JP4434922B2 - Laminated body and method for forming the same, insulating film, and semiconductor device - Google Patents

Description

  The present invention relates to a laminate in which a plurality of silica films and organic films having different compositions are laminated, a method for forming the same, an insulating film, and a semiconductor device.

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 mainly containing 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.

As an example of such an interlayer insulating film material, a coating composition for forming an insulating film having a low relative dielectric constant disclosed in Patent Document 1 can be given. The coating film forming composition described in Patent Document 1 is obtained by hydrolytic condensation of alkoxysilanes in the presence of a metal catalyst. By using this composition for forming a coating film, it is possible to obtain a film having a low relative dielectric constant, a high elastic modulus, and excellent CMP resistance.
JP 2000-256621 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 and reduce processing damage to the insulating film, a process of forming an organic film on a silica-based film has recently been proposed. However, when a process such as CMP is performed on a laminated film of a silica-based film and an organic film, peeling may occur between the silica-based film and the organic film due to insufficient adhesion between the two. there were.

  An object of the present invention is to provide a laminate in which a silica film and an organic film having a low relative dielectric constant and excellent adhesion are laminated, and a method for forming the laminate.

  Another object of the present invention is to provide an insulating layer including the laminate.

  Another object of the present invention is to provide a semiconductor device having the insulating layer.

1. Laminate The laminate of the present invention includes a first silica-based film, a second silica-based film, and an organic film,
The second silica-based film has a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond.

  In the laminate of the present invention, the second silica-based film is obtained by hydrolytic condensation of the following silane compound (A) and the following silane compound (B) in the presence of an acidic or basic or metal chelate compound. The film can be a film obtained by forming a coating film using the film-forming composition containing the resulting hydrolysis condensate and curing the coating film.

(A) At least one silane compound selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2) and a compound represented by the following general formula (3) ,
R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 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 to} R ⁶ are the same or different, each is a monovalent organic group, b and c are the same or different, and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or — (CH ₂ ) A group represented by _m- (where m is an integer of 1 to 6), d represents 0 or 1.)
(B) At least one silane compound selected from the group of compounds represented by the following general formula (4) and compounds represented by the following general formula (5).

・・・・・（４）
（式中、Ｒ_ｘは炭素−炭素二重結合または炭素−炭素三重結合を有する１価の有機基、Ｒ^８１〜Ｒ^８３は同一または異なり、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)
(In the formula, R _x is a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, R ^{81 to} R ⁸³ are the same or different, and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, Alternatively, it represents a monovalent organic group, 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−炭素二重結合または炭素−炭素三重結合を有する２価の有機基、Ｒ^９１〜Ｒ^９６は同一または異なり、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。）
本発明の積層体において、前記第１のシリカ系膜は、下記一般式（１）で表される化合物、下記一般式（２）で表される化合物および下記一般式（３）で表される化合物の群から選ばれた少なくとも１種のシラン化合物を加水分解縮合して得られる加水分解縮合物を含む膜形成用組成物を用いて塗膜を形成し、該塗膜を硬化して得られる膜であることができる。

(5)
(Wherein R _y is a divalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, R ^{91 to} R ⁹⁶ are the same or different, and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, Alternatively, it represents a monovalent organic group, and in the combination of R ^{91 to} R ⁹³ and R ^{94 to} R ⁹⁶ , all are not simultaneously monovalent organic groups.)
In the laminate of the present invention, the first silica-based film is represented by a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following general formula (3). Obtained by forming a coating film using a film-forming composition containing a hydrolysis-condensation product obtained by hydrolytic condensation of at least one silane compound selected from the group of compounds, and curing the coating film It can be a membrane.

R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 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 to} R ⁶ are the same or different, each is a monovalent organic group, b and c are the same or different, and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or — (CH ₂ ) A group represented by _m- (where m is an integer of 1 to 6), d represents 0 or 1.)

  In the laminate of the present invention, the organic film may be made of at least one compound selected from polyarylene, polyarylene ether, polybenzoxazole, and polyimide.

  In the laminate of the present invention, the compound constituting the organic film 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^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 ¹⁹ and R ^{22 to} R ²⁴ are 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, Or an aryl group is shown, k represents the integer of 0-3, l represents the integer of 2-3, tz represents the integer of 0-4 independently. )

・・・・・（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 is 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. )

  In the laminate of the present invention, the relative dielectric constant can be 2.8 or less.

2. Method for forming laminate The method for forming a laminate of the present invention is to form a first coating film for a first silica-based film on a substrate,
Forming a second coating film having a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond for the second silica-based film on the first coating film;
Forming a third coating for the organic film on the second coating;
Curing the laminated film composed of the first to third coating films.

  In the method for forming a laminate of the present invention, the curing can be performed by heating.

  In the method for forming a laminate of the present invention, the curing can be performed by electron beam irradiation.

3. Insulating film The insulating film of this invention contains the laminated body in any one of the above-mentioned.

4). Semiconductor Device A semiconductor device of the present invention includes the above-described insulating film.

  In the laminate of the present invention, a second silica-based film is provided between the first silica-based film and the organic film. The film-forming composition for forming the second silica-based film has a carbon-carbon double bond or a carbon-carbon triple bond in the polymer skeleton. It can react with an organic polymer. Moreover, the 2nd silica type film | membrane has an unreacted silanol group in a polymer, and can condense with the coating film for forming another silica type film | membrane with a heat | fever. That is, the second silica-based film has both adhesiveness with the first silica-based film and adhesiveness with the organic film. Therefore, according to the present invention, it is possible to provide a laminate having a low dielectric constant and sufficient adhesion. As a result, an insulating layer that can be suitably used as an interlayer insulating film or a planarizing insulating film of a semiconductor device can be provided.

  In the present invention, the “coating film” refers to a film obtained after applying the film-forming composition to a substrate and removing the organic solvent.

  According to the method for forming a laminate of the present invention, various curing treatments are performed after laminating the respective coating films of the first silica-based film, the second silica-based film, and the organic film. When the curing process is performed in a state where the respective coating films are laminated, the carbon-carbon double bond or the carbon-carbon triple bond of the second silica-based film reacts with the organic polymer. On the other hand, the unreacted silanol group in the coating film for the second silica-based film causes a condensation reaction with the coating film for the first silica-based film. Therefore, it is possible to form a laminated body in which the first silica-based film and the organic film are sufficiently adhered via the second silica-based film.

