JPWO2008096656A1 - Silicon-containing polymer and method for synthesizing the same, film-forming composition, and silica-based film and method for forming the same - Google Patents

Abstract

A method for synthesizing a silicon-containing polymer includes: a first liquid containing at least one hydrolyzable silane compound selected from (A) a hydrolyzable silane monomer and (B) a hydrolyzable polycarbosilane; water and a catalyst; And a step of hydrolyzing and condensing the hydrolyzable silane compound.

Description

  The present invention relates to a silicon-containing polymer and a synthesis method thereof, a film-forming composition, a silica-based film, and a method for forming the same.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is frequently used as an interlayer insulating film in a semiconductor element or the like. In recent years, for the purpose of forming an interlayer insulating film having a more uniform film thickness, a coating type insulating film called a SOG (Spin on Glass) film mainly composed of a hydrolyzed product of tetraalkoxylane is also available. It has come to be used. In addition, with the 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.

  However, with further higher integration and multi-layering of semiconductor devices and the like, better electrical insulation between conductors is required, and therefore, storage stability is better, lower relative permittivity, and more mechanical An interlayer insulating film having excellent strength has been demanded.

  In the manufacturing process of the semiconductor device, a CMP (Chemical Mechanical Planarization) process for planarizing the insulating layer and various cleaning processes are performed. Therefore, in order to be applied to an interlayer insulating film or a protective film of a semiconductor device, in addition to the dielectric constant characteristics, it is also required to have chemical strength that can withstand mechanical strength and chemical attack.

  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.

  Also proposed are methods for preparing a coating solution by mixing a polycarbosilane solution and a polysiloxane solution to form a low dielectric constant insulating film (JP 2001-127152 A, JP 2001-345317 A). However, this method has a problem that the domains of carbosilane and polysiloxane are dispersed in the coating film in a non-uniform state.

  Further, a method using an organic silicate polymer obtained by hydrolytic condensation after producing a carbon bridge-containing silane oligomer from an organometallic silane compound (International Publication No. 2002/098955) has also been proposed. The material obtained by the method has a problem that the stability of the reaction product is poor and is not suitable for long-term storage, and in addition, the adhesion to the substrate is poor.

  Furthermore, a method for forming a low dielectric constant insulating film obtained by hydrolytic condensation of a highly branched polycarbosilane (US Pat. No. 6,807,041) has also been proposed, but after applying a polymer to a substrate, Process treatments such as aging treatment with ammonia, trimethylsilylation treatment, and high-temperature curing at 500 ° C. are necessary, and are not suitable for practical processes.

  The object of the present invention can be suitably used in a semiconductor device or the like for which high integration and multilayering are desired, generation of coarse particles is suppressed, storage stability is excellent, and a low relative dielectric constant and low Provided are a silicon-containing polymer that can be used to form an insulating film that is hygroscopic and has excellent mechanical strength and chemical resistance, a method for synthesizing the same, and a film-forming composition containing the silicon-containing polymer and a method for producing the same. There is.

  Another object of the present invention is to provide a silica-based film having a low relative dielectric constant and a low hygroscopic property and excellent in mechanical strength and chemical resistance and a method for forming the same.

A method for synthesizing a silicon-containing polymer according to one embodiment of the present invention includes:
A first liquid containing at least one hydrolyzable silane compound selected from (A) a hydrolyzable silane monomer and (B) a hydrolyzable polycarbosilane is added to a second liquid containing water and a catalyst. And hydrolyzing and condensing the hydrolyzable silane compound.

  In the present invention, “hydrolyzable” means having a group that can be hydrolyzed during the production of a silicon-containing polymer.

  In the method for synthesizing a silicon-containing polymer, when the first liquid is added to the second liquid, the temperature of the second liquid may be 40 ° C. or higher.

In the method for synthesizing a silicon-containing polymer, the (A) hydrolyzable silane monomer may be a silane compound selected from the group of compounds represented by the following general formulas (1) to (3).
R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 3.)
Si (OR ² ) ₄ (2)
(Wherein R ² represents a monovalent organic group.)
^{_{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ····· (3)
[Wherein R ^{3 to} R ⁶ are the same or different and each represents a monovalent organic group, b and c are the same or different, and represent a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or-( CH ₂ ) represents a group represented by _m — (where m is an integer of 1 to 6), and d represents 0 or 1. ]

  In the method for synthesizing a silicon-containing polymer, the (B) hydrolyzable polycarbosilane may be a polycarbosilane having a structural unit represented by the following general formula (4).

・・・・・（４）
（式中、Ｒ^８は水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^９はハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１０，Ｒ^１１は同一または異なり、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、炭素数２〜６のアルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１２〜Ｒ^１４は同一または異なり、置換または非置換のメチレン基、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基を示し、ｘ，ｙ，ｚは、それぞれ０〜１０，０００の数を示し、５＜ｘ＋ｙ＋ｚ＜１０，０００の条件を満たす。）

(4)
Wherein R ⁸ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ is a group selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups, aryl groups, allyl groups, and glycidyl groups. R ¹⁰ and R ¹¹ are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group Selected from the group consisting of a group and a glycidyl group Are ^shown, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, x, y, z are the number of each of 0 to 10,000 (5 <x + y + z <10,000 is satisfied)

  In the method for synthesizing a silicon-containing polymer, the hydrolyzable silane compound is the (A) hydrolyzable silane monomer and the (B) hydrolyzable polycarbosilane, and the (A) hydrolyzable polycarbosilane. The hydrolyzable silane compound (B) may be 1-1000 parts by weight with respect to 100 parts by weight of the completely hydrolyzed condensate.

  In the method for synthesizing a silicon-containing polymer, the catalyst may be at least one compound selected from a basic compound, an acidic compound, and a metal chelate compound. In this case, the basic compound can be a nitrogen-containing compound represented by the following general formula (5).

(X ¹ X ² X ³ X ⁴ N) _g Y (5)
(In the formula, X ¹ , X ² , X ³ and X ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group, an aryl group, or an arylalkyl group, and Y represents a halogen atom. Or 1 to 4 valent anionic groups, and g represents an integer of 1 to 4.
In this case, the acidic compound may be an organic acid. Alternatively, in this case, the metal chelate compound can be a metal chelate compound represented by the following general formula (6).
R ¹⁵ _e M (OR ¹⁶ ) _fe (6)
[Wherein R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, and f represents the valence of metal M. E represents an integer of 1 to f. ]

  The silicon-containing polymer according to one embodiment of the present invention is synthesized by the above method.

  The film forming composition according to one embodiment of the present invention includes the silicon-containing polymer and an organic solvent.

  The method for forming a silica-based film according to one embodiment of the present invention includes a step of applying the film-forming composition to a substrate to form a coating film, and a step of performing a curing process on the coating film.

  The silica film according to one embodiment of the present invention is obtained by the method for forming a silica film.

  According to the method for producing a silicon-containing polymer, the first liquid containing at least one hydrolyzable silane compound selected from (A) a hydrolyzable silane monomer and (B) a hydrolyzable polycarbosilane, Addition to the second liquid containing water and catalyst, and including a step of hydrolyzing and condensing the hydrolyzable silane compound provides excellent storage stability and suppresses the generation of coarse particles, resulting in variation in molecular weight. Therefore, it is possible to obtain a silicon-containing polymer with less gelation.

  The film-forming composition comprises the silicon-containing polymer and an organic solvent, and the silicon-containing polymer has a uniform tertiary structure with little variation in molecular weight, and thus gelation is suppressed and a relative dielectric constant. Therefore, by forming an insulating film using the film forming composition, an insulating film having excellent mechanical strength and chemical resistance, no layer separation in the film, and low relative dielectric constant and hygroscopicity is obtained. be able to.

