JP2002129103A - Composition for forming film and material for forming insulating film - Google Patents

Abstract

(57) [abstract] (with correction) [Problem] It can be fired for a short time, has excellent crack resistance,
A film-forming composition capable of forming a silica-based film having a low relative dielectric constant with low temperature is obtained. SOLUTION: (A) a condensate obtained by hydrolyzing and condensing at least one compound selected from the group of compounds represented by general formulas 1 to 3 in the presence of an acid catalyst, (B) nitrogen onium A film-forming composition comprising a salt compound and (C) a solvent represented by Formula 4. ^{_{R a Si (OR 1) 4}} -a ····· (1) Si (OR 2) 4 ····· (2) R 3 b (R 4 O) 3-b Si- (R 7) d -Si (OR
^{_{5) 3-c R 6 c}} ····· (3) R 15 O (R 17 0) g R 16 ····· (4) (R is H, F or a monovalent organic group, R ¹ R ⁶ is a monovalent organic group, R ⁷ is O, a phenylene group or — (CH ₂ ) _n
—, R ¹⁵ and R ¹⁶ are H, a C1-4 alkyl group or CH ₃
A CO-group, R ¹⁷ is an alkylene group, a is 1-2, b and c are 0-2, d is 0 or 1, g is 1-2, and n is 1-6. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition, and more particularly, to a material for an interlayer insulating film in a semiconductor device or the like, which can be fired in a short time, has excellent crack resistance, and has a relative dielectric constant temperature. The present invention relates to a film-forming composition and an insulating film-forming material that can form a silica-based film with little dependence.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is often used as an interlayer insulating film in a semiconductor device or the like. 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 higher integration and multi-layering of semiconductor devices and the like, better electrical insulation between conductors is required, and therefore, it is possible to perform firing at a lower relative dielectric constant and for a shorter time, and to have crack resistance. There has been a demand for an interlayer insulating film material that is excellent and has a small relative dielectric constant temperature dependency.

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 materials obtained by these methods do not have stable properties of reaction products, are difficult to bake in a short time, have poor crack resistance, and have a temperature dependence of the relative dielectric constant. Due to its large size, it was not suitable for industrial production.

[0004]

The present invention relates to a film-forming composition for solving the above-mentioned problems. More specifically, the present invention relates to a film-forming composition which can be baked for a short time as an interlayer insulating film in a semiconductor device or the like, and which can be cracked. It is an object of the present invention to provide a film-forming composition having excellent resistance and a small temperature dependence of the relative dielectric constant, and an insulating film-forming material obtained from the composition.

[0005]

Means for Solving the Problems The present invention, (A) (A-1) a compound represented by the following general formula (1) (hereinafter "Compound (1)" hereinafter), 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.) A-2) A compound represented by the following general formula (2)
(Referred to as “compound (2)”) and Si (OR ² ) ₄ ... (2) (wherein, R ² represents a monovalent organic group.) (A-3) The following general formula (3) A compound represented by
_{^{4 O) 3-b Si- (}} R 7) d -Si (OR 5) 3-c R 6 c ··· ·· (3) wherein "Compound (3)" hereinafter) R ³ _b (R, R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, b to c are the same or different, an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
(Where n is an integer of 1 to 6), d
Represents 0 or 1. At least one selected from the group of
A hydrolyzed condensate obtained by hydrolyzing and condensing a kind of compound in the presence of an acidic catalyst; (B) a nitrogen onium salt compound; and (C) a solvent R ¹⁵ O (R ¹⁷ 0) _g R ¹⁶ (4) (R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a monovalent organic group selected from CH ₃ CO—. And R ¹⁷ represents an alkylene group, and g represents an integer of 1 to 2.). Next, the present invention relates to a material for forming an insulating film comprising the above-described composition for forming a film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the (A) hydrolyzed condensate is a hydrolyzate or condensate of at least one silane compound selected from the above-mentioned compounds (1) to (3). is there. Here, in the hydrolysis of the component (A), the R ¹ O—, R ² O—, R ⁴ O— and R ⁴ O-groups contained in the compounds (1) to (3) constituting the component (A) are included. ⁵ O-
Not all of the groups need be hydrolyzed, for example,
It may be one in which only one is hydrolyzed, one in which two or more are hydrolyzed, or a mixture thereof. Further, the condensation in the component (A) means that the silanol groups of the hydrolyzates of the compounds (1) to (3) constituting the component (A) condense to form a Si—O—Si bond. In the present invention, it is not necessary that all of the silanol groups are condensed, but the concept encompasses a mixture of a small amount of silanol groups condensed and a mixture of those having different degrees of condensation.

(A) Hydrolysis condensate (A) The hydrolysis 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. 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, and these alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane and tri-silane. sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane 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, 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 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.

Among them, 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 compounds of 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, compound (1)
As (1) to (3), one or more kinds can be used.

When hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3), 0.1 mol / mol of the compounds (1) to (3) is used.
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.

In producing the hydrolyzed condensate (A) of the present invention, a catalyst is used for hydrolyzing and condensing at least one silane compound selected from the group of the compounds (1) to (3). The feature is to use. Examples of the acidic catalyst that can be used in this case include, for example, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, and oxalic acid; acetic acid, propionic acid, butanoic acid, pentanoic acid, and hexane. Acid, heptanoic acid, octanoic acid, nonanoic acid,
Decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, melitic acid,
Arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid,
Of dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid Organic acids such as hydrolysates, hydrolysates of maleic anhydride and hydrolysates of phthalic anhydride can be mentioned, and organic acids can be mentioned as more preferred examples. One or more of these acidic catalysts may be used simultaneously.

The amount of the above-mentioned catalyst to be used depends on the amount of the compound (1)
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
５5 mol. If the amount of catalyst used is within the above range,
There is little risk of polymer precipitation or gelation during the reaction. Ma
In the present invention, when the component (A) is hydrolyzed,
The temperature is usually 0 to 100 ° C, preferably 15 to 80 ° C.
You.

In the component (A), when each component is converted into a completely 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. Further, the 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 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 complete hydrolysis 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.

Component (B) Examples of the component (B) used in the present invention include compounds represented by the following general formulas (5) and (6). (R ⁸ R ⁹ R ¹⁰ R ¹¹ N) _e R ¹² ... (4) R ¹³ (R ¹⁴ ) _h ... (5) (where R ^{8 to} R ¹¹ are the same or different. Each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, an aryl group, or an arylalkyl group, R ¹² represents a halogen atom, a 1 to 4 valent anionic group, and e represents 1
Represents an integer of from 1 to 4, R ¹³ represents a g-valent cyclic cationic group containing a nitrogen atom, R ¹⁴ represents a halogen atom, a f-valent anionic group, f is an integer of 1 to 4, g is Represents an integer of 1 to f, and gh? F. )

In the above, the alkyl group having 1 to 10 carbon atoms is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc., the aryl group is a phenyl group, a tolyl group, etc. Represents a benzyl group and the like, and a halogen atom represents a chlorine atom and a bromine atom. A monovalent to tetravalent anionic group is defined as 1 to 4
Group derived from a compound having an anionic group,
The nitrogen-containing g-valent cyclic cationic group is derived from an aromatic compound having g nitrogen atoms, a heterocyclic compound having g nitrogen atoms, and an aliphatic ring compound having g nitrogen atoms. It is a group to do.