  According to the insulating film of the present invention, an insulating film having a low dielectric constant and improved adhesion can be provided. Therefore, it can be suitably used as an interlayer insulating film or a planarizing insulating film of a semiconductor device.

  The semiconductor device of the present invention includes the above insulating film. Since the insulating film has sufficient adhesion, peeling of the film during the CMP process and the packaging process is suppressed, and a highly reliable semiconductor device can be provided.

  Hereinafter, the laminate of the present invention, the formation method thereof, the insulating film, and the semiconductor device will be specifically described.

1. Laminate The laminate of the present invention is a second silica-based compound having a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond between the first silica-based film and the organic film. A membrane is provided. Hereinafter, each film will be described.

1.1 First Silica Film The first silica film includes a compound represented by the following general formula (1) (hereinafter referred to as “compound 1”) and a compound represented by the following general formula (2) (hereinafter referred to as “compound 1”). , “Compound 2”) and hydrolysis obtained by hydrolytic condensation of at least one silane compound selected from the group of compounds represented by the following general formula (3) (hereinafter referred to as “compound 3”) It is a film | membrane obtained by hardening | curing the coating film formed using the composition (I) for film formation containing a condensate.

R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 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 to R ⁶ may be the same or different, each represents a monovalent organic group, b and c may be the same or different, represents the number of 0 to 2, R ⁷ is An oxygen atom, a phenylene group, or a group represented by — (CH ₂ ) _m —, wherein m represents an integer of 1 to 6, and d represents 0 or 1.

  In the present invention, the “hydrolyzate” does not require that all of the alkoxy groups contained in at least one silane compound selected from the compounds 1 to 3 are hydrolyzed, for example, only one May be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. Here, the “condensate” is a product in which the silanol groups of the hydrolyzates of the above compounds 1 to 3 are condensed to form a Si—O—Si bond. It is not necessary to condense all of them, and it is a concept that includes a mixture of a small part of silanol groups, a mixture of those having different degrees of condensation, and the like.

1.1.1 Compound 1
In the general formula (1), examples of the monovalent organic group represented by R and R ¹ include an alkyl group, an 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-butoxysilane, Triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, fluorotri-tert -Butoxysilane, fluorotriphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxy , Methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxy Silane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxy Silane, vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propi Triethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert -Butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri- n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri- n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane , Sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxy Silane, -Butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane , Phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, 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, divinyldimethoxysilane, di-γ-aminopropyldimethoxysilane, di-γ -Glycidoxypropyl dimeth Xysilane, di-γ-trifluoropropyldimethoxysilane and the like.

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

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

1.1.3 Compound 3
In the general formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as those shown in the general formula (1). Among the compounds 3, compounds in which R ⁷ in the general formula (3) is an oxygen atom include 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-penta Phenoxy-3-phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3 3,3-tetraphenoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diethyl Disiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetra Ethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxa 1,1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3, 3-triethyldisiloxane, 1,1,3-triethoxy-1,3,3-triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,1,3-trimethoxy -1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3-triphenyldisiloxane 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy-1,1, , 3-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 include 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.

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.

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.

  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.

  In the present invention, at least one of the compounds 1 to 3 may be used, and two or more of the compounds 1 to 3 may be used. It is preferable that it is the hydrolysis-condensation product of the compound 1 and the compound 2 at the point that the storage stability of the composition obtained is favorable.

1.1.4 Metal Chelate Compound, Acidic Compound, or Basic Compound In the present invention, the hydrolysis condensation of the above compounds 1 to 3 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.

1.1.4a Metal Chelate Compound A metal chelate compound that can be used at the time of hydrolytic condensation of a silane compound selected from Compounds 1 to 3 is represented by the following general formula (17).

R ²⁷ _β M (OR ²⁸ ) _α-β (17)
(In the formula (17), R ²⁷ is a chelating agent, M is a metal atom, R ²⁸ 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 Represents an integer of 1 to 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 nattobis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium; triethoxy mono (acetylacetonato) aluminum, tri-n-propoxy mono (acetylacetate) Nato) aluminum, triisopropoxy mono (acetylacetonato) aluminum, tri-n-butoxy mono (acetylacetonato) aluminium , Tri-sec-butoxy mono (acetylacetonato) aluminum, tri-tert-butoxy mono (acetylacetonato) aluminum, diethoxybis (acetylacetonato) aluminum, di-n-propoxybis (acetylacetonate) ) Aluminum, diisopropoxy bis (acetylacetonato) aluminum, di-n-butoxy bis (acetylacetonato) aluminum, di-sec-butoxy bis (acetylacetonato) aluminum, di-tert-butoxy bis (Acetylacetonato) aluminum, monoethoxy tris (acetylacetonato) aluminum, mono-n-propoxy tris (acetylacetonato) aluminum, monoisopropoxy tris (acetylacetate) Tonato) aluminum, mono-n-butoxy tris (acetylacetonato) aluminum, mono-sec-butoxy tris (acetylacetonato) aluminum, mono-tert-butoxy tris (acetylacetonato) aluminum, tetrakis (acetylacetate) Natto aluminum, triethoxy mono (ethyl acetoacetate) aluminum, tri-n-propoxy mono (ethyl acetoacetate) aluminum, triisopropoxy mono (ethyl acetoacetate) aluminum, tri-n-butoxy mono (ethyl aceto) Acetate) aluminum, tri-sec-butoxy mono (ethyl acetoacetate) aluminum, tri-tert-butoxy mono (ethyl acetoacetate) aluminum, di Toxi bis (ethyl acetoacetate) aluminum, di-n-propoxy bis (ethyl acetoacetate) aluminum, diisopropoxy bis (ethyl acetoacetate) aluminum, di-n-butoxy bis (ethyl acetoacetate) aluminum, Di-sec-butoxy bis (ethyl acetoacetate) aluminum, di-tert-butoxy bis (ethyl acetoacetate) aluminum, monoethoxy tris (ethyl acetoacetate) aluminum, mono-n-propoxy tris (ethyl acetoacetate) ) Aluminum, monoisopropoxy tris (ethyl acetoacetate) aluminum, mono-n-butoxy tris (ethyl acetoacetate) aluminum, mono-sec-butoxy tris Ethyl acetoacetate) aluminum, mono-tert-butoxy-tris (ethylacetoacetate) aluminum, tetrakis (ethylacetoacetate) aluminum, mono (acetylacetonato) tris (ethylacetoacetate) aluminum, bis (acetylacetonato) bis ( 1 type or 2 types or more of aluminum chelate compounds, such as ethyl acetoacetate) aluminum and tris (acetylacetonato) mono (ethyl acetoacetate) aluminum, etc. are mentioned.

