JP2005097443A - Method for producing film-forming composition, film-forming composition and insulated film-forming material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a film-forming composition having low dielectric constant and excellent in chemical liquid resistance and insulating properties, a film-forming composition obtained by the method and a film-forming material. <P>SOLUTION: The method for producing a film-forming composition comprises hydrolyzing and condensing (A) at least one kind of silane compound selected from (A-1) a compound represented by following general formula (1), (A-2) a compound represented by following general formula (2), and (A-3) a compound represented by following general formula (3), R<SB>a</SB>Si(OR<SP>1</SP>)<SB>4-a</SB>(1), Si(OR<SP>2</SP>)<SB>4</SB>(2), R<SP>3</SP><SB>b</SB>(R<SP>4</SP>O)<SB>3-b</SB>Si-(R<SP>7</SP>)<SB>d</SB>-Si(OR<SP>5</SP>)<SB>3-c</SB>R<SP>6</SP><SB>c</SB>(3), and (B) a cyclic silane compound represented by following general formula (4), in the presence of (C) a basic compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a film-forming composition, a film-forming composition, and an insulating film-forming material, and more specifically, forms a film having a low relative dielectric constant and excellent chemical resistance and insulating properties. The present invention relates to a method for producing a film-forming composition, the film-forming composition, and an insulating film-forming material.

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

  On the other hand, with further higher integration of semiconductor elements and the like, better electrical insulation between conductors is required, and therefore, a lower dielectric constant interlayer insulating film material has been required.

  Therefore, a coating composition for forming an insulating film having a lower relative dielectric constant is disclosed as an interlayer insulating film material (see, for example, Patent Documents 1 to 3). The coating-type composition described in Patent Document 1 is intended to provide an insulating film of a semiconductor device having low water absorption and excellent crack resistance, and its structure is composed of titanium, zirconium, niobium and tantalum. Insulation mainly composed of an oligomer having a number average molecular weight of 500 or more obtained by polycondensation of an organometallic compound containing at least one selected element and an organosilicon compound having at least one alkoxy group in the molecule It is a coating-type composition for film formation.

The coating film forming compositions described in Patent Documents 2 and 3 are obtained by hydrolytic condensation of alkoxysilanes in the presence of a metal catalyst. The coating film forming composition described in Patent Document 2 has a low relative dielectric constant and a high elastic modulus, and is excellent in crack resistance and CMP resistance. Moreover, the composition for coating-film formation described in patent document 3 has the characteristics that it is a low dielectric constant and low hygroscopicity, is excellent in coating-film uniformity, and there is little increase in the film thickness at the time of long-term storage.
Japanese Patent Laid-Open No. 6-181201 JP 2000-256621 A JP 2002-285086 A

  On the other hand, in the semiconductor element manufacturing process, a normal cleaning process is performed after a process such as etching or ashing. In this cleaning process, a chemical solution such as dilute hydrofluoric acid is used. Further, a chemical solution such as dilute hydrofluoric acid may be used as an etchant for wet etching. Insulating films formed using conventional film-forming compositions sometimes have a reduced insulating property as a result of erosion of the contact surface with the chemical used in the cleaning process or etching process. Here, even if the contact surface with the chemical solution is not eroded, the surface undergoes a chemical change and absorbs moisture, resulting in a decrease in insulation.

  The objective of this invention is providing the manufacturing method of the composition for film formation which can form the film | membrane which has a low dielectric constant and was excellent in chemical | medical solution tolerance and insulation.

  Another object of the present invention is to provide a film-forming composition obtained by the above production method and an insulating film-forming material comprising the film-forming composition.

(1) The method for producing the film forming composition of the present invention comprises:
(A) Compound (A-1) represented by the following general formula (1), compound (A-2) represented by the following general formula (2), and compound represented by the following general formula (3) ( At least one silane compound selected from A-3), and R _a Si (OR ¹ ) _4-a (1)
[Wherein, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2. ]
Si (OR ² ) ₄ (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 , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a monovalent organic group; b and c may be the same or different; R ⁷ represents an oxygen atom, a phenylene group or a group represented by — (CH ₂ ) _m —, m represents an integer of 1 to 6, and d represents 0 or 1. ]
(B) Cyclic silane compound represented by the following general formula (4)

・・・・・（４)
〔式中、Ｘ，Ｙは同一でも異なっていてもよく、それぞれ水素原子または１価の有機基を示し、ｎは２〜８の整数を表す。〕
を、（Ｃ）塩基性化合物の存在下で加水分解縮合することを含む。

(4)
[Wherein X and Y may be the same or different and each represents a hydrogen atom or a monovalent organic group, and n represents an integer of 2 to 8. ]
(C) hydrolytic condensation in the presence of a basic compound.

  Here, the said (B) component can be 1-200 weight part with respect to 100 weight part of said (A) component (complete hydrolysis-condensation product conversion).

  Moreover, the density | concentration of the said (A) component and the said (B) component at the time of hydrolysis condensation can be 0.1-10 weight% (completely hydrolysis-condensation product conversion) here.

