JP5218765B2 - Method for producing polymer, polymer, composition for forming polymer film, method for forming polymer film, and polymer film - Google Patents

Description

  The present invention relates to a method for producing a polymer, a polymer, a composition for forming a polymer film, a method for forming a polymer film, and a polymer 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 higher integration and multi-layering of semiconductor elements, etc., better electrical insulation between conductors is required. Therefore, interlayer insulation with lower relative permittivity, crack resistance and mechanical strength is required. A membrane material is required.

  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 for 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 is a problem that the siloxane domains are dispersed in the coating film in a non-uniform state.

  Furthermore, in recent semiconductor device manufacturing processes, a CMP (Chemical Mechanical Polishing) process is used for the purpose of planarizing the film. Therefore, high CMP resistance is required for the insulating film material. In the manufacturing process of a semiconductor device, cleaning is performed after etching of an interlayer insulating film or ashing of a resist, and a chemical such as dilute hydrofluoric acid is used in this cleaning process. Therefore, high chemical resistance is required for the insulating film material.

  Already, we have proposed a method for improving resistance to semiconductor manufacturing processes by mixing (A) a hydrolyzable group-containing silane compound and / or its hydrolysis condensate and (B) a cyclic silane compound and heating. However, when there is a site where four oxygen atoms are substituted on one silicon atom in the polymer structure, the above process resistance is inferior to that without the site. Was a problem.

  An object of the present invention is to provide a method for producing a polymer and a polymer capable of forming an insulating film having a uniform film quality, a low relative dielectric constant, and excellent mechanical strength, CMP resistance and chemical resistance.

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

The method for producing a polymer according to the present invention includes:
(A) At least one hydrolyzable group-containing silane compound selected from the group of compounds represented by the following general formulas (1) and (2), and (B) represented by the following general formula (3) A polymer film-forming composition containing a polymer obtained by cocondensing at least one cyclic silane monomer selected from the group of compounds and an organic solvent is included.

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

(Wherein R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, halogen atom, hydroxyl group, alkoxyl group, acyloxy group, sulfone group, methanesulfone group, trifluoromethanesulfone group or monovalent hydrocarbon group, m is (The integer of 1-6, n shows the integer of 1-10.)

  (A) At least one hydrolyzable group-containing silane compound selected from the group of compounds represented by the following general formulas (1) and (2), and (B) represented by the following general formula (3) Mixing and heating at least one cyclic silane monomer selected from the group of compounds in the presence of an organic solvent.

R _a SiX _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, X represents an alkoxy group, an acyloxy group or a halogen element, and a represents an integer of 1 to 3.)

_{^{R 1 b Y 3-b Si-}} (R 3) d -SiZ 3-c R 2 c ··· (2)
[Wherein, R ¹ and R ² are the same or different, and each is a monovalent organic group, b and c are the same or different and each represents an integer of 0 to 3, and R ³ represents an oxygen atom, a phenylene group, or — (CH ₂ ) A group represented by _e- (wherein e is an integer of 1 to 6), Y and Z are the same or different, an alkoxy group, an acyloxy group or a halogen element, and d represents 0 or 1. ]

(Wherein R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, halogen atom, hydroxyl group, alkoxyl group, acyloxy group, sulfone group, methanesulfone group, trifluoromethanesulfone group or monovalent hydrocarbon group, m is (The integer of 1-6, n shows the integer of 1-10.)

  According to the method for producing a polymer of the present invention, (A) a hydrolyzable group-containing silane compound and / or a hydrolysis condensate thereof and (B) a cyclic silane monomer are mixed and heated to obtain a polysiloxane. And a polymer in which polycarbosilane is complexed. This polymer does not cause phase separation in the membrane as in the case of blending polysiloxane and polycarbosilane. By using such a film-forming composition containing a specific polymer, a polymer film having a low relative dielectric constant and excellent mechanical strength, CMP resistance and chemical resistance can be obtained.

  The polymer according to the present invention is obtained by the production method according to the present invention described above.

  The method for forming a polymer film according to the present invention can include applying the composition for forming a polymer film according to the present invention to a substrate and heating to 30 to 450 ° C.

  The method for forming a polymer film according to the present invention may include applying the composition for forming a polymer film according to the present invention to a substrate and heating to 30 to 450 ° C. under irradiation of high energy rays.

  The silica-based polymer film according to the present invention is obtained by the method for forming a polymer film according to the present invention.

  Hereinafter, the present invention will be described in more detail.

  The polymer of the present invention includes, for example, at least one silane compound selected from the group of compounds represented by the general formulas (1) and (2) and a group of compounds represented by the general formula (3). It is obtained by mixing at least one cyclic silane monomer selected from the above in the presence of a catalyst in an organic solvent and heating.

