JP2001164186A - Composition for film forming, process for forming film and insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a polyorganosiloxane film which composition gives a film having a low dielectric constant and a high elastic modulus which film is useful as an insulating film between layers in a semiconductor device or the like. SOLUTION: The composition for forming a film contains (A) a condensed material obtained by hydrolyzing and condensing at least one selected from the group consisting of compounds of general formulas (1), (2) and (3) in the presence of an alkali metal catalyst and (B) a condensed material obtained by hydrolyzing and condensing at least one selected from the group consisting of compounds of general formulas (1), (2) and (3) in the presence of an acid catalyst. Ra(Si)(OR1)4-a (1) Si(OR2)4 (2) R3a(R4O)3-b Si-(R7)d-Si(OR5)3-c R6c (3) (wherein R is hydrogen, fluorine or a monovalent organic group; R1 to R6 are each a monovalent organic group; R7 is oxygen, phenylene or -(CH2)n-, a is an integer of 1-2; b and d are each a number of 0-2; d is 0 or 1; and n is an integer of 1-6).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyorganosiloxane-based film-forming composition, and more specifically, a film having a low relative dielectric constant and a high elastic modulus is used as an interlayer insulating film material in a semiconductor device or the like. The present invention relates to a polyorganosiloxane-based film-forming composition that can be formed.

[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 containing a hydrolysis product of tetraalkoxylane as a main component has also been used. In addition, with the high integration of semiconductor elements and the like, an interlayer insulating film called organic SOG having a low relative dielectric constant containing polyorganosiloxane as a main component has been developed. However, at present, the relative permittivity of known organic SOG is about 3 to 4, and no one having a low relative permittivity superior to that and sufficient mechanical strength is known.

[0003]

The present invention relates to a film forming composition for solving the above-mentioned problems, and more specifically, it has a low relative dielectric constant and is used as an interlayer insulating film in a semiconductor device or the like. An object of the present invention is to provide a polyorganosiloxane-based film-forming composition capable of forming a cured film having a high elastic modulus.

[0004]

[In the formula, 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 A group represented by -(wherein n is an integer of 1 to 6), and d represents 0 or 1. ]

Here, the weight average molecular weight of the (A) hydrolysis-condensation product by the GPC method is preferably 50,000 to 10,000,000. The weight average molecular weight of the hydrolyzed condensate of the component (B) by the GPC method is preferably 500 to 300,000. Further, the component (A) preferably contains 25 to 75% by weight of a hydrolysis-condensation product (calculated as a complete hydrolysis-condensation product) of the compound represented by the general formula (2). Furthermore, the component (A) is preferably a hydrolysis-condensation product of a silane compound consisting of a compound represented by the general formula (1) and a compound represented by the general formula (2). In addition, the ratio of the component (A) to the component (B) is 1 to 900 for the component (B) (completely hydrolyzed condensate) to 100 parts by weight of the component (A) (completely hydrolyzed condensate). Parts by weight are preferred. Further, the pH of the film forming composition of the present invention is preferably 7 or less. Next, the present invention relates to a method for forming a film, which comprises applying the film forming composition to a substrate and heating the substrate. Here, an insulating film is preferable as a use of the film obtained by the film forming method. Next, the present invention relates to a semiconductor device having the insulating film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention uses, as a base polymer for forming a film, at least one selected from the group of the component (A) [compounds (1), (2) and (3) as an alkali catalyst]. Selected from the group consisting of hydrolysis condensates (hydrolysates and/or condensates thereof) obtained by hydrolysis and condensation in the presence of the present invention, and component (B) [compounds (1), (2) and (3)] Polyorganosiloxane-based film-forming composition using a hydrolyzed condensate (hydrolyzed product and/or condensate thereof) obtained by hydrolyzing and condensing at least one selected from the above in the presence of an acid catalyst. It is a thing. This composition of the present invention is applied to a substrate such as a silicon wafer by a dipping or spin coating method, and heated (A) to (B).
When the components are subjected to thermal polycondensation, the components (A) to (B) form a glassy or macromolecular film, and the resulting film has a low relative dielectric constant and a high elastic modulus, and thus has a high mechanical strength. It is excellent and an interlayer insulating film material can be formed.

Here, in the present invention, hydrolysis means
Compound (1)-constituting the components (A)-(B)
(3) in R ¹ O-, R ² O- group, R ⁴ O-group and R
^{The 5} O-group reacts with water to form a silanol group. Further, in the present invention, the condensation means (A) to
The silanol groups of the hydrolysates of the compounds (1) to (3) constituting the component (B) are condensed to form a Si—O—Si bond, but in the present invention, all the silanol groups are condensed. It is not necessary that the silanol groups are condensed, and it is a concept including generation of a mixture of a small amount of silanol groups, a mixture of different degrees of condensation, and the like.