  Here, the amount of the component (C) used is 0.00001 to 1 with respect to the total amount of alkoxy groups in the component (A) at the time of hydrolysis condensation and 1 mol in total of the component (B). Can be moles.

  Here, the component (A) and the component (B) can be further hydrolytically condensed in the presence of (D) water and an alcohol having a boiling point (E) of 100 ° C. or lower.

  Moreover, the usage-amount of the said (D) water here can be 0.5-150 mol with respect to 1 mol of total amounts of the said (A) component and the said (B) component.

  Here, (F) a solvent represented by the following general formula (5) may be contained.

R ⁸ O (CHCH ₃ CH ₂ O) _e R ⁹ (5)
[R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monovalent organic group selected from CH ₃ CO—, and e represents an integer of 1 to 2. ]
(2) The film forming composition of the present invention can be obtained by any one of the above production methods.

  (3) The insulating film forming material of the present invention comprises the film forming composition.

  According to the method for producing a film-forming composition of the present invention, the component (B) and the component (A) are condensed in the presence of the basic compound (C). Here, by using the component (B), the organic component (carbon content) in the obtained film-forming composition can be increased. In general, a chemical solution such as hydrofluoric acid has a function of cutting a Si—O—Si bond. Therefore, by using the component (B), Si—O—Si bonds in the coating film can be reduced by increasing the organic component (carbon content) in the obtained composition. As a result, resistance to chemicals such as hydrofluoric acid can be increased. By the above, the film forming composition excellent in chemical | medical solution tolerance and insulation can be obtained. In addition, since the insulating film forming material of the present invention is composed of the film forming composition, by forming an insulating film using this insulating film forming material, it has a low relative dielectric constant, chemical resistance and insulation. An insulating film having excellent properties can be formed.

  Hereinafter, the manufacturing method of the film forming composition of the present invention and the film forming composition obtained by the manufacturing method will be described in detail.

<Method for producing film-forming composition>
The method for producing a film-forming composition of the present invention includes hydrolytic condensation in the presence of a component (A), a component (B), and a basic compound (C). In the present application, “hydrolysis” not only means that all of the alkoxy groups of the component (A) contained in the reaction system are hydrolyzed, but, for example, only one is hydrolyzed, or 2 It includes that at least one of them is hydrolyzed, and further includes that some or all of the Si—O bonds of the component (B) are hydrolyzed. In the present application, “condensation” means that the silanol groups in the component (A) are condensed with each other, or the silanol groups in the component (A) and the silanol groups in the component (B) are condensed. This refers to forming an O-Si bond, and it is not necessary that all silanol groups contained in the component (A) and the component (B) are condensed, and it is a concept including a case where some silanol groups are condensed. .

  In the present invention, the complete hydrolysis-condensation product of the component (A) means that the alkoxy group bonded to Si in the component (A) is 100% hydrolyzed to become a SiOH group, and further completely condensed to form a siloxane structure. The thing that became. Further, the completely hydrolyzed condensate in the component (B) means a product in which the Si—O bond of the component (B) is hydrolyzed to become a SiOH group and further completely condensed to have a siloxane structure. The component (A) is preferably a hydrolysis-condensation product of the compound (A-1) and the compound (A-2) in that the storage stability of the resulting composition is good.

  Hereafter, each substance used for the manufacturing method of the film forming composition of this invention is demonstrated.

[(A) component]
The component (A) is represented by the compound (A-1) represented by the following general formula (1), the compound (A-2) represented by the following general formula (2), and the following general formula (3). It is a silane compound which consists of at least 1 sort (s) chosen from this compound (A-3).

R _a Si (OR ¹ ) _4-a (1)
[Wherein, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2. ]
Si (OR ² ) ₄ (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 , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a monovalent organic group; b and c may be the same or different; R ⁷ represents an oxygen atom, a phenylene group or a group represented by — (CH ₂ ) _m —, m represents an integer of 1 to 6, and d represents 0 or 1. ]
Next, each of the compounds (A-1) to (A-3) will be described.

Compound (A-1): In the general formula (1), examples of the monovalent organic group represented by R and R ¹ include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Especially, in General formula (1), it is preferable that R is a monovalent organic group, especially an alkyl group or an aryl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and preferably 1 to 5 carbon atoms. These alkyl groups may be linear or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Preferred compounds as the compound (A-1) are trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, tri-tert. -Butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, Fluorotri-tert-butoxysilane, fluorotriphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butyl Xysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxy Silane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxy Silane, vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n Propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri- tert-butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri -N-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri -N-propoxy Silane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxy Silane, sec-butyltriethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec- Butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso -Propoxy Run, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n -Propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxy Such as a silane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert -Butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec -Butoxysilane, diethyl-di-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di- n-propyl- -Iso-propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl -Di-phenoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di -Iso-propyl-di-n-butoxysilane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-iso-propyl-di-phenoxysilane, di -N-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-n-pro Xysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di-tert -Butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl -Di-iso-propoxysilane, di-sec-butyl-di-n-butoxysilane, di-sec-butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec -Butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert -Butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di -Tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxy Silane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyldimethoxysilane, di-γ-aminopropyldimethoxysilane, di-γ -Glycidoxypropyl dimeth Xysilane, di-γ-trifluoropropyldimethoxysilane and the like.