1. Hydrolyzable group-containing silane compound First, the silane compound represented by the general formula (1) or (2) will be described.

1.1. Compound represented by general formula (1) In the general formula (1), R is a hydrogen atom, a fluorine atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group. In the general formula (1), R 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, a vinyl group, etc. are mentioned, Preferably it is C1-C5. These alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom 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 the general formula (1), X is an alkoxy group, an acyloxy group, or a halogen atom. With respect to the hydrocarbon moiety of the alkoxyl group of X, those exemplified as the monovalent organic group for R can be exemplified.

  Specific examples of the compound represented by the general formula (1) (hereinafter also referred to as “compound 1”) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri- n-butoxysilane, tri-sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane, fluoro Tri-n-butoxysilane, fluorotri-sec-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, 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;

  Trichlorosilane, tribromosilane, triiodosilane, triacetoxysilane, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, n-butyltrichlorosilane, t-butyltrichlorosilane, cyclohexyltrichlorosilane, phenethyl Trichlorosilane, 2-norbornyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, methyltribromosilane, ethyltribromosilane, n-propyltribromosilane, isopropyltribromosilane, n-butyltribromosilane, t- Butyltribromosilane, cyclohexyltribromosilane, phenethyltribromosilane, 2-norbornyltribromosilane, vinyltribromosilane, Enyltribromosilane, methyltriiodosilane, ethyltriiodosilane, n-propyltriiodosilane, isopropyltriiodosilane, n-butyltriiodosilane, t-butyltriiodosilane, cyclohexyltriiodosilane, phenethyltriiodosilane 2-norbornyltriiodosilane, vinyltriiodosilane, phenyltriiodosilane, methyltriacetoxysilane, ethyltriacetoxysilane, n-propyltriacetoxysilane, isopropyltriacetoxysilane, n-butyltriacetoxysilane, t -Butyltriacetoxysilane, cyclohexyltriacetoxysilane, phenethyltriacetoxysilane, 2-norbornyltriacetoxysilane, vinyltriacetoxysilane, phenyl Acetoxysilane, dimethyldichlorosilane, diethyldichlorosilane, di-n-propyldichlorosilane, diisopropyldichlorosilane, di-n-butyldichlorosilane, di-t-butyldichlorosilane, dicyclohexyldichlorosilane, diphenethyldichlorosilane, di- 2-norbornyldichlorosilane, divinyldichlorosilane, diphenyldichlorosilane, dimethyldibromosilane, diethyldibromosilane, di-n-propyldibromosilane, diisopropyldibromosilane, di-n-butyldibromosilane, di-t-butyldibromo Silane, dicyclohexyldibromosilane, diphenethyldibromosilane, di-2-norbornyldibromosilane, divinyldibromosilane, diphenyldibromosilane, dimethyldiiodo Silane, diethyldiiodosilane, di-n-propyldiiodosilane, diisopropyldiiodosilane, di-n-butyldiiodosilane, di-t-butyldiiodosilane, dicyclohexyldiiodosilane, diphenethyldiiodosilane, Di-2-norbornyldiiodosilane, divinyldiiodosilane, diphenyldiiodosilane, dimethyldiacetoxysilane, diethyldiacetoxysilane, di-n-propyldiacetoxysilane, diisopropyldiacetoxysilane, di-n-butyl Diacetoxysilane, di-t-butyldiacetoxysilane, dicyclohexyldiacetoxysilane, diphenethyldiacetoxysilane, di-2-norbornyldiacetoxysilane, divinyldiacetoxysilane, diphenyldiacetoxysilane, trime Ruchlorosilane, triethylchlorosilane, tri-n-propylchlorosilane, triisopropylchlorosilane, tri-n-butylchlorosilane, tri-t-butylchlorosilane, tricyclohexylchlorosilane, triphenethylchlorosilane, tri-2-norbornylchlorosilane, trivinyl Chlorosilane, triphenylchlorosilane, trimethylbromosilane, triethylbromosilane, tri-n-propylbromosilane, triisopropylbromosilane, tri-n-butylbromosilane, tri-t-butylbromosilane, tricyclohexylbromosilane, triphenethyl Bromosilane, tri-2-norbornylbromosilane, trivinylbromosilane, triphenylbromosilane, trimethyliodosilane, triethyliodo Lan, tri-n-propyliodosilane, triisopropyliodosilane, tri-n-butyliodosilane, tri-t-butyliodosilane, tricyclohexyliodosilane, triphenethyliodosilane, tri-2-norbornyliodosilane , Trivinyliodosilane, triphenyliodosilane, trimethylacetoxysilane, triethylacetoxysilane, tri-n-propylacetoxysilane, triisopropylacetoxysilane, tri-n-butylacetoxysilane, tri-t-butylacetoxysilane, tricyclohexyl Examples include silicon compounds such as acetoxysilane, triphenethylacetoxysilane, tri-2-norbornylacetoxysilane, trivinylacetoxysilane, and triphenylacetoxysilane. Yes. These compounds can be used alone or in a mixture of two or more.

