JP5403204B2 - Insulating film forming composition, insulating film manufacturing method, and insulating film obtained thereby - Google Patents

Description

  The present invention relates to an insulating film forming composition, an insulating film manufacturing method, and an insulating film obtained thereby.

  In recent years, large-scale semiconductor integrated circuits (ULSI) have been strongly demanded for higher-speed processing in order to cope with an increasing amount of information processing and complexity of functions. The speeding up of ULSI has been realized by miniaturization and high integration of elements in a chip and multilayering of films. However, with the miniaturization of elements, wiring resistance and inter-wiring parasitic capacitance increase, and wiring delay is becoming a dominant factor in signal delay of the entire device. In order to avoid this problem, introduction of a low resistivity wiring material or a low dielectric constant (Low-k) interlayer insulating film material is an essential technique.

Examples of the low dielectric constant interlayer insulating film include inorganic interlayer insulating films such as a porous silica film having a reduced silica (SiO ₂ ) film density, FSG which is a silica film doped with F, and a SiOC film doped with C. Examples thereof include an organic interlayer insulating film such as a film, polyimide, polyarylene, and polyarylene ether.

In addition, for the purpose of forming a more uniform interlayer insulating film, a coating type interlayer insulating film mainly composed of a hydrolytic condensation product of tetraalkoxysilane called an SOG film or an organic alkoxysilane is hydrolyzed and condensed. An organic SOG film made of polysiloxane has been proposed.
JP 2007-324283 A

  The interlayer insulating film may be composed of two or more different layers. However, in the case of forming an interlayer insulating film formed of two or more different layers by coating, it is necessary to apply each layer separately to form a film, which is troublesome.

  In view of the above-described conventional situation, the present invention provides a composition for easily forming an insulating film having two or more different layers, a method for manufacturing the insulating film, and an insulating film obtained thereby.

A composition for forming an insulating film according to one embodiment of the present invention includes:
Hydrolyzing and condensing at least one 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 polycarbosilane having a hydrolyzable group. Hydrolyzed condensate obtained in the following (hereinafter referred to as polymer A),
R ¹ _a Si (OR ² ) _4-a (1)
(In the formula, R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 2.)
_{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ··· (2)
(In the formula, R ^{3 to} R ⁶ independently represent a monovalent organic group, b and c independently represent a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or (CH ₂ ) Represents a group represented by _m- (wherein m is an integer of 1 to 6), and d represents 0 or 1.)
At least one polymer selected from polyarylene, polyarylene ether, polybenzoxazole, and polyimide (hereinafter referred to as polymer B);
Solvent A and solvent B having a boiling point lower than solvent A at atmospheric pressure;
And satisfy the following formulas (i) and (ii).

Solubility of the polymer A in the solvent A> Solubility of the polymer A in the solvent B (i)
Solubility of the polymer B in the solvent A <Solubility of the polymer B in the solvent B (ii)
In the above composition, the difference between the boiling point of the solvent A and the boiling point of the solvent B may be 40 ° C. or more.

A method for forming an insulating film according to one embodiment of the present invention includes:
Applying the composition to a substrate to form a coating film;
Removing the solvent A and the solvent B from the coating film;
A step of curing the coating film;
including.

  An insulating film according to one embodiment of the present invention is obtained by the above-described insulating film formation method and includes two layers having different compositions.

  Using the above composition, an insulating film having two layers having different compositions can be easily formed by, for example, one application by a coating method.

  The present invention will be specifically described below.

1. Composition for Forming Insulating Film A composition according to an embodiment of the present invention is a composition for forming an insulating film, and has a polymer A and a polymer B, a solvent A and a boiling point at atmospheric pressure lower than that of the solvent A. Solvent B, and satisfy the following formulas (i) and (ii).

Solubility of the polymer A in the solvent A> Solubility of the polymer A in the solvent B (i)
Solubility of the polymer B in the solvent A <Solubility of the polymer B in the solvent B (ii)
By applying the composition according to the present embodiment to a substrate to form a coating film and curing the coating film, an insulating film having two layers having different compositions can be easily formed by a single application. it can. In this case, each layer constituting the insulating film may have a different concentration of a specific component (for example, carbon atom).

  In the composition according to this embodiment, the mixing ratio of the solvent A and the solvent B (solvent A / solvent B) is preferably 0.01 to 100, particularly 0.1 to 10 in terms of weight ratio. preferable.