  The silica-based film has a small relative dielectric constant, is excellent in mechanical strength, adhesion, and chemical resistance, and has no phase separation in the film.

  Hereinafter, a silicon-containing polymer and a synthesis method thereof, a film-forming composition, a silica-based film and a formation method thereof according to an embodiment of the present invention will be specifically described.

1. Silicon-containing polymer and method for synthesizing the same A method for synthesizing a silicon-containing polymer according to an embodiment of the present invention includes (A) a hydrolyzable silane monomer (hereinafter also referred to as “component (A)”) and (B) hydrolysis. A first liquid containing at least one hydrolyzable silane compound selected from water-soluble polycarbosilane (hereinafter also referred to as “component (B)”) is added to a second liquid containing water and a catalyst. And hydrolyzing and condensing the hydrolyzable silane compound.

In the method for synthesizing a silicon-containing polymer according to this embodiment, when the first liquid is added to the second liquid, the temperature of the second liquid is preferably 40 ° C. or higher, and is preferably 50 ° C. or higher. More preferred. When the temperature of the second liquid is less than 40 ° C., the degree of hydrolysis condensation is low, and the effects of the present invention may not be sufficiently obtained. Moreover, although the speed | rate at the time of adding a 1st liquid to a 2nd liquid is based also on the density | concentration of the silane compound in a 1st liquid, and the density | concentration of the water and a catalyst in a 2nd liquid, Usually 30 minutes-10 It's time. Specifically, the addition rate of the hydrolyzable silane compound is 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ (g · min ⁻¹ · g ⁻¹ ) per unit time and unit second liquid amount. It is preferably 5 × 10 ^{−4 to} 5 × 10 ⁻² (g · min ⁻¹ · g ⁻¹ ).

  The concentration of the hydrolyzable silane compound with respect to the first liquid is preferably 1 to 50% by weight, more preferably 2 to 30% by weight, and particularly preferably 3 to 20% by weight. When the concentration exceeds 50% by weight or less than 1% by weight, a polymer having a wide molecular weight distribution may be obtained. In addition, by forming a film using a polymer obtained by hydrolytic condensation using both the component (A) and the component (B) as the hydrolyzable silane compound, it has excellent chemical resistance and moisture absorption. A film having low properties can be obtained.

  The water content of the second liquid is preferably 5 to 80% by weight, and more preferably 10 to 70% by weight. When the water content exceeds 80% by weight, a polymer obtained by polymerization may be precipitated, or when it is less than 5% by weight, hydrolysis and condensation may not proceed.

  The concentration of the catalyst in the second liquid is preferably 0.001 to 10% by weight, and more preferably 0.005 to 1% by weight. When the concentration of the catalyst is more than 10% by weight or less than 0.001% by weight, the molecular weight may become too large and coarse particles may be generated, or the reaction may hardly proceed.

  As the solvent that can be used for the first liquid, alcohol, ketone, ester, and ether solvents are preferable. Specific examples of the solvent that can be used for the first liquid will be described later.

  As the solvent that can be used in the second liquid, alcohol, ketone, ester, and ether solvents are preferable, and the same solvent as that used in the first liquid is particularly preferable.

  Hereinafter, each component used in order to manufacture the silicon-containing polymer which concerns on this embodiment is demonstrated.

1.1. Component (A) The component (A) is preferably a silane compound selected from the group of compounds represented by the following general formulas (1) to (3). The component (A) can be condensed with another component (A) or a component (B) described later to form a Si—O—Si bond.
R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 3.)
Si (OR ² ) ₄ (2)
(Wherein R ² represents a monovalent organic group.)
^{_{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ····· (3)
[Wherein R ^{3 to} R ⁶ are the same or different and each represents a monovalent organic group, b and c are the same or different, and represent a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or-( CH ₂ ) represents a group represented by _m — (where m is an integer of 1 to 6), and d represents 0 or 1. ]

  (A) a compound represented by the above general formula (1) that can constitute the component (hereinafter referred to as “compound 1”), a compound represented by the above general formula (2) (hereinafter referred to as “compound 2”), As the compound represented by the general formula (3) (hereinafter referred to as “compound 3”), the following can be used. Among these, it is preferable to use Compound 1 and Compound 2 as the component (A). In this case, the amount of Compound 1 and Compound 2 used is Compound 1: Compound 2 = 100: 0 to 50:50. More preferred.

1.1.1. Compound 1
In the general formula (1), examples of the monovalent organic group represented by R and R ¹ include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group. Especially, it is preferable that the monovalent organic group represented by R and R ¹ is an alkyl group or a phenyl group.

  Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like. Preferably, the alkyl group has 1 to 5 carbon atoms, and these alkyl groups may be linear or branched. Further, 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. 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.

  Specific examples of the compound 1 include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert. -Butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert- Butoxysilane, ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopro Xysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyl Tri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n -Butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec- Toxisilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert- Butyl-n-propoxysilane, tert-butyltriisopropoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyl Rutri-tert-butoxysilane, tert-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec -Butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec- Butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propo Sisilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane Di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi- tert-butoxysilane, di-n-propyldi-phenoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxy Silane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane , Di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-n-butyldi- Phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxy Silane, di-sec-butyl di-sec-butoxy Sisilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldi-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, Di-tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldi-phenoxy Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-ter - butoxysilane include diphenyl phenoxy silanes. These may be used alone or in combination of two or more.

  Particularly preferred compounds as Compound 1 are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy. Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. These may be used alone or in combination of two or more.

1.1.2. Compound 2
In the general formula (2), examples of the monovalent organic group represented by R ² include the same groups as those exemplified as R and R ^{1 in} the general formula (1).

  Specific examples of the compound 2 include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxy. Silane, tetraphenoxysilane and the like can be mentioned, and particularly preferred compounds include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination of two or more.

1.1.3. Compound 3
In the general formula (3), examples of R ^{3 to} R ⁶ include the same groups as those exemplified as R and R ^{1 in} the general formula (1).

  As the compound 3 in which d = 0 in the general formula (3), 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, , 1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-pentamethoxy-2- Phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy 1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2 -Tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1 , 2,2-Tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2-diphenyldisilane 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2- Trime Rudisilane, 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-1,1,2,2-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.

  In addition, as the compound 3 in which d = 1 in the general formula (3), bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri-iso-) Propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane, 1,2-bis (tri-iso-propoxysilyl) ethane, 1,2-bis (tri- n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2-bis (tri-tert-butoxy) L) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-iso-propoxymethylsilyl) -1- (tri-iso-propoxysilyl) methane, 1- (di-n-butoxymethylsilyl) -1 -(Tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- ( Tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) 2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-iso-propoxymethylsilyl) -2- (tri -Iso-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- (tri-sec -Butoxysilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (tri-tert-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (di -N-propoxymethylsilyl) methane, bis (di-iso-propoxymethylsilyl) methane, bis (di-n-butoxymethylsilyl) ) Methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ) Ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-iso-propoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (Triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-iso-propoxysilyl) , 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-tert-butoxysilyl) benzene, 1,3 -Bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1,3-bis (tri-iso-propoxysilyl) benzene 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri-tert-butoxysilyl) benzene, 1,4- Bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) benzene, , 4-bis (tri-iso-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis ( And tri-tert-butoxysilyl) benzene.

  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.

  The above-mentioned compound 3 may be used alone or in combination of two or more.

1.2. (B) Component As mentioned above, the (B) component is hydrolyzable polycarbosilane.

  The component (B) can be, for example, a polycarbosilane compound having a structural unit represented by the following general formula (4) (hereinafter referred to as “compound 4”).