  The compound 1 is preferably methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy. Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. These may be used alone or in combination of two or more.

1.2. Compound represented by general formula (2) (hereinafter also referred to as “compound 2”)
In the general formula (2), examples of the monovalent organic group represented by R ¹ and R ² include the same organic groups exemplified as R in the compound represented by the general formula (1). it can.
Among the compounds represented by the general formula (2), R ³ is an oxygen atom, such as hexachlorodisiloxane, hexabromodisiloxane, hexaiodosidisiloxane, 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 3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pe Tert-ethoxy-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-diethyl Disiloxane, 1,1,3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetra Methoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldishiro Sun, 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-triethyl Phenoxy-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-tetraphenyldisiloxane 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane, and the like.

  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, in the general formula (2), as the compound where d is 0, 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, , 1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2, Pentapentoxy-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-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-tetraethyl Rudisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2- Examples thereof include 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, in the general formula (2), R ³ is a group represented by — (CH ₂ ) _e —, and examples thereof include bis (trichlorosilyl) methane, bis (tribromosilyl) methane, and 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-bis (tri-n-pro Xylyl) 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- (tri Ethoxysilyl) 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- (di Ethoxymethylsilyl) -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-butoxymethylsilyl) -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-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-bis (trimethoxysilane) L) 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) Examples include 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. it can.

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- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, Bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (trimethoxy) Silyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) Preferred examples include benzene and 1,4-bis (triethoxysilyl) benzene.

  As compounds 1 and 2, one type or two or more types can be used.

2. Cyclic Silane Monomer The cyclic silane monomer may be at least one cyclic silane monomer selected from the group of compounds represented by the general formula (3).

2.1. Compound represented by general formula (3) (hereinafter also referred to as “compound 3”)
As compound 3, 1,1-dimethyl-silacyclobutane, 1,1-dichloro-silacyclobutane, 1,1-dibromo-silacyclobutane, 1,1-diiodo-silacyclobutane, 1,1-diacetoxy-silacyclobutane, 1,1-dimethoxy-silacyclobutane, 1,1-diethoxy-silacyclobutane, 1,1-diisopropoxy-silacyclobutane, 1,1-didimethyl-silacyclopentane, 1,1-dimethoxy-silacyclopentane, 1,1-diethoxy-silacyclopentane, 1,1-diisopropoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,1,3,3-tetrachloro -1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1, , 3,3-tetraiodo-1,3-disilacyclobutane, 1,1,3,3-tetraacetoxy-1,3-disilacyclobutane, 1,1,3,3-tetramethoxy-1,3-di Silacyclobutane, 1,1,3,3-tetraethoxy-1,3-disilacyclobutane, 1,1,3,3-tetraisopropoxy-1,3-disilacyclobutane, 1,3-dimethyl-1, 3-dichloro-1,3-disilacyclobutane, 1,3-dimethyl-1,3-dibromo-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diiodo-1,3-disila Cyclobutane, 1,3-dimethyl-1,3-diacetoxy-1,3-disilacyclobutane, 1,3-dimethyl-1,3-dimethoxy-1,3-disilacyclobutane, 1,3-dimethyl-1, 3-diethoxy- , 3-disilacyclobutane, 1,3-dimethyl-1,3-diisopropoxy-1,3-disilacyclobutane, 1,1,3,3,5,5-hexamethyl-1,3,5-tri Silacyclohexane, 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane, 1,1,3,3,5,5-hexabromo-1,3,5-trisilacyclohexane 1,1,3,3,5,5-hexaiodo-1,3,5-trisilacyclohexane, 1,1,3,3,5,5-hexaacetoxy-1,3,5-trisilacyclohexane, 1,1,3,3,5,5-hexamethoxy-1,3,5-trisilacyclohexane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,1,3,3,5,5-hexaethoxy-1 , 3,5-trisilacyclohexane, 1,1,3,3,5,5-hexaisopropoxy-1,3,5-trisilacyclohexane, and the like. These cyclic silane monomers can be used alone or in combination of two or more.