  In the composition according to this embodiment, the difference between the boiling point of the solvent A and the boiling point of the solvent B is more preferably 40 ° C. or higher. When the difference between the boiling point of the solvent A and the boiling point of the solvent B is less than 40 ° C., the layer containing the polymer A and the layer containing the polymer B may not be sufficiently separated when the membrane is formed.

  The mixing ratio of the polymer A and the polymer B can be appropriately set according to the ratio of the thickness of the film to be formed, but the polymer B is 0.1% with respect to 100 parts by weight of the complete hydrolysis condensate of the polymer A. The amount is preferably 01 to 100 parts by weight, more preferably 0.1 to 10 parts by weight. When the polymer B is less than 0.01 parts by weight, sufficient chemical resistance may not be exhibited after film formation, and when it exceeds 100 parts by weight, it may not be possible to achieve a low dielectric constant of the film. is there.

  The mixing ratio of the polymer A and the polymer B can be appropriately set according to the thickness of the film to be formed, and is usually 0.01% to 50% by weight, preferably 0.1% to 30%. % By weight, particularly preferably 0.5% by weight to 20% by weight.

1.1. Polymer A
Polymer A includes a compound represented by the following general formula (1) (hereinafter also referred to as “compound 1”), a compound represented by the following general formula (2) (hereinafter also referred to as “compound 2”), and hydrolyzable It is a hydrolysis condensate obtained by hydrolytic condensation of at least one compound selected from the group consisting of polycarbosilane having a group (hereinafter also referred to as “compound 3”).

R ¹ _a Si (OR ² ) _4-a (1)
(In the formula, R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 2.)
_{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ··· (2)
(In the formula, R ^{3 to} R ⁶ independently represent a monovalent organic group, b and c independently represent a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or (CH ₂ ) Represents a group represented by _m- (wherein m is an integer of 1 to 6), and d represents 0 or 1.)
Preferable examples of the polymer A include hydrolysis condensates obtained by hydrolytic condensation of tetraethoxysilane, methyltrimethoxysilane, and dimethoxypolycarbosilane described later.

1.1.1. Compound 1
In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an alkenyl group, and an aryl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. The alkyl group preferably has 1 to 5 carbon atoms, and these alkyl groups may be chained or branched. In the general formula (1), examples of the alkenyl group include a vinyl group and an allyl group. 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.

Specific examples of compound 1 include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane;
Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, n- Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n Butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltri Isopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri N-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-t rt-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n- Butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltri-n-propoxysilane Tert-butyltriisopropoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert-butoxysilane , Tert-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri -Tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri- trialkoxysilanes such as tert-butoxysilane and vinyltriphenoxysilane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxy Silane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n- Propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-pro Ludi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane, di-n-propyldi-phenoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi- n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxysilane, di-n-butyldimethoxysilane, di- n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-but Sisilane, di-n-butyldi-tert-butoxysilane, di-n-butyldi-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, Di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldi-phenoxy Silane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane , Di-tert-butyldi-sec- Butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldi-phenoxysilane, diphenyldimethoxysilane, diphenyldi-ethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi- Examples include dialkoxysilanes such as n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert-butoxysilane, diphenyldiphenoxysilane, and divinyldimethoxysilane. These may be used alone or in combination of two or more.

  Particularly preferred compounds as Compound 1 are tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxy. Silane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane Diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like.

1.1.2. Compound 2
In the general formula (2), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same groups as the monovalent organic groups exemplified as R ¹ and R ² in the general formula (1). .

In addition, when R ⁷ is a phenylene group or a group represented by (CH ₂ ) _m —, when b or c is 0 in the general formula (2), one silicon atom is four oxygen atoms. Generation of substituted sites can be prevented.

  In the general formula (2), 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.