  Preferably, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, particularly preferably methyltrimethoxysilane, methyltriethoxysilane, ethyl Trimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. These may be used alone or in combination of two or more.

Compound (A-2): In the general formula (2), examples of the monovalent organic group represented by R ² include the same organic groups as those shown in the general formula (1). . Specific examples of the compound (A-2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra- Examples thereof include tert-butoxysilane and tetraphenoxysilane. Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, and tetraphenoxysilane are preferable, and tetramethoxysilane and tetraethoxysilane are particularly preferable. These may be used alone or in combination of two or more.

Compound (A-3): In the general formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as those shown in the general formula (1). be able to. Among the compounds (A-3), the compound in which R ⁷ in the general formula (3) is an oxygen atom includes hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-penta Methoxy-3-methyldisiloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-methyldisiloxane, 1,1, 1,3,3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-ethyl Disiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,1,3,3 -Pentaphenoxy-3-phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1, 1,3,3-tetraphenoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraethoxy-1,3 -Diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3 -Tetraethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane Loxane, 1,1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3 , 3-triethyldisiloxane, 1,1,3-triethoxy-1,3,3-triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,1,3- Trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3-triphenyldisiloxane Siloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy- , 1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraethyldisiloxane, 3-diphenoxy-1,1,3,3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetra Examples thereof include phenyldisiloxane and 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane.

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

  In the general formula (3), examples of the compound where d = 0 include 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.

Furthermore, in the general formula (A-3), R ⁷ is a group represented by — (CH ₂ ) _m —, and 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-butoxysilyl) 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-butoxy) Methylsilyl) -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 and the like can be mentioned. 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 Preferred examples include ethoxymethylsilyl) ethane and the like.

Furthermore, in the general formula (A-3), examples of the compound in which R ⁷ is a phenylene group include 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-iso-propoxysilyl) benzene, 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-butoxy) Silyl) 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, 1,4-bis (tri-iso-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) ) Benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis (tri-tert-butoxysilyl) benzene, and the like.

  Of these, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) Preferred examples include benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene and the like.

  In this invention, as (A) component, at least 1 sort (s) is used among the said compound (A-1), a compound (A-2), and a compound (A-3) component, and a compound (A-1)-a compound ( A-3) Two or more types of components can be used.

[Component (B)]
The component (B) is a cyclic silane compound represented by the following general formula (4).

・・・・・（４)
〔式中、Ｘ，Ｙは同一でも異なっていてもよく、それぞれ水素原子または１価の有機基を示し、ｎは２〜８の整数を表す。〕
上記一般式（４）において、Ｘ，Ｙで表される１価の有機基としては、先の一般式（１）において示したものと同様の有機基を挙げることができる。なお、本発明においては、Ｘ，Ｙで表される基がともにアルキル基であるものが特に好ましい。

(4)
[Wherein X and Y may be the same or different and each represents a hydrogen atom or a monovalent organic group, and n represents an integer of 2 to 8. ]
In the general formula (4), examples of the monovalent organic group represented by X and Y include the same organic groups as those shown in the general formula (1). In the present invention, it is particularly preferable that the groups represented by X and Y are both alkyl groups.

  Specific examples of the component (B) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5-triethylcyclotrisiloxane, 1,3,5-trivinylcyclotrisiloxane, 1,3,5- Triphenylcyclotrisiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexavinylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 1 , 3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane, , 3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethyl Tetrasiloxane, 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetraphenylcyclotetrasiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, octavinylcyclotetrasiloxane, octa Phenylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetra Phenylcyclotetrasiloxane, 1,3,5,7-tetrakis (3,3,3-trifluoropropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9- Pentamethylcyclopentasiloxane, 1,3,5,7,9-pentaethylcyclopentasiloxane, , 3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9-pentaphenylcyclopentasiloxane, decamethylcyclopentasiloxane, decaphenylcyclopentasiloxane, 1,3,5,7 , 9-pentavinyl-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane, 3,5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11-hexavinylcyclohexasiloxane, 1,3,5,7,9,11-hexaphenylcyclohexa Sasiloxane, dodecamethylcyclohexasiloxane, dodecavinylcyclohexasiloxane, dodecaphenylcyclohexasiloxane, etc. Can be mentioned. These may be used alone or in combination of two or more.

  The amount of the component (B) used is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the component (A) (completely hydrolyzed condensate). . Here, when the amount of component (B) used is less than 1 part by weight relative to 100 parts by weight of component (A) (completely hydrolyzed condensate), sufficient chemical resistance cannot be obtained, and 200 parts by weight If it exceeds, applicability at the time of application deteriorates and it becomes difficult to maintain in-plane uniformity of the applied film. Here, the usage-amount of (A) component is a usage-amount in the case of converting into a complete hydrolysis condensate.

