JP2005133040A - Film-forming composition, silica-based film, method for forming the same and laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming a film having a low specific dielectric constant and excellent in close adhesion, a silica-based film formed by using the film-forming composition, a method for forming the same and a laminated film including the silica-based film. <P>SOLUTION: This film-forming composition contains (A) at least 1 kind of a silane compound selected from a compound (1) expressed by the following general formula (1), a compound (2) expressed by the general formula (2) and a compound (3) expressed by the general formula (3), and (B) a hydrolyzed condensate obtained by performing the hydrolyzing condensation of at least 1 kind of the silane compound selected from a compound (4) expressed by the general formula (4) and a compound (5) expressed by the general formula (5). The general formulae (1): R<SB>a</SB>Si(OR<SP>1</SP>)<SB>4-a</SB>, (2): Si(OR<SP>2</SP>)<SB>4</SB>, (3): 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>. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a film-forming composition, a silica-based film, a method for forming the same, and a laminated film, and more particularly, a film-forming composition having a low relative dielectric constant and excellent adhesion, The present invention relates to a silica-based film formed using a composition, a method for forming the same, and a laminated film including the silica-based film.

As an interlayer insulating film in a semiconductor device, a silica (SiO ₂ ) -based film formed by a vacuum process such as a CVD method or an organic film mainly composed of an organic polymer is used.

  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, has been used. It has become to. Further, with the high integration of semiconductor devices, 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 devices, 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 made of titanium, zirconium, niobium and tantalum. Insulation mainly composed of an oligomer having a number average molecular weight of 500 or more obtained by polycondensing an organometallic compound containing at least one selected element and an organosilicon compound having at least one alkoxyl 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

  In recent semiconductor device manufacturing processes, a CMP (Chemical Mechanical Polishing) process is frequently used for the purpose of planarizing a laminated film. On the other hand, in order to simplify the processing process, it is recently required to form an organic film on a silica film. However, when a process such as CMP is performed on the laminated film of the silica-based film and the organic film, peeling may occur between the silica-based film and the organic film due to insufficient adhesion. .

  An object of the present invention is to provide a film-forming composition that can form a coating film having a low dielectric constant and excellent adhesion to an object to be coated.

  Moreover, the objective of this invention is providing the laminated film containing the silica type film | membrane formed using the said film formation composition, its formation method, and the said silica type film | membrane.

(1) The film forming composition of the present invention comprises:
(A) Selected from compound (1) represented by the following general formula (1), compound (2) represented by the following general formula (2), and compound (3) represented by the following general formula (3) At least one silane compound (hereinafter also referred to as “component (A)”), 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)
[In the formula, 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) At least one silane compound selected from the group consisting of compound (4) represented by the following general formula (4) and compound (5) represented by the following general formula (5) (hereinafter referred to as “(B ) "Ingredients")

・・・・・（４）
〔式中、Ｒ_ｘは炭素−炭素二重結合あるいは炭素−炭素三重結合を有する１価の有機基を示し、Ｒ^８１〜Ｒ^８３は同一でも異なっていてもよく、それぞれ水素原子、ハロゲン原子、ヒドロキシル基、アルコキシル基、または１価の有機基を示し、Ｒ^８１〜Ｒ^８３のすべてが同時に１価の有機基になることはない。〕

(4)
[Wherein, R _x represents a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, and R ^{81 to} R ⁸³ may be the same or different, and each represents a hydrogen atom, a halogen atom, A hydroxyl group, an alkoxyl group, or a monovalent organic group is shown, and all of R ^{81 to} R ⁸³ do not become a monovalent organic group at the same time. ]

・・・・・（５）
〔式中、Ｒ_ｙは炭素−炭素二重結合あるいは炭素−炭素三重結合を有する２価の有機基を示し、Ｒ^９１〜Ｒ^９６は同一でも異なっていてもよく、それぞれ水素原子、ハロゲン原子、ヒドロキシル基、アルコキシル基、または１価の有機基を示し、Ｒ^９１〜Ｒ^９３およびＲ^９４〜Ｒ^９６の組み合わせにおいてすべてが同時に１価の有機基になることはない。〕
を加水分解縮合して得られる加水分解縮合物を含む。

(5)
[Wherein, R _y represents a divalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, and R ^{91 to} R ⁹⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom, A hydroxyl group, an alkoxyl group, or a monovalent organic group is shown, and in the combination of R ^{91 to} R ⁹³ and R ^{94 to} R ⁹⁶ , not all become a monovalent organic group at the same time. ]
The hydrolytic condensate obtained by hydrolytic condensation is included.

  Here, the hydrolysis condensation can be performed in the presence of a metal chelate compound, an acidic compound, or a basic compound.

Here, the R _x may be at least one selected from a vinyl group, an ethynyl group, an allyl group, a phenylvinyl group, a vinylphenyl group, a phenylethynyl group, and an ethynylphenyl group.

から選ばれる少なくとも１種であることができる。 Here, R _y is

It can be at least one selected from

  (2) The method for forming a silica-based film of the present invention comprises applying the film-forming composition to a substrate to form a coating film, and performing heat treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, and oxygen plasma treatment. Curing the coating film by at least one treatment.

  (3) The silica film of the present invention is obtained by the method for forming the silica film.

(4) The laminated film of the present invention comprises (C) a compound (1) represented by the following general formula (1), a compound (2) represented by the following general formula (2), and the following general formula (3). It is obtained by curing a coating film formed using a film-forming composition containing a hydrolysis-condensation product obtained by hydrolysis-condensation of at least one silane compound selected from the compound (3) represented by A first silica-based film (hereinafter also referred to as “(C) film”),
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)
[In the formula, 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. ]
(D) Second obtained by curing a coating film formed using a film-forming composition containing a hydrolysis-condensation product obtained by hydrolysis-condensation of component (A) and component (B). A silica-based film (hereinafter also referred to as “(D) film”),
(E) an organic film having a carbon content of 60% by weight or more (hereinafter also referred to as “(E) film”);
Are laminated.

  Here, the film thickness of the (D) film may be 1/10 to 1/1000 with respect to the film thickness of the (C) film.

  Here, the (E) film includes an organic polymer, and the organic polymer may be at least one polymer selected from the group of the following general formulas (6) to (9).

・・・・・（６）

(6)

・・・・・（７）

(7)

・・・・・（８）

(8)

・・・・・（９）
（式（６）〜（９）中、Ｒ^８〜Ｒ^１２はそれぞれ独立して炭素数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、アリール基、またはハロゲン原子を示し、Ｘは−ＣＱＱ’−（ここで、Ｑ、Ｑ’は同一であっても異なっていてもよく、ハロゲン化アルキル基、アルキル基、水素原子、ハロゲン原子、またはアリール基を示す）で示される基およびフルオレニレン基からなる群から選ばれる少なくとも１種を示し、Ｙは−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−Ｓ−、−ＳＯ_２−、およびフェニレン基の群から選ばれる少なくとも１種を示し、ｅは０または１を表し、ｏ〜ｓは０〜４の整数を表し、ｆは５〜１００モル％、ｇは０〜９５モル％、ｈは０〜９５モル％（ただし、ｆ＋ｇ＋ｈ＝１００モル％）、ｉは０〜１００モル％、ｊは０〜１００モル％（ただし、ｉ＋ｊ＝１００モル％）であり、ＡおよびＢはそれぞれ独立に、下記一般式（１０）〜（１２）で表される２価の芳香族基からなる群から選ばれる少なくとも１種の基を示し、Ｒ^１３，Ｒ^１３’は水素原子または下記一般式（１３）および（１４）で表される芳香族基の群から選ばれる少なくとも１種の基を示し、Ｗ^１，Ｗ^２は下記一般式（１５）および（１６）で表される２価の芳香族基からなる群から選ばれる少なくとも１種の基を示す。）

(9)
(In formulas (6) to (9), R ^{8 to} R ¹² are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or X represents —CQQ′— (wherein Q and Q ′ may be the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom, or an aryl group. ) And at least one selected from the group consisting of fluorenylene groups, Y represents —O—, —CO—, —COO—, —CONH—, —S—, —SO ₂ —, and a phenylene group. E represents 0 or 1, o to s represent an integer of 0 to 4, f represents 5 to 100 mol%, g represents 0 to 95 mol%, and h represents 0. -95 mol% (however, f + g + h = 100 mol) %), I is 0 to 100 mol%, j is 0 to 100 mol% (where i + j = 100 mol%), and A and B are independently represented by the following general formulas (10) to (12). At least one group selected from the group consisting of divalent aromatic groups, wherein R ¹³ and R ^{13 ′} are a hydrogen atom or an aromatic group represented by the following general formulas (13) and (14) At least one group selected from the group, and W ¹ and W ² represent at least one group selected from the group consisting of divalent aromatic groups represented by the following general formulas (15) and (16): Show.)

・・・・・（１０）

(10)

・・・・・（１１）

(11)

・・・・・（１２）
〔式（１０）〜（１２）中、Ｒ^１４、Ｒ^１５、Ｒ^２０およびＲ^２１は独立に、単結合、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−ＣＯＯ−、−ＣＯＮＨ−、−Ｓ−、−ＳＯ_２−、フェニレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、ジフェニルメチリデン基、フルオレニレン基、または式

(12)
[In the formulas (10) to (12), R ¹⁴ , R ¹⁵ , R ²⁰ and R ²¹ are each independently a single bond, —O—, —CO—, —CH ₂ —, —COO—, —CONH—, -S _-, - SO 2 -, a phenylene group, an isopropylidene group, a hexafluoro isopropylidene group, diphenylmethylidene group, fluorenylene group, or a group of the formula,

で表される基を示し、Ｒ^１６〜Ｒ^１８、Ｒ^１９およびＲ^２２〜Ｒ^２４は独立に、炭素原子数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素原子数１〜２０のアルコキシル基、またはアリール基を示し、ｋは０〜３の整数を表し、ｌは２〜３の整数を表し、ｔ〜ｚは独立に０〜４の整数を表す。〕

R ^{16 to} R ¹⁸ , R ¹⁹ and R ^{22 to} R ²⁴ are independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, or a group having 1 to 20 carbon atoms. An alkoxyl group or an aryl group is shown, k represents an integer of 0 to 3, l represents an integer of 2 to 3, and tz independently represents an integer of 0 to 4. ]

・・・・・（１３）

(13)

・・・・・（１４）
〔式（１３）および（１４）中、Ｒ^２５はハロゲン原子、炭素原子数１〜２０の炭化水素基、ハロゲン化アルキル基、炭素原子数１〜２０のアルコキシル基、フェノキシ基またはアリール基を示し、ｍ’は０〜５の整数を表し、ｎ’は０〜７の整数を表す。〕

(14)
[In the formulas (13) and (14), R ²⁵ represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group, an alkoxyl group having 1 to 20 carbon atoms, a phenoxy group or an aryl group. , M ′ represents an integer of 0 to 5, and n ′ represents an integer of 0 to 7. ]

・・・・・（１５）

(15)

・・・・・（１６）
〔式（１５）および（１６）中、Ｒ^２５はハロゲン原子、炭素原子数１〜２０の炭化水素基、ハロゲン化アルキル基、炭素原子数１〜２０のアルコキシル基、フェノキシ基またはアリール基を示し、Ｒ^２６は単結合、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−ＣＯＯ−、−ＣＯＮＨ−、−Ｓ−、−ＳＯ_２−、フェニレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、ジフェニルメチリデン基、メチルフェニルメチリデン基、トリフルオロメチルメチルメチリデン基、トリフルオロメチルフェニルメチリデン基、フルオレニレン基、または式

(16)
[In the formulas (15) and (16), R ²⁵ represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group, an alkoxyl group having 1 to 20 carbon atoms, a phenoxy group or an aryl group. , R ²⁶ represents a single bond, —O—, —CO—, —CH ₂ —, —COO—, —CONH—, —S—, —SO ₂ —, a phenylene group, an isopropylidene group, a hexafluoroisopropylidene group, Diphenylmethylidene, methylphenylmethylidene, trifluoromethylmethylmethylidene, trifluoromethylphenylmethylidene, fluorenylene, or formula

で表される基を示し、上式中Ｒ^２７は、独立に水素原子、炭素原子数１〜４の炭化水素基、またはフェニル基を表し、ａ１、ａ２は独立に０〜４の整数を表し、ａ３は０〜６の整数を表す。）

Wherein R ²⁷ independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group, and a1 and a2 independently represent an integer of 0 to 4. , A3 represents an integer of 0-6. )

  According to the film-forming composition of the present invention, the hydrolysis condensate contains the hydrolysis condensate, and the hydrolysis condensate contains a carbon-carbon double bond or a carbon-carbon triple bond. Can react with other polymers (eg organic polymers). As a result, the silica-based film formed using the film-forming composition reacts with the polymer in the other film in contact with the silica-based film, thereby causing the silica-based film and the other film to react with each other. Adhesion can be improved. Therefore, according to the film forming composition of the present invention, it is possible to form a coating film having a low relative dielectric constant and excellent adhesion to an object to be coated. As a result, for example, when a CMP process is performed on a laminated film of a silica-based film and an organic film formed using the film-forming composition, peeling occurs between the silica-based film and the organic film. Can be prevented.

  Further, for example, when the hydrolysis condensate contains unreacted silanol, the silanol can be condensed with silanol in other silica-based films by heat. Thereby, the adhesiveness of the silica-type film | membrane formed using the said film formation composition, and the other silica-type film | membrane which contact | connects this silica-type film | membrane can further be improved.

  In addition, by forming a silica-based film using the film-forming composition of the present invention, silica having a low relative dielectric constant and excellent adhesion to an organic film that has been considered to have poor adhesion. A system membrane can be obtained. This silica-based film is useful, for example, as a planarizing film or an interlayer insulating film that can be used in the manufacture of semiconductor devices.

  Furthermore, the laminated film of the present invention includes the silica-based film of the present invention as the second silica-based film, thereby improving the adhesion between the organic film and the first silica-based film.

  Hereinafter, the film-forming composition of the present invention, the silica-based film formed using the film-forming composition, the forming method thereof, and the laminated film will be specifically described.

<Film-forming composition (I)>
The film-forming composition (I) of the present invention includes a hydrolysis condensate obtained by hydrolytic condensation of the component (A) and the component (B). In the present application, “hydrolysis” not only means that all of the alkoxyl 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, and further, the silanol group in the component (A) and the silanol group in the component (B) are condensed. -O-Si bond is formed, and it is not necessary that all silanol groups contained in the component (A) and the component (B) are condensed, and a concept including a case where some silanol groups are condensed. is there.

  In the present invention, the complete hydrolysis-condensation product of the component (A) means that the alkoxyl 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.

  Hereafter, each substance used for manufacture of composition (I) for film formation of this invention is demonstrated.

