JP2000309753A - Composition for forming film and material for forming insulation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition capable of forming a coating film excellent in resistances to oxygen plasma and cracks and in dielectric properties by incorporating (A) a hydrolyzate of an alkoxy silane and (B) a hydrolyzate of a silane compound comprising an alkoxycyclosilane and a silane polymer and/or the condensates of ingredients A and B into the same. SOLUTION: This composition contains (A) a hydrolyzate of a compound of the formula: R1aSi(OR2)4-a and (B) a hydrolyzate of a silane compound comprising a compound of the formula and a polymer having repeating units of the formula: -Si(OR5)2-b(R6)bO- and/or the condensates of ingredients A and B. In the formulas, R1 to R6 are each a monovalent organic group; a is 0-2; b is 0-1; and n is 3-10, These hydrolyzates and/or condensates form a two-dimensional or three-dimensional structure, forming a high-mol.-wt. polyorganosiloxane. When applied to a substrate (e.g. a silicone wafer) and subjected to thermal polycondensation, the composition, containing the polyorganosiloxane, forms a glassy or macromolecular film excellent in adbesiveness.

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 composition suitable for use as an interlayer insulating film in semiconductor devices and the like, which has good oxygen plasma resistance, hardly causes cracks, and has a dielectric constant. The present invention relates to a film-forming composition having excellent properties and the like.

[0002]

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

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

[0004] WO96 / 00758 also discloses that
Silica-based insulation, which is used for forming interlayer insulation films of multilayer wiring boards and consists of alkoxysilanes, metal alkoxides other than silane, organic solvents, etc., is capable of thick film coating and has excellent oxygen plasma ashing resistance. A film forming material is disclosed.

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

[0006] However, when a metal chelate compound such as titanium or zirconium is combined with a silane compound as described above, oxygen plasma resistance, dielectric constant, crack resistance and the like are not balanced.

[0007]

The present invention relates to a film-forming composition for solving the above problems, and more particularly, to a composition suitable for an interlayer insulating film in a semiconductor device or the like.
It has oxygen plasma resistance and is hard to crack.
An object of the present invention is to provide a film-forming composition having excellent dielectric constant characteristics.

The present invention relates to (A) a compound represented by the following general formula (1) (hereinafter also referred to as “component (A)”): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ and R ² may be the same or different and each represents a monovalent organic group, and a represents an integer of 0 to 2). (B) (B-1) In the following general formula (2) A compound represented by the formula (hereinafter, also referred to as “component (B-1)”):

[0009]

Embedded image

(R ³ and R ⁴ may be the same or different and each represents a monovalent organic group, and n represents an integer of 3 to 10.) (B-2) Formula (3): Polymer having a repeating unit (hereinafter also referred to as “component (B-2)”) —Si (OR ⁵ ) _2-b (R ⁶ ) _b O— (3) (R ⁵ and R ⁶ are the same or different. Each represents a monovalent organic group, and b represents an integer of 0 to 1.)
A hydrolyzate and / or condensate (hereinafter also referred to as "hydrolysis condensate") of a silane compound comprising: Here, the weight of the component (B) is preferably from 1 to 80 parts by weight based on 100 parts by weight of the component (A) (in terms of a completely hydrolyzed condensate).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a component (A) and a component (B) are hydrolyzed and condensed as components forming a film, so that these hydrolyzates and / or condensates thereof (hydrolysis) Decomposition condensate) has a two-dimensional to three-dimensional structure to produce a polyorganosilane having a high molecular weight. When the composition of the present invention containing the generated polyorganosilane is applied to a substrate such as a silicon wafer by dipping or spin coating, for example, the grooves between the fine patterns can be sufficiently filled. When the organic solvent is removed and heat condensation polymerization is performed by heating, a glassy or macromolecular film can be formed. The obtained film has good adhesion, is excellent in flattening, and can form a thick insulator without cracks.

Here, the above-mentioned hydrolyzate is the above (A)
R ² contained in the ~ (B) component O-, R ⁴ O- and R ⁵
It is not necessary that all O-groups are hydrolyzed. For example, only one may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. Further, the condensate is formed by condensing the silanol groups of the hydrolyzate of the components (A) and (B) to form Si—O—Si
Although a bond is formed, in the present invention, it is not necessary that all silanol groups are condensed, and the present invention also includes those in which a small amount of silanol groups are condensed and those in which the degree of condensation is different. It is a concept that was.

