JP2001203197A - Membrane and forming method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyorganosiloxane membrane of low permittivity and high elasticity which is useful as an interlayer insulating film for a semiconductor element and the like. SOLUTION: A polyorganosiloxane film is provided whose film density is 0.5-1.4 g/cm3 and which has a structure represented by a general equation SiOxCyHz where 1.3<x<1.9, 0.2<y<8.0, and 0.6<z<7.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-density film having a specific structure and a method for forming the film.
The present invention relates to a film having excellent dielectric constant and mechanical strength, and a method for forming the film.

[0002]

2. Description of the Related Art Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method has been frequently used as an interlayer insulating film in a semiconductor device or the like. 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 of semiconductor devices and the like, more excellent electrical insulation between conductors is required, and therefore, an interlayer insulating film material having a lower dielectric constant is required.

[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. However, the dielectric constant of the conventional inorganic interlayer insulating film material is 3.0 or more, which is insufficient for high integration.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a film suitable for an interlayer insulating film having improved dielectric constant characteristics and excellent balance in mechanical strength and the like.

[0005]

The present invention comprises a structure represented by the following general formula (1) and has a film density of 0.5 to 0.5.
A membrane characterized by a weight of 1.4 g / cm ³ . SiOxCyHz (1) (where 1.3 <x <1.9, 0.2 <y <8.0,
0.6 <z <7.0. Here, the film has a carbon content of 1.0 × 10 ^{21 to} 3.
It is preferably 0 × 10 ²² atm / cm ³ . Further, the film preferably has a thickness of 3 μm or less. Further, the film preferably has 5% or less vacancies of 10 nm or more as measured by a vacancy distribution measurement by the BJH method. Furthermore, the film is preferably 1nm or more holes by pore size measurement using an electron microscope is 5/100 nm ² or less. Further, the film has the following (a)
It is preferable to satisfy the following conditions. (A) elastic modulus ≧ 2.5 GPa (b) cohesive fracture strength ≧ 30 MPa (c) refractive index ≦ 1.40 (d) 1% weight loss temperature ≧ 400 ° C. Further, the film is formed on a semiconductor substrate. Film. In addition, examples of the film include a film which forms part of a semiconductor device. Further, as the film, an insulating film may be used. Next, the present invention relates to (A) a compound represented by the following general formula (2) (hereinafter referred to as “compound (2)”).
At least one silane compound selected from the group of compounds represented by the following general formula (3) (hereinafter also referred to as “compound (3)”), a hydrolyzate thereof and / or
Or a condensate thereof, R ² _n Si (OR ¹ ) _4-n ... (2) [In the general formulas (2) and (3), R ¹ and R ² may be the same or different, and each is a monovalent organic group and R is 2
N represents an integer of 0 to 2, and s and t represent 0
-1. A film-forming composition comprising (B) an organic polymer and (C) an organic solvent (hereinafter also referred to as “composition (1)”) is applied to a substrate and heated, wherein the film is heated. The present invention relates to a formation method (hereinafter, also referred to as “formation method (1)”). Next, the present invention relates to (A) a compound [compound (2)] represented by the following general formula (2) and the following general formula (3)
At least one silane compound selected from the group of compounds [compound (3)] represented by the following formula: R ² _n Si (OR ¹ ) _4-n ... (2) [In the general formulas (2) and (3), R ¹ and R ² may be the same or different, and each is a monovalent organic group and R is 2
N represents an integer of 0 to 2, and s and t represent 0
-1. (D) A film-forming composition (hereinafter referred to as “Composition (2)”) in which the weight-average molecular weight of a hydrolysis-condensation product obtained by hydrolysis and condensation in the presence of an alkali catalyst is 50,000 to 10,000,000. )) Is applied to a substrate and heated (hereinafter, also referred to as “formation method (2)”).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The film of the present invention has a structure represented by the following general formula (1), and has a film density of 0.5 to 1.4 g / cm ³ . SiOxCyHz (1) (where 1.3 <x <1.9, 0.2 <y <8.0,
0.6 <z <7.0. In the general formula (1), the numerical ranges of x, y, and z are preferably 1.4 <x <1.9, 0.2 <y <7.0,
0.6 <z <6.0, more preferably 1.5 <x <
1.9, 0.2 <y <6.0, 0.6 <z <5.0. In the general formula (1), by setting x, y, and z in the above ranges, the film of the present invention can exhibit low dielectric constant and high mechanical strength. In the present invention, the above numerical values of x, y and z can be formed by applying and heating the film-forming composition according to the present invention by the method according to the present invention.

[0007] The density of the film of the present invention is 0.5-1.
4 g / cm ³ , preferably 0.6 to 1.4 g / cm ³ ,
More preferably, it is 0.6 to 1.3 g / cm ³ . If the film density is less than 0.5 g / cm ³ , sufficient mechanical strength cannot be obtained, while if it exceeds 1.4 g / cm ³ , the dielectric constant may not be low. The film density was determined by a combination of Rutherford backscattering and hydrogen forward scattering.
It is a measured value.

The carbon content of the film of the present invention is usually 1.0
× 10 ^{21 to} 3.0 × 10 ²² atm / cm ³ , preferably 1.0 × 10 ^{21 to} 2.5 × 10 ²² atm / cm ³ , more preferably 1.0 × 10 ^{21 to} 2.0 × 10 ²² atm /
cm ³ . The film has a carbon content of 1.0 × 10 ²¹ atm
If it is less than / cm ³ , the water absorption of the film may increase,
On the other hand, if it exceeds 3.0 × 10 ²² atm / cm ³ , sufficient mechanical strength may not be obtained. The carbon content of the film is a value measured by a combination of Rutherford backscattering method and hydrogen forward scattering method.

The thickness of the film of the present invention is usually 3 μm or less,
Preferably 2.8 μm or less, more preferably 2.5 μm
m or less. If the thickness exceeds 3.0 μm, cracking or peeling may occur. The film thickness can be easily controlled by adjusting the solid content concentration of the film forming composition and / or each application condition in each application method described in the present invention. The film thickness is measured by an optical film thickness meter (ellipsometer).

[0010] In the film of the present invention, pores having a diameter of 10 nm or more as measured by a pore distribution measurement by the BJH method are usually 5% or less, preferably 4% or less, more preferably 3% or less. B
If the number of vacancies of 10 nm or more measured by the vacancy distribution measurement by the JH method exceeds 5%, uniformity of film properties such as dielectric constant and mechanical strength may be impaired, which is not preferable. In addition,
The pore distribution measurement by the BJH method is a method of calculating a pore diameter from nitrogen adsorption / desorption behavior in a porous body.

In the film of the present invention, the number of pores having a diameter of 1 nm or more as measured by pore diameter measurement with an electron microscope is usually 5/100.
nm ² or less, preferably 4/100 nm ² or less, more preferably 5/100 nm ² or less. The number of pores of 1 nm or more determined by pore diameter measurement by electron microscope observation was 5
If the number exceeds 100 nm ² , the uniformity of film characteristics such as dielectric constant and mechanical strength may be impaired, which is not preferable. The pore size measurement by electron microscope observation is a method of measuring the number of pores having a diameter of 1 nm or more per 100 nm ² in an arbitrary observation range in transmission electron microscope observation.

The film of the present invention preferably satisfies the above conditions (a) to (d). That is, in the film of the present invention, (a) the elastic modulus is 2.5 GPa or more, preferably 2.8 GPa or more, and more preferably 3.0 GPa or more. If it is less than 2.5 GPa, for example, when used as an insulating film for a semiconductor, sufficient film strength may not be obtained during molding. The elastic modulus (a) is a value measured by a continuous rigidity measuring method.

In the membrane of the present invention, (b) the cohesive failure strength is 3.0 MPa or more, preferably 3.5 MPa.
The pressure is more preferably 3.0 MPa or more. 3.
If it is less than 0 MPa, for example, sufficient film strength may not be obtained at the time of molding processing when used as a semiconductor insulating film. In addition, (b) the cohesive failure strength is a value measured by a stud bull test by the Sebastian method.