Further, as compound 2, in the general formula (2), R ⁷ is a group represented by — (CH ₂ ) _m —, and bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (Tri-n-propoxysilyl) methane, bis (tri-iso-propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxy Silyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane, 1,2-bis (tri -Iso-propoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) Ethane, 1,2-bis (tri-tert-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) Methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-iso-propoxymethylsilyl) -1- (tri-iso-propoxysilyl) methane, 1- (di-n-butoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, (Di-tert-butoxymethylsilyl) -1- (tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimetho Xylsilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di -Iso-propoxymethylsilyl) -2- (tri-iso-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec -Butoxymethylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (tri-tert-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, Bis (diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-iso-propoxymethyl) Silyl) methane, bis (di-n-butoxymethylsilyl) methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) Ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-iso-propoxymethylsilyl) ethane, 1,2 -Bis (di-n-butoxymethylsilyl) ethane, 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethylsilyl) ethane, 1,2-bis (Trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene 1,2-bis (tri-iso-propoxysilyl) 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, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) ) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (di Ethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (di Ethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxy) Silyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) Benzene etc. can be mentioned as a preferable example. Compound 1 and Compound 2 may be used alone or in combination of two or more.

Group 1 represented by R ² O—, R ⁴ O— and R ⁵ O— in General Formula (1) and General Formula (2) above when hydrolyzing and condensing Compound 1 and / or Compound 2 It is preferred to use 0.1 to 100 moles of water per mole. In the present invention, the “completely hydrolyzed condensate” means that the group represented by R ² O—, R ⁴ O— and R ⁵ O— in the condensate component is hydrolyzed to 100%. Shows a completely condensed product.

1.1.3. Compound 3
Compound 3 has a hydrolyzable group and is, for example, a compound represented by the following general formula (3), which is condensed with another monomer for forming polymer A to form a Si—O—Si bond. can do. The hydrolyzable group here refers to an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, or a trifluoromethanesulfone group.

・・・・・（３）
（式中、Ｒ^８は、水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基、およびグリシジル基からなる群より選ばれる基を示し、Ｒ^９はハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、アルキル基、アリール基、アリル基、およびグリシジル基からなる群より選ばれる基を示し、Ｒ^９およびＲ^１０は独立して、ハロゲン原子、ヒドロキシ基、アルコキシ基、アシロキシ基、スルホン基、メタンスルホン基、トリフルオロメタンスルホン基、炭素数２〜６のアルキル基、アリール基、アリル基、およびグリシジル基からなる群より選ばれる基を示し、Ｒ^１１〜Ｒ^１３は独立して、置換または非置換のメチレン基、アルキレン基、アルケニレン基、アルキニレン基、およびアリーレン基からなる群より選ばれる基を示し、ｅ，ｆ，ｇはそれぞれ、１０＜ｅ＋ｆ＋ｇ＜１０，０００の条件を満たす０〜１０，０００の数を示す。）

(3)
(Wherein R ⁸ is a group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ represents a group selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group. R ⁹ and R ¹⁰ independently represent a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl Selected from the group consisting of a group, an allyl group, and a glycidyl group R ^{11 to} R ¹³ independently represent a group selected from the group consisting of a substituted or unsubstituted methylene group, alkylene group, alkenylene group, alkynylene group, and arylene group, and e, f, and g are Each represents a number from 0 to 10,000 that satisfies the condition of 10 <e + f + g <10,000.)

  The weight average molecular weight in terms of polystyrene of compound 3 is preferably 500 to 10,000, more preferably 600 to 5,000, and still more preferably 600 to 3,000. When the polystyrene equivalent weight average molecular weight of Compound 3 exceeds 10,000, layer separation may occur with other monomers for forming the polymer A, and a uniform film may not be formed.

1.2. Polymer B
The polymer B is at least one polymer selected from polyarylene, polyarylene ether, polybenzoxazole, and polyimide.

  Specifically, the polymer B preferably comprises at least one repeating structural unit selected from the group of the following general formulas (4) to (7).

・・・・・（４）

(4)

・・・・・（５）

(5)

・・・・・（６）

(6)

・・・・・（７）
（式（４）〜（７）中、Ｒ^３１〜Ｒ^３５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（８）〜（１０）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^３６，Ｒ^３６’は水素原子または下記一般式（１１）および（１２）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（１３）および（１４）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。）

(7)
(In the formulas (4) to (7), R ^{31 to} R ³⁵ 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 each independently represented by the following general formulas (8) to (10): And at least one group selected from the group consisting of divalent aromatic groups represented by R ³⁶ and R ^{36 ′} is a hydrogen atom or an aromatic group represented by the following general formulas (11) and (12) at least one represents a group, W ^1, W ² is at least one group selected from the group consisting of divalent aromatic groups represented by the following general formula (13) and (14) selected from the group consisting of Is shown.)