Hereinafter, the component (A) used in the present invention,
The component (B) will be described, and then the method for preparing the composition of the present invention will be described in detail.

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

Specific examples of the compound represented by the general formula (1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-
Propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, 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-te
rt-butoxysilane, ethyltriphenoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-
iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-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-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, s
ec-butyl-i-triethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec
-Butoxysilane, sec-butyl-tri-tert-
Butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyl
Butyltri-n-butoxysilane, t-butyltri-s
ec-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, 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-is
o-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-
n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-is
o-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-i
so-propoxysilane, di-iso-propyl-di-
n-butoxysilane, di-iso-propyl-di-se
c-butoxysilane, di-iso-propyl-di-te
rt-butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-
n-propoxysilane, di-n-butyl-di-iso-
Propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di-tert-butoxysilane,
Di-n-butyl-di-phenoxysilane, di-sec-
Butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane, di-sec-butyl-di-n-butoxy Silane,
Di-sec-butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec-butyl-di-phenoxysilane, di-ter
t-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-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane, diphenyldimethoxysilane, diphenyl-di-ethoxy Silane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-
sec-butoxysilane, diphenyl-di-tert-
Butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane and the like can be mentioned.

Preferably, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltrisilane -Iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyl Diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane,
Trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triphenylmonomethoxysilane, and triphenylmonoethoxysilane. These may be used alone or in combination of two or more.