・・・・・（４）
（式中、Ｒ^８は水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^９はハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１０，Ｒ^１１は同一または異なり、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、炭素数２〜６のアルキル基、アリール基、アリル基およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１２〜Ｒ^１４は同一または異なり、置換または非置換のメチレン基、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基を示し、ｘ，ｙ，ｚは、それぞれ０〜１０，０００の数を示し、５＜ｘ＋ｙ＋ｚ＜１０，０００の条件を満たす。）

(4)
Wherein R ⁸ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ is a group selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups, aryl groups, allyl groups, and glycidyl groups. R ¹⁰ and R ¹¹ are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group Selected from the group consisting of a group and a glycidyl group Are ^shown, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, x, y, z are the number of each of 0 to 10,000 (5 <x + y + z <10,000 is satisfied)

In the general formula (4), examples of the halogen atom represented by R ^{8 to} R ¹¹ include a fluorine atom, a chlorine atom, and a bromine atom, and examples of the alkoxy group represented by R ^{8 to} R ¹¹ include Can include, for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like, and examples of the acyloxy group represented by R ^{8 to} R ¹¹ include an acetyloxy group and a propionyloxy group. Examples of the alkyl group represented by R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, and an aryl group represented by R ^{8 to} R ^11. Examples of groups include phenyl, naphthyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, and phenyl. Or the like can be mentioned Orofeniru group.

In the general formula (4), examples of the alkylene group represented by R ^{12 to} R ¹⁴ include an ethylene group, a propylene group, a butylene group, a hexylene group, and a decylene group. The alkylene group has 2 to 6 carbon atoms, and these alkylene groups may be chain-like or branched or may form a ring, and a hydrogen atom is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom May be substituted. Examples of the alkenylene group represented by R ^{12 to} R ¹⁴ include straight-chain or branched alkenylene groups having 2 to 6 carbon atoms (preferably 1 to 4), such as vinylene group, propenylene group, butenylene group, and pentenylene. Group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methylpentenylene group, 3-methylpentenylene group, 1-ethylvinylene group, 1-ethylpropenylene group 1-ethylbutenylene group, 3-ethylbutenylene group and the like. The hydrogen atom in these alkenylene groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkynylene group represented by R ^{12 to} R ¹⁴ include straight-chain or branched alkynylene groups having 2 to 6 carbon atoms (preferably 1 to 4), such as ethynylene group, 1-propynylene group, 1- Examples include butynylene, 1-pentynylene, 1-hexynylene, 2-butynylene, 2-pentynylene, 1-methylethynylene, 3-methyl-1-propynylene, and 3-methyl-1-butynylene. it can. The hydrogen atom in these alkynylene groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the arylene group represented by R ^{12 to} R ¹⁴ include a phenylene group and a naphthylene group, and a hydrogen atom is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Also good.

  Moreover, in the said General formula (4), x, y, z is a number of 0-10,000, and is 5 <x + y + z <10,000. In the case of x + y + z <5, the storage stability of the polymer may be inferior, and in the case of 10,000 <x + y + z, the obtained polymer may cause layer separation and may not form a uniform film. Preferably, x, y, and z are 0 ≦ x ≦ 800, 0 ≦ y ≦ 500, and 0 ≦ z ≦ 1,000, and more preferably 0 ≦ x ≦ 500, 0 ≦ y ≦ 300, 0, respectively. ≦ z ≦ 500, and more preferably 0 ≦ x ≦ 100, 0 ≦ y ≦ 50, and 0 ≦ z ≦ 100.

  In the general formula (4), 5 <x + y + z <1,000 is preferable, 5 <x + y + z <500 is more preferable, 5 <x + y + z <250 is further preferable, and 5 <x + y + z. Most preferred is <100.

  Compound 4 is, for example, chloromethyltrichlorosilane, bromomethyltrichlorosilane, chloromethylmethyldichlorosilane, chloromethylethyldichlorosilane, chloromethylvinyldichlorosilane, chloromethylphenyldichlorosilane, bromomethylmethyldichlorosilane, bromomethylvinyldichlorosilane. , Chloromethyldimethylchlorosilane, chloromethyldivinylchlorosilane, bromomethyldimethylchlorosilane, (1-chloroethyl) trichlorosilane, (1-chloropropyl) trichlorosilane, chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, chloromethylmethyldimethoxysilane , Chloromethylvinyldimethoxysilane, chloromethylphenyldimethoxysilane, bromomethylmethyldimethoxy Run, bromomethylvinyldimethoxysilane, bromomethylphenyldimethoxysilane, chloromethyldimethylmethoxysilane, chloromethyldivinylmethoxysilane, chloromethyldiphenylmethoxysilane, bromomethyldimethylmethoxysilane, bromomethyldiisopropylmethoxysilane, chloromethyltriethoxysilane, Bromomethyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylethyldiethoxysilane, chloromethylvinyldiethoxysilane, chloromethylphenyldiethoxysilane, bromomethylmethyldiethoxysilane, bromomethylvinyldiethoxysilane, bromomethyl Phenyldiethoxysilane, chloromethyldimethylethoxysilane, chloromethyldiethylethoxysilane, bromine At least one compound selected from methyldivinylethoxysilane, chloromethyltriisopropoxysilane and bromomethyltriisopropoxysilane is reacted in the presence of at least one of an alkali metal and an alkaline earth metal, and if necessary Further, it can be obtained by treatment with alcohol, organic acid, reducing agent or the like.

  (B) It is preferable that the weight average molecular weights of a component are 300-100,000, and it is more preferable that it is 500-10,000. When the weight average molecular weight of the component (B) is larger than this range, particles are likely to be formed, and the pores in the silica-based film formed using the resulting silicon-containing polymer become too large, which is not preferable.

1.3. Amounts of Component (A) and Component (B) In the method for synthesizing a silicon-containing polymer according to this embodiment, the first liquid contains the component (A) and the component (B) as hydrolyzable silane compounds. Is preferred. In this case, the mixing ratio of the component (A) and the component (B) is preferably 1 to 1000 parts by weight of the component (A) with respect to 100 parts by weight of the completely hydrolyzed condensate of the component (B). 5 to 200 parts by weight, more preferably 5 to 100 parts by weight. When component (A) is less than 1 part by weight, there may be cases where sufficient chemical resistance cannot be achieved after film formation, and when the amount exceeds 1000 parts by weight, the dielectric constant of the film cannot be reduced. There is.

1.4. (C) Catalyst (C) The catalyst is contained in the second liquid. (C) The catalyst is preferably at least one compound selected from a basic compound, an acidic compound, and a metal chelate compound.

1.4.1. Metal chelate compound (C) The metal chelate compound which can be used as a catalyst is represented by the following general formula (6).

R ¹⁵ _e M (OR ¹⁶ ) _fe (6)
(In the formula, R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ represents an alkyl group or an aryl group, f represents a valence of the metal M, and e represents an integer of 1 to f.)

Here, the metal M is preferably at least one metal selected from Group IIIB metals (aluminum, gallium, indium, thallium) and Group IVA metals (titanium, zirconium, hafnium). Titanium, aluminum, zirconium Is more preferable. Examples of the alkyl group or aryl group represented by R ¹⁶ include the alkyl group or aryl group represented by R ¹ in the general formula (1).