As the compound represented by the general formula (4),
For example, ammonium hydroxide, ammonium chloride, bromide
Ammonium, ammonium iodide, ammonium fluoride
Ammonium sulfate, ammonium sulfate, hydrogen sulfate
Ammonium, ammonium phosphate, ammonium carbonate,
Phenol ammonium, ammonium acetate, adipine
Ammonium, ammonium alginate, benzoic acid
Ammonium, ammonium sulfate, ammonium citrate
, Ammonium formate, ammonium bicarbonate, phthalate
Ammonium, ammonium salicylate, ammonium succinate
Ammonium, ammonium maleate, propionate
Ammonium, ammonium butanoate, ammonium pentanoate
Ammonium, ammonium hexanoate, ammonium heptanoate
Ammonium, ammonium octoate, ammonium nonanoate
System, ammonium decanoate, ammonium oxalate,
Ammonium tilmalonate, ammonium sebacate,
Ammonium gallate, ammonium butyrate, melitic acid
Ammonium, arachidonic acid, shikimic acid
Ammonium, ammonium 2-ethylhexanoate, ole
Ammonium inmate, ammonium stearate, Reno
Ammonium oleate, ammonium linoleate, p-
Ammonium aminobenzoate, p-toluenesulfonic acid
Ammonium, ammonium benzenesulfonate, mono
Ammonium chloroacetate, ammonium dichloroacetate,
Ammonium trichloroacetate, ammonium trifluoroacetate
, Ammonium malonate, ammonium sulfonate
, Ammonium fumarate, ammonium tartrate, ita
Ammonium cononate, ammonium mesaconate, citrus
Ammonium conate, ammonium malate, glutar
Ammonium acid; methyl ammonium hydroxide, methyl chloride
Ammonium, methyl ammonium bromide, methyl iodide
Ammonium, methyl ammonium fluoride, methyl nitrate
Ammonium, methyl ammonium sulfate, hydrogen sulfate methyl
Ammonium, methylammonium phosphate, methyl carbonate
Ruammonium, phenol methyl ammonium, acetic acid
Methyl ammonium, methyl ammonium adipate,
Methyl ammonium alginate, methyl ammonium benzoate
, Methyl ammonium sulfate, methyl citrate
Monium, methyl ammonium formate, methyl hydrogen carbonate
Ammonium, methyl ammonium phthalate, salicylic acid
Methyl ammonium, methyl ammonium succinate,
Methyl ammonium oleate, methyl propionate
Monium, methyl ammonium butanoate, pentanoic acid
Tillammonium, methylammonium hexanoate, f
Methyl ammonium ptanoate, methyl ammonium octoate
, Methyl ammonium nonanoate, methyl decanoate
Ammonium, methyl ammonium oxalate, methyl
Methyl ammonium lonate, methyl ammonium sebacate
, Methyl ammonium gallate, methyl ammonium butyrate
, Methylammonium melitate, arachidonic acid
Methyl ammonium, methyl ammonium shikimate, 2
-Methyl ammonium hexanoate, methyl oleate
Tyl ammonium, methyl ammonium stearate,
Methyl ammonium linoleate, methyl linoleate
Ammonium, methyl ammonium p-aminobenzoate,
methyl ammonium p-toluenesulfonate, benzene
Methyl ammonium sulfonate, methyl monochloroacetate
Ammonium, methyl ammonium dichloroacetate, tri
Methyl ammonium chloroacetate, methyl trifluoroacetate
Ammonium, methyl ammonium malonate, sulfo
Ammonium fumarate, methyl ammonium fumarate
System, methyl ammonium tartrate, methyl itaconate
Monium, methyl ammonium mesaconate, citracone
Ammonium methylate, methylammonium malate,
Methyl ammonium glutarate; dimethyl ammonium hydroxide
, Dimethyl ammonium chloride, dimethyl ammonium bromide
Monium, dimethyl ammonium iodide, dimethyl fluoride
Ammonium, dimethyl ammonium nitrate, dimethyl sulfate
Ammonium, dimethyl ammonium hydrogen sulfate, phosphorus
Dimethyl ammonium acid, dimethyl ammonium carbonate,
Phenol dimethyl ammonium, dimethyl ammonium acetate
, Ammonium dimethylammonium adipate, alginic acid
Dimethyl ammonium, dimethyl ammonium benzoate
Dimethyl ammonium sulfate, dimethyl ammonium citrate
Monium, dimethyl ammonium formate, hydrogen carbonate
Ammonium, dimethyl ammonium phthalate, sari
Dimethyl ammonium citrate, dimethyl ammonium succinate
, Ammonium dimethylammonate, propion
Dimethyl ammonium, dimethyl ammonium butanoate
Dimethyl ammonium pentanoate, hexanoic acid
Tyl ammonium, dimethyl ammonium heptanoate,
Dimethyl ammonium octanoate, dimethyl ammonium nonanoate
Ammonium, dimethyl ammonium decanoate, oxalic acid
Dimethyl ammonium, dimethyl ammonium malonate
, Ammonium dimethylammonium sebacate, digallate
Methyl ammonium, dimethyl ammonium butyrate,
Dimethyl ammonium citrate, Dimethyl arachidonic acid
Ammonium, dimethylammonium shikimate, 2-ethyl
Dimethyl ammonium hexanoate, dimethyl oleate
Ammonium, dimethyl ammonium stearate,
Dimethyl ammonium linoleate, dimethyl linoleate
Luammonium, p-aminobenzoic acid dimethyl ammonium
, Ammonium dimethyl ammonium p-toluenesulfonate,
Dimethyl ammonium benzenesulfonate, monochloro
Dimethyl ammonium acetate, dimethyl dichloroacetate
Monium, dimethyl ammonium trichloroacetate, tri
Dimethyl ammonium fluoroacetate, dimethyl malonate
Ammonium, dimethyl ammonium sulfonate, fuma
Dimethyl ammonium oxalate, dimethyl ammonium tartrate
Dimethyl ammonium itaconate, dimesameconate
Thilammonium, dimethyl ammonium citraconic acid
Dimethyl ammonium malate, glutaric acid dimethyl
Ammonium, trimethylammonium hydroxide, chloride
Trimethylammonium, trimethylammonium bromide
System, trimethyl ammonium iodide, trimethyl ammonium fluoride
Ammonium, trimethylammonium nitrate, trime sulfate
Tyl ammonium, trimethyl ammonium hydrogen sulfate,
Trimethylammonium phosphate, trimethylammonium carbonate
, Phenoltrimethylammonium, triacetate
Methyl ammonium, trimethylammonium adipate
Trimethylammonium alginate, tribenzoic acid
Methyl ammonium, trimethyl ammonium sulfate,
Trimethylammonium formate, trimethylammonium formate
, Trimethyl ammonium bicarbonate, phthalic acid
Limethyl ammonium, trimethyl ammonium salicylate
And trimethylammonium succinate, maleate
Limethylammonium, trimethylammonium propionate
, Trimethylammonium butanoate, pentanoic acid
Trimethylammonium, trimethylammonium hexanoate
, Trimethylammonium heptanoate, octane
Ammonium trimethylammonate, trimethylammonium nonanoate
, Trimethylammonium decanoate, oxalate
Limethylammonium, trimethylan methyl malonate
Monium, trimethylammonium sebacate, gallic
Trimethylammonium, trimethylammonium butyrate
System, trimethylammonium melitate, arachidonic acid
Trimethyl ammonium, trimethyl ammonium shikimate
, Trimethylammonium 2-ethylhexanoate,
Trimethylammonium oleate, Tristearate
Methyl ammonium, trimethylammonium linoleate
Trimethylammonium linoleate, p-amino
Trimethylammonium benzoate, p-toluenesulfo
Trimethylammonium phosphate, tribenzenesulfonate
Methyl ammonium, trimethylammonium monochloroacetate
, Trimethylammonium dichloroacetate, Trik
Trimethylammonium loloacetate, trifluoroacetic acid
Limethylammonium, trimethylammonium malonate
Trimethylammonium sulfonate, trimethyl fumarate
Methyl ammonium, trimethyl ammonium tartrate,
Trimethylammonium itaconate, trime mesaconate
Thilammonium, trimethylammonium citraconic acid
, Trimethylammonium malate, triglutarate
Methyl ammonium; ethyl ammonium hydroxide, chloride
Ethyl ammonium, ethyl ammonium bromide, ethyl iodide
Tillammonium, ethylammonium fluoride, nitric acid
Tilammonium, ethylammonium sulfate, hydrogen sulfate
Ethyl ammonium, ethyl ammonium phosphate, carbonic acid
Ethyl ammonium, phenol ethyl ammonium,
Ethyl ammonium acetate, ethyl ammonium adipate
, Ethyl ammonium alginate, ethyl benzoate
Ammonium, ethyl ammonium sulfate, ethyl citrate
Ammonium, ethyl ammonium formate, hydrogen bicarbonate
Ammonium, ethyl ammonium phthalate, salicy
Ethyl ammonium oxalate, ethyl ammonium succinate
, Ethyl ammonium maleate, ethyl propionate
Ammonium, ethyl ammonium butanoate, penta
Ethyl ammonium phosphate, ethyl ammonium hexanoate
System, ethyl ammonium heptanoate, ethyl octanoate
Ammonium, ethyl ammonium nonanoate, decanoic acid
Ethyl ammonium, ethyl ammonium oxalate,
Ethyl ammonium tilmaronate, ethyl acetate sebacate
Ammonium, ethyl ammonium gallate, ethyl butyrate
Ammonium, ethyl ammonium melitate, arachi
Ethyl ammonium donate, ethyl ammonium shikimate
System, ethyl ammonium 2-ethylhexanoate, Olay
Ethyl ammonium, ethyl ammonium stearate
, Ethyl ammonium linoleate, linoleate
Tylammonium, ethyl ammonium p-aminobenzoate
, Ethyl ammonium p-toluenesulfonate,
Ethylammonium sulfonate, monochloroacetic acid
Ethyl ammonium, ethyl ammonium dichloroacetate
System, ethyl ammonium trichloroacetate, trifluoro
Ethyl ammonium acetate, ethyl ammonium malonate
System, ethyl ammonium sulfonate, ethyl ammonium fumarate
Ammonium, ethyl ammonium tartrate, itaconic acid
Tyl ammonium, ethyl ammonium mesaconate,
Ethyl ammonium traconic acid, ethyl ammonium malate
, Ethylammonium glutarate; diethyl hydroxide
Ammonium, diethylammonium chloride, diem bromide
Tilammonium, diethylammonium iodide, fluoride
Diethyl ammonium, diethyl ammonium nitrate, sulfuric acid