[(A) component]
The component (A) is composed of the compound (1) represented by the following general formula (1), the compound (2) represented by the following general formula (2), and the compound (3) represented by the following general formula (3). At least one silane compound selected from (1).

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 (1) to (3) will be described.

(Compound (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 compound (1) are trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, tri-tert-butoxy. Silane, 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-butoxy Silane, 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, 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-propyltriphenoxy Silane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri -Sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri- iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltri Ethoxy Run, 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-propoxysilane, t-butyltri -N-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyl bird iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, etc .;
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, di-γ-aminopropyldimethoxysilane, di-γ-glycidoxy Propyldimethoxysilane, di-γ-trif Etc. b propyl dimethoxy silane; and the like.

  Preferably, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane Dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, particularly preferably methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyl Dimethoxysilane and dimethyldiethoxysilane. These may be used alone or in combination of two or more.

(Compound (2))
In the general formula (2), the monovalent organic group represented by R ² is the same as the monovalent organic group represented by R and R ¹ in the general formula (1). Mention may be made of organic groups. Specific examples of the compound (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert- Examples include 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 (3))
In the general formula (3), the monovalent organic group represented by R ^{3 to} R ⁶ is the monovalent organic group represented by R and R ¹ in the general formula (1). And the same organic group. Among the compounds (3), as compounds in which R ⁷ in the general formula (3) is an oxygen atom, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy- 3-methyldisiloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-methyldisiloxane, 1,1,1, 3,3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-ethyldisiloxane 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,1,3,3-pe Ntaphenoxy-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-trimethyldishiro Sun, 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, 1,3- Diphenoxy-1,1,3,3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane Examples thereof include siloxane 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 (3), R ⁷ is a group represented by — (CH ₂ ) _m —, and examples thereof include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, and 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-propoxy) Silyl) 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-butoxy Methylsilyl) -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 (3), as the compound in which R ⁷ is a phenylene group, 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-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, 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 (1), a compound (2), and a compound (3) component, and a compound (1)-compound (3) component is 2 types or more, respectively. It can also be used. (A) As a component, it is preferable that it is a hydrolysis-condensation product of a compound (1) and a compound (2) at the point that the storage stability of the composition (I) obtained is favorable.

[Component (B)]
The component (B) is at least one silane compound selected from the group consisting of the compound (4) represented by the following general formula (4) and the compound (5) represented by the following general formula (5).

・・・・・（４）
〔式中、Ｒ_ｘは炭素−炭素二重結合あるいは炭素−炭素三重結合を有する１価の有機基を示し、Ｒ^８１〜Ｒ^８３は同一でも異なっていてもよく、それぞれ水素原子、ハロゲン原子、ヒドロキシル基、アルコキシル基、または１価の有機基を示し、Ｒ^８１〜Ｒ^８３のすべてが同時に１価の有機基になることはない。〕

(4)
[Wherein, R _x represents a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, and R ^{81 to} R ⁸³ may be the same or different, and each represents a hydrogen atom, a halogen atom, A hydroxyl group, an alkoxyl group, or a monovalent organic group is shown, and all of R ^{81 to} R ⁸³ do not become a monovalent organic group at the same time. ]

・・・・・（５）
〔式中、Ｒ_ｙは炭素−炭素二重結合あるいは炭素−炭素三重結合を有する２価の有機基を示し、Ｒ^９１〜Ｒ^９６は同一でも異なっていてもよく、それぞれ水素原子、ハロゲン原子、ヒドロキシル基、アルコキシル基、または１価の有機基を示し、Ｒ^９１〜Ｒ^９３およびＲ^９４〜Ｒ^９６の組み合わせにおいてすべてが同時に１価の有機基になることはない。〕

(5)
[Wherein, R _y represents a divalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, and R ^{91 to} R ⁹⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom, A hydroxyl group, an alkoxyl group, or a monovalent organic group is shown, and in the combination of R ^{91 to} R ⁹³ and R ^{94 to} R ⁹⁶ , not all become a monovalent organic group at the same time. ]

In the general formulas (4) and (5), the monovalent organic groups represented by R ^{81 to} R ⁸³ and R ^{91 to} R ⁹⁶ are represented by R and R ¹ in the general formula (1). And the same organic groups as those shown as the monovalent organic group. R _x can be, for example, at least one selected from a vinyl group, an ethynyl group, an allyl group, a phenylvinyl group, a vinylphenyl group, a phenylethynyl group, and an ethynylphenyl group. As R _y , for example,

から選ばれる少なくとも１種であることができる。

It can be at least one selected from

Specific examples of the compound (4) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri- tert-butoxysilane, vinyltriphenoxysilane, ethynyltrimethoxysilane, ethynyltriethoxysilane, ethynyltri-n-propoxysilane, ethynyltri-iso-propoxysilane, ethynyltri-n-butoxysilane, ethynyltri-sec-butoxysilane, ethynyltri- tert-Butoxysilane, Ethynyltriphenoxysilane, Vinylchlorosilane, Vinyldichlorosilane, Vinyltrichlorosilane, Vinylmethoxysilane, Vinyldimethoxy Run, Vinylethoxysilane, Vinyldiethoxysilane, Vinyldichloromethylsilane, Vinylchlorodimethylsilane, Vinyldimethylmethoxysilane, Vinylmethyldimethoxysilane, Vinyldimethylethoxysilane, Vinylmethyldiethoxysilane, Vinyldimethylhydroxysilane, Ethynylchlorosilane, Ethynyldichlorosilane, ethynyltrichlorosilane, ethynylmethoxysilane, ethynyldimethoxysilane, ethynylethoxysilane, ethynyldiethoxysilane, ethynyldichloromethylsilane, ethynylchlorodimethylsilane, ethynyldimethylmethoxysilane, ethynylmethyldimethoxysilane, ethynyldimethylethoxysilane, Ethynylmethyldiethoxysilane, ethynyldimethylhydroxysilane, divinyldi Toxisilane, divinyldiethoxysilane, divinyldipropoxysilane, divinyldichlorosilane, diethynyldimethoxysilane, diethynyldiethoxysilane, diethynyldipropoxysilane, diethynyldichlorosilane, trivinylmethoxysilane, trivinylethoxysilane, trivinyl There may be mentioned propoxysilane, trivinylchlorosilane, triethynylmethoxysilane, triethynylethoxysilane, triethynylpropoxysilane, triethynylchlorosilane and the like. Preferably vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyldimethylmethoxysilane, vinylmethyldimethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, ethynyltrimethoxysilane, Ethynyltriethoxysilane, ethynyltri-n-propoxysilane, ethynyltri-iso-propoxysilane, ethynyltri-n-propoxysilane, ethynyldimethylmethoxysilane, ethynylmethyldimethoxysilane, diethynyldimethoxysilane, and diethynyldiethoxysilane. These may be used alone or in combination of two or more.
Specific examples of the compound (5) include bis (trimethoxysilyl) ethylene, bis (triethoxysilyl) ethylene, bis (tri-n-propoxysilyl) ethylene, bis (tri-iso-propoxysilyl) ethylene, bis ( Trichlorosilyl) ethylene, bis (dimethylmethoxysilyl) ethylene, bis (dimethylethoxysilyl) ethylene, bis (dimethylchlorosilyl) ethylene, bis (dimethylhydroxysilyl) ethylene, bis (trimethoxysilyl) acetylene, bis (triethoxysilyl) ) Acetylene, bis (tri-n-propoxysilyl) acetylene, bis (tri-iso-propoxysilyl) acetylene, bis (trichlorosilyl) acetylene, bis (dimethylmethoxysilyl) acetylene, bis (dimethylethoxysilyl) Acetylene, bis (dimethylchlorosilyl) acetylene, bis (dimethylhydroxysilyl) acetylene, 1,2-bis [(trimethoxysilyl) vinyl] benzene, 1,3-bis [(trimethoxysilyl) vinyl] benzene, 1, 4-bis [(trimethoxysilyl) vinyl] benzene, 1,2-bis [(trimethoxysilyl) ethynyl] benzene, 1,3-bis [(trimethoxysilyl) ethynyl] benzene, 1,4-bis [( Trimethoxysilyl) ethynyl] benzene, 1,2-bis [(triethoxysilyl) vinyl] benzene, 1,3-bis [(triethoxysilyl) vinyl] benzene, 1,4-bis [(triethoxysilyl) vinyl ] Benzene, 1,2-bis [(triethoxysilyl) ethynyl] benzene, 1,3-bis [(triethoxysilyl) ethynyl] ben 1,4-bis [(triethoxysilyl) ethynyl] benzene, 1,2-bis [(trichlorosilyl) vinyl] benzene, 1,3-bis [(trichlorosilyl) vinyl] benzene, 1,4-bis [(Trichlorosilyl) vinyl] benzene, 1,2-bis [(trichlorosilyl) ethynyl] benzene, 1,3-bis [(trichlorosilyl) ethynyl] benzene, 1,4-bis [(trichlorosilyl) ethynyl] benzene 1,2-bis [(chlorodimethylsilyl) vinyl] benzene, 1,3-bis [(chlorodimethylsilyl) vinyl] benzene, 1,4-bis [(chlorodimethylsilyl) vinyl] benzene, 1,2- Bis [(chlorodimethylsilyl) ethynyl] benzene, 1,3-bis [(chlorodimethylsilyl) ethynyl] benzene, 1,4-bis [(chlorodimethylsilyl) Ethynyl] benzene, 1,2-bis [(methoxydimethylsilyl) vinyl] benzene, 1,3-bis [(methoxydimethylsilyl) vinyl] benzene, 1,4-bis [(methoxydimethylsilyl) vinyl] benzene, 1 , 2-bis [(methoxydimethylsilyl) ethynyl] benzene, 1,3-bis [(methoxydimethylsilyl) ethynyl] benzene, 1,4-bis [(methoxydimethylsilyl) ethynyl] benzene, and the like. Preferably, bis (trimethoxysilyl) ethylene, bis (triethoxysilyl) ethylene, bis (dimethylethoxysilyl) ethylene, bis (trimethoxysilyl) acetylene, bis (triethoxysilyl) acetylene, bis (dimethylmethoxysilyl) acetylene 1,2-bis [(trimethoxysilyl) vinyl] benzene, 1,3-bis [(trimethoxysilyl) vinyl] benzene, 1,4-bis [(trimethoxysilyl) vinyl] benzene, 1,2- Bis [(trimethoxysilyl) ethynyl] benzene, 1,3-bis [(trimethoxysilyl) ethynyl] benzene, 1,4-bis [(trimethoxysilyl) ethynyl] benzene. These may be used alone or in combination of two or more.

  The amount of the component (B) used is preferably 1 to 100 parts by weight, more preferably 2 to 25 parts by weight, based on 100 parts by weight of the component (A) (in terms of complete hydrolysis 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 adhesion cannot be obtained, and 100 parts by weight If it exceeds, applicability at the time of application deteriorates and it becomes difficult to maintain the 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 30 weight%, and it is more preferable that it is 1 to 10 weight%. Here, if the weight is less than 0.1%, the condensation reaction may not proceed sufficiently and a coating solution may not be obtained. 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.

  In addition, the hydrolytic condensation between the component (A) and the component (B) can be performed in the presence of a metal chelate compound, an acidic compound, or a basic compound. Hereinafter, each of the metal chelate compound, the acidic compound, and the basic compound will be described.

(Metal chelate compound)
The metal chelate compound that can be used at the time of the hydrolytic condensation of the component (A) and the component (B) is represented by the following general formula (17).

R ²⁸ _β M (OR ²⁹ ) _α-β (17)
[Wherein R ²⁸ is a chelating agent, M is a metal atom, R ²⁹ is an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, α is the valence of metal M, β is 1 to represents an integer of α. ]

  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.

  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 nato) bis (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 an ethyl acetoacetate) aluminum and a tris (acetylacetonate) 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) 1 or more kinds of such _t is 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 with respect to 100 parts by weight (in terms of complete hydrolysis condensate) of the component (A) and component (B) during hydrolysis condensation. 0.001 to 5 parts by weight. When the use ratio of the metal chelate compound is less than 0.0001 parts by weight, the coating property of the coating film may be inferior, and when it exceeds 10 parts by weight, the crack resistance of the coating film may be lowered. Further, the metal chelate compound may be added in advance to the organic solvent together with the components (A) and (B) at the time of hydrolysis condensation, or may be dissolved or dispersed in water at the time of addition of water. .

  When hydrolyzing and condensing the component (A) and the component (B) in the presence of the metal chelate compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of the components (A) and (B). It is particularly preferred to add 1-10 moles of water. If the amount of water added is less than 0.5 mol, the crack resistance of the coating film may be inferior, and if it exceeds 20 mol, precipitation or gelation of the polymer may occur during hydrolysis and condensation reactions. Moreover, it is preferable that water is added intermittently or continuously.

(Acidic compounds)
Examples of the acidic compound that can be used during the hydrolytic condensation of the component (A) and the component (B) include organic acids and inorganic acids. 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, hydrolyzate of glutaric acid, hydrolyzed maleic anhydride Objects, and the like hydrolyzate 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 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 100 parts by weight (in terms of complete hydrolysis condensate) of the total amount of component (A) and component (B) during hydrolysis condensation. 001 to 5 parts by weight. When the use ratio of the acidic compound is less than 0.0001 part by weight, the coating property of the coating film may be inferior, and when it exceeds 10 parts by weight, the crack resistance of the coating film may be lowered. The acidic compound may be added in advance to the organic solvent together with the components (A) and (B) during the hydrolysis condensation, or may be dissolved or dispersed in water during the addition of water.

  When hydrolyzing and condensing the component (A) and the component (B) in the presence of an acidic compound, it is preferable to use 0.5 to 20 moles of water per mole of the total amount of the components (A) and (B). It is particularly preferred to add 1-10 moles of water. If the amount of water added is less than 0.5 mol, the crack resistance of the coating film may be inferior, and if it exceeds 20 mol, precipitation or gelation of the polymer may occur during hydrolysis and condensation reactions. Moreover, it is preferable that water is added intermittently or continuously.

(Basic compound)
Examples of basic compounds that can be used at the time of hydrolytic condensation of component (A) and component (B) 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, tetra Chill ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, may be mentioned benzyl trimethylammonium hydroxide, choline, and the like. Among these, ammonia, organic amines, and ammonium hydroxides can be mentioned as preferred examples, and tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide are particularly preferable. These basic compounds may be used alone or in combination of two or more.

The amount of the basic compound used is the total amount of alkoxyl groups in the component (A) (groups represented by R ¹ O-group, R ² O-group, R ⁴ O-group and R ⁵ O-group) and ( B) It is usually 0.00001 to 1 mol, preferably 0.00005 to 0.5 mol, per 1 mol of the total of components. If the usage-amount of a basic compound is in the said range, there is little possibility of polymer precipitation or gelatinization during reaction.

