JP2007204626A - Method for producing polymer, polymer, composition for forming insulation film, method for producing insulation film and silica-based insulation film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer giving a film having small relative dielectric constant, excellent mechanical strength and adhesiveness and uniform film quality while reducing the quantity of a metallic reaction agent and suppressing the generation of by-product to be removed and provide the polymer, a composition for forming an insulation film, a method for producing an insulation film and a silica-based insulation film. <P>SOLUTION: The method for the production of the polymer contains the hydrolytic condensation of (B) a silane monomer having a hydrolyzable group in the presence of (A) a polycarbosilane, wherein the polycarbosilane (A) is particularly defined polymer (I) or polymer (II). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer, a polymer, a composition for forming an insulating film, a method for producing an insulating film, and a silica-based insulating film.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD (Chemical Vapor Deposition) method is frequently used as an interlayer insulating film in a semiconductor element or the like. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become. In addition, with high integration of semiconductor elements and the like, an interlayer insulating film having a low relative dielectric constant, which is mainly composed of polyorganosiloxane called organic SOG, has been developed.

  In particular, with further higher integration and multi-layering of semiconductor elements and the like, there is a demand for better electrical insulation between conductors, and therefore lower dielectric constant, crack resistance, mechanical strength and adhesion. An excellent interlayer insulating film material has been demanded.

  As a material having a low relative dielectric constant, a composition comprising a mixture of fine particles obtained by condensation of alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (Japanese Patent Laid-Open No. 5-263045, particularly Kaihei 5-315319) and coating liquids obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia (Japanese Patent Laid-Open Nos. 11-340219 and 11-340220) Has been proposed. However, the materials obtained by these methods are not stable in the properties of the reaction products, and have large variations in the dielectric constant, crack resistance, mechanical strength, adhesion, etc. of the coating film. It was unsuitable. In addition, a method of preparing a coating solution by mixing a polycarbosilane solution and a polysiloxane solution and forming a low dielectric constant insulating film (Japanese Patent Laid-Open No. 2001-127152) has been proposed. There was a problem that the carbosilane domain and the siloxane domain were dispersed in the coating film in a non-uniform state.

On the other hand, by previously reacting a hydrolyzable group-containing silane monomer in the presence of polycarbosilane, a co-condensate of polysiloxane and polycarbosilane derived from such hydrolyzable group-containing silane monomer is obtained. The present inventor has proposed a method of using a film-forming composition containing the polymer (International Patent Application Publication No. WO2005 / 068538). According to this method, it is possible to obtain a cocondensation polymer film having a small relative dielectric constant, excellent mechanical strength and adhesion, and no phase separation in the film. However, the polycarbosilane used in this method is usually obtained by a coupling reaction of an organosilane monomer using a metal having a reaction equivalent or more, and it is necessary to remove by-products generated by this reaction. is there. In this case, it is possible to remove most metal compounds by filtration or extraction, but it is often difficult to remove impurities to the level for use in electronic materials, and they are used from the reaction stage. There is a need for a method for synthesizing polycarbosilanes with low metal content.
JP-A-5-263045 JP-A-5-315319 Japanese Patent Laid-Open No. 11-340219 Japanese Patent Laid-Open No. 11-340220 JP 2001-127152 A International Patent Application Publication WO2005 / 068538 Pamphlet

  An object of the present invention is to provide a polymer production method and a polymer that can reduce the amount of metal reactant used and can suppress the generation of by-products that require removal.

  Another object of the present invention is to provide a film that can be suitably used as an interlayer insulating film in, for example, a semiconductor element, has a small relative dielectric constant, excellent mechanical strength and adhesion, and has a uniform film quality. It is to provide a method for producing a polymer and a polymer that can be formed.

  Another object of the present invention is to provide a composition for forming an insulating film using the polymer of the present invention, a method for producing the insulating film, and a silica-based insulating film.

The method for producing the polymer according to the first aspect of the present invention includes:
(A) Polycarbosilane obtained by ring-opening polymerization of at least one silane compound selected from the group of compounds represented by the following general formula (1) and the following general formula (2) (B) hydrolyzing and condensing a hydrolyzable group-containing silane monomer.

・・・・・（１）
（式中、Ｒ^１およびＲ^２は同一または異なり、水素原子または１価の有機基を示し、ＸおよびＹは同一または異なり、ハロゲン原子またはアルコキシ基を示し、lは２〜４の整数を示す。）

(1)
(Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or a monovalent organic group, X and Y are the same or different, represent a halogen atom or an alkoxy group, and l represents an integer of 2 to 4) .)

・・・・・（２）
（式中、Ｒ^３およびＲ^４は同一または異なり、水素原子または１価の有機基を示し、Ｒ^５は水素原子またはアルコキシ基以外の１価の有機基を示し、Ｚはハロゲン原子またはアルコキシ基を示し、ｍは２〜４の整数を示す。）
この場合、前記一般式（１）および（２）において、ｌおよびｍが２であることができる。

(2)
(Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom or a monovalent organic group, R ⁵ represents a monovalent organic group other than a hydrogen atom or an alkoxy group, and Z represents a halogen atom or an alkoxy group. M represents an integer of 2 to 4.)
In this case, in the general formulas (1) and (2), l and m can be 2.

The method for producing the polymer according to the second aspect of the present invention includes:
(A) At least one silane compound selected from the group of compounds represented by the following general formula (1) and the following general formula (2), and represented by the following general formula (3) (B) hydrolyzing and condensing a hydrolyzable group-containing silane monomer in the presence of polycarbosilane obtained by ring-opening polymerization with at least one silane compound.

・・・・・（１）
（式中、Ｒ^１およびＲ^２は同一または異なり、水素原子または１価の有機基を示し、ＸおよびＹは同一または異なり、ハロゲン原子またはアルコキシ基を示し、lは２〜４の整数を示す。）

(1)
(Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or a monovalent organic group, X and Y are the same or different, represent a halogen atom or an alkoxy group, and l represents an integer of 2 to 4) .)

・・・・・（２）
（式中、Ｒ^３およびＲ^４は同一または異なり、水素原子または１価の有機基を示し、Ｒ^５は水素原子またはアルコキシ基以外の１価の有機基を示し、Ｚはハロゲン原子またはアルコキシ基を示し、ｍは２〜４の整数を示す。）

(2)
(Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom or a monovalent organic group, R ⁵ represents a monovalent organic group other than a hydrogen atom or an alkoxy group, and Z represents a halogen atom or an alkoxy group. M represents an integer of 2 to 4.)