3. Polymer Production Method The polymer of the present invention comprises, for example, an organic solvent comprising at least one silane compound selected from the group of compounds 1 and 2, and at least one cyclic silane monomer selected from the group of compounds 3. The compounds 1 to 3 are obtained by hydrolysis and condensation by mixing and heating.

  When at least one silane compound selected from the group of compounds 1 and 2 and at least one cyclic silane monomer selected from the group of compounds 3 are mixed and heated, per mole of compounds 1 and 2 It is preferable to use more than 0.5 mol and not more than 150 mol of water, and it is particularly preferable to add more than 0.5 mol and not more than 130 mol of water.

  In producing the polymer of the present invention, at least one silane compound selected from the group of compounds 1 and 2 and at least one cyclic silane monomer selected from the group of compounds 3 are hydrolyzed and condensed. In this case, a specific catalyst can be used. As a catalyst, at least 1 sort (s) chosen from the group of a basic catalyst, a metal chelate catalyst, and an acid catalyst can be used.

3.1. Basic catalyst In the production of a polymer according to an embodiment of the present invention, (C) present in the molecular structure of the polymer obtained by co-condensing component (A) and component (B) in the presence of a basic catalyst. The degree of branching of the molecular chain can be increased, and the molecular weight can be increased. Thereby, the polymer which has the structure mentioned above can be obtained.

Examples of the basic catalyst include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N- Ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine, N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanol Min, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N -Propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) butanolamine, N -(Aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N- (aminopropyl) Ethanor Ruamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) propanolamine, N- ( Aminobutyl) butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethyl Amine, butoxyethylamine, butoxypropylamine, butoxybutylamine, methylamine, ethylamine, propylamine, butylamine N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydroxide, tetraethylammonium Hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine , Ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylamino Butylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, Examples thereof include morpholine, methylmorpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

The basic catalyst is particularly preferably a nitrogen-containing compound represented by the following general formula (4) (hereinafter also referred to as “compound 4”).
(X1X2X3X4N) _f Y (4)
In the general formula (4), X1, X2, X3, and X4 are the same or different and are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc. ), A hydroxyalkyl group (preferably a hydroxyethyl group etc.), an aryl group (preferably a phenyl group etc.), an arylalkyl group (preferably a phenylmethyl group etc.), Y is a halogen atom (preferably a fluorine atom, a chlorine atom) , A bromine atom, an iodine atom, etc.), a 1-4 valent anionic group (preferably a hydroxy group, etc.), and f represents an integer of 1-4.

  Specific examples of compound 4 include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-iso-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-hydroxide iso-butylammonium hydroxide, tetra-tert-butylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraheptylammonium hydroxide, tetraoctylammonium hydroxide, tetranonylammonium hydroxide, tetradecylammonium hydroxide, Tetraundecyl ammonium hydroxide, tetradodecyl ammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, teto chloride Ethylammonium, tetra-n-propylammonium bromide, tetra-n-propylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, hexadecyltrimethylammonium hydroxide, -n-hexabromide Decyltrimethylammonium hydroxide, hydroxide-n-octadecyltrimethylammonium, bromide-n-octadecyltrimethylammonium bromide, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, benzyltrimethylammonium chloride, didecyldimethylammonium chloride, distearyldimethylammonium chloride, chloride Tridecylmethylammonium, tetrabutylammonium hydrogen sulfate, tributylmethylammonium bromide, trioctyl chloride Methyl ammonium, trilauryl methyl ammonium chloride, benzyl trimethyl ammonium hydroxide, benzyl bromide triethylammonium, and the like are preferable benzyl bromide tributylammonium bromide phenyl trimethyl ammonium, choline and the like. Among these, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethyl bromide are particularly preferable. Ammonium, tetraethylammonium chloride, tetra-n-propylammonium bromide, tetra-n-propylammonium chloride. Compound 4 may be used alone or in combination of two or more.

3.2. Metal chelate catalyst 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, diethoxy bis (acetylacetonato) titanium Di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (Acetylacetonate) 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-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (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) Chita , 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) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono- n-Butoxy Tris Ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris ( Titanium chelate compounds such as ethyl acetoacetate) 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.

3.3. Acid catalyst medium Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, and oxalic 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 Hydrolysis of 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 Organic acid such as hydrolyzate of maleic anhydride, hydrolyzate of maleic anhydride, hydrolyzate of phthalic anhydride Bets can be, can be exemplified organic carboxylic acids as a more preferable example. These acid catalysts may be used alone or in combination of two or more.