Further, in the film of the present invention, (c) the refractive index is 1.40 or less, preferably 1.39 or less, more preferably 1.38 or less. If it exceeds 1.40,
The dielectric constant of the film may increase, which is not preferable. In addition,
(C) The refractive index is a value measured by an optical film thickness meter (ellipsometer).

Further, in the film of the present invention, (d) 1%
The weight loss temperature is 400 ° C. or higher, preferably 425 ° C. or higher. If the temperature is lower than 400 ° C., for example, when used as a semiconductor insulating film, decomposition gas or the like may be generated by heating during the manufacture of a semiconductor device, which is not preferable. In addition,
(D) 1% weight loss temperature was measured using a thermogravimetric analyzer (TGA)
Was determined by measuring the temperature at which the weight loss was 1% when heated at a rate of 10 ° C./min in a nitrogen atmosphere.

The film of the present invention can be prepared, for example, by the above composition (1)
(1) or composition (2)
Can be manufactured by a film forming method (2) using Hereinafter, the composition (1) and a method (1) for forming a film thereof,
The composition (2) and the method (2) for forming the film will be sequentially described.

Composition (1) In the composition (1), the component (A) [compounds (2) to (3), a hydrolyzate thereof and / or a condensate thereof (hereinafter referred to as "the compound") is used as a base polymer for forming a film. The “hydrolysate and / or condensate thereof” is also referred to as “hydrolysis condensate”)), and (B) an organic polymer as a material for forming the porous material, and a solvent for the components (A) to (B). ,
(C) Use an organic solvent. Thus, the composition (1) containing the components (A) to (C) is applied to a substrate such as a silyl wafer by dipping or spin coating, and then heated to heat the (B) organic polymer and (C) organic polymer. When the solvent is removed and the component (A) is subjected to thermal polycondensation, the component (A) forms a glassy or macromolecular film,
(B) Micropores are formed by decomposing and removing all or most of the organic polymer. The resulting membrane is
It is a porous low-density film, excellent in CMP resistance, low in dielectric constant, and excellent in stability of electrical characteristics due to low water absorption, and can form an interlayer insulating film material.

Here, the above-mentioned hydrolyzate in the component (A) refers to the compounds (2) to
It is not necessary that all of the R ¹ O— groups contained in (3) are hydrolyzed, for example, one having only one hydrolyzed, two or more having been hydrolyzed, or
A mixture of these may be used. The condensate in the component (A) is a compound (2) constituting the component (A).
The silanol groups of the hydrolyzates of (3) to (3) condense to form Si-
In the present invention, all of the silanol groups need not be condensed, but a mixture of those having a small amount of silanol groups condensed, those having different degrees of condensation, etc. Is a concept that also includes.

The following (A) to (A) are used in the composition (1).
The component (C) will be described, and then the composition (1)
The method for preparing the compound will be described in detail. Component (A): As the component (A), a compound (2) having 2 to 4 R ¹ O— groups and / or a compound (3) having 4 to 6 R ¹ O— groups are used. In the present invention, the use of the compound (3) particularly improves the CMP resistance. In the above general formulas (2) and (3), R
^{1 to} R ² may be the same or different;
Is a valence organic group. 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, and a butyl group.
It preferably has 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom or the like. In addition, examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, and an ethylphenyl group.

As specific examples of the compound represented by the general formula (2), compounds having n = 0 in the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra- iso-propoxysilane, tetra-n-butoxysilane, tetra-se
Examples thereof include c-butoxysilane, tetra-tert-butoxysilane, and tetraphenoxysilane.

Specific examples of the compound where n = 1 in the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxy. Silane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxy Silane, ethyltri-s
ec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, 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-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, s
ec-butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyl
Butyl tri-n-propoxy silane, t-butyl tri-iso-propoxy silane, t-butyl tri-n-butoxy silane, t-butyl tri sec-butoxy silane, t-butyl tri-tert-butoxy silane, t-butyl
Butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n
-Propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-te
Examples thereof include rt-butoxysilane and phenyltriphenoxysilane.

Specific examples of the compound where n = 2 in the general formula (2) include 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-
tert-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-i
so-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-
Propoxysilane, di-iso-propyl-di-iso
-Propoxysilane, di-iso-propyl-di-n-
Butoxysilane, di-iso-propyl-di-sec-
Butoxysilane, di-iso-propyl-di-tert
-Butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n
-Butyldiethoxysilane, di-n-butyl-di-n-
Propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di- tert-butoxysilane, di-n
-Butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane,
Di-sec-butyl-di-iso-propoxysilane,
Di-sec-butyl-di-n-butoxysilane, di-s
ec-butyl-di-sec-butoxysilane, di-se
c-butyl-di-tert-butoxysilane, di-se
c-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxy Silane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxy Silane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-s
ec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

Among the compounds represented by the general formula (2), tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, alkyltrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane, dimethyldiethoxysilane Dialkyldialkoxysilanes such as silane and dimethyldimethoxysilane are preferred.

In the composition (1) of the present invention, the compounds represented by the above general formula (2) are preferably used in combination of two or more, especially the compounds of n = 0 and n = 1
It is particularly preferable to use the compound (1) in combination with heat resistance, dielectric properties, and mechanical properties. In the present invention, the compound of n = 0 in the general formula (2) / the compound of n = 1 in the general formula (2) / n = 2 in the general formula (2)
The use ratio of the compound is 10-70 / 100-0 / 0
30 (% by weight) is preferred.

On the other hand, in the general formula (3), R is
It shows a divalent organic group, and s and t show the integer of 0-1. Here, in the general formula (3), examples of the divalent organic group include an alkylene group and an arylene group. Here, the alkylene group includes a methylene group, an ethylene group, and the like, and preferably has 1 to 1 carbon atoms.
2, and a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (3), examples of the arylene group include a phenylene group and a naphthalene group.

Specific examples of the compound represented by the general formula (3) include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri- bis (trialkoxysilyl) methanes such as i-propoxysilyl) 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,
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,
1,2-bis (trialkoxysilyl) ethanes such as 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
1- (dialkoxymethylsilyl) -1- (trialkoxysilyl) methanes such as -butoxysilyl) methane and 1- (di-tert-butoxymethylsilyl) -1- (tri-tert-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
1- (dialkoxymethylsilyl) -2- (trialkoxysilyl) ethanes such as -butoxysilyl) ethane and 1- (di-tert-butoxymethylsilyl) -2- (tri-tert-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-butoxy) Bis (dialkoxymethylsilyl) methanes such as methylsilyl) 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 (dialkoxymethylsilyl) ethanes such as 1,2-bis (di-sec-butoxymethylsilyl) ethane and 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, 1,4-bis (Tri-sec-butoxysilyl)
Benzene, 1,4-bis (tri-t-butoxysilyl)
Bis (trialkoxysilyl) benzenes such as benzene; and the like. These compounds (3)
May be used alone or in combination of two or more.

In the compound (3), bis (trialkoxysilyl) methane such as bis (trimethoxysilyl) methane and bis (triethoxysilyl) methane;
1,2-bis (trialkoxysilyl) ethane such as -bis (trimethoxysilyl) ethane and 1,2-bis (triethoxysilyl) ethane; 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane , 1-
1- (dialkoxymethylsilyl)-such as (diethoxymethylsilyl) -1- (triethoxysilyl) methane
1- (dialkoxysilyl) methane; 1- (dialkoxy) such as 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane and 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane Methylsilyl) -2- (trialkoxysilyl) ethane; bis (dialkoxymethylsilyl) methane such as bis (dimethoxymethylsilyl) methane and bis (diethoxymethylsilyl) methane; 1,2-bis (dimethoxymethylsilyl) Ethane, 1,2-bis (diethoxymethylsilyl)
1,2-bis (dialkoxymethylsilyl) ethane such as ethane; 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene,
1,3-bis (trimethoxysilyl) benzene, 1,3
Bis (trialkoxysilyl) benzene such as -bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene; Bis (trialkoxysilyl) methane such as silyl) methane and bis (triethoxysilyl) methane; 1,2-
1,2-bis (trialkoxysilyl) ethane such as bis (trimethoxysilyl) ethane and 1,2-bis (triethoxysilyl) ethane is preferred.