(A) Hydrolytic Condensate The (A) hydrolytic condensate is obtained by hydrolyzing at least one silane compound selected from the group consisting of the compounds (1) to (3) in the presence of an alkali catalyst. -It is obtained by condensation. The compounds (1) to (3) and the alkali catalyst will be described below. Compound (1); R and R in the general formula (1)
The ¹ monovalent organic group, an alkyl group, an aryl group,
Examples thereof include allyl group and glycidyl group. Further, in the general formula (1), R is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like, preferably having 1 to 1 carbon atoms.
5, these alkyl groups may be linear or branched, and the 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-. 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;

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,
Ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-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-
Butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri -Sec-butoxysilane, phenyltri-tert-
Butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltrisilane Ethoxysilane etc.;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane,
Dimethyl-di-iso-propoxysilane, dimethyl-
Di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n
-Propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-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, J-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;

Preferably, methyltrimethoxysilane,
Methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
It is vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane. These are 1 or 2
More than one species may be used simultaneously.

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

Compound (3): In the above general formula (3), examples of the monovalent organic group include the same organic groups as in the above general formula (1). R in the general formula (3)
Compounds in which ⁷ is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldisiloxane, 1,1,1,3 ,3-pentaethoxy-3-methyldisiloxane, 1,1,1,
3,3-pentaphenoxy-3-methyldisiloxane,
1,1,1,3,3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaethoxy-3-
Ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3
-Pentamethoxy-3-phenyldisiloxane, 1,
1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-
Phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-
Tetraethoxy-1,3-dimethyldisiloxane, 1,
1,3,3-tetraphenoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-
Diethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3,3-
Tetraphenoxy-1,3-diethyldisiloxane,
1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,
3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,
1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-
1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triethyldisiloxane,
1,1,3-triethoxy-1,3,3-triethyldisiloxane, 1,1,3-triphenoxy-1,3,3
-Triethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3
-Triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,
3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,
3-diphenoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diethoxy-1,1,
3,3-tetraethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraethyldisiloxane,
1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-
Tetraphenyldisiloxane, 1,3-diphenoxy-
1,1,3,3-tetraphenyldisiloxane etc. can be mentioned.

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

Further, in the general formula (3), as the compound in which d is 0, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 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-1,1,2,2-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,
Examples thereof include 1,2-diethoxy-1,1,2,2-tetraphenyldisilane and 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane.

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,
Preferred examples include 2,2-tetraphenyldisilane and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane.

Further, in the general formula (3), R ⁷ is −
Examples of the compound represented by (CH ₂ ) _n − include bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(tri-n-propoxysilyl)methane, 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-t-butoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1, 2-bis(diethoxymethylsilyl)ethane, 1,2-bis(di-n-propoxymethylsilyl)ethane, 1,2-bis(di-i-propoxymethylsilyl)ethane, 1,2-
Bis(di-n-butoxymethylsilyl)ethane, 1,2
-Bis(di-sec-butoxymethylsilyl)ethane,
1,2-bis(di-t-butoxymethylsilyl)ethane, 1,2-bis(trimethoxysilyl)benzene,
1,2-bis(triethoxysilyl)benzene, 1,2
-Bis(tri-n-propoxysilyl)benzene, 1,
2-bis(tri-i-propoxysilyl)benzene,
1,2-bis(tri-n-butoxysilyl)benzene,
1,2-bis(tri-sec-butoxysilyl)benzene, 1,2-bis(tri-t-butoxysilyl)benzene, 1,3-bis(trimethoxysilyl)benzene,
1,3-bis(triethoxysilyl)benzene, 1,3
-Bis(tri-n-propoxysilyl)benzene, 1,
3-bis(tri-i-propoxysilyl)benzene,
1,3-bis(tri-n-butoxysilyl)benzene,
1,3-bis(tri-sec-butoxysilyl)benzene, 1,3-bis(tri-t-butoxysilyl)benzene, 1,4-bis(trimethoxysilyl)benzene,
1,4-bis(triethoxysilyl)benzene, 1,4
-Bis(tri-n-propoxysilyl)benzene, 1,
4-bis(tri-i-propoxysilyl)benzene,
1,4-bis(tri-n-butoxysilyl)benzene,
Examples thereof include 1,4-bis(tri-sec-butoxysilyl)benzene and 1,4-bis(tri-t-butoxysilyl)benzene.

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

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

When at least one silane compound selected from the group consisting of the compounds (1) to (3) constituting the component (A) is hydrolyzed and condensed, R ¹ O-group, R
It is preferable to use 5 to 50 mol of water per 1 mol of the total amount of ² O-groups, R ⁴ O-groups and R ⁵ O-groups, and 7 to
It is particularly preferred to add 30 mol of water. When the amount of water added is less than 5 mol, sufficient relative dielectric constant and elastic modulus may not be obtained, while when it is more than 50 mol, precipitation of polymer or gel during hydrolysis and condensation reaction may occur. May occur.