Component (B) Component (B-1): In the above formula (2), examples of the monovalent organic group include the same organic groups as those in the above formula (1). Specific examples of the compound represented by the general formula (2) include 1,3,5-trimethoxy-1,3,5-
Trimethylcyclotrisiloxane, 1,3,5-triethoxy-1,3,5-trimethylcyclotrisiloxane, 1,3,5-trimethoxy-1,3,5-triphenylcyclotrisiloxane, 1,3,5- Triethoxy-1,3,5-triphenylcyclotrisiloxane,
1,3,5,7-tetramethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-
Tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetra-n-propoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 , 7-Tetra-iso-propoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetra-n-butoxy-1,
3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra-sec-butoxy-1,3,3
5,7-tetramethylcyclotetrasiloxane, 1,
3,5,7-tetra-tert-butoxy-1,3,3
5,7-tetramethylcyclotetrasiloxane, 1,
3,5,7-tetraphenoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethoxy-1,3,5,7-tetravinylcyclotetrasiloxane, 1, 3,5,7-tetraethoxy-
1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetra-n-propoxy-1,
3,5,7-tetravinylcyclotetrasiloxane,
1,3,5,7-tetra-iso-propoxy-1,
3,5,7-tetravinylcyclotetrasiloxane,
1,3,5,7-tetra-n-butoxy-1,3,5
7-tetravinylcyclotetrasiloxane, 1,3
5,7-tetra-sec-butoxy-1,3,5,7-
Tetravinylcyclotetrasiloxane, 1,3,5,7
-Tetra-tert-butoxy-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetraphenoxy-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3 5,7-tetramethoxy-
1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3,5,7
-Tetraphenylcyclotetrasiloxane, 1,3
5,7-tetra-n-propoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7
-Tetra-iso-propoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-
Tetra-n-butoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetra-
sec-butoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetra-te
rt-butoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetraphenoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7 , 9-pentamethoxy-1,
3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pentaethoxy-1,3
5,7,9-pentamethylcyclopentasiloxane,
1,3,5,7,9-penta-n-propoxy-1,
3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-penta-iso-propoxy-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3 5,7,9-penta-n-butoxy-
1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-penta-sec-butoxy-1,3,5,7,9-pentamethylcyclopentasiloxane, 3,5,7,9-penta-tert-butoxy-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pentaphenoxy-
1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pentamethoxy-1,3,3
5,7,9-pentavinylcyclopentasiloxane,
1,3,5,7,9-pentaethoxy-1,3,5
7,9-pentavinylcyclopentasiloxane, 1,
3,5,7,9-penta-n-propoxy-1,3,3
5,7,9-pentavinylcyclopentasiloxane,
1,3,5,7,9-penta-iso-propoxy-
1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9-penta-n-butoxy-
1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9-penta-sec-butoxy-1,3,5,7,9-pentavinylcyclopentasiloxane, 1, 3,5,7,9-penta-tert-butoxy-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9-pentaphenoxy-
1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9-pentamethoxy-1,3,3
5,7,9-pentaphenylcyclopentasiloxane,
1,3,5,7,9-pentaethoxy-1,3,5
7,9-pentaphenylcyclopentasiloxane, 1,
3,5,7,9-penta-n-propoxy-1,3,3
5,7,9-pentaphenylcyclopentasiloxane,
1,3,5,7,9-penta-iso-propoxy-
1,3,5,7,9-pentaphenylcyclopentasiloxane, 1,3,5,7,9-penta-n-butoxy-
1,3,5,7,9-pentaphenylcyclopentasiloxane, 1,3,5,7,9-penta-sec-butoxy-1,3,5,7,9-pentaphenylcyclopentasiloxane, 3,5,7,9-penta-tert-
Butoxy-1,3,5,7,9-pentaphenylcyclopentasiloxane, 1,3,5,7,9-pentaphenoxy-1,3,5,7,9-pentaphenylcyclopentasiloxane, 1,3 , 5,7,9,11-Hexamethoxy-1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11-hexaethoxy-1,3,5 , 7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11-hexa-n-propoxy-1,3,5,7,9,11-hexamethylcyclohexasiloxane, , 3,5,7,
9,11-hexa-iso-propoxy-1,3,5
7,9,11-hexamethylcyclohexasiloxane,
1,3,5,7,9,11-hexa-n-butoxy-
1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11-hexa-se
c-butoxy-1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11
-Hexa-tert-butoxy-1,3,5,7,9,
11-hexamethylcyclohexasiloxane, 1,3
5,7,9,11-hexaphenoxy-1,3,5
7,9,11-hexamethylcyclohexasiloxane,
1,3,5,7,9,11-hexamethoxy-1,3,3
5,7,9,11-hexavinylcyclohexasiloxane, 1,3,5,7,9,11-hexaethoxy-1,
3,5,7,9,11-hexavinylcyclohexasiloxane, 1,3,5,7,9,11-hexa-n-propoxy-1,3,5,7,9,11-hexavinylcyclohexa Siloxane, 1,3,5,7,9,11-hexa-iso-propoxy-1,3,5,7,9,11-
Hexavinylcyclohexasiloxane, 1,3,5
7,9,11-hexa-n-butoxy-1,3,5
7,9,11-hexavinylcyclohexasiloxane,
1,3,5,7,9,11-hexa-sec-butoxy-1,3,5,7,9,11-hexavinylcyclohexasiloxane, 1,3,5,7,9,11-hexa- t
tert-butoxy-1,3,5,7,9,11-hexavinylcyclohexasiloxane, 1,3,5,7,9,
11-hexaphenoxy-1,3,5,7,9,11-
Hexavinylcyclohexasiloxane, 1,3,5
7,9,11-hexamethoxy-1,3,5,7,9,
11-hexaphenylcyclohexasiloxane, 1,
3,5,7,9,11-hexaethoxy-1,3,5
7,9,11-hexaphenylcyclohexasiloxane, 1,3,5,7,9,11-hexa-n-propoxy-1,3,5,7,9,11-hexaphenylcyclohexasiloxane, 1, 3,5,7,9,11-hexa-iso-propoxy-1,3,5,7,9,11-hexaphenylcyclohexasiloxane, 1,3,5
7,9,11-hexa-n-butoxy-1,3,5
7,9,11-hexaphenylcyclohexasiloxane, 1,3,5,7,9,11-hexa-sec-butoxy-1,3,5,7,9,11-hexaphenylcyclohexasiloxane, 1, 3,5,7,9,11-hexa-tert-butoxy-1,3,5,7,9,11-
Hexaphenylcyclohexasiloxane, 1,3,5
7,9,11-hexaphenoxy-1,3,5,7,
9,11-hexaphenylcyclohexasiloxane and the like can be mentioned.