  Moreover, it is preferable that the density | concentration of (A) component and (B) component at the time of hydrolysis condensation is 0.1 to 10 weight%, and it is more preferable that it is 1 to 8 weight%. Here, if it is less than 0.1% by weight, the condensation reaction does not proceed sufficiently and a coating solution may not be obtained. If it exceeds 10% by weight, polymer precipitation or gelation may occur during the reaction. There is sex. In addition, the density | concentration of (A) component and (B) component is a density | concentration when these are converted into a complete hydrolysis condensate. Moreover, as reaction temperature in this case, it is 0-100 degreeC normally, Preferably it is 15-90 degreeC.

[Component (C)]
Component (C) is a basic compound. Examples of the basic compound used as the component (C) include sodium hydroxide, potassium hydroxide, lithium hydroxide, cerium hydroxide, barium hydroxide, calcium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, Picoline, ammonia, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine , Triethanolamine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, urea, tetramethylammonium hydro Kisaido, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, can be cited benzyltrimethylammonium hydroxide, choline, and the like. Among these, ammonia, organic amines, and ammonium hydroxides can be given as preferable examples, and tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide are particularly preferable. These basic compounds used as component (C) may be used alone or in combination of two or more.

The amount of component (C) used is the total amount of alkoxyl groups in component (A) (groups represented by R ¹ O-group, R ² O-group, R ⁴ O-group and R ⁵ O-group). And it is 0.00001-1 mol normally with respect to 1 mol in total of (B) component, Preferably it is 0.00005-0.5 mol. When the amount of component (C) used is within the above range, there is little risk of polymer precipitation or gelation during the reaction.

[Component (D) and Component (E)]
In the present invention, when hydrolyzing and condensing the component (A) and the component (B), 0.5 to 150 mol of (D) water is used per 1 mol of the total amount of the component (A) and the component (B). It is particularly preferable to add 0.5 to 130 mol of water. (D) When the amount of water to be added is less than 0.5 mol, the crack resistance of the coating film may be inferior, and when it exceeds 150 mol, polymer precipitation or gelation occurs during hydrolysis and condensation reaction. There is.

  In the present invention, when the components (A) and (B) are hydrolytically condensed, it is preferable to use an alcohol having a boiling point of 100 ° C. or lower as the component (E) together with the water (D).

  (E) As alcohol with a boiling point of 100 degrees C or less used as a component, methanol, ethanol, n-propanol, and isopropanol can be mentioned, for example. The amount of the alcohol having a boiling point of 100 ° C. or less is usually 3 to 100 mol, preferably 5 to 80 mol, per 1 mol of the total amount of the component (A) and the component (B).

  Alcohol having a boiling point of 100 ° C. or less may be produced during hydrolysis and / or condensation of the component (A) and the component (B), and the content thereof is 20% by weight or less, preferably 5% by weight or less. It is preferable to remove by distillation or the like. Further, as additives, a dehydrating agent such as methyl orthoformate, a further metal complex, or a leveling agent may be contained.

[(F) component]
The film-forming composition obtained by the present invention preferably contains a solvent (F) represented by the following general formula (5).

R ⁸ O (CHCH ₃ CH ₂ O) _g R ⁹ (5)
[R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monovalent organic group selected from CH ₃ CO—, and g represents an integer of 1 to 2. ]
In the said General formula (5), the thing similar to what was shown in previous General formula (1) can be mentioned as a C1-C4 alkyl group.

  Specific examples of the organic solvent (F) represented by the general formula (5) include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene Glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl Ether, dipropylene glycol dipropyl ether , Dipropylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene Glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol diacetate, etc., especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, B propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate are preferable. These can use 1 type (s) or 2 or more types simultaneously. In addition to the (F) solvent represented by the general formula (5), some other solvents such as ester solvents and amide solvents may be contained.

As a specific method for producing the film-forming composition of the present invention, for example, (C) component, (E) component are mixed with (A) component and (B) component, and (D) water is added. It may be added continuously or intermittently to be hydrolyzed and condensed, and is not particularly limited, and examples thereof include the following methods 1) to 11).
1) A method in which a predetermined amount of (D) water is added to a mixture composed of (A) component, (B) component, (C) component, and (E) component to perform hydrolysis / condensation reaction.
2) A predetermined amount of (D) water is continuously or intermittently added to a mixture comprising the components (A), (B), (C), and (E) to perform hydrolysis and condensation reactions. How to do.
3) A method of performing a hydrolysis / condensation reaction by adding a predetermined amount of (D) water and (C) component to a mixture composed of (A) component, (B) component and (E) component.
4) A method in which a predetermined amount of (D) water and (C) component are continuously or intermittently added to a mixture comprising components (A) and (E) to carry out hydrolysis and condensation reactions.
5) A method of performing a hydrolysis / condensation reaction by adding a predetermined amount of the component (A) to a mixture comprising the component (E), the component (D) and the component (C).
6) A method of performing a hydrolysis / condensation reaction by continuously or intermittently adding a predetermined amount of the component (A) to a mixture comprising the component (E), the component (D), and the component (C).
7) A method in which a predetermined amount of the component (A) is added to a mixture comprising the component (E), the component (D) and the component (C), followed by hydrolysis / condensation reaction and addition of a pH adjuster.
8) Add a predetermined amount of component (A) to a mixture of component (E), component (D) and water (C), conduct hydrolysis / condensation reaction, concentrate to a certain concentration in the solution, and adjust pH A method of adding an agent.
9) A method of extracting the solution obtained by the methods 1) to 8) with an organic solvent.
10) A method of replacing the solution obtained by the methods 1) to 8) with an organic solvent.
11) A method in which the solution obtained by the above methods 1) to 8) is extracted with an organic solvent and then replaced with another organic solvent.

