (3),
Preferably 10 to 70% by weight, more preferably 15 to 70% by weight.
70% by weight. In addition, compound (1) and / or (3) is 95 to 25 in the total amount of compounds (1) to (3).
%, Preferably 90 to 30% by weight, more preferably 85 to 30% by weight. When the amount of the compound (2) is 5 to 75% by weight based on the total amount of the compounds (1) to (3), the resulting coating film has a high elastic modulus and is particularly excellent in low dielectric properties. Further, it is preferably a hydrolyzed condensate of the compound (1) and the compound (2) in that the obtained composition has more excellent storage stability. Here, the hydrolysis means an R ¹ O— group, R ² O— contained in the compounds (1) to (3).
It is not necessary that all of the groups, R ⁴ O— and R ⁵ O— be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or Or a mixture thereof. In addition, the condensate is a product in which the silanol groups of the hydrolyzates of the compounds (1) to (3) are condensed to form a Si—O—Si bond. In the present invention, all the silanol groups are condensed. It is not necessary, and is a concept including a mixture of a small amount of condensed silanol groups and a mixture of compounds having different degrees of condensation. In the present invention, the completely hydrolyzed condensate refers to R ¹ O—, R ² O—, R ^{4 in} compounds (1) to (3).
O-group and R ⁵ O-group are hydrolyzed by 100% to form SiO
It is an H group, which is completely condensed to form a siloxane structure.

As a reaction solvent for synthesizing the hydrolysis-condensation product (A), at least one selected from the group consisting of an alcohol solvent, a ketone solvent, an amide solvent and an ester solvent can be mentioned. Here, as the alcohol solvent,
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, 3,
Monoalcohol solvents such as 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 more of these alcohol solvents may be used at the same time.

Among these alcohol solvents, 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, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Preferred are propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and the like.

As the ketone solvent, 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, trimethyl nonanone, cyclohexanone,
2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone,
In addition to fencheon, acetylacetone, 2,4-
Hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4 Hexanedione, 2,2
6,6-tetramethyl-3,5-heptanedione, 1,
Β-diketones such as 1,1,5,5,5-hexafluoro-2,4-heptanedione and the like can be mentioned. One or two or more of these ketone solvents may be used simultaneously.

As the amide solvent, formamide, N-
Methylformamide, N, N-dimethylformamide,
N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, 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. These amide solvents may be used alone or in combination of two or more.

As the ester solvent, 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, acetic acid 3
-Methoxybutyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetic acid
Nonyl, methyl acetoacetate, 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-acetate
-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, methoxy acetate 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, diethyl malonate , Dimethyl phthalate, diethyl phthalate and the like. One or more of these ester solvents may be used simultaneously. The above reaction solvents can be used alone or in combination of two or more.

(A) The concentration of the hydrolyzed condensate with respect to the reaction solvent is 1 to 20% by weight (in terms of a completely hydrolyzed condensate).
Preferably it is 1.5 to 18% by weight. The reaction temperature is usually 0 to 100 ° C, preferably 15 to 90 ° C.
° C.

In the method for producing a film-forming composition of the present invention,
The solution obtained by the above reaction may be directly concentrated by an ultrafiltration membrane, or may be further added with an organic solvent for concentration. The pore size of the ultrafiltration membrane that can be used when performing the concentration operation using the ultrafiltration membrane is smaller than the particle size of the hydrolyzed condensate (A), and is used as a substitute for the pore size in this technical field. When expressed as the molecular weight cut-off of the ultrafiltration membrane,
00, more preferably 3,000 to 200,000, particularly preferably 3,000 to 100,000. Examples of the material of the ultrafiltration membrane include cellulose, polysulfone, polyamide, and ceramics, and ceramics are particularly preferable from the viewpoint of solvent resistance. The shape of the ultrafiltration membrane may be any shape such as a flat membrane, a cylinder, a hollow fiber, and a spiral, but is preferably a cylinder because of its high permeation flow rate and little clogging. The circulating flow rate of the solution at the time of concentration by the ultrafiltration membrane is 1 to 10 m / sec, preferably 2 to 8 m / sec, in terms of linear velocity with the ultrafiltration membrane surface.
m / sec.

Other Additives The film-forming composition obtained by the present invention further comprises β-diketone, colloidal silica, colloidal alumina, organic polymer, surfactant, silane coupling agent, radical generator, triazene Components such as compounds may be added.

Examples of the β-diketone include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, and 2,4-hexanedione. Nonanion,
3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro- Examples thereof include 2,4-heptanedione, and more preferred are acetylacetone, 2,4-hexanedione, 2,4-heptanedione, and 3,5-heptanedione. These may be used alone or in combination of two or more.

The colloidal silica is, for example, a dispersion obtained by dispersing high-purity silicic anhydride in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 μm, preferably 10 to 30 μm.
It has a solid content of about 20 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. Examples of the organic polymer include a compound having a sugar chain structure, a vinylamide polymer, and (meth)
Acrylic polymer, aromatic vinyl compound, dendrimer, polyimide, polyamic acid, polyarylene, polyamide, polyquinoxaline, polyoxadiazole,
Examples include a fluorine-based polymer and a compound having a polyalkylene oxide structure.