  Specific examples of metal chelate compounds include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, triisopropoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-tert-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, diisopropoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonato) titanium J-tert-but Si-bis (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, monoisopropoxy-tris (acetylacetonato) titanium, mono-n -Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-tert-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, triisopropoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, Re-sec-butoxy mono (ethyl acetoacetate) titanium, tri-tert-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) Titanium, diisopropoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-tert-butoxy bis ( Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, monoisopropoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tri Sus (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) Titanium chelate compounds such as tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonate) Zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, triisopropoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-tert-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nate) zirconium, diisopropoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-tert-butoxy Bis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, monoisopropoxytris Acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-tert-butoxy-tris (acetylacetonato) zirconium, tetrakis ( Acetylacetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, triisopropoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono ( Ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-tert-butoxy mono (ethyl acetoacetate) zirconium Konium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, diisopropoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) Zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-tert-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl) Acetoacetate) zirconium, monoisopropoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-but Si-tris (ethylacetoacetate) zirconium, mono-tert-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetate) Zirconium chelate compounds such as nattobis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium; triethoxy mono (acetylacetonato) aluminum, tri-n-propoxy mono (acetylacetate) Nato) aluminum, triisopropoxy mono (acetylacetonato) aluminum, tri-n-butoxy mono (acetylacetonato) aluminium , Tri-sec-butoxy mono (acetylacetonato) aluminum, tri-tert-butoxy mono (acetylacetonato) aluminum, diethoxybis (acetylacetonato) aluminum, di-n-propoxybis (acetylacetonate) ) Aluminum, diisopropoxy bis (acetylacetonato) aluminum, di-n-butoxy bis (acetylacetonato) aluminum, di-sec-butoxy bis (acetylacetonato) aluminum, di-tert-butoxy bis (Acetylacetonato) aluminum, monoethoxy tris (acetylacetonato) aluminum, mono-n-propoxy tris (acetylacetonato) aluminum, monoisopropoxy tris (acetylacetate) Tonato) aluminum, mono-n-butoxy tris (acetylacetonato) aluminum, mono-sec-butoxy tris (acetylacetonato) aluminum, mono-tert-butoxy tris (acetylacetonato) aluminum, tetrakis (acetylacetate) Natto aluminum, triethoxy mono (ethyl acetoacetate) aluminum, tri-n-propoxy mono (ethyl acetoacetate) aluminum, triisopropoxy mono (ethyl acetoacetate) aluminum, tri-n-butoxy mono (ethyl aceto) Acetate) aluminum, tri-sec-butoxy mono (ethyl acetoacetate) aluminum, tri-tert-butoxy mono (ethyl acetoacetate) aluminum, di Toxi bis (ethyl acetoacetate) aluminum, di-n-propoxy bis (ethyl acetoacetate) aluminum, diisopropoxy bis (ethyl acetoacetate) aluminum, di-n-butoxy bis (ethyl acetoacetate) aluminum, Di-sec-butoxy bis (ethyl acetoacetate) aluminum, di-tert-butoxy bis (ethyl acetoacetate) aluminum, monoethoxy tris (ethyl acetoacetate) aluminum, mono-n-propoxy tris (ethyl acetoacetate) ) Aluminum, monoisopropoxy tris (ethyl acetoacetate) aluminum, mono-n-butoxy tris (ethyl acetoacetate) aluminum, mono-sec-butoxy tris Ethyl acetoacetate) aluminum, mono-tert-butoxy-tris (ethylacetoacetate) aluminum, tetrakis (ethylacetoacetate) aluminum, mono (acetylacetonato) tris (ethylacetoacetate) aluminum, bis (acetylacetonato) bis ( 1 type or 2 types or more of aluminum chelate compounds, such as ethyl acetoacetate) aluminum and tris (acetylacetonato) mono (ethyl acetoacetate) aluminum, etc. are mentioned.

In _{particular, (CH 3 (CH 3)} HCO) 4-t Ti (CH 3 COCH 2 COCH 3) t, (CH 3 (CH 3) HCO) 4-t Ti (CH 3 COCH 2 COOC 2 H 5) t, _{(C 4 H 9 O) 4} -t Ti (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 4-t Ti (CH 3 COCH 2 COOC 2 H 5) t, (C 2 H 5 ( CH ₃ ) CO) _4-t Ti (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _4-t Ti (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t , (CH ₃ ( CH ₃ ) HCO) _4-t Zr (CH ₃ COCH ₂ COCH ₃ ) _t , (CH ₃ (CH ₃ ) HCO) _4-t Zr (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t , (C ₄ H ₉ O ) _4-t Zr (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₄ H ₉ O) _4-t Zr (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _4-t Zr (CH ₃ COCH _{2 COCH 3) t, (C} 2 H 5 (CH 3) CO) 4-t Zr (CH 3 COCH 2 COOC 2 H 5) t, (CH 3 (CH 3) HCO) 3-t Al (CH 3 COCH _{2 COCH 3) t, (CH} 3 (CH 3) HCO) 3-t Al (CH 3 COCH 2 COOC 2 H 5) t, (C 4 H 9 O) 3-t Al (CH 3 COCH 2 COCH 3) _{t, (C 4 H 9 O} ) 3-t Al (CH 3 COCH 2 COOC 2 H 5) t, (C 2 H 5 (CH 3) CO) 3-t Al (CH 3 COCH 2 COCH 3) t, (C ₂ H ₅ (CH ₃ ) CO) _3-t Al (CH ₃ COCH ₂ COOC ₂ H ₅ ) One or more types such as _t are preferred as the metal chelate compound used.

  The amount of the metal chelate compound used is 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight (in terms of complete hydrolysis condensate) of the hydrolyzable silane compound. When the use ratio of the metal chelate compound is less than 0.0001 part by weight, the coatability of the coating film may be inferior, and when it exceeds 10 parts by weight, the polymer growth cannot be controlled and gelation may occur.

  When hydrolyzing and condensing a hydrolyzable silane compound in the presence of a metal chelate compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of the hydrolyzable silane compound, and 1 to 10 mol of water is used. It is particularly preferred to add. If the amount of water to be added is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in coating properties and storage stability, and if it exceeds 20 mol, the hydrolysis and condensation reactions may occur. Polymer precipitation or gelation may occur. Moreover, it is preferable that water is added intermittently or continuously.

1.4.2. Acidic compound (C) As an acidic compound which can be used as a catalyst, an organic acid or an inorganic acid can be illustrated, and an organic acid is preferable. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid Acid, butyric acid, meritic 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, benzenesulfone Acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, itaconic acid, succinic acid, mesaconic acid, Citraconic acid, malic acid, malonic acid, hydrolyzed glutaric acid, hydrolyzed maleic anhydride Object can include hydrolysis products of phthalic anhydride. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Of these, organic acids are preferred in that there is little risk of polymer precipitation or gelation during hydrolysis and condensation reactions, and among these, compounds having a carboxyl group are more preferred. Among these, acetic acid, oxalic acid, maleic acid, Particularly preferred are organic acids such as hydrolysates of formic acid, malonic acid, phthalic acid, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid and maleic anhydride. These may be used alone or in combination of two or more.

  The amount of the acidic compound used is 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight (in terms of complete hydrolysis condensate) of the hydrolyzable silane compound. When the amount of the acidic compound used is less than 0.0001 parts by weight relative to 100 parts by weight of the total amount of the hydrolyzable silane compound, the coatability of the coating film may be inferior. In some cases, the hydrolytic condensation reaction proceeds to cause gelation.

  When hydrolyzing and condensing a hydrolyzable silane compound in the presence of an acidic compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of hydrolyzable silane compound, and 1 to 10 mol of water is added. It is particularly preferred. If the amount of water to be added is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in coating properties and storage stability, and if it exceeds 20 mol, the hydrolysis and condensation reactions may occur. Polymer precipitation or gelation may occur. Moreover, it is preferable that water is added intermittently or continuously.