  When hydrolyzing and condensing the component (A) and the component (B) in the presence of a basic compound, it is preferable to use 0.5 to 150 mol of water per mol of the total amount of the components (A) and (B). It is particularly preferred to add 0.5 to 130 mol of water. 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, precipitation or gelation of the polymer may occur during hydrolysis and condensation reactions.

  In this case, it is preferable to use alcohol having a boiling point of 100 ° C. or lower together with water. Here, examples of the alcohol having a boiling point of 100 ° C. or lower include methanol, ethanol, n-propanol, and isopropanol. 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.

  Moreover, it is preferable to adjust the pH of the film-forming composition (I) of the present invention to 7 or less after obtaining a hydrolysis-condensation product from the components (A) and (B) in the presence of a basic compound. . As a method for adjusting the pH, 1) a method of adding a pH adjusting agent, 2) a method of distilling a basic compound from the composition under normal pressure or reduced pressure, and 3) bubbling a gas such as nitrogen or argon. (Method to remove basic compound from composition) 4) Method to remove basic compound from composition by ion exchange resin 5) Remove basic compound from system by extraction and washing And the like. 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. The effect that the storage stability of the composition (I) is improved can be obtained by adjusting the pH within the above range with the pH adjusting agent. The amount of the pH adjuster used is an amount that makes the pH of the composition (I) within the above range, and the amount used is appropriately selected.

(Organic solvent)
In the present invention, the components (A) and (B) can be hydrolytically condensed in an organic solvent. Here, the organic solvent is preferably a solvent represented by the following general formula (18).

R ³⁰ O (CHCH ₃ CH ₂ O) _γ R ³¹ (18)
[R ³⁰ and R ³¹ each independently represents a monovalent organic group selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—, and γ represents an integer of 1 to 2. ]
In the general formula (18), examples of the alkyl group having 1 to 4 carbon atoms include the same as those shown as the alkyl group in the general formula (1).

  Specific examples of the organic solvent represented by the general formula (18) include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether. , Propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, di Propylene glycol dipropyl ether, Propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono Propyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol diacetate, etc., especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate are preferable. These can use 1 type (s) or 2 or more types simultaneously. In addition to the solvent represented by the general formula (18), other solvents such as ester solvents and amide solvents may be included to some extent.

  The total solid concentration of the film-forming composition (I) of the present invention is preferably 0.1 to 10% 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 0.1 to 10% 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 (I) of the present invention may further contain 50% by weight or less of the following organic 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 (I) of the present invention may further contain components such as a surfactant and a silane coupling agent.

  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 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 above SH28PA and SH30PA The polymer represented by (19) is particularly preferred.

・・・・・（１９）
〔式中、Ｒ^３２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。〕

(19)
[Wherein, R ³² 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 (equivalent to a complete hydrolysis-condensation product) of the 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.

  In the film-forming composition (I) of the present invention, the content of alcohol having a boiling point of 100 ° C. or less is preferably 20% by weight or less, particularly preferably 5% by weight or less. Alcohol having a boiling point of 100 ° C. or less may be generated 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 preferably removed 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.

<Silica-based membrane>
The film-forming composition (I) 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, a silica-based film can be obtained by baking after applying the film-forming composition (I) of the present invention. Since this silica-based film exhibits a low relative dielectric constant, an interlayer insulating film for a semiconductor device such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM, a protective film such as a surface coat film of a semiconductor device, a multilayer resist It is useful for applications such as an intermediate layer in a semiconductor manufacturing process using a substrate, 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 a silica-based film using the film-forming composition (I) 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.

  Further, the silica-based film of the present invention is formed by coating the film-forming composition (I) of the present invention on a substrate to form a coating film, and heat treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, and oxygen plasma. It can be formed by curing the coating film by at least one treatment.

  In the case of performing the heat treatment, for example, it is dried at room temperature, or is heated and dried at a temperature of about 80 to 600 ° C. for about 5 to 240 minutes. In this case, a hot plate, an oven, a furnace, or the like can be used as a heating means, and a heating atmosphere is performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. Can do. Moreover, in order to control the curing rate of the coating film, it is possible to heat stepwise or select an atmosphere such as nitrogen, air, oxygen, reduced pressure, etc. as necessary. Examples of the electron beam include X-rays and γ-rays. The irradiation time of the electron beam or the ultraviolet ray varies depending on the material and type of the coating film, but is generally 1 to 30 minutes, more preferably 1 to 10 minutes. More preferably, hot plate heating can be used in combination at a temperature of about 80 to 600 ° C. for the purpose of enhancing the effect of electron beams or ultraviolet rays. The oxygen plasma treatment is a treatment in which plasma treatment (for example, a mixed gas of oxygen and argon) is performed in an atmosphere containing oxygen.

<Laminated film>
The laminated film of the present invention is formed by laminating (C) a first silica-based film, (D) a second silica-based film, and (E) an organic film having a carbon content of 60% by weight or more. . In the laminated film of the present invention, specifically, (D) a second silica-based film is formed between (C) the first silica-based film and (E) the organic film. In the laminated film of the present invention, each layer may be laminated on the laminate in the order of (C) the first silica-based film, (D) the second silica-based film, and (E) the organic film. Alternatively, each layer may be laminated on the stack in the order of (E) organic film, (D) second silica film, and (C) first silica film. In addition, the formation method and the curing method of the coating film when forming the films (C) to (E) are the same as the coating method and the curing method of the coating film of the present invention. Can be applied.

  Moreover, in the laminated film of the present invention, the film thickness of the (D) film is preferably 1/10 to 1/1000 with respect to the film thickness of the (C) film, and preferably 1/100 to 1 / 1,000 is more preferable. Here, when it exceeds 1/10 or less than 1/1000, the adhesion between the (D) film and the (C) film and between the (D) film and the (E) film. The adhesion may not be sufficient. Hereinafter, the films (C) to (E) will be described.

[(C) membrane]
(C) The film (first silica-based film) includes a compound (1) represented by the following general formula (1), a compound (2) represented by the following general formula (2), and the following general formula (3). And a film-forming composition (II) containing a hydrolysis-condensation product obtained by hydrolysis-condensation of at least one silane compound selected from the compound (3) represented by Is used to form a coating film (first coating film) and to cure the coating film.

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)
[In the formula, 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. ]
In the formulas (1) to (3), R, R ^{1 to} R ⁷ , a to d, m represent the same configuration as the characters included in the general formulas (1) to (3) indicating the component (A), The same can be applied to each specific example.

  (C) The film can be obtained by using the film forming composition (II) by the same formation method as that of the silica-based film of the present invention described above. The film-forming composition (II) used for forming the film (C) is an organic solvent, colloidal silica, colloidal alumina, as with the film-forming composition (I) of the present invention described above. Further, it may further contain components such as an organic polymer, a surfactant, a silane coupling agent, a radical generator, and a triazene compound. Specific examples of these components include those exemplified as the components contained in the film-forming composition (I) of the present invention described above.

[(D) film]
(D) The 2nd silica type film | membrane which is a film | membrane can form a coating film using the film formation composition (I) of this invention, and can obtain this coating film by hardening.

[(E) membrane]
(E) The organic film which is a film can contain an organic polymer as a main component. This (E) film is preferably polyarylene and / or polyarylene ether, and specifically comprises at least one repeating structural unit selected from the group of the following general formulas (6) to (9). Including polymers.

・・・・・（６）

(6)

・・・・・（７）

(7)

・・・・・（８）

(8)

・・・・・（９）
（式（６）〜（９）中、Ｒ^８〜Ｒ^１２はそれぞれ独立して炭素数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、アリール基、またはハロゲン原子を示し、Ｘは−ＣＱＱ’−（ここで、Ｑ、Ｑ’は同一であっても異なっていてもよく、ハロゲン化アルキル基、アルキル基、水素原子、ハロゲン原子、またはアリール基を示す）で示される基およびフルオレニレン基からなる群から選ばれる少なくとも１種を示し、Ｙは−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−Ｓ−、−ＳＯ_２−、およびフェニレン基の群から選ばれる少なくとも１種を示し、ｅは０または１を表し、ｏ〜ｓは０〜４の整数を表し、ｆは５〜１００モル％、ｇは０〜９５モル％、ｈは０〜９５モル％（ただし、ｆ＋ｇ＋ｈ＝１００モル％）、ｉは０〜１００モル％、ｊは０〜１００モル％（ただし、ｉ＋ｊ＝１００モル％）であり、ＡおよびＢはそれぞれ独立に、下記一般式（１０）〜（１２）で表される２価の芳香族基からなる群から選ばれる少なくとも１種の基を示し、Ｒ^１３，Ｒ^１３’は水素原子または下記一般式（１３）および（１４）で表される芳香族基の群から選ばれる少なくとも１種の基を示し、Ｗ^１，Ｗ^２は下記一般式（１５）および（１６）で表される２価の芳香族基からなる群から選ばれる少なくとも１種の基を示す。）

(9)
(In formulas (6) to (9), R ^{8 to} R ¹² are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or X represents —CQQ′— (wherein Q and Q ′ may be the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom, or an aryl group. ) And at least one selected from the group consisting of fluorenylene groups, Y represents —O—, —CO—, —COO—, —CONH—, —S—, —SO ₂ —, and a phenylene group. E represents 0 or 1, o to s represent an integer of 0 to 4, f represents 5 to 100 mol%, g represents 0 to 95 mol%, and h represents 0. -95 mol% (however, f + g + h = 100 mol) %), I is 0 to 100 mol%, j is 0 to 100 mol% (where i + j = 100 mol%), and A and B are independently represented by the following general formulas (10) to (12). At least one group selected from the group consisting of divalent aromatic groups, wherein R ¹³ and R ^{13 ′} are a hydrogen atom or an aromatic group represented by the following general formulas (13) and (14) At least one group selected from the group, and W ¹ and W ² represent at least one group selected from the group consisting of divalent aromatic groups represented by the following general formulas (15) and (16): Show.)

・・・・・（１０）

(10)

・・・・・（１１）

(11)

・・・・・（１２）
〔式（１０）〜（１２）中、Ｒ^１４、Ｒ^１５、Ｒ^２０およびＲ^２１は独立に、単結合、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−ＣＯＯ−、−ＣＯＮＨ−、−Ｓ−、−ＳＯ_２−、フェニレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、ジフェニルメチリデン基、フルオレニレン基、または式

(12)
[In the formulas (10) to (12), R ¹⁴ , R ¹⁵ , R ²⁰ and R ²¹ are each independently a single bond, —O—, —CO—, —CH ₂ —, —COO—, —CONH—, -S _-, - SO 2 -, a phenylene group, an isopropylidene group, a hexafluoro isopropylidene group, diphenylmethylidene group, fluorenylene group, or a group of the formula,

で表される基を示し、Ｒ^１６〜Ｒ^１８、Ｒ^１９およびＲ^２２〜Ｒ^２４は独立に、炭素原子数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素原子数１〜２０のアルコキシル基、またはアリール基を示し、ｋは０〜３の整数を表し、ｌは２〜３の整数を表し、ｔ〜ｚは独立に０〜４の整数を表す。〕

R ^{16 to} R ¹⁸ , R ¹⁹ and R ^{22 to} R ²⁴ are independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, or a group having 1 to 20 carbon atoms. An alkoxyl group or an aryl group is shown, k represents an integer of 0 to 3, l represents an integer of 2 to 3, and tz independently represents an integer of 0 to 4. ]

・・・・・（１３）

(13)

・・・・・（１４）
〔式（１３）および（１４）中、Ｒ^２５はハロゲン原子、炭素原子数１〜２０の炭化水素基、ハロゲン化アルキル基、炭素原子数１〜２０のアルコキシル基、フェノキシ基またはアリール基を示し、ｍ’は０〜５の整数を表し、ｎ’は０〜７の整数を表す。〕

(14)
[In the formulas (13) and (14), R ²⁵ represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group, an alkoxyl group having 1 to 20 carbon atoms, a phenoxy group or an aryl group. , M ′ represents an integer of 0 to 5, and n ′ represents an integer of 0 to 7. ]

・・・・・（１５）

(15)

・・・・・（１６）
〔式（１５）および（１６）中、Ｒ^２５はハロゲン原子、炭素原子数１〜２０の炭化水素基、ハロゲン化アルキル基、炭素原子数１〜２０のアルコキシル基、フェノキシ基またはアリール基を示し、Ｒ^２６は単結合、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−ＣＯＯ−、−ＣＯＮＨ−、−Ｓ−、−ＳＯ_２−、フェニレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、ジフェニルメチリデン基、メチルフェニルメチリデン基、トリフルオロメチルメチルメチリデン基、トリフルオロメチルフェニルメチリデン基、フルオレニレン基、または式

(16)
[In the formulas (15) and (16), R ²⁵ represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group, an alkoxyl group having 1 to 20 carbon atoms, a phenoxy group or an aryl group. , R ²⁶ represents a single bond, —O—, —CO—, —CH ₂ —, —COO—, —CONH—, —S—, —SO ₂ —, a phenylene group, an isopropylidene group, a hexafluoroisopropylidene group, Diphenylmethylidene, methylphenylmethylidene, trifluoromethylmethylmethylidene, trifluoromethylphenylmethylidene, fluorenylene, or formula

で表される基を示し、上式中Ｒ^２７は、独立に水素原子、炭素原子数１〜４の炭化水素基、またはフェニル基を表し、ａ１、ａ２は独立に０〜４の整数を表し、ａ３は０〜６の整数を表す。）
（Ｅ）膜の炭素含有量は６０重量％以上である。

Wherein R ²⁷ independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group, and a1 and a2 independently represent an integer of 0 to 4. , A3 represents an integer of 0-6. )
(E) The carbon content of the film is 60% by weight or more.

(Compound (6))
The polymer (compound (6)) represented by the general formula (6) is polymerized in the presence of a catalyst system containing a transition metal compound, for example, using the compound (6) represented by the following general formula (20) as a monomer. Can be manufactured.

・・・・・（２０）
〔式中、Ｒ^８，Ｒ^９はそれぞれ独立して炭素数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、アリール基、またはハロゲン原子、Ｘは−ＣＱＱ’−（ここで、Ｑ、Ｑ’は同一であっても異なっていてもよく、ハロゲン化アルキル基、アルキル基、水素原子、ハロゲン原子、またはアリール基を示す）で示される基およびフルオレニレン基からなる群から選ばれる少なくとも１種を示し、ｏ，ｐは０〜４の整数を表し、Ｚはアルキル基、ハロゲン化アルキル基またはアリール基を示す。〕
上記一般式（２０）中のＸを構成するＱ，Ｑ’のうち、アルキル基としては、メチル基、エチル基、ｉ−プロピル基、ｎ−プロピル基、ブチル基、ペンチル基、ヘキシル基など；ハロゲン化アルキル基としては、トリフルオロメチル基、ペンタフルオロエチル基など；アリールアルキル基としては、ベンジル基、ジフェニルメチル基など；アリール基としては、フェニル基、ビフェニル基、トリル基、ペンタフルオロフェニル基などを挙げることができる。

(20)
[Wherein R ⁸ and R ⁹ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and X is —CQQ A group represented by '-(wherein Q and Q' may be the same or different and each represents a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom, or an aryl group) and a fluorenylene group. At least one selected from the group consisting of o and p represents an integer of 0 to 4, and Z represents an alkyl group, a halogenated alkyl group or an aryl group. ]
Of Q and Q ′ constituting X in the general formula (20), examples of the alkyl group include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a butyl group, a pentyl group, and a hexyl group; Examples of halogenated alkyl groups include trifluoromethyl groups and pentafluoroethyl groups; examples of arylalkyl groups include benzyl groups and diphenylmethyl groups; examples of aryl groups include phenyl groups, biphenyl groups, tolyl groups, and pentafluorophenyl groups. And so on.