In _{particular, (CH 3 (CH 3)} HCO) 4-t Ti (CH 3 COCH 2 COCH 3) t, (CH 3 (CH 3) HCO) 4-t Ti (CH 3 COCH 2 COOC 2 H 5) t ( _{C 4 H 9 O) 4-} t Ti (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 4-t Ti (CH 3 COCH 2 COOC 2 H 5) t, (C 2 H 5 (CH _{3) CO) 4-t Ti} (CH 3 COCH 2 COCH 3) t, (C 2 H 5 (CH 3) CO) 4-t Ti (CH 3 COCH 2 COOC 2 H 5) t (CH 3 (CH 3 _{) HCO) 4-t Zr (} CH 3 COCH 2 COCH 3) t (CH 3 (CH 3) HCO) 4-t Zr (CH 3 COCH 2 COOC 2 H 5) t (C 4 H 9 O) 4-t Zr (CH _{3 COCH 2 COCH 3) t, (} C 4 H 9 O) 4-t Zr (CH 3 COCH 2 COOC 2 H 5) t, (C 2 H 5 (CH 3) CO) 4-t Zr (CH 3 COCH 2 _{COCH 3) t, (C 2} H 5 (CH 3) CO) 4-t Zr (CH 3 COCH 2 COOC 2 H 5) t (CH 3 (CH 3) HCO) 3-t Al (CH 3 COCH 2 COCH _{3) t (CH 3 (CH} 3) HCO) 3-t Al (CH 3 COCH 2 COOC 2 H 5) t (C 4 H 9 O) 3-t Al (CH 3 COCH 2 COCH 3) t, (C _{4 H 9 O) 3-t} Al (CH 3 COCH 2 COOC 2 H 5) t, (C 2 H 5 (CH 3) CO) 3-t Al (CH 3 COCH 2 COCH 3) t, (C 2 H ₅ (CH _{3 CO) 3-t Al (CH} 3 COCH 2 COOC 2 H 5) 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 silane compound selected from compounds 1 to 3 at the time of 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. The metal chelate compound may be added in advance to an organic solvent together with a silane compound selected from compounds 1 to 3 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 a silane compound selected from Compounds 1 to 3 in the presence of a metal chelate compound, it is preferable to use 0.5 to 20 mol of water per 1 mol of the total amount of silane compounds selected from Compounds 1 to 3. 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.

1.1.4b Acidic compounds Examples of acidic compounds that can be used at the time of hydrolytic condensation of silane compounds selected from compounds 1 to 3 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, hydrolyzed 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 silane compound selected from compounds 1 to 3 at the time of 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 silane compound selected from Compounds 1 to 3 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 a silane compound selected from Compounds 1 to 3 in the presence of an acidic compound, it is preferable to use 0.5 to 20 mol of water per 1 mol of the total amount of silane compounds selected from Compounds 1 to 3, 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.

1.1.4c Basic compound Examples of basic compounds that can be used at the time of hydrolytic condensation of a silane compound selected from Compounds 1 to 3 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, tripropyl Amine, tributylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclononane Diazabicycloundecene, urea, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, can be cited benzyltrimethylammonium hydroxide, choline, and the like. Among these, ammonia, organic amines, and ammonium hydroxides can be 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, the total amount of alkoxy groups of the silane compound selected from the compounds 1 to 3 ^(R 1 ^{O-group, R} 2 ^O-group, represented by ^R 4 O-group and ^R 5 O-group The group is usually 0.00001 to 1 mol, preferably 0.00005 to 0.5 mol, relative to a total of 1 mol of the group). If the usage-amount of a basic compound is in the said range, there is little possibility of polymer precipitation or gelation during reaction.

  When hydrolyzing and condensing a silane compound selected from Compounds 1 to 3 in the presence of a basic compound, it is preferable to use 0.5 to 150 mol of water per 1 mol of the total amount of silane compounds selected from Compounds 1 to 3. 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, polymer precipitation or gelation 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 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 silane compounds selected from compounds 1 to 3.

  The alcohol having a boiling point of 100 ° C. or less may be generated during hydrolysis and / or condensation of the silane compound selected from the compounds 1 to 3, 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, after obtaining a hydrolysis-condensation product from the silane compound chosen from the compounds 1-3 in presence of a basic compound, it is preferable to adjust the pH of the film forming composition of this invention to 7 or less. 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. By adjusting the pH within the above range with the pH adjusting agent, the effect of improving the storage stability of the composition can be obtained. The amount of the pH adjuster used is an amount that makes the pH of the composition within the above range, and the amount used is appropriately selected.

1.1.5 Organic Solvent In the present invention, a silane compound selected from Compounds 1 to 3 can be subjected to hydrolysis condensation in an organic solvent. Here, the organic solvent is preferably a solvent represented by the following general formula (18).

R ²⁹ O (CHCH ₃ CH ₂ O) _γ R ³⁰ (18)
(In the formula (18), R ²⁹ and R ³⁰ each independently represent 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 1 to 2 Represents an integer.)

  In the general formula (18), examples of the alkyl group having 1 to 4 carbon atoms include the same groups as those shown 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 of the present invention 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 film-forming composition of the present invention is 1 to 30% by weight, the film thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The total solid content concentration is adjusted by concentration and dilution with an organic solvent, if necessary.