When the compound (2) and the compound (3) are used in combination in the composition (1), the ratio of the compound (2) / compound (3) is 100 to 20/0 to 80 (% by weight). preferable. In the composition (1), the compound (3)
In particular, the resistance to CMP is improved.

Compound (2) to Component (A)
When hydrolyzing and condensing (3), it is preferable to use 0.25 to 3 mol of water and preferably 0.3 to 2.5 mol of water per mol of the group represented by R ¹ O—. It is particularly preferred to add. If the amount of water to be added is in the range of 0.25 to 3 mol, there is no possibility that the uniformity of the coating film is reduced,
In addition, there is little risk of polymer precipitation and gelation during the hydrolysis and condensation reactions. When the component (A) is a hydrolyzed condensate of the compound (2) and / or the compound (3), the molecular weight is preferably from 500 to 100,000 as a weight average molecular weight according to the GPC method.

Catalyst: When the compounds (2) and (3) constituting the component (A) 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, 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, -N-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy.
Bis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-
Propoxy bis (acetylacetonate) titanium, di-n-butoxybis (acetylacetonate) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonate) Titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy.
Tris (acetylacetonate) titanium, mono-n-butoxytris (acetylacetonate) titanium, mono-sec-butoxytris (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) Acetate) titanium, tri-s
ec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t
-Butoxy bis (ethyl acetoacetate) titanium,
Monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) ) Titanium, mono-sec
-Butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxytris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate)
Titanium chelate compounds such as titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetyl) (Acetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxy.
Bis (acetylacetonate) zirconium, di-n-
Propoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di-n-butoxybis (acetylacetonate) zirconium, di-sec-butoxy.
Bis (acetylacetonate) zirconium, di-t-
Butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (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 (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, Tri-s
ec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy.
Bis (ethylacetoacetate) zirconium, di-i
-Propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) ) Zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) 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 (acetylacetonate) Zirconium chelate compounds such as mono (ethylacetoacetate) zirconium;
Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; 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 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, benzenesulfonic acid, p-toluenesulfonic acid, phthalic acid, fumaric acid, citric acid And tartaric acid. 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, diazabicyclookran, 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, more preferably titanium chelate compounds, organic acids, particularly preferably organic acids, especially acetic acid, oxalic acid, maleic acid, malonic acid and the like.
The amount of the catalyst to be used is generally 0.0001 to 1 mol, preferably 0.001 to 0.1 mol, per 1 mol of the total amount of the compounds (2) to (3) before hydrolysis.

(B) Organic polymer; Examples of (B) organic polymer include polyether, polyester, polycarbonate, polyanhydride, and (meth)
At least one selected from the group of acrylic polymers is exemplified.

Among them, examples of the polyether constituting the component (B) include polyalkylene glycol compounds having 2 to 12 carbon atoms in the repeating unit. Examples thereof include polyethylene glycol, polypropylene glycol, and polytrimethylene. Glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, polyethylene glycol-polypropylene glycol block copolymer, polyethylene glycol-polytetramethylene glycol block copolymer, polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer, and methyl ether thereof , Ethyl ether, propyl ether, trimethoxysilyl ether, triethoxysilyl ether Le, tripropoxysilyl ethers, trimethoxysilylmethyl ethers, triethoxysilylmethyl ethers, 2-trimethoxysilylethyl ethers, 2-triethoxysilylethyl ethers, 3
-In addition to trimethoxysilylpropyl ether, 3-triethoxysilylpropyl ether, etc., polyethylene glycol monopentyl ether, polyethylene glycol monohexyl ether, polyethylene glycol monopeptyl ether, polyethylene glycol monooctyl ether, polyethylene glycol monononyl ether, polyethylene glycol Monodecanyl ether,
Polyethylene glycol monoundecanyl ether, polyethylene glycol monododecanyl ether, polyethylene glycol monotridecanyl ether, polyethylene glycol monotetradecanyl ether, polyethylene glycol monopentadecanyl ether, polyethylene glycol monohexadecanyl ether, polyethylene glycol monoheptade Canyl ether, polyethylene glycol monooctadecanyl ether, polyethylene glycol monononadecanyl ether, polyethylene glycol monoicosanyl ether, polyethylene glycol monohenicosanyl ether, polyethylene glycol monodocosanyl ether, polyethylene glycol monotricosanyl ether, polyethylene glycol mono Tetra Kosani Ether, polyethylene glycol monopentacosanyl ether, polyethylene glycol monohexacosanyl ether, polyethylene glycol monoheptacosanyl ether, polyethylene glycol monooctacosanyl ether, polyethylene glycol monononacosanyl ether, polyethylene glycol monotriacontanyl ether, etc. Polyethylene glycol alkyl ethers and their methyl ether, ethyl ether, propyl ether, trimethoxysilyl ether, triethoxysilyl ether, tripropoxysilyl ether, trimethoxysilyl methyl ether, triethoxysilyl methyl ether, 2-trimethoxysilyl ethyl ether , 2-triethoxysilyl ethyl ether, 3-trimethoxysilyl Polyethylene glycol alkyl ether derivatives such as propyl ether, 3-triethoxysilylpropyl ethers;

Polyethylene glycol mono-p-methylphenyl ether, polyethylene glycol mono-p-
Ethyl phenyl ether, polyethylene glycol mono-p-propyl phenyl ether, polyethylene glycol mono-p-butyl phenyl ether, polyethylene glycol mono-p-pentyl phenyl ether, polyethylene glycol mono-p-hexyl phenyl ether, polyethylene glycol mono-p- Peptyl phenyl ether, polyethylene glycol mono-p-octyl phenyl ether, polyethylene glycol mono-p
-Nonylphenyl ether, polyethylene glycol mono-p-decanylphenyl ether, polyethylene glycol mono-p-undecanylphenyl ether, polyethylene glycol mono-p-dodecanylphenyl ether, polyethylene glycol mono-p-tridecanylphenyl ether , Polyethylene glycol mono-p-
Tetradecanyl phenyl ether, polyethylene glycol mono-p-pentadecanyl phenyl ether, polyethylene glycol mono-p-hexadecanyl phenyl ether, polyethylene glycol mono-p-heptadecanyl phenyl ether, polyethylene glycol mono-p-octadeca Nyl phenyl ether, polyethylene glycol mono-p-nonadecanyl phenyl ether,
Polyethylene glycol mono-p-icosanyl phenyl ether, polyethylene glycol mono-p-henicosanyl phenyl ether, polyethylene glycol mono-
Polyethylene glycol-p-alkylphenyl ethers such as p-docosanyl phenyl ether, polyethylene glycol mono-p-tricosanyl phenyl ether, polyethylene glycol mono-p-tetracosanyl phenyl ether and methyl ether, ethyl ether, propyl thereof Ether, trimethoxysilyl ether, triethoxysilyl ether, tripropoxysilyl ether, trimethoxysilylmethyl ether, triethoxysilylmethyl ether, 2-trimethoxysilylethyl ether, 2-triethoxysilylethylether, 3-trimethoxysilyl Propyl ether, 3-
Polyethylene glycol-p-alkylphenyl ether derivatives such as triethoxysilylpropyl ether;

Polyethylene glycol monopentanoate, polyethylene glycol monohexanoate, polyethylene glycol monoheptanoate,
Polyethylene glycol monooctanoate, polyethylene glycol monononanoate, polyethylene glycol monodecanoate, polyethylene glycol monoundecanoate, polyethylene glycol monododecanoate, polyethylene glycol monotridecanoate, polyethylene glycol monotetradecanoate, Polyethylene glycol monopentadecanoate, polyethylene glycol monohexadecanoate, polyethylene glycol monoheptadecanoate, polyethylene glycol monooctadecanoate, polyethylene glycol monononadecanoate, polyethylene glycol monoicosanoate, polyethylene glycol monohexanoate Sanate ester Polyethylene glycol monodocosanoate, polyethylene glycol monotricosanoate, polyethylene glycol monotetracosanoate, polyethylene glycol monopentacosanoate, polyethylene glycol monohexacosanoate, polyethylene glycol monoheptacosanoate, polyethylene glycol Polyethylene glycol alkyl esters such as monooctacosanoate, polyethylene glycol monononaconate, and polyethylene glycol monotriacontanate, and methyl ether and ethyl ether thereof,
Propyl ether, trimethoxysilyl ether, triethoxysilyl ether, tripropoxysilyl ether, trimethoxysilylmethyl ether, triethoxysilylmethyl ether, 2-trimethoxysilylethyl ether, 2-triethoxysilylethylether, 3
And polyethylene glycol alkyl ester derivatives such as -trimethoxysilylpropyl ether and 3-triethoxysilylpropyl ether. These polyethers can be used alone or in combination of two or more.