Alkali catalyst: In producing the hydrolysis-condensation product (A) of the present invention, the above compounds (1) to (3) are used.
When hydrolyzing and condensing at least one silane compound selected from the group, an alkali catalyst is used. Examples of the alkali catalyst include inorganic bases and organic bases. Here, examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Examples of the organic base include methanol amine, ethanol amine, propanol amine, butanol amine, N-methyl methanol amine, N-ethyl methanol amine, N-propyl methanol amine, N-butyl methanol amine, N-methyl ethanol amine. , N-
Ethylethanolamine, N-Propylethanolamine, N-Butylethanolamine, N-Methylpropanolamine, N-Ethylpropanolamine, N-Propylpropanolamine, N-Butylpropanolamine, N-Methylbutanolamine, N-Ethylbutanol Amine, N-propylbutanolamine, N-butylbutanolamine, N,N-dimethylmethanolamine, N,N-diethylmethanolamine, N,N-dipropylmethanolamine, N,N-dibutylmethanolamine, N,N -Dimethylethanolamine, N,N-
Diethylethanolamine, N,N-dipropylethanolamine, N,N-dibutylethanolamine, N,
N-dimethylpropanolamine, N,N-diethylpropanolamine, N,N-dipropylpropanolamine, N,N-dibutylpropanolamine, N,N-
Dimethylbutanolamine, N,N-diethylbutanolamine, N,N-dipropylbutanolamine, N,
N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N −
Butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-propyldibutanol Amine, N
-Butyldibutanolamine, N-(aminomethyl)methanolamine, N-(aminomethyl)ethanolamine, N-(aminomethyl)propanolamine, N-
(Aminomethyl)butanolamine, N-(aminoethyl)methanolamine, N-(aminoethyl)ethanolamine, N-(aminoethyl)propanolamine,
N-(aminoethyl)butanolamine, N-(aminopropyl)methanolamine, N-(aminopropyl)
Ethanolamine, N-(aminopropyl)propanolamine, N-(aminopropyl)butanolamine,
N-(aminobutyl)methanolamine, N-(aminobutyl)ethanolamine, N-(aminobutyl)propanolamine, N-(aminobutyl)butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, Ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine,
Butoxybutylamine, methylamine, ethylamine,
Propylamine, butylamine, N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydroxide , Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, Methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine,
Butylaminoethylamine, butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole,
Piperazine, pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicyclooclan,
Examples thereof include diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and the like. These alkali catalysts may be used either individually or in combination of two or more.

The amount of the alkali catalyst used is such that R ¹ O-group, R ² O-group and R ⁴ O-in the compounds (1) to (3).
It is usually 0.00001 to 0.5 mol, preferably 0.00005 to 0.5 mol, based on 1 mol of the total amount of the group and the group represented by the R ⁵ O-group. When the amount of the alkali catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction.

The molecular weight of the (A) hydrolyzed condensate thus obtained is GPC (refractive index, viscosity, light scattering measurement).
Weight average molecular weight according to the method, preferably 50,000 to 1,000
It is preferably 100,000, more preferably 100,000 to 9,000,000, and particularly preferably 200,000 to 8,000,000. If it is less than 50,000, sufficient relative dielectric constant and elastic modulus may not be obtained, while
If it is more than ,000,000, the uniformity of the coating film may be deteriorated. Further, the hydrolysis-condensation product (A) thus obtained is characterized in that it is not in the form of particles and therefore has excellent coatability on a substrate. The fact that it does not have a particulate form is confirmed by, for example, transmission electron microscope observation (TEM).

In the component (A), when each component is converted into a complete hydrolysis-condensation product, the compound (2) is 5 to 75% by weight, preferably 5 to 75% by weight in the total amount of the compounds (1) to (3). Is 10 to 70% by weight, more preferably 15 to 70% by weight
Is. Further, the compound (1) and/or (3) is
In the total amount of the compounds (1) to (3), 95 to 25% by weight, preferably 90 to 30% by weight, more preferably 85 to 3% by weight.
It is 0% by weight. Compound (2) is compound (1)-
When it is 5 to 75% by weight in the total amount of (3), the elastic modulus of the obtained coating film is high and the low dielectric property is particularly excellent. Here, in the present invention, the complete hydrolysis-condensation product means the R ¹ O-group, R ² O-group and R ⁴ O in the compounds (1) to (3).
- group and R ⁵ O-group 100% hydrolyzed to the SiOH
It is a base and is further condensed completely to form a siloxane structure. Further, the component (A) is preferably a hydrolysis-condensation product of the compound (1) and the compound (2), because the storage stability of the obtained composition is more excellent.

Further, in the hydrolysis-condensation product (A), at least one silane compound selected from the group consisting of compounds (1) to (3) is hydrolyzed and condensed in the presence of an alkali catalyst to give a hydrolysis product. The decomposition-condensation product is used, and the weight average molecular weight thereof is preferably 50,000 to 10,000,000. After that, it is preferable to adjust the pH of the composition to 7 or less. As a method of adjusting pH, (1) a method of adding a pH adjusting agent,
(2) A method of distilling the alkali catalyst from the composition under normal pressure or a reduced pressure, (3) A method of removing the alkali catalyst from the composition by bubbling a gas such as nitrogen or argon, (4) ) A method of removing the alkali catalyst from the composition with an ion exchange resin, and the like. Each of these methods may be used in combination.

Here, examples of the pH adjusting agent include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, oxalic acid and the like. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid. , Gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, Benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid,
Examples thereof include malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and succinic acid. It is also possible to blend (B) a hydrolyzed condensate, which will be described later, synthesized using the above acid as a catalyst.