  The radius of inertia of the hydrolyzed condensate of component (A) and component (B) thus obtained is the radius of inertia according to the GPC (refractive index, viscosity, light scattering measurement) method, preferably 4 to 50 nm, more preferably Is 6 to 40 nm, particularly preferably 7 to 30 nm. When the inertial radius of the hydrolysis-condensation product is 4 to 50 nm, the silica-based film obtained can be particularly excellent in relative dielectric constant, elastic modulus and film uniformity. In addition, the hydrolyzed condensate of the component (A) and the component (B) obtained in this manner has a feature that the coating property to the substrate is excellent because it does not take a particulate form. . The absence of the particulate form is confirmed, for example, by transmission electron microscope observation (TEM).

  Furthermore, it is preferable to adjust the pH of the obtained film-forming composition to 7 or less after hydrolyzing and condensing the component (A) and the component (B). As a method for adjusting pH, 1) a method of adding a pH adjusting agent, 2) a method of distilling off component (C) from the composition under normal pressure or reduced pressure, and 3) a gas such as nitrogen or argon. A method of removing the component (C) from the composition by bubbling, 4) a method of removing the component (C) from the composition by ion exchange resin, and 5) a component (C) by extraction or washing. The method of removing outside, etc. are mentioned. Each of these methods may be used in combination.

  Here, examples of the pH adjusting agent include inorganic acids and organic acids. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, oxalic acid, and the like. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, and sebacic acid. Gallic 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, Benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid , Malic acid, glutaric acid hydrolyzate, maleic anhydride hydrolyzate, phthalic anhydride Water decomposition products, and the like. These compounds may be used alone or in combination of two or more.

  The pH of the composition by the pH adjuster is adjusted to 7 or less, preferably 1 to 6. Thus, after making the inertial radius of a hydrolysis-condensation product into 4-50 nm, the effect that the storage stability of the composition obtained improves by adjusting pH in the said range with the said pH adjuster. can get. The amount of the pH adjuster used is an amount that makes the pH of the composition within the above range, and the amount used is appropriately selected.

Examples of the organic solvent used in the production methods 9) to 11) include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents, and aprotic solvents. Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2- Ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol Phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol solvents such as ethyl hexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether , Ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether Ter, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, di And polyhydric alcohol partial ether solvents such as propylene glycol monoethyl ether and 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. In addition to ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, acetylacetone, 2,4-hexanedione, 2 , 4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3, - heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like. These ketone solvents may be used alone or in combination of two or more.

  Examples of amide solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide solvents may be used alone or in combination of two or more.

  Examples of ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, and i-acetate. -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl acetate Glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester solvents may be used alone or in combination of two or more. As aprotic solvents, acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N -Methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone and the like can be mentioned.

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

  The film-forming composition of the present invention may further contain the following organic solvent at 50% by weight or less of the solvent. Examples of the organic solvent used in the present invention include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i -Aliphatic hydrocarbon solvents such as octane, cyclohexane, methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, Aromatic hydrocarbon solvents such as di-i-propyl benzene, n-amyl naphthalene and trimethylbenzene; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone Ketone solvents such as alcohol, acetophenone, fenchon; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, Dioxane, dimethyl dioxane, ethylene glycol monomethyl 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 monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, Ether solvents such as diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, acetic acid Methyl, ethyl acetate, γ- Tyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl acetate Pentyl, 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 acetate Monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, propio Ester solvents such as i-amyl acid, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate Nitrogen-containing solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone And sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These can be used alone or in combination of two or more.

  The film-forming composition of the present invention may further contain components such as colloidal silica, colloidal alumina, organic polymer, surfactant, silane coupling agent, radical generator, and triazene compound. Colloidal silica is, for example, a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent. Usually, the average particle size is 5 to 30 μm, preferably 10 to 20 μm, and the solid content concentration is 10 to 40. It is about wt%. Examples of such colloidal silica include Nissan Chemical Industries, Ltd., methanol silica sol and isopropanol silica sol; Catalyst Kasei Kogyo Co., Ltd., Oscar. Examples of the colloidal alumina include Alumina Sol 520, 100 and 200 manufactured by Nissan Chemical Industries, Ltd .; Alumina Clear Sol, Alumina Sol 10 and 132 manufactured by Kawaken Fine Chemical Co., Ltd., and the like. Examples of the organic polymer include a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, a polyquinoxaline, and a polyoxadi. Examples thereof include azoles, fluorine-based polymers, and compounds having a polyalkylene oxide structure.