The catalysts may be used alone or in combination of two or more. The amount of the catalyst used is the hydrolysis represented by the hydrolyzable groups X, Y and Z in the compounds 1 and 2 and the substituents R ⁴ , R ⁵ , R ⁶ and R ⁷ in the compound 3. The amount is usually 0.00001 to 10 mol, preferably 0.00005 to 5 mol, per 1 mol of the total amount of the sex groups. When the amount of the catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction. Moreover, in this invention, the temperature when hydrolyzing the compounds 1 and 2 is 0-100 degreeC normally, Preferably it is 15-80 degreeC. In this invention, the usage-amount of the compounds 1 and 2 with respect to a cyclic silane monomer (compound 3) is 10-4000 weight part of the total amount component of the compounds 1 and 2 with respect to 100 weight part of cyclic silane monomers, More preferably, it is 1000-3000. Parts by weight. When the amount used is within this range, the mechanical strength of the coating film is effectively improved.

4). Polymer film-forming composition In addition to the polymer of the present invention, the polymer film-forming composition of the present invention (hereinafter referred to as “film-forming composition”) further comprises β-diketone, colloidal silica, colloidal alumina, organic Components such as a polymer, a surfactant, a silane coupling agent, and a radical generator may be added. The composition for forming a polymer film of the present invention can be used, for example, as a composition for forming an insulating film.

  β-diketones include 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, 1,1,1,5,5,5-hexafluoro-2 , 4-heptanedione, and more preferably acetylacetone, 2,4-hexanedione, 2,4-heptanedione, and 3,5-heptanedione. These may be used alone or in combination of two or more.

  Colloidal silica is, for example, a dispersion in which high-purity silicic acid is dispersed in the hydrophilic organic solvent. Usually, the average particle size is 5 to 30 nm, preferably 10 to 20 nm, and the solid content concentration is 10 to 10. About 40% by weight. Examples of such colloidal silica include Nissan Chemical Industries, Ltd., methanol silica sol and isopropanol silica sol; Catalyst Chemical Industries, Ltd., Oscar.

  Examples of the colloidal alumina include Alumina Sol 520, 100 and 200 manufactured by Nissan Chemical Industries, Ltd .; Alumina Clear Sol, Alumina Sol 10 and 132 manufactured by Kawaken Fine Chemical Co., Ltd., and the like.

  Examples of the organic polymer include a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, a polyquinoxaline, and a polyoxadi. Examples thereof include azoles, fluorine-based 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, amphoteric surfactants, and further, 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, and F183 (above, manufactured by Dainippon Ink & Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Kasei). , FLORARD FC-430, FC-431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SB-101, SB-102, SB-103, SB-104, SB -105, SB-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15 (Neos Co., Ltd.), etc. Mention may be made of 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 the polymer (complete hydrolysis-condensation product) of this invention. These may be used alone or in combination of two or more.

  Examples of the silane coupling agent include 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-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (Oxyethylene)- - aminopropyltrimethoxysilane, etc. N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. These may be used alone or in combination of two or more.

Examples of radical generators include isobutyryl peroxide, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-npropylperoxydicarbonate, diisopropylperoxydicarbonate. 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di- 2-ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy ) Dicarbonate, t-butyl pero Cineodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide , Stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) Hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluoyl and benzoyl par Oxide, benzoyl peroxide, t-butyl Peroxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl) Peroxy) 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) hexa T-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxy Oxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyiso Phthalate, 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- Examples include butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, and the like. The blending amount of the radical generator is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer (completely hydrolyzed condensate). These may be used alone or in combination of two or more.

  In the film forming composition of the present invention, a polymer (hydrolysis condensate) and the above-mentioned additive used as necessary are dissolved or dispersed in a solvent.

  Examples of the 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, heptanol-3, n-octanol, 2- Ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol Phenol, cyclohexanol, 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, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol solvents such as ethylhexanediol-1,3, 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 ketones, 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, etc. 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 invention 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 further improved. In addition, adjustment of this total solid content concentration is performed by concentration and dilution with the organic solvent, if necessary.

5. Polymer film The polymer film of the present invention can be obtained by applying the film-forming composition to form a coating film, and then heating and / or irradiating the coating film with high energy rays.
When the film-forming composition of the present invention is applied to a substrate such as a silicon wafer, SiO ₂ wafer, or 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 0.05 to 2.5 μm can be formed by one coating and a thickness of 0.1 to 5.0 μm can be formed by two coatings. Thereafter, it is dried at room temperature, or usually heated at 80 to 600 ° C., preferably 30 to 450 ° C., more preferably 60 to 430 ° C., usually for about 5 to 240 minutes to dry the glass. Alternatively, a coating film of a large polymer can be formed.