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

  Examples of the compound having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene poly Ether type compounds such as oxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structure.

− (A ′) _{j ′} − (B ′) _{k ′} −
− (A ′) _{j ′} − (B ′) _{k ′} − (A ′) _{l ′} −
(In the formula, A ′ represents a group represented by —CH ₂ CH ₂ O—, B ′ represents a group represented by —CH ₂ CH (CH ₃ ) O—, j ′ represents 1 to 90, k 'Is a number from 10 to 99, and l' is a number from 0 to 90.)

  Among these, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, More preferred examples include ether type compounds. These may be used alone or in combination of two or more.

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

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

  Examples of the silicone surfactant include SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.). Among these, the following general formulas corresponding to the SH28PA and SH30PA are used. The polymer represented by (9) is particularly preferred.

・・・・・（１９）
（式（１９）中、Ｒ^３１は水素原子または炭素数１〜５のアルキル基であり、ｚ’は１〜２０の整数であり、ｘ’、ｙ’はそれぞれ独立に２〜１００の整数である。）
界面活性剤の使用量は、化合物１〜３から選択されたシラン化合物の総量１００重量部（完全加水分解縮合物換算）に対して通常０．０００１〜１０重量部である。これらは１種あるいは２種以上を同時に使用しても良い。

(19)
(In formula (19), R ³¹ 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. is there.)
The usage-amount of surfactant is 0.0001-10 weight part normally with respect to 100 weight part (total hydrolysis-condensation product conversion) of the total amount of the silane compound selected from the compounds 1-3. 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 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.

1.2 Second Silica-Based Film The second silica-based film is prepared by adding a silane compound of the following component (A) and a silane compound of the following component (B) in the presence of an acidic or basic or metal chelate compound. It is a film obtained by forming a coating film using a hydrolysis-condensation product obtained by decomposition condensation and curing the coating film. In the laminate of the present invention, the second silica-based film is provided between the first silica-based film and the organic film, thereby improving the adhesion between the organic film and the first silica-based film. be able to.

  More specifically, when the hydrolysis condensate contains a carbon-carbon double bond or a carbon-carbon triple bond, the second silica-based film obtained using the hydrolysis condensate, and the second Polymers in other films (first silica film and organic film) in contact with the silica film react with each other to improve the adhesion between the second silica film and the other film. Therefore, by forming the second silica-based film using the hydrolysis condensate, it is possible to form a coating film having a low dielectric constant and excellent adhesion to other films. .

1.2.1 Component (A) As the silane compound of the component (A) used for forming the second silica-based film, the compound represented by the following general formula (1) (compound 1), the following general formula Mention may be made of at least one silane compound of the compound represented by (2) (compound 2) and the compound represented by the following general formula (3) (compound 3).

R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 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 to} R ⁶ are the same or different, each is a monovalent organic group, b and c are the same or different, and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or — (CH ₂ ) A group represented by _m- (where m is an integer of 1 to 6), d represents 0 or 1.)
About compounds 1-3, the same thing as compounds 1-3 used for formation of the above-mentioned 1st silica system film can be mentioned.

1.2.2 (B) Component As the silane compound of the (B) component used for forming the second silica-based film, a compound represented by the following general formula (4) (hereinafter referred to as “compound 4”) And at least one silane compound selected from the group of compounds represented by the following general formula (5) (hereinafter referred to as “compound 5”) can be used.

・・・・・（４）
（式中、Ｒ_ｘは炭素−炭素二重結合または炭素−炭素三重結合を有する１価の有機基。Ｒ^８１〜Ｒ^８３は同一または異なり、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)
(In the formula, R _x is a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond. R ^{81 to} R ⁸³ are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, Alternatively, it represents a monovalent organic group, and all of R ^{81 to} R ⁸³ do not become a monovalent organic group at the same time.)

  In the general formula (4), examples of the monovalent organic group having a carbon-carbon double bond or carbon-carbon triple bond include a vinyl group, an ethynyl group, an allyl group, a phenylethynyl group, and an ethynylphenyl group. Can be mentioned.

・・・・・（５）
（式中、Ｒ_ｙは炭素−炭素二重結合または炭素−炭素三重結合を有する２価の有機基、Ｒ^９１〜Ｒ^９６は同一または異なり、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。）
上記一般式（５）において、Ｒ_ｙとしては、例えば、

(5)
(Wherein R _y is a divalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, R ^{91 to} R ⁹⁶ are the same or different, and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, Alternatively, it represents a monovalent organic group, and in the combination of R ^{91 to} R ⁹³ and R ^{94 to} R ⁹⁶ , all are not simultaneously monovalent organic groups.)
In the general formula (5), 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

1.2.2a Compound 4
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, Vinyldimethoxysila , Vinyl ethoxysilane, vinyl diethoxysilane, vinyl dichloromethyl silane, vinyl chlorodimethyl silane, vinyl dimethyl methoxy silane, vinyl methyl dimethoxy silane, vinyl dimethyl ethoxy silane, vinyl methyl diethoxy silane, vinyl dimethyl hydroxy silane, ethynyl chloro silane, ethynyl Dichlorosilane, ethynyltrichlorosilane, ethynylmethoxysilane, ethynyldimethoxysilane, ethynylethoxysilane, ethynyldiethoxysilane, ethynyldichloromethylsilane, ethynylchlorodimethylsilane, ethynyldimethylmethoxysilane, ethynylmethyldimethoxysilane, ethynyldimethylethoxysilane, ethynyl Methyldiethoxysilane, ethynyldimethylhydroxysilane, divinyldimeth Sisilane, divinyldiethoxysilane, divinyldipropoxysilane, divinyldichlorosilane, diethynyldimethoxysilane, diethynyldiethoxysilane, diethynyldipropoxysilane, diethynyldichlorosilane, trivinylmethoxysilane, trivinylethoxysilane, trivinyl Examples thereof include propoxysilane, trivinylchlorosilane, triethynylmethoxysilane, triethynylethoxysilane, triethynylpropoxysilane, and triethynylchlorosilane. 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.

