JP2001206710A - Forming method of silica base film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silica based film useful as an interlaminar insulating film in a semiconductor element or the like and having low density, low dielectric constant, high elastic modulus and low water absorption. SOLUTION: The silica based film is obtained by applying a coating composition containing polysiloxane A, an organic polymer B and an organic solvent C on a substrate and after removing the organic solvent, heating the substrate at 250-400 deg.C in an vacuum or inert gas atmosphere, next heating it at 250-400 deg.C in an atmosphere of oxygen partial pressure not less than 1 Pa and further heating it at a temperature of 350-470 deg.C in an atmosphere of oxygen partial pressure less than 1 Pa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a silica-based film, and more particularly, to a method for forming an interlayer insulating film in a semiconductor device or the like, which is excellent in dielectric properties, water absorption properties, mechanical strength, and low density. The present invention relates to a method for forming a silica-based film as a cured 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. And in recent years,
In order to form a more uniform interlayer insulating film, S
A coating type insulating film called a OG (Spin on Glass) film, which is mainly composed of a hydrolysis product of tetraalkoxylan, has been used. Also, with the high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant and mainly containing polyorganosiloxane called organic SOG has been developed. However, with higher integration and multilayering of semiconductor devices and the like, better electrical insulation between conductors is required, and therefore, an interlayer insulating film material having a lower dielectric constant and excellent surface hardness characteristics is required. It has become.

[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
A silica-based coating-type insulating film that is used for forming an interlayer insulating film of a multilayer wiring board and that is made of an alkoxysilane, a metal alkoxide other than silane, and an organic solvent, and that can be applied in a thick film and has excellent oxygen plasma resistance. A 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. This coating liquid for forming an oxide film provides a uniform coating liquid without generation of a gel-like substance. Further, by using this coating liquid, 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.

However, when a metal chelate compound such as titanium or zirconium is combined with a silane compound as described above, the uniformity of the coating film and the long-term storage stability of the solution are not excellent, and the dielectric constant and surface hardness are not balanced. I don't have much.

[0007]

The present invention relates to a film-forming composition for solving the above-mentioned problems, and more particularly to a dielectric composition and a water-absorbing property as an interlayer insulating film in a semiconductor device or the like. It is an object of the present invention to provide a silica-based film which is a cured film having excellent mechanical strength and low density.

[0008]

According to the present invention, a coating composition containing (A) a polysiloxane, (B) an organic polymer and (C) an organic solvent is applied to a substrate, and the organic solvent is removed (hereinafter, referred to as "prebaking"). ), And then heated to 250 to 400 ° C in a vacuum or inert gas atmosphere (hereinafter also referred to as “first soft bake”), and then heated to 250 to 400 ° C in an atmosphere having an oxygen partial pressure of 1 Pa or more. (Hereinafter, also referred to as “secondary soft bake”), and further heated to 350 to 470 ° C. in an atmosphere having an oxygen partial pressure of less than 1 Pa (hereinafter, also referred to as “final annealing”), to form a silica-based film About the method. Here, (A)
Polysiloxane includes (A-1) a compound represented by the following general formula (1) (hereinafter also referred to as “compound (A-1)”), and R ¹ _a Si (OR ² ) _4-a. (1) (wherein, R ¹ represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 2.) 2) Compound represented by the following general formula (2) (hereinafter also referred to as “compound (A-2)”) R ³ _b (R ⁴ O) _3-b Si— (R ⁷ ) _d —Si (OR ⁵ ) _{3 -c} R ⁶ _c (2) (wherein R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a monovalent organic group; b and c May be the same or different and represent a number of 0 to 2, R ⁷ represents an oxygen atom or a group represented by — (CH ₂ ) _n —, n represents 1 to 6, d represents 0 or 1 is shown.) It is preferable to use a hydrolyzate of at least one silane compound and / or a condensate thereof (hereinafter, also referred to as “(A) hydrolysis condensate”). The compound is preferably hydrolyzed and condensed in the presence of at least one catalyst selected from the group consisting of a metal chelate compound, an acidic compound and an alkaline compound. And at least one selected from the group consisting of polyether, polyester, polycarbonate, polyanhydride, and (meth) acrylic polymer. C. It is preferable to carry out the heating by heating to 2 ° C. Further, in the second soft bake, the oxygen partial pressure is reduced to 1P. Heating in an atmosphere of at least a is preferably performed for 1 minute to 2 hours, and in final annealing, an atmosphere having an oxygen partial pressure of less than 1 Pa is preferably an inert atmosphere.
Furthermore, in the final annealing, the oxygen partial pressure is 1P
Heating in an atmosphere less than a is preferably performed for 1 minute to 3 hours.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention uses (A) a hydrolytic condensate as a base polymer for forming a film, and a specific (B) organic polymer as a material for forming a porous material.
(C) An organic solvent is used as a solvent for the components (A) and (B). Thus, the composition containing the components (A) to (C)
The substrate is applied to a substrate such as a silicon wafer by an immersion method or a spin coat method, and then the organic solvent is first removed from the substrate by pre-baking, and then, under a certain condition, the first and second soft baking are performed. And a final annealing treatment. As a result, when the (B) organic polymer and the (C) organic solvent are removed and the component (A) is subjected to thermal polycondensation, the component (A) forms a glassy or macromolecular film and the component (B) ) The organic polymer is decomposed and removed, whereby the density is reduced. Further, by performing the pre-bake, soft bake, and final annealing treatment as described above, a mechanical strength is improved, and a film having a low residual volatile content can be formed. The obtained silica-based film is a film excellent in electrical insulation, process chemical resistance, and CMP resistance while maintaining a low density and a low dielectric constant.