1.4.3. Basic compounds (C) Examples of basic compounds that can be used as catalysts 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-butyl Propanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanol Amine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanol Amine, 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-ethyldie Nolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyl Dibutanolamine, 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) methano Ruamine, N- (aminopropyl) ethanolamine, 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, butoxymethylamine, butoxyethylamine, butoxypropylamine, butoxybutylamine, methylamine , Ethylamine, propylamine, butylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium Hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine, methylaminoethylamine, methylamino Propylamine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine Ethylaminopropylamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole, piperazine Pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. Can do.

  The basic compound is particularly preferably a nitrogen-containing compound represented by the following general formula (5) (hereinafter also referred to as compound 5).

(X ¹ X ² X ³ X ⁴ N) _g Y (5)
In the general formula (5), X ¹ , X ² , X ³ , and X ⁴ are the same or different and are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, or a butyl group). Hexyl group), hydroxyalkyl group (preferably hydroxyethyl group etc.), aryl group (preferably phenyl group etc.), arylalkyl group (preferably phenylmethyl group etc.), Y is a halogen atom (preferably fluorine) An atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a 1 to 4 valent anionic group (preferably a hydroxy group), and g represents an integer of 1 to 4.

  Specific examples of compound 5 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 5 may be used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.00001-10 mol normally with respect to 1 mol of total amounts of the hydrolysable group in a hydrolysable silane compound, Preferably it is 0.00005-5 mol.

1.5. Organic Solvent In the production of the silicon-containing polymer according to this embodiment, the hydrolyzable silane compound can be dissolved in an organic solvent to prepare the first liquid.

  Examples of preferable organic solvents constituting the first liquid include alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, and t-butanol; 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-ethyl Polyhydric alcohol solvents such as 1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether Polyhydric alcohol partial ether solvents such as ethylene glycol monobutyl ether; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4- Ether solvents such as methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, Diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-he Such as silketone, di-i-butylketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, etc. Examples include ketone solvents. Moreover, as an organic solvent which comprises a 2nd solution, the solvent similar to the preferable organic solvent which comprises the said 1st liquid can be mentioned.

1.6. Silicon-containing polymer The silicon-containing polymer according to the present embodiment is obtained by the above synthesis method, has a carbon atom content of 8 to 40 atomic% (preferably 8 to 20 atomic%), and Mw / Mn is 1. 0.5 to 4.0 (preferably 1.5 to 3.5, more preferably 1.5 to 2.8). Since the silicon-containing polymer according to the present embodiment has little variation in molecular weight, gelation is suppressed, and a predetermined amount of carbon atoms is contained, a silica-based film is formed using a film-forming composition containing the polymer. When formed, a silica-based film having excellent process resistance and a low relative dielectric constant can be obtained. Here, when Mw / Mn exceeds 4.0, the generation of a high molecular weight body that affects filterability and a low molecular weight body that inhibits the decrease in k value may be a problem.

  In addition, the carbon atom content (atomic%) of the silicon-containing polymer is such that the hydrolyzable group of the component (hydrolyzable silane compound) used for the preparation of the silicon-containing polymer is completely hydrolyzed to become a silanol group. It can be determined from the elemental composition when the generated silanol group is completely condensed to form a siloxane bond, and specifically from the following formula.

Carbon atom content (atomic%) = (number of carbon atoms in organic silica sol) / (total number of atoms in organic silica sol) × 100
The weight average molecular weight (Mw) of the silicon-containing polymer is preferably 1,000 to 200,000, and more preferably 5,000 to 150,000. When the weight average molecular weight of the silicon-containing polymer is larger than 200,000, gelation tends to occur, and the pores in the resulting silica-based film become too large, which is not preferable. On the other hand, if the weight average molecular weight of the silicon-containing polymer is less than 1,000, problems are likely to occur in coating properties and storage stability.

1.7. Effects According to the method for synthesizing a silicon-containing polymer according to the present embodiment, the method includes at least one hydrolyzable silane compound selected from (A) a hydrolyzable silane monomer and (B) a hydrolyzable polycarbosilane. By adding the first liquid to the second liquid containing water and a catalyst and hydrolyzing and condensing the hydrolyzable silane compound, the generation of huge particles is suppressed and the variation in molecular weight is small. A silicon-containing polymer having a predetermined carbon content can be obtained. Therefore, a film formed using the film-forming composition containing the silicon-containing polymer has a small relative dielectric constant and hygroscopicity, and is excellent in mechanical strength and chemical resistance.

2. Film-Forming Composition The film-forming composition according to this embodiment includes the silicon-containing polymer and an organic solvent.

2.1. Organic Solvent The organic solvent used in the film forming composition according to this embodiment includes alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic solvents. Examples thereof include at least one selected from the group consisting of a system solvent and a halogen-containing solvent.

Examples of alcohol solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 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, full Lil 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 And the like; monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether. 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. Ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, Mention may be made of ketone solvents such as fenchon. These ketone solvents may be used alone or in combination of two or more.

Examples of amide solvents include N, N-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- Examples thereof include nitrogen-containing solvents such as methylpropionamide and N-methylpyrrolidone. These amide solvents may be used alone or in combination of two or more.

  As ether solvents, ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene Glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether , Ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol Dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl ether Le, can be mentioned ether solvents such as anisole. These ether solvents may be used alone or in combination of two or more.

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

  Examples of the aliphatic hydrocarbon solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, Examples thereof include aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane. These aliphatic hydrocarbon solvents may be used alone or in combination of two or more.

  As aromatic hydrocarbon solvents, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethyl benzene, i-butyl benzene, triethyl benzene, di-i-propyl benzene, Examples thereof include aromatic hydrocarbon solvents such as n-amylnaphthalene and trimethylbenzene. These aromatic hydrocarbon solvents may be used alone or in combination of two or more. Examples of the halogen-containing solvent include halogen-containing solvents such as dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, and dichlorobenzene.

  In the film-forming composition according to the present embodiment, it is desirable to use an organic solvent having a boiling point of less than 150 ° C. Among these, alcohol solvents, ketone solvents, and ester solvents are particularly desirable, and further 1 It is desirable to use seeds or two or more simultaneously.

  These organic solvents may be the same as those used for the synthesis of the silicon-containing polymer, or the solvent can be replaced with a desired organic solvent after the synthesis of the silicon-containing polymer is completed.

  The total solid concentration of the film-forming composition according to one embodiment of the present invention is preferably 0.1 to 20% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the film-forming composition according to one embodiment of the present invention is 0.1 to 20% by mass, the film thickness of the coating film is in an appropriate range and has better storage stability. It will be a thing. The total solid content concentration is adjusted by concentration and dilution with an organic solvent, if necessary.

2.2. Other Additives Components such as organic polymers and surfactants may be further added to the film forming composition according to this embodiment.

2.2.1. Organic polymer As the organic polymer, for example, a polymer having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound polymer, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, Examples thereof include polyquinoxaline, polyoxadiazole, a fluorine-based polymer, and a polymer having a polyalkylene oxide structure.

  Examples of the polymer 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 ′) ₁ − (Y ′) _m −
-(X ') _1- (Y') _m- (X ') _n-
(Wherein X ′ represents a group represented by —CH ₂ CH ₂ O—, Y ′ represents a group represented by —CH ₂ CH (CH ₃ ) O—, l is 1 to 90, and m is 10 to 99, n 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. The aforementioned organic polymers may be used alone or in combination of two or more. The amount of the organic polymer used is usually 1 to 200 parts by weight with respect to 100 parts by weight of the resulting silicon polymer.

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

  The usage-amount of surfactant is 0.00001-1 weight part normally with respect to 100 weight part of silicon-type polymers obtained. These may be used alone or in combination of two or more.