Of these, preferably 1, 3, 5,
7-tetramethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 7-tetra-n-propoxy-1,
3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra-iso-propoxy-1,
3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra-n-butoxy-1,3,5
7-tetramethylcyclotetrasiloxane, 1,3
5,7-tetra-sec-butoxy-1,3,5,7-
Tetramethylcyclotetrasiloxane, 1,3,5,7
-Tetra-tert-butoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraphenoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3 5,7-tetramethoxy-
1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3,5,7
-Tetraphenylcyclotetrasiloxane, 1,3
5,7-tetra-n-propoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7
-Tetra-iso-propoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-
Tetra-n-butoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetra-
sec-butoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetra-te
rt-butoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetraphenoxy-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7 , 9-pentamethoxy-1,
3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pentaethoxy-1,3
5,7,9-pentamethylcyclopentasiloxane,
1,3,5,7,9-penta-n-propoxy-1,
3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-penta-iso-propoxy-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3 5,7,9-penta-n-butoxy-
1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-penta-sec-butoxy-1,3,5,7,9-pentamethylcyclopentasiloxane, 3,5,7,9-penta-tert-butoxy-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pentaphenoxy-
1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9,11-hexamethoxy-
1,3,5,7,9,11-hexaphenylcyclohexasiloxane, 1,3,5,7,9,11-hexaethoxy-1,3,5,7,9,11-hexaphenylcyclohexasiloxane 1,3,5,7,9,11-hexa-n-propoxy-1,3,5,7,9,11-hexaphenylcyclohexasiloxane, 1,3,5,7,
9,11-hexa-iso-propoxy-1,3,5
7,9,11-hexaphenylcyclohexasiloxane, 1,3,5,7,9,11-hexa-n-butoxy-1,3,5,7,9,11-hexaphenylcyclohexasiloxane, 1, 3,5,7,9,11-hexa-
sec-butoxy-1,3,5,7,9,11-hexaphenylcyclohexasiloxane, 1,3,5,7,
9,11-hexa-tert-butoxy-1,3,5
7,9,11-hexaphenylcyclohexasiloxane, 1,3,5,7,9,11-hexaphenoxy-
1,3,5,7,9,11-hexaphenylcyclohexasiloxane can be mentioned. . These may be used alone or in combination of two or more.

Component (B-2): In the above formula (3), examples of the monovalent organic group include the same organic groups as those in the above formula (1). Specific examples of the polymer represented by the general formula (3) include, for example, polymethylmethoxysiloxane, polymethylethoxysiloxane, polymethyl-n-propoxysiloxane, and polymethyl-iso.
-Propoxysiloxane, polymethyl-n-butoxysiloxane, polymethyl-sec-butoxysiloxane,
Polymethyl-tert-butoxysiloxane, polymethylphenoxysiloxane, polyvinylmethoxysiloxane, polyvinylethoxysiloxane, polyvinyl-n-
Propoxysiloxane, polyvinyl-iso-propoxysiloxane, polyvinyl-n-butoxysiloxane,
Polyvinyl-sec-butoxysiloxane, polyvinyl-tert-butoxysiloxane, polyvinylphenoxysiloxane, polyphenylmethoxysiloxane, polyphenylethoxysiloxane, polyphenyl-n-propoxysiloxane, polyphenyl-iso-propoxysiloxane, polyphenyl-n-butoxy Siloxane,
Polyphenyl-sec-butoxysiloxane, polyphenyl-tert-butoxysiloxane, polyphenylphenoxysiloxane, polydimethoxysiloxane, polydiethoxysiloxane, polydi-n-propoxysiloxane, polydi-iso-propoxysiloxane, polydi-n-butoxysiloxane, Polydi-sec-butoxysiloxane, polydi-tert-butoxysiloxane,
Examples thereof include polydiphenoxysiloxane.

Of these, preferably, polymethylmethoxysiloxane, polymethylethoxysiloxane, polymethyl-n-propoxysiloxane, polymethyl-i
so-propoxysiloxane, polymethyl-n-butoxysiloxane, polymethyl-sec-butoxysiloxane, polymethyl-tert-butoxysiloxane, polymethylphenoxysiloxane, polydimethoxysiloxane, polydiethoxysiloxane, polydi-n-propoxysiloxane, polydi-iso- Propoxysiloxane, polydi-n-butoxysiloxane, polydi-sec
-Butoxysiloxane, polydi-tert-butoxysiloxane, polydiphenoxysiloxane.
At this time, the molecular weight of the polymer having a repeating unit of the general formula (3) is 300 to 200,000, preferably 300 to 10 in terms of polystyrene equivalent weight average molecular weight.
It is 0000. These may be used alone or in combination of two or more.

In hydrolyzing and condensing the above components (A) and (B), R ² O—, R ⁴ O— and R ⁵
It is preferable to use 0.25 to 3 mol of water, and it is particularly preferable to add 0.3 to 2.5 mol of water per 1 mol of the group represented by O-. The amount of water to add is 0.25
When the value is within the range of 3 mol, there is no possibility that the uniformity of the coating film is reduced, and the storage stability of the film-forming composition is not likely to be reduced.