Examples of the compound having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene poly Ether type compounds such as oxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structure.
− (A) _j − (B) _k − (A) _j − (B) _k − (A) _l −
[Wherein, A represents a group represented by —CH ₂ CH ₂ O—, B represents a group represented by —CH ₂ CH (CH ₃ ) O—, j represents 1 to 90, and k represents 10 to 10]. 99 and l are numbers from 0 to 90. ]
Among these, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, More preferred examples include ether type compounds. These may be used alone or in combination of two or more.

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

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8 , 9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluoroo Tansulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorophosphate) Octylsulfonyl-N-ethylaminoethyl), monoperfluoroalkylethyl phosphate ester, etc., a fluorine-based surfactant comprising a compound having a fluoroalkyl or fluoroalkylene group at least at any one of its terminal, main chain and side chain Can be mentioned. Commercially available products include MegaFuck F142D, F172, F173, F173, and F183 (above, Dainippon Ink & Chemicals, Inc.), F-Top EF301, 303, and 352 (made by Shin-Akita Kasei). , FLORARD FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC -105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15 (Neos Co., Ltd.), etc. Mention may be made of surfactants. Among these, the above-mentioned Megafac F172, BM-1000, BM-1100, and NBX-15 are particularly preferable.

  As the silicone-based surfactant, for example, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd., etc.) can be used. Among these, the following general formulas corresponding to the SH28PA and SH30PA are used. The polymer represented by (6) is particularly preferred.

・・・・・（６）
〔式中、Ｒ^１０は水素原子または炭素数１〜５のアルキル基であり、ｚは１〜２０の整数であり、ｘ、ｙはそれぞれ独立に２〜１００の整数である。〕
界面活性剤の使用量は、（Ａ）成分および（Ｂ）成分の総量１００重量部（完全加水分解縮合物換算）に対して通常０．０００１〜１０重量部である。これらは１種あるいは２種以上を同時に使用しても良い。

(6)
[Wherein, R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, z is an integer of 1 to 20, and x and y are each independently an integer of 2 to 100. ]
The usage-amount of surfactant is 0.0001-10 weight part normally with respect to 100 weight part (total hydrolysis-condensation product conversion) total amount of (A) component and (B) component. These may be used alone or in combination of two or more.

  Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1- Methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl 3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 , 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N -Benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (Oxyethylene)- - aminopropyltrimethoxysilane, etc. N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. These may be used alone or in combination of two or more.

  Examples of the radical generator include isobutyryl peroxide, α, α ′ bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-npropylperoxydicarbonate, diisopropylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t- Butyl peroxyneodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, Lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) Peroxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluoyl Andbenzoyl peroxide, benzoy Peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1 -Bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2 -Bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t -Butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2 5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5- Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4- Bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5- Di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, and the like. The blending amount of the radical generator is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer. These may be used alone or in combination of two or more.

  Examples of the triazene compound include 1,2-bis (3,3-dimethyltriazenyl) benzene, 1,3-bis (3,3-dimethyltriazenyl) benzene, and 1,4-bis (3,3 -Dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis (3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, Bis (3,3-dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) ben 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3- Dimethyltriazenyl) -9,9-bis [3-methyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9, 9-bis [3-phenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-propenyl- 4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro-4- (3,3-dimethyl) Triazenyl) phenyl] fluorene, 2,7-bis ( , 3-Dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazeni) ) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene. These may be used alone or in combination of two or more.

  The film-forming composition of the present invention is preferable as an insulating film-forming material because it can form a uniform coating film and has a low relative dielectric constant. That is, an insulating film can be obtained by applying and baking the film forming composition of the present invention. Since this insulating film exhibits a low relative dielectric constant, an interlayer insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, a protective film such as a surface coat film of the semiconductor device, and a multilayer resist are used. It is useful for applications such as an intermediate layer of a used semiconductor manufacturing process, an interlayer insulating film of a multilayer wiring board, a protective film or an insulating film for a liquid crystal display device.

  In the case of forming an insulating film using the film-forming composition of the present invention, examples of the method for applying the composition include spin coating, dipping, roller blades, spraying methods and the like. In this case, as a dry film thickness, it is possible to form a coating film having a thickness of about 0.05 to 1.5 μm by one coating and a thickness of about 0.1 to 3 μm by two coatings.

  In the case of heat-curing, for example, it is dried at room temperature, or usually heated at a temperature of about 80 to 600 ° C. for about 5 to 240 minutes for drying. In this case, a hot plate, an oven, a furnace, or the like can be used as a heating method, and the heating atmosphere is an atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. Can do. Moreover, in order to control the curing rate of the coating film, it is possible to heat stepwise or select an atmosphere such as nitrogen, air, oxygen, reduced pressure, etc. as necessary.

  Next, the present invention will be described more specifically with reference to examples. In addition, unless otherwise indicated, the part and% in an Example and a comparative example have shown that they are a weight part and weight%, respectively. Moreover, the following description shows the aspect of this invention generally, and this invention is not limited by this description without a particular reason. Moreover, the coating film was formed with the following method using the composition solution (A-1-5) obtained in the Example.