3. Method for Forming Silica-Based Film A method for forming a silica-based film (insulating film) according to an embodiment of the present invention includes a step of applying the film-forming composition to a substrate to form a coating film, and curing to the coating film. And a process of applying a treatment.

Examples of the substrate on which the film-forming composition is applied include Si-containing layers such as Si, SiO ₂ , SiN, SiC, and SiCN. As a method for applying the film-forming composition to the substrate, a coating means such as spin coating, dipping method, roll coating method, spray method or the like is used. After the film forming composition is applied to the substrate, the solvent is removed to form a coating film. 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. Then, a silica-type film | membrane can be formed by performing a hardening process with respect to the obtained coating film.

Examples of the curing treatment include heating, irradiation with high energy rays such as electron beams and ultraviolet rays, plasma treatment, and combinations thereof, and heat treatment or irradiation with high energy rays is preferable.
In the case of curing by heating, the coating film is heated to 80 to 450 ° C. (preferably 300 ° C. to 450 ° C.) under an inert atmosphere or reduced pressure. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere can be performed under an inert atmosphere or under reduced pressure.

  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. Through such a process, a silica-based film can be manufactured.

4). Silica-based film A silica-based film according to an embodiment of the present invention has a low dielectric constant and excellent surface flatness. Therefore, an interlayer for semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM is used. It is particularly excellent as an insulating film, and it is an etching stopper film, a protective film such as a surface coating film of a semiconductor element, an intermediate layer of a semiconductor manufacturing process using a multilayer resist, an interlayer insulating film of a multilayer wiring board, and a liquid crystal display element It can be suitably used for a protective film or an insulating film. The silica-based film according to this embodiment is useful for a semiconductor device including a copper damascene process.

The relative dielectric constant of the silica-based film according to this embodiment is preferably 1.5 to 3.5, more preferably 1.8 to 3.0, still more preferably 1.8 to 2.5, Its elastic modulus is preferably 2.5 to 15.0 GPa, more preferably 3.0 to 12.0 GPa, and its film density is preferably 0.7 to 1.3 g / cm ³ , more preferably 0. 0.8 to 1.27 g / cm ³ . From these, it can be said that the organic silica film according to the present embodiment is extremely excellent in insulating film characteristics such as mechanical characteristics, chemical resistance, and low relative dielectric constant.

5). 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 mass%, respectively, unless otherwise specified.

5.1. Evaluation method Various evaluations were performed as follows.

  In addition, about the elasticity modulus and chemical | medical solution tolerance, the polymer film (silica-type film | membrane) formed with the following method was used. That is, the composition obtained in each example and comparative example was applied on a silicon wafer by spin coating, and then 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. Further, the substrate was baked on a hot plate for 60 minutes in a nitrogen atmosphere at 400 ° C. to obtain a polymer film having a film thickness of 500 μm, and this polymer film was used for the various evaluations described above.

5.1.1. Dielectric constant measurement, Δk
A film-forming composition was applied onto an 8-inch N-type silicon wafer having a resistivity of 0.1 Ω · cm or less by using a spin coating method, and then on a hot plate at 90 ° C. for 3 minutes, and then in a nitrogen atmosphere The film was dried at 200 ° C. for 3 minutes and further baked for 1 hour in a vertical furnace at 420 ° C. under reduced pressure of 50 mTorr (vacuum atmosphere) to obtain a film.

  An aluminum electrode pattern was formed on the obtained film by a vapor deposition method, and a sample for measuring relative permittivity was prepared. With respect to the sample, the relative dielectric constant of the film at room temperature (24 ° C.) and 200 ° C. was measured by a CV method using an HP 16451B electrode and an HP4284A precision LCR meter manufactured by Agilent, Inc. at a frequency of 100 kHz.

  Δk is the difference between the relative dielectric constant (k @ RT) measured at room temperature (24 ° C.) and 40% RH and the relative dielectric constant (k @ 200 ° C.) measured at 200 ° C. in a dry nitrogen atmosphere ( Δk = k @ RT−k @ 200 ° C.). With this Δk, it is possible to mainly evaluate the increase in relative dielectric constant due to moisture absorption of the film. Usually, when Δk is 0.15 or more, it can be said that the organic silica film has high hygroscopicity.

5.1.2. Evaluation of Elastic Modulus (Young's Modulus) of Film The elastic modulus of the film was measured by a continuous stiffness measurement method.

5.1.3. Chemical Solution Resistance An 8-inch wafer on which a silica-based film was formed was immersed in a 0.2% dilute hydrofluoric acid aqueous solution at room temperature for 1 minute, and changes in the thickness of the silica-based film before and after immersion were observed. If the remaining film rate defined below is 99% or more, it is judged that the chemical resistance is good.

Remaining film ratio (%) = (film thickness after immersion) / (film thickness before immersion) × 100
A: The remaining film rate is 99% or more.

    B: The remaining film rate is less than 99%.

5.1.4. Weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution dispersion Mw / Mn
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrolysis condensate were measured by a size exclusion chromatography (SEC) method under the following conditions.

Sample: A 2-methoxyethanol solution of LiBr—H ₃ PO _{4 at} a concentration of 10 mmol / L was used as a solvent, and 0.1 g of a hydrolysis condensate was added to 100 cc of 10 mmol / L LiBr—H ₃ PO _{4 in} a 2-methoxyethanol solution. And dissolved.

  Standard sample: Polyethylene oxide manufactured by WAKO was used.

  Apparatus: A high-speed GPC apparatus (model HLC-8120GPC) manufactured by Tosoh Corporation was used.

  Column: Tosoh Co., Ltd. product, TSK-GEL SUPER AWM-H (15 cm in length) was installed in series and used.

Measurement temperature: 40 ° C
Flow rate: 0.6 ml / min.
Detector: Detected by RI of a built-in high-speed GPC device (model HLC-8120GPC) manufactured by Tosoh Corporation.

  Moreover, the dispersion | distribution of molecular weight distribution was computed by Mw / Mn. The smaller this value is, the closer the molecular weight distribution is to the normal distribution.

5.2. Production of composition for film formation 5.2.1. Synthesis example 1
Solution (2): 69.93 g of 10% tetrapropylammonium hydroxide aqueous solution, 122.96 g of ultrapure water, and 235.73 g of ethanol were weighed and dissolved in a quartz three-necked flask equipped with a condenser. Next, solution (1): polycarbosilane having 46.20 g of methyltrimethoxysilane, 30.28 g of tetraethoxysilane, and a structure represented by the following formula (7) (wherein n represents a number of 1 or more). A mixed solution of 7.96 g (Mw = 800) and 192.87 g of ethanol was charged into the dropping funnel. While the solution (2) was stirred at 60 ° C., the solution (1) was added dropwise over 3 hours, and then stirred for 3 hours at 60 ° C. After cooling the reaction solution to room temperature, 669.57 g of propylene glycol monopropyl ether and 30.43 g of 20% aqueous acetic acid solution were added. The reaction solution was concentrated under reduced pressure until the solid content concentration became 10%, whereby a film-forming composition 1 was obtained.

・・・・・（７）

(7)

5.2.2. Comparative Synthesis Example 1
In a quartz three-necked flask equipped with a condenser, solution (1): methyltrimethoxysilane 46.20 g, tetraethoxysilane 30.28 g, polycarbosilane having a structure represented by the above formula (7) (Mw = 800) 7.96 g and 192.87 g of ethanol were weighed and dissolved. Subsequently, a dropping funnel was filled with a solution (2): a mixed solution of 69.93 g of 10% tetrapropylammonium hydroxide aqueous solution, 122.96 g of ultrapure water, and 235.73 g of ethanol. While the solution (1) was stirred at 60 ° C., the solution (2) was added dropwise over 3 hours, and then stirred for 3 hours at 60 ° C. After cooling the reaction solution to room temperature, 669.57 g of propylene glycol monopropyl ether and 30.43 g of 20% aqueous acetic acid solution were added. The reaction solution was concentrated under reduced pressure until the solid content concentration became 10%, whereby a film-forming composition 2 was obtained.