Ammonium diethyl sulfate, diethyl ammonium hydrogen sulfate
, Diethylammonium phosphate, diethylammonium carbonate
Phenol, diethylammonium, diethyl acetate
Ammonium, diethylammonium adipate,
Diethyl ammonium luginate, diethyl benzoate
Monium, diethylammonium sulfate, diethyl citrate
Luammonium, diethylammonium formate, hydrogen carbonate
Diethylammonium, diethylammonium phthalate
System, diethylammonium salicylate, diethyl succinate
Ammonium, diethylammonium maleate,
Diethylammonium lopionate, diethylabutanoate
Ammonium, diethyl ammonium pentanate, hexa
Diethyl ammonium phosphate, diethyl heptanoate
Ammonium, diethyl ammonium octoate, nonanoic acid di
Ethyl ammonium, diethyl ammonium decanoate,
Diethyl ammonium oxalate, methyl malonate
Ammonium, diethylammonium sebacate,
Diethylammonium succinate, diethylammonium butyrate
System, diethylammonium melitate, diarachidonic acid
Ethyl ammonium, diethyl ammonium shikimate,
Diethyl ammonium 2-ethylhexanoate, olein
Ammonium diethylate, diethylammonium stearate
, Diethylammonium linoleate, linolein
Ammonium diethylate, diethyl p-aminobenzoate
Ammonium, diethyl ammonium p-toluenesulfonate
Ammonium, diethylammonium benzenesulfonate,
Diethylammonium dichloroacetate
Thilammonium, diethylammonium trichloroacetate
System, diethylammonium trifluoroacetate, malonic acid
Diethyl ammonium, diethyl ammonium sulfonate
System, diethyl ammonium fumarate, diethyl ammonium tartrate
Ammonium, diethylammonium itaconate, mesaco
Ammonium diethylate, diethylanthrate citraconic acid
Monium, diethylammonium malate, glutaric acid
Diethylammonium; triethylammonium hydroxide
Triethylammonium chloride, triethylammonium bromide
Monium, triethylammonium iodide, trifluoride
Tyl ammonium, triethyl ammonium nitrate, sulfuric acid
Triethylammonium, triethylammonium hydrogen sulfate
, Triethylammonium phosphate, triethyl carbonate
Ammonium, phenol triethyl ammonium, vinegar
Triethylammonium, triethylammonium adipate
Monium, triethylammonium alginate, benzoic
Triethylammonium, triethylammonium sulfate
System, triethylammonium citrate, triethyl formate
Ammonium, triethylammonium bicarbonate, lid
Triethylammonium luate, triethyl ammonium salicylate
Ammonium, triethylammonium succinate, male
Triethylammonium, Triethylpropionate
Ammonium, triethylammonium butanoate, pen
Triethylammonium titanate, triethylhexanoate
Ammonium, triethylammonium heptanoate,
Triethylammonium butanoate, triethyl nonanoate
Ammonium, triethylammonium decanoate,
Triethylammonium oxalate, triethyl methylmalonate
Ammonium, triethylammonium sebacate,
Triethylammonium gallate, triethylanbutyrate
Monium, triethylammonium melitate, arachi
Triethyl ammonium donate, triethyl ammonium shikimate
Ammonium, triethylammonium 2-ethylhexanoate
, Triethylammonium oleate, stearin
Triethylammonium linoleate
Monium, triethylammonium linoleate, p-
Triethylammonium aminobenzoate, p-toluene
Triethylammonium sulfonate, benzene sulfone
Ammonium triethylate, triethyl monochloroacetate
Ammonium, triethylammonium dichloroacetate,
Triethylammonium trichloroacetate, trifluoro
Triethyl ammonium acetate, triethyl ammonium malonate
Monium, triethylammonium sulfonate, fumar
Ammonium triethylate, triethylammonium tartrate
, Triethylammonium itaconate, mesaconic acid
Triethyl ammonium, triethyl citrate
Monium, triethylammonium malate, glutar
Triethylammonium acid; tripropylammonium hydroxide
, Tripropylammonium chloride, Triprobromide
Pyrammonium, tripropylammonium iodide,
Tripropylammonium nitride, tripropylan nitrate
Monium, tripropylammonium sulfate, hydrogen sulfate
Lipropyl ammonium, tripropyl ammonium phosphate
, Tripropyl ammonium carbonate, phenol tri
Propyl ammonium, tripropyl ammonium acetate
, Tripropyl ammonium adipate, alginic acid
Tripropyl ammonium, tripropyl benzoate
Monium, tripropylammonium sulfate, citric acid
Lipropylammonium, tripropylammonium formate
Tripropyl ammonium bicarbonate, triphthalic phthalate
Propyl ammonium, tripropyl ammonium salicylate
, Tripropylammonium succinate, maleic
Ammonium tripropylate, tripropionate propionate
Ammonium, tripropylammonium butanoate,
Tripropylammonium pentanoate, trihexanoate
Propyl ammonium, tripropyl heptanoate
, Tripropylammonium octoate, nonane
Ammonium tripropylate, tripropyl ammonium decanoate
Ammonium, tripropylammonium oxalate, methyl
Tripropyl ammonium lumaronate, tri sebacate
Propyl ammonium, tripropyl ammonium gallate
, Tripropylammonium butyrate, trimeritate
Propyl ammonium, tripropyl arachidonic acid
Monium, tripropylammonium shikimate, 2-d
Tripropylammonium tylhexanoate, oleic acid
Tripropyl ammonium, tripropyl stearate
Ammonium, tripropylammonium linoleate,
Tripropyl ammonium linoleate, p-amino ammonium
Tripropyl ammonium benzoate, p-toluene sulfo
Ammonium tripropylate, benzenesulfonic acid
Lipropyl ammonium, tripropyl monochloroacetate
Ammonium, tripropylammonium dichloroacetate
System, tripropylammonium trichloroacetate, torif
Tripropylammonium fluoroacetate, triplon malonate
Ropylammonium, tripropylammonium sulfonate
, Tripropylammonium fumarate, tritartrate
Propyl ammonium, tripropylammonate itaconate
, Tripropylammonium mesaconate, citrus
Tripropyl ammonium conate, tripropyl malate
Luammonium, tripropylammonium glutarate
Tributyl ammonium hydroxide, tributyl ammonium chloride
Ammonium, tributylammonium bromide, trib iodide
Tyl ammonium, tributyl ammonium fluoride, nitrate
Ammonium tributylate, ammonium tributyl sulfate
System, tributylammonium hydrogen sulfate, tributyl phosphate
Ammonium, tributylammonium carbonate, pheno
Tributylammonium, tributylammonium acetate
, Tributylammonium adipate, alginic acid
Tributyl ammonium, tributyl ammonium benzoate
, Tributylammonium sulfate, Tributyl citrate
Luammonium, tributylammonium formate, carbonated water
Tributyl ammonium hydrogen, tributyl ammonium phthalate
, Tributylammonium salicylate, succinic acid
Tributyl ammonium, tributyl ammonium maleate
, Tributylammonium propionate, butane
Ammonium tributylate, tributyl ammonium pentanate
Monium, tributylammonium hexanoate, hepta
Tributyl ammonium octoate, tributyl ammonium octoate
Ammonium, tributylammonium nonanoate, decane
Tributyl ammonium oxalate, tributyl ammonium oxalate
, Tributylammonium methylmalonate, SEVA
Tributyl ammonium succinate, tributyl ammonium gallate
Ammonium, tributylammonium butyrate, melitic acid
Tributylammonium, tributylan arachidonic acid
Monium, tributylammonium shikimate, 2-ethyl
Tributylammonium hexanoate, trioleate
Butyl ammonium, tributyl ammonium stearate
, Tributylammonium linoleate, linolein
Ammonium tributyl, tri-p-aminobenzoate
Tyl ammonium, tributyl p-toluenesulfonate
Ammonium, tributylammonium benzenesulfonate
, Tributyl ammonium monochloroacetate, dichloromethane
Tributylammonium roacetate, Trib trichloroacetate
Thilammonium, tributylammonium trifluoroacetate
, Tributylammonium malonate, sulfonic acid
Tributyl ammonium, tributyl ammonium fumarate
, Tributylammonium tartrate, triitaconate
Butyl ammonium, tributyl ammonium mesaconate
System, tributylammonium citraconic acid, malic acid
Libutyl ammonium, tributyl ammonium glutarate
Um; tetramethylammonium hydroxide, tetramethyl chloride
Tyl ammonium, tetramethyl ammonium bromide, iodine
Tetramethylammonium fluoride, tetramethylammonium fluoride
Monium, tetramethylammonium nitrate, tetrasulfate
Methyl ammonium, tetramethylammonium hydrogen sulfate
System, tetramethylammonium phosphate, tetramethyl carbonate
Luammonium, phenol tetramethylammonium
System, tetramethylammonium acetate, tetraadipate
Methyl ammonium, tetramethylammonium alginate
, Tetramethylammonium benzoate, tetrasulfate
Methyl ammonium, tetramethyl ammonium citrate
Tetramethylammonium formate, hydrogen carbonate
Tylammonium, tetramethylammonium phthalate
Tetramethylammonium salicylate,
Tramethylammonium, tetramethylan maleate
Monium, tetramethylammonium propionate,
Tetramethylammonium tannate, tetramepentanoate
Thilammonium, tetramethylammonium hexanoate
System, tetramethylammonium heptanoate, octanoic acid
Tetramethyl ammonium, tetramethyl ammonium nonanoate
Monium, Tetramethylammonium decanoate, Shu
Ammonium tetramethylammonate, tetramethyl methylmalonate
Thilammonium, tetramethylammonium sebacate
Tetramethylammonium gallate, tetrame butyrate
Thilammonium, tetramethylammonium melitate
System, tetramethylammonium arachidonic acid, shikimic acid
Tetramethylammonium, 2-ethylhexanoic acid tet
Lamethylammonium, tetramethylammonium oleate
, Tetramethylammonium stearate, Reno
Tetramethylammonium oleate, Tetralinoleate
Methyl ammonium, tetramethyl p-aminobenzoate
Ammonium, tetramethyl ammonium p-toluenesulfonate