The weight average molecular weight of the polyether measured by the GPC method is usually 300 to 300,000, preferably 3
00 to 200,000, particularly preferably 300 to 10
It is 0000.

Examples of the polyester constituting the component (B) include compounds containing an aliphatic chain having 2 to 12 carbon atoms and an ester bond in a repeating unit.
For example, polycaprolactone, polypivalolactone, polyethylene oxalate, polyethylene malonate, polyethylene succinate, polyethylene glutarate,
Polyethylene adipate, polyethylene pimerate, polyethylene suberate, polyethylene azelate, polyethylene sebacate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polypropylene glulate, polypropylene adipate, polypropylene pimerate, polypropylene suberate, polypropylene Azelate, polypropylene sebacate, polybutylene oxalate, polybutylene malonate, polybutylene succinate, polybutylene glitarate, polybutylene adipate, polybutylene pimerate, polybutylene belate, polybutylene azelate, polybutylene Sebacate, polyoxydiethylene oxalate, polyoxydiethylene malonate,
Polyoxydiethylene succinate, polyoxydiethylene glitarate, polyoxydiethylene adipate,
Aliphatic polyesters such as polyoxydiethylene pimerate, polyoxydiethylene suberate, polyoxydiethylene azelate, and polyoxydiethylene sebacate, and their methyl ether, ethyl ether, propyl ether, trimethoxysilyl ether, triethoxysilyl Ether, tripropoxysilyl ether,
Trimethoxysilyl methyl ether, triethoxysilyl methyl ether, 2-trimethoxysilylethyl ether, 2-triethoxysilylethyl ether, 3-trimethoxysilylpropyl ether, 3-triethoxysilylpropyl ether, methyl ester, ethyl ester, Propyl ester, trimethoxysilyl ester, triethoxysilyl ester, tripropoxysilyl ester, trimethoxysilylmethyl ester, triethoxysilylmethyl ester, 2-trimethoxysilylethyl ester, 2-triethoxysilylethyl ester, 3-trimethoxy Silyl propyl ester, 3-
Examples thereof include aliphatic polyester alkyl ether derivatives such as triethoxysilylpropyl ester and aliphatic polyester alkyl ester derivatives. These polyesters can be used alone or in combination of two or more.

The weight average molecular weight of the polyester by GPC is usually from 300 to 300,000, preferably from 3 to 300,000.
00 to 200,000, particularly preferably 300 to 10
It is 0000.

Further, as the polycarbonate constituting the component (B), there may be mentioned an aliphatic polycarbonate having 2 to 12 carbon atoms in the repeating unit.
Polyethylene carbonate, polypropylene carbonate, polytrimethylene carbonate, polytetramethylene carbonate, polypentamethylene carbonate, polyhexamethylene carbonate, polyheptamethylene carbonate, polyoctamethylene carbonate, polynonamethylene carbonate, polydecamethylene carbonate, polyoxydiethylene carbonate , Poly-3,6
-Dioxyoctane carbonate, poly-3,6,9-
Aliphatic polycarbonates such as trioxyundecane carbonate, polyoxydipropylene carbonate, polycyclopentane carbonate, and polycyclohexane carbonate, and their methyl esters, ethyl esters, propyl esters, trimethoxysilyl esters, triethoxysilyl esters, and tripropoxysilyl esters , Trimethoxysilylmethyl ester, triethoxysilylmethyl ester, 2-trimethoxysilylethyl ester, 2-triethoxysilylethyl ester, 3-trimethoxysilylpropyl ester, 3-
Examples include aliphatic polycarbonate alkyl ester derivatives such as triethoxysilyl propyl ester. These polycarbonates can be used alone or in combination of two or more.

The weight average molecular weight of the polycarbonate according to the GPC method is usually from 300 to 300,000, preferably from 300 to 200,000, particularly preferably from 300 to 1,000,000.
00,000.

Examples of the polyanhydride constituting the component (B) include polyanhydrides obtained from aliphatic dicarboxylic acids having 2 to 12 carbon atoms, such as polyoxalic anhydride, polymalonic anhydride, and the like. Aliphatic polyanhydrides such as polysuccinic anhydride, polyglutaric anhydride, polyazipic anhydride, polypimeric anhydride, polysberic anhydride, polyazelic anhydride, polysebasic anhydride, and methyl ester thereof , Ethyl ester, propyl ester, trimethoxysilyl ester, triethoxysilyl ester,
Tripropoxysilyl ester, trimethoxysilylmethyl ester, triethoxysilylmethyl ester, 2
And aliphatic polyanhydride alkyl ester derivatives such as -trimethoxysilylethyl ester, 2-triethoxysilylethyl ester, 3-trimethoxysilylpropyl ester, and 3-triethoxysilylpropyl ester. These polyanhydrides can be used alone or in combination of two or more.

The weight average molecular weight of the polyanhydride determined by the GPC method is usually 300 to 300,000, preferably 300 to 200,000, particularly preferably 300.
~ 100,000.

Further, as the (meth) acrylic polymer constituting the component (B), at least one selected from the group consisting of a polyoxyethyl group, a polyoxypropyl group, an amide group, a hydroxyl group and a carboxyl group is used. (Meth) acrylic polymer having the same. The (meth) acrylic polymer includes acrylic acid, methacrylic acid, an acrylic acid derivative having the above functional group, a methacrylic acid derivative having the above functional group, an acrylate ester having no above functional group, and having the above functional group. Methacrylic acid ester.

Specific examples of the acrylic acid derivative having the above functional group include 2-hydroxyethyl acrylate, diethylene glycol acrylate, polyethylene glycol acrylate, methoxy diethylene glycol acrylate, methoxy polyethylene glycol acrylate, ethoxy diethylene glycol acrylate, ethoxy polyethylene glycol acrylate, Hydroxypropyl acrylate, dipropylene glycol acrylate, polypropylene glycol acrylate,
Methoxy dipropylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy dipropylene glycol acrylate, ethoxy polypropylene glycol acrylate, 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, N-vinylpyrrolidone, vinylpyridine, acrylamide, N-methylacrylamide, Monoacrylates such as N, N-dimethylacrylamide, N-methylolacrylamide and glycidyl acrylate; diacrylates such as diethylene glycol diacrylate and polyethylene glycol diacrylate; These may be used alone or in combination of two or more.

Specific examples of the methacrylic acid derivative having the above functional group include 2-hydroxyethyl methacrylate, diethylene glycol methacrylate, polyethylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, Hydroxypropyl methacrylate, dipropylene glycol methacrylate, polypropylene glycol methacrylate, methoxy dipropylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxy dipropylene glycol methacrylate, ethoxy polypropylene glycol methacrylate, 2-di Monomethacrylates such as tylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, methacrylamide, N-methyl methacrylamide, N, N-dimethyl methacrylamide, N-methylol methacrylamide, glycidyl methacrylate; diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate And dimethacrylates such as dipropylene glycol dimethacrylate and polypropylene glycol dimethacrylate. These may be used alone or in combination of two or more.

