JP2002097274A - Silicone polymer, film-forming composition and insulation film-forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-forming composition and an insulation film-forming material capable of forming a silicious film having small specific dielectric constant, excellent crack resistance, mechanical strength and adhering ability for use as an interlayer insulation material in a semiconductor element or the like. SOLUTION: This silicone polymer is obtained by reacting (A) carbon tetrahalide, (B) silicon tetrahalide and (C) at least one compound selected from the group consisting of a compound expressed by formula (1), a compound expressed by formula (2) and a compound expressed by formula (3) in the existence of either metallic Li or metallic Mg: R10nSiX4-n (1), R10nCX4-n (2), R10MgX (3) (where R10 represents one valence organic group, X represents a halogen atom, and n is an integer of 1 to 3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon polymer and a film forming composition containing the silicon polymer. The present invention relates to a film-forming composition and an insulating film-forming material capable of forming a silica-based film having excellent resistance, mechanical strength, and adhesion.

[0002]

2. Description of the Related Art Conventionally, CVD (Chemical Vapor Deposit) has been used as an interlayer insulating film in a semiconductor device or the like.
A silica (SiO ₂ ) film formed by a vacuum process such as a position method is frequently used. 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. Further, with the increase in integration of semiconductor elements and the like, an interlayer insulating film having a low relative dielectric constant and mainly containing polyorganosiloxane called organic SOG has been developed. In particular, with higher integration and multi-layering of semiconductor devices, etc., better electrical insulation between conductors is required, and therefore, it has a lower dielectric constant and excellent crack resistance, mechanical strength and adhesion. In addition, a material for an interlayer insulating film has been required.

As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensing alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (JP-A-5-263045, 5-315
319) and a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (JP-A-11-340219, JP-A-11-34022).
0) has been proposed, but the materials obtained by these methods are not stable in the nature of the product of the reaction and the relative dielectric constant of the coating film,
Because of large variations in crack resistance, mechanical strength, adhesion and the like, it was not suitable for industrial production.

[0004]

The present invention relates to a method for producing a silicon polymer and a film-forming composition for solving the above-mentioned problems. It is an object of the present invention to provide a film-forming composition having a small relative dielectric constant and excellent in crack resistance, mechanical strength, and adhesion, and a material for forming an insulating film obtained from the composition.

[0005]

According to the present invention, there are provided (A) a tetrahalogenated carbon, (B) a silicon tetrahalide, and (C) a compound represented by the following general formula (1).
And at least one compound selected from the group consisting of compounds represented by general formula (3) and R ¹⁰ _n SiX _4-n ... (1) R ¹⁰ _n CX _4-n. (2) R ¹⁰ MgX (3) (wherein R ¹⁰ is a monovalent organic group, X is a halogen atom, and n is an integer of 1 to 3). (D) a silicon polymer obtained by reacting in the presence of lithium metal and / or magnesium metal
A compound represented by the following general formula (4), and a compound represented by the following general formula (5)
And a hydrolyzed condensate R _a Si (OR ¹ ) _4-a obtained by hydrolyzing and condensing at least one silane compound selected from the group of compounds represented by the following general formula (6) _: (4) (In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2.) Si (OR ² ) ( ₄ ) (wherein, R ² represents a monovalent organic group.) R ³ _b (R ⁴ O) _3-b Si— (R ⁷ ) _d —Si (OR ⁵ ) _{^{3-c R 6 c ····· (}} 6) wherein, R ³ to R ⁶ are the same or different and each represents a monovalent organic group, b-c are the same or different, an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or a group represented by — (CH ₂ ) _m — (where m is an integer of 1 to 6), and d is 0 or 1. ], And a material for forming an insulating film, comprising the film-forming composition.

The silicon polymer of the present invention comprises (A) a tetrahalogenated carbon (B) a silicon tetrahalide and (C) a compound represented by the following general formula (1),
And at least one compound R ¹⁰ _n selected from the group consisting of compounds represented by the general formula (3)
SiX _4-n ... (1) R ¹⁰ _n CX _4-n ... (2) R ¹⁰ MgX... (3) (where R ¹⁰ is a monovalent organic group) , X is a halogen atom, and n is an integer of 1 to 3) in the presence of metallic lithium and / or metallic magnesium.

(A) Tetrahalogenated Carbon Examples of the component (A) include carbon tetrachloride, carbon tetrabromide and carbon tetraiodide. Two or more of these components (A) may be used simultaneously.

(B) Silicon tetrahalide [0008] Examples of the component (B) include tetrachlorosilane, tetrabromosilane, tetraiodosilane, and tetraiodofluorosilane, with tetrachlorosilane and tetrabromosilane being particularly preferred. These (B)
Two or more components may be used simultaneously.

(C) Component In the general formula (1), R ¹⁰ is a monovalent organic group. Specific examples thereof include linear or branched aliphatic groups having 1 to 10 carbon atoms such as alkyl groups, alkenyl groups, and alkynyl groups; and those having 3 carbon atoms such as cycloalkyl groups, cycloalkenyl groups, and bicycloalkyl groups. To 20 alicyclic groups; aryl groups having 6 to 20 carbon atoms; and aralkyl groups having 6 to 20 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, texyl, and the like. No. Examples of the alkenyl group include a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group. Examples of the alkynyl group include a propargyl group, a 3-methylpropagyl group, and a 3-ethylpropagyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and the like. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, an α-naphthyl group, a β-naphthyl group,
-Thiophene group, β-thiophene group and the like. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, and a phenylbutyl group. As these substituents, a t-butyl group, a hexyl group, a phenethyl group, and a norbornyl group are preferable in view of the stability of the resulting silicon polymer and the ease of decomposition when decomposed by heat and / or light.