(A) Polysiloxane The (A) polysiloxane constituting the coating composition used in the method for forming a silica-based film of the present invention is a condensation in which siloxane bonds (—Si—O— bonds) are linked. Any compound may be used as long as it is a compound.
-1) and / or (A-2), or any one of them, is preferred. Compound (A-1); a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) wherein R ¹ is a hydrogen atom, a fluorine atom or Represents a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 2.) Compound (A-2); Compound R ³ represented by the following general formula (2) _{^{b (R 4 O) 3-}} b Si- (R 7) d -Si (oR 5) 3-c R 6 c ····· (2) ( ^{wherein, R 3, R 4, R} 5 and R ⁶ may be the same or different and each represents a monovalent organic group, b and c may be the same or different and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or — (CH _{2) n} - represents a group represented, n is a 1 to 6, d is 0 or 1).

Here, as a base polymer for forming a silica-based film, compound (A-1) and compound (A-2)
Alternatively, using either one of the hydrolysis condensate [(A) polysiloxane] and a composition containing (B) an organic polymer and (C) an organic solvent, a silicon wafer is immersed or spin-coated to obtain a silicon wafer. When applied to a substrate such as, and subjected to a heat treatment (pre-bake, primary-secondary soft bake, and final annealing treatment), (B) in parallel with the thermal polycondensation of the hydrolysis condensate (A) Decomposition of the organic polymer occurs, and the component (A) forms a vitreous or macromolecular film. The resulting film is an interlayer insulating film having excellent low density, low water absorption, low dielectric constant, and mechanical strength. The material can be formed.

Here, in the present invention, the hydrolysis means
Compounds (A-1) to (A-) constituting the component (A)
R ² O—, R ⁴ O— and R ⁵ O— contained in 2)
Not all groups need to be hydrolyzed;
That is, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof. In the present invention, the condensation refers to (A)
The silanol groups of the hydrolyzate constituting the component condense to form S
Although the i-O-Si bond is formed, in the present invention, it is not necessary that all the silanol groups are condensed. This is a concept that includes generating a mixture and the like.

In the present invention, the component (A) is a hydrolysis-condensation product obtained by (co) hydrolysis-condensation of the compounds (A-1) and / or (A-2). Compound (A-1): In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Further, in the general formula (1), R ¹ is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and preferably have 1 to 5 carbon atoms.
It may be branched, and a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri- sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane,
Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane and the like;

Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n
-Butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n -Butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane,
Ethyl triphenoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-n-propoxy silane, vinyl tri-iso-propoxy silane, vinyl tri-n-butoxy silane, vinyl tri-s
ec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane , N-propyltri-n-butoxysilane, n-propyltri-sec
-Butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-
Propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane,
i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-
sec-butoxysilane, i-propyltri-tert
-Butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-
Butyltri-n-butoxysilane, n-butyltri-s
ec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, se
c-butyltrimethoxysilane, sec-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
Butyltri-n-propoxysilane, t-butyltri-
iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-
Butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n
-Propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-te
rt-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane and the like;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane,
Dimethyl-di-iso-propoxysilane, dimethyl-
Di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n
-Propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-te
rt-butoxysilane, diethyldiphenoxysilane,
Di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di -N-butoxysilane, di-n-propyl-di-sec-butoxysilane,
Di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-
Propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxy Silane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n -Butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl -Di-sec-butoxysilane, di-n-
Butyl-di-tert-butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, Di-s
ec-butyl-di-iso-propoxysilane, di-s
ec-butyl-di-n-butoxysilane, di-sec-
Butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, Di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxy Silane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane,
Diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-
Butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, and the like.

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.

Compound (A-2): In the above formula (2), examples of the monovalent organic group include the same organic groups as in the above formula (1). Examples of the divalent organic group represented by R ⁷ in the general formula (2) include a methylene group and an alkylene group having 2 to 6 carbon atoms. In the general formula (2), examples of the compound in which R ⁷ is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,
3-pentamethoxy-3-methyldisiloxane, 1,
1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3 -Phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,
3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-
1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,
1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-
1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane,
1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,
1,3,3-tetraphenyldisiloxane and the like can be mentioned.

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

In the general formula (2), the compound in which d is 0 includes hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,1
2,2-pentamethoxy-2-methyldisilane, 1,
1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2
-Phenyldisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2
-Tetramethoxy-1,2-diphenyldisilane, 1,
1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2
-Trimethyldisilane, 1,1,2-trimethoxy-
1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,2
-Dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane , 1,2-diethoxy-1,1,1,
2,2-tetraphenyldisilane and the like can be mentioned.