Specific examples of the acrylate having no functional group include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, and the like. ter
-Butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxypropyl acrylate, 2-ethoxypropyl acrylate, benzyl acrylate, phenylcarbitol acrylate, nonylphenyl acrylate, nonylphenylcarbitol acrylate, dicyclopentenyloxyethyl acrylate, tetrahydrofurfuryl acrylate, isovol Nil access relay Monoacrylate such as, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, neopentyl glycol diacrylate,
1,6-hexane glycol diacrylate, 2,2-
Diacrylates such as bis (4-acryloxypropoxyoxyphenyl) propane and 2,2-bis (4-acryloxydiethoxyphenyl) propane; trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and the like Triacrylates; and tetraacrylates such as pentaerythritol tetraacrylate. These may be used alone or in combination of two or more.

Specific examples of the methacrylates having no functional group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate and iso-methacrylate.
Propyl methacrylate, n-butyl methacrylate,
iso-butyl methacrylate, sec-butyl methacrylate, ter-butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-methoxypropyl methacrylate, 2-ethoxypropyl methacrylate, benzyl methacrylate, phenyl carbitol methacrylate, nonylphenyl methacrylate, nonylphenyl carbitol methacrylate DOO, dicyclopentenyl oxyethyl methacrylate, tetrahydrofurfuryl methacrylate, monomethacrylate such as isobornyl methacrylate, ethylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,4
-Dimethacrylates such as butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, 2,2-bis (4-methacryloxydiethoxyphenyl) propane; trimethylolethanetriethacrylate, trimethylol And trimethacrylates such as methylolpropane trimethacrylate. These may be used alone or in combination of two or more.

In the present invention, the (meth) acrylic polymer having at least one selected from the group consisting of polyoxyethyl group, polyoxypropyl group, amide group, hydroxyl group, carboxyl group and glycidyl group is acrylic acid. , Methacrylic acid, an acrylic acid derivative having the above functional group and a methacrylic acid derivative having the above functional group are usually 5 mol% or more, preferably 10 mol%, based on all the monomers constituting the above (meth) acrylate polymer. Mol%
The content is more preferably 20 mol% or more. When the content of acrylic acid, methacrylic acid, the acrylic acid derivative having the above functional group and the methacrylic acid derivative having the above functional group is less than 5 mol%, the size of the voids in the obtained cured product coating film becomes large and the interlayer between fine wirings becomes large. It is not preferable as an insulating film material.

In the present invention, the (meth) acrylate polymer may be copolymerized with a radical polymerizable monomer other than acrylic acid, methacrylic acid, an acrylic acid derivative and a methacrylic acid derivative in an amount of 40 mol% or less. Examples of the radical polymerizable monomer include unsaturated nitriles such as acrylonitrile, unsaturated ketones such as methyl vinyl ketone, and aromatic compounds such as styrene and α-methylstyrene.

In the present invention, the average molecular weight of the (meth) acrylic polymer by GPC is from 1,000 to 20.
000, preferably 1,000 to 50,000. The above (B) organic polymers can be used alone or in combination of two or more.

In the present invention, by using the organic polymer (B), the density of the obtained coating film can be reduced and a low dielectric constant can be achieved, and it is useful as an interlayer insulating film in a semiconductor device or the like. The amount of the organic polymer (B) to be used is generally 1 to 80 parts by weight, preferably 5 to 6 parts by weight, per 100 parts by weight of the component (A) (in terms of complete hydrolysis condensate).
5 parts by weight. If the amount is less than 1 part by weight, the effect of lowering the dielectric constant is small, while if it exceeds 80 parts by weight, the mechanical strength decreases. In the present invention, the completely hydrolyzed condensate refers to a compound (2) or (3) having an SiOR ¹ group of 100.
% Hydrolyzed to form a SiOH group and further completely condensed to form a siloxane structure.

(C) Organic solvent; In the present invention, the above components (A) and (B) are usually dissolved in the (C) organic solvent. Examples of the (C) organic solvent used in the present invention include n-pentane, i-pentane, n-hexane and i-pentane.
Hexane, n-heptane, i-heptane, 2,2,4-
Aliphatic hydrocarbon solvents such as trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene,
aromatic hydrocarbon solvents such as n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene and trimethylbenzene;
Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-
Butanol, t-butanol, n-pentanol, i-
Pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol,
n-hexanol, 2-methylpentanol, sec-
Hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-
Decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,
Monoalcohol solvents such as 3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol; ethylene glycol, 1,2-propylene glycol, 1,
3-butylene glycol, pentanediol-2,4,
2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, etc. Polyhydric alcohol solvents: 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, methylcyclohexanone,
2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchol, acetylacetone, 2,4-hexanedione, 2,4-heptanedion, 3,5-heptanedion, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5
Ketone solvents such as -heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione;
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, ethylene 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 glycol Ether solvents such as 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-valero Lactone, n-propyl acetate, i-propyl acetate, acetic acid n-butyl, 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 acetate,
Ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol mono acetate Butyl ether, dipropylene glycol monomethyl acetate, dipropylene glycol monoethyl acetate,
Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactic acid n Ester solvents such as amyl, diethyl malonate, dimethyl phthalate and diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Nitrogen-containing solvents such as dimethylacetamide, N-methylpropionamide and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone; Can be mentioned . These can be used alone or in combination of two or more.

In the present invention, it is preferable to use an organic solvent having a boiling point of less than 250 ° C. as an organic solvent. Monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether,
Glycol ether solvents such as propylene glycol monopropyl ether and dipropylene glycol monoethyl ether; glycol acetate ether solvents such as ethylene glycol monomethyl acetate, diethylene glycol monobutyl ether acetate, ethylene glycol diacetate and propylene glycol methyl ether acetate; N, N-dimethyl Acetamide,
Amide solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidone, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, methyl amyl ketone, ethyl lactate, methoxymethyl propionate, ethoxyethyl One type alone or a combination of two or more types such as carboxylic acid ester solvents such as propionate can be exemplified. In the present invention, the amount of the organic solvent (C) used is (A) to (A).
It is in the range of 0.3 to 25 times (weight) the total amount of the component (B).

The composition (1) of the present invention comprises the above (A) to
In addition to the component (C), other components can be mixed as necessary. Other components include fillers such as surfactants, colloidal silica, colloidal alumina and the like. In constituting the composition (1),
When the content of alcohol having a boiling point of 100 ° C. or less in the composition is 2
It is preferably 0% by weight or less, particularly preferably 5% by weight or less. The alcohol having a boiling point of 100 ° C. or less may be generated during the hydrolysis / condensation reaction of the component (A), and is removed by distillation or the like so that the content is 20% by weight or less, preferably 5% by weight or less. Is preferred.

Method for preparing composition (1): Specific examples of the method for preparing the composition (1) of the present invention include the following (1) to (1).
The method (4) can be used. (1) After a predetermined amount of water is added to a mixture of the compound (2) and / or (3) constituting the component (A), the catalyst and the organic solvent (C) to carry out a hydrolysis / condensation reaction, (B) The organic polymer is mixed. (2) A predetermined amount of water is continuously or intermittently added to a mixture of the compound (2) and / or (3) constituting the component (A), the catalyst, and the organic solvent (C) to carry out hydrolysis. After the condensation reaction, the organic polymer (B) is mixed. (3) A predetermined amount of water is added to a mixture composed of the compound (2) and / or (3) constituting the component (A), the catalyst, the organic polymer (B) and the organic solvent (C) to hydrolyze and condense. Perform the reaction. (4) A predetermined amount of water is continuously or intermittently added to a mixture of the compound (2) and / or (3) constituting the component (A), the catalyst, the (B) organic polymer and the (C) organic solvent. Hydrolysis and condensation reactions are carried out.

The total solids concentration of the composition (1) 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. Is done. When the total solid content of the composition is 2 to 50% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The adjustment of the total solid content concentration is performed by concentration and dilution with the above organic solvent, if necessary.

Method for Forming Film Using Composition (1) (1) In order to form a film using the composition (1) of the present invention, first, the composition (1) of the present invention is applied to a substrate. , To form a coating film. Here, examples of the substrate on which the composition (1) of the present invention can be applied include semiconductors, glass, ceramics, and metals, and examples of the application method include spin coating, dipping, and roller blades. The composition (1) of the present invention is applied particularly on a silicon wafer, a SiO ₂ wafer, a SiN wafer or the like, and is suitable for forming an insulating film.