The component (C) includes, for example, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, n-butyltrichlorosilane, t-butyltrichlorosilane, cyclohexyltrichlorosilane, phenethyltrichlorosilane, 2-norbornyltrichlorosilane, phenyltrichlorosilane, methyltribromosilane, ethyltribromosilane, n-propyltribromosilane, isopropyltribromosilane, n-butyltribromosilane, t-butyltribromosilane, cyclohexyltri Bromosilane, phenethyltribromosilane, 2-norbornyltribromosilane, phenyltribromosilane, methyltriiodosilane, ethyltriiodosilane, n-propyl Pills triiodo silane, isopropyl-triiodo silane, n- butyl triiodo silane,
t-butyltriiodosilane, cyclohexyltriiodosilane, phenethyltriiodosilane, 2-norbornyltriiodosilane, phenyltriiodosilane, dimethyldichlorosilane, diethyldichlorosilane, di-
n-propyldichlorosilane, diisopropyldichlorosilane, di-n-butyldichlorosilane, di-t-butyldichlorosilane, dicyclohexyldichlorosilane,
Diphenethyldichlorosilane, di-2-norbornyldichlorosilane, diphenyldichlorosilane, dimethyldibromosilane, diethyldibromosilane, di-n-propyldibromosilane, diisopropyldibromosilane,
Di-n-butyldibromosilane, di-t-butyldibromosilane, dicyclohexyldibromosilane, diphenethyldibromosilane, di-2-norbornyldibromosilane, diphenyldibromosilane, dimethyldiiodosilane, diethyldiiodosilane, -N-propyldiiodosilane, diisopropyldiiodosilane, di-n-
Butyldiiodosilane, di-t-butyldiiodosilane, dicyclohexyldiiodosilane, diphenethyldiiodosilane, di-2-norbornyldiiodosilane,
Diphenyldiiodosilane, trimethylchlorosilane,
Triethylchlorosilane, tri-n-propylchlorosilane, triisopropylchlorosilane, tri-n-butylchlorosilane, tri-t-butylchlorosilane, tricyclohexylchlorosilane, triphenethylchlorosilane, tri-2-norbornylchlorosilane, triphenylchlorosilane, trimethyl Bromosilane, triethylbromosilane, tri-n-propylbromosilane, triisopropylbromosilane, tri-n-butylbromosilane, tri-t-butylbromosilane, tricyclohexylbromosilane, triphenethylbromosilane, tri-2- Norbornylbromosilane, triphenylbromosilane, trimethyliodosilane, triethyliodosilane, tri-n-propyliodosilane, triisopropyliodosila , Birds -n- butyl iodine silane,
Tri-t-butyliodosilane, tricyclohexyliodosilane, triphenethyliodosilane, tri-2-
Silicon compounds such as norbornyl iodosilane and triphenyliodosilane; methyl magnesium chloride, ethyl magnesium chloride, n-propyl magnesium chloride, isopropyl magnesium chloride, n-butyl magnesium chloride, t-butyl magnesium chloride, texyl magnesium chloride, Cyclohexyl magnesium chloride, phenethyl magnesium chloride, 2-norbornyl magnesium chloride, phenyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-propyl magnesium bromide, isopropyl magnesium bromide,
n-butyl magnesium bromide, t-butyl magnesium bromide, texyl magnesium bromide, cyclohexyl magnesium bromide, phenethyl magnesium bromide, 2-norbornyl magnesium bromide,
Phenyl magnesium bromide, methyl magnesium iodide, ethyl magnesium iodide, n-propyl magnesium iodide, isopropyl magnesium iodide, n-butyl magnesium iodide, t-butyl magnesium iodide, texyl magnesium iodide, cyclohexyl magnesium iodide Organic magnesium compounds such as phenethyl magnesium iodide, 2-norbornyl magnesium iodide, and phenyl magnesium iodide; methyltrichlorocarbon, ethyltrichlorocarbon, n-propyltrichlorocarbon, isopropyltrichlorocarbon, n-butyltrichlorocarbon, t -Butyl trichlorocarbon, cyclohexyl trichlorocarbon, E phenethyl trichloro-carbon, 2
-Norbornyltrichlorocarbon, phenyltrichlorocarbon, methyltribromocarbon, ethyltribromocarbon, n-propyltribromocarbon, isopropyltribromocarbon, n-butyltribromocarbon, t-butyltribromocarbon, cyclohexyltribromo Carbon, phenethyltribromocarbon, 2-norbornyltribromocarbon, phenyltribromocarbon, methyltriiodocarbon, ethyltriiodocarbon, n-propyltriiodocarbon, isopropyltriiodocarbon, n-butyltriiodocarbon, t-butyltriiodocarbon, cyclohexyltriiodocarbon, phenethyltriiodocarbon, 2-norbornyltriiodocarbon, phenyltriiodocarbon , Dimethyldichlorosilane carbon,
Diethyldichlorocarbon, di-n-propyldichlorocarbon, diisopropyldichlorocarbon, di-n-
Butyldichlorocarbon, di-t-butyldichlorocarbon, dicyclohexyldichlorocarbon, diphenethyldichlorocarbon, di-2-norbornyldichlorocarbon, diphenyldichlorocarbon, dimethyldibromocarbon, diethyldibromocarbon, di-n-propyldibromocarbon , Diisopropyldibromocarbon, di-n-butyldibromocarbon, di-t-butyldibromocarbon, dicyclohexyldibromocarbon, diphenethyldibromocarbon, di-2-norbornyldibromocarbon, diphenyldibromocarbon,
Dimethyldiiodocarbon, diethyldiiodocarbon, di-n-propyldiiodocarbon, diisopropyldiiodocarbon, di-n-butyldiiodocarbon, di-t-butyldiiodocarbon, dicyclohexyldiiodocarbon, diphenethyldi Iodine carbon,
Di-2-norbornyldiiodocarbon, diphenyldiiodocarbon, trimethylchlorocarbon, triethylchlorocarbon, tri-n-propylchlorocarbon, triisopropylchlorocarbon, tri-n-butylchlorocarbon, tri-t-butyl Chlorocarbon,
Tricyclohexylchlorocarbon, triphenethylchlorocarbon, tri-2-norbornylchlorocarbon, triphenylchlorocarbon, trimethylbromocarbon, triethylbromocarbon, tri-n-propylbromocarbon, triisopropylbromocarbon,
Tri-n-butylbromocarbon, tri-t-butylbromocarbon, tricyclohexylbromocarbon, triphenethylbromocarbon, tri-2-norbornylbromocarbon, triphenylbromocarbon, trimethyliodocarbon, triethyliodocarbon, triethyliodocarbon -N-propyliodocarbon, triisopropyliodocarbon, tri-n-butyliodocarbon, tri-
t-butyliodocarbon, tricyclohexyliodocarbon, triphenethyliodocarbon, tri-2-
Carbon compounds such as norbornyl iodocarbon and triphenyliodocarbon can be mentioned. These compounds can be used alone or in combination of two or more.