・・・・・（８）

(8)

・・・・・（９）

(9)

・・・・・（１０）
（式（８）〜（１０）中、Ｒ^３７、Ｒ^３８、Ｒ^４３およびＲ^４４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

で表される基を示し、Ｒ^３９〜Ｒ^４２およびＲ^４５〜Ｒ^４７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。）

(10)
(In the formulas (8) to (10), R ³⁷ , R ³⁸ , R ⁴³ and R ⁴⁴ are 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 ^{39 to} R ⁴² and R ^{45 to} R ⁴⁷ 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. )

・・・・・（１１）

(11)

・・・・・（１２）
（式（１１）および（１２）中、Ｒ^４８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。）

(12)
(In the formulas (11) and (12), R ⁴⁸ 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.)

・・・・・（１３）

(13)

・・・・・（１４）
（式（１３）および（１４）中、Ｒ^４８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^４９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

で表される基を示し、上記式中Ｒ^５０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。）

(14)
(In the formulas (13) and (14), R ⁴⁸ 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 ⁴⁹ is a single bond, —O—, —CO—, —CH ₂ —, —COO—, —CONH—, —S—, —SO ₂ —, a phenylene group, an isopropylidene group, a hexafluoroisopropylidene group, Diphenylmethylidene group, methylphenylmethylidene group, trifluoromethylmethylmethylidene group, trifluoromethylphenylmethylidene group, fluorenylene group, or formula

In the above formula, R ⁵⁰ independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group, and a1 and a2 each independently represents an integer of 0 to 4. , A3 represents an integer of 0-6. )

  Details of the compounds represented by the general formulas (4) to (7) will be described below.

1.2.1. Compound 4
The polymer represented by the general formula (4) (hereinafter also referred to as “compound 4”) 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 (15) as a monomer. Can be manufactured.

・・・・・（１５）
（式中、Ｒ^３１，Ｒ^３２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。）

(15)
(Wherein R ³¹ and R ³² 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 (15), 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 the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group; examples of the arylalkyl group include a benzyl group and a diphenylmethyl group; examples of the aryl group include a phenyl group, a biphenyl group, a tolyl group, and a pentafluorophenyl group. And so on.

As the Z constituting the -OSO 2 _Z in the above formula (15), as the alkyl group, methyl group, ethyl group; Examples of the halogenated alkyl group, a trifluoromethyl group, etc. pentafluoroethyl group; an aryl Examples of the group include a phenyl group, a biphenyl group, a p-tolyl group, and a p-pentafluorophenyl group. X in the general formula (15) is preferably a divalent group represented by the following general formulas (16) to (21). Of these, the fluorenylene group represented by the general formula (27) is more preferable.

-C (CH ₃ ) _2- (16)
-C (CF ₃ ) _2- (17)
-C (CF ₃ ) (C ₆ H ₅ )-(18)
—CH (CH ₃ ) — (19)
-C (C ₆ H ₅ ) _2- (20)