When the components (A) and (B) are hydrolyzed and condensed, a catalyst may be used. Examples of the catalyst used at this time include a metal chelate compound, an organic acid, an inorganic acid, an organic base, and an inorganic base. Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-
Propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) Titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetate) Nart) titanium, di-n-butoxybis (acetylacetonate) titanium, di-se
c-butoxy bis (acetylacetonate) titanium,
Di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n-propoxytris (acetylacetonato) titanium, mono-i-propoxytris (acetylacetonate) ) Titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) ) Titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate)
Titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy.
Mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-
n-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (ethylacetoacetate) titanium, di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetate) Acetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxytris (ethylacetoacetate) titanium, mono-n-propoxytris (ethylacetoacetate) titanium,
Mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris ( Ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl acetoacetate)
Titanium chelate compounds such as titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxymono (acetylacetonato) zirconium, tri-n-propoxy Mono (acetylacetonato) zirconium, tri-i-propoxymono (acetylacetonato) zirconium, tri-n-butoxymono (acetylacetonato) zirconium, tri-sec-butoxymono (acetylacetonato) zirconium Tri-t-butoxy mono (acetylacetonate) zirconium, diethoxybis (acetylacetonate) zirconium,
Di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxybis (acetylacetonato) zirconium, di-n-butoxybis (acetylacetonato) zirconium, di-sec-butoxybis ( Acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxy・ Tris (acetylacetonate) zirconium,
Mono-n-butoxy tris (acetylacetonate)
Zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri- n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium,
Tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) Zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-
t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium, mono-n-propoxytris (ethylacetoacetate) zirconium, mono-i-propoxytris (ethylacetoacetate) zirconium Mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-
Butoxy / tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) zirconium, tris (acetylacetate) Zirconium chelate compounds such as (nate) mono (ethylacetoacetate) zirconium; aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum;

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid and sebacin Acid, gallic acid, butyric acid, melitic acid, arachidonic acid, shikimic acid,
2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-
Aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like. it can. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, Examples thereof include diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Among these catalysts, metal chelate compounds,
Organic acids and inorganic acids are preferred, and more preferred are titanium chelate compounds and organic acids. They are,
One type or two or more types may be used simultaneously.

The amount of the catalyst used is usually 0.1 to 100 parts by weight of the total of the components (A) and (B).
001 to 10 parts by weight, preferably 0.01 to 10 parts by weight.

The film-forming composition of the present invention is obtained by dissolving or dispersing the hydrolyzate and / or condensate of the component (A) and the component (B) in an organic solvent. As the organic solvent used in the present invention, for example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-pentane
Aliphatic hydrocarbon solvents such as heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene,
Methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene,
Aromatic hydrocarbon solvents such as n-amylnaphthalene and trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-
Pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol , Heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetra Decyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol Le, monoalcohol solvents such as cresol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol -2,4,2- methyl pentanediol -2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl- n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethyl nonanone, cyclohexanone, 2-
Ketone solvents such as hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone and fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl Ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-methyldioxolan, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono -N-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, Chi glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono -
n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Ether solvents such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl 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, vinegar N-butyl acid, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate,
Benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono acetate -N-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, Methoxytriglycol acetate,
Ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-oxalate
-Butyl, methyl lactate, ethyl lactate, n-butyl lactate,
Ester solvents such as n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide,
Nitrogen-containing solvents such as N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide;
Examples thereof include sulfur-containing solvents such as sulfolane and 1,3-propane sultone. These can be used alone or in combination of two or more.

The film-forming composition of the present invention contains the above-mentioned organic solvent, but the same solvent can be used when the component (A) and the component (B) are hydrolyzed and / or condensed. .

Specifically, water is added intermittently or continuously to an organic solvent in which the components (A) and (B) are dissolved. At this time, the catalyst may be added in advance to the organic solvent, or may be dissolved or dispersed in water at the time of adding water. The reaction temperature at this time is usually 0 to 100 ° C, preferably 15 to 80 ° C.