・・・・・（３）
（式中、Ｒ^６〜Ｒ^９は同一または異なり、水素原子または１価の有機基を示し、ｎは２〜４の整数を示す。）
この場合、前記一般式（１）〜（３）において、ｌ、ｍおよびｎが２であることができる。

(3)
^(Wherein, R 6 to R ⁹ individually represent a hydrogen atom or a monovalent organic group, n is an integer of 2-4.)
In this case, in the general formulas (1) to (3), l, m, and n may be 2.

In the method for producing the polymer,
The (B) hydrolyzable group-containing silane monomer is at least one silane compound selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (5). be able to.

R ¹⁰ _a SiX _4-a (4)
(Wherein R ¹⁰ represents a hydrogen atom, a fluorine atom or a monovalent organic group, X represents a halogen atom or an alkoxyl group, and a represents an integer of 0 to 3)
_{^{R 11 b Y 3-b Si-}} (R 13) d -SiZ 3-c R 12 c ····· (5)
[Wherein R ¹¹ and R ¹² are the same or different and each represents a monovalent organic group, b and c are the same or different and represent an integer of 0 to 2, and R ¹³ represents an oxygen atom, a phenylene group or — (CH ₂ ) represents a group represented by _e- (wherein e is an integer of 1 to 6), Y and Z are the same or different and represent a halogen atom or an alkoxyl group, and d represents 0 or 1 . ]

  The polymer according to the third aspect of the present invention is obtained by the above-described polymer production method.

  The composition for insulating film formation of the 4th aspect of this invention contains the said polymer and organic solvent.

  The manufacturing method of the insulating film of the 5th aspect of this invention includes apply | coating the said film forming composition to a board | substrate, and heating.

  The manufacturing method of the insulating film of the 6th aspect of this invention includes apply | coating the said film forming composition to a board | substrate, and irradiating an electron beam or an ultraviolet-ray.

  The silica type insulating film of the 7th aspect of this invention is obtained by the manufacturing method of the said insulating film.

  According to the method for producing the polymer, (A) hydrolyzing and condensing a hydrolyzable group-containing silane monomer in the presence of polycarbosilane, and (A) polycarbosilane is obtained by ring-opening polymerization. By using the obtained polymer (I) or polymer (II), the amount of the metal reactant used can be reduced, and generation of a by-product that needs to be removed can be suppressed. Therefore, using the composition for forming an insulating film containing the polymer obtained by the above method, an insulating film having a low relative dielectric constant, excellent mechanical strength and adhesion, and no phase separation in the film is obtained. Can do.

  Hereinafter, a polymer according to an embodiment of the present invention and a method for producing the same, a composition for forming an insulating film containing the polymer, a method for producing an insulating film using the insulating film, and a silica obtained by the method for producing the insulating film The system insulating film will be described.

1. Polymer and Production Method Thereof A polymer production method according to an embodiment of the present invention includes (B) a hydrolyzable group-containing silane in the presence of (A) polycarbosilane (hereinafter also referred to as “component (A)”). It includes hydrolytic condensation of a monomer (hereinafter also referred to as “component (B)”).

1.1. (A) component (A) Polycarbosilane is the following polymer (I) or polymer (II).

Polymer (I): a polymer obtained by ring-opening polymerization of at least one silane compound selected from the group of compounds represented by the following general formula (1) and the following general formula (2) Polymer (II): represented by the following general formula (3), at least one silane compound selected from the group of compounds represented by the following general formula (1) and the following general formula (2) Obtained by ring-opening polymerization of at least one silane compound

・・・・・（１）
（式中、Ｒ^１およびＲ^２は同一または異なり、水素原子または１価の有機基を示し、ＸおよびＹは同一または異なり、ハロゲン原子またはアルコキシ基を示し、lは２〜４の整数を示す。）

(1)
(Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or a monovalent organic group, X and Y are the same or different, represent a halogen atom or an alkoxy group, and l represents an integer of 2 to 4) .)

・・・・・（２）
（式中、Ｒ^３およびＲ^４は同一または異なり、水素原子または１価の有機基を示し、Ｒ^５は水素原子またはアルコキシ基以外の１価の有機基を示し、Ｚはハロゲン原子またはアルコキシ基を示し、ｍは２〜４の整数を示す。）

(2)
(Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom or a monovalent organic group, R ⁵ represents a monovalent organic group other than a hydrogen atom or an alkoxy group, and Z represents a halogen atom or an alkoxy group. M represents an integer of 2 to 4.)

・・・・・（３）
（式中、Ｒ^６〜Ｒ^９は同一または異なり、水素原子または１価の有機基を示し、ｎは２〜４の整数を示す。）

(3)
^(Wherein, R 6 to R ⁹ individually represent a hydrogen atom or a monovalent organic group, n is an integer of 2-4.)

In the above general formulas (1) to (3), specific examples of the monovalent organic group that can be used as R ^{1 to} R ⁹ include linear chains having 1 to 10 carbon atoms such as an alkyl group, an alkenyl group, and an alkynyl group. Or branched aliphatic groups; alicyclic groups having 3 to 20 carbon atoms such as cycloalkyl groups, cycloalkenyl groups, and bicycloalkyl groups; aryl groups having 6 to 20 carbon atoms; and 6 to 6 carbon atoms There may be mentioned 20 aralkyl groups.

  Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group.

  Examples of the alkenyl group include a vinyl group, 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-methylpropargyl group, and a 3-ethylpropargyl group.

  Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a norbornyl group.

  Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, an α-naphthyl group, a β-naphthyl group, an α-thiophene group, and a β-thiophene group.

  Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, and a phenylbutyl group.

  Examples of the halogen atom that can be used as X, Y, and Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of R of the alkoxy group (—OR) that can be used as X, Y, and Z include those described above as the alkyl group and the aryl group.

  In the general formulas (1) to (3), l, m, and n are preferably 2.

The ring-opening polymerization of the silane compound can be performed, for example, by using a halogenated platinic acid (for example, chloroplatinic acid) as a catalyst in a nonpolar solvent (for example, toluene). Furthermore, ring-opening polymerization is usually preferably performed in an inert atmosphere such as argon or nitrogen.