  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 is possible to heat stepwise or select an atmosphere such as nitrogen, air, oxygen, reduced pressure, etc. as necessary.

  In the present invention, the film-forming composition can be applied to a substrate and heated to usually 25 to 500 ° C., preferably 30 to 450 ° C., more preferably 60 to 430 ° C. under irradiation with high energy rays.

  The high energy ray can be at least one kind of high energy ray selected from electron beam, ultraviolet ray and X-ray. Below, the irradiation conditions at the time of using an electron beam as an example are described.

Here, the energy (acceleration voltage) when irradiating an electron beam is 0.1 to 50 keV, preferably 1 to 30 keV, and the electron beam irradiation amount is 1 to 1000 μC / cm ² , preferably 10 to 500 μC / cm ² . . In addition, when the acceleration voltage is 0.1 to 50 keV, the electron beam can penetrate the film sufficiently without penetrating the film and damaging the lower semiconductor element, and can sufficiently enter the coating film. Furthermore, when the electron beam irradiation amount is 1 to 1000 μC / cm ² , the entire coating film is reacted, and damage to the coating film is reduced. The substrate temperature at the time of electron beam irradiation is usually 25 to 500 ° C., preferably 30 to 450 ° C. Prior to the electron beam irradiation of the coating film, the substrate can be heated to 250 to 500 ° C., and the coating film of the present invention can be pre-cured and then irradiated with an electron beam. According to this method, it is possible and effective to reduce film thickness unevenness depending on the non-uniformity of the electron beam dose. The electron beam irradiation is preferably performed in an atmosphere having an oxygen concentration of 10,000 ppm or less, preferably 1,000 ppm. Moreover, electron beam irradiation can also be performed in inert gas atmosphere. Here, examples of the inert gas used include N ₂ , He, Ar, Kr, and Xe, preferably He and Ar. By performing the electron beam irradiation in an inert gas atmosphere, the film is hardly oxidized, and the low dielectric constant of the obtained coating film can be maintained. The electron beam irradiation may be performed in a reduced pressure atmosphere, and the degree of reduced pressure is usually 1000 mTorr or less, preferably 1 to 200 mTorr. In addition, the time required for electron beam curing is about 1 to 5 minutes, which is much shorter than 15 minutes to 2 hours required for thermosetting, and electron beam irradiation is used for wafer single wafer processing. It can be said that it is suitable.

The silica-based polymer film of the present invention 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 , more preferably 0. .5 to 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 polymer film of the present invention is generally 3.2 to 1.2, preferably 3.0 to 1.5, and more preferably 2.7 to 1.8.

  The polymer film obtained by the present invention is characterized by having many silicon-carbon bonds in the film structure. In addition, the polymer obtained by the present invention is obtained by hydrolyzing and condensing a hydrolysable group-containing silane compound and / or a hydrolysis condensate thereof and a cyclic silane monomer in the presence of a polysiloxane and a polysiloxane. It is a polymer in which carbosilane is complexed. Since this polymer is a cocondensate, a homogeneous film can be obtained without causing phase separation in the film as in the case of blending polysiloxane and polycarbosilane. By using this film-forming composition containing a polymer, a polymer film having a small relative dielectric constant and excellent mechanical strength, CMP resistance and chemical resistance can be obtained.

  Since the polymer film of the present invention has a low relative dielectric constant and excellent mechanical strength, CMP resistance and chemical resistance, an interlayer insulating film for semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM Useful for applications such as etching stopper films, protective films such as semiconductor element surface coat films, intermediate layers in semiconductor fabrication processes using multilayer resists, interlayer insulating films on multilayer wiring boards, protective films and insulating films for liquid crystal display elements It is.

6). 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.

6.1. Evaluation method Various evaluations were performed as follows.

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

  Sample: Tetrahydrofuran was used as a solvent, and 1 g of a polymer (cocondensate) was dissolved 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

6.1.2. 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 sample was measured for the relative dielectric constant of the polymer film at room temperature by a CV method using a HP16451B electrode and a HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. at a frequency of 100 kHz.

6.1.3. Mechanical strength (elastic modulus / hardness)
A Barcovic indenter was attached to an ultra-small hardness meter (Nanoindentator XP) manufactured by MTS, and the universal hardness of the resulting polymer film was determined. The elastic modulus of the polymer film was measured by a continuous stiffness measurement method.

6.1.4. CMP Resistance The obtained polymer film was polished under the following conditions.

Slurry: Silica-hydrogen peroxide system Polishing pressure: 280 g / cm ²
Polishing time: 120 seconds The appearance of the film after CMP was observed with a light source of 350,000 lux and evaluated according to the following criteria.

  A: No change.