In forming the film-forming composition, the content of alcohol having a boiling point of 100 ° C. or less in the composition is preferably 20% by weight or less, particularly preferably 5% by weight or less. The alcohol having a boiling point of 100 ° C. or less can be obtained from the above (A)
It may occur during hydrolysis and / or condensation of the component and the component (B), and it is preferable to remove the component by distillation or the like so that the content is 20% by weight or less, preferably 5% by weight or less.

(A) in the film-forming composition of the present invention
Component (B) is used in an amount of 1 to 80 parts by weight, more preferably 1 to 60 parts by weight, based on 100 parts by weight of component (A) (complete hydrolyzed condensate). is there. When the use ratio of the component (B) is 1 to 80 parts by weight, the crack resistance and the storage stability of the composition become better. In the present invention, the term "completely hydrolyzed condensate" refers to a product in which the group represented by OR ² in the compound (1) is hydrolyzed to 100% to form an OH group and is completely condensed.

The film forming composition of the present invention may further contain the following components.

Β-diketone β-diketone includes acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, , 4-Nonandione, 3,5-nonandione, 5-methyl-2,4-hexanedione, 2,2
6,6-tetramethyl-3,5-heptanedione, 1,
One or more kinds such as 1,1,5,5,5-hexafluoro-2,4-heptanedione. In the present invention, the content of β-diketone in the film forming composition is preferably 1 to 50% by weight, more preferably 3 to 30% by weight of the total solvent. If the β-diketone is added in such a range, a certain storage stability can be obtained, and characteristics such as uniformity of the coating film of the film-forming composition are less likely to deteriorate.

Other Additives Components such as colloidal silica, colloidal alumina, organic polymer, and surfactant may be further added to the film-forming composition obtained in the present invention. 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 m.
μ, preferably 10-20 μm, solid content concentration of 10-4
It is about 0% by weight. Examples of such colloidal silica include methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industry Co., Ltd .; and Oscar manufactured by Catalyst Chemicals Co., Ltd. Examples of the colloidal alumina include alumina sols 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; and 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 polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylate compound, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, and a polyamide. Examples thereof include polyquinoxaline, polyoxadiazole, and a fluoropolymer. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a silicone surfactant, a polyalkylene oxide surfactant Agents, fluorine-containing surfactants and the like.

Method for Preparing Film Forming Composition In preparing the film forming composition of the present invention, as described above, the components (A) and (B) are mixed in a solvent and water is continuously added. Hydrolysis and condensation may be carried out by adding them periodically or intermittently, and there is no particular limitation. However, when the above-mentioned metal chelate compound and β-diketones are used, a method of preparing the composition and then finally adding β-diketone is adopted.

Specific examples of the method for preparing the composition of the present invention include the following methods. A predetermined amount of water is added to a mixture of the components (A) and (B), the required amount of the organic solvent and the metal chelate compound, and the mixture is subjected to a hydrolysis / condensation reaction. To remove low-boiling alcohol components in the reaction solution. After a predetermined amount of water is added to a mixture of the components (A) and (B) and the required amount of an organic solvent and a catalyst to carry out a hydrolysis / condensation reaction, a low-boiling alcohol component in the reaction solution is removed. how to. Water is continuously or intermittently added to a mixture consisting of the components (A) and (B), and the required amount of an organic solvent and a catalyst to carry out hydrolysis and condensation reactions. , Β-diketone to remove low-boiling alcohol components in the reaction solution. Water is continuously or intermittently added to a mixture of the components (A) and (B) and the required amounts of the organic solvent and the catalyst to carry out hydrolysis and condensation reactions. A method of removing the boiling alcohol component. The components (A) and (B) are hydrolyzed and condensed in separate reaction vessels by adding a predetermined amount of water in the presence of an organic solvent and a catalyst. A method in which the components are removed and the respective hydrolysis / condensates are mixed. The components (A) and (B) are hydrolyzed and condensed by adding a predetermined amount of water in separate reaction vessels in the presence of an organic solvent and a catalyst. -A method of adding a diketone, removing a low-boiling alcohol component in a reaction solution, and mixing respective hydrolyzed and condensed products.

The total solid content of the composition of the present invention thus obtained is preferably 2 to 30% by weight,
It is appropriately adjusted according to the purpose of use. When the total solid content of the composition is 2 to 30% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The weight average molecular weight of all polyorganosilane components [hydrolyzate and / or condensate of component (A) and component (B)] in the composition thus obtained is usually 1,0.
00 to 120,000, preferably 1,200 to 10
It is about 0000.