In the method for producing a silicon polymer of the present invention,
By reacting component (A), component (B), component (C) and metal lithium and metal magnesium,
A silicon polymer having an R ¹⁰ group or a halogen group at the terminal of the molecule can be obtained. (A) in silicon polymer
The use ratio of the component and the component (B) is (A) / component (B) = 0.01 to 100 (mol / mol), more preferably 0.1 to 10, and particularly preferably 0.1 to 10. 5-5
It is. Further, the use ratio of the component (C) to the total amount of the components (A) and (B) in the silicon polymer is as follows: ((A) component + total amount of (B) component) / (C) component = 0.01 to 10
0 (mol / mol), more preferably 0.1 to 10
And particularly preferably 0.5 to 5.

The metal lithium and magnesium metal to be reacted therewith are used to reductively remove halogen atoms from component (A), component (B) and component (C) to form lithium halide and magnesium halide. And the amount used is preferably (A)
It is equivalent to the total amount of component, component (B) and component (C).

In the method for producing a silicon polymer of the present invention, the reaction can be promoted by irradiating an ultrasonic wave from the outside as necessary. The frequency of the ultrasonic wave used here is desirably about 10 to 70 KHz.

In the production of the silicon polymer of the present invention,
As a solvent to be used, an ether solvent can be preferably used. The yield of the target soluble polysilane oligomer tends to be low with a hydrocarbon-based solvent used in a normal Kipping reaction. Examples of ether solvents include diethyl ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethyl propyl ether, anisole, phenetole, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether,
Dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol methyl ethyl ether,
Examples thereof include tetrahydrofuran and dioxane. Among these, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like are preferable from the viewpoint of the solubility of the component (C).

It is desirable to remove water from these ether solvents in advance. As a method for removing water, a degassing distillation method in the presence of sodium-benzophenone ketyl and the like are preferable. The use amount of these solvents is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on the total amount of the above components (A), (B) and (C). It is.

The reaction temperature is preferably -78.
° C to + 100 ° C. If the reaction temperature is below -78 ° C,
The reaction rate is slow and productivity does not increase, and the reaction temperature is +10
If the temperature is higher than 0 ° C, the reaction may be complicated.
The solubility of the iodine polymer tends to decrease. In addition, the reaction
Is usually performed in an inert gas such as argon or nitrogen.
Is preferred. In the method for producing the silicon polymer of the present invention
Has an unreacted hydrolysable halogen atom at the molecular end.
Is reduced by a reducing agent.
Resolvable halogen atoms may be replaced with stable hydrogen atoms.
No. Such reducing agents include, for example, LiAlH_Four, Na
H, LiBu_ThreeBH, (C_FiveH₁₁)_TwoBH, B_TwoH₆, Na
BH_Four, Zn (BH_Four)_Two, NaBH_ThreeCN, Bu_TwoAl
H, Li (OBu)_ThreeAlH and the like can be mentioned,
LiAlH_Four, NaH, B _TwoH₆, NaBH_FourMore preferred
A good example. Reduce the amount of reducing agent used
Hydrogen atoms in the base agent are less than residual halogen atoms
At least equivalent, preferably 1.0 to 4.0 times equivalent
It is. The solvent used at this time is a reducing agent.
There is no particular limitation as long as the solvent does not react,
Ter solvents are preferred, and the ether solvents exemplified above.
The same can be used. These are alone
Alternatively, two or more kinds can be used as a mixture.

The reaction temperature at this time is preferably -78 ° C.
＋+ 60 ° C. When the temperature is lower than -78 ° C, the reaction is slow and the productivity does not increase. When the temperature is higher than + 60 ° C, the solubility of the reaction product is lowered, and the yield of the silicon polymer of the present invention is easily lowered. Further, the reaction is usually preferably performed in an inert gas such as argon or nitrogen.

The film-forming composition of the present invention further comprises (D)
A compound represented by the following general formula (4) (hereinafter, referred to as “compound (4)”), a compound represented by the following general formula (5) (hereinafter, referred to as “compound (5)”), and a compound represented by the following general formula ( At least one silane compound selected from the group of compounds represented by 6) (hereinafter referred to as “compound (6)”) may be hydrolyzed to contain a condensed hydrolyzed condensate. R _a Si (OR ¹ ) _4-a (4) (wherein, R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is 1-2) of an _{^{integer.) Si (OR 2) 4}} ····· (5) ( wherein, R ² represents a monovalent organic ^{_{group.) R 3 b (R 4}} O) 3-b Si- ( R ⁷ ) _d -Si (OR ⁵ ) _{3 -c} R ⁶ _c ··· (6) wherein R ^{3 to} R ⁶ are the same or different, each is a monovalent organic group, and b to c are the same Or differently, an integer from 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or — (CH ₂ ) _m —
(Where m is an integer of 1 to 6), d
Represents 0 or 1. ]

(D) Hydrolysis condensate (D) The hydrolysis condensate is obtained by hydrolyzing at least one silane compound selected from the group of compounds (4) to (6) in the presence of a catalyst. Obtained by condensation. Compound (4): In the above formula (4), ^one of R and R 1
Examples of the valent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group. In the general formula (4), R is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, as the alkyl group, a methyl group, an ethyl group, a propyl group,
Examples thereof include a butyl group and the like, which preferably has 1 to 5 carbon atoms. These alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted by a fluorine atom or the like. In the general formula (4), as the aryl group,
Examples 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 (4) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane and tri-silane. sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane and the like;

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

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

Preferred compounds as compound (4) are methyltrimethoxysilane, methyltriethoxysilane,
Methyltri-n-propoxysilane, methyltri-is
o-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Vinyl triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like. These may be used alone or in combination of two or more.