As the Z constituting a -OSO 2 _Z in the above formula (20), as the alkyl group, methyl group, ethyl group; Examples of the halogenated alkyl group, a trifluoromethyl group, etc. pentafluoroethyl group; an aryl Examples of the group include a phenyl group, a biphenyl group, a p-tolyl group, and a p-pentafluorophenyl group. X in the general formula (20) is preferably a divalent group represented by the following general formulas (21) to (26). Of these, the fluorenylene group represented by the general formula (26) is more preferable.

-C (CH ₃ ) _2- (21)
-C (CF ₃ ) _2- (22)
-C (CF ₃ ) (C ₆ H ₅ )-(23)
—CH (CH ₃ ) — (24)
-C (C ₆ H ₅ ) _2- (25)

・・・・・（２６）
上記一般式（２０）に示す化合物（６）（モノマー）の具体例としては、例えば、２，２−ビス（４−メチルスルフォニロキシフェニル）ヘキサフルオロプロパン、 ビス（４−メチルスルフォニロキシフェニル）メタン、 ビス（４−メチルスルフォニロキシフェニル）ジフェニルメタン、 ２，２−ビス（４−メチルスルフォニロキシ−３−メチルフェニル）ヘキサフルオロプロパン、 ２，２−ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）ヘキサフルオロプロパン、 ２，２−ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、 ２，２−ビス（４−メチルスルフォニロキシフェニル）プロパン、 ２，２−ビス（４−メチルスルフォニロキシ−３−メチルフェニル）プロパン、 ２，２−ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）ロパン、 ２，２−ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）プロパン、 ２，２−ビス（４−メチルスルフォニロキシ−３−フルオロフェニル）プロパン、 ２，２−ビス（４−メチルスルフォニロキシ−３，５−ジフルオロフェニル）プロパン、 ２，２−ビス（４−トリフルオロメチルスルフォニロキシフェニル）プロパン、 ２，２−ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）プロパン、２，２−ビス（４−フェニルスルフォニロキシフェニル）プロパン、 ２，２−ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）プロパン、 ２，２−ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）プロパン、 ２，２−ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）プロパン、 ２，２−ビス（４−フェニルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、 ２，２−ビス（ｐ−トリルスルフォニロキシフェニル）プロパン、 ２，２−ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）プロパン、 ２，２−ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）プロパン、 ２，２−ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）プロパン、 ２，２−ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）プロパン、 ２，２−ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）プロパン、 ２，２−ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）プロパン、 ビス（ｐ−トリルスルフォニロキシ−３−フルオロフェニル）プロパン、ビス（ｐ−トリルスルフォニロキシ−３，５−ジフルオロフェニル）プロパン ９，９−ビス（４−メチルスルフォニロキシフェニル）フルオレン、 ９，９−ビス（４−メチルスルフォニロキシ−３−メチルフェニル）フルオレン、 ９，９−ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）フルオレン、 ９，９−ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）フルオレン、 ９，９−ビス（４−メチルスルフォニロキシ−３−フェニルフェニル）フルオレン、 ビス（４−メチルスルフォニロキシ−３−メチルフェニル）ジフェニルメタン、 ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）ジフェニルメタン、ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）ジフェニルメタン、 ビス（４−メチルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、 ビス（４−メチルスルフォニロキシ−３，５−ジフルオロフェニル）ジフェニルメタン、 ９，９−ビス（４−メチルスルフォニロキシ−３−フルオロフェニル）フルオレン、 ９，９−ビス（４−メチルスルフォニロキシ−３，５−ジフルオロフェニル）フルオレン、 ビス（４−メチルスルフォニロキシフェニル）メタン、 ビス（４−メチルスルフォニロキシ−３−メチルフェニル）メタン、 ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）メタン、 ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）メタン、 ビス（４−メチルスルフォニロキシフェニル）トリフルオロメチルフェニルメタン、 ビス（４−メチルスルフォニロキシフェニル）フェニルメタン、２，２−ビス（４−トリフルオロメチルスルフォニロキシフェニル）ヘキサフルオロプロパン、 ビス（４−トリフルオロメチルスルフォニロキシフェニル）メタン、 ビス（４−トリフルオロメチルスルフォニロキシフェニル）ジフェニルメタン、 ２，２−ビス（４−トリフルオロメチルスルフォニロキシ−３−メチルフェニル）ヘキサフルオロプロパン、 ２，２−ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）ヘキサフルオロプロパン、 ２，２−ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、 ９，９−ビス（４−トリフルオロメチルスルフォニロキシフェニル）フルオレン、 ９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３−メチルフェニル）フルオレン、 ９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジメチルフェニル）フルオレン、９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）フルオレン、 ９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３−フェニルフェニル）フルオレン、 ビス（４−トリフルオロメチルスルフォニロキシ−３−メチルフェニル）ジフェニルメタン、 ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジメチルフェニル）ジフェニルメタン、ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）ジフェニルメタン、 ビス（４−トリフルオロメチルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、 ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジフルオロフェニル）ジフェニルメタン、 ９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３−フルオロフェニル）フルオレン、 ９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジフルオロフェニル）フルオレン、 ビス（４−トリフルオロメチルスルフォニロキシフェニル）メタン、 ビス（４−トリフルオロメチルスルフォニロキシ−３−メチルフェニル）メタン、 ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジメチルフェニル）メタン、 ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）メタン、 ビス（４−トリフルオロメチルスルフォニロキシフェニル）トリフルオロメチルフェニルメタン、 ビス（４−トリフルオロメチルスルフォニロキシフェニル）、 ２，２−ビス（４−フェニルスルフォニロキシフェニル）ヘキサフルオロプロパン、 ビス（４−フェニルスルフォニロキシフェニル）メタン、 ビス（４−フェニルスルフォニロキシフェニル）ジフェニルメタン、 ２，２−ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）ヘキサフルオロプロパン、 ２，２−ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）ヘキサフルオロプロパン、 ２，２−ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、 ９，９−ビス（４−フェニルスルフォニロキシフェニル）フルオレン、 ９，９−ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）フルオレン、 ９，９−ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）フルオレン、 ９，９−ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）フルオレン、 ９，９−ビス（４−フェニルスルフォニロキシ−３−フェニルフェニル）フルオレン、 ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）ジフェニルメタン、 ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）ジフェニルメタン、 ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）ジフェニルメタン、 ビス（４−フェニルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、 ビス（４−フェニルスルフォニロキシ−３，５−ジフルオロフェニル）ジフェニルメタン、 ９，９−ビス（４−フェニルスルフォニロキシ−３−フルオロフェニル）フルオレン、 ９，９−ビス（４−フェニルスルフォニロキシ−３，５−ジフルオロフェニル）フルオレン、 ビス（４−フェニルスルフォニロキシフェニル）メタン、 ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）メタン、 ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）メタン、 ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）メタン、 ビス（４−フェニルスルフォニロキシフェニル）トリフルオロメチルフェニルメタン、 ビス（４−フェニルスルフォニロキシフェニル）フェニルメタン、 ２，２−ビス（ｐ−トリルスルフォニロキシフェニル）ヘキサフルオロプロパン、 ビス（ｐ−トリルスルフォニロキシフェニル）メタン、 ビス（ｐ−トリルスルフォニロキシフェニル）ジフェニルメタン、 ２，２−ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）ヘキサフルオロプロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）ヘキサフルオロプロパン、 ２，２−ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、 ９，９−ビス（ｐ−トリルスルフォニロキシフェニル）フルオレン、 ９，９−ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）フルオレン、 ９，９−ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）フルオレン、 ９，９−ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）フルオレン、 ９，９−ビス（ｐ−トリルスルフォニロキシ−３−フェニルフェニル）フルオレン、 ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）ジフェニルメタン、 ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）ジフェニルメタン、ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）ジフェニルメタン、 ビス（ｐ−トリルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、 ビス（ｐ−トリルスルフォニロキシ−３，５−ジフルオロフェニル）ジフェニルメタン、 ９，９−ビス（ｐ−トリルスルフォニロキシ−３−フルオロフェニル）フルオレン、 ９，９−ビス（ｐ−トリルスルフォニロキシ−３，５−ジフルオロフェニル）フルオレン、 ビス（ｐ−トリルスルフォニロキシフェニル）メタン、 ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）メタン、 ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）メタン、 ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）メタン、 ビス（ｐ−トリルスルフォニロキシフェニル）トリフルオロメチルフェニルメタン、 ビス（ｐ−トリルスルフォニロキシフェニル）フェニルメタンなどを挙げることができる。本発明においては、上記一般式（２０）に示す化合物（６）を２種以上共重合することもできる。

(26)
Specific examples of the compound (6) (monomer) represented by the general formula (20) include, for example, 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane, bis (4-methylsulfonyloxyphenyl) ) Methane, bis (4-methylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy- 3-propenylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxyphenyl) propane, 2 , 2-bis (4-methylsulfonyloxy-3-methylphenyl) propane, 2 2-bis (4-methylsulfonyloxy-3-propenylphenyl) ropane, 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (4-methylsulfone) Phonyloxy-3-fluorophenyl) propane, 2,2-bis (4-methylsulfonyloxy-3,5-difluorophenyl) propane, 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) propane, 2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxyphenyl) propane, 2,2-bis (4-phenylsulfonyloxy) -3-methylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-propenyl phen Propane, 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, 2,2- Bis (p-tolylsulfonyloxyphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) Propane, 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-bis ( p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3- Propenylphenyl) propane, bis (p-tolylsulfonyloxy-3-fluorophenyl) propane, bis (p-tolylsulfonyloxy-3,5-difluorophenyl) propane 9,9-bis (4-methylsulfonyloxy) Phenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9- Bis (4-methylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-methylsulfonyloxy-3-methylphenyl) Diphenylmethane, bis (4-methylsulfonyloxy-3,5-dimethylphenol Nyl) diphenylmethane, bis (4-methylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-difluoro Phenyl) diphenylmethane, 9,9-bis (4-methylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4- Methyl sulfonyloxyphenyl) methane, bis (4-methylsulfonyloxy-3-methylphenyl) methane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-methylsulfonyloxy) -3-propenylphenyl) methane, bi (4-methylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-methylsulfonyloxyphenyl) phenylmethane, 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane, bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) hexafluoropropane 2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane , 9, 9 -Bis (4-trifluoromethylsulfonyloxyphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyl) Loxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3- Phenylphenyl) fluorene, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-trifluoromethyl) Sulfonoxy-3-propenyl fe ) Diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4- Trifluoromethylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4-trifluoromethylsulfonyloxyphenyl) Methane, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-trifluoromethylsulfonyloxy) -3-propenyl Nyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-trifluoromethylsulfonyloxyphenyl), 2,2-bis (4-phenylsulfonyloxyphenyl) hexa Fluoropropane, bis (4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2 , 2-bis (4-phenylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-phenylsulfoni Xylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9- Bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-phenylsulfonyloxy-3-methylphenyl) Diphenylmethane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-fluorophenyl) Diphenylmethane, bis (4- Phenylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3,5 -Difluorophenyl) fluorene, bis (4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxy-3-methylphenyl) methane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) Methane, bis (4-phenylsulfonyloxy-3-propenylphenyl) methane, bis (4-phenylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-phenylsulfonyloxyphenyl) phenylmethane, 2,2 -Bis (p-tolylsulfonyl) Xylphenyl) hexafluoropropane, bis (p-tolylsulfonyloxyphenyl) methane, bis (p-tolylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) hexafluoro Propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9, 9-bis (p-tolylsulfonyloxyphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3,5 -Dimethylphenyl) fluorene, 9,9-bis (p-tolylsulfur Phonyloxy-3-propenylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-phenylphenyl) fluorene, bis (p-tolylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (p-tolyl) Sulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (p-tolyl) Sulphonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (p-tolylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3,5- Difluorophenyl) fluorene Bis (p-tolylsulfonyloxyphenyl) methane, bis (p-tolylsulfonyloxy-3-methylphenyl) methane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) methane, bis (p -Tolylsulfonyloxy-3-propenylphenyl) methane, bis (p-tolylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (p-tolylsulfonyloxyphenyl) phenylmethane, and the like. In the present invention, two or more compounds (6) represented by the general formula (20) may be copolymerized.

  In the present invention, at least one compound (6) represented by the general formula (20) and at least one compound selected from the group consisting of compounds represented by the following general formula (27) and general formula (28) are used in combination. It may be polymerized.

・・・・・（２７）
〔式中、Ｒ^１０，Ｒ^１１はそれぞれ独立して炭素数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、アリール基、またはハロゲン原子、Ｒ^３３，Ｒ^３４は、−ＯＳＯ_２Ｚ（ここで、Ｚはアルキル基、ハロゲン化アルキル基またはアリール基を示す。）、塩素原子、臭素原子、またはヨウ素原子を示し、Ｙは−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−Ｓ−、−ＳＯ_２−、およびフェニレン基の群から選ばれた少なくとも１種を示し、ｅは０または１を表し、ｑ，ｒは０〜４の整数を表す。］

(27)
[Wherein R ¹⁰ and R ¹¹ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, R ³³ , R ³⁴ represents —OSO ₂ Z (wherein Z represents an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom, and Y represents —O—, —CO—, At least one selected from the group of —COO—, —CONH—, —S—, —SO ₂ —, and a phenylene group, e represents 0 or 1, q and r each represents an integer of 0 to 4; Represent. ]

In the general formula (27), among R ¹⁰ and R ¹¹ , the halogen atom is a fluorine atom, etc. The monovalent organic group is an alkyl group, a methyl group, an ethyl group, etc., as a halogenated alkyl group, Examples of the allyl group such as a trifluoromethyl group and pentafluoroethyl group include a propenyl group, and examples of the aryl group include a phenyl group and a pentafluorophenyl group. Further, as Z constituting -OSO ₂ Z in R ³³ and R ³⁴ , as an alkyl group, a methyl group, an ethyl group, etc., as a halogenated alkyl group, as a trifluoromethyl group, as an aryl group, as a phenyl group, Examples thereof include a p-tolyl group and a p-fluorophenyl group.