The film thickness at this time is 0.1% as a dry film thickness.
A coating film of about 3 μm can be formed. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used.
The reaction can be performed in the air, in a nitrogen atmosphere, in an argon atmosphere, in a vacuum, or under a reduced pressure in which the oxygen concentration is controlled.
As the heating method, the formed coating film is heated at a temperature lower than the decomposition temperature of the organic polymer (B) to partially cure the component (A), and then heated to a temperature equal to or higher than the decomposition temperature of the organic polymer (B). A method of heating from a temperature to a final curing temperature to obtain a cured product having a low density can be given. Further, in order to control the curing rate of the component (A) and the decomposition rate of the organic polymer (B), if necessary, heating may be performed stepwise,
An atmosphere such as nitrogen, air, oxygen, or reduced pressure can be selected. Usually, the decomposition temperature of (B) the organic polymer is 250
Since the temperature is ４５０450 ° C., the coating film includes a step of being finally heated to this temperature or more. This step is preferably performed under reduced pressure or under an inert gas.

Composition (2) The composition (2) of the present invention comprises, as a base polymer for forming a film, component (A) [compound (2) and compound (3)
At least one member selected from the group consisting of (A) is hydrolyzed and condensed in the presence of (D) an alkali catalyst to give a hydrolyzed condensate having a weight average molecular weight of 50,000 to 10,000,000 (hydrolysis condensate) Decomposition products and / or condensates thereof)
It is a polyorganosiloxane composition. The composition of the present invention is applied to a substrate such as a silicon wafer by dipping or spin coating, and the component (A) is subjected to thermal polycondensation by heating. Form a polymer film, the resulting film has a low dielectric constant,
In addition, it has excellent mechanical strength due to its high elastic modulus, and can form an interlayer insulating film material. Here, as for the component (A) [compound (2) or compound (3)] used in the composition (2), the compound (2) to the compound (2) used in the composition (1) are used.
Since it is the same as (3), the description is omitted.

(D) Alkali catalyst: In the present invention, at the time of hydrolyzing and condensing at least one silane compound selected from the group of compounds (2) to (3) constituting component (A), Use an alkaline catalyst. Examples of the alkali catalyst include an inorganic base and an organic base. Here, examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. Examples of the organic base include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine,
-Propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine,
N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, 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-propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N-
(Aminomethyl) propanolamine, N- (aminomethyl) butanolamine, N- (aminoethyl) methanolamine, N- (aminoethyl) ethanolamine,
N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl)
Methanolamine, N- (aminopropyl) ethanolamine, N- (aminopropyl) propanolamine,
N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) propanolamine, N- (aminobutyl) butanolamine, methoxymethylamine, methoxy Ethylamine, 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, propyl Aminoethylamine, propylami Propylamine, propylamino butyl amine, butyl amino methyl amine, butyl aminoethyl amine, butyl aminopropylamine, butyl amino tributylamine, pyridine, pyrrole, piperazine,
Pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicyclookran, diazabicyclononane, diazabicycloundecene and the like can be mentioned. One or two or more of these alkali catalysts may be used simultaneously.

The amount of the alkali catalyst used is based on 1 mol of the total R ¹ O— group in the compounds (2) and (3).
Usually, 0.00001 to 0.5 mol, preferably 0.0
0005-0.1 mole. When the amount of the alkali catalyst used is within the above range, there is little danger of polymer precipitation or gelation during the reaction.

The molecular weight of the hydrolyzed condensate of the component (A) thus obtained is 50,000 to 10,000,000, preferably 100,000 to 900, as a weight average molecular weight by the GPC method.
And more preferably 200,000 to 8,000,000. If it is less than 50,000, sufficient dielectric constant and elastic modulus may not be obtained, while if it is more than 10,000,000, the uniformity of the coating film may be reduced. Further, the hydrolyzed condensate of the component (A) obtained in this manner has a characteristic that it has excellent coatability on a substrate because it does not have a particulate form. The absence of the particulate form is confirmed, for example, by transmission electron microscopy (TEM).

As described above, in the composition (2), (A)
The compounds (2) to (3) constituting the components are hydrolyzed and condensed in the presence of (D) an alkali catalyst to make the weight average molecular weight of the hydrolyzed condensate 50,000 to 10,000,000. Thereafter, the pH of the composition is preferably adjusted to 7 or less.
Here, examples of the pH adjuster include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid 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, and sebacic acid. , Gallic acid, butyric acid, melitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p
-Toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

The pH of the composition with the above pH adjuster is 7
Hereinafter, it is preferably adjusted to 1 to 6. After the weight average molecular weight of the hydrolyzed condensate is adjusted to 50,000 to 10,000,000, the storage stability of the obtained composition is adjusted by adjusting the pH to the above range with the pH adjuster. The effect of improving is obtained. The amount of the pH adjuster used is
The amount is such that the pH of the composition falls within the above range, and the amount used is appropriately selected.

The composition (2) of the present invention is obtained by dissolving or dispersing the hydrolyzed condensate of the component (A) in an organic solvent.
Examples of the organic solvent include those similar to the organic solvent (C) used in the composition (1), and a description thereof will not be repeated. Although the composition (2) contains the above-mentioned organic solvent, the same solvent can be used when the component (A) is hydrolyzed and / or condensed.

Specifically, after the component (A) is added all at once or intermittently or continuously to the above organic solvent to which water and an alkali catalyst have been added, hydrolysis and condensation reactions are further performed. The reaction temperature at this time is usually 0
-100 ° C, preferably 15-90 ° C.

Other additives: The composition (2) used in the present invention may further contain components such as a surfactant. 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. Incidentally, in the composition of the present invention, in order to make the coating film uniform,
Desirably, no silica particles are included.

Method for Preparing Composition (2): In preparing the composition (2), for example, the silane compound (A) is batchwise or intermittently mixed in an organic solvent to which water and (D) an alkali catalyst are added. Alternatively, they are added continuously, usually in the range of 0 to 10
Stir at 0 ° C, preferably 15-90 ° C for 1-12 hours,
Perform hydrolysis and condensation reactions. At each stage of the preparation, the concentration can be adjusted to an arbitrary concentration by performing concentration or dilution by adding an organic solvent. When a pH adjuster is added, it can be added at any stage after the completion of the hydrolysis reaction.

Specific examples of the method for preparing the composition (2) include the following methods (1) to (12). (1) A predetermined amount of the (A) silane compound is added to a mixture of water, (D) an alkali catalyst and an organic solvent, and a hydrolysis / condensation reaction is performed to obtain a hydrolysis / condensation product of the (A) silane compound. . (2) A predetermined amount of (A) a silane compound is continuously or intermittently added to a mixture of water, (D) an alkali catalyst and an organic solvent to carry out hydrolysis and condensation reactions,
(A) A hydrolytic condensate of a silane compound is obtained. (3) To a predetermined amount of a mixture of (A) a silane compound and an organic solvent, water, (D) a mixture of an alkali catalyst and, if necessary, an organic solvent are added, and a hydrolysis / condensation reaction is carried out. ) A hydrolyzed condensate of a silane compound is obtained. (4) A mixture of water, (D) an alkali catalyst and, if necessary, an organic solvent is continuously or intermittently added to a predetermined amount of a mixture of (A) a silane compound and an organic solvent, and the mixture is hydrolyzed. The condensation reaction is carried out to obtain (A) a hydrolyzed condensate of the silane compound.