The pH of the composition prepared by the above pH adjusting agent is 7
Hereinafter, it is preferably adjusted to 1 to 6. Thus, after the hydrolysis-condensation product has a weight average molecular weight of 50,000 to 10,000,000 and the pH is adjusted within the above range by the pH adjusting agent, the storage stability of the obtained composition is improved. The effect of improvement is obtained. The amount of pH adjuster used is
The pH of the composition is within the above range, and the amount used is appropriately selected.

(B) Hydrolytic Condensate The (B) hydrolytic condensate is obtained by hydrolyzing at least one silane compound selected from the group consisting of the compounds (1) to (3) in the presence of an acid catalyst. -It is obtained by condensation. Here, the types of the compounds (1) to (3) and the amount of water used for hydrolysis/condensation are the same as the amounts of the silane compound and water used for the (A) hydrolysis-condensation product, and therefore omitted. .. In addition, at the time of hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (1) to (3) constituting the component (B), an R ¹ O— group and an R ² O— group are used. , R ⁴ O- group and R ⁵ O- group are preferably used in an amount of 0.25 to 5 mol, and particularly preferably 0.3 to 3 mol of water per mol. The amount of water added is 0.25
This is because if it is within the range of 5 mol, the uniformity of the coating film is not likely to be deteriorated, and the precipitation or gelation of the polymer during the hydrolysis and condensation reaction is less likely to occur.

Acid catalyst: To produce the (B) hydrolysis-condensation product of the present invention, at the time of hydrolyzing and condensing at least one silane compound selected from the group of the above-mentioned compounds (1) to (3). An acid catalyst is used. Here, since the type of the acid catalyst is the same as the inorganic acid or the organic acid which is the pH adjuster which may be used in the preparation of the (A) hydrolysis-condensation product, the description thereof will be omitted. The acid catalyst is preferably an organic acid.

The amount of the above-mentioned acid catalyst to be used is also compound (1) to
Usually, based on 1 mol of the total amount of the groups represented by R ¹ O-group, R ² O-group, R ⁴ O-group and R ⁵ O-group in (3),
0.00001 to 0.5 mol, preferably 0.0000
It is 5 to 0.1 mol. When the amount of the acid catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction.

The molecular weight of the (B) hydrolyzed condensate thus obtained is GPC (refractive index, viscosity, light scattering measurement).
Weight average molecular weight by the method, preferably 500 to 30
10,000, more preferably 700 to 200,000, and particularly preferably 1,000 to 100,000. If it is less than 500, the uniformity of the coating film may deteriorate, while if it is more than 300,000, storage stability may not be obtained. Further, the hydrolyzed condensate (B) thus obtained is characterized in that it is not in the form of particles and thus has excellent coatability on a substrate. The fact that it does not have a particulate form is confirmed by, for example, transmission electron microscope observation (TEM).

Ratio of Component (A) and Component (B) The film-forming composition of the present invention contains the above-mentioned components (A) to (B). (B) (completely hydrolyzed condensate) based on 100 parts by weight (decomposed condensate), preferably 1 to 900 parts by weight, more preferably 3 to 800 parts by weight, and particularly preferably 5 to 80 parts by weight.
0 parts by weight. If the amount of component (B) is less than 1 part by weight, the resulting coating film may not have sufficient mechanical strength.
If it exceeds 900 parts by weight, a sufficient low relative dielectric constant may not be obtained.

(C) Solvent The film-forming composition of the present invention comprises (A) a hydrolytic condensate and (B) a hydrolytic condensate dissolved or dispersed in a (C) solvent. Examples of the solvent (C) include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents and ester solvents.

Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-
Hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol -4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, s
ec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-
Trimethylcyclohexanol, benzyl alcohol,
Monoalcohol solvents such as diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,
Ethylene glycol mono-2-ethylbutyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether,
Examples thereof include polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether. These alcohol solvents are used alone or in combination.
More than one species may be used simultaneously.

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

As the ketone solvent, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-
n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-
Butyl ketone, methyl-n-hexyl ketone, di-i-
Butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4
-Pentanedione, acetonylacetone, acetophenone, fenchon, etc., as well as acetylacetone, 2,
4-hexanedione, 2,4-heptanedione, 3,5
-Heptanedione, 2,4-octanedione, 3,5-
Octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,
2,6,6-tetramethyl-3,5-heptanedione,
Examples include β-diketones such as 1,1,1,5,5,5-hexafluoro-2,4-heptanedione.
These ketone solvents may be used either individually or in combination of two or more.

As the amide solvent, formamide, N
-Methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,
N-dimethylacetamide, N-ethylacetamide,
Examples include N,N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. Be done. These amide solvents may be used either individually or in combination of two or more.

Ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ.
-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoacetate
n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxytriglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents are 1
One kind or two or more kinds may be used at the same time. The above (C) solvent may be used alone or in combination of two or more.

The film-forming composition of the present invention has the above-mentioned (C).
Although containing a solvent, the same solvent can be used when the compounds (1) to (3) constituting the components (A) to (B) are hydrolyzed and/or condensed.

Specifically, at least one of the compounds (1) to (3) is added all at once, intermittently or continuously to the solvent (C) to which water and an alkali catalyst (or acid catalyst) are added. After that, hydrolysis and condensation reactions are further performed. The reaction temperature at this time is usually 0 to
The temperature is 100°C, preferably 15 to 90°C.