1.2.2b Compound 5
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) a Tylene, 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] benzene 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) e Nyl] 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 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 it is less than 0.1% by weight, the condensation reaction may not proceed sufficiently and a coating solution may not be obtained. If it exceeds 30% by weight, precipitation of the polymer during the reaction or gelation will occur. there is a possibility. In addition, the density | concentration of (A) component and (B) component is a density | concentration when these are converted into a complete hydrolysis condensate.

1.2.3 Others The hydrolysis condensate contained in the film-forming composition (II) can be formed in the presence of at least one of a metal chelate compound, an acidic compound and a basic compound. As a metal chelate compound, an acidic compound, and a basic compound, what was illustrated in formation of the above-mentioned 1st silica type film | membrane can be used.

  When a metal chelate compound is used, the amount used is 0.0001 to 10 weights with respect to 100 parts by weight (in terms of complete hydrolysis condensate) of the total amount of component (A) and component (B) at the time of hydrolysis condensation. Parts, preferably 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.

  When an acidic compound is used, the amount used is 0.0001 to 10 parts by weight with respect to 100 parts by weight (in terms of complete hydrolysis condensate) of the total amount of component (A) and component (B) during hydrolysis condensation The amount is preferably 0.001 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.

When a basic compound is used, the amount used is represented by the total amount of alkoxyl groups in the component (A) (R ¹ O-group, R ² O-group, R ⁴ O-group and R ⁵ O-group). Group) and (B) component, the total amount is usually 0.00001 to 1 mol, preferably 0.00005 to 0.5 mol. If the usage-amount of a basic compound is in the said range, there is little possibility of polymer precipitation or gelation 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, polymer precipitation or gelation may occur during hydrolysis and condensation reactions.

  The film-forming composition (II) may contain an organic solvent. At this time, as the organic solvent that can be used, those exemplified in the first silica-based film can be used. The film-forming composition 2 further includes, as other additives, the colloidal silica, colloidal alumina, organic polymer, surfactant, silane coupling agent and the like exemplified in the first silica film. You may contain.

1.3 Organic Film In the laminate of the present invention, the organic film is coated with a film-forming composition (III) containing at least one compound of polyarylene, polyarylene ether, polybenzoxazole, and polyimide, It is the film | membrane obtained by hardening | curing the coating film obtained by removing a solvent. Specifically, the film-forming composition (III) includes a polymer composed of at least one repeating structural unit 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^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 ¹⁹ and R ^{22 to} R ²⁴ are 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, Or an aryl group is shown, k represents the integer of 0-3, l represents the integer of 2-3, tz represents the integer of 0-4 independently. )

・・・・・（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 is 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. )

  Details of the compounds represented by the general formulas (6) to (9) will be described below.

1.3.1 Compound 6
The polymer represented by the general formula (6) (hereinafter also referred to as “compound 6”) is polymerized in the presence of a catalyst system containing a transition metal compound using, for example, a compound 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。）

(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, 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. And 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.

In addition, as Z constituting -OSO ₂ Z in the above formula (20), an alkyl group such as a methyl group or an ethyl group; a halogenated alkyl group such as a trifluoromethyl group or a pentafluoroethyl group; 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）

(26)

  Specific examples of the compound (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-propenyl) Phenyl) 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 ( -Methylsulfonyloxy-3-propenylphenyl) ropane, 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (4-methylsulfonyloxy-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-propenylphenyl) propane, , 2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, 2,2-bis (p-tolyl) Sulfonyloxyphenyl) 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-tolylsulfonyl) Loxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propyl Lopan, bis (p-tolylsulfonyloxy-3-fluorophenyl) propane, bis (p-tolylsulfonyloxy-3,5-difluorophenyl) propane 9,9-bis (4-methylsulfonyloxyphenyl) 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-dimethylphenyl) diphenylmethane, bi (4-methylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9 , 9-bis (4-methylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4-methylsulfonyloxyphenyl) ) Methane, bis (4-methylsulfonyloxy-3-methylphenyl) methane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-methylsulfonyloxy-3-propenylphenyl) ) Methane, bis (4-methylsulfoniloxif) Nyl) trifluoromethylphenylmethane, bis (4-methylsulfonyloxyphenyl) phenylmethane, 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane, bis (4-trifluoromethylsulfonyl) Loxyphenyl) 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 -Trifluoromethylsulfo Nyloxyphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-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-trifluoromethylsulfonyloxy-3-propenylphenyl) Diphenylmethane, bis (4-trifluoro Romethylsulfonyloxy-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-trifluoromethyl) Sulfonyloxy-3-methylphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) methane, bis (4-trifluoromethyls Phonyloxyphenyl) trifluoromethylphenylmethane, bis (4-trifluoromethylsulfonyloxyphenyl), 2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane, 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-phenylsulfonyloxyphenyl) fluorene, 9 , 9-Bis (4-phenyl Sulfonyloxy-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) diph Nylmethane, 9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4-phenylsulfone) Phonyloxyphenyl) 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-tolylsulfonyloxyphenyl) hexa Fluoropropane, bis (p-tolylsulfo Loxyphenyl) methane, bis (p-tolylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyl) Loxy-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 -Tolylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (p-to Ryl sulfonyloxy-3-phenylphenyl) fluorene, bis (p-tolylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (p- Tolylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (p-tolylsulfonyloxy-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-tolylsulf Nyloxy-3-methylphenyl) methane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) methane, bis (p-tolylsulfonyloxy-3-propenylphenyl) methane, bis (p-tolylsulfonyl) Roxyphenyl) trifluoromethylphenylmethane, bis (p-tolylsulfonyloxyphenyl) phenylmethane, and the like. In the present invention, two or more compounds represented by the general formula (20) may be copolymerized.

  In the present invention, at least one compound represented by the general formula (20) is copolymerized with at least one compound selected from the group consisting of compounds represented by the following general formula (27) and general formula (28). Also good.

・・・・・（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, r represents an integer of 0 to 4; To express.)