Further, in the general formula (2), R ⁷ is-
Examples of the compound of the group represented by (CH ₂ ) _n — include bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (hexaphenoxysilyl) methane, bis (dimethoxymethylsilyl) methane, and bis ( Diethoxymethylsilyl) methane, bis (dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, bis ( Ethoxydiphenylsilyl) methane, bis (hexamethoxysilyl)
Ethane, bis (hexaethoxysilyl) ethane, bis (hexaphenoxysilyl) ethane, bis (dimethoxymethylsilyl) ethane, bis (diethoxymethylsilyl) ethane, bis (dimethoxyphenylsilyl) ethane, bis (diethoxyphenylsilyl) Ethane, bis (methoxydimethylsilyl) ethane, bis (ethoxydimethylsilyl) ethane, bis (methoxydiphenylsilyl) ethane, bis (ethoxydiphenylsilyl) ethane, 1,3-bis (hexamethoxysilyl) propane,
1,3-bis (hexaethoxysilyl) propane, 1,
3-bis (hexaphenoxysilyl) propane, 1,3
-Bis (dimethoxymethylsilyl) propane, 1,3-
Bis (diethoxymethylsilyl) propane, 1,3-bis (dimethoxyphenylsilyl) propane, 1,3-bis (diethoxyphenylsilyl) propane, 1,3-bis (methoxydimethylsilyl) propane, 1,3- Examples thereof include bis (ethoxydimethylsilyl) propane, 1,3-bis (methoxydiphenylsilyl) propane, and 1,3-bis (ethoxydiphenylsilyl) propane.

Of these, hexamethoxydisilane,
Hexaethoxydisilane, hexaphenoxydisilane,
1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-
1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,
2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-
Tetraphenyldisilane, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (dimethoxyphenylsilyl) methane, bis (diethoxyphenyl) Preferred examples include (silyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, and bis (ethoxydiphenylsilyl) methane.
In the present invention, as the component (A), the compound (A)
It is preferable to use -1), and in particular, in the general formula (1), it is preferable to use a compound of a = 0 and a compound of a = 1 together.

When the compounds (A-1) to (A-2) constituting the component (A) are hydrolyzed and condensed,
It is preferable to use 0.25 to 3 mol of water, and 0.3 to 2.5 mol of water per 1 mol of the total amount of the R ² O— group, R ⁴ O— group and R ⁵ O— group. Is particularly preferred. When 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, and there is a risk of precipitation or gelation of the polymer during the hydrolysis and condensation reactions. Is less.

Further, the compound (A-
When hydrolyzing and condensing 1) to (A-2), a catalyst may be used. Examples of the catalyst used at this time include metal chelate compounds, acidic compounds (organic acids and inorganic acids), and alkaline compounds (organic bases and inorganic bases). As the polyorganosiloxane (A), at least one of the compounds (A-1) and (A-2) is used as a catalyst, that is, a metal chelate compound, an acidic compound or an alkaline compound. And then hydrolyzed and condensed, and another component (A) prepared with another catalyst may be used in combination.

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 aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate);

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, organic bases, inorganic bases,
Organic acids, inorganic acids are preferred, more preferably, organic acids,
Inorganic bases can be mentioned. As the organic acid, acetic acid, oxalic acid, maleic acid, and malonic acid are particularly preferable. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst used is determined by the amount of the compound (A-1)
R ² O—, R ⁴ O—, and R ² contained in (A-2)
0.00001 is usually used per 1 mol of the total amount of ⁵ O-groups.
~ 0.05 mol, preferably 0.00001-0.01
Is a mole.

The molecular weight of the component (A) is GPC (refractive index,
(Viscosity, light scattering measurement) method, preferably 500 to 10 million, more preferably 700 to 10
9,000,000, particularly preferably from 1,000 to 8,000,000. If it is less than 500, the uniformity of the coating film may decrease.

(B) Organic Polymer The component (B) is at least one selected from the group consisting of polyether, polyester, polycarbonate, polyanhydride, and (meth) acrylic polymer.

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, examples of the polycarbonate constituting the component (B) include aliphatic polycarbonates 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 by 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 polyoxyethyl group, polyoxypropyl group, amide group, hydroxyl group and carboxyl group is used. (Meth) acrylic polymer. 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, methoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate, ethoxydiethylene 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 acrylic acid ester having no functional group include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, 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, the acrylic acid derivative having the above functional group and the methacrylic acid derivative having the above functional group are usually 5 mol% or more, preferably 10 mol%, based on all monomers constituting the (meth) acrylate polymer. The content is more preferably 20 mol% or more. Acrylic acid,
5 mol% of methacrylic acid, acrylic acid derivative having the above functional group and methacrylic acid derivative having the above functional group
If it is less than 1, the size of the voids in the obtained cured product coating film increases, which is not preferable as an interlayer insulating film material between fine wirings.

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, (meth) acrylic polymerization
The number average molecular weight of the body by GPC method is 1,000 to 20
000, preferably 1,000 to 50,000
You. The above-mentioned (B) organic polymer is one kind or two or more kinds.
The above can be mixed and used. In the present invention
By using the component (B), the density of the obtained coating film can be reduced.
Lower dielectric constant to achieve lower
It is useful as an interlayer insulating film in any area. (B) Organic po
The amount of the rimer used is determined based on the component (A) (completely hydrolyzed
Calculation) Usually, 1 to 80 parts by weight, preferably 100 parts by weight,
Or 5 to 65 parts by weight. If less than 1 part by weight, dielectric
The effect of lowering the rate is small, while exceeding 80 parts by weight
Then, the mechanical strength decreases. Here, complete hydrolysis condensation
Is the SiOR of compounds (A-1) to (A-2)
^TwoGroup, SiOR^FourGroup and SiOR^FiveThe group is 100% hydrolyzed
To form SiOH groups, which are further completely condensed to form siloxane
It is a structure.