Other Additives The film-forming composition obtained in the present invention may further contain components such as a surfactant. As a surfactant,
Examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Furthermore, silicone surfactants, polyalkylene oxide surfactants, fluorine-containing surfactants, etc. An agent etc. can be mentioned. The composition of the present invention preferably contains no silica particles in order to make the coating film uniform.

Method for Preparing Composition When preparing the composition of the present invention, for example, at least compounds (1) to (3) are added to a solvent (C) containing water and an alkali catalyst (or an acid catalyst). One kind (hereinafter, also referred to as “silane compound”) is added all at once or intermittently or continuously, and usually 0 to 100° C., preferably 15
Stir at ~90°C for 1-12 hours to carry out hydrolysis and condensation reactions. At each stage of preparation, the concentration can be adjusted to any concentration by concentrating or diluting by adding a solvent (C).

As a specific example of the method for preparing the composition of the present invention, the component (A) or the component (B) is prepared by the following methods (1) to (12), and then obtained (A). )-(B) components may be blended. (1) Water, alkali catalyst (or acid catalyst) and (C)
A predetermined amount of a silane compound is added to a mixture of solvents to carry out a hydrolysis/condensation reaction to obtain (A) hydrolysis-condensation product [or (B) hydrolysis-condensation product]. (2) Water, alkali catalyst (or acid catalyst) and (C)
A predetermined amount of a silane compound is continuously or intermittently added to a mixture of solvents to carry out hydrolysis and condensation reaction to obtain (A) hydrolysis-condensation product [or (B) hydrolysis-condensation product]. (3) A mixture of water, an alkali catalyst (or an acid catalyst) and, if necessary, a solvent of (C) is added to a mixture of a predetermined silane compound and a solvent of (C) to carry out a hydrolysis/condensation reaction, (A) Hydrolytic condensate [or (B) Hydrolytic condensate] is obtained. (4) To a mixture of a predetermined silane compound and (C) solvent, water, an alkali catalyst (or an acid catalyst) and, if necessary, a mixture of (C) solvent are added continuously or intermittently to obtain water. Carry out decomposition and condensation reaction (A)
A hydrolysis-condensation product [or (B) hydrolysis-condensation product] is obtained.

(5) A mixture of a predetermined silane compound, an alkali catalyst (or acid catalyst) and (C) solvent,
A mixture of water and, if necessary, a solvent (C) is added to carry out a hydrolysis/condensation reaction to obtain a hydrolysis-condensation product (A) (or a hydrolysis-condensation product (B)). (6) Water and, if necessary, a mixture composed of the solvent (C) are continuously or intermittently added to a mixture composed of a predetermined silane compound, an alkali catalyst (or an acid catalyst) and a solvent (C) to add water. Decomposition/condensation reaction (A)
A hydrolysis-condensation product [or (B) hydrolysis-condensation product] is obtained. (7) To a mixture of a predetermined amount of water and, if necessary, a solvent (C), a mixture of a predetermined amount of a silane compound, an alkali catalyst (or an acid catalyst) and, if necessary, a solvent (C) is added, A hydrolysis/condensation reaction is performed to obtain (A) hydrolysis-condensation product [or (B) hydrolysis-condensation product]. (8) A mixture of a predetermined amount of water and, if necessary, a solvent (C) is continuously added with a mixture of a predetermined amount of a silane compound, an alkali catalyst (or an acid catalyst) and, if necessary, a solvent (C). Or add it intermittently to
A condensation reaction is carried out to obtain (A) hydrolysis-condensation product [or (B) hydrolysis-condensation product].

(9) To a mixture of a predetermined amount of water, a silane compound and, if necessary, a solvent (C), a mixture of a predetermined amount of an alkali catalyst (or acid catalyst) and, if necessary, a solvent (C). In addition, hydrolysis/condensation reaction is performed to obtain (A) hydrolysis-condensation product [or (B) hydrolysis-condensation product]. (10) A mixture of a predetermined amount of water, a silane compound and, if necessary, a solvent (C) is continuously added with a mixture of a predetermined amount of an alkali catalyst (or an acid catalyst) and, if necessary, a solvent (C). Alternatively, it is added intermittently to carry out hydrolysis/condensation reaction to obtain (A) hydrolysis-condensation product [or (B) hydrolysis-condensation product]. (11) A mixture of a predetermined amount of an alkali catalyst (or an acid catalyst) and, if necessary, a solvent (C) is added with a mixture of a predetermined amount of water, a silane compound, and optionally a solvent (C), Conducts hydrolysis and condensation reactions,
(A) Hydrolytic condensate [or (B) Hydrolytic condensate]
To get (12) A mixture of a predetermined amount of an alkali catalyst (or an acid catalyst) and, if necessary, a solvent (C) is continuously added with a mixture of a predetermined amount of water, a silane compound and, if necessary, a solvent (C). Alternatively, it is added intermittently to carry out hydrolysis/condensation reaction to obtain (A) hydrolysis-condensation product [or (B) hydrolysis-condensation product]. In the present invention, the solid content concentration of the reaction liquid when the silane compound is hydrolyzed/condensed is usually 0.1 to 50% by weight.