  B: Scratches and peeling are confirmed on the film.

6.1.5. Chemical Solution Resistance An 8-inch wafer on which a polymer film was formed was immersed in a 0.2% dilute hydrofluoric acid aqueous solution at room temperature for 1 minute, and the change in film thickness before and after immersion of the polymer film was observed. If the remaining film rate defined below is 99% or more, it is judged that the chemical solution resistance is good ("A" in Table 1), and if the remaining film rate is less than 99%, the chemical solution resistance is not good. ("B" in Table 1).

Remaining film ratio (%) = (film thickness after immersion) / (film thickness before immersion) × 100
6.2. Examples and comparative examples

6.2.1. Example 1
In a quartz separable flask, 55 g of methyltrimethoxysilane, 36 g of 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, and 16 g of 20% aqueous solution of tetrapropylammonium hydroxide were added to 500 g of methanol. Then, the mixture was stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 44 g of ion exchange water and 500 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

  Then, after making it react at 55 degreeC for 4 hours, 22 g of 10% propylene glycol monopropyl ether solutions of acetic acid were added, it was made to react for 30 minutes, and the solution was cooled to room temperature. A solution containing methanol and water was removed from the solution at 50 ° C. by evaporation to obtain a solution (H-1). The condensate of the present invention thus obtained had a weight average molecular weight of 52,000.

6.2.2. Comparative Example 1
In a quartz separable flask, 40 g of methyltrimethoxysilane, 18 g of tetramethoxysilane, 36 g of 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, and 20% aqueous solution of tetrapropylammonium hydroxide 17 g was dissolved in 500 g of methanol and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 47 g of ion-exchanged water and 500 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

  Then, after making it react at 55 degreeC for 4 hours, 24 g of 10% propylene glycol monopropyl ether solutions of acetic acid were added, it was made to react for 30 minutes, and the solution was cooled to room temperature. The solution containing methanol and water was removed from the solution at 50 ° C. by evaporation to obtain a solution (H-2). The condensate of the present invention thus obtained had a weight average molecular weight of 61,000.

6.2.3. Example 2
In a quartz separable flask, 71 g of methyltrimethoxysilane, 27 g of 1,1,3,3-tetramethoxy-1,3-disilacyclobutane, and 21 g of 20% aqueous solution of tetramethylammonium hydroxide were added to 500 g of methanol. After dissolution, the solution was stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 58 g of ion exchange water and 500 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

  Then, after reacting at 55 ° C. for 4 hours, 29 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added and reacted for another 30 minutes, and the solution was cooled to room temperature. The solution containing methanol and water was removed from the solution at 50 ° C. by evaporation to obtain a solution (H-3). The condensate of the present invention thus obtained had a weight average molecular weight of 74,000.

6.2.4. Comparative Example 2
In a quartz separable flask, 46 g of methyltrimethoxysilane, 31 g of tetramethoxysilane, 28 g of 1,1,3,3-tetramethoxy-1,3-disilacyclobutane, and 24 g of a 20% aqueous solution of tetramethylammonium hydroxide Was dissolved in 500 g of methanol and then stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 65 g of ion-exchanged water and 500 g of propylene glycol monoethyl ether was added to the solution over 1 hour.

  Then, after reacting at 55 ° C. for 4 hours, 32 g of 10% propylene glycol monopropyl ether solution of acetic acid was added and reacted for another 30 minutes, and the solution was cooled to room temperature. The solution containing methanol and water was removed from the solution at 50 ° C. by evaporation to obtain a solution (H-4). The condensate of the present invention thus obtained had a weight average molecular weight of 82,000.

6.2.5. Example 3
In a quartz separable flask, 58 g of methyltrimethoxysilane, 41 g of 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane and 56 g of ion-exchanged water were mixed with propylene glycol mono After dissolving in 5000 g of ethyl ether, the solution was 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 solution was cooled to room temperature. A solution containing methanol and water was removed from the solution at 50 ° C. by evaporation to obtain a solution (H-5). The condensate of the present invention thus obtained had a weight average molecular weight of 5,300.

6.2.6. Comparative Example 3
In a quartz separable flask, 42 g of methyltrimethoxysilane, 19 g of tetramethoxysilane, 42 g of 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane and 61 g of ion-exchanged water Was dissolved in 5000 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 solution was cooled to room temperature. The solution containing methanol and water was removed from the solution at 50 ° C. by evaporation to obtain a solution (H-6). The condensate of the present invention thus obtained had a weight average molecular weight of 6,800.