(C) Organic Solvent The coating composition used in the present invention is obtained by dissolving or dispersing the components (A) and (B) in the organic solvent (C). Here, (C) the organic solvent includes at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, and ester solvents.
Among them, the alcohol solvents include methanol, ethanol, n-propanol, i-propanol and n-propanol.
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, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc. Alcoholic solvents;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,
Ethylene glycol mono-2-ethyl butyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether,
Polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether; and the like. One or two of these alcohol solvents are used.
More than one species may be used simultaneously.

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

Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-
n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-
Butyl ketone, methyl-n-hexyl ketone, di-i-
Butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4
-In addition to pentanedione, acetonylacetone, acetophenone, fenchone, etc., acetylacetone, 2,
4-hexanedione, 2,4-heptanedione, 3,5
-Heptanedione, 2,4-octanedione, 3,5-
Octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,
2,6,6-tetramethyl-3,5-heptanedione,
Β-diketones such as 1,1,1,5,5,5-hexafluoro-2,4-heptanedione and the like can be mentioned.
These ketone solvents may be used alone or in combination of two or more.

As the amide solvent, formamide, N
-Methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide,
N-dimethylacetamide, N-ethylacetamide,
N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. Can be One or two or more of these amide solvents may be used simultaneously.

As ester solvents, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ
-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl 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, acetic acid Methoxy triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents include 1
Species or two or more species may be used simultaneously. The above (C) organic solvents can be used alone or in combination of two or more.

The coating composition used in the present invention contains the above-mentioned (C) organic solvent. When decomposing and condensing, the same solvent can be used.

Specifically, the compounds (A-1) and (A
-2) water or water diluted in the above (C) organic solvent is intermittently or continuously added to a solvent in which one or both are dissolved. At this time, the catalyst may be added to the solvent in advance, 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 90 ° C.

Other additives; components such as colloidal silica, colloidal alumina, a surfactant, and a pH adjuster may be further added to the coating composition used 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 μm, preferably 10 to 30 μm.
２０20 mμ and a solid concentration of about 10-40% by weight. Examples of such colloidal silica include, for example, methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industries, Ltd .;
And Oscar. Examples of the colloidal alumina include alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.
Examples 100 and 200 include alumina clear sol, alumina sol 10 and 132, manufactured by Kawaken Fine Chemicals Co., Ltd. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like.
Examples thereof include a silicone-based surfactant, a polyalkylene oxide-based surfactant, and a fluorine-containing surfactant. As a pH adjuster, organic acids, inorganic acids, organic bases,
Inorganic bases and the like are specifically mentioned. Specifically, the compound (A-
Compounds similar to the acidic compounds and alkaline compounds used in the hydrolysis and condensation of 1) and (A-2) can be exemplified.

Method for Preparing Composition: In preparing the composition used in the present invention, for example, the compounds (A-1) to (A-) constituting the component (A) may be dissolved in an organic solvent (C).
2) mixing and adding water continuously or intermittently,
After hydrolyzing and condensing to prepare the component (A), the component (B) may be added thereto, and there is no particular limitation.

Specific examples of the method for preparing the composition of the present invention include the following methods. Compounds (A-1) to (A-) constituting the component (A)
2) and (C) a predetermined amount of water is added to a mixture comprising an organic solvent to carry out a hydrolysis / condensation reaction.
(B) A method of mixing the components. Compounds (A-1) to (A-2) constituting component (A)
A method wherein a predetermined amount of water is continuously or intermittently added to a mixture consisting of the component (C) and a hydrolysis and condensation reaction is carried out, and then the component (B) is mixed. Compounds (A-1) to (A-) constituting the component (A)
2) The mixture comprising the components (B) and (C)
A method of performing a hydrolysis / condensation reaction by adding a predetermined amount of water. Compounds (A-1) to (A-) constituting the component (A)
2) The mixture comprising the components (B) and (C)
A method in which a predetermined amount of water is added continuously or intermittently to carry out hydrolysis and condensation reactions.

The total solid content of the composition thus obtained is preferably from 2 to 30% by weight, which is appropriately adjusted according to the purpose of use. When the total solid content of the composition is 2 to 30% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The adjustment of the total solid content concentration is performed by concentration or dilution with the organic solvent (C), if necessary.

The composition thus obtained can be used after being filtered with a filter, if necessary. The filters are polyester, polycarbonate, cellulose, cellulose acetate, polypropylene, polyethersulfone, ethylene tetrafluoride (PTF
E), a material such as polyamide can be used. Preferably, the filter is made of PTFE having a pore size of 0.2 μm or less, and particularly preferably, a P filter having a pore size of 0.05 μm or less.
It is preferable to use a TFE filter 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.

Substrate In order to form a film using the composition used in the present invention, first, the composition of the present invention is applied to a substrate to form a coating film. Here, examples of the substrate 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. The film thickness at this time is about 0.05 to 1.5 μm as a dry film thickness when applied once, and a coating film with a thickness about 0.1 to 3 μm can be formed when applied twice. The thickness of the coating film to be formed is usually 0.2 to 20 μm.
m.

Pre-bake, primary and secondary soft bake
In the present invention, a low dielectric material having excellent insulation and heat resistance is obtained from a composition obtained by dissolving (dispersing) (A) a polysiloxane and (B) an organic polymer in (C) an organic solvent. When forming a film, first, preferably, the substrate is heated to a temperature of 60 ° C. to 250 ° C. to evaporate the organic solvent from the substrate (pre-bake), and then heated to 250 to 400 ° C. in a vacuum or an inert gas atmosphere.
° C (first soft bake), then oxygen partial pressure 1
Heat to 250 to 400 ° C under an atmosphere of Pa or more (second
(Next soft bake), and further heated to 350 to 470 ° C. in an atmosphere having an oxygen partial pressure of less than 1 Pa (final annealing) to obtain a silica-based film.