Ammonium, benzenesulfonic acid tetramethylammonium
Ium, tetramethylammonium monochloroacetate, dik
Tetramethyl ammonium roloacetate, trichloroacetic acid
Tramethylammonium, tetramethyl trifluoroacetate
Ammonium, tetramethylammonium malonate,
Tetramethyl ammonium sulfonate, tetra fumarate
Methyl ammonium, tetramethylammonium tartrate
, Tetramethylammonium itaconate, mesaconic acid
Tetramethyl ammonium, tetramethyl citraconic acid
Ammonium, tetramethylammonium malate,
Tetramethylammonium rutharate; Tetraethyl hydroxide
Ammonium, tetraethylammonium chloride, bromide
Tetraethylammonium, tetraethylammonium iodide
, Tetraethylammonium fluoride, tetraethyl nitrate
Tillammonium, tetraethylammonium sulfate, sulfuric acid
Tetraethylammonium hydrogen acid, tetraethyl phosphate
Ammonium, tetraethylammonium carbonate, pheno
Tetraethylammonium, tetraethylammonium acetate
Monium, tetraethylammonium adipate, aluminum
Tetraethylammonium formate, tetraethyl benzoate
Ammonium, tetraethylammonium sulfate, que
Tetraethylammonium formate, tetraethylammonium formate
Monium, tetraethylammonium bicarbonate, phthalate
Ammonium tetraethyl salicylate
Ammonium, tetraethylammonium succinate,
Tetraethylammonium oleate, Tetopropionate
Laethyl ammonium, tetraethyl ammonium butanoate
, Tetraethylammonium pentanoate, hexane
Ammonium tetraethyl, tetraethyl heptanoate
Ammonium, tetraethylammonium octoate,
Tetraethylammonium nonanoate, Tetraethyl decanoate
Tylammonium, tetraethylammonium oxalate
System, tetraethylammonium methylmalonate, SEBASHI
Tetraethylammonium acid, tetraethyl gallate
Ammonium, tetraethylammonium butyrate,
Tetraethylammonium tomate, arachidonic acid tetraet
Thilammonium, tetraethylammonium shikimate
Tetraethylammonium 2-ethylhexanoate,
Tetraethylammonium oleate, Te stearate
Traethylammonium, tetraethylanole linoleate
Monium, tetraethylammonium linoleate, p
Tetraethylammonium aminobenzoate, p-toluene
Tetraethylammonium enesulfonate, benzenes
Tetraethylammonium sulfonate, monochloroacetic acid
Traethylammonium, tetraethyl acetate dichloroacetate
Ammonium, tetraethylammonium trichloroacetate
System, tetraethylammonium trifluoroacetate, malo
Ammonium tetraethylammonium, sulfonic acid tetraethyl
Ammonium, tetraethylammonium fumarate,
Tetraethylammonium tartrate, tetraethyl itaconate
Thilammonium, tetraethylammonium mesaconate
System, tetraethylammonium citraconic acid, malic acid
Tetraethyl ammonium, tetraethyl glutarate
Ammonium; tetrapropylammonium hydroxide, chloride
Tetrapropylammonium, tetrapropylanbromide
Monium, tetrapropylammonium iodide,
Trapropylammonium, tetrapropylammonium nitrate
Ammonium, tetrapropylammonium sulfate, hydrogen sulfate
Trapropylammonium, tetrapropylan phosphate
Monium, tetrapropylammonium carbonate, phenol
Tetrapropyl ammonium, tetrapropyl ammonium acetate
Ammonium, tetrapropylammonium adipate,
Tetrapropylammonium alginate, Tetobenzoate
Lapropyl ammonium, tetrapropyl ammonium sulfate
, Tetrapropyl ammonium citrate, tet
Lapropylammonium, tetrapropylan bicarbonate
Monium, tetrapropylammonium phthalate, sari
Tetrapropyl ammonium citrate, tetrap succinate
Ropylammonium, tetrapropylammonate maleate
, Tetrapropylammonium propionate,
Tetrapropylammonium tannate, tetrapentanoate
Propyl ammonium, tetrapropylan hexanoate
Monium, tetrapropylammonium heptanoate,
Tetrapropylammonium butanoate, tetranonanoate
Propyl ammonium, tetrapropyl ammonium decanoate
Ium, tetrapropylammonium oxalate, methyl
Tetrapropylammonium malonate, tetose sebacate
Lapropylammonium, tetrapropylan gallate
Monium, tetrapropyl ammonium butyrate, benefits
Ammonium tetraacrylate, tetrap arachidonic acid
Ropylammonium, tetrapropylammonium shikimate
Um, tetrapropylammonium 2-ethylhexanoate
System, tetrapropylammonium oleate, stearyl
Ammonium tetrapropylate, tetrap linoleate
Ropylammonium, tetrapropyl linoleate
Monium, tetrapropylammonium p-aminobenzoate
And p-toluenesulfonic acid tetrapropyl ammonium
Ium, tetrapropylammonium benzenesulfonate
System, tetrapropylammonium monochloroacetate, dik
Tetrapropylammonium loroacetate, trichloroacetic acid
Tetrapropylammonium, tetratrifluoroacetate
Propylammonium, tetrapropylammonate malonate
, Tetrapropylammonium sulfonate, Fuma
Tetrapropylammonium luate, tetrapropyl tartrate
Luammonium, tetrapropylammonium itaconate
, Tetrapropylammonium mesaconate, citraco
Ammonium tetrapropylate, tetrapromalate
Pyrammonium, tetrapropylammonium glutarate
: Tetrabutylammonium hydroxide, Tetrabu chloride
Tyl ammonium, tetrabutyl ammonium bromide, iodine
Tetrabutylammonium fluoride, tetrabutylammonium fluoride
Monium, tetrabutylammonium nitrate, tetrasulfate
Butyl ammonium, tetrabutylammonium hydrogen sulfate
System, tetrabutylammonium phosphate, tetrabutyl carbonate
Luammonium, phenol tetrabutylammonium
Tetrabutylammonium acetate, tetraadipate
Butylammonium, tetrabutylammonium alginate
, Tetrabutylammonium benzoate, tetrasulfate
Butyl ammonium, tetrabutyl ammonium citrate
, Tetrabutylammonium formate, tetrabu bicarbonate
Tylammonium, tetrabutylammonium phthalate
Tetrabutylammonium salicylate,
Trabutylammonium, tetrabutylan maleate
Monium, tetrabutylammonium propionate,
Tetrabutylammonium tannate, tetrabupentanoate
Thilammonium, tetrabutylammonium hexanoate
System, tetrabutylammonium heptanoate, octanoic acid
Tetrabutylammonium, tetrabutylannonate
Monium, Tetrabutylammonium decanoate, Shu
Ammonium tetrabutylate, tetramale methyl malonate
Thilammonium, tetrabutylammonium sebacate
Tetrabutylammonium gallate, tetrabutyrate
Thilammonium, tetrabutylammonium melitate
System, tetrabutylammonium arachidonic acid, shikimic acid
Tetrabutylammonium, 2-ethylhexanoic acid tet
Labutylammonium, tetrabutylammonium oleate
, Tetrabutylammonium stearate, Reno
Tetrabutylammonium oleate, tetralinoleate
Butyl ammonium, tetrabutyl p-aminobenzoate
Ammonium, tetrabutyl toluene p-toluenesulfonate
Nummonium, tetrabutylammonium benzenesulfonate
Ium, tetrabutylammonium monochloroacetate, dik
Tetrabutylammonium roloacetate, tetrachloroacetate
Trabutylammonium, tetrabutyl acetate trifluoroacetate
Ammonium, tetrabutylammonium malonate,
Tetrabutyl ammonium sulfonate, tetra fumarate
Butyl ammonium, tetrabutylammonium tartrate
System, tetrabutyl ammonium itaconate, mesaconic acid
Tetrabutylammonium, tetrabutyl citrate
Ammonium, tetrabutylammonium malate,
Tetrabutylammonium rutalate; trimethyl hydroxide
Benzyl ammonium, trimethylbenzylammonium chloride
, Trimethylbenzylammonium bromide, iodide
Limethylbenzylammonium, trimethylbenfluoride
Zylammonium, trimethylbenzylammonium nitrate
System, trimethylbenzyl ammonium sulfate, hydrogen sulfate
Limethylbenzylammonium, trimethylbenphosphate
Zylammonium, trimethylbenzylammonium carbonate
Phenol, trimethylbenzylammonium, acetic acid
Trimethylbenzylammonium, trimethyl adipate
Rubenzyl ammonium, trimethyl benzyl alginate
Luammonium, trimethylbenzylammonium benzoate
, Trimethylbenzylammonium sulfate, citric acid
Trimethylbenzylammonium, trimethylbenformate
Zylammonium, trimethylbenzylammonium hydrogen carbonate
, Trimethylbenzylammonium phthalate
Trimethylbenzylammonium lithate, succinate
Limethylbenzyl ammonium, trimethyl maleate
Benzyl ammonium, trimethylbenzene propionate
Luammonium, trimethylbenzyl ammonium butanoate
And trimethylbenzylammonium pentanoate,
Trimethylbenzyl ammonium xanate, heptanoic acid
Trimethylbenzyl ammonium, trimethyl octanoate
Rubenzyl ammonium, trimethylbenzyl nonanoate
Ammonium, trimethylbenzylammonium decanoate
Trimethylbenzyl ammonium oxalate, methyl
Trimethylbenzyl ammonium malonate, sebacic acid
Trimethylbenzyl ammonium, trimethyl gallate
Benzyl ammonium, trimethylbenzyl ammonium butyrate
, Trimethylbenzylammonium melitate,
Trimethylbenzyl ammonium arachidonic acid, shikimi
Trimethylbenzylammonium acid, 2-ethylhexa
Trimethylbenzylammonium phosphate, trioleate
Methylbenzylammonium, trimethyl stearate
Benzyl ammonium, trimethylbenzyl linoleate
Ammonium, trimethylbenzylammonium linoleate
Ium, trimethylbenzylammonium p-aminobenzoate
And p-toluenesulfonate trimethylbenzyl acetate
Ammonium, trimethylbenzyl benzenesulfonate
Nmonium, trimethylbenzylammonium monochloroacetate
And trimethylbenzylammonium dichloroacetate
Trimethylbenzylammonium trichloroacetate,
Trimethylbenzylammonium trifluoroacetate
Trimethylbenzylammonium lonate, sulfonate
Limethylbenzylammonium, trimethylbefumarate
Ammonium diammonium, trimethylbenzylammonium tartrate
, Trimethylbenzylammonium itaconate,
Trimethylbenzyl ammonium mesaconate, Citraco
Trimethylbenzyl ammonium phosphate, Trime malate
Tylbenzyl ammonium, trimethylben glutarate
Diammonium;