  The ring-opening polymerization of the silane compound can be carried out without a solvent or in an organic solvent. Examples of the organic solvent that can be used here include hydrocarbon solvents such as hexane, toluene, xylene, and benzene.

1.1.1. Compound 1
As the compound represented by the general formula (1) (hereinafter referred to as “compound 1”), for example, 1,1,3,3-tetramethoxy-1,3-disilacyclobutane, 1,1,3,3 -Tetraethoxy-1,3-disilacyclobutane, 1,1,3,3-tetra-n-propoxy-1,3-disilacyclobutane, 1,1,3,3-tetraisopropoxy-1,3- Disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetra Fluoro-1,3-disilacyclobutane is mentioned. Compound 1 can be used alone or in combination of two or more.

1.1.2. Compound 2
Examples of the compound represented by the general formula (2) (hereinafter referred to as “compound 2”) include 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-dimethoxy- 1,3-diethyl-1,3-disilacyclobutane, 1,3-dimethoxy-1,3-divinyl-1,3-disilacyclobutane, 1,3-dimethoxy-1,3-diphenyl-1,3- Disilacyclobutane, 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-diethoxy-1,3-diethyl-1,3-disilacyclobutane, 1,3-diethoxy- 1,3-divinyl-1,3-disilacyclobutane, 1,3-diethoxy-1,3-diphenyl-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3- Disilacyclo Pig 1,3-dichloro-1,3-diethyl-1,3-disilacyclobutane, 1,3-dichloro-1,3-divinyl-1,3-disilacyclobutane, 1,3-dichloro-1,3 -Diphenyl-1,3-disilacyclobutane, 1,3-dibromo-1,3-dimethyl-1,3-disilacyclobutane, 1,3-dibromo-1,3-diethyl-1,3-disilacyclobutane 1,3-dibromo-1,3-divinyl-1,3-disilacyclobutane, 1,3-dibromo-1,3-diphenyl-1,3-disilacyclobutane. Compound 2 can be used alone or in combination of two or more.

1.1.3. Compound 3
Examples of the compound represented by the general formula (3) (hereinafter referred to as “compound 3”) include 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,1,3,3, and the like. -Tetraethyl-1,3-disilacyclobutane, 1,1,3,3-tetravinyl-1,3-disilacyclobutane, 1,1,3,3-tetra-n-propyl-1,3-disila Cyclobutane, 1,1,3,3-tetraisopropyl-1,3-disilacyclobutane, 1,1,3,3-tetraphenyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3- Diethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-divinyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diphenyl-1,3-disilacyclobutane Can be mentioned. Compound 3 can be used singly or in combination of two or more.

  In addition, when manufacturing polymer (II) by ring-opening polymerization, it is preferable that the ratio of the sum total of the compound 1 and the compound 2, and the compound 3 is 95 / 5-30 / 70, and 90 / 10-50 / More preferably, it is 50.

1.2. (B) component In this invention, a "hydrolyzable group" means the group which can be hydrolyzed at the time of manufacture of the polymer of this invention. Specific examples of the hydrolyzable group are not particularly limited, and examples thereof include a hydrogen atom bonded to a silicon atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, and a trifluoromethanesulfone group. Can be mentioned.

  (B) The hydrolyzable group-containing silane monomer is, for example, at least one silane compound selected from the group of compounds represented by the following general formula (4) and compounds represented by the following general formula (5). Can be.

R ¹⁰ _a SiX _4-a (4)
(Wherein R ¹⁰ represents a hydrogen atom, a fluorine atom or a monovalent organic group, X represents a halogen atom or an alkoxyl group, and a represents an integer of 0 to 3)
_{^{R 11 b Y 3-b Si-}} (R 13) d -SiZ 3-c R 12 c ····· (5)
[Wherein R ¹¹ and R ¹² are the same or different and each represents a monovalent organic group, b and c are the same or different and represent an integer of 0 to 2, and R ¹³ represents an oxygen atom, a phenylene group or — (CH ₂ ) represents a group represented by _e- (wherein e is an integer of 1 to 6), Y and Z are the same or different and represent a halogen atom or an alkoxyl group, and d represents 0 or 1 . ]

In the general formulas (4) and (5), examples of the monovalent organic group that can be used as R ^{10 to} R ¹² include an alkyl group, an aryl group, an allyl group, a glycidyl group, and a vinyl group. In the general formula (4), R ¹⁰ is preferably a monovalent organic group, particularly an alkyl group or a phenyl group.

  Here, as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned, Preferably it is C1-C5. These alkyl groups may be chain-like or branched, and may be further substituted with a hydrogen atom, a fluorine atom, an amino group, or the like.

  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.

  In addition, specific examples of halogen atoms that can be used as X, Y, and Z in the general formulas (4) and (5) include those used as X, Y, and Z in the general formulas (1) to (3). What was illustrated as a possible halogen atom can be mentioned.

Furthermore, as the hydrocarbon moiety of the alkoxy group of X, those mentioned as the monovalent organic group for R ¹⁰ can be applied as they are.