Compound (5): In the above formula (5), examples of the monovalent organic group represented by R ² include the same organic groups as in the above formula (4). Specific examples of the compound represented by the general formula (5) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxysilane. , Tetra-tert-butoxysilane, tetraphenoxysilane and the like.

Compound (6): In the above formula (6), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as in the above formula (4). . In the general formula (6), as a compound in which R ⁷ is an oxygen atom,
Hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,
3,3-pentamethoxy-3-methyldisiloxane,
1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3
-Methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3
-Pentaethoxy-3-ethyldisiloxane, 1,1,
1,3,3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyl Disiloxane, 1,1,1,3,3-pentaphenoxy-3-phenyldisiloxane, 1,1,
3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraphenoxy-
1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,
3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-
1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,
1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-
Trimethyldisiloxane, 1,1,3-triethoxy-
1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane,
1,1,3-trimethoxy-1,3,3-triethyldisiloxane, 1,1,3-triethoxy-1,3,3
Triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,
1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3 -Triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy- 1,1,3
3-tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraethyldisiloxane, 1,3-
Diethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,3
3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 1,
Examples thereof include 3-diphenoxy-1,1,3,3-tetraphenyldisiloxane.

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 (6), the compound in which d is 0 includes hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,1
2,2-pentamethoxy-2-methyldisilane, 1,
1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2
-Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2
-Pentamethoxy-2-phenyldisilane, 1,1,
1,2,2-pentaethoxy-2-phenyldisilane,
1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-
Dimethyldisilane, 1,1,2,2-tetraethoxy-
1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2
-Tetramethoxy-1,2-diethyldisilane, 1,
1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1,
2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-
Tetraphenoxy-1,2-diphenyldisilane, 1,
1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2
-Trimethyldisilane, 1,1,2-trimethoxy-
1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,
1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,
2,2-triphenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, 1,2
-Dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-
Tetramethyldisilane, 1,2-dimethoxy-1,1,1
2,2-tetraethyldisilane, 1,2-diethoxy-
1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane,
1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1,1
2,2-tetraphenyldisilane and the like can be mentioned.

Of these, hexamethoxydisilane,
Hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,
2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,1
Preferred examples include 2,2-tetraphenyldisilane and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane.

Further, in the general formula (6), R ⁷ is-
Examples of the compound of the group represented by (CH ₂ ) _m — include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, and bis (tri-i-propoxy). Silyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-
sec-butoxysilyl) methane, bis (tri-t-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri- n-propoxysilyl) ethane, 1,2-bis (tri-i-propoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) Ethane, 1,2-bis (tri-t-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl)
-1- (triethoxysilyl) methane, 1- (di-n-
Propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-i-propoxymethylsilyl) -1- (tri-i-propoxysilyl) methane,
1- (di-n-butoxymethylsilyl) -1- (tri-
n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-t-butoxymethylsilyl)
-1- (tri-t-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl)
Ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-i -Propoxymethylsilyl) -2-
(Tri-i-propoxysilyl) ethane, 1- (di-n
-Butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-t-butoxy) Methylsilyl) -2- (tri-t-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl)
Methane, bis (di-n-propoxymethylsilyl) methane, bis (di-i-propoxymethylsilyl) methane,
Bis (di-n-butoxymethylsilyl) methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1, 2-bis (diethoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-i-propoxymethylsilyl) ethane, 1,2-
Bis (di-n-butoxymethylsilyl) ethane, 1,2
-Bis (di-sec-butoxymethylsilyl) ethane,
1,2-bis (di-t-butoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene,
1,2-bis (triethoxysilyl) benzene, 1,2
-Bis (tri-n-propoxysilyl) benzene, 1,
2-bis (tri-i-propoxysilyl) benzene,
1,2-bis (tri-n-butoxysilyl) benzene,
1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-t-butoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene,
1,3-bis (triethoxysilyl) benzene, 1,3
-Bis (tri-n-propoxysilyl) benzene, 1,
3-bis (tri-i-propoxysilyl) benzene,
1,3-bis (tri-n-butoxysilyl) benzene,
1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri-t-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene,
1,4-bis (triethoxysilyl) benzene, 1,4
-Bis (tri-n-propoxysilyl) benzene, 1,
4-bis (tri-i-propoxysilyl) benzene,
1,4-bis (tri-n-butoxysilyl) benzene,
Examples include 1,4-bis (tri-sec-butoxysilyl) benzene and 1,4-bis (tri-t-butoxysilyl) benzene.

Of these, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane,
2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1-
(Diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2-
(Trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethyl) (Silyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) )benzene,
1,3-bis (triethoxysilyl) benzene, 1,4
Preferred examples include -bis (trimethoxysilyl) benzene and 1,4-bis (triethoxysilyl) benzene. In the present invention, compound (4)
As (6), one kind or two or more kinds can be used.

In hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (4) to (6), 0.1 mol / mol of the compounds (4) to (6) is used.
It is preferred to use more than 5 mol and up to 150 mol of water, particularly preferred to add more than 0.5 mol and 130 mol of water.