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 a pentafluoroethyl group include a propenyl group, and examples of the aryl group include a phenyl group and a pentafluorophenyl group. Moreover, 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 thereof 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)
(In the formula, R ¹² is 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 ³⁵ and R ³⁶ are —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 to 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 Methyl 2,4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, methyl 3,5-dibromobenzoate, methyl 2,4-dibromobenzoate, tert-butyl 2,4-dichlorobenzoate, 3, , 5-dichlorobenzoate-t-butyl, 2,4-dibromobenzoate-t-butyl, 3,5-dibromobenzoate-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%, g is 0 to 95 mol%, preferably 0 to 90 mol%. , H is 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 the production of compound 6 is preferably a catalyst system containing a transition metal compound, and this catalyst system includes (I) a transition metal salt and a ligand, or a transition metal coordinated with a ligand. (Salt) and (II) A reducing agent is an essential component, 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, nickel acetylacetonate, palladium compounds such as palladium chloride, palladium bromide, palladium iodide, iron chloride, 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, nickel bromide and the like are particularly preferable.

  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 include potassium compounds such as potassium, potassium iodide, and potassium sulfate, and 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 use ratio of the ligand is usually 0.1 to 100 mol, preferably 1 to 10 mol, relative to 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. The above compound 6 has a polystyrene-equivalent weight average molecular weight of usually 1,000 to 1,000,000.

1.3.2 Compound 7
The polymer represented by the general formula (7) (hereinafter also referred to as “compound 7”), for example, polymerizes monomers containing compounds represented by the following general formulas (29) to (31) in the presence of a catalyst system. Can be manufactured.

・・・・・（２９）
（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、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 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 ′. -(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 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—, And at least one selected from the group of —S—, —SO ₂ — and a phenylene group, e represents 0 or 1, and q and r represent integers 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)
(In the formula, 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 to 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. %).

  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 dihalogenated compound are used in a proportion of 45 to 55 mol%, preferably 48 to 52 mol%, and 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 for the reaction include pyridine, quinoline, benzophenone, diphenyl ether, dialkoxybenzene (the alkoxyl group has 1 to 4 carbon atoms), trialkoxybenzene (the alkoxyl group has 1 to 4 carbon atoms), diphenylsulfone, 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 that 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.

1.3.3 Compound 8
The polymer represented by the general formula (8) (hereinafter also referred to as “compound 8”) is, for example, at least one selected from the group consisting of compounds represented by the following general formula (32) and general formula (33) And at least one compound selected from the group consisting of the 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 in relation to 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 general formula (11) and the 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 -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-bromopheno C) 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-iodo) Benzoyl) 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) diphenylmethylidene, 9, 9-bis (4-chlorophenyl) fluorene, 9,9-bis (4-iodophenyl) 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-terphenyl, Examples include 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 includes the compound represented by the general formula (32) and / or the compound represented by the general formula (33), the compound represented by the general formula (34) and / or the general formula. Produced by polymerizing the compound represented by (35) in the presence of a catalyst, wherein the compound represented by the general formula (32) and / or the compound represented by the general formula (33), 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 0.8 to 1 mol with respect to 1 mol of the total amount of the former compound. 1.2 mol, preferably 0.9 to 1.1 mol, particularly preferably 0.95 to 1.05. When the total amount of the latter compound 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 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 capable of binding to a palladium salt and palladium as a ligand or forming a complex (including a complex ion) by supplying a group (atomic group) binding as a ligand (hereinafter referred to as a ligand) Formed body), or a 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 it 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 use 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 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, per 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 1 mol, polymerization may not proceed sufficiently, while if it exceeds 100 mol, it is not economical.

1.3.4 Compound 9
The polymer represented by the general formula (9) (hereinafter also referred to as “compound 9”) is obtained by reacting, for example, the following general formula (36) with the compounds represented by the following general formulas (37) and (38). Can be manufactured by.

・・・・・（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) can be obtained by Diels-Alder reaction of the cyclopentadienone group of the general formula (36) and the acetylene groups of the general formulas (37) and (38). it can.

  The number average molecular weight (Mn) of compound 9 is greater than 3,500, preferably greater than 4,000, preferably less than 6,400, more preferably less than 6,000. Moreover, the weight average molecular weight (Mw) of the compound 9 is larger than 500, Preferably it is larger than 8,000, Preferably it is less than 15,000, More preferably, it is less than 12,000. Further, 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 organic film 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 an organic film in the present invention, a film-forming composition (III) is obtained by dissolving at least one polymer selected from the group of compounds 6 to 9 in an organic solvent. The coating composition (III) is applied to a substrate to form a coating film (third coating film), and this coating film is heated. Thereby, an organic film is obtained. Here, as an organic solvent that 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 includes colloidal silica, an organic polymer other than compounds 6 to 9 used for forming an organic film, a surfactant, a silane coupling agent, and radical generation. Components such as an agent, a compound containing a polymerizable double bond, and a polymerizable triple bond may be added. Examples of organic polymers other than compounds 6 to 9 include polymers having a sugar chain structure, vinylamide polymers, (meth) acrylic polymers, aromatic vinyl compound polymers, dendrimers, polyimides, polyamic acids, polyamides. , Polyquinoxaline, polyoxadiazole, fluorine-based polymer, polymer having a polyalkylene oxide structure, and the like.

  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, and amphoteric surfactants, and further include fluorine surfactants, silicone surfactants, Polyalkylene oxide surfactants, poly (meth) acrylate surfactants and the like can be mentioned, and fluorine surfactants and silicone surfactants can be preferably mentioned.

  Examples of the 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, it 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 0-5, and v ′ and w ′ each independently represent an integer of 2-6.)

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.

2. Method for Forming Laminate In the method for forming a laminate of the present invention, a first coating film for a first silica-based film is formed on a substrate, and a second silica is formed on the first coating film. A second coating film having a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond is formed for the system film, and an organic film is formed on the second coating film. Forming a third coating film for curing the laminated film composed of the first to third coating films.

In the method for forming a laminate of the present invention, examples of the substrate on which the first coating film is formed include Si-containing layers such as Si, SiO ₂ , SiN, SiC, and SiCN. When applying the film-forming composition, coating means such as spin coating, dipping method, roll coating method and spray method are used. Next, the organic solvent is removed by, for example, performing a heat treatment on the base material on which the composition for forming an insulating film has been applied. In this way, the first coating film is formed on the substrate. The film thickness of the first coating film is preferably 30 to 500 nm, more preferably 50 to 300 nm.