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 poly 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 polyoxytylene polyoxypropylene block copolymer include compounds having the following block structures. - (X) j- (Y) k- - (X) j- (Y) k- (X) l- ( wherein, X is a group represented by -CH ₂ CH ₂ O-, Y is -
A group represented by CH ₂ CH (CH ₃ ) O—, wherein j is 1 to
90, k is a number from 10 to 99, and l is a number from 0 to 90).
Polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
And the like. More preferred examples include ether-type compounds such as 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.), Florado 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, and S7PA.
H30PA and ST94PA (both are available from Dow Corning Toray Silicone Co., Ltd.).
Among them, SH28PA and SH30PA are particularly preferable. The amount of the surfactant used is usually 0.0001 to 10 parts by weight based on the specific organic solvent (completely hydrolyzed condensate). These may be used alone or in combination of two or more.

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

Examples of the radical generator include, for example, isobutyryl peroxide, α, α'bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxy Dicarbonate,
1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl par Oxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy ) Hexane, 1-cyclohexyl-
1-methylethyl peroxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,
m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-
Butylperoxycyclohexyl) propane, 1,1-
Bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-
3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, -Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis ( t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like can be mentioned. The mixing amount of the radical generator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. These may be used alone or in combination of two or more.

As the triazene compound, for example, 1,
2-bis (3,3-dimethyltriazenyl) benzene,
1,3-bis (3,3-dimethyltriazenyl) benzene, 1,4-bis (3,3-dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis ( 3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3-dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3 ,
3-dimethyltriazenylphenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) benzene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl)- 9,9-bis [3-methyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3- Phenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-propenyl-4- (3,3 -Dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro-4- (3,3-dimethyltriazenyl) phenyl] Fluorene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3
-Dimethyltriazenyl) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl)
Phenyl] fluorene and the like. These may be used alone or in combination of two or more.

The total solids concentration 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 (D) organic solvent.

The composition of the present invention was applied to a silicon wafer, Si
When applying to a substrate such as an O ₂ wafer or a SiN wafer, a coating method such as spin coating, dipping, roll coating, or spraying is used. The film thickness at this time is about 0.05 to 2.5 μm in a single coating, and a coating film with a thickness of about 0.1 to 5 μm in a double coating can be formed. 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. Further, the coating film can be formed by irradiating an electron beam or an ultraviolet ray. Further, in order to control the curing speed of the coating film, if necessary, heating may be performed stepwise, or an atmosphere such as nitrogen, air, oxygen, or reduced pressure may be selected. Further, the relative permittivity of the silica-based film of the present invention is usually 3.0 to 1.2, preferably 3.0 to 1.8, and more preferably 3.0 to 2.0.

The interlayer insulating film thus obtained is excellent in low dielectric constant characteristics, oxygen plasma resistance, and crack resistance after PCT.
M, SDRAM, RDRAM, D-RDRAM, and other interlayer insulating films for semiconductor devices and etching stopper films, protective films such as surface coating films for semiconductor devices, intermediate layers in the semiconductor manufacturing process using a multilayer resist, and layers between multilayer wiring substrates. It is useful for applications such as insulating films, protective films for liquid crystal display elements and insulating films.

[0043]

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.

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) (refractive index, viscosity, light scattering measurement) under the following conditions. Sample solution: A hydrolyzed condensate of a silane compound is diluted with methanol containing 10 mM LiBr so that the solid concentration becomes 0.25%, and the sample solution for GPC (refractive index, viscosity, light scattering measurement) is prepared. did. 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 sending rate: 1 ml / min Column temperature: 40 ° C.

A composition sample was coated on a silicon wafer having a relative dielectric constant of 8 inches by a spin coating method, and was applied on a hot plate at 100 ° C. for 3 hours.
The substrate was dried at 200 ° C. for 3 minutes in a nitrogen atmosphere for 3 minutes, and further baked on a hot plate at 415 ° C. for 20 minutes in a nitrogen atmosphere. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for relative dielectric constant measurement. The sample is taken at a frequency of 100 kHz,
HP1645, manufactured by Yokogawa Hewlett-Packard Co., Ltd.
The relative dielectric constant of the coating film was measured by a CV method using a 1B electrode and an HP4284A precision LCR meter.

For the solution filtered through a Teflon (registered trademark) filter having a number of foreign substances of 0.2 μm, the number of foreign substances per 1 ml of the solution was measured using an automatic particle size measuring device KL-20A manufactured by RION. (0.2 μm or more) was measured and judged according to the following criteria. ：: Number of foreign substances is 10 / ml or less ×: Number of foreign substances exceeds 10 / ml

Synthesis Example 1 5700 distilled ethanol was placed in a separable flask made of quartz.
g, ion-exchanged water (1600 g) and a 10% aqueous solution of tetramethylammonium hydroxide (300 g) were added and uniformly stirred. To this solution, a mixture of 1360 g of methyltrimethoxysilane and 2090 g of tetraethoxysilane was slowly added over 2 hours. While maintaining the solution at 55 ° C.,
A time reaction was performed. An aqueous solution of nitric acid was added to this solution to adjust the pH of the solution to 3.5 to obtain a reaction solution. When the weight average molecular weight of this solution was measured, it was 1,150,000.