In producing the hydrolyzed condensate (D) of the present invention, when hydrolyzing and condensing at least one silane compound selected from the group consisting of the compounds (4) to (6), And at least one selected from the group consisting of an alkali catalyst, a metal chelate catalyst and an acid catalyst. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, and diethanolamine. Zabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
Tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine,
Butylamine, pentylamine, hexylamine, pentylamine, octylamine, nonylamine, decylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, Tripropylamine, tributylamine, cyclohexylamine,
Trimethylimidine, 1-amino-3-methylbutane,
Dimethylglycine, 3-amino-3-methylamine and the like can be mentioned, and amines or amine salts are preferable, and organic amines or organic amine salts are particularly preferable.
Alkylamine and tetraalkylammonium hydroxide are most preferred. These alkaline catalysts are 1
Species or two or more species may be used simultaneously.

Examples of the metal chelate catalyst 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, diethoxybis (acetylacetonate) titanium , Di-n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n
-Butoxybis (acetylacetonato) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, Mono-n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris (acetylacetonate) titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-s
ec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy. Mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, Tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di-i-propoxy bis (ethyl acetoacetate) Chita , Di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetoacetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) Acetate) 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 (ethyl acetoacetate) titanium, mono-
t-butoxy-tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris ( Titanium chelate compounds such as acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetyl) (Acetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-
Butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxybis (acetylacetonato) zirconium, di- n-butoxy
Bis (acetylacetonate) zirconium, di-se
c-butoxybis (acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium , Mono-i
-Propoxy tris (acetylacetonato) zirconium, mono-n-butoxy tris (acetylacetonato) zirconium, mono-sec-butoxy tris (acetylacetonato) 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 (ethylacetoacetate) zirconium, tri-
n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, Jee
n-propoxybis (ethylacetoacetate) zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetate) Acetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, mono-n-propoxy.
Tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate)
Zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium,
Mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate)
Zirconium chelate compounds such as zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium; tris (acetylacetonate) aluminum, tris (ethylacetoacetate)
An aluminum chelate compound such as aluminum; and the like, preferably a titanium or aluminum chelate compound, particularly preferably a titanium chelate compound. One or more of these metal chelate catalysts may be used simultaneously.

Examples of the acid catalyst include, for example, hydrochloric acid,
Inorganic acids such as nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, oxalic acid; acetic acid, propionic acid, butanoic acid, pentanoic acid,
Hexanoic, heptanoic, octanoic, nonanoic, decanoic, oxalic, maleic, methylmalonic, adipic, sebacic, gallic, butyric, melitic, arachidonic, shikimic, 2-ethylhexanoic , 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, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid hydrolyzate, maleic anhydride hydrolyzate, Organic acids such as a hydrolyzate of phthalic anhydride can be mentioned, and organic carboxylic acids can be mentioned as more preferable examples. These acid catalysts may be used alone or in combination of two or more.

The amount of the above-mentioned catalyst to be used depends on the amount of the compound (4)
R in (6)¹ O-group, R^Two O-group, R ^Four An O-group and
R^Five Usually, based on 1 mol of the total amount of the group represented by the O- group,
0.00001 to 10 mol, preferably 0.00005
５5 mol. If the amount of catalyst used is within the above range,
There is little risk of polymer precipitation or gelation during the reaction. Ma
In the present invention, the compounds (4) to (6) are hydrolyzed.
The temperature at the time is usually 0 to 100 ° C, preferably 15 to 100 ° C.
80 ° C.

When the compounds (4) to (6) are converted to a complete hydrolyzed condensate, the compound (5) is preferably 5 to 75% by weight based on the total amount of the compounds (4) to (6). Is 10 to 70% by weight, more preferably 15 to 70% by weight
It is. Compound (4) and / or (6)
95 to 25% by weight, preferably 90 to 30% by weight, more preferably 85 to 3% by weight, based on the total amount of compounds (4) to (6)
0% by weight. Compound (5) is the compound (4)
When the amount is 5 to 75% by weight based on the total amount of (6), the resulting coating film has a high elastic modulus and is particularly excellent in low dielectric properties. Here, in the present invention, the completely hydrolyzed condensate refers to R ¹ O—, R ² O—, R ⁴ O in compounds (4) to (6).
- group and R ⁵ O-group 100% hydrolyzed to the SiOH
It is a group that becomes a group and is further completely condensed to form a siloxane structure. In addition, the component (D) is preferably a hydrolyzed condensate of the compound (4) and the compound (5) because the obtained composition has better storage stability. In the present invention, the amount of the component (D) used with respect to the silicon polymer is from 0 to 4000 parts by weight, more preferably from 0 to 3 parts by weight, based on 100 parts by weight of the silicon polymer.
000 parts by weight.

The film-forming composition of the present invention further comprises, in addition to the silicon polymer and the hydrolyzed condensate, β-diketone, colloidal silica, colloidal alumina, organic polymer, surfactant, silane coupling agent, Components such as a radical generator may be added. As β-diketone, 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, 1,1,1,5,
Examples thereof include 5,5-hexafluoro-2,4-heptanedione, and more preferred are acetylacetone, 2,4-hexanedione, 2,4-heptanedione, and 3,5-heptanedione. These may be used alone or in combination of two or more.

The colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 nm, preferably 10 to 30 nm.
It has a thickness of 20 nm and a solid concentration of about 10 to 40% by weight. Examples of such colloidal silica include, for example, methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industries, Ltd .;
And Oscar. Examples of the colloidal alumina include alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.
Examples 100 and 200 include alumina clear sol, alumina sol 10 and 132, manufactured by Kawaken Fine Chemicals Co., Ltd. Examples of the organic polymer include a compound having a sugar chain structure, a vinylamide polymer, and (meth)
Acrylic polymer, aromatic vinyl compound, dendrimer, polyimide, polyamic acid, polyarylene, polyamide, polyquinoxaline, polyoxadiazole,
Examples include a fluorine-based polymer and a compound having a polyalkylene oxide structure.