  Next, a second coating film for the second silica-based film and a third coating film for the organic insulating film are formed on the first coating film. The formation of the second and third coating films can be performed in the same manner as the formation of the first coating film described above. The film thickness of the second coating film is preferably 5 to 100 nm, more preferably 10 to 50 nm. The film thickness of the third coating film is preferably 30 to 500 nm, more preferably 50 to 300 nm.

  Next, a curing process is performed on the laminated film in which the first to third coating films are laminated. The curing process can be performed by heating or electron beam irradiation. When hardening by heating, it can carry out on conditions of 300-500 degreeC, More preferably, 350-450 degreeC preferably.

3. Insulating film The insulating layer of this invention contains the above-mentioned laminated body. Therefore, the insulating layer of the present invention is an insulating layer having a low dielectric constant and improved adhesion. As a result, according to the present invention, 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 the semiconductor device, and semiconductor fabrication using a multilayer resist It is possible to provide an insulating layer that is useful for applications such as an intermediate layer of a process, an interlayer insulating film of a multilayer wiring board, a protective film for a liquid crystal display device, and an insulating film.

4). Semiconductor Device The semiconductor device of the present invention includes the above-described insulating layer. When an insulating layer is used as, for example, an interlayer insulating layer or a planarized insulating layer, the adhesion of the insulating layer is sufficiently secured, so that film peeling during CMP processing or packaging processing is suppressed, and reliability is improved. It is possible to provide a semiconductor device with high accuracy.

5). EXAMPLES 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. In this example, first, film forming composition solutions (I) to (III) for the first silica film, the second silica film, and the organic film were respectively prepared. Thereafter, a laminate was formed using the obtained film-forming composition solutions (I) to (III). The adhesion and relative dielectric constant of the obtained laminate were measured according to the following method.

5.1 Evaluation Method 5.1.1 Adhesiveness The fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate is measured by a four-point bending method, and this fracture toughness is determined as an adhesive property. It was used as an index.

5.1.2 Measurement of relative dielectric constant Aluminum was vapor-deposited on the wafer on which the laminate 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 an HP4284A Precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd.

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

5.2 Synthesis Example 1 (Preparation of film-forming composition solution (I))
In a quartz separable flask, 109.0 g of methyltrimethoxysilane (53 g in terms of complete hydrolysis condensate) in a mixed solution of 80.0 g of 25% tetramethylammonium hydride aqueous solution, 113.0 g of ultrapure water and 1846 g of ethanol And 42 g of tetraethoxysilane (12 g of completely hydrolyzed condensate) were reacted at 60 ° C. for 3 hours, 3920 g of propylene glycol monopropyl ether was added, and then concentrated under reduced pressure to a total solution amount of 630 g. . Thereafter, 30 g of a 10% propylene glycol monopropyl ether solution of acetic acid is added, and the solid content is adjusted to 10% to obtain a film-forming composition solution (I) for the first silica-based film. It was.

5.3 Synthesis Example 2 (Preparation of film-forming composition solution (II))
In a quartz separable flask, 136.23 g of methyltrimethoxysilane (66. conversion in terms of complete hydrolysis condensate) in a mixed solution of 15.84 g of 40% methylamine aqueous solution, 725.72 g of ultrapure water and 1541.7 g of ethanol. 75 g), 166.66 g of tetraethoxysilane (48.33 g of completely hydrolyzed condensate) and 29.65 g of vinyltrimethoxysilane (15.71 g of completely hydrolyzed condensate) were added and reacted at 60 ° C. for 2 hours. Then, after cooling to room temperature, 42.85 g of 60% nitric acid aqueous solution was added to this solution, and the mixture was stirred at room temperature for 1 hour. To this solution, 392.37 g of propylene glycol monopropyl ether was added, and then concentrated under reduced pressure to a total solution amount of 1307.9 g. Thereafter, 65.40 g of a 10% propylene glycol monopropyl ether solution of acetic acid is added to adjust the solid content to 10%, and a film-forming composition solution (II) for the second silica-based film Got.

5.4 Synthesis Example 3 (Preparation of film-forming composition solution (III))
In a 1000 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), 20 ml of piperidine, 4 , 4′-bis (2-iodophenoxy) benzophenone 185.72 g was 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, washed twice with ultrapure water, reprecipitated with 5 liters of methanol, the precipitate was filtered and dried, and the weight average molecular weight was 35,000. The polymer was obtained. 20 g of this polymer was dissolved in 180 g of cyclohexanone to obtain a film-forming composition solution (III) for an organic film.

5.5 Synthesis Example 4 (Preparation of film-forming composition solution (II))
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 is concentrated under reduced pressure to a total solution amount of 13,312.3 g, adjusted to a solid content of 10%, and used for film formation for the second silica-based film. A composition solution (II) was obtained.

5.6 Synthesis Example 5 (Preparation of film-forming composition solution (II))
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, followed by stirring 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 adjust the solid content to 10%, and a film-forming composition solution (II for the second silica-based film) )

5.7 Synthesis Example 6 (Preparation of film-forming composition solution (II))
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 is concentrated under reduced pressure until the total solution amount is 1,353.7 g, adjusted to have a solid content of 10%, and used for film formation for the second silica-based film. A composition solution (II) was obtained.

5.8 Experimental Example 1
The film-forming composition solution (I) obtained in Synthesis Example 1 was filtered with a 0.2 micron pore diameter Teflon (registered trademark) filter, and then applied to an 8-inch silicon wafer with a thickness of 5000 mm. Thereafter, the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute to obtain a first coating film. Next, on the first coating film, the film-forming composition solution (II) obtained in Synthesis Example 2 was filtered through a Teflon (registered trademark) filter having a 0.2 micron pore diameter to obtain a 100-mm film. After coating with a thickness, the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute to obtain a second coating film. Further, on this second coating film, the film-forming composition solution (III) obtained in Synthesis Example 3 was filtered with a 0.2 micron pore diameter Teflon (registered trademark) filter, and a 5000 膜 film was obtained. After coating with a thickness, the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute. Then, this board | substrate was baked for 30 minutes with the hotplate in 400 degreeC nitrogen atmosphere, and the laminated body was created. In order to evaluate the adhesion of the laminate, the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured by a 4-point bending method, and the result was 10 J / m ² . there were. The relative dielectric constant of the laminate was 2.8.