  Examples of the compound represented by the general formula (27) include 4,4′-dimethylsulfonyloxybiphenyl, 4,4′-dimethylsulfonyloxy-3,3′-dipropenylbiphenyl, and 4,4′-dibromo. Biphenyl, 4,4′-diiodobiphenyl, 4,4′-dimethylsulfonyloxy-3,3′-dimethylbiphenyl, 4,4′-dimethylsulfonyloxy-3,3′-difluorobiphenyl, 4,4 '-Dimethylsulfonyloxy-3,3', 5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl, 4,4-methylsulfonyloxyoctafluorobiphenyl, 3,3'-diallyl- 4,4′-bis (4-fluorobenzenesulfonyloxy) biphenyl, 4,4′-dichloro-2,2′-trifluoro Methylbiphenyl, 4,4′-dibromo-2,2′-trifluoromethylbiphenyl, 4,4′-diiodo-2,2′-trifluoromethylbiphenyl, bis (4-chlorophenyl) sulfone, 4,4′- Examples include dichlorobenzophenone and 2,4-dichlorobenzophenone. The compounds represented by the general formula (27) can be used singly or in combination of two or more.

・・・・・（２８）
〔式中、Ｒ^１２は、炭素数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、アリール基、またはハロゲン原子、Ｒ^３５，Ｒ^３６は、−ＯＳＯ_２Ｚ（ここで、Ｚはアルキル基、ハロゲン化アルキル基、またはアリール基を示す。）、塩素原子、臭素原子、またはヨウ素原子を示し、ｓは０〜４の整数を表す。〕

(28)
[Wherein, R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and R ³⁵ and R ³⁶ represent —OSO ₂ Z (wherein Z represents an alkyl group, a halogenated alkyl group, or an aryl group), a chlorine atom, a bromine atom, or an iodine atom, and s represents an integer of 0-4. ]

In the general formula (28), among R ¹² , as a halogen atom, a fluorine atom, etc., a monovalent organic group, an alkyl group, a methyl group, an ethyl group, etc., a halogenated alkyl group, such as trifluoromethyl Groups, pentafluoroethyl groups, etc., allyl groups, propenyl groups, etc., aryl groups, phenyl groups, pentafluorophenyl groups, and the like. Further, as Z constituting -OSO ₂ Z in R ³⁵ and R ³⁶ , as an alkyl group, a methyl group, an ethyl group, etc., as a halogenated alkyl group, as a trifluoromethyl group, as an aryl group, as a phenyl group, Examples thereof include a p-tolyl group and a p-fluorophenyl group.

  Examples of the compound represented by the general formula (28) include o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, and 2,3-dibromo. Toluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4-dimethylsulfonyloxy Benzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene, 2,4-diiodotoluene, 3, 5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichloro Toluene, 2,6-dibromotoluene, 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4- Dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzotrifluoride, 1,3-dibromo-2, 4,5,6-tetrafluorobenzene, 2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4-dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3 , 5-Dibromophenol, 3,5-dichloro-t-but Cycyloxyphenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid 2,4-dichloromethyl benzoate, methyl 3,5-dichlorobenzoate, methyl 3,5-dibromobenzoate, methyl 2,4-dibromobenzoate, tert-butyl 2,4-dichlorobenzoate, 3, , 5-dichlorobenzoic acid-t-butyl, 2,4-dibromobenzoic acid-t-butyl, 3,5-dibromobenzoic acid-t-butyl, etc., preferably m-dichlorobenzene, 2, 4-dichlorotoluene, 3,5-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dichlorobenzophenone, 2,4- Such as dichlorophenoxybenzene. The compounds represented by the general formula (28) can be used singly or in combination of two or more.

  The proportion of the repeating structural unit in the compound (6) is as follows. In the general formula (6), f is 5 to 100 mol%, preferably 5 to 95 mol%, and g is 0 to 95 mol%, preferably 0 to 90 mol%. Mol% and h are 0 to 95 mol%, preferably 0 to 90 mol% (provided that f + g + h = 100 mol%). If f is less than 5 mol% (g or h exceeds 95 mol%), the solubility of the polymer in an organic solvent may be poor.

  The catalyst used in producing the compound (6) is preferably a catalyst system containing a transition metal compound, and as this catalyst system, (i) a transition metal salt and a ligand, or a ligand is coordinated. A transition metal (salt) and (ii) a reducing agent are essential components, and a “salt” may be added to increase the polymerization rate. Here, transition metal salts include nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate, palladium compounds such as palladium chloride, palladium bromide and palladium iodide, iron chloride and iron bromide. And iron compounds such as iron iodide and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferred.

  Examples of the ligand include triphenylphosphine, 2,2′-bipyridine, 1,5-cyclooctadiene, 1,3-bis (diphenylphosphino) propane, and the like. 2,2′-bipyridine is preferred. The said ligand can be used individually by 1 type or in combination of 2 or more types. Furthermore, as the transition metal (salt) in which the ligand is coordinated in advance, for example, nickel chloride 2-triphenylphosphine, nickel bromide 2-triphenylphosphine, nickel iodide 2-triphenylphosphine, nickel nitrate 2 -Triphenylphosphine, nickel chloride 2,2'-bipyridine, nickel bromide 2,2'-bipyridine, nickel iodide 2,2'-bipyridine, nickel nitrate 2,2'-bipyridine, bis (1,5-cyclo Octadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like can be mentioned, but nickel chloride 2-triphenylphosphine, nickel chloride 2,2 '-Bipyridine is preferred.

  Examples of the reducing agent that can be used in such a catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium, and the like, and zinc and manganese are preferable. These reducing agents can be used after being more activated by bringing them into contact with an acid or an organic acid. “Salts” that can be used in such a catalyst system include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, potassium fluoride, potassium chloride, bromide. Examples thereof include potassium compounds such as potassium, potassium iodide, and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate. Sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide are preferred.

  The proportion of each component used in such a catalyst system is such that the transition metal salt or transition metal (salt) coordinated with a ligand is represented by the general formula (20), the general formula (27), and the general formula. It is 0.0001-10 mol normally with respect to 1 mol of total amounts of the compound shown by (28), Preferably it is 0.01-0.5 mol. When the amount is less than 0.0001 mol, the polymerization reaction does not proceed sufficiently. On the other hand, when the amount exceeds 10 mol, the molecular weight may decrease. In such a catalyst system, when a transition metal salt and a ligand are used, the proportion of the ligand used is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the transition metal salt. It is. If the amount is less than 0.1 mol, the catalytic activity becomes insufficient. On the other hand, if the amount exceeds 100 mol, the molecular weight decreases. The ratio of the reducing agent used in the catalyst system is the total amount of the compound represented by the general formula (20), the compound represented by the general formula (27) and the compound represented by the general formula (28) 1 It is 0.1-100 mol normally with respect to mol, Preferably it is 1-10 mol. When the amount is less than 0.1 mol, the polymerization does not proceed sufficiently. On the other hand, when the amount exceeds 100 mol, purification of the resulting polymer may be difficult.

  Further, when “salt” is used in the catalyst system, the use ratio is represented by the compound represented by the general formula (20), the compound represented by the general formula (27) and the general formula (28). The amount is usually 0.001 to 100 mol, preferably 0.01 to 1 mol, relative to 1 mol of the total amount of compounds to be formed. If the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient. On the other hand, if the amount exceeds 100 mol, purification of the resulting polymer may be difficult.

  Examples of the polymerization solvent that can be used in the present invention include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, γ-butyrolactone, γ- Butyrolactam can be mentioned, and tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone are preferable. These polymerization solvents are preferably used after sufficiently dried. The concentration of the total amount of the compound represented by the general formula (20), the compound represented by the general formula (27) and the compound represented by the general formula (28) in the polymerization solvent is usually 1 to 100% by weight. , Preferably 5 to 40% by weight. Moreover, the polymerization temperature at the time of superposing | polymerizing the said polymer is 0-200 degreeC normally, Preferably it is 50-80 degreeC. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours. In addition, the weight average molecular weight of polystyrene conversion of the said compound (6) is 1,000-1,000,000 normally.

(Compound (7))
The polymer represented by the general formula (7) (compound (7)) is produced, for example, by polymerizing a monomer containing the compounds represented by the following general formulas (29) to (31) in the presence of a catalyst system. be able to.

・・・・・（２９）
〔式中、Ｒ^１０，Ｒ^１１はそれぞれ独立して炭素数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、アリール基またはハロゲン原子、Ｘは−ＣＱＱ’−（ここでＱ，Ｑ’は同一であっても異なっていてもよく、ハロゲン化アルキル基、アルキル基、水素原子、ハロゲン原子またはアリール基を示す）で示される基およびフルオレニレン基からなる群から選ばれる少なくとも１種を示し、ｏ、ｐは０〜４の整数を表し、Ｒ^３７，Ｒ^３８は水酸基、ハロゲン原子、−ＯＭ’基（Ｍ’はアルカリ金属である）からなる群から選ばれる少なくとも１種を示す。〕

(29)
[Wherein, R ¹⁰ and R ¹¹ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group or a halogen atom, and X is —CQQ ′. -(Wherein Q and Q ′ may be the same or different and each represents a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) and a group consisting of a fluorenylene group At least one selected, o and p represent an integer of 0 to 4, R ³⁷ and R ³⁸ are selected from the group consisting of a hydroxyl group, a halogen atom, and an —OM ′ group (M ′ is an alkali metal). At least one species is shown. ]

  Specific examples of the compound (monomer) represented by the general formula (29) include, for example, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) methane, and bis (4-hydroxyphenyl). Diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-) 3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy) -3-propenylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) Nyl) propane, 2,2-bis (4-hydroxy-3-fluorophenyl) propane, 2,2-bis (4-hydroxy-3,5-difluorophenyl) propane, 2,2-bis (4-chlorophenyl) Hexafluoropropane, bis (4-chlorophenyl) methane, bis (4-chlorophenyl) diphenylmethane, 2,2-bis (4-chloro-3-methylphenyl) hexafluoropropane, 2,2-bis (4-chloro-3) -Propenylphenyl) hexafluoropropane, 2,2-bis (4-chloro-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-chlorophenyl) propane, 2,2-bis (4-chloro) -3-methylphenyl) propane, 2,2-bis (4-chloro-3-propenylphenyl) propane, 2 2-bis (4-chloro-3,5-dimethylphenyl) propane, 2,2-bis (4-chloro-3-fluorophenyl) propane, 2,2-bis (4-chloro-3,5-difluorophenyl) ) Propane, 2,2-bis (4-chlorophenyl) hexafluoropropane, bis (4-bromophenyl) methane, bis (4-bromophenyl) diphenylmethane, 2,2-bis (4-bromo-3-methylphenyl) Hexafluoropropane, 2,2-bis (4-bromo-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-bromo-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis ( 4-bromophenyl) propane, 2,2-bis (4-bromo-3-methylphenyl) propane, 2,2-bis (4-bromo-3- Propenylphenyl) propane, 2,2-bis (4-bromo-3,5-dimethylphenyl) propane, 2,2-bis (4-bromo-3-fluorophenyl) propane, 2,2-bis (4-bromo) -3,5-difluorophenyl) propane, bis (4-fluorophenyl) methane, bis (4-fluorophenyl) diphenylmethane, 2,2-bis (4-fluoro-3-methylphenyl) hexafluoropropane, 2,2 -Bis (4-fluoro-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-fluoro-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-fluorophenyl) propane, 2,2-bis (4-fluoro-3-methylphenyl) propane, 2,2-bis (4-fluoro-3-propenyl) Phenyl) propane, 2,2-bis (4-fluoro-3,5-dimethylphenyl) propane, 2,2-bis (4-fluoro-3-fluorophenyl) propane, 2,2-bis (4-fluoro-) 3,5-difluorophenyl) propane and the like. In the bisphenol compound, a hydroxyl group may be substituted with a -OM 'group (M' is an alkali metal) with a basic compound containing sodium, potassium, or the like. In the present invention, two or more compounds represented by the general formula (29) can be copolymerized.

・・・・・（３０）
〔式中、Ｒ^１０，Ｒ^１１はそれぞれ独立して炭素数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、アリール基、またはハロゲン原子、Ｒ^３９，Ｒ^４０は水酸基、ハロゲン原子、−ＯＭ’基（Ｍ’はアルカリ金属である）からなる群から選ばれる少なくとも１種を示し、Ｙは−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−Ｓ−、−ＳＯ_２−およびフェニレン基の群から選ばれた少なくとも１種を示し、ｅは０または１を表し、ｑ，ｒは０〜４の整数を表す。］

(30)
[Wherein, R ¹⁰ and R ¹¹ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, R ³⁹ , R ⁴⁰ represents at least one selected from the group consisting of a hydroxyl group, a halogen atom, and an —OM ′ group (M ′ is an alkali metal), and Y represents —O—, —CO—, —COO—, —CONH—, At least one selected from the group of —S—, —SO ₂ — and a phenylene group is shown, e represents 0 or 1, and q and r each represents an integer of 0 to 4. ]

  Examples of the compound represented by the general formula (30) include 4,4′-dichlorobiphenyl, 4,4′-dibromobiphenyl, 4,4′-difluorobiphenyl, 4,4′-diiodobiphenyl, and 4,4. '-Dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-dipropenylbiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-diethylbiphenyl 4,4′-dimethylhydroxy-3,3 ′, 5,5′-tetrafluorobiphenyl, 4,4′-dibromooctafluorobiphenyl, 4,4-dihydroxyoctafluorobiphenyl, 3,3′-diallyl-4 , 4′-bis (4-hydroxy) biphenyl, 4,4′-dichloro-2,2′-trifluoromethylbiphenyl, 4,4 -Dibromo-2,2'-trifluoromethylbiphenyl, 4,4'-diiodo-2,2'-trifluoromethylbiphenyl, bis (4-chlorophenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (4 -Chlorophenyl) ether, bis (4-hydroxyphenyl) ether, 4,4'-dichlorobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dichlorobenzophenone, 2,4-dihydroxybenzophenone and the like. In the bisphenol compound, a hydroxyl group may be substituted with a -OM 'group (M' is an alkali metal) with a basic compound containing sodium, potassium, or the like. The compounds represented by the general formula (30) can be used singly or in combination of two or more.