Prebaking: Here, in order to form a coating film, a coating composition obtained by dissolving (dispersing) the components (A) and (B) in an organic solvent (C) is applied to a substrate.
Remove the organic solvent. This step is called "prebake". The temperature required for this pre-bake is preferably 60 to 250 ° C., more preferably 70 to 230 ° C.
The temperature of the pre-bake depends on the type of the organic solvent (C) used. If the temperature is lower than 60 ° C., the evaporation of the solvent is not complete, and the solvent may be rapidly evaporated during the soft baking, so that a film having good uniformity may not be obtained. At this time, the heating source used for removing the organic solvent (C) is usually a hot plate, but an amp anneal, an oven, a vertical heating furnace, or the like can be used. The time required for removing the organic solvent is preferably about 30 seconds to 5 minutes, and this time depends on the heating temperature and the type of the organic solvent. In this prebaking step, a condensation reaction of a part of the component (A) may occur along with the evaporation of the solvent.

First soft bake; The coating film from which the organic solvent has been removed (hereinafter also referred to as “coating film”) is then heated at 250 to 400 ° C., preferably 300 to 390 ° C. in a vacuum or an inert gas atmosphere. At temperature, preferably 1 minute to
Heat treatment is performed for 2 hours, more preferably for 3 minutes to 1 hour (referred to as “first soft bake”). This first soft bake treatment disperses the organic polymer component (B), lowers the film density, promotes the curing of the component (A), and promotes the silanol groups and alkoxides contained in the component (A). The groups are efficiently bonded to each other to help form a tough film having excellent electric insulation. The inert gas atmosphere used in the first soft bake is, for example, nitrogen, argon, helium, or the like. Usually, the treatment in an inert gas atmosphere is performed at normal pressure, but may be performed under reduced pressure of, for example, about 1 Pa to 10,000 Pa.

If the primary soft bake treatment is performed in an atmosphere having an oxygen partial pressure of 1 Pa or more or at a temperature lower than 250 ° C., the mechanical properties are not sufficiently improved. When the temperature of the first soft bake treatment is higher than 400 ° C., the organic group such as the alkyl group contained in the component (A) is oxidized, and the oxidized site is changed to silanol. As a result, the film becomes highly hygroscopic and is not suitable as an insulating film used for a semiconductor device. Furthermore, if the primary soft bake treatment time is less than 1 minute, the mechanical properties are not sufficiently improved, while if it exceeds 2 hours, the mechanical properties are not significantly improved. The heating source used for the first soft bake is usually a hot plate as in the case of the pre-bake, but a lamp anneal, an oven, a vertical heating furnace, or the like can be used. In this case, the members of the heating device need to have sufficient oxidation resistance.

Second soft bake; The coating film subjected to the first soft bake treatment is then subjected to an oxygen partial pressure of 1 Pa or more, preferably 1 to 19,000 Pa in an atmosphere.
At a temperature of 50 to 400C, preferably 300 to 390C, preferably 1 minute to 2 hours, more preferably 3 minutes to
Heat treatment for one hour (referred to as "secondary soft bake"). This second soft bake treatment completely removes the decomposition residue of the organic polymer (B), eliminates volatile components after film formation, and efficiently removes silanol groups and alkoxide groups contained in the component (A). It is well bonded to each other and helps to form a tough film with excellent electrical insulation.
The atmosphere containing oxygen used in the second soft bake may be, for example, air, or a mixed gas of an inert gas such as nitrogen, argon, or helium and oxygen. Usually, this process is performed under normal pressure, but it is also possible to perform the process under reduced pressure of, for example, about 1 Pa to 10,000 Pa.

This soft bake treatment is performed at an oxygen partial pressure of 1 Pa
When performed in an atmosphere of less than or less than 250 ° C., the improvement in mechanical properties is insufficient. When the temperature of the soft bake treatment is higher than 400 ° C., the above (A)
An organic group such as an alkyl group contained in a component is oxidized, and the oxidized site is changed to silanol or the like, resulting in a film having high hygroscopicity, which is not suitable as an insulating film used for a semiconductor device. Further, if the soft bake treatment time is less than 1 minute, the mechanical properties are insufficiently improved, and the volatile components after film formation increase. On the other hand, even if it exceeds 2 hours, there is not much improvement in mechanical properties. The heating source used for this soft bake is usually a hot plate, similar to the pre-bake, but lamp annealing, an oven, a vertical heating furnace, or the like can be used. In this case, the members of the heating device need to have sufficient oxidation resistance.

Final annealing treatment: Finally, the coated film after the soft bake (first-secondary) is treated under an inert atmosphere having an oxygen partial pressure of less than 1 Pa, preferably 0 to 50 Pa, in an inert atmosphere. ~ 470 ° C, preferably 400 ~
Heat treatment is performed at 450 ° C., preferably for 1 minute to 3 hours (hereinafter referred to as “final annealing”). Oxygen partial pressure is 1
An inert atmosphere of less than Pa means that the oxygen content is 1,000 p
An inert gas such as nitrogen, argon, helium, krypton, or the like, which is less than pm, or a reduced-pressure atmosphere in which the oxygen partial pressure is less than 1 Pa.