・・・・・（２１）
上記一般式（２１）に示す化合物（モノマー）の具体例としては、例えば、２，２−ビス（４−メチルスルフォニロキシフェニル）ヘキサフルオロプロパン、ビス（４−メチルスルフォニロキシフェニル）メタン、ビス（４−メチルスルフォニロキシフェニル）ジフェニルメタン、２，２−ビス（４−メチルスルフォニロキシ−３−メチルフェニル）ヘキサフルオロプロパン、２，２−ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）ヘキサフルオロプロパン、２，２−ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、２，２−ビス（４−メチルスルフォニロキシフェニル）プロパン、２，２−ビス（４−メチルスルフォニロキシ−３−メチルフェニル）プロパン、２，２−ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）ロパン、２，２−ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（４−メチルスルフォニロキシ−３−フルオロフェニル）プロパン、２，２−ビス（４−メチルスルフォニロキシ−３，５−ジフルオロフェニル）プロパン、２，２−ビス（４−トリフルオロメチルスルフォニロキシフェニル）プロパン、２，２−ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）プロパン、２，２−ビス（４−フェニルスルフォニロキシフェニル）プロパン、２，２−ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）プロパン、２，２−ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）プロパン、２，２−ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（４−フェニルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、２，２−ビス（ｐ−トリルスルフォニロキシフェニル）プロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）プロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）プロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）プロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）プロパン、ビス（ｐ−トリルスルフォニロキシ−３−フルオロフェニル）プロパン、ビス（ｐ−トリルスルフォニロキシ−３，５−ジフルオロフェニル）プロパン９，９−ビス（４−メチルスルフォニロキシフェニル）フルオレン、９，９−ビス（４−メチルスルフォニロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）フルオレン、９，９−ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）フルオレン、９，９−ビス（４−メチルスルフォニロキシ−３−フェニルフェニル）フルオレン、ビス（４−メチルスルフォニロキシ−３−メチルフェニル）ジフェニルメタン、ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）ジフェニルメタン、ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）ジフェニルメタン、ビス（４−メチルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、ビス（４−メチルスルフォニロキシ−３，５−ジフルオロフェニル）ジフェニルメタン、９，９−ビス（４−メチルスルフォニロキシ−３−フルオロフェニル）フルオレン、９，９−ビス（４−メチルスルフォニロキシ−３，５−ジフルオロフェニル）フルオレン、ビス（４−メチルスルフォニロキシフェニル）メタン、ビス（４−メチルスルフォニロキシ−３−メチルフェニル）メタン、ビス（４−メチルスルフォニロキシ−３，５−ジメチルフェニル）メタン、ビス（４−メチルスルフォニロキシ−３−プロペニルフェニル）メタン、ビス（４−メチルスルフォニロキシフェニル）トリフルオロメチルフェニルメタン、ビス（４−メチルスルフォニロキシフェニル）フェニルメタン、２，２−ビス（４−トリフルオロメチルスルフォニロキシフェニル）ヘキサフルオロプロパン、ビス（４−トリフルオロメチルスルフォニロキシフェニル）メタン、ビス（４−トリフルオロメチルスルフォニロキシフェニル）ジフェニルメタン、２，２−ビス（４−トリフルオロメチルスルフォニロキシ−３−メチルフェニル）ヘキサフルオロプロパン、２，２−ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）ヘキサフルオロプロパン、２，２−ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、９，９−ビス（４−トリフルオロメチルスルフォニロキシフェニル）フルオレン、９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジメチルフェニル）フルオレン、９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）フルオレン、９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３−フェニルフェニル）フルオレン、ビス（４−トリフルオロメチルスルフォニロキシ−３−メチルフェニル）ジフェニルメタン、ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジメチルフェニル）ジフェニルメタン、ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）ジフェニルメタン、ビス（４−トリフルオロメチルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジフルオロフェニル）ジフェニルメタン、９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３−フルオロフェニル）フルオレン、９，９−ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジフルオロフェニル）フルオレン、ビス（４−トリフルオロメチルスルフォニロキシフェニル）メタン、ビス（４−トリフルオロメチルスルフォニロキシ−３−メチルフェニル）メタン、ビス（４−トリフルオロメチルスルフォニロキシ−３，５−ジメチルフェニル）メタン、ビス（４−トリフルオロメチルスルフォニロキシ−３−プロペニルフェニル）メタン、ビス（４−トリフルオロメチルスルフォニロキシフェニル）トリフルオロメチルフェニルメタン、ビス（４−トリフルオロメチルスルフォニロキシフェニル）、２，２−ビス（４−フェニルスルフォニロキシフェニル）ヘキサフルオロプロパン、ビス（４−フェニルスルフォニロキシフェニル）メタン、ビス（４−フェニルスルフォニロキシフェニル）ジフェニルメタン、２，２−ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）ヘキサフルオロプロパン、２，２−ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）ヘキサフルオロプロパン、２，２−ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、９，９−ビス（４−フェニルスルフォニロキシフェニル）フルオレン、９，９−ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）フルオレン、９，９−ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）フルオレン、９，９−ビス（４−フェニルスルフォニロキシ−３−フェニルフェニル）フルオレン、ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）ジフェニルメタン、ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）ジフェニルメタン、ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）ジフェニルメタン、ビス（４−フェニルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、ビス（４−フェニルスルフォニロキシ−３，５−ジフルオロフェニル）ジフェニルメタン、９，９−ビス（４−フェニルスルフォニロキシ−３−フルオロフェニル）フルオレン、９，９−ビス（４−フェニルスルフォニロキシ−３，５−ジフルオロフェニル）フルオレン、ビス（４−フェニルスルフォニロキシフェニル）メタン、ビス（４−フェニルスルフォニロキシ−３−メチルフェニル）メタン、ビス（４−フェニルスルフォニロキシ−３，５−ジメチルフェニル）メタン、ビス（４−フェニルスルフォニロキシ−３−プロペニルフェニル）メタン、ビス（４−フェニルスルフォニロキシフェニル）トリフルオロメチルフェニルメタン、ビス（４−フェニルスルフォニロキシフェニル）フェニルメタン、２，２−ビス（ｐ−トリルスルフォニロキシフェニル）ヘキサフルオロプロパン、ビス（ｐ−トリルスルフォニロキシフェニル）メタン、ビス（ｐ−トリルスルフォニロキシフェニル）ジフェニルメタン、２，２−ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）ヘキサフルオロプロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）ヘキサフルオロプロパン、２，２−ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、９，９−ビス（ｐ−トリルスルフォニロキシフェニル）フルオレン、９，９−ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）フルオレン、９，９−ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）フルオレン、９，９−ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）フルオレン、９，９−ビス（ｐ−トリルスルフォニロキシ−３−フェニルフェニル）フルオレン、ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）ジフェニルメタン、ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）ジフェニルメタン、ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）ジフェニルメタン、ビス（ｐ−トリルスルフォニロキシ−３−フルオロフェニル）ジフェニルメタン、ビス（ｐ−トリルスルフォニロキシ−３，５−ジフルオロフェニル）ジフェニルメタン、９，９−ビス（ｐ−トリルスルフォニロキシ−３−フルオロフェニル）フルオレン、９，９−ビス（ｐ−トリルスルフォニロキシ−３，５−ジフルオロフェニル）フルオレン、ビス（ｐ−トリルスルフォニロキシフェニル）メタン、ビス（ｐ−トリルスルフォニロキシ−３−メチルフェニル）メタン、ビス（ｐ−トリルスルフォニロキシ−３，５−ジメチルフェニル）メタン、ビス（ｐ−トリルスルフォニロキシ−３−プロペニルフェニル）メタン、ビス（ｐ−トリルスルフォニロキシフェニル）トリフルオロメチルフェニルメタン、ビス（ｐ−トリルスルフォニロキシフェニル）フェニルメタンなどを挙げることができる。本発明においては、上記一般式（２１）に示す化合物を２種以上共重合することもできる。