・・・・・（３１）
〔式中、Ｒ^１２は炭素数１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、アリール基，またはハロゲン原子を示し、Ｒ^３５，Ｒ^３６は−ＯＳＯ_２Ｚ（ここで、Ｚはアルキル基、ハロゲン化アルキル基、またはアリール基を示す。）、塩素原子、臭素原子、またはヨウ素原子を示し、ｓは０〜４の整数を表す。〕

(31)
[Wherein, R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and R ³⁵ and R ³⁶ represent —OSO ₂ Z (wherein Z represents an alkyl group, a halogenated alkyl group, or an aryl group), a chlorine atom, a bromine atom, or an iodine atom, and s represents an integer of 0-4. ]

  Examples of the compound represented by the general formula (31) include 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2,3-dihydroxytoluene, 2,5-dihydroxytoluene, 2 , 6-dihydroxytoluene, 3,4-dihydroxytoluene, 3,5-dihydroxytoluene, o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene 2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3, 4-dimethylsulfonyloxybenzene, m-dichlorobenzene, m-dibromo , M-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene, 2,4-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromo Toluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxy Toluene, 2,4-dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5 -Diiodobenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluoride Lobenzene, 2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4-dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3, 5-dichloro-t-butoxycarbonyloxyphenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, methyl 2,4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, methyl 3,5-dibromobenzoate, methyl 2,4-dibromobenzoate, 2,4-dichlorobenzoate Acid-t-butyl, 3,5-dichlorobenzoate-t-butyl, 2,4-dibromobenzoate-t-butyl, Mention may also be made of tert-butyl 3,5-dibromobenzoate. In the bisphenol compound, a hydroxyl group may be substituted with a —OM ′ group (M ′ is an alkali metal) with a basic compound containing sodium, potassium, or the like. The compounds represented by the general formula (31) can be used singly or in combination of two or more. The ratio of the repeating structural unit in the compound (7) represented by the general formula (7) is as follows. 100 mol%).

  As a synthesis method of the compound (7) represented by the general formula (7), for example, it can be obtained by heating a bisphenol compound and a dihalogenated compound in a solvent in the presence of an alkali metal compound. The bisphenol compound and the dihalogenated compound are used in an amount of 45 to 55 mol%, preferably 48 to 52 mol%, and the dihalogenated compound is 55 to 45 mol%, preferably 52 to 48 mol%. When the proportion of the bisphenol compound used is less than 45 mol% or exceeds 55 mol%, the molecular weight of the polymer is hardly increased and the coatability of the coating film may be inferior. Examples of the alkali metal compound used in this case include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium hydride, hydrogenated Examples include potassium, lithium hydride, metallic sodium, metallic potassium, metallic lithium and the like. These may be used alone or in combination of two or more. The usage-amount of an alkali metal compound is 100-400 mol% normally with respect to a bisphenol compound, Preferably it is 100-250 mol%. In order to promote the reaction, metal copper, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous sulfate, Cocatalysts such as cupric sulfate, cuprous acetate, cupric acetate, cuprous formate, and cupric formate may be used. The usage-amount of this promoter is 1-50 mol% normally with respect to a bisphenol compound, Preferably it is 1-30 mol%.

  Examples of the solvent used in the reaction include pyridine, quinoline, benzophenone, diphenyl ether, dialkoxybenzene (the alkoxy group has 1 to 4 carbon atoms), trialkoxybenzene (the alkoxy group has 1 to 4 carbon atoms), diphenyl sulfone, Dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrofuran, tetrahydrothiophene, sulfolane, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, dimethylformamide, Dimethylacetamide and the like can be used. These may be used alone or in combination of two or more. The reaction concentration when synthesizing the compound (7) represented by the general formula (7) is 2 to 50% by weight based on the weight of the monomer, and the reaction temperature is 50 to 250 ° C. Moreover, in order to remove the metal salt and unreacted monomer generated at the time of polymer synthesis, the reaction solution is filtered, or the reaction solution is reprecipitated with a solvent which is a poor solvent for the polymer, or washed with an acidic or alkaline aqueous solution. Is preferred. Thus, the weight average molecular weight by GPC method of the compound (7) obtained is 500-500,000 normally, Preferably it is 800-100,000.

(Compound (8))
The polymer represented by the general formula (8) (compound (8)) is, for example, at least one compound selected from the group consisting of compounds represented by the following general formula (32) and general formula (33); It can be obtained by polymerizing at least one compound selected from the group consisting of compounds represented by the following general formula (34) and general formula (35) in the presence of a catalyst.

・・・・・（３２）

... (32)

・・・・・（３３）
〔式中、Ｒ^１４〜Ｒ^１９およびｋ，ｔ，ｕ，ｖ，ｗは上記一般式（１０）および上記一般式（１１）に関して定義した通りである。〕

(33)
[Wherein, R ^{14 to} R ¹⁹ and k, t, u, v, and w are as defined for the general formula (10) and the general formula (11). ]

・・・・・（３４）

(34)

・・・・・（３５）
〔式中、Ｒ^１９〜Ｒ^２４およびｌ，ｗ，ｘ，ｙ，ｚは上記一般式（１１）および上記一般式（１２）に関して定義した通りであり、Ｘ’はハロゲン原子を示す。〕

(35)
[Wherein, R ^{19 to} R ²⁴ and l, w, x, y, z are as defined in relation to the above general formula (11) and the above general formula (12), and X ′ represents a halogen atom. ]

  Examples of the compound represented by the general formula (32) include 4,4′-diethynylbiphenyl, 3,3′-diethynylbiphenyl, 3,4′-diethynylbiphenyl, and 4,4′-diethynyldiphenyl ether. 3,3'-diethynyl diphenyl ether, 3,4'-diethynyl diphenyl ether, 4,4'-diethynyl benzophenone, 3,3'-diethynyl benzophenone, 3,4'-diethynyl benzophenone, 4,4 ' -Diethynyldiphenylmethane, 3,3'-diethynyldiphenylmethane, 3,4'-diethynyldiphenylmethane, 4,4'-diethynylbenzoic acid phenyl ester, 3,3'-diethynylbenzoic acid phenyl ester, 3 , 4'-diethynyl benzoic acid phenyl ester, , 4'-diethynylbenzanilide, 3,3'-diethynylbenzanilide, 3,4'-diethynylbenzanilide, 4,4'-diethynyldiphenyl sulfide, 3,3'-diethynyldiphenyl sulfide, 3 , 4'-diethynyl diphenyl sulfide, 4,4'-diethynyl diphenyl sulfone, 3,3'-diethynyl diphenyl sulfone, 3,4'-diethynyl diphenyl sulfone, 2,4,4'-triethynyl diphenyl ether, 9,9-bis (4-ethynylphenyl) fluorene, 4,4 "-diethynyl-p-terphenyl, 4,4" -diethynyl-m-terphenyl, 4,4 "-diethynyl-o-terphenyl, etc. These compounds may be used alone or in combination of two or more.

  Examples of the compound represented by the general formula (33) include 1,2-diethynylbenzene, 1,3-diethynylbenzene, 1,4-diethynylbenzene, 2,5-diethynyltoluene, 3,4, and the like. -Diethynyl toluene etc. can be mentioned. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously.

  Examples of the compound represented by the general formula (34) include 1,2-bis (2-bromophenoxy) benzene, 1,2-bis (2-iodophenoxy) benzene, 1,2-bis (3-bromo). Phenoxy) benzene, 1,2-bis (3-iodophenoxy) benzene, 1,2-bis (4-bromophenoxy) benzene, 1,2-bis (4-iodophenoxy) benzene, 1,3-bis (2 -Bromophenoxy) benzene, 1,3-bis (2-iodophenoxy) benzene, 1,3-bis (3-bromophenoxy) benzene, 1,3-bis (3-iodophenoxy) benzene, 1,3-bis (4-Bromophenoxy) benzene, 1,3-bis (4-iodophenoxy) benzene, 1,4-bis (3-bromophenoxy) benzene, 1,4-bis (3 Iodophenoxy) benzene, 1,4-bis (2-bromophenoxy) benzene, 1,4-bis (2-iodophenoxy) benzene, 1,4-bis (4-bromophenoxy) benzene, 1,4-bis ( 4-iodophenoxy) benzene, 1- (2-bromobenzoyl) -3- (2-bromophenoxy) benzene, 1- (2-iodobenzoyl) -3- (2-iodophenoxy) benzene, 1- (3- Bromobenzoyl) -3- (3-bromophenoxy) benzene, 1- (3-iodobenzoyl) -3- (3-iodophenoxy) benzene, 1- (4-bromobenzoyl) -3- (4-bromophenoxy) Benzene, 1- (4-iodobenzoyl) -3- (4-iodophenoxy) benzene, 1- (3-bromobenzoyl) -4- (3-bromo Phenoxy) benzene, 1- (3-iodobenzoyl) -4- (3-iodophenoxy) benzene, 1- (4-bromobenzoyl) -4- (4-bromophenoxy) benzene, 1- (4-iodobenzoyl) -4- (4-iodophenoxy) benzene, 2,2'-bis (2-bromophenoxy) benzophenone, 2,2'-bis (2-iodophenoxy) benzophenone, 2,4'-bis (2-bromophenoxy) ) Benzophenone, 2,4′-bis (2-iodophenoxy) benzophenone, 4,4′-bis (2-bromophenoxy) benzophenone, 4,4′-bis (2-iodophenoxy) benzophenone, 2,2′- Bis (3-bromophenoxy) benzophenone, 2,2′-bis (3-iodophenoxy) benzophenone, 2,4 ′ Bis (3-bromophenoxy) benzophenone, 2,4′-bis (3-iodophenoxy) benzophenone, 4,4′-bis (3-bromophenoxy) benzophenone, 4,4′-bis (3-iodophenoxy) benzophenone 2,2′-bis (4-bromophenoxy) benzophenone, 2,2′-bis (4-iodophenoxy) benzophenone, 2,4′-bis (4-bromophenoxy) benzophenone, 2,4′-bis ( 4-iodophenoxy) benzophenone, 4,4′-bis (4-bromophenoxy) benzophenone, 4,4′-bis (4-iodophenoxy) benzophenone, 2,2′-bis (2-bromobenzoyl) benzophenone, 2, , 2′-bis (2-iodobenzoyl) benzophenone, 2,4′-bis (2-bromo) Nzoyl) benzophenone, 2,4′-bis (2-iodobenzoyl) benzophenone, 4,4′-bis (2-bromobenzoyl) benzophenone, 4,4′-bis (2-iodobenzoyl) benzophenone, 2,2 ′ -Bis (3-bromobenzoyl) benzophenone, 2,2'-bis (3-iodobenzoyl) benzophenone, 2,4'-bis (3-bromobenzoyl) benzophenone, 2,4'-bis (3-iodobenzoyl) Benzophenone, 4,4′-bis (3-bromobenzoyl) benzophenone, 4,4′-bis (3-iodobenzoyl) benzophenone, 2,2′-bis (4-bromobenzoyl) benzophenone, 2,2′-bis (4-Iodobenzoyl) benzophenone, 2,4′-bis (4-bromobenzoyl) benzof Enone, 2,4′-bis (4-iodobenzoyl) benzophenone, 4,4′-bis (4-bromobenzoyl) benzophenone, 4,4′-bis (4-iodobenzoyl) benzophenone, 3,4′-bis (2-bromophenoxy) diphenyl ether, 3,4'-bis (2-iodophenoxy) diphenyl ether, 3,4'-bis (3-bromophenoxy) diphenyl ether, 3,4'-bis (3-iodophenoxy) diphenyl ether, 3,4′-bis (4-bromophenoxy) diphenyl ether, 3,4′-bis (4-iodophenoxy) diphenyl ether, 4,4′-bis (2-bromophenoxy) diphenyl ether, 4,4′-bis (2 -Iodophenoxy) diphenyl ether, 4,4'-bis (3-bromo Enoxy) diphenyl ether, 4,4′-bis (3-iodophenoxy) diphenyl ether, 4,4′-bis (4-bromophenoxy) diphenyl ether, 4,4′-bis (4-iodophenoxy) diphenyl ether, 3,4 ′ -Bis (2-bromobenzoyl) diphenyl ether, 3,4'-bis (2-iodobenzoyl) diphenyl ether, 3,4'-bis (3-bromobenzoyl) diphenyl ether, 3,4'-bis (3-iodobenzoyl) Diphenyl ether, 3,4'-bis (4-bromobenzoyl) diphenyl ether, 3,4'-bis (4-iodobenzoyl) diphenyl ether, 4,4'-bis (2-bromobenzoyl) diphenyl ether, 4,4'-bis (2-Iodobenzoyl) diphenyl Ether, 4,4′-bis (3-bromobenzoyl) diphenyl ether, 4,4′-bis (3-iodobenzoyl) diphenyl ether, 4,4′-bis (4-bromobenzoyl) diphenyl ether, 4,4′-bis (4-iodobenzoyl) diphenyl ether, 2,2′-bis (4-chlorophenyl) diphenylmethylidene, 2,2′-bis (4-iodophenyl) diphenylmethylidene, 2,2′-bis (4-bromophenyl) ) Diphenylmethylidene, 2,2′-bis (3-chlorophenyl) diphenylmethylidene, 2,2′-bis (3-iodophenyl) diphenylmethylidene, 2,2′-bis (3-bromophenyl) diphenylmethyl Redene, 9,9-bis (4-chlorophenyl) fluorene, 9,9-bis (4-iodophene) L) fluorene, 9,9-bis (4-bromophenyl) fluorene, 9,9-bis (3-chlorophenyl) fluorene, 9,9-bis (3-iodophenyl) fluorene, 9,9-bis (3- Bromophenyl) fluorene, 4,4 "-dichloro-m-terphenyl, 4,4" -diiodo-m-terphenyl, 4,4 "-dibromo-m-terphenyl, 4,4" -dichloro-p- Examples include terphenyl, 4,4 "-diiodo-p-terphenyl, 4,4" -dibromo-p-terphenyl, and the like. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously.

  Examples of the compound represented by the general formula (35) include 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-diiodobenzene, 1,3-diiodo. Benzene, 1,4-diiodobenzene, 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene, 2,3-dichlorotoluene, 2,4-dichlorotoluene, 2,5-dichloro Toluene, 2,6-dichlorotoluene, 3,4-dichlorotoluene, 2,3-diiodotoluene, 2,4-diiodotoluene, 2,5-diiodotoluene, 2,6-diiodotoluene, 3, 4-diiodotoluene, 2,3-dibromotoluene, 2,4-dibromotoluene, 2,5-dibromotoluene, 2,6-dibromotoluene, 3,4-dibro Or the like can be mentioned toluene. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously.

  In the present invention, the compound (8) is a compound represented by the general formula (32) and / or a compound represented by the general formula (33), a compound represented by the general formula (34) and / or Produced by polymerizing a compound represented by the general formula (35) in the presence of a catalyst. At this time, a compound represented by the general formula (32) and / or a compound represented by the general formula (33) And the use ratio of the compound represented by the general formula (34) and / or the compound represented by the general formula (35) is such that the total amount of the latter compound is 0. It is 8 to 1.2 mol, preferably 0.9 to 1.1 mol, particularly preferably 0.95 to 1.05. When the total amount of the latter compounds is less than 0.8 mol or exceeds 1.2 mol, the molecular weight of the resulting polymer is unlikely to increase.

  In the production of the compound (8), it is preferable to polymerize the compounds represented by the general formulas (32) to (35) in the presence of a catalyst containing a transition metal compound. Furthermore, a catalyst containing a transition metal compound and a basic compound is more preferable, and a catalyst composed of the following components (a), (b) and (c) is particularly preferable.