(5) A predetermined amount of (A) a silane compound,
(D) a mixture comprising an alkali catalyst and an organic solvent,
A mixture comprising water and, if necessary, an organic solvent is added to carry out a hydrolysis / condensation reaction to obtain a hydrolysis-condensation product of the silane compound (A). (6) To a predetermined amount of a mixture of (A) a silane compound, (D) an alkali catalyst and an organic solvent, continuously or intermittently adding a mixture of water and, if necessary, an organic solvent, The condensation reaction is carried out to obtain (A) a hydrolyzed condensate of the silane compound. (7) To a mixture comprising a predetermined amount of water and, if necessary, an organic solvent, add a predetermined amount of a mixture comprising (A) a silane compound, (D) an alkali catalyst and, if necessary, an organic solvent, and subject the mixture to hydrolysis and The condensation reaction is carried out to obtain (A) a hydrolyzed condensate of the silane compound. (8) A mixture comprising a predetermined amount of (A) a silane compound, (D) an alkali catalyst and, if necessary, an organic solvent is added to a mixture comprising a predetermined amount of water and, if necessary, an organic solvent.
Hydrolysis / condensation reaction is carried out continuously or intermittently to obtain a hydrolysis-condensation product of (A) a silane compound.

(9) A mixture of a predetermined amount of water, (A) a silane compound and, if necessary, an organic solvent is added to a mixture of a predetermined amount of (D) an alkali catalyst and, if necessary, an organic solvent. Perform hydrolysis and condensation reactions,
(A) A hydrolytic condensate of a silane compound is obtained. (10) A mixture consisting of a predetermined amount of (D) an alkali catalyst and optionally an organic solvent is continuously or intermittently added to a mixture consisting of a predetermined amount of water, (A) a silane compound and, if necessary, an organic solvent. To obtain a hydrolysis-condensation product of the silane compound (A). (11) A mixture of a predetermined amount of water, (A) a silane compound and, if necessary, an organic solvent is added to a mixture of a predetermined amount of (D) an alkali catalyst and, if necessary, an organic solvent, and the mixture is subjected to hydrolysis. The condensation reaction is carried out to obtain (A) a hydrolyzed condensate of the silane compound. (12) A mixture comprising a predetermined amount of water, (A) a silane compound and optionally an organic solvent is continuously or intermittently added to a mixture comprising a predetermined amount of (D) an alkali catalyst and, if necessary, an organic solvent. To obtain a hydrolysis-condensation product of the silane compound (A). In the present invention, the solid concentration of the reaction solution when hydrolyzing and condensing the silane compound (A) is usually
0.1 to 50% by weight.

The total solid content of the composition (2) 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. Is done. When the total solid content of the composition is 2 to 50% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The adjustment of the total solid content concentration is performed by concentration and dilution with the above organic solvent, if necessary.

The composition (2) of the present invention thus obtained is, if necessary, filtered through a filter.
Can be used. The filter is polyester,
Materials such as polycarbonate, cellulose, cellulose acetate, polypropylene, polyethersulfone, ethylene tetrafluoride (PTFE), and polyamide can be used. Preferably, the filter is made of PTFE having a pore size of 0.2 μm or less, and particularly preferably has a pore size of 0.2 μm.
It is possible to use a PTFE filter of
It is preferable in that foreign matters in the composition are removed and the resulting coating film has excellent uniformity. The above-mentioned filters can be used in combination of different materials and different pore sizes, and a plurality of filters having the same material and different pore sizes can be used.

Method (2) for forming a film using composition (2): A film is formed using composition (2) of the present invention in the same manner as in composition (1). That is, first, the composition (2) of the present invention is applied to a substrate to form a coating film. Here, examples of the substrate on which the composition of the present invention can be applied include a semiconductor, glass, ceramics, and metal. In addition, examples of the coating method include spin coating, dipping, and a roller blade. The compositions of the present invention, in particular a silicon wafer, SiO ₂
It is applied on a wafer, a SiN wafer, or the like, and is suitable for forming an insulating film.

At this time, a coating film having a thickness of about 0.1 to 3 μm as a dry film thickness can be formed. As a heating method at this time, a hot plate, an oven,
A furnace or the like can be used, and the heat treatment is preferably performed at a temperature of 450 ° C. or less under air, a nitrogen atmosphere, an argon atmosphere, a vacuum, or a reduced pressure controlled at an oxygen concentration of 100 ppm or less. In order to control the curing rate of the component (A), if necessary, the composition may be heated stepwise, or may be heated with nitrogen, air,
An atmosphere such as oxygen or reduced pressure can be selected.

Uses of the Film of the Present Invention The film of the present invention has excellent insulating properties and a high modulus of elasticity. Furthermore, the film has uniformity, dielectric constant characteristics, crack resistance of the coating film, and surface hardness of the coating film. LSI, system LS
I, DRAM, SDRAM, RDRAM, D-RDRA
It is useful for applications such as interlayer insulating films for semiconductor devices such as M, protective films such as surface coat films for semiconductor devices, interlayer insulating films for multilayer wiring boards, protective films and insulating films for liquid crystal display devices.

[0086]

The present invention will now be described more specifically with reference to examples. However, the following description generally shows an embodiment of the present invention, and the present invention is not limited by the description without any particular reason. Parts and% in Examples and Comparative Examples indicate parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 (1) Maleic acid 10.0 was added to a mixed solution of 140.5 g of tetramethoxysilane, 182.7 g of methyltrimethoxysilane, 56.0 g of dimethyldimethoxysilane, and 394.0 g of propylene glycol monopropyl ether.
g was dissolved in 116.8 g of water at room temperature over 1 hour. After the addition of the mixture was completed, the mixture was further reacted at 60 ° C. for 1 hour, and the produced methanol was distilled off under reduced pressure to obtain a polysiloxane sol having a weight average molecular weight of 3,500. (2) For 100 g of the polysiloxane sol obtained in (1) above, a polyethylene oxide block-polypropylene oxide block-polyethylene oxide block copolymer [Newpole PE61 manufactured by Sanyo Chemical Co., Ltd.] 8.9
g was added, and the resulting mixture was applied on an 8-inch silicon wafer by spin coating, heated at 80 ° C. for 5 minutes, then heated at 200 ° C. under nitrogen for 5 minutes, and further heated under vacuum at 340 ° C., 360 ° ° C, 380 ° C
The mixture was heated for 0 minutes, and further heated at 425 ° C. for 1 hour to form a colorless and transparent film. Further, the obtained film was evaluated as follows. Table 1 shows the results.

Evaluation of Film and Composition for Forming Film Elemental analysis of film The elemental composition of the film was determined by X-ray photoelectron analysis (XPS). 2. Film density The density was calculated from the analysis results of Rutherford backscattering method and hydrogen recoil forward scattering method. 3. Like the measurement of the film density, the carbon content was calculated from the analysis results of the Rutherford backscattering method and the hydrogen recoil forward scattering method.

4. Film thickness Multiple incidence angle ellipsometer (Rudolph Tech)
Spectra Laser from Nologies
200). 5. Void distribution measurement by BJH method OMNISORP 100/36 manufactured by COULTER
0 SERIES was measured by the BJH method and evaluated according to the following criteria. ；: 5% or less of pores of 10 nm or more. ×: pores of 10 nm or more exceed 5%. 6. Pore size measurement by electron microscopy

7. Elastic Modulus (Young's Modulus) The elastic modulus (Young's modulus) was measured by a continuous stiffness measuring method using a nano indenter XP (manufactured by Nano Instruments). 8. 8. Cohesive failure strength Refractive index Multi-incidence angle ellipsometer (Rudolph Tech)
Spectra Laser from Nologies
200). 10.1% weight loss temperature 10 ° C./mi in a nitrogen atmosphere using an SSC5200 thermogravimetric analyzer (TGA) manufactured by Seiko Denshi Kogyo KK
n, and the 1% weight loss temperature was measured.

11. Dielectric constant An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for dielectric constant measurement. The dielectric constant of the coating film was measured at a frequency of 100 kHz by a CV method using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. 12. CMP resistance The obtained film was polished under the following conditions. Slurry: silica-hydrogen peroxide polishing pressure: 300 g / cm ² polishing time: 60 seconds The evaluation was performed according to the following criteria. ：: No change Δ: Partially peeled or scratched. X: All are peeled.