(21)
Specific examples of the compound (monomer) represented by the general formula (21) 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 (21) may be copolymerized.

  In the present invention, at least one compound represented by the general formula (15) is copolymerized with at least one compound selected from the group consisting of compounds represented by the following general formula (22) and general formula (23). Also good.

・・・・・（２２）
（式中、Ｒ^３３，Ｒ^３４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^５６，Ｒ^５７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。）

(22)
(In the formula, R ³³ and R ³⁴ 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 ⁵⁶ , R ⁵⁷ 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; Represents.)

In the general formula (22), among R ³³ and R ³⁴ , the halogen atom is a fluorine atom, etc. The monovalent organic group is an alkyl group, a methyl group, an ethyl group, or the like, as a halogenated alkyl group, Examples of the allyl group such as a trifluoromethyl group and pentafluoroethyl group include a propenyl group, and examples of the aryl group include a phenyl group and a pentafluorophenyl group. Further, as Z constituting -OSO ₂ Z in R ⁵⁶ and R ⁵⁷ , 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 (22) include 4,4′-dimethylsulfonyloxybiphenyl, 4,4′-dimethylsulfonyloxy-3,3′-dipropenylbiphenyl, and 4,4′-dibromo. Biphenyl, 4,4′-diiodobiphenyl, 4,4′-dimethylsulfonyloxy-3,3′-dimethylbiphenyl, 4,4′-dimethylsulfonyloxy-3,3′-difluorobiphenyl, 4,4 '-Dimethylsulfonyloxy-3,3', 5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl, 4,4-methylsulfonyloxyoctafluorobiphenyl, 3,3'-diallyl- 4,4′-bis (4-fluorobenzenesulfonyloxy) biphenyl, 4,4′-dichloro-2,2′-trifluoro Methylbiphenyl, 4,4′-dibromo-2,2′-trifluoromethylbiphenyl, 4,4′-diiodo-2,2′-trifluoromethylbiphenyl, bis (4-chlorophenyl) sulfone, 4,4′- Examples include dichlorobenzophenone and 2,4-dichlorobenzophenone. The compounds represented by the general formula (22) can be used singly or in combination of two or more.