Synthesis Example 2 60 g of a 40% aqueous methylamine solution, 2280 g of ultrapure water, and 5700 ethanol were placed in a separable quartz flask.
136 g of methyltrimethoxysilane in a mixed solution of
And 209 g of tetraethoxysilane.
After reacting for an hour, 2000 g of propylene glycol monopropyl ether was added, and then concentrated under reduced pressure until the total solution amount reached 1160 g.
Propylene glycol monopropyl ether solution 100
g was added to obtain a reaction solution having a solid content of 10%. When the weight average molecular weight of this solution was measured, it was found to be 1,25.
It was 0000.

Example 1 Propylene glycol monopropyl ether was added to 3 kg of the reaction solution obtained in Synthesis Example 1 at a rate of 1 kg / hr for 3 hours, and a circulation flow rate of 10 liter / min and a pressure of 1 kg / c.
m ^{2, and} the ultrafiltration module (Co., Ltd. Tri-Tech)
5 hours using an alumina ultrafiltration membrane (manufactured by Nippon Glass, trade name: ceramic UF element, use: 4 mmφ, 19 holes, length 1 m, molecular weight cut off: 150,000, membrane area: 0.24 m ² ) Ultrafiltration was performed. When the weight average molecular weight of the obtained solution was measured, it was 1,150,000, and no change in the molecular weight was observed before and after the treatment. The obtained solution was filtered through a 0.2 μm Teflon filter, and the number of foreign substances in the solution was measured.
1 and a very small number of foreign substances. The above solution is applied on an 8-inch silicon wafer using a spin coating method,
Nitrogen atmosphere 20 at 100 ° C for 3 minutes on hot plate
The substrate was dried at 0 ° C. for 3 minutes, and further baked on a hot plate at 415 ° C. in a nitrogen atmosphere for 20 minutes. The relative dielectric constant of this coating film was 2.18, which was a very low value.

Example 2 Evaluation was performed in the same manner as in Example 1 except that the reaction solution obtained in Synthesis Example 2 was used. When the weight average molecular weight of the obtained solution was measured, it was 1,250,000, and no change in the molecular weight was observed before and after the treatment. In addition, the obtained solution was filtered through a 0.2 μm Teflon filter, and the number of foreign substances in the solution was measured. The above solution is applied on an 8-inch silicon wafer by using a spin coating method, and the substrate is dried on a hot plate at 100 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was baked for 20 minutes. The dielectric constant of this coating film was 2.22, which was a very low value.

Comparative Example 1 The reaction solution obtained in Synthesis Example 1 was filtered through a 0.2 μm Teflon filter without ultrafiltration. When the number of foreign substances in the solution was measured, 1090 particles /
There were very many foreign substances in ml. When the above solution was applied on an 8-inch silicon wafer by spin coating, a large striation (poor coating) was applied to the coating.
Was observed.

Comparative Example 2 500 g of propylene glycol monopropyl ether was added to 1000 g of the reaction solution obtained in Synthesis Example 2, and
Concentration was performed at 65 ° C. for 1 hour using a rotary evaporator at a reduced pressure of 0 mmHg. When the weight average molecular weight of the obtained solution was measured, it was 1,630,000, and an increase in the molecular weight was recognized by the concentration operation. Also,
The obtained solution was filtered through a 0.2-μm Teflon filter, and the number of foreign substances in the solution was measured.
1 and many foreign substances were observed. The above solution is applied on an 8-inch silicon wafer by using a spin coat method, and is placed on a hot plate at 100 ° C. for 3 minutes in a nitrogen atmosphere at 200 ° C.
The substrate was dried for 3 minutes and further baked on a hot plate at 415 ° C. in a nitrogen atmosphere for 20 minutes. The relative dielectric constant of this coating film was a relatively low dielectric constant of 2.52.

[0053]

According to the present invention, the polymer solution of alkoxysilane is concentrated by using an ultrafiltration membrane,
It is possible to provide a film-forming composition (material for an interlayer insulating film) that can form a silica-based film having a very low dielectric constant and a small number of foreign substances in a solution.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Michinori Nishikawa 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JAE Suare Co., Ltd. F term (reference) 4J038 DL021 DL031 DL051 DL161 JA19 JA20 JA21 JA25 JA32 JA56 JB01 JB03 JB13 KA04 KA06 MA14 NA21 PA19 PB09 PC02

Claims (5)

[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) A hydrolytic condensate obtained by hydrolyzing and condensing one kind of silane compound in the presence of an alkylamine or onium salt, R _a Si (OR ¹ ) _4-a (1) , 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) ( In the formula, 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 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 solution containing an organic solvent, which is filtered through an ultrafiltration membrane. 2. The method according to claim 1, wherein the solution further contains (C) a salt. 3. A film-forming composition obtained by the method according to claim 1. 4. A method for forming a film, comprising applying the film-forming composition according to claim 3 to a substrate and heating the substrate. 5. A silica-based film obtained by the method for forming a film according to claim 4.