When this final annealing treatment is performed in an atmosphere having an oxygen partial pressure of 1 Pa or more, an organic group such as an alkyl group contained in the component (A) is oxidized to generate a silanol group, and the film easily absorbs moisture. Become. As a result, when the film absorbs moisture, the dielectric constant of the film increases, and the film tends to have poor insulating properties. This final anneal is typically at a higher temperature than soft bake, ie, 350 ° C. to 470 ° C.
C., and this final annealing process
The film achieves low dielectric, high insulation and high strength characteristics required for an insulating film for a semiconductor device. If the final annealing treatment is insufficient, the obtained silica-based film according to the present invention does not achieve the expected low dielectric properties, high insulating properties, and high strength properties. On the other hand, when the temperature of the final annealing treatment is too high, the organic group such as the alkyl group contained in the component (A) is decomposed, and the film density increases,
The dielectric constant increases. Furthermore, if the final annealing time is less than 1 minute, the final degree of condensation of the component (A) will be low, and a low dielectric constant cannot be maintained. Not so much. As a heating source for the final annealing treatment, a hot plate, a lamp annealing device, an oven, a vertical firing furnace, or the like can be used.

In each of these pre-baking, soft baking, and final annealing, step processing in which different conditions (temperature, atmosphere) are performed a plurality of times in each processing may be performed. For example, there is a method in which prebaking is performed at 80 ° C. for 1 minute, and then performed at 200 ° C. for 3 minutes.

The thus obtained silica-based film of the present invention has a low dielectric constant, usually 2.6 to 1.
2, preferably 2.5 to 1.2, more preferably 2.
4 to 1.2. This dielectric constant can be adjusted by the content of the component (B) in the composition used in the present invention. Incidentally, the carbon content of the silica-based film of the present invention is usually
5 to 20% by weight.

The silica-based film of the present invention has a high modulus of elasticity and a Young's modulus of usually 3 to 10 GPa, preferably 4 to 10 GPa. This elastic modulus can be obtained by firing the hydrolyzed condensate of the component (A) prepared by the method described in the present invention by the method described in the present invention.

Further, the silica-based film of the present invention has a film density of usually 0.35 to 1.25 g / cm ³ , preferably 0.4 to 1.1 g / cm ³ , more preferably 0.5 to 1.1 g / cm ³ .
1.0 g / cm ³ . The film density is 0.35 g / cm ³
If less, the mechanical strength of the coating film decreases, while 1.25
If it exceeds g / cm ³ , a low dielectric constant cannot be obtained. This film density can be easily adjusted by the content of the component (B) in the composition used in the present invention.

Further, the silica-based film of the present invention is characterized in that it has low water absorption.
When left in an environment of atm and 100% RH for 1 hour, no adsorption of water to the coating film is observed from the IR spectrum observation of the coating film after standing. This low water absorption can be obtained, for example, by adjusting the content of the compound (A-2) in the film-forming composition of the present invention to the range described in the present invention.

The silica-based film of the present invention has a low density, an excellent insulating property, a high modulus of elasticity, and a uniformity of the coating film, dielectric constant characteristics, crack resistance of the coating film, and surface hardness of the coating film. LSI, system LSI, DRAM, SDR
Protective films such as interlayer insulating films for semiconductor devices such as AM, RDRAM, and D-RDRAM, surface coating films of semiconductor devices;
It is useful for applications such as interlayer insulating films of multilayer wiring boards, protective films and insulating films for liquid crystal display elements. Further, the semiconductor device having the silica-based film of the present invention has the film of the present invention as an insulating film between metal wirings.

[0080]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
Will be described. However, the following description refers to an embodiment of the present invention.
It is a general indication and, for no particular reason,
The present invention is not limited. Note that the examples
Parts and% in Comparative Examples and Comparative Examples are each unless otherwise specified.
% By weight and% by weight. Also,
In the examples, R^TwoO-group, R ^FourO-group and R^FiveO-
Groups may be abbreviated as "OR" in some cases. further,
Various evaluations were performed as follows.

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

[0082] to form an aluminum electrode pattern was prepared a sample for dielectric constant measurement by vapor deposition relative permittivity resulting film. The sample was sampled at a frequency of 100 kHz using an HP16451B electrode and HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd.
The dielectric constant of the coating film was measured by the V method. The film density was calculated from the volume obtained from the film thickness and the film area and the weight of the film. Modulus of elasticity (Young's modulus ) The obtained film was measured by a continuous rigidity measuring method using Nanoindenter XP (manufactured by MST).

Water absorption The obtained coating film was prepared at 127 ° C., 2.5 atm, 100% R
H, was left for 1 hour in the environment, and the IR spectrum of the coating film after the standing was observed. Compared to the IR spectrum of the coating film before standing, the presence or absence of absorption due to H ₂ O near 3,500 cm ⁻¹ was observed, and the water absorption was evaluated according to the following criteria. ○: No absorption ×: Absorption

Production Example 1 [Synthesis of (meth) acrylic polymer] In a 100 ml flask, 20.0 g of methoxypolyethylene glycol methacrylate, 0.33 g of azoisobutyronitrile (AIBN), 0.20 g of 2-mercaptoethanol and 3 -Methoxymethyl propionate 3
0 g was 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 in terms of polystyrene was measured by GPC, the number average molecular weight was 7,500 and the weight average molecular weight was 14,000.