Compounds having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure,
Examples include a polytetramethylene oxide structure and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyether Oxypropylene block copolymers, ether compounds such as polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid alkanolamide sulfates and the like Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures. - (X) j- (Y) k- - (X) j- (Y) k- (X) l- ( wherein, X is a group represented by -CH ₂ CH ₂ O-, Y is -
And represents a group represented by CH ₂ CH (CH ₃ ) O—, wherein j is 1 to
90, k is a number from 10 to 99, and l is a number from 0 to 90) Among these, polyoxyethylene alkyl ether,
Polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
And ether-type compounds such as those described above as more preferable examples. These may be used alone or in combination of two or more.

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a fluorine-based surfactant, a silicone-based surfactant, and the like. Examples of the surfactant include a surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant, and preferably a fluorine-based surfactant and a silicone-based surfactant.

As the fluorine-based surfactant, for example, 1,
1,2,2-tetrafluorooctyl (1,1,2,2-
Tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl)
Ether, hexaethylene glycol (1, 1, 2,
2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro) Pentyl) ether, sodium perfluorododecyl sulfonate,
1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctanesulfone Amido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt,
At least one of terminal, main chain and side chain of perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, etc. And a fluorine-based surfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the position (1). Commercially available products are MegaFac F142D, F172, F173, F1
83 (manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC-430, and FC-431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, SC-103, SC-104, SC-1
05, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-10
00, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15
(Neos Co., Ltd.) and other commercially available fluorosurfactants. Among them, the above MegaFac F172, BM-1000, BM-11
00, NBX-15 is particularly preferred.

Examples of the silicone surfactant include SH7PA, SH21PA, SH30PA and ST94P.
A (All are Dow Corning Toray Silicone Co., Ltd.)
And the like can be used. Among them, the above S
H28PA and SH30PA are particularly preferred. The amount of the surfactant to be used is generally 0.0001 to 10 parts by weight relative to the component (A) (completely hydrolyzed condensate). These may be used alone or in combination of two or more.

As the silane coupling agent, for example, 3
-Glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- 1,4,7-triazadecane, 10-
Triethoxysilyl-1,4,7-triazadecane, 9
-Trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriacetate Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-
Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the radical generator include isobutyryl peroxide, α, α'bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate and diisopropylperoxy. Dicarbonate,
1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl par Oxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy ) Hexane, 1-cyclohexyl-
1-methylethyl peroxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,
m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-
Butylperoxycyclohexyl) propane, 1,1-
Bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-
3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t -Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis ( t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like can be mentioned. The mixing amount of the radical generator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. These may be used alone or in combination of two or more.

In the film-forming composition of the present invention, the above-mentioned silicon polymer, hydrolytic condensate and, if necessary, further additives are dissolved or dispersed in a solvent. Solvents that can be used at this time include alcohol solvents, ketone solvents,
At least one selected from the group consisting of amide solvents, ester solvents and aprotic solvents is exemplified. Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol,
-Methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, s
ec-octanol, n-nonyl alcohol, 2,6-
Dimethylheptanol-4, n-decanol, sec-
Undecyl alcohol, trimethyl nonyl alcohol,
mono-alcohol solvents such as sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,
Ethylene glycol mono-2-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.

Examples of the ketone solvent 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 amide solvents, 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.

Examples of the ester solvent include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ
-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, 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.

Examples of the aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole,
Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N −
Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1
H) -pyrimidinone and the like. These aprotic solvents may be used alone or in combination of two or more.

The total solid content of the composition of the present invention thus obtained is preferably 2 to 30% by weight,
It is adjusted appropriately 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, if necessary, by concentration and dilution with the organic solvent. When applying the composition of the present invention to a substrate such as a silicon wafer, SiO ₂ wafer, or SiN wafer, spin coating, dipping,
Coating means such as a roll coating method and a spray method are used.

The film thickness at this time is about 0.05 to 2.5 μm in a single application as a dry film thickness, and about 0.1 to 5.0 μm in a second application. be able to. Then dry at room temperature or 80-600
By heating and drying at a temperature of about 5 ° C. for about 5 to 240 minutes, a glassy or macromolecular insulating film can be formed. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used.
The reaction can be performed in an argon atmosphere, under vacuum, under reduced pressure with controlled oxygen concentration, or the like. Further, the coating film can be formed by irradiating an electron beam or an ultraviolet ray. Further, in order to control the curing speed of the coating film, if necessary, heating may be performed stepwise, or an atmosphere such as nitrogen, air, oxygen, or reduced pressure may be selected. The silica-based film of the present invention thus obtained has a film density of usually 0.1.
35-1.2 g / cm ³ , preferably 0.4-1.1 g
/ Cm ³ , more preferably 0.5 to 1.0 g / cm ³
It is. If the film density is less than 0.35 g / cm ³ , the mechanical strength of the coating film will decrease, while if it exceeds 1.2 g / cm ³ , a low dielectric constant cannot be obtained. Furthermore, the relative dielectric constant of the silica-based film of the present invention is usually 3.2 to 1.2, preferably 3.0 to 1.5, and more preferably 2.7 to 1.8.

The interlayer insulating film thus obtained has a low relative dielectric constant and excellent crack resistance, mechanical strength, and adhesion.
Interlayer insulating films and etching stopper films for semiconductor devices such as DRAM, RDRAM, and D-RDRAM, protective films such as surface coat films of semiconductor devices, intermediate layers in the semiconductor manufacturing process using a multilayer resist, and interlayer insulating films for multilayer wiring substrates It is useful for applications such as protective films and insulating films for liquid crystal display elements.

[0054]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the following description generally shows an embodiment of the present invention, and the present invention is not limited by the description without any particular reason. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, respectively, unless otherwise specified. Also,
Various evaluations were performed as follows.