When the thus obtained composition of the present invention is applied to a substrate such as a silicon wafer, a SiO ₂ wafer or a SiN wafer, a spin coating, a dipping method, a roll coating method, a spraying method or the like is used. Painting means is used.

In this case, a dry film thickness may be about 0.05 to 1.5 μm in a single coating and about 0.1 to 3 μm in a double coating. it can. Thereafter, by drying at room temperature or by heating at a temperature of about 80 to 600 ° C., usually for about 5 to 240 minutes, a glassy or macromolecular insulating film can be formed. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used. As a heating atmosphere, the heating is performed in the atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure in which the oxygen concentration is controlled, or the like. Can be.

The interlayer insulating film thus obtained is excellent in insulation, uniformity of coating film, dielectric constant, crack resistance of coating film, and surface hardness of coating film.
System L, DRAM, SDRAM, RDRAM, D
-It is useful for applications such as interlayer insulating films for semiconductor devices such as RDRAMs, protective films such as surface coat films for semiconductor devices, interlayer insulating films for multilayer wiring boards, protective films for liquid crystal display devices, and insulating films.

[0041]

The present invention will now be described more specifically with reference to examples. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, respectively, unless otherwise specified. Further, the evaluation of the film-forming composition in the examples was measured as follows.

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

Oxygen plasma ashing resistance A composition sample was applied on an 8-inch silicon wafer by spin coating, and the substrate was dried on a hot plate at 80 ° C. for 5 minutes and at 200 ° C. for 5 minutes. The substrate was baked in a vacuum oven for 60 minutes. The absorption intensity of the organic group in the obtained coating film was measured using a Fourier transform infrared spectrophotometer (FT-IR) (JIR-5, manufactured by JEOL Ltd.).
500). Then, using a barrel-type oxygen plasma ashing apparatus, this coating film was subjected to 1 to
rr, 800 W, 500 Sccm for 20 minutes,
An oxygen plasma treatment was performed. Next, Si near 1,270 cm ⁻¹ of the organic group in the coating film after the oxygen plasma treatment was applied.
The intensity of the bending vibration of the methyl group bonded to the FT-I
It measured using R. From the change in the intensity measured in this way, the oxygen plasma ashing property was evaluated according to the following criteria. ：: Change in absorption strength of organic group is less than 40% Δ: Change in absorption strength of organic group is 40% or more and less than 60% X: Change in absorption strength of organic group is 60% or more

The crack resistance 8-inch silicon on the wafer is coated with a composition sample by spin coating, for 5 minutes at 80 ° C. on a hot plate, and dried for 5 minutes the substrate at 200 ° C., further 380 ° C. The substrate was baked in a vacuum oven for 60 minutes. The appearance of the obtained coating film was observed with a 350,000 lux surface observation lamp, and evaluated according to the following criteria. ：: No crack is observed on the coating film surface. X: Cracks are observed on the coating film surface.

[0045] On the dielectric constant 8-inch silicon wafer, and applying the composition sample by spin coating, for 5 minutes at 80 ° C. on a hot plate, and dried for 5 minutes the substrate at 200 ° C., further vacuum 380 ° C. The substrate was baked in an oven for 60 minutes. Aluminum was vapor-deposited on the obtained substrate to produce a substrate for permittivity evaluation. The dielectric constant was calculated from the capacitance value at 10 kHz using an HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd. and an HP4284A precision LCR meter.

Synthesis Example 1 1,6.0 g of 1,3,5,7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane was dissolved in 170 g of propylene glycol monomethyl ether, followed by stirring with a three-one motor. , Solution temperature 6
Stabilized at 0 ° C. Next, 64 g of ion-exchanged water in which 4.4 g of maleic acid was dissolved and methyltrimethoxysilane 1
35.7 g was added simultaneously to the solution over 1 hour. Then, after reacting at 60 ° C. for 3 hours, the reaction solution was cooled to room temperature. 215 g of propylene glycol monomethyl ether was added to this reaction solution, and 215 g of a solution containing methanol and ethanol was removed from the reaction solution by evaporation at 50 ° C. to obtain a reaction solution (A-1). The weight-average molecular weight of the hydrolyzed condensate thus obtained is 3,
600.