Example 1 Preparation of component (A); tetramethoxysilane 101.3
g (complete hydrolyzed condensate: 40.0 g), methyltrimethoxysilane (203.0 g) (complete hydrolyzed condensate: 100.0 g), dimethyldimethoxysilane
In a mixed solution of 3 g (completely hydrolyzed condensate conversion: 60.0 g), 559.3 g of propylene glycol monopropyl ether, and 239.7 g of methyl-n-pentyl ketone,
Maleic acid 1.0g (catalyst / SiOR = 0.001mo)
157.7 g of water (H ₂ O / SiOR = 1.0 m)
aqueous solution) was added dropwise over 1 hour at room temperature. After the addition of the mixture was completed, the mixture was further reacted at 60 ° C. for 2 hours, and then concentrated under reduced pressure until the total solution amount reached 1,000 g, to obtain a polysiloxane sol having a solid content of 20%. Preparation of composition; 100 g of polysiloxane sol obtained above
(Solid content: 20 g), a polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer (manufactured by Sanyo Chemical Co., Ltd., Newpole 62 (HO-PEO)
3.5 g of _5- PPO ₃₀ -PEO ₅ -OH) was added, and the resulting mixture was applied on an 8-inch silicon wafer by a spin coating method.
After heating at 0 ° C. for 3 minutes and then as a first soft bake at 350 ° C. for 30 minutes under nitrogen, further as a second soft bake at 350 ° C. under an oxygen partial pressure of 18 kPa.
The mixture was heated for 5 minutes and further heated at 42 ° C. for 1 hour under vacuum to form a colorless and transparent film. The film thus obtained was evaluated. Table 1 shows the results.

Example 2 Preparation of component (A); 101.3 tetramethoxysilane
g (complete hydrolyzed condensate: 40.0 g), methyl trimethoxysilane 324.7 g (complete hydrolyzed condensate: 160.0 g), propylene glycol monomethyl ether acetate 783.3 g, di-i-propoxy bis (Ethyl acetoacetate) titanium (catalyst / SiOR =
176.8 g of water was added to the mixed solution (0.004 mol ratio).
(H ₂ O / SiOR = 1.0 mol ratio) was added dropwise over 1 hour while heating at 60 ° C. After the addition of the mixture was completed, the mixture was further reacted at 60 ° C. for 2 hours.
0.0 g was added, and then the total solution volume was reduced to 1,000 under reduced pressure.
g to obtain a polysiloxane sol having a solid content of 20%. Preparation of composition; 100 g of polysiloxane sol obtained above
(20 g of solid content), 3.5 g of polyoxydiethylene adipate (weight average molecular weight: about 5,000) was added,
The obtained mixture is applied on an 8-inch silicon wafer by a spin coating method, and is prebaked at 80 ° C. in the air.
For 3 minutes, then under nitrogen at 200 ° C. for 90 seconds, and then as a first soft bake under reduced pressure of 10 Pa at 380 ° C.
After heating at 380 ° C. for 15 minutes under a partial pressure of oxygen of 10 Pa as a second soft bake, and then performing final annealing at 42 ° C. under vacuum
The mixture was heated at 5 ° C. for 1 hour to form a colorless and transparent film. The film thus obtained was evaluated. Table 1 shows the results.

Example 3 Preparation of Component (A): Tetramethoxysilane 152.0
g (complete hydrolyzed condensate: 60.0 g), methyltrimethoxysilane 284.1 g (complete hydrolyzed condensate: 140.0 g), N, N-dimethylacetamide 7
To a mixed solution of 98.8 g, 1.0 g of oxalic acid (catalyst / S
iOR = 0.001 mol ratio was converted to 157.7 g of water (H ₂
(O / SiOR = 1.0 mol ratio) was added dropwise over 1 hour at room temperature. After the addition of the mixture was completed, the mixture was further reacted at 60 ° C. for 2 hours, and then concentrated under reduced pressure until the total solution amount reached 1,000 g, to obtain a polysiloxane sol having a solid content of 20%. Preparation of composition; 100 g of polysiloxane sol obtained above
(Solid content: 20 g), 8.6 g of polyhexamethylene carbonate (weight average molecular weight: about 2,000) was added,
The obtained mixture is applied on an 8-inch silicon wafer by a spin coating method, and is prebaked at 80 ° C. in the air.
For 3 minutes, then under nitrogen at 200 ° C. for 60 seconds, and as a first soft bake under a reduced pressure in a nitrogen atmosphere (133
Pa), after heating at 350 ° C. for 30 minutes,
As the next soft bake, under an oxygen partial pressure of 133 Pa, 350
After heating at 15 ° C. for 15 minutes, the film was heated at 400 ° C. for 1 hour under vacuum as a final annealing treatment to form a colorless and transparent film. The film thus obtained was evaluated. Table 1 shows the results.

Example 4 101.3 g of tetramethoxysilane (completely hydrolyzed condensate: 40.0 g), methyltrimethoxysilane 3
24.7 g (complete hydrolysis condensate conversion: 160.0
g), 783.3 g of N, N-dimethylacetamide and 786.8 g of di-i-propoxybis (ethylacetoacetate) titanium (catalyst / SiOR = 0.004 mol ratio) were mixed with 176.8 g of water (H ₂ O / SiOR = 1.0mo
l ratio) was added dropwise over 1 hour while heating at 60 ° C. After the mixture was dropped, the mixture was further reacted at 60 ° C. for 2 hours.
100.0 g of acetylacetone was added, and then concentrated under reduced pressure until the total solution amount reached 1,000 g, to obtain a polysiloxane sol having a solid content of 20%. Preparation of composition; 100 g of polysiloxane sol obtained above
(Solid content: 20 g), 3.5 g of polysebasic anhydrite (weight average molecular weight: about 4000) was added, and the obtained mixture was applied on an 8-inch silicon wafer by a spin coating method, and prebaked to form an atmosphere. Medium 180 ° C
For 3 minutes, then 1.3P as first soft bake
After heating at 380 ° C. for 30 minutes in the nitrogen atmosphere of a,
Further, as a second soft bake, heating is performed at 380 ° C. for 30 minutes in an oxygen atmosphere of 1.3 Pa,
The mixture was heated at 50 ° C. for 0.5 hour to form a colorless and transparent film.
The film thus obtained was evaluated. Table 1 shows the results.