The total solid content concentration of the composition of the present invention thus obtained is preferably 2 to 50% by weight, preferably 2 to 30% by weight, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 2 to 50% by weight, the film thickness of the coating film is in an appropriate range and the storage stability is further excellent. In addition, adjustment of this total solid content concentration,
If necessary, it is carried out by concentration and dilution with the solvent (C).

The composition of the present invention thus obtained can be used after filtering with a filter, if necessary. The filter may be made of polyester, polycarbonate, cellulose, cellulose acetate, polypropylene, polyether sulfone, tetrafluoroethylene (PTFE), polyamide or the like. Preferably, a PT with a pore size of 0.2 μm or less
FE filter, particularly preferably pore size 0.05 μm
It is preferable to use the following PTFE filter because foreign matter in the composition is removed and the resulting coating film has excellent uniformity. The filters described above can be used in combination with different materials and different pore diameters, or a plurality of filters with the same material and different pore diameters can be used in combination.

To form a film using the composition of the present invention, first, the composition of the present invention is applied to a substrate to form a coating film. Here, examples of the substrate to which the composition of the present invention can be applied include semiconductors, glass, ceramics, metals and the like. The coating method may, for example, be spin coating, dipping or roller blade. The composition according to the invention is especially suitable for silicon wafers, SiO ₂
It is suitable for forming an insulating film by coating on a wafer, SiN wafer, or the like.

As a heating method at this time, a hot plate, an oven, a furnace or the like can be used,
The heating atmosphere may be an atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like. Here, the heat treatment conditions are a nitrogen atmosphere, an argon atmosphere, a vacuum, or an oxygen concentration of 10
It is preferable to perform the treatment at a temperature of 450° C. or lower under a reduced pressure controlled to 0 ppm or less. In addition, in order to control the curing speed of the component (A), if necessary,
Stepwise heating or an atmosphere such as nitrogen, air, oxygen or reduced pressure can be selected.

The relative permittivity of the film of the present invention thus obtained is a low relative permittivity, usually 2.7 to 1.5, preferably 2.6 to 1.5, and more preferably 2. .5-
It is 1.5.

The film of the present invention has a high elastic modulus and a Young's modulus of usually 3 to 10 GPa, preferably 4 to 10 GPa.
GPa. This elastic modulus can be obtained by firing the hydrolysis-condensation product of the components (A) to (B) prepared by the method described in the present invention by the method described in the present invention.

Further, the film of the present invention usually has a film density of
0.5-1.4 g/cm ³ , preferably 0.5-1.3
g/cm ³ , more preferably 0.5 to 1.2 g/cm
^{Is 3} . When the film density is less than 0.5 g/cm ³ , the mechanical strength of the coating film decreases, while when it exceeds 1.4 g/cm ³ , a low relative dielectric constant cannot be obtained.

Further, the film of the present invention is characterized in that it has a low water absorption property. For example, a coating film at 127° C., 2.5 atm,
When left in an environment of 100% RH for 1 hour, adsorption of water to the coating film is not observed from the IR spectrum observation of the coating film after standing. This low water absorption can be obtained, for example, by setting the content of the compound (2) in the film forming composition of the present invention to the range described in the present invention.

The film of the present invention is excellent in insulating property, has a high elastic modulus, and is excellent in uniformity of the coating film, relative dielectric constant characteristics, crack resistance of the coating film, and surface hardness of the coating film.
I, system LSI, DRAM, SDRAM, RDRA
It is useful for applications such as an interlayer insulating film for semiconductor elements such as M and D-RDRAM, a protective film such as a surface coating film for semiconductor elements, an interlayer insulating film for a multilayer wiring board, a protective film or an insulating film for liquid crystal display elements. .. A semiconductor device having the insulating film of the present invention has the film of the present invention as an insulating film between metal wirings.

[0056]

EXAMPLES The present invention will be described more specifically below with reference to examples. However, the following description generally shows an example of the embodiment of the present invention, and the present invention is not limited to the description by no particular reason. In the examples and comparative examples, parts and% are parts by weight and% by weight, respectively, unless otherwise specified. Also,
Various evaluations were performed as follows.

Weight average molecular weight It was measured by gel permeation chromatography (GPC) (refractive index, viscosity, light scattering measurement) method under the following conditions. Sample solution: Hydrolyzed condensate of silane compound
10 mM Li so that the solid content concentration is 0.25%.
It was diluted with methanol containing Br to prepare a sample solution for GPC (refractive index, viscosity, light scattering measurement). Equipment: Tosoh Corp., GPC system model GP
C-8020 Tosoh Corp. column, Alpha 5000/300
0 Viscotec, viscosity detector and light scattering detector model T-60 dual meter Carrier solution: Methanol containing 10 mM LiBr Carrier transfer rate: 1 ml/min Column temperature: 40°C