(A) a substance that binds to a palladium salt and palladium as a ligand or can form a complex (including complex ions) by supplying a group (atomic group) that binds as a ligand (hereinafter referred to as a ligand) Formed body), or palladium complex (additional ligand-forming body may be added if necessary)
(B) Monovalent copper compound (c) Basic compound Among the components (a), examples of the palladium salt include palladium chloride, palladium bromide, palladium iodide and the like. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously. Here, the use ratio of the palladium salt is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol with respect to 1 mol of the total amount of the compounds represented by the general formulas (32) to (35). 1 mole. If the amount is less than 0.0001 mol, polymerization may not proceed sufficiently. On the other hand, if it exceeds 10 mol, purification may be difficult.

  Among the components (a), examples of the ligand-forming body include triphenylphosphine, tri-o-tolylphosphine, tricyanophenylphosphine, and tricyanomethylphosphine. Of these, triphenylphosphine is preferable. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously. The proportion of the ligand-former used is preferably 0.0004 to 50 mol, more preferably 0.004 to 5 with respect to 1 mol of the total amount of the compounds represented by the general formulas (32) to (35). Is a mole. If the amount is less than 0.0004 mol, polymerization may not proceed sufficiently, while if it exceeds 50 mol, purification may be difficult.

  Among the components (a), examples of the palladium complex include dichlorobis (triphenylphosphine) palladium, dibromobis (triphenylphosphine) palladium, diiodobis (triphenylphosphine) palladium, dichlorobis (tri-o-tolylphosphine) palladium, dichlorobis ( Tricyanophenylphosphine) palladium, dichlorobis (tricyanomethylphosphine) palladium, dibromobis (tri-o-tolylphosphine) palladium, dibromobis (tricyanophenylphosphine) palladium, dibromobis (tricyanomethylphosphine) palladium, diiodobis (tri-o -Tolylphosphine) palladium, diiodobis (tricyanophenylphosphine) palladium, diiodobis (tricyanomethyl) Sufin) palladium, tetrakis (triphenylphosphine) palladium, tetrakis (tri -o- tolyl phosphine) palladium, tetrakis (tricyanophenylphosphine) palladium, tetrakis (tricyanomethylphosphine) palladium. Of these, dichlorobis (triphenylphosphine) palladium and tetrakis (triphenylphosphine) palladium are preferable. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously. Here, the usage ratio of the palladium complex is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol with respect to 1 mol of the total amount of the compounds represented by the general formulas (32) to (35). Is a mole. If the amount is less than 0.0001 mol, polymerization may not proceed sufficiently, while if it exceeds 10 mol, purification may be difficult.

  (B) As a monovalent copper compound, copper chloride (I), copper bromide (I), copper iodide (I) etc. can be mentioned, for example. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously. Here, (b) the usage ratio of the monovalent copper compound is preferably 0.0001 to 10 mol, more preferably, relative to 1 mol of the total amount of the compounds represented by the general formulas (32) to (35). Is 0.001-1 mol. If the amount is less than 0.0001 mol, polymerization may not proceed sufficiently, while if it exceeds 10 mol, purification may be difficult.

  (C) Examples of basic compounds include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, Examples thereof include diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, diethylamine, ammonia, n-butylamine, and imidazole. Of these, diethylamine, piperidine, and n-butylamine are preferable. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously. Here, the proportion of the basic compound (c) used is preferably 1 to 1000 mol, more preferably 1 to 100 mol, per 1 mol of the total amount of the compounds represented by the general formulas (32) to (35). Is a mole. If it is less than 1 mol, polymerization may not proceed sufficiently, while if it exceeds 100 mol, it is not economical.

(Compound (9))
The polymer represented by the general formula (9) (compound (9)) is produced, for example, by reacting the following general formula (36) with the compounds represented by the following general formulas (37) and (38). Can do.

・・・・・（３６）

(36)

・・・・・（３７）

(37)

・・・・・（３８）
（式（３６）〜（３８）中、Ｒ^１３，Ｒ^１３’は水素原子または上記一般式（１３）および（１４）で表される芳香族基の群から選ばれる少なくとも１種の基を示し、Ｗ^１，Ｗ^２は上記一般式（１５）および（１６）で表される２価の芳香族基からなる群から選ばれる少なくとも１種の基を示す。）

(38)
(In the formulas (36) to (38), R ¹³ and R ^{13 ′} represent a hydrogen atom or at least one group selected from the group of aromatic groups represented by the general formulas (13) and (14). W ¹ and W ² represent at least one group selected from the group consisting of divalent aromatic groups represented by the general formulas (15) and (16).

  The compound (9) represented by the general formula (9) is obtained by performing a Diels-Alder reaction between the cyclopentadienone group of the general formula (36) and the acetylene groups of the general formulas (37) and (38). be able to.

  The number average molecular weight (Mn) of the compound (9) is more than 3,500, preferably more than 4,000, preferably less than 6,400, more preferably less than 6,000. Further, the weight average molecular weight (Mw) of the compound (9) is larger than 500, preferably larger than 8,000, preferably smaller than 15,000, more preferably smaller than 12,000. Furthermore, compound (9) preferably has a polydispersity (Mw / Mn) of less than about 2.5, more preferably less than about 2.3.

  In the step of forming the film (E) of the present invention, a solvent can be used as necessary. The polymerization solvent is not particularly limited. For example, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene and diethylbenzene; Ether solvents such as diethyl ether, tetrahydrofuran, dioxane, diglyme, anisole, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-heptanone, cyclohexanone, cyclpentanone; acetic acid Ester solvents such as methyl, ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate and γ-butyrolactone; N N- dimethylformamide, N, N- dimethylacetamide may be mentioned amide solvents such as N- methyl-2-pyrrolidone. These solvents are preferably used after sufficiently dried and deoxygenated. These solvents may be used alone or in combination of two or more. The monomer (polymerization component) concentration in the polymerization solvent is preferably 1 to 80% by weight, more preferably 5 to 60% by weight. The polymerization temperature is preferably 0 to 150 ° C, more preferably 5 to 100 ° C. The polymerization time is preferably 0.5 to 100 hours, more preferably 1 to 40 hours.

  In order to form the film (E) in the present invention, the film-forming composition (III) is prepared by dissolving at least one polymer selected from the group of the compounds (6) to (9) in an organic solvent. The film-forming composition (III) is applied to a substrate to form a coating film (third coating film), and the coating film is heated. Thereby, (E) film | membrane is obtained. Here, as an organic solvent which can be used for the film-forming composition (III), for example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2, 2, 4 -Aliphatic hydrocarbon solvents such as trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethyl benzene , I-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene and other aromatic hydrocarbon solvents; 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, 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, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarb Monoalcohol solvents such as alcohol, diacetone alcohol, cresol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexane Polyhydric alcohol solvents such as diol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; 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, trimethyl Ketone solvents such as lunananone, cyclohexanone, cyclopentanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone 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, dimethyldioxane, 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, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy Triglycol, 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 Ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, I-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, N-Nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene acetate Recall monoethyl ether, diethylene glycol acetate 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 acetate Monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-lactic acid Ester solvents such as butyl, lactate n-amyl, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N- Nitrogen-containing solvents such as dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydro Examples thereof include sulfur-containing solvents such as thiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more.

  In the present invention, the film-forming composition (III) further comprises colloidal silica, (E) an organic polymer other than the compounds (6) to (9) used for forming the film, a surfactant, a silane cup Components such as a ring agent, a radical generator, a compound containing a polymerizable double bond, and a polymerizable triple bond may be added. Examples of organic polymers other than the compounds (6) to (9) include polymers having a sugar chain structure, vinylamide polymers, (meth) acrylic polymers, aromatic vinyl compound polymers, dendrimers, polyimides, Examples thereof include polyamic acid, polyamide, polyquinoxaline, polyoxadiazole, a fluorine-based polymer, and a polymer having a polyalkylene oxide structure.

  Examples of the polymer having a polyalkylene oxide structure include polymers having a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, a polybutylene oxide structure, and the like.

  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 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-ethoxycarboni -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) 3-aminopropyltrimethoxysilane, N- bis (oxyethylene) -3-aminopropyltriethoxysilane, poly (vinyl main methoxypropane siloxane), poly (vinyl ethoxy siloxane) 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, diisopropylperoxydi. Carbonate, 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-methoxybutylperoxide Oxy) dicarbonate, t-butyl peroxyneodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide Oxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethyl) Hexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m- Toluoyl and benzoyl peroxide, ben Yl 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, Organic peroxides such as 3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide; dibenzyl, 2,3-dimethyl-2,3-diphenylbutane , Α, α'-dimethoxy-α, α'-diphenylbibenzyl, α, α'-diphenyl-α-methoxybibenzyl, α, α'-diphenyl-α, α'-dimethoxybibenzyl, α, α ' -Dimethoxy-α, α'-dimethylbibenzyl, α, α'-dimethoxybibenzyl, 3,4 Dimethyl-3,4-diphenyl -n- hexane, can be mentioned bibenzyl compounds such as 2,2,3,3-tetraphenyl succinonitrile. These may be used alone or in combination of two or more.

  Examples of the compound containing a polymerizable double bond include allylbenzene, diallylbenzene, triallylbenzene, allyloxybenzene, diallyloxybenzene, triallyloxybenzene, α, ω-diallyloxyalkanes, α, ω -Diallylalkenes, α, ω-diallylalkenes, allylamine, diallylamine, triallylamine, N-allylphthalimide, N-allylpyromellitimide, N, N'-diallylurea, triallyl isocyanurate, 2,2'-diallyl Allyl compounds such as bisphenol A; styrene, divinylbenzene, trivinylbenzene, stilbene, propenylbenzene, dipropenylbenzene, tripropenylbenzene, phenyl vinyl ketone, methyl styryl ketone, α, α'-divinylalkane , Α, α′-divinylalkenes, α, α′-divinylalkynes, α, α′-divinyloxyalkanes, α, α′-divinylalkenes, α, α′-divinylalkynes, α, α′-diacryloxyalkanes, α, α′-diacrylalkenes, α, α′-diacrylalkenes, α, α′-dimethacryloxyalkanes, α, α′-dimethacrylalkenes, Vinyl compounds such as α, α'-dimethacrylalkenes, bisacryloxybenzene, trisacryloxybenzene, bismethacryloxybenzene, trismethacryloxybenzene, N-vinylphthalimide, N-vinylpyromellitimide; 2,2 ' -Polyarylene ethers containing diallyl-4,4'-biphenol, including 2,2'-diallyl-4,4'-biphenol Or the like can be mentioned polyarylene. These may be used alone or in combination of two or more. Examples of the compound containing a polymerizable triple bond include compounds represented by the following general formula (39) and general formula (40), or any one of them.

・・・・・（３９）

(39)

・・・・・（４０）
〔式（３９）および（４０）中、Ｒ^４１は炭素数１〜３のアルキル基を示し、Ｒ^４２はｖ’価の芳香族基を示し、Ｒ^４３はｗ’価の芳香族基を示し、ｕ’は０〜５の整数を表し、ｖ’およびｗ’はそれぞれ独立に２〜６の整数を表す。〕

(40)
[In the formulas (39) and (40), R ⁴¹ represents an alkyl group having 1 to 3 carbon atoms, R ⁴² represents a v′-valent aromatic group, and R ⁴³ represents a w′-valent aromatic group. , U ′ represents an integer of 0 to 5, and v ′ and w ′ each independently represents an integer of 2 to 6. ]

In the general formula (39), examples of the alkyl group having 1 to 3 carbon atoms represented by R ⁴¹ include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

  Other compounds containing polymerizable triple bonds include ethynylbenzene, bis (trimethylsilylethynyl) benzene, tris (trimethylsilylethynyl) benzene, tris (trimethylsilylethynyl) benzene, bis (trimethylsilylethynylphenyl) ether, trimethylsilylethynylbenzene, etc. Can be mentioned. These compounds containing a polymerizable triple bond may be used alone or in combination of two or more.

  The total solid concentration of the film-forming composition (III) is preferably 1 to 30% by weight, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 1 to 30% by weight, the film thickness of the coating film is in an appropriate range, and the storage stability is further improved.

  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 following evaluation was performed with respect to the silica-type film | membrane formed using the composition (reaction liquids 1-4) obtained in the Example.

[Evaluation methods]
(Adhesion)
Ten stud pins were fixed using epoxy resin on the wafer on which the silica-based film was formed in Examples 1 to 4 described later, and dried at 150 ° C. for 1 hour. Subsequently, the stud pin was subjected to a pull-out test using the Sebastian method, and the adhesion was evaluated according to the following criteria.

○: With 10 stud pins, no peeling occurred at the interface between the silicon wafer and the coating film. X: With any 10 stud pins, peeling occurred at the interface between the silicon wafer and the coating film (relative dielectric constant).
Using each of reaction solutions 1 to 5 obtained in Synthesis Examples 1 to 5 described later, a coating film is formed by applying each of them on an 8-inch silicon wafer by spin coating, and then in the atmosphere at 80 ° C. for 5 minutes, The wafer was heated in a nitrogen atmosphere at 200 ° C. for 5 minutes and further under vacuum at 400 ° C. for 1 hour to obtain a colorless and transparent silica-based film.

  Aluminum was vapor-deposited on the wafer on which the silica-based film was formed 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.

[(D) Preparation of film-forming composition]
(Synthesis Example 1)
In a quartz separable flask, in a mixed solution of 15.84 g of 40% methylamine aqueous solution, 725.72 g of ultrapure water and 1,541.7 g of ethanol, 136.23 g of methyltrimethoxysilane (in terms of complete hydrolysis condensate) 66.75 g), 166.66 g of tetraethoxysilane (48.33 g in terms of complete hydrolysis condensate) and 29.65 g of vinyltrimethoxysilane (in terms of complete hydrolysis condensate 15.71 g) were added, and the mixture was heated at 60 ° C. for 2 hours. Reacted. Next, after cooling to room temperature, 42.85 g of a 60% nitric acid aqueous solution was added to this solution and stirred at room temperature for 1 hour. After adding 392.37 g of propylene glycol monopropyl ether to this solution, the solution was concentrated under reduced pressure until the total amount of the solution was 1,307.9 g. Next, 65.40 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a reaction solution 1 having a solid content of 10%. Further, a silica-based film was formed using the reaction solution 1, and the relative dielectric constant of the silica-based film was measured. As a result, the relative dielectric constant was 2.51.