Inertia radius 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 as to have a solid concentration of 0.25%. did. Apparatus: Tosoh Corporation, GPC system model GPC-8020 Tosoh Corporation, Column Alpha5000 / 3000 manufactured by Viscotec, Viscosity detector and light scattering detector Model T-60 dual meter Carrier solution: 10 mM LiBr Containing methanol Carrier feed rate: 1 ml / min Column temperature: 40 ° C

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

A composition sample was applied on a silicon wafer having a relative dielectric constant of 8 inches by a spin coating method, and the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was baked on a hot plate in a nitrogen atmosphere at 20 ° C. for 20 minutes. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for relative dielectric constant measurement. The sample is taken at a frequency of 100 kHz,
HP1645, manufactured by Yokogawa Hewlett-Packard Co., Ltd.
The relative dielectric constant of the coating film at room temperature was measured by a CV method using a 1B electrode and an HP4284A precision LCR meter.

A composition sample was applied on an 8-inch silicon wafer by crack coating using a spin coating method. The substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was baked on a hot plate in a nitrogen atmosphere for 20 minutes. At this time, the thickness of the coating film was 1.2 μm. A part of the obtained coating film was scratched with a knife and immersed in warm water at 60 ° C. for 10 hours. A knife scar in the coating film was observed with a microscope, and evaluated according to the following criteria. ：: No crack propagation was observed. ×: Propagation of cracks observed

Mechanical Strength (Hardness) A composition sample was applied on an 8-inch silicon wafer by spin coating, and the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. Then, the substrate was baked on a hot plate at 430 ° C. for 20 minutes in a nitrogen atmosphere. The obtained film was measured by a continuous stiffness measuring method using a nano indenter XP (manufactured by Nano Instruments).

Adhesion A sample of the composition was applied on an 8-inch silicon wafer by spin coating, and the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. The substrate was baked on a hot plate in a nitrogen atmosphere for 20 minutes. An SiN film having a thickness of 100 nm was formed on the obtained silica-based film by a CVD method, and ten stud pins were fixed on the substrate using an epoxy resin, followed by drying at 150 ° C. for one hour. This stud pin was subjected to a pull-out test using the Sebastian method, and the adhesion was evaluated according to the following criteria. ：: No peeling at the interface between the coating film and SiN with 10 stud pins ×: Occurrence of peeling at the interface between the coating film and SiN

Synthesis Example 1 In a quartz separable flask, 276.01 g of methyltrimethoxysilane and 86.14 of tetramethoxysilane were used.
g and 0.0092 g of tetrakis (acetylacetonato) titanium were dissolved in 101 g of propylene glycol monoethyl ether, and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 225.52 g of ion-exchanged water and 263.00 g of propylene glycol monoethyl ether was added to the solution over 1 hour. Then, after reacting at 55 ° C. for 4 hours, 48.12 g of acetylacetone was added, the reaction was further performed for 30 minutes, and the reaction solution was cooled to room temperature. 50 ℃
Then, 227 g of a solution containing methanol and water was removed from the reaction solution by evaporation to obtain a reaction solution A. The weight average molecular weight of the condensate and the like thus obtained was 1,230.

Synthesis Example 2 In a quartz separable flask, 205.50 g of methyltrimethoxysilane and 85.51 of tetramethoxysilane were used.
g of propylene glycol monoethyl ether 426
g, then stirred with a three-one motor,
The solution temperature was stabilized at 50 ° C. Next, succinic acid 0.63
182 g of ion-exchanged water in which g was dissolved was added to the solution over 1 hour. Then, after reacting at 50 ° C. for 3 hours, the reaction solution was cooled to room temperature. At 50 ° C., 360 g of a solution containing methanol was removed from the reaction solution by evaporation to obtain a reaction solution B. The weight average molecular weight of the condensate and the like thus obtained was 1,400.

Synthesis Example 3 Distilled ethanol 370 was placed in a separable quartz flask.
g, distilled propylene glycol monopropyl ether 2
00 g, 160 g of ion-exchanged water and 90 g of a 10% aqueous solution of methylamine were added and stirred uniformly. 136 g of methyltrimethoxysilane and tetraethoxysilane 2 were added to this solution.
09 g of the mixture were added. The reaction was performed for 2 hours while keeping the solution at 55 ° C. 300 g of propylene glycol monopropyl ether was added to this solution, and then 5 g
The solution was concentrated using an evaporator at 0 ° C. until the solution became 10% (in terms of a completely hydrolyzed condensate).
0% propylene glycol monopropyl ether solution 1
0 g was added to obtain a reaction solution C. The radius of inertia of the condensate and the like thus obtained was 15.4 nm.

Synthesis Example 4 Distilled ethanol 428 was placed in a separable quartz flask.
g, 215 g of ion-exchanged water and 15.6 g of a 25% aqueous solution of tetramethylammonium hydroxide were uniformly stirred. To this solution, add methyltrimethoxysilane 4
A mixture of 0.8 g and 61.4 g of tetraethoxysilane was added. The reaction was performed for 2 hours while keeping the solution at 60 ° C. 300 g of propylene glycol monopropyl ether was added to this solution, and then the solution was concentrated to 10% (complete hydrolyzed condensate) using an evaporator at 50 ° C., and then 10% propylene glycol monopropyl maleate was added. 20 g of an ether solution was added to obtain a reaction solution D. The radius of inertia of the condensate and the like thus obtained was 20.4 nm.

Example 1 After replacing the inside of a three-liter four-necked flask equipped with a thermometer, a cooling condenser, a dropping funnel and a stirrer with argon gas, 1 L of dried tetrahydrofuran was used.
And 60 g of magnesium metal were charged and bubbled with argon gas. To this was added a solution of tert-butylmagnesium chloride in tetrahydrofuran (1000 ml, 1.0 mol).
And stirring at 20 ° C. with tetrachlorosilane 8
A mixture of 5 g and 166 g of carbon tetrabromide was slowly added from a dropping funnel. After completion of the dropwise addition, stirring was continued at room temperature for another 3 hours. The resulting polymer was precipitated by pouring into 15 L of ice water. The resulting polymer is thoroughly washed with water and vacuum dried to obtain a brown solid polymer (40 g).
I got The weight average molecular weight of the silicon polymer thus obtained was 18,000.