[0026] Ethanol ammonium hydroxide, ethanol ammonium chloride, ethanol ammonium bromide, ethanol ammonium iodide, ethanol ammonium fluoride, ethanol ammonium nitrate, ethanol ammonium sulfate, ethanol ammonium hydrogen sulfate, ethanol ammonium phosphate, ethanol ammonium carbonate, phenol Ethanol ammonium, ethanol ammonium acetate, ethanol ammonium adipate,
Ethanolammonium alginate, ethanolammonium benzoate, ethanolammonium sulfate, ethanolammonium citrate, ethanolammonium formate, ethanolammonium hydrogen carbonate, ethanolammonium phthalate, ethanolammonium salicylate, ethanolammonium succinate, ethanolammonium maleate, ethanolammonium propionate Ethanolammonium butanoate, ethanolammonium pentanoate, ethanolammonium hexanoate, ethanolammonium heptanoate, ethanolammonium octoate, ethanolammonium nonanoate, ethanolammonium decanoate, ethanolammonium oxalate, ethanolammonium methylmalonate, sebacic acid Ethanol ammonium, ethanol ammonium gallic acid, butyric acid ethanol ammonium, mellitic acid ethanol ammonium, ethanol ammonium arachidonic acid, ethanol ammonium shikimic acid, 2-ethylhexanoic acid in ethanol ammonium,
Ethanolammonium oleate, ethanolammonium stearate, ethanolammonium linoleate, ethanolammonium linoleate, ethanolammonium p-aminobenzoate, ethanolammonium p-toluenesulfonate, ethanolammonium benzenesulfonate, ethanolammonium monochloroacetate, ethanol dichloroacetate Ammonium, ethanol ammonium trichloroacetate, ethanol ammonium trifluoroacetate, ethanol ammonium malonate, ethanol ammonium sulfonate, ethanol ammonium fumarate, ethanol ammonium tartrate,
Ethanolammonium itaconic acid, ethanolammonate mesaconate, ethanolammonium citraconic acid, ethanolammonium malate, ethanolammonium glutarate; diethanolammonium hydroxide, diethanolammonium chloride, diethanolammonium bromide, diethanolammonium iodide, diethanolammonium fluoride, nitric acid nitrate Diethanol ammonium, diethanol ammonium sulfate, diethanol ammonium hydrogen sulfate, diethanol ammonium phosphate, diethanol ammonium carbonate, phenol diethanol ammonium, diethanol ammonium acetate,
Diethanol ammonium adipate, diethanol ammonium alginate, diethanol ammonium benzoate, diethanol ammonium sulfate, diethanol ammonium citrate, diethanol ammonium formate,
Diethanol ammonium bicarbonate, diethanol ammonium phthalate, diethanol ammonium salicylate, diethanol ammonium succinate, diethanol ammonium maleate, diethanol ammonium propionate, diethanol ammonium butanoate, diethanol ammonium pentanoate, diethanol ammonium hexanoate, diethanol ammonium heptanoate, octane Ammonium diethanolate, diethanolammonium nonanoate, diethanolammonium decanoate, diethanolammonium oxalate, diethanolammonium methylmalonate, diethanolammonium sebacate, diethanolammonium gallate, diethanolammonium butyrate, diethanolammonium melitate Diethanol ammonium arachidonic acid, diethanol ammonium shikimate, diethanol ammonium 2-ethylhexanoate, diethanol ammonium oleate, diethanol ammonium stearate, diethanol ammonium linoleate, diethanol ammonium linoleate, diethanol ammonium p-aminobenzoate, p-toluene sulfone Ammonium diethanolate, diethanolammonium benzenesulfonate, diethanolammonium monochloroacetate, diethanolammonium dichloroacetate,
Diethanolammonium trichloroacetate, diethanolammonium trifluoroacetate, diethanolammonium malonate, diethanolammonium sulfonate, diethanolammonium fumarate, diethanolammonium tartrate, diethanolammonium itaconate, diethanolammonium mesaconate, diethanolammonium citraconic acid, diethanolammonium malate, Diethanol ammonium glutarate;
Triethanol ammonium hydroxide, triethanol ammonium chloride, triethanol ammonium bromide, triethanol ammonium iodide, triethanol ammonium fluoride, triethanol ammonium nitrate, triethanol ammonium sulfate, triethanol ammonium hydrogen sulfate, triethanol ammonium phosphate , Triethanol ammonium carbonate, phenol triethanol ammonium, triethanol ammonium acetate,
Triethanol ammonium adipate, triethanol ammonium alginate, triethanol ammonium benzoate, triethanol ammonium sulfate, triethanol ammonium citrate, triethanol ammonium formate, triethanol ammonium bicarbonate, triethanol ammonium phthalate, triethanol ammonium salicylate, Triethanol ammonium succinate, triethanol ammonium maleate, triethanol ammonium propionate, triethanol ammonium butanoate, triethanol ammonium pentanoate, triethanol ammonium hexanoate, triethanol ammonium heptanoate, triethanol ammonium octanoate, nonanoic acid Triethanol ammonium, decane Triethanol ammonium, triethanol ammonium oxalate, triethanol ammonium methyl malonate, triethanol ammonium sebacate, triethanol ammonium gallate, triethanol ammonium butyrate, triethanol ammonium melitate, triethanol ammonium arachidonic acid, triethanol shikimate Ammonium, triethanolammonium 2-ethylhexanoate, triethanolammonium oleate, triethanolammonium stearate, triethanolammonium linoleate, triethanolammonium linoleate, p
-Triethanolammonium aminobenzoate, triethanolammonium p-toluenesulfonate, triethanolammonium benzenesulfonate, triethanolammonium monochloroacetate, triethanolammonium dichloroacetate, triethanolammonium trichloroacetate, triethanolammonium trifluoroacetate, malon Triethanol ammonium sulfonic acid, triethanol ammonium sulfonic acid, triethanol ammonium fumarate, triethanol ammonium tartrate, triethanol ammonium itaconate, triethanol ammonium mesaconate, triethanol ammonium citraconic acid, triethanol ammonium malate, triethanol glutarate Ammonium;