13. Weight average molecular weight / number average molecular weight Measured by gel permeation chromatography (GPC) (refractive index, viscosity, light scattering measurement) under the following conditions. Sample solution: A hydrolyzed condensate of a silane compound is diluted with methanol containing 10 mM LiBr so that the solid concentration becomes 0.25%, and the sample solution for GPC (refractive index, viscosity, light scattering measurement) is prepared. did. Equipment: Tosoh Corporation, GPC system model GP
C-8020 Tosoh Corporation, Column Alpha5000 / 300
0 Viscotec Co., Ltd., viscosity detector and light scattering detector Model T-60 dual meter Carrier solution: methanol containing 10 mM LiBr Carrier sending rate: 1 ml / min Column temperature: 40 ° C.

Synthesis Example 1 Synthesis of (meth) acrylic polymer; In a 100 ml flask, 18.32 g of isobutyl methacrylate, 1.68 g of 3- (trimethoxysilyl) propyl methacrylate,
Azoisobutyronitrile (AIBN) 0.33 g, 2-
0.20 g of mercaptoethanol and 30 g of 3-methoxymethyl propionate were added and dissolved. After the inside of the system was replaced with nitrogen gas, the mixture was stirred for 7 hours while heating in an oil bath at 80 ° C. to obtain a viscous polymer solution. When the average molecular weight was measured by the GPC method, the number average molecular weight was 4,830 and the weight average molecular weight was 8,900.

Example 2 (1) In a mixed solution of 91.2 g of tetramethoxysilane and 292.3 g of methyltrimethoxysilane, 387.0 g of propylene glycol monopropyl ether, 10.0 g of maleic acid was dissolved in 119.4 g of water. The aqueous solution was added dropwise at room temperature over 1 hour. After addition of the mixture, 6
After reacting at 0 ° C. for 1 hour, the produced methanol was distilled off under reduced pressure to obtain a polysiloxane sol having a weight average molecular weight of 3,000. (2) To 100 g of the polysilica sol obtained in the above (1), 21.2 g (solid content 8.5 g) of the (meth) acrylic polymer solution obtained in Synthesis Example 1 was added. Stirred for hours. The obtained solution is applied on an 8-inch wafer by spin coating, and is heated to 80 ° C. by a hot plate.
After drying at 200 ° C. for 5 minutes and baking at 425 ° C. for 1 hour under vacuum, a transparent coating film was obtained. Evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that the polyethylene oxide block-polypropylene oxide block-polyethylene oxide block copolymer was not used, and the composition was applied to a substrate and heated. Thus, a film was formed. Evaluation of the obtained film was performed in the same manner as in Example 1. Table 1 shows the results.

[0096]

[Table 1]

Example 3 In a mixed solution of 5 g of a 25% aqueous ammonia solution, 320 g of ultrapure water and 600 g of ethanol, 15 g of methyltrimethoxysilane (7.4 g in terms of a completely hydrolyzed condensate) and 20 g of tetraethoxysilane (completely hydrolyzed and condensed) Product conversion5.
8 g) and reacted at 60 ° C. for 3 hours, and then 200 g of propylene glycol monopropyl ether was added.
Thereafter, the solution was concentrated under reduced pressure until the total solution amount reached 200 g,
A composition solution having a solid content of 6.6% was obtained. The weight average molecular weight of the obtained composition was 5.2 million. The obtained composition is applied on an 8-inch silicon wafer by a spin coating method, and is applied at 80 ° C. in the air for 5 minutes and then under nitrogen for 20 minutes.
After heating at 0 ° C for 5 minutes, further under vacuum at 340 ° C,
The film was heated in the order of 360 ° C. and 380 ° C. for 30 minutes each, and further heated at 425 ° C. for 1 hour under vacuum to form a colorless and transparent film. Table 2 shows the results.

Example 4 200 g of the composition described in Example 3 was further added to a total volume of 140
g, and then 10 g of a 10% solution of acetic acid in propylene glycol monopropyl ether is added.
A composition solution having a solid content of 8.8% was obtained. The weight average molecular weight of the obtained composition was 5.2 million. The count of residual silanol determined by conductivity titration did not change before and after the addition of acetic acid. The obtained composition is applied on an 8-inch silicon wafer by spin coating, heated in air at 80 ° C. for 5 minutes, and then under nitrogen at 200 ° C. for 5 minutes, and then further heated under vacuum at 340 ° C., 360 °
C. and 380.degree. C. in that order for 30 minutes each, and further heated under vacuum at 425.degree. C. for 1 hour to form a colorless and transparent film. Table 2 shows the results.

Comparative Example 2 Instead of 320 g of ultrapure water, 32 g of ultrapure water and ethanol 6
Except that 888 g of ethanol was used instead of 00 g.
The same operation as in Example 1 was performed to obtain a composition solution having a solid content of 6.6%. The weight average molecular weight of the obtained composition was 12,000. The obtained composition is applied on an 8-inch silicon wafer by a spin coating method, heated at 80 ° C. for 5 minutes in the air, then at 200 ° C. for 5 minutes under nitrogen, and further heated at 340 ° C., 360 ° C., 380 ° C. under vacuum.
Heat in order of 30 ° C for 30 minutes each, and
The mixture was heated at 25 ° C. for 1 hour to form a colorless and transparent film. Table 2 shows the results.

[0100]

[Table 2]

[0101]

The film of the present invention is excellent in dielectric properties and mechanical strength.

 ────────────────────────────────────────────────── ─── Continued on front page (72) Inventor Kinji Yamada 2--11-24 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Corporation (reference) 4J038 CG002 DD002 DE002 DF002 DL051 HA236 JA35 JC32 JC38 KA04 KA06 NA11 NA17 NA19 NA21 PA19 PB09 PC02 PC03 PC08 5F058 AA10 AC03 AF04 AG01 AH01 AH02 BA20 BC05 BF46 BH01 BJ01 BJ02

Claims (11)

[Claims] 1. A film having a structure represented by the following general formula (1) and having a film density of 0.5 to 1.4 g / cm ³ . SiOxCyHz (1) (where 1.3 <x <1.9, 0.2 <y <8.0,
0.6 <z <7.0. ) 2. A carbon content of 1.0 × 10^{twenty one}~ 3.0x
10^{twenty two}atm / cm ^ThreeThe membrane according to claim 1, which is: 3. The film according to claim 1, wherein the film thickness is 3 μm or less. 4. The method according to claim 1, wherein the pore distribution is measured by the BJH method.
2. The film according to claim 1, wherein vacancies of not less than nm are not more than 5%. 5. The film according to claim 1, wherein the number of pores having a diameter of 1 nm or more determined by pore diameter measurement by electron microscopy is 5/100 nm ² or less. 6. The film according to claim 1, wherein the following conditions (a) to (d) are satisfied. (A) elastic modulus ≧ 2.5 GPa (b) cohesive fracture strength ≧ 30 MPa (c) refractive index ≦ 1.40 (d) 1% weight loss temperature ≧ 400 ° C. 7. The film according to claim 1, which is formed on a semiconductor substrate. 8. The film according to claim 1, which forms part of a semiconductor device. 9. An insulating film comprising the film according to claim 1. (A) at least one silane compound selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3), a hydrolyzate thereof and / or Or a condensate thereof, R ² _n Si (OR ¹ ) _4-n ... (2) [In the general formulas (2) and (3), R ¹ and R ² may be the same or different, and each is a monovalent organic group and R is 2
N represents an integer of 0 to 2, and s and t represent 0
-1. The method for forming a film according to any one of claims 1 to 9, wherein a film-forming composition containing (B) an organic polymer and (C) an organic solvent is applied to a substrate and heated. . (A) at least one silane compound selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3): R ² _n Si ( OR ¹ ) _4-n ... (2) [In the general formulas (2) and (3), R ¹ and R ² may be the same or different, and each is a monovalent organic group and R is 2
N represents an integer of 0 to 2, and s and t represent 0
-1. (D) In the presence of an alkali catalyst, a film-forming composition having a weight average molecular weight of 50,000 to 10,000,000 obtained by hydrolysis and condensation obtained by hydrolysis and condensation is applied to a substrate, The method for forming a film according to claim 1, wherein the film is heated.