5.9 Experimental Example 2
The same operation as in Experimental Example 1 was performed except that the film forming composition solution (II) obtained in Synthesis Example 4 was used instead of the film forming composition solution (II) obtained in Synthesis Example 2. And a laminate was made. In order to evaluate the adhesion of the laminate, the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured by a 4-point bending method, and was 10 J / m ² . there were. The relative dielectric constant of the laminate was 2.8.

5.10 Experimental Example 3
The same operation as in Experimental Example 1 was performed except that the film-forming composition solution (II) obtained in Synthesis Example 5 was used instead of the film-forming composition solution (II) obtained in Synthesis Example 2. And a laminate was made. In order to evaluate the adhesion of the laminate, the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured by a 4-point bending method, and was 10 J / m ² . there were. The relative dielectric constant of the laminate was 2.8.

5.11 Experimental Example 4
The same operation as in Experimental Example 1 was performed except that the film forming composition solution (II) obtained in Synthesis Example 6 was used instead of the film forming composition solution (II) obtained in Synthesis Example 2. And a laminate was made. In order to evaluate the adhesion of the laminate, the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured by a 4-point bending method, and was 10 J / m ² . there were. The relative dielectric constant of the laminate was 2.8.

5.12 Comparative Example The film-forming composition solution (I) obtained in Synthesis Example 1 was filtered through a Teflon (registered trademark) filter having a 0.2 micron pore diameter, and then 5000 mm on an 8-inch silicon wafer. After coating with a film thickness, the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute to obtain a first coating film. Next, the film-forming composition solution (III) obtained in Synthesis Example 3 was filtered on the first coating film through a Teflon (registered trademark) filter having a 0.2 micron pore diameter, and a 5000-mm film was obtained. After coating with a thickness, the substrate was dried at 80 ° C. for 1 minute and at 200 ° C. for 1 minute. Thereafter, the substrate was baked for 30 minutes on a hot plate in a nitrogen atmosphere at 400 ° C.

When the adhesiveness of this laminated film was measured by a four-point bending method, the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminated body was 4 J / m ² . The relative dielectric constant of the laminate was 2.7.

  As is clear from Experimental Examples 1 to 4 described above, it was found that the laminates of Experimental Examples 1 to 4 had improved adhesion as compared with the comparative example (when there was no second silica-based film). . Thereby, the effect of the laminated body of this invention was confirmed. As a result, according to the laminate of the present invention and the method for forming the same, it is possible to provide an insulating film having a low relative dielectric separation and high adhesion.

Claims (9)

Including a first silica-based film, an organic film, and a second silica-based film provided between the first silica-based film and the organic film ,
It said second silica-based film, a carbon - have a monovalent organic group having a carbon triple bond, - carbon double bond or carbon
The compound which comprises the said organic type film is a laminated body which is a polymer represented by following General formula (8) .

(8)
(Wherein, A and B are each independently represented by the following general formula (10) to (it indicates to at least one group selected from the group consisting of divalent aromatic groups represented by 12).)

(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 ¹⁹ and R ^{22 to} R ²⁴ are 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, Or an aryl group is shown, k represents the integer of 0-3, l represents the integer of 2-3, tz represents the integer of 0-4 independently. ) In claim 1,
The second silica-based film is a hydrolytic condensate obtained by hydrolytic condensation of a silane compound (A) below and a silane compound (B) below in the presence of an acidic or basic or metal chelate compound. The laminated body which is a film | membrane obtained by forming a coating film using the film forming composition containing and hardening | curing this coating film.
(A) At least one silane compound selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2) and a compound represented by the following general formula (3) ,
R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2)
Si (OR ² ) ₄ (2)
(In the formula, 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 to} R ⁶ are the same or different, each is a monovalent organic group, b and c are the same or different, and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or — (CH ₂ ) A group represented by _m- (where m is an integer of 1 to 6), d represents 0 or 1.)
(B) At least one silane compound selected from the group of compounds represented by the following general formula (4) and compounds represented by the following general formula (5).

(4)
(In the formula, R _x is a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, R ^{81 to} R ⁸³ are the same or different, and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, Alternatively, it represents a monovalent organic group, and all of R ^{81 to} R ⁸³ do not become a monovalent organic group at the same time.)

(5)
(Wherein R _y is a divalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond, R ^{91 to} R ⁹⁶ are the same or different, and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, Alternatively, it represents a monovalent organic group, and in the combination of R ^{91 to} R ⁹³ and R ^{94 to} R ⁹⁶ , not all are monovalent organic groups at the same time.) In claim 1 or 2,
The first silica-based film is selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3). A film formed by forming a coating film using a film-forming composition containing a hydrolysis-condensation product obtained by hydrolytic condensation of at least one silane compound, and curing the coating film. body.
R _a Si (OR ¹ ) _4-a (1)
(In the formula, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 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 to} R ⁶ are the same or different, each is a monovalent organic group, b and c are the same or different, and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or — (CH ₂ ) A group represented by _m- (where m is an integer of 1 to 6), d represents 0 or 1.) In any one of Claims 1-3 ,
A laminate having a relative dielectric constant of 2.8 or less. Forming a first coating for the first silica-based film on the substrate;
Forming a second coating film having a monovalent organic group having a carbon-carbon double bond or a carbon-carbon triple bond for the second silica-based film on the first coating film;
Forming a third coating for the organic film on the second coating;
The formation method of the laminated body of Claim 1 including hardening the laminated film which consists of a said 1st-3rd coating film. In claim 5 ,
The said hardening is a formation method of a laminated body performed by heating. In claim 5 ,
The said hardening is a formation method of a laminated body performed by electron beam irradiation. The insulating film which consists of a laminated body in any one of Claims 1-4 . A semiconductor device comprising the insulating film according to claim 8 .