Storage stability 80 ml of the composition of the present invention was placed in a glass screw cap bottle having a volume of 100 ml, sealed, and left for 1 month in a 40° C. autoclave. Samples before and after standing at 2,500 rpm,
The film thickness when applied under a spin coating condition of 31 seconds and baked by the method of the example is an optical film thickness meter (Rudolph T
Spectra Las manufactured by technologies
er200), and the rate of change {[(thickness of sample after leaving-thickness of sample before leaving)/thickness of sample before leaving]×100} is calculated and evaluated according to the following criteria. did. ⊚: Thickness change rate <5% ◯: Thickness change rate <10% ×: Thickness change rate ≧10%

Relative permittivity An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for measuring a relative permittivity. The relative dielectric constant of the coating film was measured by the CV method using a HP16451B electrode and HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. at a frequency of 100 kHz. The film density was calculated from the volume obtained from the film thickness and film area, and the film weight. Elastic Modulus (Young's Modulus ) The obtained film was measured by a continuous stiffness measuring method using Nanoindenter XP (manufactured by MST).

Water absorption The coating film obtained was applied at 127° C., 2.5 atm, 100% R
It was left in the environment of H for 1 hour, and the IR spectrum of the coating film after standing was observed. The presence or absence of absorption due to H ₂ O around 3,500 cm ⁻¹ was observed by comparing with the IR spectrum of the coating film before standing, and water absorption was evaluated according to the following criteria. ○: Not absorbed ×: Absorbed

Reference Example 1 [Preparation of component (A-1)] 15 g of methyltrimethoxysilane (7.4 g in terms of complete hydrolysis condensate) in a mixed solution of 5 g of 25% aqueous ammonia, 320 g of ultrapure water and 600 g of ethanol. And 20 g of tetraethoxysilane (5.
8 g) was added and reacted at 60° C. for 3 hours, then 200 g of propylene glycol monopropyl ether was added,
Then, concentrate under reduced pressure until the total solution amount becomes 200 g,
A (A-1) component composition solution having a solid content of 6.6% was obtained. The weight average molecular weight of the obtained component (A-1) was 30.
It was good.

Reference Example 2 [Preparation of component (A-1)] 200 g of the component (A-1) solution described in Reference Example 1 was further concentrated to a total volume of 140 g, and then 10 parts of acetic acid was added.
% Propylene glycol monopropyl ether solution 10
g was added to obtain a composition solution having a solid content of 8.8%. The weight average molecular weight of the obtained component (A) was 300,000. In addition, the residual silanol count determined by conductivity titration did not change before and after the addition of acetic acid.

Reference Example 3 [Preparation of component (B)] 101.3 g of tetramethoxysilane (in terms of complete hydrolysis-condensation product; 40.0 g), methyltrimethoxysilane 20
3.0 g (completely hydrolyzed condensate; 100.0 g),
Dimethyldimethoxysilane 97.3 g (completely hydrolyzed condensate; 60.0 g), propylene glycol monopropyl ether 559.3 g, and methyl-n-pentyl ketone 239.7 g were mixed with 1.0 g of maleic acid.
(Catalyst/SiOR=0.001 mol ratio) was added to water 157.
An aqueous solution dissolved in 7 g (H ₂ O/SiOR=1.0 mol ratio) was added dropwise at room temperature over 1 hour. After the addition of the mixture was completed, the mixture was further reacted at 60° C. for 2 hours and then concentrated under reduced pressure until the total amount of the solution reached 1,000 g to obtain a component (B) having a solid content of 20%. The weight average molecular weight of the obtained component (B) was 3,000.

Reference Example 4 [Preparation of component (A-2)] Reference Example 1 except that 0.5 g of 25% tetramethylammonium hydroxide was used instead of 5 g of 25% aqueous ammonia solution. Similarly, a component having a weight average molecular weight of 1,000,000 was obtained. This component was treated as in Reference Example 2. The weight average molecular weight of the obtained component (A-2) was 1,000,000. In addition, the residual silanol count determined by conductivity titration did not change before and after the addition of acetic acid.

Comparative Reference Example 1 32 g of ultrapure water and 6 parts of ethanol were used instead of 320 g of ultrapure water.
Other than using 888 g of ethanol instead of 00 g,
The same operation as in Reference Example 1 was performed to obtain a composition solution having a solid content of 6.6%. The polystyrene reduced molecular weight of the obtained composition was 40,000.

Example 1 96.5 g of the component (A-1) solution described in Reference Example 1 and 3.5 g of the component (B) solution described in Reference Example 3 were mixed to give a composition having a solid content of 7.1%. A product solution was obtained. The composition obtained,
It is applied on an 8-inch silicon wafer by spin coating, and the temperature is 80° C. for 5 minutes, and then under nitrogen at 200° C. for 5 minutes.
After heating for 3 minutes, further vacuum at 340 ℃, 360
℃, 380 ℃ in that order, each heating for 30 minutes,
Further, it was heated under vacuum at 425° C. for 1 hour to form a colorless transparent film. The evaluation results of the obtained film are shown in Table 1.

Example 2 84.1 g of the component (A-1) solution described in Reference Example 2 and 15.9 g of the component (B) solution described in Reference Example 3 were mixed to give a composition having a solid content of 10.6%. A product solution was obtained. The obtained composition was applied onto an 8-inch silicon wafer by a spin coating method, and the atmosphere was heated at 80° C. for 5 minutes, and then under nitrogen at 200° C.
After heating at 340°C for 5 minutes in vacuum,
The film was heated in the order of 0° C. and 380° C. for 30 minutes each, and further heated under vacuum at 425° C. for 1 hour to form a colorless transparent film. The evaluation results of the obtained film are shown in Table 1.