1.2.1. Compound 4
Specific examples of the compound represented by the general formula (4) (hereinafter also referred to as “compound 4”) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetra-iso-propoxysilane. , Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, 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, fluoroto -n- butoxysilane, fluorotriazinyl -sec- butoxysilane, fluoro tri -tert- butoxysilane, etc. fluoro triphenoxy silane;
Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxy Vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri- iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i -Propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri -Ter -Butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxy Silane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyl-tri-n-propoxy Silane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl- Triphenoki Sisilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxy Silane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxy Silane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 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-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di- n-propyl- -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-butoxysilane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-iso-propyl-di-phenoxysilane, di -N-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-n-pro Xysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di-tert -Butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl -Di-iso-propoxysilane, di-sec-butyl-di-n-butoxysilane, di-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-butoxysilane, di -Tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxy Silane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane and the like;
Tetrachlorosilane, tetrabromosilane, tetraiodosilane, trichlorosilane, tribromosilane, triiodosilane, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, n-butyltrichlorosilane, t-butyltri Chlorosilane, cyclohexyltrichlorosilane, phenethyltrichlorosilane, 2-norbornyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, methyltribromosilane, ethyltribromosilane, n-propyltribromosilane, isopropyltribromosilane, n- Butyltribromosilane, t-butyltribromosilane, cyclohexyltribromosilane, phenethyltribromosilane, 2-norbornyltri Lomosilane, vinyltribromosilane, phenyltribromosilane, methyltriiodosilane, ethyltriiodosilane, n-propyltriiodosilane, isopropyltriiodosilane, n-butyltriiodosilane, t-butyltriiodosilane, cyclohexyltri Iodosilane, phenethyltriiodosilane, 2-norbornyltriiodosilane, vinyltriiodosilane, phenyltriiodosilane, dimethyldichlorosilane, diethyldichlorosilane, di-n-propyldichlorosilane, diisopropyldichlorosilane, di-n -Butyldichlorosilane, di-t-butyldichlorosilane, dicyclohexyldichlorosilane, diphenethyldichlorosilane, di-2-norbornyldichlorosilane, divinyldichlorosilane, diph Nyldichlorosilane, dimethyldibromosilane, diethyldibromosilane, di-n-propyldibromosilane, diisopropyldibromosilane, di-n-butyldibromosilane, di-t-butyldibromosilane, dicyclohexyldibromosilane, diphenethyldibromosilane, di 2-norbornyldibromosilane, divinyldibromosilane, diphenyldibromosilane, dimethyldiiodosilane, diethyldiiodosilane, di-n-propyldiiodosilane, diisopropyldiiodosilane, di-n-butyldiiodosilane, Di-t-butyldiiodosilane, dicyclohexyldiiodosilane, diphenethyldiiodosilane, di-2-norbornyldiiodosilane, divinyldiiodosilane, diphenyldiiodosilane, trimethylchloro Rosilane, triethylchlorosilane, tri-n-propylchlorosilane, triisopropylchlorosilane, tri-n-butylchlorosilane, tri-t-butylchlorosilane, tricyclohexylchlorosilane, triphenethylchlorosilane, tri-2-norbornylchlorosilane, trivinylchlorosilane , Triphenylchlorosilane, trimethylbromosilane, triethylbromosilane, tri-n-propylbromosilane, triisopropylbromosilane, tri-n-butylbromosilane, tri-t-butylbromosilane, tricyclohexylbromosilane, triphenethylbromo Silane, tri-2-norbornylbromosilane, trivinylbromosilane, triphenylbromosilane, trimethyliodosilane, triethyliodosilane, Ri-n-propyliodosilane, triisopropyliodosilane, tri-n-butyliodosilane, tri-t-butyliodosilane, tricyclohexyliodosilane, triphenethyliodosilane, tri-2-norbornyliodosilane, tri Examples thereof include silicon compounds such as vinyliodosilane and triphenyliodosilane. These compounds can be used alone or in a mixture of two or more.

  The compound 4 is preferably methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy. Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, tetramethoxysilane and the like.

  These may be used alone or in combination of two or more.

1.2.2. Compound 5
Among the compounds represented by the general formula (5) (hereinafter also referred to as “compound 5”), in the general formula (5), as the compound in which R ¹³ is an oxygen atom, hexachlorodisiloxane, hexabromodisiloxane, Hexaiodosidisiloxane, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldisiloxane, 1,1,1,3,3-penta Ethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-ethyldisiloxane, 1,1, 1,3,3-pentaethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-ethyldisiloxane, 1,1,1, 3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-phenyldisiloxane 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraphenoxy- 1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3 3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyl Siloxane, 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-tetramethyldi Siloxane, 1,3-dimethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diphenoxy-1,1,3 3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diphenoxy- Examples thereof include 1,1,3,3-tetraphenyldisiloxane.

  Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane Siloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1, 3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane and the like are preferable. As an example.

  In addition, among the compounds 5, in the general formula (5), the compound in which d is 0 includes hexachlorodisilane, hexabromodisilane, hexaiodosidisilane, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1, 1,2,2-pentamethoxy-2-methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2 -Ethyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,2,2-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-G Ethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2-trimethyldisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1, 2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1 , 1,2-Triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2- Tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1, 2 , 2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1, Examples include 2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane, and the like.

  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-tetramethyl Preferred examples include disilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, and the like.

Furthermore, among the compounds 5, in the general formula (5), R ¹³ is a group represented by — (CH ₂ ) _e —, and bis (trichlorosilyl) methane, bis (tribromosilyl) methane, bis (Triiodosilyl) methane, bis (trichlorosilyl) ethane, bis (tribromosilyl) ethane, bis (triiodosilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri- n-propoxysilyl) methane, bis (tri-i-propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-t-butoxysilyl) methane 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bi (Tri-n-propoxysilyl) ethane, 1,2-bis (tri-i-propoxysilyl) ethane, 1,2-bis (tri-n-1, butoxysilyl) ethane, 1,2-bis (tri- sec-butoxysilyl) ethane, 1,1,2,2-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-butoxy) Methylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-t-butoxymethylsilyl) -2- (tri-t-butoxysilyl) ethane, bis (di Toximethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-i-propoxymethylsilyl) methane, bis (di-n-butoxymethylsilyl) methane Bis (di-sec-butoxymethylsilyl) methane, bis (di-t-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-i-propoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane, 1, 2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-t-butoxymethylsilyl) ethane, 1,2-bi (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) L) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) benzene, 1,4-bis (tri -I-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis (tri-t-butoxysilyl) ) Benzene and the like.

  Of these, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) ) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (di Ethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (di Ethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxy) Silyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) Benzene etc. can be mentioned as a preferable example.

  Compound 5 can be used alone or in combination of two or more.

1.3. Polymer Production In the polymer production method of the present embodiment, in the presence of the component (A), the component (B) (at least one silane compound selected from the group of compounds 4 and 5) is hydrolytically condensed. In addition, it is preferable to use more than 0.5 mol and less than 150 mol of water, and particularly preferably more than 0.5 mol and less than 130 mol of water per mol of the total amount of component (B).

1.3.1. Catalyst In the method for producing a polymer according to an embodiment of the present invention, a specific catalyst can be used when hydrolyzing and condensing the component (B) in the presence of the component (A). As a catalyst, at least 1 sort (s) chosen from the group of a basic catalyst, a metal chelate catalyst, and an acidic catalyst can be used, for example.

  Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, Diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine , Pentylamine, hexylamine, pentylamine, octylamine, nonylamine, Silamine, 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, amines or amine salts are preferable, organic amines or organic amine salts are particularly preferable, and alkylamines and tetraalkylammonium hydroxides are preferable. Most preferred. These basic catalysts may be used alone or in combination of two or more.

Examples of the metal chelate catalyst include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy bis Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy Tris (acetylacetonato) titanium, mono-sec-butoxytris (acetylacetonato) titanium, mono-t-butoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethyl) Acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec Butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-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) Acetate) 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 Tate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Titanium chelate compounds such as acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;
Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis ( Ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-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 (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium;
Aluminum chelate compounds such as tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum;
Preferred examples include titanium or aluminum chelate compounds, and particularly preferred are titanium chelate compounds. These metal chelate catalysts may be used alone or in combination of two or more.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and boric acid;
Acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, merit acid, Arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid , Trichloroacetic acid, trifluoroacetic acid, formic acid, oxalic 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 Organic products such as hydrolyzate of hydrolyzate, hydrolyzate of maleic anhydride, hydrolyzate of phthalic anhydride It can be exemplified, and organic carboxylic acids as a more preferable example. These acidic catalysts may be used alone or in combination of two or more.

  The use amount of the catalyst is usually based on 1 mol of the total group represented by X, Y, Z in the compounds 4, 5 when using at least one of the compounds 4, 5 as the component (B). It is 0.00001-10 mol, preferably 0.00005-5 mol. If the amount of the catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction. Moreover, the temperature when hydrolyzing and condensing (B) component is 0-100 degreeC normally, Preferably it is 15-80 degreeC.

  In the present invention, the term “completely hydrolyzed condensate” means that the hydrolyzable group in the component (A) and the component (B) is 100% hydrolyzed to become a SiOH group, and further completely condensed into a siloxane structure. Say something.

  Moreover, since the polymer obtained by this embodiment is more excellent in the storage stability of the composition obtained, it is preferable that it is a hydrolysis-condensation product of (A) component and the compound 4.

  In the polymer production method of the present embodiment, the amount of component (B) used relative to component (A) is such that the total amount of component (B) is 10 to 1,000,000 parts by weight per 100 parts by weight of component (A). More preferably, it is 100 to 1,000 parts by weight.

  The weight average molecular weight in terms of polystyrene of the polymer obtained by the production method of the present embodiment is usually preferably 5,000 to 500,000, more preferably 10,000 to 300,000, and 20,000. More preferably, it is -200,000. When the polystyrene-reduced weight average molecular weight of the polymer of this embodiment is less than 5,000, the intended relative dielectric constant may not be obtained. On the other hand, when it exceeds 500,000, the storage stability and the coating film In-plane uniformity may be inferior.

1.3.2. Organic solvent Hydrolytic condensation of component (B) can be carried out in an organic solvent. Here, the organic solvent is preferably a solvent represented by the following general formula (6) among the organic solvents described later.

R ¹⁴ O (CHCH ₃ CH ₂ O) _γ R ¹⁵ (6)
(R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a C 1-4 alkyl group or a monovalent organic group selected from CH ₃ CO—, and γ represents an integer of 1-2.)

  In the said General formula (6), as a C1-C4 alkyl group, the thing similar to what was shown as an alkyl group in previous General formula (1) can be mentioned.

  Specific examples of the organic solvent represented by the general formula (6) include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether. , Propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, di Propylene glycol dipropyl ether, di Lopylene glycol dibutyl 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, dipropylene glycol mono Propyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol diacetate, etc., especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate are preferable. These can use 1 type (s) or 2 or more types simultaneously. In addition to the solvent represented by the general formula (6), other solvents such as alcohol solvents, ester solvents, amide solvents may be included to some extent.

2. Composition for Forming Insulating Film The composition for forming an insulating film according to one embodiment of the present invention (hereinafter referred to as “film forming composition”) includes an organic polymer, a surfactant and the like in addition to the polymer of the above embodiment. You may contain a component.

  Examples of the organic polymer include (meth) acrylic polymers and compounds having a polyalkylene oxide structure.

  Examples of the compound having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, 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 poly Ether type compounds such as oxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. 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 structure.

-(X ') j- (Y') k-
-(X ') j- (Y') k- (X ') 1-
(In the formula, X ′ represents a group represented by —CH ₂ CH ₂ O—, Y ′ represents a group represented by —CH ₂ CH (CH ₃ ) O—, j is 1 to 90, k is 10 to 99, l represents 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, More preferred examples include ether type compounds. These may be used alone or in combination of two or more.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and further include fluorine surfactants, silicone surfactants, Polyalkylene oxide surfactants, poly (meth) acrylate surfactants and the like can be mentioned, and fluorine surfactants and silicone surfactants can be preferably mentioned.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene 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-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8 , 9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluoroo Tansulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorophosphate) Octylsulfonyl-N-ethylaminoethyl), monoperfluoroalkylethyl phosphate ester, etc., a fluorine-based surfactant comprising a compound having a fluoroalkyl or fluoroalkylene group at least at any one of its terminal, main chain and side chain Can be mentioned.

  Commercially available products include MegaFuck F142D, F172, F173, F173 and F183 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Ftop EF301, 303, 352 (produced by Shin-Akita Kasei Co., Ltd.) , FLORARD FC-430, FC-431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC -105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15 (Neos Co., Ltd.), etc. There may be mentioned surfactants. Among these, the Megafac F172, BM-1000, BM-1100, and NBX-15 are particularly preferable.

  As the silicone-based surfactant, for example, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.) can be used. Among these, the SH28PA and SH30PA are particularly preferable.

  The usage-amount of surfactant is 0.0001-10 weight part normally with respect to a polymer (complete hydrolysis-condensation product). These may be used alone or in combination of two or more.

  The film forming composition of this embodiment can dissolve or disperse the polymer (hydrolysis condensate) of the above embodiment and, if necessary, an additive in an organic solvent.

  Examples of the organic solvent that can be used in this case include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents, and aprotic solvents.

Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2- Ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol , Phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether;
And so on. These alcohol solvents may be used alone or in combination of two or more.

  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, and methyl-n-hexyl. In addition to ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, 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, - heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like. These ketone solvents may be used alone or in combination of two or more.