As the compound represented by the general formula (5),
Pyridinium hydroxide, pyridinium chloride, pyridinium bromide, pyridinium iodide, pyridinium fluoride, pyridinium nitrate, pyridinium sulfate, pyridinium hydrogen sulfate, pyridinium phosphate, pyridinium carbonate, phenol pyridinium, pyridinium acetate, pyridinium adipate, pyridinium alginate, benzoic acid Pyridinium phosphate, pyridinium sulfate, pyridinium citrate, pyridinium formate, pyridinium hydrogencarbonate, pyridinium phthalate, pyridinium salicylate, pyridinium succinate, pyridinium maleate, pyridinium propionate, pyridinium butanoate, pyridinium pentanate,
Pyridinium hexanoate, pyridinium heptanoate, pyridinium octanoate, pyridinium nonanoate, pyridinium decanoate, pyridinium oxalate, methylmalonate, pyridinium sebacate, pyridinium gallate, pyridinium butyrate, pyridinium melitate, pyridinium arachidonate, shikimic acid Pyridinium, pyridinium 2-ethylhexanoate, pyridinium oleate, pyridinium stearate, pyridinium linoleate, pyridinium linoleate, pyridinium p-aminobenzoate, pyridinium p-toluenesulfonate, pyridinium benzenesulfonate, pyridinium monochloroacetate, dichloroacetic acid Pyridinium, pyridinium trichloroacetate, pyridinium trifluoroacetate,
Pyridinium malonate, pyridinium sulfonate, pyridinium fumarate, pyridinium tartrate, pyridinium itaconate, pyridinium mesaconate, pyridinium citraconic acid, pyridinium malate, pyridinium glutarate; quinolinium hydroxide, quinolinium chloride, quinolinium bromide, quinolinium iodide, Quinolinium fluoride, quinolinium nitrate, quinolinium sulfate, quinolinium hydrogen sulfate, quinolinium phosphate, quinolinium carbonate,
Phenolquinolinium, quinolinium acetate, quinolinium adipate, quinolinium alginate, quinolinium benzoate, quinolinium sulfate, quinolinium citrate, quinolinium formate, quinolinium hydrogen carbonate, quinolinium phthalate, quinolinium salicylate, quinolinium succinate, quinolinium maleate, quinolinium maleate Quinolinium, quinolinium butanoate, quinolinium pentanoate, quinolinium hexanoate, quinolinium heptanoate, quinolinium octanoate, quinolinium nonanoate, quinolinium decanoate, quinolinium oxalate, quinolinium methylmalonate, quinolinium sebacate,
Quinolinium gallate, quinolinium butyrate, quinolinium melitate, quinolinium arachidonic acid, quinolinium shikimate, quinolinium 2-ethylhexanoate, quinolinium oleate, quinolinium stearate, quinolinium linoleate, quinolinium linoleate, p-
Quinolinium aminobenzoate, quinolinium p-toluenesulfonate, quinolinium benzenesulfonate, quinolinium monochloroacetate, quinolinium dichloroacetate,
Quinolinium trichloroacetate, quinolinium trifluoroacetate, quinolinium malonate, quinolinium sulfonate, quinolinium fumarate, quinolinium tartrate, quinolinium itaconate, quinolinium mesaconate, quinolinium citraconic acid, quinolinium malate, quinolinium glutarate; piperidinium hydroxide; , Piperidinium bromide, piperidinium iodide, piperidinium fluoride, piperidinium nitrate, piperidinium sulfate, piperidinium hydrogen sulfate, piperidinium phosphate, piperidinium carbonate, phenol piperidinium, piperidinium acetate, piperidinium adipate,
Piperidinium alginate, piperidinium benzoate,
Piperidinium sulfate, piperidinium citrate, piperidinium formate, piperidinium hydrogen carbonate, piperidinium phthalate, piperidinium salicylate, piperidinium succinate, piperidinium maleate, piperidinium propionate, piperidinium butanoate, piperidinium pentanoate, piperidinium hexanoate, heptanepiperium Piperidinium acid, piperidinium nonanoate, piperidinium decanoate, piperidinium oxalate, piperidinium methylmalonate, piperidinium sebacate, piperidinium gallate, piperidinium butyrate, piperidinium meritate, piperidinium arachidonic acid, piperidinium shikimate, piperidinium 2-ethylhexanoate Piperidinium oleate, stearin Piperidinium, piperidinium linoleate, piperidinium linoleate, piperidinium p-aminobenzoate, piperidinium p-toluenesulfonate, piperidinium benzenesulfonate, piperidinium monochloroacetate, piperidinium dichloroacetate, piperidinium trichloroacetate, piperidinium trifluoroacetate, piperidinium malonate, Piperidinium sulfonate, piperidinium fumarate, piperidinium tartrate, piperidinium itaconate, piperidinium mesaconate, piperidinium citraconic acid, piperidinium malate, piperidinium glutarate; piperazinium hydroxide, piperazinium chloride, piperazinium bromide, piperazinium iodide, piperazinium fluoride, Piperazinium nitrate, piperazinium sulfate Bisulfate piperazinium, piperazinium phosphoric acid, carbonic piperazinium, phenol piperazinium, acetic piperazinium,
Piperazinium adipate, piperazinium alginate, piperazinium benzoate, piperazinium sulphate, piperazinium citrate, piperazinium formate, piperazinium hydrogen carbonate, piperazinium phthalate, piperazinium salicylate, piperazinium succinate, piperazinium succinate, piperazinium piperazine Piperazinium, piperazinium hexanoate, piperazinium heptanoate, piperazinium octoate, piperazinium nonanoate, piperazinium decanoate, piperazinium oxalate, piperazinium methylmalonate, piperazinium sebacate,
Piperazinium gallate, piperazinium butyrate, piperazinium melitate, piperazinium arachidonic acid, piperazinium shikimate, piperazinium 2-ethylhexanoate, piperazinium oleate, piperazinium stearate, piperazinium linoleate, piperazinium linoleate, p-perazinium benzoate
Piperazinium p-toluenesulfonate, piperazinium benzenesulfonate, piperazinium monochloroacetate, piperazinium dichloroacetate, piperazinium trichloroacetate, piperazinium trifluoroacetate, piperazinium malonate, piperazinium sulfonate, piperazinium fumarate, piperazinium tartrate, itaconipemateronate, itaconate piradiconium Piperazinium, piperazinium citraconic acid, piperazinium malate, piperazinium glutarate; diazabicyclooctane hydrochloride,
Diazabicyclooctane bromate, diazabicyclooctane nitrate, diazabicyclooctane sulfate, diazabicyclooctane hydrogen sulfate, diazabicyclooctane carbonate, diazabicyclooctane hydrogen carbonate, diazabicyclooctane acetate , Diazabicyclooctane maleate, diazabicyclooctane phthalate, diazabicyclooctane oxalate, diazabicyclooctane itaconate, diazabicyclooctane malonate, diazabicyclooctane formate, diaza Bicyclooctane butyrate, diazabicyclooctane malate, diazabicyclononane hydrochloride, diazabicyclononane bromide, diazabicyclononane nitrate, diazabicyclononane sulfate,
Diazabicyclononane hydrogen sulfate, diazabicyclononane carbonate, diazabicyclononane hydrogen carbonate, diazabicyclononane acetate, diazabicyclononane maleate, diazabicyclononane phthalate, diazabicyclononane Oxalate, diazabicyclononane itaconate, diazabicyclononane malonate, diazabicyclononanate, diazabicyclononane butyrate, diazabicyclononane malate, diazabicycloundecene hydrochloride, Diazabicycloundecene hydrobromide, diazabicycloundecene nitrate, diazabicycloundecene sulfate, diazabicycloundecene hydrogen sulfate, diazabicycloundecene carbonate, diazabicycloundecene hydrogencarbonate, Diazabicycloundecene acetate, diazabicycloundecene maleate Salt, diazabicycloundecene phthalate, diazabicycloundecene Senshu salt,
Examples thereof include diazabicycloundecene itaconate, diazabicycloundecene malonate, diazabicycloundecene formate, diazabicycloundecene butyrate, and diazabicycloundecene malate. Among them, preferred examples include a nitrogen hydroxide onium salt compound and a nitrogen carboxylate onium salt compound, and an ammonium hydroxide compound and an ammonium carboxylate compound are particularly preferred. These components (B)
One type or two or more types may be used simultaneously.