Example 3 84.1 g of the component (A-2) solution described in Reference Example 4 and 15.9 g of the component (B) solution described in Reference Example 3 were mixed to give a composition having a solid content of 10.6%. A product solution was obtained. The obtained composition was applied onto an 8-inch silicon wafer by a spin coating method, heated in the atmosphere at 80° C. for 5 minutes and then under nitrogen at 200° C. for 5 minutes, and further under vacuum at 340° C. and 360°.
C. and 380.degree. C. in that order for 30 minutes each, and further under vacuum at 425.degree. C. for 1 hour to form a colorless transparent film. The evaluation results of the obtained film are shown in Table 1.

Comparative Example 1 87.6 g of the composition solution described in Comparative Reference Example 1 and Reference Example 3
The component solution (12.4 g) described above was mixed to obtain a composition solution having a solid content of 8.3%. The obtained composition was
It is coated on an inch silicon wafer by a spin coating method at 80° C. in the atmosphere for 5 minutes, and then under nitrogen at 200° C. for 5 minutes.
After heating for 3 minutes, further vacuum at 340 ℃, 360
℃, 380 ℃ in that order, each heating for 30 minutes,
Further, it was heated under vacuum at 425° C. for 1 hour to form a colorless transparent film. The evaluation results of the obtained film are shown in Table 1.

[0070]

[Table 1]

[0071]

According to the present invention, a polyorganosiloxane-based film-forming composition having a low relative dielectric constant and a high elastic modulus, which is useful as an interlayer insulating film material in a semiconductor device or the like, is provided. be able to.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eihide Xu, 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd.(72) Keiji Konno 2-11-24 Tsukiji, Chuo-ku, Tokyo JS-R Incorporated (72) Inventor Atsushi Shiota 2-11-24 Tsukiji, Chuo-ku, Tokyo JR S Co., Ltd. (72) Inventor Kinji Yamada 2-11-24 Tsukiji, Chuo-ku, Tokyo JS R F Term (reference) 4J035 BA06 CA01K CA022 CA06K CA162 EA01 EB03 LA03 LB01 4J038 DL021 DL022 DL031 DL032 DL041 DL042 DL161 DL162 HA096 HA336 HA376 HA416 HA476 JA37 JA38 JB01 JB03 JB04 PA10 MA21 NA0A02 MAB09 JA08 A19 MA14 NA21 MA02 MAB09 A02 MA10 A02 MA03 A02 MA02 AB07 AC03 AF04 AG01 AH01 AH02

Claims (10)

[Claims] 1. At least one selected from the group consisting of: (A) a compound represented by the following general formula (1), a compound represented by the following general formula (2) and a compound represented by the following general formula (3). Hydrolysis condensate obtained by hydrolyzing and condensing one kind of silane compound in the presence of an alkali catalyst, and (B) a compound represented by the following general formula (1) and a compound represented by the following general formula (2) And a film containing a hydrolyzed condensate obtained by hydrolyzing at least one silane compound selected from the group of compounds represented by the following general formula (3) in the presence of an acid catalyst. Forming composition. R _a Si(OR ¹ ) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is 1 to 2). Si(OR ² ) ₄ (2) (In the formula, R ² represents a monovalent organic group.) R ³ _b (R ⁴ O) _3-b Si-( R ⁷ ) _d- Si(OR ⁵ ) _3-c R ⁶ _c (3) [In the formula, R ^{3 to} R ⁶ are the same or different and each is a monovalent organic group, and b to c are the same. Or differently, an integer from 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or —(CH ₂ ) _n —
A group represented by (where n is an integer of 1 to 6), d
Represents 0 or 1. ] 2. The film-forming composition according to claim 1, wherein the hydrolyzed condensate of the component (A) has a weight average molecular weight of 50,000 to 10,000,000 as measured by the GPC method. 3. The weight average molecular weight of the hydrolyzed condensate of the component (B) according to the GPC method is 500 to 300,000.
The film-forming composition as described above. 4. The component (A) is a hydrolysis-condensation product (converted to a complete hydrolysis-condensation product) of the compound represented by the general formula (2).
The film-forming composition according to any one of claims 1 to 3, wherein the film-forming composition contains 5 to 75% by weight. 5. The component (A) is a hydrolyzed condensate of a silane compound comprising a compound represented by the general formula (1) and a compound represented by the general formula (2). A film-forming composition as described in the item. 6. Component (A) (in terms of complete hydrolysis condensate)
The film-forming composition according to claim 1, which contains 1 to 900 parts by weight of the component (B) (completely hydrolyzed condensate) based on 100 parts by weight. 7. The film-forming composition according to claim 1, which has a pH of 7 or less. 8. A method for forming a film, which comprises applying the film-forming composition according to claim 1 to a substrate and heating the substrate. 9. An insulating film obtained by the method for forming a film according to claim 8. 10. A semiconductor device having the insulating film according to claim 9.