  Examples of amide solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, 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 mentioned. These amide solvents may be used alone or in combination of two or more.

  Examples of ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, and i-acetate. -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl acetate Glycol mono-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, dipropylene Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester solvents may be used alone or in combination of two or more.

As aprotic solvents, acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N -Methyl- [Delta] ₃ -pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl- Examples include 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone. These aprotic solvents may be used alone or in combination of two or more.

  The total solid concentration of the film-forming composition of the present embodiment thus obtained is preferably 2 to 30% by weight, and is appropriately adjusted according to the purpose of use. When the total solid concentration of the film-forming composition is 2 to 30% by weight, the film thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The total solid content concentration is adjusted by concentration and dilution with an organic solvent, if necessary.

3. Insulating film The insulating film (silica-based insulating film) of one embodiment of the present invention is obtained by applying the film-forming composition to form a coating film, and then heating the coating film. Here, heating can be performed at 30-450 degreeC.

When the film forming composition of the above embodiment is applied to a substrate such as a silicon wafer, a SiO ₂ wafer, or a SiN wafer, a coating means such as spin coating, dipping method, roll coating method, spray method or the like is used.

  In this case, as a dry film thickness, a coating film having a thickness of about 0.05 to 2.5 μm can be formed by one coating, and a coating film having a thickness of about 0.1 to 5.0 μm can be formed by two coatings. . Thereafter, it is dried at room temperature, or usually heated at a temperature of about 80 to 600 ° C. for about 5 to 240 minutes to dry, thereby forming a glassy or macromolecular coating film.

  As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere is performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. Can do.

  Moreover, in order to control the curing rate of the coating film, it can be heated stepwise or an atmosphere such as nitrogen, air, oxygen, or reduced pressure can be selected as necessary.

  Moreover, in this embodiment, the said film forming composition can be apply | coated to a board | substrate, and it can also heat at 30-450 degreeC under high energy rays (for example, an electron beam, an ultraviolet-ray) irradiation.

The silica-based insulating film of this embodiment thus obtained has a film density of usually 0.35 to 1.2 g / cm ³ , preferably 0.4 to 1.1 g / cm ³ , Preferably it is 0.5-1.0 g / cm < ³ >. When the film density is less than 0.35 g / cm ³ , the mechanical strength of the coating film decreases, and when it exceeds 1.2 g / cm ³ , a low relative dielectric constant cannot be obtained. Furthermore, the relative dielectric constant of the insulating film of the present embodiment is usually 3.2 to 1.2, preferably 3.0 to 1.5, and more preferably 2.7 to 1.8. .

  The insulating film of this embodiment is characterized by having many silicon-carbon bonds in the film structure. Due to this feature, the insulating property, the uniformity of the coating film, the dielectric constant characteristics, the elastic modulus of the coating film, and the adhesion of the coating film are excellent.

  Since the insulating film of this embodiment has a low relative dielectric constant and excellent crack resistance, mechanical strength, and adhesion, an interlayer insulating film for semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM Protective films such as coating films, etching stopper films, surface coating films for semiconductor elements, intermediate layers in semiconductor fabrication processes using multilayer resists, interlayer insulating films for multilayer wiring boards, protective films and insulating films for liquid crystal display elements Useful.

4). EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In the examples and comparative examples, “parts” and “%” indicate parts by weight and% by weight, respectively, unless otherwise specified.

4.1. Evaluation method Various evaluations were performed as follows.

4.1.1. Polymer weight average molecular weight (Mw)
It measured by the gel permeation chromatography (GPC) method by the following conditions.

Sample: Prepared by using tetrahydrofuran as a solvent and dissolving 1 g of a polymer (hydrolysis condensate) in 100 cc of tetrahydrofuran.
Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Company was used.
Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, USA
Column: SHODEX A-80M (length: 50 cm) manufactured by Showa Denko K.K.
Measurement temperature: 40 ° C
Flow rate: 1cc / min

4.1.2. Relative permittivity An aluminum electrode pattern was formed on the obtained polymer film by vapor deposition to prepare a sample for measuring relative permittivity. The relative permittivity of the coating film at room temperature was measured by the CV method using the HP16451B electrode and HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd., at a frequency of 100 kHz.

4.1.3. Mechanical strength (elastic modulus / hardness)
About the obtained polymer film, elastic modulus and hardness were measured by a continuous stiffness measurement method using Nanoindenter XP (manufactured by Nano Instruments).

4.1.4. Adhesion A SiO ₂ film having a thickness of 400 nm is formed on the obtained polymer film by sputtering, and this is cut into an appropriate size, and an epoxy resin is used on the wafer piece to form a blank silicon wafer of the same size. Bonded and heated in an oven at 135 ° C. for 2 hours. This was cut into small pieces with a dicing machine, and a peel test was performed on each by a four-point bending adhesion measurement method. The results are shown as follows.
A: Adhesion energy of more than 3.0 joules per square meter B: Adhesion energy of less than 3.0 joules per square meter

4.1.5. Confirmation of presence / absence of phase separation of membrane The cross section of the polymer membrane was processed for observation by the focused ion beam method, and the appearance was examined at 18,000 times using TEM. The judgment results are shown as follows.
A: Uniform coating is obtained by cross-sectional shape observation B: Sea-island domain phase separation is confirmed in coating

4.2. Production Example of Polymer 4.2.1. Synthesis example 1
After replacing the inside of a four-necked flask equipped with a thermometer, a cooling condenser, a dropping funnel and a stirrer with a capacity of 100 ml with argon gas, 1,1,3,3-tetraethoxy-1,3-disilacyclobutane 4 g (Compound 1) was added into the flask. Further, 10 g of toluene and 5 mg of chloroplatinic acid were added, followed by stirring at 100 ° C. for 10 hours. The reaction solution was filtered through a 1 μm diameter disposable cup filter to remove the platinum catalyst, and the filtrate was concentrated to obtain 3.8 g of polymer (i) (polymer (I)). The polymer (i) had a weight average molecular weight of 5,100.