The amount of the component (B) used in the film-forming composition is 0.0001 to 5 parts by weight, more preferably 100 parts by weight (in terms of a completely hydrolyzed condensate) of the component (A). 0.0002 to 2 parts by weight. If the amount of the component (B) is less than 0.0001 part by weight, the coating may have insufficient crack resistance, and if it exceeds 5 parts by weight, the storage stability of the solution may be poor.

(C) Solvent The film-forming composition of the present invention comprises the component (A) and the component (B), usually (C) a solvent represented by the following general formula (4): R ¹⁵ O (R ¹⁷ 0) _g R ¹⁶ (4) (R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a monovalent organic group selected from CH ₃ CO—. R ¹⁷ represents an alkylene group, and g represents an integer of 1 to 2.). In the general formula (4), the alkyl group of R ¹⁵ and R ¹⁶ is a methyl group, an ethyl group, an n-propyl group, an I-propyl group, a butyl group and the like, and the alkylene group of R ¹⁷ is an ethylene group, n- Examples thereof include a propylene group and an isopropylene group. Specific examples of the solvent represented by the general formula (4) include propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene Glycol diacetate, dipropylene glycol diacetate, propylene glycol; ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol diacetate, ethylene glycol, etc. In particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate are preferable. These can be used alone or in combination of two or more.