(23)
(In the formula, R ³⁵ 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, and R ⁵⁸ and R ⁵⁹ 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 (23), among R ³⁵ , a halogen atom such as a fluorine atom, a monovalent organic group such as an alkyl group, a methyl group, an ethyl group, or the like as 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 ⁵⁸ and R ⁵⁹ , 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 (23) 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 (23) can be used singly or in combination of two or more.

  In the general formula (4), the proportion of the repeating structural unit in the compound 4 is 5 to 100 mol%, preferably 5 to 95 mol%, and 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 4 is preferably a catalyst system containing a transition metal compound. 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 a 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 Examples include octadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium, and the like. 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 above general formula (15), the above general formula (22), and the above general formula. It is 0.0001-10 mol normally with respect to 1 mol of total amounts of the compound shown by (23), 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 (15), the compound represented by the general formula (22) and the compound represented by the general formula (23) 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 proportion of use is represented by the compound represented by the general formula (15), the compound represented by the general formula (22) and the general formula (23). 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 total concentration of the compound represented by the general formula (15), the compound represented by the general formula (22) and the compound represented by the general formula (23) in the polymerization solvent is usually 1 to 100% by weight. It is preferably 5 to 40% by weight. Moreover, the polymerization temperature at the time of superposing | polymerizing the said polymer is 0-200 degreeC normally, Preferably it is 50-80 degreeC. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours. In addition, the weight average molecular weight of the above-mentioned compound 4 in terms of polystyrene is usually 1,000 to 1,000,000.

1.2.2. Compound 5
The polymer represented by the general formula (5) (hereinafter also referred to as “compound 5”), for example, polymerizes a monomer containing a compound represented by the following general formulas (24) to (26) in the presence of a catalyst system. Can be manufactured.

・・・・・（２４）
（式中、Ｒ^３１，Ｒ^３２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^６０，Ｒ^６１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。）

(24)
(In the formula, R ³¹ and R ³² 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 ⁶⁰ and R ⁶¹ 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 (24) 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 (24) may be copolymerized.

・・・・・（２５）
（式中、Ｒ^３３，Ｒ^３４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^６２，Ｒ^６３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。）

(25)
(Wherein R ³³ and R ³⁴ 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 ⁶² , R ⁶³ 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 (25) 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 (25) can be used singly or in combination of two or more.

・・・・・（２６）
（式中、Ｒ^３５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^５８，Ｒ^５９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。）、水酸基、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。）

(26)
(In the formula, R ³⁵ 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 ⁵⁸ and R ⁵⁹ represent —OSO _2. Z (wherein Z represents an alkyl group, a halogenated alkyl group, or an aryl group), a hydroxyl 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 (26) 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 (26) can be used singly or in combination of two or more. The proportion of the repeating structural unit in the compound 5 represented by the general formula (5) is as follows: in the general formula (5), I is 0 to 100 mol%, j is 0 to 100 mol% (where I + j = 100 mol) %).

  As a synthesis method of the compound 5 represented by the general formula (5), for example, it can be obtained by heating a bisphenol compound and a dihalogenated compound in a solvent in the presence of an alkali metal compound. The bisphenol compound and the dihalogenated compound are used in an amount of 45 to 55 mol%, preferably 48 to 52 mol%, and 55 to 45 mol%, preferably 52 to 48 mol%, of the dihalogenated compound. 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 accelerate the reaction, metal copper, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous sulfate, Co-catalysts such as cupric sulfate, cuprous acetate, cupric acetate, cuprous formate, and cupric formate may be used. The amount of the cocatalyst used is usually 1 to 50 mol%, preferably 1 to 30 mol%, based on the bisphenol compound.

  Examples of the solvent used in the reaction include pyridine, quinoline, benzophenone, diphenyl ether, dialkoxybenzene (the alkoxy group has 1 to 4 carbon atoms), trialkoxybenzene (the alkoxy group has 1 to 4 carbon atoms), diphenyl sulfone, Dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrofuran, tetrahydrothiophene, sulfolane, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, dimethylformamide, Dimethylacetamide and the like can be used. These may be used alone or in combination of two or more. The reaction concentration when synthesizing the compound 5 represented by the general formula (5) is 2 to 50% by weight based on the weight of the monomer, and the reaction temperature is 50 to 250 ° C. Moreover, in order to remove the metal salt and unreacted monomer generated at the time of polymer synthesis, the reaction solution is filtered, or the reaction solution is reprecipitated with a solvent which is a poor solvent for the polymer, or washed with an acidic or alkaline aqueous solution. Is preferred. Thus, the weight average molecular weight by GPC method of the compound 5 obtained is 500-500,000 normally, Preferably it is 800-100,000.