Example 5 Preparation of Component (A): Tetramethoxysilane 101.3
g (complete hydrolyzed condensate: 40.0 g), methyltrimethoxysilane (203.0 g) (complete hydrolyzed condensate: 100.0 g), dimethyldimethoxysilane
In a mixed solution of 3 g (completely hydrolyzed condensate conversion: 60.0 g), 559.3 g of propylene glycol monopropyl ether, and 239.7 g of methyl-n-pentyl ketone,
Maleic acid 1.0g (catalyst / SiOR = 0.001mo)
157.7 g of water (H ₂ O / SiOR = 1.0 m)
aqueous solution) was added dropwise over 1 hour at room temperature. After the addition of the mixture was completed, the mixture was further reacted at 60 ° C. for 2 hours, and then concentrated under reduced pressure until the total solution amount reached 1,000 g, to obtain a polysiloxane sol having a solid content of 20%. Preparation of composition; 100 g of polysiloxane sol obtained above
(Solid content 20 g), 3.5 component (B) described in Production Example 1
g was added, and the resulting mixture was applied on an 8-inch silicon wafer by a spin coating method.
After heating at 80 ° C. in the air for 3 minutes and then as a first soft bake at 350 ° C. for 30 minutes under nitrogen, further as a second soft bake and heating at 350 ° C. for 15 minutes under an oxygen atmosphere at a pressure of 13 Pa, Next, as a final annealing treatment, heating was performed at 420 ° C. for 1 hour under vacuum to form a colorless and transparent film. The film thus obtained was evaluated. Table 1 shows the results.

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that the polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer was not used. A film was formed. Evaluation of the obtained composition and film was performed in the same manner as in Example 1.
Table 1 shows the results.

[0091]

[Table 1]

[0092]

According to the present invention, it is possible to obtain a silica-based film having a low density, a low dielectric constant, a low water absorption, excellent mechanical strength, and useful as an interlayer insulating film material in a semiconductor device or the like.

Continued on the front page (72) Inventor Takahiko Kurosawa 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Kinji 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. F-term (reference) 4G072 AA28 BB09 CC13 FF01 FF02 FF04 FF09 GG03 HH29 HH30 JJ11 JJ13 JJ47 KK01 KK07 KK09 KK17 LL11 LL13 LL14 LL15 MM01 NN21 PP17 RR05 UU01 UU30 JJ0138 DF02 PB09 PC02 PC03 PC04 5F058 AA04 AA10 AC03 AF04 AG01 AH01 AH02

Claims (8)

[Claims] 1. A coating composition comprising (A) a polysiloxane, (B) an organic polymer, and (C) an organic solvent is applied to a substrate, and after removing the organic solvent, the coating composition is dried under a vacuum or an inert gas atmosphere. It is heated to 400 ° C., and then heated to 250 to 400 ° C. in an atmosphere having an oxygen partial pressure of 1 Pa or more, and further heated to 350 to 400 ° C. in an atmosphere having an oxygen partial pressure of less than 1 Pa.
A method for forming a silica-based film, comprising heating to 470 ° C. 2. A polysiloxane comprising: (A-1) a compound represented by the following general formula (1); and R ¹ _a Si (OR ² ) _4-a (1) In the formula, R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 2.) (A-2) The following general formula A compound represented by the following formula (2): R ³ _b (R ⁴ O) _3-b Si— (R ⁷ ) _d —Si (OR ⁵ ) _3-c R ⁶ _c (2) R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a monovalent organic group, and b and c may be the same or different and represent a number of 0 to 2 , R ⁷ represents an oxygen atom or a group represented by — (CH ₂ ) _n —, n represents 1 to 6, and d represents 0 or 1.) Of the hydrolyzate and its Method of forming a silica film according to claim 1, wherein condensates or is either. 3. A polysiloxane obtained by hydrolyzing and condensing (A) a siloxane compound in the presence of at least one catalyst selected from the group consisting of a metal chelate compound, an acidic compound and an alkaline compound. The method for producing a silica-based film according to claim 2. (B) The organic polymer is a polyether,
The method for producing a silica-based film according to claim 1, wherein the method is at least one selected from the group consisting of polyester, polycarbonate, polyanhydride, and (meth) acrylic polymer. 5. The method according to claim 5, wherein the removing of the organic solvent is performed by
The method for forming a silica-based film according to claim 1, which is performed by heating to 250 ° C. 6. The method for forming a silica-based film according to claim 1, wherein the heating is performed in an atmosphere having an oxygen partial pressure of 1 Pa or more for 1 minute to 2 hours. 7. The method according to claim 1, wherein the atmosphere having an oxygen partial pressure of less than 1 Pa is an inert atmosphere. 8. The method according to claim 1, wherein the heating is performed in an atmosphere having an oxygen partial pressure of less than 1 Pa for 1 minute to 3 hours.