Synthesis Example 2 305.4 g of methyltrimethoxysilane and 6.4 g of polydiethoxysiloxane having a weight average molecular weight of about 2,000 in terms of polystyrene were dissolved in 143 g of propylene glycol monopropyl ether, followed by stirring with a three-one motor to obtain a solution. The temperature was stabilized at 60 ° C. Next, 70 g of ion-exchanged water in which 4.4 g of malonic acid was dissolved 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. 482 g of propylene glycol monopropyl ether was added to this reaction solution, and a solution containing methanol and ethanol was removed from the reaction solution at 50 ° C. by evaporation of 482 g to obtain a reaction solution (A-2). The weight-average molecular weight of the hydrolyzed condensate thus obtained was 5,400.

Synthesis Example 3 305.4 g of methyltrimethoxysilane, 6.4 g of polydiethoxysiloxane having a weight average molecular weight of about 2,000 in terms of polystyrene, and 1.1 g of diisopropoxytitanium bisethylacetyl acetate were dissolved in 143 g of propylene glycol monopropyl ether. After that, the mixture was stirred by a three-one motor, and the solution temperature was stabilized at 60 ° C. Next, 70 g of ion-exchanged water 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. To this reaction solution, 482 g of propylene glycol monopropyl ether was added, and at 50 ° C., 482 g of a solution containing methanol and ethanol was added from the reaction solution.
It was removed by evaporation to obtain a reaction solution (A-3).
The weight-average molecular weight of the hydrolyzed condensate thus obtained was 5,100.

Synthesis Example 4 The reaction solution (B-B) was prepared in the same manner as in Synthesis Example 3 except that polydiethoxysiloxane having a weight average molecular weight of about 2,000 in terms of polystyrene was not added.
1) was obtained. The weight average molecular weight of the hydrolyzed condensate thus obtained was 3,500.

Example 1 The reaction solution (A-1) obtained in Synthesis Example 1 was filtered through a Teflon filter having a pore size of 0.2 μm, and applied to a silicon wafer by spin coating. When the oxygen plasma ashing resistance of the obtained coating film was evaluated, the change in the absorption intensity of the organic group was as good as 22%. The maximum film thickness without cracks was evaluated by changing the film thickness of the coating film.
It showed excellent crack resistance of 1,750 nm. Also,
When the dielectric constant of the coating film was evaluated, it showed a very low dielectric constant of 2.68.

Examples 2-3 The coatings were evaluated in the same manner as in Example 1 except that the reaction solutions (A-2) and (A-3) obtained in Synthesis Examples 2 and 3 were used. Table 1 shows the evaluation results.

[0052]

[Table 1]

Comparative Example 1 The coating film was evaluated in the same manner as in Example 1 except that the reaction solution (B-1) obtained in Synthesis Example 4 was used. Although the dielectric constant of the coating film was as good as 2.63, the oxygen plasma ashing resistance was 43%, and the crack limit thickness of the obtained coating film was 9%.
It was inferior to 50 nm.

[0054]

According to the present invention, by containing a hydrolyzate of a specific alkoxysilane and / or a condensate thereof, the coating film is excellent in balance of oxygen plasma ashing resistance, crack resistance, dielectric constant and the like. It is possible to provide a composition for forming a film (material for an interlayer insulating film).

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kinji Yamada 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F term (reference) 4J038 DL051 DL052 JC32 NA11 NA12 NA17 NA21 5F033 QQ74 RR25 SS22 WW04 XX17 XX24 5F058 AA02 AA10 AC03 AC06 AD01 AD05 AF04 AG01 AG04 AH01 AH02

Claims (3)

[Claims] (A) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) wherein R ¹ and R ² are the same or different Each represents a monovalent organic group, and a represents an integer of 0 to 2.)
And (B) (B-1) a compound represented by the following general formula (2), and / or (R ³ and R ⁴ may be the same or different and each represents a monovalent organic group, and n represents an integer of 3 to 10.) and / or (B-2) In the following general formula (3) Polymer having a repeating unit represented by -Si (OR ⁵ ) _2-b (R ⁶ ) _b O- (3) (R ⁵ and R ⁶ may be the same or different, and are each a monovalent organic compound. And b represents an integer of 0 to 1.)
A film-forming composition comprising a hydrolyzate and / or condensate of a silane compound comprising: 2. Component (A) (in terms of complete hydrolysis condensate)
The film forming composition according to claim 1, wherein the component (B) is 1 to 80 parts by weight based on 100 parts by weight. 3. A material for forming an insulating film, comprising the composition according to claim 1.