The film-forming composition of the present invention may further contain the following organic solvent in addition to the solvent represented by the general formula (4).

As the organic solvent used in the present invention, for example, n-pentane, i-pentane, n-hexane, i-pentane
Hexane, n-heptane, i-heptane, 2,2,4-
Aliphatic hydrocarbon solvents such as trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene,
Aromatic hydrocarbon solvents such as n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene and trimethylbenzene; acetone, methylethylketone, 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, Ketone solvents such as cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-butyl Ether, n- hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-
Methyl dioxolane, dioxane, dimethyl dioxane, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethoxytriglycol, tetraethylene glycol di-n-
Ether solvents such as butyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; 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, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-oxalate Ester solvents such as -butyl, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide; N-diethylformamide,
Acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-
Nitrogen-containing solvents such as methylpyrrolidone; dimethyl sulfide,
Diethyl sulfide, thiophene, tetrahydrothiophene,
Examples thereof include sulfur-containing solvents such as dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These can be used alone or in combination of two or more.

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.

As the β-diketone, acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- 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 in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 nm, preferably 10 to 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. 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 polyoxyethylene 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.), Florad FC-430, and FC-431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, SC-103, SC-104, SC-1
05, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-10
00, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15
(Neos Co., Ltd.) and other commercially available fluorosurfactants. Among them, the above MegaFac F172, BM-1000, BM-11
00, NBX-15 is particularly preferred.

As the silicone surfactant, for example, SH7PA, SH21PA, SH30PA, ST94P
A (All are Dow Corning Toray Silicone Co., Ltd.)
And the like can be used. Among them, the above S
H28PA and SH30PA are particularly preferred. The amount of the surfactant to be used is generally 0.0001 to 10 parts by weight relative to the component (A) (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 isobutyryl peroxide, α, α'bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate and 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 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 film thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The adjustment of the total solid concentration is performed by concentration and dilution with the above (C) organic solvent, if necessary.

When the composition of the present invention is applied to a silicon wafer, Si
When coating on 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 as a dry film thickness, and a coating film with a thickness of about 0.1 to 5.0 μm in a double coating can be formed. . Then, it is dried at room temperature or at a temperature of about 80 to 600 ° C., usually for 5 to 240
By heating and drying for about a minute, 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. Furthermore, 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 can be fired for a short time, has excellent crack resistance, and has a low temperature dependence of the relative dielectric constant.
Interlayer insulating films and etching stopper films for semiconductor devices such as DRAM, SDRAM, RDRAM, and D-RDRAM, protective films such as surface coat films for semiconductor devices, intermediate layers in a 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.

[0045]

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 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) under the following conditions. Sample: Prepared by dissolving 1 g of a hydrolyzed condensate in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical Co., USA was used. Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, USA Column: SHOdex A-80M manufactured by Showa Denko KK
(Length 50cm) Measurement temperature: 40 ° C Flow rate: 1cc / min

The relative dielectric constant of the temperature-dependent 8-inch silicon on the wafer is coated with a composition sample by spin coating, 3 minutes at 90 ° C. on a hot plate for 3 minutes substrate in a nitrogen atmosphere 200 ° C. and dried The substrate was further baked on a hot plate at 420 ° C. in a nitrogen atmosphere for 10 minutes. 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 at room temperature and 200 ° C. was measured by a CV method using a 1B electrode and an HP4284A precision LCR meter.

[0048] cracking resistance 8-inch silicon on the wafer is coated with a composition sample by spin coating, 3 minutes at 90 ° C. on a hot plate for 3 minutes substrate in a nitrogen atmosphere 200 ° C. and dried, further 420 ° C. The substrate was baked on a hot plate in a nitrogen atmosphere for 10 minutes. At this time, the thickness of the coating film was 1.4 μm. A part of the obtained coating film was scratched with a knife and immersed in pure water for 52 hours. Observe the knife scar in the coating film with a microscope,
Evaluation was made according to the following criteria. ：: No crack propagation was observed. ×: Propagation of cracks observed

Synthesis Example 1 In a quartz separable flask, 205.50 g of distilled methyltrimethoxysilane and distilled tetramethoxysilane 8 were added.
After dissolving 5.51 g in 426 g of distilled propylene glycol monoethyl ether, the solution was stirred with a three-one motor and stabilized at a solution temperature of 60 ° C. Next, ion-exchanged water 18 in which 0.013 g of maleic anhydride was dissolved.
2 g was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, the reaction solution was cooled to room temperature. 5
At 0 ° C., 360 g of a solution containing methanol was removed from the reaction solution by evaporation to obtain a reaction solution. The weight average molecular weight of the condensate and the like thus obtained was 1,000.

Example 1 To 100 g of the reaction solution obtained in Synthesis Example 1, 0.002 g of tributylammonium hydroxide was added and sufficiently stirred. This solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a film-forming composition of the present invention. The obtained composition was applied on a silicon wafer by spin coating. The relative dielectric constant of the coating at room temperature is 2.83, 200 ° C
Was 2.75, and the temperature dependence of the relative dielectric constant was a small value. No crack propagation was observed even when the coating film was immersed in water.

Example 2 Evaluation was performed in the same manner as in Example 1 except that the reaction solution shown in Table 1 and the component (B) were used. The evaluation results are also shown in Table 1.

[0052]

[Table 1]

Comparative Example 1 The coating film was evaluated in the same manner as in Example 1 except that only the reaction solution obtained in Synthesis Example 1 was used. The relative dielectric constant of the coating at room temperature is 3.10, and the relative dielectric constant at 200 ° C. is 2.85.
And the temperature dependence of the relative permittivity was recognized. Further, when the coating film was immersed in water, propagation of cracks was observed.

Comparative Example 2 A coating film was evaluated in the same manner as in Example 1 except that only the reaction solution obtained in Synthesis Example 2 was used. The relative dielectric constant of the coating at room temperature is 3.18, and the relative dielectric constant at 200 ° C. is 2.86.
And the temperature dependence of the relative permittivity was recognized. Further, when the coating film was immersed in water, propagation of cracks was observed.

[0055]

According to the present invention, by using a film-forming composition containing an alkoxysilane hydrolyzed polymer, a nitrogen onium salt compound, and a specific glycol-based solvent, short-time calcination is possible, It is possible to provide a film-forming composition (material for an interlayer insulating film) which is excellent in crack resistance and in which the relative dielectric constant is less dependent on temperature.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kinji Yamada 2-11-24 Tsukiji, Chuo-ku, Tokyo J-S-R Co., Ltd. F-term (reference) 4J038 DL021 DL041 DL071 DL161 GA07 GA12 HA096 HA376 HA416 HA476 JA21 JA26 JA27 JA36 JA38 JA39 JA41 JA42 JA44 JA45 JA57 JB01 JB11 JB29 JB30 JC13 KA04 KA06 MA07 MA10 NA11 NA21 PA19 PB09 PC02 5F058 AA02 AA10 AC03 AF04 AG01 AH02

Claims (4)

[Claims] (A) (A-1) a compound represented by the following general formula (1): R _a Si (OR ¹ ) _4-a (1) wherein R is hydrogen An atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is an integer of 1 to 2.) (A-2) a compound represented by the following general formula (2); (OR ² ) ₄ (2) (wherein, R ² represents a monovalent organic group.) (A-3) Compound represented by the following general formula (3) 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 same or different and each represents a monovalent Organic groups, b to c are the same or different, an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _n —
(Where n is an integer of 1 to 6), d
Represents 0 or 1. At least one selected from the group of
In the presence of an acid catalyst a compound of the species, hydrolysis, condensation formed by hydrolysis-condensation product, a solvent R ¹⁵ O (R ¹⁷ 0 (B) represented by nitrogen onium salt compound and (C) the general formula (4) _G R ¹⁶ (4) (R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a monovalent organic group selected from CH ₃ CO—. , R ¹⁷ represents an alkylene group, and g represents an integer of 1 to 2.). 2. The method according to claim 1, wherein the component (B) is a compound represented by the following general formulas (5) and (6). (R ⁸ R ⁹ R ¹⁰ R ¹¹ N) _e R ¹² ... (4) R ¹³ (R ¹⁴ ) _h ... (5) (where R ^{8 to} R ¹¹ are the same or different. Each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, an aryl group, or an arylalkyl group, R ¹² represents a halogen atom, a 1 to 4 valent anionic group, and e represents 1
Represents an integer of from 1 to 4, R ¹³ represents a g-valent cyclic cationic group containing a nitrogen atom, R ¹⁴ represents a halogen atom, a f-valent anionic group, f is an integer of 1 to 4, g is Represents an integer of 1 to f, and gh? F. ) 3. The use ratio of the component (B) to the component (A) is 0.0001 to 5 parts by weight of the component (B) based on 100 parts by weight of the component (A) (in terms of a completely hydrolyzed condensate). The composition for forming a film according to claim 1, wherein: 4. An insulating film forming material comprising the film forming composition according to claim 1.