5.2.3. Comparative Synthesis Example 2
In a quartz three-necked flask equipped with a condenser, solution (1): methyltrimethoxysilane 46.20 g, tetraethoxysilane 30.28 g, polycarbosilane having a structure represented by the above formula (7) (Mw = 800) 7.96 g and 192.87 g of ethanol were weighed and dissolved. Next, a solution (2): a mixed solution of 69.93 g of 10% tetrapropylammonium hydroxide aqueous solution, 122.96 g of ultrapure water, and 235.73 g of ethanol was prepared. While the solution (1) was stirred at 60 ° C., the solution (2) was added all at once, and then stirred for 6 hours at 60 ° C. After cooling the reaction solution to room temperature, 669.57 g of propylene glycol monopropyl ether and 30.43 g of 20% aqueous acetic acid solution were added. The reaction solution was concentrated under reduced pressure until the solid concentration became 10%, whereby a film-forming composition 3 was obtained.

5.2.4. Synthesis example 2
In a quartz three-necked flask equipped with a condenser, 87.74 g of ion exchange water in which 264.37 g of solution (2): γ-butyrolactone and 0.37 g of oxalic acid were dissolved was weighed and dissolved. Next, the solution (1): represented by 57.51 g of methyltriethoxysilane, 47.36 g of tetramethoxysilane, and the following formula (8) (the numbers shown outside the parentheses in the formula represent the composition ratio of each unit) A solution obtained by dissolving 26.15 g of polycarbosilane (Mw = 1000) having a structure as described above in 216.30 g of methyl isobutyl ketone was charged into a dropping funnel. While the solution (2) was stirred at 55 ° C., the solution (1) was added dropwise over 2 hours, and then stirred for 3 hours at 55 ° C. Further, 1050.23 g of propylene glycol monoethyl ether was added and the reaction solution was cooled to room temperature, and then concentrated under reduced pressure until the solid content concentration became 10%, whereby a film-forming composition 4 was obtained.

・・・・・（８）

(8)

5.2.5. Comparative Synthesis Example 3
In a quartz three-necked flask equipped with a condenser, solution (1): 57.51 g of methyltriethoxysilane, 47.36 g of tetramethoxysilane, polycarbosilane having a structure represented by the above formula (8) (Mw = 1000) 26.15 g and methyl isobutyl ketone 216.30 g were weighed and dissolved. Next, solution (2): a solution in which 87.74 g of ion-exchanged water in which 264.37 g of γ-butyrolactone and 0.37 g of oxalic acid were dissolved was prepared. While the solution (1) was stirred at 55 ° C., the solution (2) was added all at once and then stirred at 55 ° C. for 5 hours. Further, 1050.23 g of propylene glycol monoethyl ether was added and the reaction solution was cooled to room temperature, and then concentrated under reduced pressure until the solid content concentration became 10%, whereby a film-forming composition 5 was obtained.

5.2.6. Synthesis example 3
Solution (2): 85.21 g of propylene glycol monoethyl ether, 132.82 g of ion-exchanged water, and 0.011 g of tetrakis (acetylacetonato) titanium were added to a quartz three-necked flask equipped with a condenser, and the mixture was heated to 50 ° C. And stirred. Next, solution (1): 26.62 g of dimethyldimethoxysilane, 75.37 g of methyltrimethoxysilane, 50.54 g of tetramethoxysilane, and a structure represented by the following formula (9) (wherein n represents a number of 1 or more) A solution of 42.64 g polycarbosilane (Mw = 840) and 242.52 g propylene glycol monoethyl ether was charged to the dropping funnel. While the solution (2) was stirred at a temperature of 50 ° C., the solution (1) was added dropwise over 2 hours, followed by reaction at 50 ° C. for 2 hours, and 1021.74 g of propylene glycol monoethyl ether was added and the reaction solution was cooled to room temperature. did. The reaction solution was concentrated under reduced pressure until the solid concentration became 10%, whereby a film-forming composition 6 was obtained.

・・・・・（９）

(9)

5.2.7. Comparative Synthesis Example 4
In a quartz three-necked flask equipped with a condenser, solution (1): dimethyldimethoxysilane 26.62 g, methyltrimethoxysilane 75.37 g, tetramethoxysilane 50.54 g, and the structure represented by the above formula (9). A solution of polycarbosilane having 42.64 g of polycarbosilane (Mw = 840) and 242.52 g of propylene glycol monoethyl ether was stirred at 50 ° C. Next, solution (2): 85.21 g of propylene glycol monoethyl ether, 132.82 g of ion-exchanged water, and 0.011 g of tetrakis (acetylacetonate) titanium were mixed and charged into the dropping funnel. While the solution (1) was stirred at a temperature of 50 ° C., the solution (2) was added dropwise over 2 hours, followed by reaction at 50 ° C. for 2 hours, and 1021.71 g of propylene glycol monoethyl ether was added and the reaction solution was cooled to room temperature. did. The reaction solution was concentrated under reduced pressure until the solid concentration became 10%, whereby a film-forming composition 7 was obtained.

5.2.8. Synthesis example 4
Solution (2): 72.25 g of 10% tetrapropylammonium hydroxide aqueous solution, 127.05 g of ultrapure water, and 228.64 g of ethanol were weighed and dissolved in a quartz three-necked flask equipped with a condenser. Then, a dropping funnel was filled with a mixed solution of solution (1): 51.34 g of methyltrimethoxysilane, 33.65 g of tetraethoxysilane, and 187.07 g of ethanol. While the solution (2) was stirred at 60 ° C., the solution (1) was added dropwise over 3 hours, and then stirred for 3 hours at 60 ° C. After the reaction solution was cooled to room temperature, 669.57 g of propylene glycol monopropyl ether and 31.44 g of 20% aqueous acetic acid solution were added. The reaction solution was concentrated under reduced pressure until the solid concentration became 10%, whereby a film-forming composition 8 was obtained.

5.2.9. Comparative Synthesis Example 5
Solution (1): 51.34 g of methyltrimethoxysilane, 33.65 g of tetraethoxysilane, and 187.07 g of ethanol were weighed and dissolved in a quartz three-necked flask equipped with a condenser. Next, a dropping funnel was filled with a mixed solution of solution (2): 72.25 g of 10% tetrapropylammonium hydroxide aqueous solution, 127.05 g of ultrapure water, and 228.64 g of ethanol. While the solution (1) was stirred at 60 ° C., the solution (2) was added dropwise over 3 hours, and then stirred for 3 hours at 60 ° C. After the reaction solution was cooled to room temperature, 669.62 g of propylene glycol monopropyl ether and 31.44 g of 20% acetic acid aqueous solution were added. The reaction solution was concentrated under reduced pressure until the solid concentration became 10%, whereby a film-forming composition 9 was obtained.

5.3. Formation of film (Examples 1 to 5 and Comparative Examples 1 to 7)
The composition obtained in each synthesis example was applied onto an 8-inch silicon wafer by spin coating, and heated in the atmosphere at 80 ° C. for 5 minutes, and then at 200 ° C. for 5 minutes under nitrogen. Furthermore, the crosslinking process was implemented by the method shown by each example, and the colorless and transparent film | membrane was formed. The evaluation results of the composition and film are shown in Table 2. In addition, heat processing or ultraviolet irradiation was employ | adopted as the crosslinking process method. The procedure of heat treatment and ultraviolet irradiation is as follows.