4.2.2. Example 1
In a quartz separable flask, 3.5 g of polymer (i) obtained in Synthesis Example 1 (component (A)), 40 g of methyltrimethoxysilane (component (B)), and 30 mg of triethylamine were added to 250 g of methanol. After dissolution, the mixture was stirred with a three-one motor to stabilize the temperature of the methanol solution at 55 ° C. Next, a mixed solution of 40 g of ion exchange water and 160 g of propylene glycol monoethyl ether was added to the methanol solution over 1 hour.

  Then, after reacting at 55 ° C. for 4 hours, 8 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added and reacted for another 30 minutes, and the reaction solution was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain polymer (reaction solution) A. The weight average molecular weight of the polymer A thus obtained was 25,000.

4.2.3. Synthesis example 2
After replacing the inside of a four-necked flask having a capacity of 100 ml equipped with a thermometer, a cooling condenser, a dropping funnel and a stirring device with argon gas, 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane 4 g (compound 2) was added into the flask. Furthermore, after adding toluene 10g and chloroplatinic acid 15mg, it stirred at 100 degreeC for 10 hours. The reaction solution was filtered through a 1 μm diameter disposable cup filter to remove the platinum catalyst, and the filtrate was concentrated to obtain 3.6 g of polymer (ii) (polymer (I)). The weight average molecular weight of this polymer (ii) was 12,100.

4.2.4. Example 2
In a quartz separable flask, 3.5 g of polymer (2) obtained in Synthesis Example 2 (component (A)), 40 g of methyltrimethoxysilane and 3 g of tetramethoxysilane (component (B)), and 40 mg of triethylamine Were dissolved in 250 g of methanol and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 40 g of ion-exchanged water and 160 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

  Then, after reacting at 55 ° C. for 4 hours, 8 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added and reacted for another 30 minutes, and the reaction solution was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain a polymer (reaction solution) B. The weight average molecular weight of the polymer B thus obtained was 35,000.

4.2.5. Synthesis example 3
1. After replacing the inside of a 100 ml four-necked flask equipped with a thermometer, cooling condenser, dropping funnel and stirrer with argon gas, 1,1,3,3-tetrachloro-1,3-disilacyclobutane 3 g (Compound 1) and 1,1,3,3-tetramethyl-1,3-disilacyclobutane 1.4 g (Compound 3) were added to the flask. Further, 10 g of toluene and 15 mg of chloroplatinic acid were added, followed by stirring at 100 ° C. for 10 hours. The reaction solution was filtered through a 1 μm diameter disposable cup filter to remove the platinum catalyst, and the filtrate was concentrated to obtain 3.5 g of polymer (iii) (polymer (II)). The weight average molecular weight of this polymer (iii) was 12,000.

4.2.6. Example 3
In a quartz separable flask, 3.5 g of the polymer (iii) obtained in Synthesis Example 3 (component (A)), 40 g of methyltrimethoxysilane and 3 g of tetramethoxysilane (component (B)), 500 mg of oxalic acid, Then, 40 g of ion-exchanged water was dissolved in 160 g of propylene glycol monoethyl ether, and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Then, after making it react at 55 degreeC for 4 hours, the reaction liquid was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain a polymer (reaction solution) C. The weight average molecular weight of the polymer C thus obtained was 18,000.

4.2.7. Comparative Synthesis Example 1
After replacing the inside of the 3 L four-necked flask equipped with a thermometer, a cooling condenser, a dropping funnel and a stirring device with argon gas, 1 L of dried tetrahydrofuran and 60 g of magnesium metal were charged and bubbled with argon gas. To this, 467.5 g of chloromethyltriethoxysilane was slowly added from a dropping funnel while stirring at 20 ° C.

  After completion of the dropwise addition, stirring was continued for 24 hours at 45 ° C. After cooling, the magnesium salt produced by filtration was removed from the reaction solution. Subsequently, the filtrate was heated under reduced pressure to remove tetrahydrofuran from the filtrate to obtain 260.1 g of a brown liquid polymer (iv). The molecular weight of this polymer (iv) was 1,200.

4.2.8. Comparative Example 1
In a separable flask made of quartz, 3.5 g of polymer (iv) obtained in Comparative Synthesis Example 1 (component (A)), 40 g of methyltrimethoxysilane (component (B)), and 30 mg of triethylamine were dissolved in 250 g of methanol. After that, the solution was stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 40 g of ion-exchanged water and 160 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

  Then, after reacting at 55 ° C. for 4 hours, 8 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added and reacted for another 30 minutes, and the reaction solution was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain a polymer (reaction solution) D. The weight average molecular weight of the polymer D thus obtained was 21,000.

4.2.9. Comparative Synthesis Example 2
After replacing the inside of a 3 L four-necked flask equipped with a thermometer, a cooling condenser, a dropping funnel and a stirring device with argon gas, 1 L of dry tetrahydrofuran and 55 g of magnesium metal were charged and bubbled with argon gas. To this, 80.3 g of chloromethylmethyldiethoxysilane was slowly added from a dropping funnel while stirring at 20 ° C.

  After completion of the dropping, stirring was further continued at 45 ° C. for 24 hours. After cooling, the magnesium salt produced by filtration was removed from the reaction solution. Subsequently, the filtrate was heated under reduced pressure to remove tetrahydrofuran from the filtrate to obtain 75.2 g of a brown liquid polymer (v). The molecular weight of this polymer (v) was 1,400.

4.2.10. Comparative Example 2
In a quartz separable flask, 3.5 g of polymer (v) obtained in Comparative Synthesis Example 2 (component (A)), 40 g of methyltrimethoxysilane and 3 g of tetramethoxysilane (component (B)), and triethylamine 40 mg was dissolved in 250 g of methanol, and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 40 g of ion-exchanged water and 160 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

  Then, after reacting at 55 ° C. for 4 hours, 8 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added and reacted for another 30 minutes, and the reaction solution was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation, and a polymer (reaction solution) E was obtained. The weight average molecular weight of the polymer E thus obtained was 28,000.

4.2.11. Comparative Synthesis Example 3
After replacing the inside of the 3 L four-necked flask equipped with a thermometer, a cooling condenser, a dropping funnel and a stirring device with argon gas, 1 L of dried tetrahydrofuran and 60 g of magnesium metal were charged and bubbled with argon gas. While stirring at 20 ° C., 183.9 g of chloromethyltrichlorosilane and 143.1 g of chloromethyldimethylchlorosilane were slowly added from the dropping funnel.