[Film formation]
The compositions (A-1 to 5 and B-1 and 2) obtained in Synthesis Examples 1 to 5 and Comparative Examples 1 and 2, which will be described later, were filtered using a filter having a pore diameter of 0.02 μm. The filter had no residue and could be filtered.

  Next, the composition after filtration is applied onto an 8-inch silicon wafer by using a spin coat method, and the resultant is applied at 80 ° C. for 5 minutes in the atmosphere, then at 200 ° C. for 5 minutes in a nitrogen atmosphere, and further at 400 ° C. for 1 hour in a vacuum. The wafer was heated to obtain an unemployed transparent coating film (silica film). This coating film was formed for each composition. The obtained coating film was evaluated under the following conditions. The results are shown in Table 1.

[Evaluation methods]
(Chemical resistance)
The wafer on which the coating film was formed by the above method was immersed in a 0.2 wt% dilute hydrofluoric acid aqueous solution at room temperature for 1 minute, and the change in film thickness before and after immersion of the coating film was observed. When the remaining film rate defined below was 99% or more, it was judged that the chemical resistance was good.
Residual film ratio (%) = (film thickness of the coating film after immersion) ÷ (film thickness of the coating film before immersion) × 100
(Degassing characteristics)
In order to measure chemical resistance, the wafer after being immersed in a dilute hydrofluoric acid aqueous solution was heated to 450 ° C. using a temperature-programmed desorption gas analyzer (product number: EMD-WA1000S) manufactured by Electronic Science Co., Ltd. The amount of desorbed water (the amount of desorbed water) was measured. The amount of desorbed moisture was compared with the coating film before and after immersion and evaluated according to the following criteria.

○: Desorption moisture amount below coating film before immersion ×: Desorption moisture amount exceeds coating film before immersion (dielectric constant)
Aluminum was vapor-deposited on the wafer on which the coating film was formed by the above method to produce a dielectric constant evaluation substrate. The relative dielectric constant was calculated from the capacitance value at 10 kHz using an HP16451B electrode and HP4284A Precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd.

[Synthesis Example 1]
In a mixed solution of 5.7 g of 40% methylamine aqueous solution, 391.2 g of ultrapure water and 945.7 g of ethanol, 74.9 g of methyltrimethoxysilane (36.7 g in terms of complete hydrolysis condensate), 83. 4 of tetraethoxysilane. 3 g (24.2 g of completely hydrolyzed condensate) and 14.8 g of octamethylcyclotetrasiloxane (compound represented by X = methyl group, Y = methyl group, n = 4 in the general formula (4)), After reacting at 60 ° C. for 4 hours, 2,681 g of propylene glycol monopropyl ether was added, then concentrated under reduced pressure to a total solution volume of 758 g, and then 38 g of 10% propylene glycol monopropyl ether solution of acetic acid was added. Thus, a composition (A-1) having a solid content of 10% was obtained.

[Synthesis Example 2]
In a mixed solution of 6.1 g of 40% methylamine aqueous solution, 418.0 g of ultrapure water and 1,140 g of ethanol, 68.1 g of methyltrimethoxysilane (33.4 g in terms of complete hydrolysis condensate), 83. 3 g (24.2 g of a completely hydrolyzed condensate) and 29.7 g of octamethylcyclotetrasiloxane (compound represented by X = methyl group, Y = methyl group, n = 4 in the general formula (4)), After reacting at 60 ° C. for 2 hours, 3,123 g of propylene glycol monopropyl ether was added, then concentrated under reduced pressure to a total solution volume of 873 g, and then 44 g of 10% propylene glycol monopropyl ether solution of acetic acid was added. Thus, a composition (A-2) having a solid content of 10% was obtained.

[Synthesis Example 3]
In a mixed solution of 40.5 g of 25% tetramethylammonium hydroxide aqueous solution, 769.7 g of ultrapure water and 1,605 g of ethanol, 68.1 g of methyltrimethoxysilane (33.4 g in terms of complete hydrolysis condensate), tetraethoxy 93.7 g of silane (completely hydrolyzed condensate 27.2 g) and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (in formula (4), X = vinyl Group, Y = methyl group, compound represented by n = 4), and reacted at 60 ° C. for 6 hours. Then, 4,811 g of propylene glycol monopropyl ether was added. After concentrating to a solution amount of 778 g, 39 g of 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain solid content. Yuryou 10% of the composition (A-3) was obtained.

[Synthesis Example 4]
In a mixed solution of 41.6 g of 25% tetramethylammonium hydroxide aqueous solution, 516.6 g of ultrapure water and 2,150 g of 2-propanol, 54.5 g of methyltrimethoxysilane (26.7 g in terms of complete hydrolysis condensate), 114.6 g of tetraethoxysilane (33.2 g of completely hydrolyzed condensate) and 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane (in formula (4), X = Compound represented by methyl group, Y = phenyl group, n = 4) 27.2 g was continuously added at 60 ° C. over 2 hours, and further reacted at 60 ° C. for 6 hours, and then propylene glycol monopropyl ether 5,396 g was added, and then concentrated under reduced pressure to a total solution volume of 871 g, followed by acetic acid 10% propylene glycol monopropylene. A pyrrole ether solution (44 g) was added to obtain a composition (A-4) having a solid content of 10%.