Example 2 LiAlH ₄ was added to 20 g of the polymer obtained in Synthesis Example 1.
10 g was added to a solution suspended in 300 ml of dried tetrahydrofuran, and reacted at room temperature for 5 hours. next,
The reaction mixture was poured into 15 L of ice water to precipitate the formed polymer. The resulting polymer was thoroughly washed with water and dried under vacuum to obtain 13 g of a brown solid polymer. The weight average molecular weight of the silicon polymer thus obtained is
It was 17,000.

Example 3 After replacing the inside of a 3 L four-necked flask equipped with a thermometer, a cooling condenser, a dropping funnel and a stirrer with argon gas, 1 L of dried tetrahydrofuran was used.
And 60 g of magnesium metal were charged and bubbled with argon gas. 227 g of 2-norbornyltrichlorosilane was added thereto, and a mixture of 85 g of tetrachlorosilane and 166 g of carbon tetrabromide was slowly added from a dropping funnel while stirring at 20 ° C. After completion of the dropwise addition, stirring was continued at room temperature for another 3 hours. Next, 10 g of LiAlH ₄ was added to a solution of 300 ml of dried tetrahydrofuran, and the mixture was reacted at room temperature for 5 hours. Next, the reaction mixture was poured into 15 L of ice water,
The resulting polymer was precipitated. The resulting polymer is thoroughly washed with water and dried under vacuum to obtain a brown solid polymer 6.
5 g were obtained. The weight average molecular weight of the silicon polymer thus obtained was 15,000.

Example 4 0.5 g of the polymer obtained in Example 1 was dissolved in 9.5 g of tetrahydrofuran. The reaction solution A100 was added to this solution.
g was added and stirred sufficiently. This solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a film-forming composition of the present invention. The obtained composition was applied on a silicon wafer by spin coating. The relative dielectric constant of the coating film at room temperature was 2.79, and no crack propagation was observed even when the coating film was immersed in water. Further, when the hardness of the coating film was measured, it was 2.3 GPa, which was excellent in mechanical strength. Further, when the adhesion of the coating film was evaluated, the stud pin 1
No peeling at the interface between the zero-coated film and SiN was observed.

Examples 5 to 9 Evaluations were made in the same manner as in Example 4 except that the silicon polymer and the reaction solution shown in Table 1 were used. The evaluation results are also shown in Table 1.

[0070]

[Table 1]

Comparative Example 1 The coating film was evaluated in the same manner as in Example 1 except that only the reaction solution A obtained in Synthesis Example 1 was used. Table 2 shows the evaluation results.
Shown in

Comparative Example 2 The coating film was evaluated in the same manner as in Example 1 except that only the reaction solution B obtained in Synthesis Example 2 was used. Table 2 shows the evaluation results.
Shown in

[0073]

[Table 2]

[0074]

According to the present invention, by using a film-forming composition containing a specific silicon polymer, the relative dielectric constant of the coating film is small, and the coating film has excellent crack resistance, mechanical strength, and adhesion. It is possible to provide a film-forming composition (material for an interlayer insulating film).

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09D 183/14 C09D 183/14 183/16 183/16 H01L 21/312 H01L 21/312 C 21/316 21/316 G F term (reference) 4J002 CP011 CP032 CP211 GH00 GQ01 4J035 JA01 JA04 JB03 4J038 DL022 DL042 DL072 DL162 DL171 HA066 HA076 HA476 KA03 KA04 MA07 MA09 NA11 NA12 NA21 PA19 PB09 PC02 5F058 AA08 AC03 AF04 AG01 B01BA02

Claims (6)

[Claims] (A) a tetrahalogenated carbon; (B) a silicon tetrahalide; and (C) a compound represented by the following general formula (1).
And at least one compound selected from the group consisting of compounds represented by the general formula (3) R ¹⁰ _n SiX _4-n ... (1) R ¹⁰ _n CX _4-n. (2) R ¹⁰ MgX (3) (wherein R ¹⁰ is a monovalent organic group, X is a halogen atom, and n is an integer of 1 to 3). A silicon polymer reacted in the presence of lithium metal and / or magnesium. 2. A silicon polymer obtained by further reducing the silicon polymer according to claim 1 with a reducing agent. 3. The method according to claim 1, wherein the reducing agent is LiAlH ₄ , NaH, B
₂ H _6, silicon polymer of claim 2, wherein the at least one selected from the group consisting of NaBH _4. 4. A film-forming composition comprising the silicon polymer according to claim 1. 5. A compound represented by the following general formula (1): (A) a tetrahalogenated carbon, (B) a silicon tetrahalide, and (C) a compound represented by the following general formula (1).
And at least one compound selected from the group consisting of compounds represented by the general formula (3): R ¹⁰ _n SiX _4-n ... (1) R ¹⁰ _n CX _4-n. (2) R ¹⁰ MgX (3) (wherein R ¹⁰ is a monovalent organic group, X is a halogen atom, and n is an integer of 1 to 3). A silicon polymer obtained by reacting in the presence of lithium metal and / or magnesium, and (D) a compound represented by the following general formula (4), a compound represented by the following general formula (5), and a compound represented by the following general formula: at least one silane compound selected from the group of compounds represented by formula (6) is hydrolyzed, condensed hydrolytic condensates ^{_{R a Si (OR 1) 4}} -a ····· (4) ( In the formula, R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is It represents an integer of 1 to 2.) Si (OR ² ) ₄ (5) (wherein R ² represents a monovalent organic group) R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR ⁵ ) _{3 -c} R ⁶ _c (6) [wherein R ^{3 to} R ⁶ are the same or different and each is a monovalent organic group, b to c is the same or different and is an integer of 0 to 2,
R ⁷ is an oxygen atom, a phenylene group or a group represented by — (CH ₂ ) _m — (where m is an integer of 1 to 6), and d is 0 or 1. ] The composition for film formation characterized by containing. 6. A material for forming an insulating film, comprising the composition for forming a film according to claim 4 or 5.