  After completion of the dropping, stirring was further continued at 45 ° C. for 24 hours. After cooling, the magnesium salt produced by filtration was removed from the reaction solution. Subsequently, the filtrate was heated under reduced pressure to remove tetrahydrofuran from the filtrate to obtain 162.4 g of a brown liquid polymer (vi). The molecular weight of this polymer (vi) was 2,300.

4.2.12. Comparative Example 3
In a quartz separable flask, 3.5 g of the polymer (vi) obtained in Comparative Synthesis Example 3 (component (A)), 40 g of methyltrimethoxysilane and 3 g of tetramethoxysilane (component (B)), oxalic acid 500 mg and 40 g of ion-exchanged water were dissolved in 160 g of propylene glycol monoethyl ether, and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Then, after making it react at 55 degreeC for 4 hours, the reaction liquid was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain a polymer (reaction solution) F. The weight average molecular weight of the polymer F thus obtained was 15,000.

4.3. Example of production of polymer film 4.3.1. Example 4
The polymer A obtained in Example 1 was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a film-forming composition of Example 4.

  After applying the obtained composition onto a silicon wafer by spin coating, 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, and further a nitrogen atmosphere at 400 ° C. Below, the substrate was baked on a hot plate for 60 minutes. The polymer film (hereinafter referred to as “silica-based film”) obtained after firing was evaluated according to the evaluation method. The evaluation results are shown in Table 1.

4.3.2. Example 5
A silica-based film was formed and evaluated in the same manner as in Example 4 except that polymer B was used instead of polymer A in Example 4. The evaluation results are shown in Table 1.

4.3.3. Example 6
A silica-based film was formed and evaluated in the same manner as in Example 4 except that polymer C was used instead of polymer A in Example 4. The evaluation results are shown in Table 1.

4.3.4. Comparative Example 4
A silica-based film was formed and evaluated in the same manner as in Example 4 except that polymer D was used instead of polymer A in Example 4. The evaluation results are shown in Table 1.

4.3.5. Comparative Example 5
A silica-based film was formed and evaluated in the same manner as in Example 4 except that polymer E was used instead of polymer A in Example 4. The evaluation results are shown in Table 1.

4.3.6. Comparative Example 6
A silica-based film was formed and evaluated in the same manner as in Example 4 except that polymer F was used instead of polymer A in Example 4. The evaluation results are shown in Table 1.

4.3.7. Example 7
Table 2 shows the results of measuring the metal concentrations of the polymers A, B, and C obtained in Example 1-3.

4.3.8. Comparative Example 7
Table 2 shows the results of measuring the metal concentrations of the polymers D, E, and F obtained in Comparative Example 1-3.

  According to Table 2, in Examples 1-3, compared with Comparative Synthesis Examples 1-3, the amount of the metal reactant used was small. For this reason, in Examples 1-3, the polymer obtained by hydrolytic condensation of (B) component in presence of (A) component is compared with the polymer obtained in Comparative Synthesis Examples 1-3. The residual magnesium concentration was low.

  In Examples 4 to 6, using the polymers obtained in Examples 1 to 3, an insulating film having a small relative dielectric constant, excellent mechanical strength and adhesion, and no phase separation in the film is used. I was able to get it.

Claims (10)

(A) Polycarbosilane obtained by ring-opening polymerization of at least one silane compound selected from the group of compounds represented by the following general formula (1) and the following general formula (2) (B) The manufacturing method of a polymer including hydrolyzing and condensing a hydrolysable group containing silane monomer.

(1)
(Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or a monovalent organic group, X and Y are the same or different, represent a halogen atom or an alkoxy group, and l represents an integer of 2 to 4) .)

(2)
(Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom or a monovalent organic group, R ⁵ represents a monovalent organic group other than a hydrogen atom or an alkoxy group, and Z represents a halogen atom or an alkoxy group. M represents an integer of 2 to 4.) (A) At least one silane compound selected from the group of compounds represented by the following general formula (1) and the following general formula (2), and represented by the following general formula (3) A method for producing a polymer, comprising hydrolyzing and condensing (B) a hydrolyzable group-containing silane monomer in the presence of polycarbosilane obtained by ring-opening polymerization with at least one silane compound.

(1)
(Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or a monovalent organic group, X and Y are the same or different, represent a halogen atom or an alkoxy group, and l represents an integer of 2 to 4) .)

(2)
(Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom or a monovalent organic group, R ⁵ represents a monovalent organic group other than a hydrogen atom or an alkoxy group, and Z represents a halogen atom or an alkoxy group. M represents an integer of 2 to 4.)

(3)
^(Wherein, R 6 to R ⁹ individually represent a hydrogen atom or a monovalent organic group, n is an integer of 2-4.) In claim 1,
A method for producing a polymer, wherein in the general formulas (1) and (2), l and m are 2. In claim 2,
In the said General formula (1)-(3), l, m, and n are the manufacturing methods of a polymer. In any of claims 1 to 4,
The (B) hydrolyzable group-containing silane monomer is at least one silane compound selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (5). , Production method of polymer.
R ¹⁰ _a SiX _4-a (4)
(Wherein R ¹⁰ represents a hydrogen atom, a fluorine atom or a monovalent organic group, X represents a halogen atom or an alkoxyl group, and a represents an integer of 0 to 3)
_{^{R 11 b Y 3-b Si-}} (R 13) d -SiZ 3-c R 12 c ····· (5)
[Wherein R ¹¹ and R ¹² are the same or different and each represents a monovalent organic group, b and c are the same or different and represent an integer of 0 to 2, and R ¹³ represents an oxygen atom, a phenylene group or — (CH ₂ ) represents a group represented by _e- (wherein e is an integer of 1 to 6), Y and Z are the same or different and represent a halogen atom or an alkoxyl group, and d represents 0 or 1 . ]   A polymer obtained by the method for producing a polymer according to any one of claims 1 to 5.   The composition for insulating film formation containing the polymer and organic solvent of Claim 6.   The manufacturing method of an insulating film including apply | coating the composition for insulating film formation of Claim 7 to a board | substrate, and heating.   The manufacturing method of an insulating film including apply | coating the composition for film formation of Claim 7 to a board | substrate, and irradiating an electron beam or an ultraviolet-ray.   The silica type insulating film obtained by the manufacturing method of the insulating film of Claim 8 or 9.