[Synthesis Example 5]
In a mixed solution of 25% tetramethylammonium hydroxide aqueous solution 44.9 g, ultrapure water 262 g and 2-propanol 3,965 g, methyltrimethoxysilane 40.9 g (20.0 g in terms of complete hydrolysis condensate), tetraethoxy Silane 125.0 g (completely hydrolyzed condensate 36.3 g), and octaphenylcyclotetrasiloxane (compound represented by X = phenyl group, Y = phenyl group, n = 4 in the general formula (4)) 79.3 g Was added continuously at 60 ° C. over 3 hours, and further reacted at 60 ° C. for 3 hours, followed by the addition of 8,521 g of propylene glycol monopropyl ether, and then concentrated under reduced pressure to a total solution volume of 1,355 g. After that, 68 g of 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a solid content. Yuryou 10% of the composition (A-5) was obtained.

[Comparative Example 1]
In a mixed solution of 5.5 g of 40% methylamine aqueous solution, 375.2 g of ultrapure water and 719.3 g of ethanol, 68.1 g of methyltrimethoxysilane (33.4 g in terms of complete hydrolysis condensate) and tetraethoxysilane 104. 2 g (completely hydrolyzed condensate 30.2 g) was added and reacted at 60 ° C. for 4 hours. Then, 2,195 g of propylene glycol monopropyl ether was added, and then concentrated under reduced pressure to a total solution volume of 636 g. Thereafter, 32 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a composition solution (B-1) having a solid content of 10%.

[Comparative Example 2]
In a mixed solution of 5.7 g of 40% methylamine aqueous solution, 391.2 g of ultrapure water and 953.2 g of ethanol, 74.9 g of methyltrimethoxysilane (36.7 g in terms of complete hydrolysis condensate), 83. 4 of tetraethoxysilane. 3 g (completely hydrolyzed condensate 24.2 g) and dimethyldimethoxysilane 24.0 g (14.9 g in terms of completely hydrolyzed condensate) were added and reacted at 60 ° C. for 4 hours, and then propylene glycol monopropyl ether 2 , 696 g, and then concentrated under reduced pressure to a total solution volume of 766 g, followed by the addition of 38 g of a 10% propylene glycol monopropyl ether solution of acetic acid to give a composition (B-2 )

  As shown in Table 1, according to Synthesis Examples 1 to 5, a composition excellent in chemical resistance is obtained by hydrolytic condensation of the component (B) and the component (A) in the presence of the component (C). It was confirmed that it can be obtained. On the other hand, from Comparative Examples 1 and 2, it was confirmed that the chemical solution resistance and the degassing characteristics deteriorate when the component (B) is not added.

Claims (9)

(A) Compound (A-1) represented by the following general formula (1), compound (A-2) represented by the following general formula (2), and compound represented by the following general formula (3) ( At least one silane compound selected from A-3), and R _a Si (OR ¹ ) _4-a (1)
[Wherein, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2. ]
Si (OR ² ) ₄ (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 , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a monovalent organic group; b and c may be the same or different; R ⁷ represents an oxygen atom, a phenylene group or a group represented by — (CH ₂ ) _m —, m represents an integer of 1 to 6, and d represents 0 or 1. ]
(B) Cyclic silane compound represented by the following general formula (4)

(4)
[Wherein X and Y may be the same or different and each represents a hydrogen atom or a monovalent organic group, and n represents an integer of 2 to 8. ]
(C) The manufacturing method of the composition for film formation including hydrolyzing and condensing in presence of a basic compound. In claim 1,
The manufacturing method of the composition for film formation whose said (B) component is 1-200 weight part with respect to 100 weight part of said (A) component (complete hydrolysis-condensation product conversion). In claim 1 or 2,
The manufacturing method of the composition for film | membrane formation whose density | concentration of the said (A) component and the said (B) component at the time of hydrolysis condensation is 0.1 to 10 weight% (equivalent to a complete hydrolysis condensate). In any of claims 1 to 3,
The amount of the component (C) used is 0.00001 to 1 mol with respect to the total amount of alkoxy groups in the component (A) during hydrolysis condensation and 1 mol in total of the component (B). A method for producing a forming composition. In any of claims 1 to 4,
Furthermore, (D) The manufacturing method of the composition for film formation which hydrolyzes the said (A) component and the said (B) component in presence of water and (E) alcohol whose boiling point is 100 degrees C or less. In claim 5,
(D) The manufacturing method of the film formation composition whose usage-amount of the said water is 0.5-150 mol with respect to 1 mol of total amounts of said (A) component and said (B) component. In any one of Claims 1 thru | or 6.
(F) The manufacturing method of the composition for film formation containing the solvent represented by following General formula (5).
R ⁸ O (CHCH ₃ CH ₂ O) _e R ⁹ (5)
[R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monovalent organic group selected from CH ₃ CO—, and e represents an integer of 1 to 2. ]   A film-forming composition obtained by the method for producing a film-forming composition according to claim 1.   An insulating film forming material comprising the film forming composition according to claim 8.