5.3.1. Heat treatment The obtained film was heated at 425 ° C. for 1 hour under vacuum.

5.3.2. Ultraviolet irradiation In a chamber having an oxygen partial pressure of 0.01 kPa, ultraviolet rays were irradiated while heating the coating film at 400 ° C. on a hot plate. As the ultraviolet light source, white ultraviolet light having a wavelength of 250 nm or less was used. Since this ultraviolet light is white ultraviolet light, the illuminance cannot be measured by an effective method.

5.4. Consideration of results (1) Examples 1 and 2 and Comparative Examples 1 and 2 are examples in which the coating film was subjected to crosslinking treatment by heat firing. The amount of each reagent used in the production of the film-forming composition is the same, but the reaction between the second liquid containing water and catalyst and the first liquid containing the hydrolyzable silane compound as the reaction raw material The style is different.

  The membrane obtained in Example 1 was prepared by stirring a second liquid (solution (2)) containing water and a catalyst at 60 ° C. while adding the hydrolyzable silane monomer and the hydrolyzable polysiloxane to the second liquid. Since the first liquid (solution (1)) containing carbosilane was added dropwise, and then obtained by using the polymer obtained by continuing stirring, the hygroscopicity is low (Δk is low), and It can be understood that the film is excellent in chemical resistance.

  On the other hand, the film-forming composition used in Comparative Example 1 was obtained by adding the second liquid to the first liquid, and the obtained film was equivalent at 200 ° C. Although it was a relative dielectric constant, it was recognized that the hygroscopicity was high (Δk was high). The film-forming composition used in Comparative Example 2 was obtained by adding a second liquid containing water and a catalyst to the first liquid all at once.

  In Example 2 and Comparative Examples 3 and 4, the coating film in the above example was cured using ultraviolet irradiation instead of thermal firing, but the same results were obtained from the viewpoint of the hygroscopicity of the film. It has become.

  According to Example 3 and Example 4, the film-forming composition obtained by dropping the second liquid (solution (2)) while stirring the first liquid (solution (1)) under heating conditions Any film obtained using the product has low hygroscopicity and excellent chemical resistance. On the other hand, according to Comparative Example 5 and Comparative Example 6, the film obtained by using the film-forming composition obtained by adding the second liquid (solution (2)) all at once, and the first It can be seen that the film obtained using the film-forming composition obtained by dropping the second liquid (solution (2)) into the liquid (solution (1)) is highly hygroscopic.

  Moreover, both Example 5 and Comparative Example 7 are examples in which a composition synthesized from a silane compound not containing polycarbosilane is used, and the chemical resistance of the thin film is poor. This indicates that inclusion of polycarbosilane as a polymer component is important in improving chemical resistance. In Example 5, as in Example 1, the first liquid containing the hydrolyzable silane compound was dropped into the second liquid containing water and a catalyst while heating, and the obtained film Low hygroscopicity. On the other hand, in Comparative Example 7 obtained by adding the first liquid to the second liquid, a highly hygroscopic film was obtained. Therefore, whether or not polycarbosilane is used as the hydrolyzable silane compound is determined. However, it shows that the reaction method of the present invention is effective in improving the hygroscopicity of the film.

  Further, as apparent from the molecular weight measurement results of the respective film-forming compositions in Table 1, the hydrolyzable silane was added to the second liquid (solution (2)) containing water and catalyst while heating. When the method of dropping the first liquid (solution (1)) containing the compound is applied, it can be seen that the Mw / Mn value of the obtained hydrolysis condensate is lowered. Compared with other methods, the hydrolysis condensate obtained by the above method shows a narrow molecular weight distribution, which reduces the relative dielectric constant of the film without excessively increasing the molecular weight of the entire polymer. Therefore, the generation of coarse particles, which is a concern for semiconductor wiring applications, is also suppressed, and it can be said that the present invention is excellent in this respect as well.

  As described above, the silica-based film obtained by the present invention is excellent in mechanical strength, low in relative dielectric constant and hygroscopicity, and excellent in process resistance such as chemical resistance and storage stability. It is suitable as an interlayer insulating film.

Claims (13)

  A first liquid containing at least one hydrolyzable silane compound selected from (A) a hydrolyzable silane monomer and (B) a hydrolyzable polycarbosilane is added to a second liquid containing water and a catalyst. And a method for synthesizing a silicon-containing polymer, comprising hydrolyzing and condensing the hydrolyzable silane compound. In claim 1,
A method for synthesizing a silicon-containing polymer, wherein the temperature of the second liquid is 40 ° C. or higher when the first liquid is added to the second liquid. In claim 1 or 2,
The method for synthesizing a silicon-containing polymer, wherein the (A) hydrolyzable silane monomer is a silane compound selected from the group of compounds represented by the following general formulas (1) to (3).
R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 3.)
Si (OR ² ) ₄ (2)
(Wherein R ² represents a monovalent organic group.)
^{_{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ····· (3)
[Wherein R ^{3 to} R ⁶ are the same or different and each represents a monovalent organic group, b and c are the same or different, and represent a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or-( CH ₂ ) represents a group represented by _m — (where m is an integer of 1 to 6), and d represents 0 or 1. ] In any of claims 1 to 3,
The (B) hydrolyzable polycarbosilane is a method for synthesizing a silicon-containing polymer, which is a polycarbosilane having a structural unit represented by the following general formula (4).

(4)
Wherein R ⁸ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ is a group selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, acyloxy groups, sulfone groups, methane sulfone groups, trifluoromethane sulfone groups, alkyl groups, aryl groups, allyl groups, and glycidyl groups. R ¹⁰ and R ¹¹ are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group Selected from the group consisting of a group and a glycidyl group Are ^shown, R 12 ^{to R 14} are identical or different, substituted or unsubstituted methylene group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, x, y, z are the number of each of 0 to 10,000 (5 <x + y + z <10,000 is satisfied) In any of claims 1 to 4,
The hydrolyzable silane compound is the (A) hydrolyzable silane monomer and the (B) hydrolyzable polycarbosilane.
A method for synthesizing a silicon-containing polymer, wherein (A) the hydrolyzable silane monomer is 1-1000 parts by weight with respect to 100 parts by weight of the (B) hydrolyzable polycarbosilane complete hydrolysis condensate. In any of claims 1 to 5,
The method for synthesizing a silicon-containing polymer, wherein the catalyst is at least one compound selected from a basic compound, an acidic compound, and a metal chelate compound. In claim 6,
The method for synthesizing a silicon-containing polymer, wherein the basic compound is a nitrogen-containing compound represented by the following general formula (5).
(X ¹ X ² X ³ X ⁴ N) _g Y (5)
(In the formula, X ¹ , X ² , X ³ and X ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group, an aryl group, or an arylalkyl group, and Y represents a halogen atom. Or 1 to 4 valent anionic groups, and g represents an integer of 1 to 4. In claim 6,
The method for synthesizing a silicon-containing polymer, wherein the acidic compound is an organic acid. In claim 6,
The method for synthesizing a silicon-containing polymer, wherein the metal chelate compound is a metal chelate compound represented by the following general formula (6).
R ¹⁵ _e M (OR ¹⁶ ) _fe (6)
[Wherein R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, and f represents the valence of metal M. E represents an integer of 1 to f. ]   A silicon-containing polymer synthesized by the method according to claim 1.   A film-forming composition comprising the silicon-containing polymer according to claim 10 and an organic solvent.   A method for forming a silica-based film, comprising: a step of applying the film-forming composition according to claim 11 to a substrate to form a coating film; and a step of subjecting the coating film to a curing treatment.   A silica-based film obtained by the method for forming a silica-based film according to claim 12.