6.2.7. Example 4-6, Comparative Example 4-6
The solutions H-1, H-2, H-3, H-4, H-5, and H-6 obtained in Example 1-3 and Comparative Example 1-3 were mixed with Teflon (registered trademark) having a diameter of 0.2 μm. ) Filtration was performed with a filter made to obtain a film forming composition of the present invention.

  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 on a nitrogen atmosphere hot plate at 400 ° C. The substrate was baked. 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.

6.3. Evaluation Results As is apparent from Examples 4 to 6, the insulating film prepared using the polymer film forming composition of the present invention has a lower dielectric constant and higher chemical resistance than Comparative Examples 4 to 6. all right.

  As is clear from the above examples, a polymer is formed using the method for producing a polymer of the present invention, and a polymer film forming composition containing the polymer is used. A silica-based insulating film excellent in strength, CMP resistance, and chemical resistance can be formed. Therefore, the silica-based film of the present invention is excellent in mechanical strength, CMP resistance, and chemical solution resistance, and has a low relative dielectric constant, so that it can be suitably used as an interlayer insulating film of a semiconductor device.

Claims (8)

(A) 10 to 4000 parts by weight of at least one hydrolyzable group-containing silane compound selected from the group of compounds represented by the following general formula (1 ), and (B) represented by the following general formula (3) A polymer film-forming composition comprising: a polymer obtained by hydrolyzing and cocondensing 100 parts by weight of at least one cyclic silane monomer selected from the group of compounds and an organic solvent.
R _a SiX _4-a (1)
(In the formula, R represents an alkyl group, aryl group, allyl group or glycidyl group , X represents an alkoxy group, acyloxy group or halogen element, and a represents an integer of 1 to 3)
(Wherein R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, halogen atom, hydroxyl group, alkoxyl group, acyloxy group, sulfone group, methanesulfone group, trifluoromethanesulfone group or monovalent hydrocarbon group, m is (The integer of 1-6, n shows the integer of 1-10.)   In claim 1,
  Furthermore, the composition for polymer film formation containing at least 1 sort (s) chosen from the group of the compound represented by following General formula (2) as said hydrolysable group containing silane compound.
  R ¹ _b Y _3-b Si- (R ³ ) _d -SiZ _3-c R ² _c   ... (2)
  [In the formula, R ¹ And R ² Are the same or different, and each is a monovalent organic group, b and c are the same or different and each represents an integer of 0 to 3, R ³ Is an oxygen atom, a phenylene group or-(CH ₂ ) _e A group represented by-(wherein e is an integer of 1 to 6), Y and Z are the same or different, an alkoxy group, an acyloxy group or a halogen element, and d represents 0 or 1. ] (A) 10 to 4000 parts by weight of at least one hydrolyzable group-containing silane compound selected from the group of compounds represented by the following general formula (1 ), and (B) represented by the following general formula (3) A method for producing a polymer, comprising: mixing 100 parts by weight of at least one cyclic silane monomer selected from the group of compounds in the presence of water and an organic solvent, heating the mixture , and hydrolytic condensation .
R _a SiX _4-a (1)
(In the formula, R represents an alkyl group, aryl group, allyl group or glycidyl group , X represents an alkoxy group, acyloxy group or halogen element, and a represents an integer of 1 to 3)
(Wherein R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, halogen atom, hydroxyl group, alkoxyl group, acyloxy group, sulfone group, methanesulfone group, trifluoromethanesulfone group or monovalent hydrocarbon group, m is (The integer of 1-6, n shows the integer of 1-10.)   In claim 3,
  Furthermore, the manufacturing method of a polymer containing at least 1 sort (s) chosen from the group of the compound represented by following General formula (2) as said hydrolysable group containing silane compound.
  R ¹ _b Y _3-b Si- (R ³ ) _d -SiZ _3-c R ² _c   ... (2)
  [In the formula, R ¹ And R ² Are the same or different, and each is a monovalent organic group, b and c are the same or different and each represents an integer of 0 to 3, R ³ Is an oxygen atom, a phenylene group or-(CH ₂ ) _e A group represented by-(wherein e is an integer of 1 to 6), Y and Z are the same or different, an alkoxy group, an acyloxy group or a halogen element, and d represents 0 or 1. ] The polymer obtained by the manufacturing method of Claim 3 or 4 . A method for forming a polymer film, comprising applying the composition for forming a polymer film according to claim 1 or 2 to a substrate and heating to 30 to 450 ° C. A polymer film comprising applying the composition for forming a polymer film according to claim 1 or 2 to a substrate and heating to 30 to 450 ° C. under irradiation of at least one selected from an electron beam, an ultraviolet ray and an X-ray. Forming method. A silica-based polymer film obtained by the forming method according to claim 6 .