(Synthesis Example 2)
In a quartz separable flask, 163.48 g of methyltrimethoxysilane (80.11 g in terms of complete hydrolysis condensate), 91.34 g of tetramethoxysilane (35.62 g in terms of complete hydrolysis condensate), and ethynyltrimethoxysilane 29 .24 g (15.50 g in terms of complete hydrolysis condensate) was dissolved in 590.17 g of propylene glycol monoethyl ether, and then stirred with a three-one motor to stabilize the solution temperature at 50 ° C. Next, 178.40 g of ultrapure water in which 0.64 g of maleic acid was dissolved was added to the solution over 1 hour. Then, after making it react at 50 degreeC for 1 hour, propylene glycol monoethyl ether 393.69g was added, and the reaction liquid was cooled to room temperature. Next, the reaction solution was concentrated under reduced pressure to a total solution amount of 13,312.3 g to obtain a reaction solution 2 having a solid content of 10%. Further, a silica-based film was formed using the reaction solution 2, and the relative dielectric constant of the silica-based film was measured. As a result, the relative dielectric constant was 2.97.

(Synthesis Example 3)
In a quartz separable flask, 136.23 g of methyltrimethoxysilane (completely hydrolyzed) in a mixed solution of 46.67 g of 25% tetramethylammonium hydride aqueous solution, 656.97 g of ultrapure water, and 1,633.62 g of ethanol. 66.75 g in terms of condensate, 166.66 g in tetraethoxysilane (48.33 g in terms of complete hydrolysis condensate), and 25.65 g in terms of complete hydrolysis condensate (18.21 g in terms of complete hydrolysis condensate) were added at 60 ° C. For 2 hours. Thereafter, after cooling to room temperature, 13.44 g of a 60% nitric acid aqueous solution was added to this solution and stirred at room temperature for 1 hour. Next, 399.87 g of propylene glycol monopropyl ether was added to this solution, and then concentrated under reduced pressure until the total amount of the solution was 1,332.9 g. Next, 66.65 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a reaction solution 3 having a solid content of 10%. Further, a silica-based film was formed using the reaction solution 3, and the relative dielectric constant of the silica-based film was measured. As a result, the relative dielectric constant was 2.37.

(Synthesis Example 4)
In a quartz separable flask, 163.48 g of methyltrimethoxysilane (80.11 g in terms of complete hydrolysis condensate), 145.83 g of tetraethoxysilane (42.29 g in terms of complete hydrolysis condensate), bis (triethoxysilane) ) 35.06 g of acetylene (12.97 g in terms of complete hydrolysis condensate) and 0.076 g of tetrakis (acetylacetonato) titanium were dissolved in 820.03 g of dipropylene glycol dimethyl ether and stirred with a three-one motor to obtain a solution. The temperature was stabilized at 50 ° C. Next, 189.21 g of ion-exchanged water was added to the solution over 1 hour. Subsequently, after making it react at 50 degreeC for 3 hours, distilled dipropylene glycol dimethyl ether 406.11g was added and the reaction liquid was cooled to room temperature. Thereafter, the reaction solution was concentrated under reduced pressure until the total solution amount reached 1,353.7 g, to obtain a reaction solution 4 having a solid content of 10%. Further, a silica-based film was formed using the reaction solution 4, and the relative dielectric constant of the silica-based film was measured. As a result, the relative dielectric constant was 2.72.

[(C) Preparation of film-forming composition]
(Synthesis Example 5)
In a quartz separable flask, 109.0 g of methyltrimethoxysilane (completely hydrolyzed condensate) in a mixed solution of 80.0 g of 25% tetramethylammonium hydroxide aqueous solution, 113.0 g of ultrapure water and 1,846 g of ethanol 53 g of conversion) and 42 g of tetraethoxysilane (12 g of complete hydrolysis condensate) were added and reacted at 60 ° C. for 3 hours. Next, 3,920 g of propylene glycol monopropyl ether was added, and the mixture was concentrated under reduced pressure until the total solution amount became 630 g. Thereafter, 30 g of a 10% propylene glycol monopropyl ether solution of acetic acid was added to obtain a composition (C-1) having a solid content of 10%. Further, a silica-based film was formed using the reaction solution 5 and the relative dielectric constant of the silica-based film was measured. As a result, the relative dielectric constant was 2.27.

[(E) Preparation of film-forming composition]
(Synthesis Example 6)
In a 1,000 ml three-necked flask equipped with a thermometer, an argon gas inlet tube, and a stirrer, 120 ml of tetrahydrofuran, 3.46 g of tetrakistriphenylphosphine palladium, 2.1 g of dichlorobistriphenylphosphine palladium, 1.44 g of copper iodide), piperidine 20 ml and 4,4'-bis (2-iodophenoxy) benzophenone 185.72 g were added. Next, 65.48 g of 4,4′-diethynyl diphenyl ether was added and reacted at 25 ° C. for 20 hours. This reaction solution was reprecipitated twice with 5 liters of acetic acid, then dissolved in cyclohexanone and washed twice with ultrapure water. Subsequently, reprecipitation was performed with 5 liters of methanol, and the resulting precipitate was filtered and dried to obtain a polymer having a weight average molecular weight of 35,000. 20 g of this polymer was dissolved in 180 g of cyclohexanone to obtain a composition (E-1).

In addition, the weight average molecular weight (Mw) of the polymer was measured by a gel permeation chromatography (GPC) method under the following conditions.
Sample: Tetrahydrofuran was used as a solvent, and 1 g of a polymer was dissolved in 100 cc of tetrahydrofuran.
Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Company was used.
Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, USA
Column: SHODEX A-80M (length: 50 cm) manufactured by Showa Denko K.K.
Measurement temperature: 40 ° C. Flow rate: 1 cc / min

[Formation of laminated film]
(Example 1)
The composition (C-1) obtained in Synthesis Example 5 was filtered through a Teflon (registered trademark) filter having a 0.2 micron pore size, and then applied to an 8-inch silicon wafer with a film thickness of 5000 mm at 80 ° C. The wafer was dried for 1 minute at 200 ° C. for 1 minute to form a first coating film. Next, the reaction solution 1 obtained in Synthesis Example 1 was filtered through a Teflon (registered trademark) filter having a 0.2 micron pore diameter, and then applied to the first coating film with a thickness of 100 mm, and then 80 ° C. The wafer was dried for 1 minute at 200 ° C. for 1 minute to form a second coating film. Further, after the composition (E-1) obtained in Synthesis Example 6 was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns, it was applied on the second coating film with a thickness of 5000 mm. The wafer was dried at 80 ° C. for 1 minute and 200 ° C. for 1 minute to form a third coating film. Thereafter, the wafer was baked on a hot plate at 400 ° C. for 30 minutes under a nitrogen atmosphere to obtain a laminated film 1. The laminated film 1 is composed of a laminated body of a first silica film, a second silica film, and an organic film. In addition, a first silica-based film is formed from the first coating film, a second silica-based film is formed from the second coating film, and an organic film is formed from the third coating film. The same applies to the laminated films 2 to 4 obtained in Examples 2 to 4 described later.

  When the adhesion of the laminated film 1 was evaluated, no peeling was observed at the interface between the first silica-based film and the second silica-based film and at the interface between the second silica-based film and the organic film. .

(Example 2)
In forming the second silica-based film, a laminated film 2 was prepared in the same manner as in Example 1, except that the reaction liquid 2 obtained in Synthesis Example 2 was used instead of the reaction liquid 1. When the adhesion of the laminated film 2 was evaluated, no peeling was observed at the interface between the first silica-based film and the second silica-based film and at the interface between the second silica-based film and the organic film. .

(Example 3)
In forming the second silica-based film, the same operation as in Example 1 was performed except that the reaction liquid 3 obtained in Synthesis Example 3 was used in place of the reaction liquid 1 to prepare a laminated film 3. When the adhesion of the laminated film 3 was evaluated, no peeling was observed at the interface between the first silica-based film and the second silica-based film and at the interface between the second silica-based film and the organic film. .

Example 4
In forming the second silica-based film, the same operation as in Example 1 was performed, except that the reaction solution 4 obtained in Synthesis Example 4 was used instead of the reaction solution 1, and a laminated film 4 was formed. When the adhesion of the laminated film 4 was evaluated, no peeling was observed at the interface between the first silica-based film and the second silica-based film and at the interface between the second silica-based film and the organic film. .

(Comparative example)
The composition (C-1) obtained in Synthesis Example 5 was filtered through a Teflon (registered trademark) filter having a 0.2 micron pore size, and then applied to an 8-inch silicon wafer with a film thickness of 5000 mm at 80 ° C. The wafer was dried for 1 minute at 200 ° C. for 1 minute to form a first coating film. Next, the composition (E-1) obtained in Synthesis Example 6 was filtered through a Teflon (registered trademark) filter having a 0.2 micron pore size, and then applied to the first coating film with a thickness of 5000 mm. The wafer was dried at 80 ° C. for 1 minute and 200 ° C. for 1 minute to form a third coating film. Next, the wafer was baked for 30 minutes on a hot plate at 400 ° C. in a nitrogen atmosphere to obtain a laminated film 5. The laminated film 5 is composed of a laminated body of a first silica film and an organic film, the first silica film is formed from the first coating film, and the organic film is formed from the third coating film. . When the adhesion of the laminated film 5 was evaluated, peeling at the interface between the first silica-based film and the organic film was observed with nine stud pins.

  From the above result, according to Examples 1-4, it was confirmed that the composition for film formation excellent in adhesiveness can be obtained by hydrolyzing and condensing (A) component and (B) component. . On the other hand, from the comparative example, a silica-based film is formed using a film-forming composition obtained by hydrolytic condensation of a component not containing the component (B), and an organic system is formed through this silica-based film. When the film was formed on the wafer, the adhesion between the silica-based film and the organic film was low, and it was confirmed that peeling occurred between the silica-based film and the organic film.

Claims (9)

(A) Selected from compound (1) represented by the following general formula (1), compound (2) represented by the following general formula (2), and compound (3) represented by the following general formula (3) At least one silane compound, 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)
[In the formula, 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) At least one silane compound selected from the group consisting of compound (4) represented by the following general formula (4) and compound (5) represented by the following general formula (5)

(4)
[Wherein, R _x represents a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, and R ^{81 to} R ⁸³ may be the same or different, and each represents a hydrogen atom, a halogen atom, A hydroxyl group, an alkoxyl group, or a monovalent organic group is shown, and all of R ^{81 to} R ⁸³ do not become a monovalent organic group at the same time. ]

(5)
[Wherein, R _y represents a divalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, and R ^{91 to} R ⁹⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom, A hydroxyl group, an alkoxyl group, or a monovalent organic group is shown, and in the combination of R ^{91 to} R ⁹³ and R ^{94 to} R ⁹⁶ , not all become a monovalent organic group at the same time. ]
A film-forming composition comprising a hydrolysis-condensation product obtained by hydrolysis-condensation. In claim 1,
The film-forming composition, wherein the hydrolytic condensation is performed in the presence of a metal chelate compound, an acidic compound, or a basic compound. In claim 1 or 2,
The film forming composition wherein R _x is at least one selected from a vinyl group, an ethynyl group, an allyl group, a phenylvinyl group, a vinylphenyl group, a phenylethynyl group, and an ethynylphenyl group. In any of claims 1 to 3,
R _y is

A film-forming composition, which is at least one selected from the group consisting of:   5. A film-forming composition according to claim 1 is applied to a substrate to form a coating film, and at least one of heat treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, and oxygen plasma treatment. A method for forming a silica-based film, comprising curing the coating film by a seed treatment.   A silica-based film obtained by the method for forming a silica-based film according to claim 5. (C) Selected from the compound (1) represented by the following general formula (1), the compound (2) represented by the following general formula (2), and the compound (3) represented by the following general formula (3) A first silica-based film obtained by curing a coating film formed using a film-forming composition containing a hydrolysis-condensation product obtained by hydrolysis-condensation of at least one silane compound,
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)
[In the formula, 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. ]
(D) a second silica-based film obtained by curing a coating film formed using the film-forming composition according to any one of claims 1 to 4,
(E) an organic film having a carbon content of 60% by weight or more;
A laminated film formed by laminating layers. In claim 7,
The laminated film in which the film thickness of the (D) film is 1/10 to 1/1000 with respect to the film thickness of the (C) film. In claim 7 or 8,
The (E) film includes an organic polymer, and the organic polymer is at least one polymer selected from the group of the following general formulas (6) to (9).

(6)

(7)

(8)

(9)
(In formulas (6) to (9), R ^{8 to} R ¹² are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or X represents —CQQ′— (wherein Q and Q ′ may be the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom, or an aryl group. ) And at least one selected from the group consisting of fluorenylene groups, Y represents —O—, —CO—, —COO—, —CONH—, —S—, —SO ₂ —, and a phenylene group. E represents 0 or 1, o to s represent an integer of 0 to 4, f represents 5 to 100 mol%, g represents 0 to 95 mol%, and h represents 0. -95 mol% (however, f + g + h = 100 mol) %), I is 0 to 100 mol%, j is 0 to 100 mol% (where i + j = 100 mol%), and A and B are independently represented by the following general formulas (10) to (12). At least one group selected from the group consisting of divalent aromatic groups, wherein R ¹³ and R ^{13 ′} are a hydrogen atom or an aromatic group represented by the following general formulas (13) and (14) At least one group selected from the group, and W ¹ and W ² represent at least one group selected from the group consisting of divalent aromatic groups represented by the following general formulas (15) and (16): Show.)

(10)

(11)

(12)

[In the formulas (10) to (12), R ¹⁴ , R ¹⁵ , R ²⁰ and R ²¹ are each independently a single bond, —O—, —CO—, —CH ₂ —, —COO—, —CONH—, -S _-, - SO 2 -, a phenylene group, an isopropylidene group, a hexafluoro isopropylidene group, diphenylmethylidene group, fluorenylene group, or a group of the formula,

R ^{16 to} R ¹⁸ , R ¹⁹ and R ^{22 to} R ²⁴ are independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, or a group having 1 to 20 carbon atoms. An alkoxyl group or an aryl group is shown, k represents an integer of 0 to 3, l represents an integer of 2 to 3, and tz independently represents an integer of 0 to 4. ]

(13)

(14)

[In the formulas (13) and (14), R ²⁵ represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group, an alkoxyl group having 1 to 20 carbon atoms, a phenoxy group or an aryl group. , M ′ represents an integer of 0 to 5, and n ′ represents an integer of 0 to 7. ]

(15)

(16)
[In the formulas (15) and (16), R ²⁵ represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group, an alkoxyl group having 1 to 20 carbon atoms, a phenoxy group or an aryl group. , R ²⁶ represents a single bond, —O—, —CO—, —CH ₂ —, —COO—, —CONH—, —S—, —SO ₂ —, a phenylene group, an isopropylidene group, a hexafluoroisopropylidene group, Diphenylmethylidene, methylphenylmethylidene, trifluoromethylmethylmethylidene, trifluoromethylphenylmethylidene, fluorenylene, or formula

Wherein R ²⁷ independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group, and a1 and a2 independently represent an integer of 0 to 4. , A3 represents an integer of 0-6. )