1.2.3. Compound 6
The polymer represented by the general formula (6) (hereinafter also referred to as “compound 6”) is, for example, at least one selected from the group consisting of compounds represented by the following general formula (27) and general formula (28) And at least one compound selected from the group consisting of compounds represented by the following general formula (27) and general formula (28) in the presence of a catalyst.

・・・・・（２７）

(27)

・・・・・（２８）
（式中、Ｒ^３７〜Ｒ^４２およびｋ，ｔ，ｕ，ｖ，ｗは上記一般式（８）および上記一般式（９）に関して定義した通りである。）

(28)
(In the formula, R ^{37 to} R ⁴² and k, t, u, v, and w are as defined in relation to the general formula (8) and the general formula (9).)

・・・・・（２９）

(29)

・・・・・（３０）
（式中、Ｒ^４２〜Ｒ^４７およびｌ，ｗ，ｘ，ｙ，ｚは上記一般式（９）および上記一般式（１０）に関して定義した通りであり、Ｘ’はハロゲン原子を示す。）

(30)
(In the formula, R ^{42 to} R ⁴⁷ and l, w, x, y, z are as defined in relation to the general formula (9) and the general formula (10), and X ′ represents a halogen atom.)

  Examples of the compound represented by the general formula (27) 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 (28) include 1,2-diethynylbenzene, 1,3-diethynylbenzene, 1,4-diethynylbenzene, 2,5-diethynyltoluene, 3,4, and the like. -Diethynyl toluene etc. can be mentioned. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously.

  Examples of the compound represented by the general formula (29) include 1,2-bis (2-bromophenoxy) benzene, 1,2-bis (2-iodophenoxy) benzene, and 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 (30) 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 6 includes the compound represented by the general formula (27) and / or the compound represented by the general formula (28), the compound represented by the general formula (29) and / or the general formula. Produced by polymerizing the compound represented by (30) in the presence of a catalyst, wherein the compound represented by the general formula (27) and / or the compound represented by the general formula (28), The proportion of the compound represented by the general formula (29) and / or the compound represented by the general formula (30) 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 6, it is preferable to polymerize the compounds represented by the general formulas (27) to (30) in the presence of a catalyst containing a transition metal compound. Furthermore, a catalyst containing a transition metal compound and a basic compound is more preferable, and a catalyst composed of the following components (a), (b) and (c) is particularly preferable.

(A) a substance that binds to a palladium salt and palladium as a ligand or can form a complex (including complex ions) by supplying a group (atomic group) that binds as a ligand (hereinafter referred to as a ligand) Formed body), or palladium complex (additional ligand-forming body may be added if necessary)
(B) Monovalent copper compound (c) Basic compound Among the components (a), examples of the palladium salt include palladium chloride, palladium bromide, palladium iodide and the like. These compounds may be used individually by 1 type, or may use 2 or more types simultaneously. Here, the use ratio of the palladium salt is preferably 0.0001 to 10 mol, and more preferably 0.001 to 1 mol with respect to 1 mol of the total amount of the compounds represented by the general formulas (27) to (30). 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 use ratio of the ligand-former 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 above general formulas (27) to (30). Is a mole. If the amount is less than 0.0004 mol, polymerization may not proceed sufficiently. On the other hand, if the amount 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 (27) to (30). Is a 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.

(B) Examples of monovalent copper compounds include copper chloride (I), copper bromide (I), and copper iodide (I).
Etc. 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, to 1 mol of the total amount of the compounds represented by the general formulas (33) to (36). Is 0.001-1 mol. 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.

  (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 mol with respect to 1 mol of the total amount of the compounds represented by the general formulas (27) to (30). 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.

1.2.4. Compound 7
The polymer represented by the general formula (7) (hereinafter also referred to as “compound 7”) includes, for example, the following general formula (31), the compound represented by the following general formula (32) and / or the following general formula (33). It can manufacture by making the compound shown to react.

・・・・・（３１）

(31)

・・・・・（３２）

... (32)

・・・・・（３３）
（式（３１）〜（３３）中、Ｒ^３６，Ｒ^３６’は水素原子または上記一般式（１１）および（１２）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（１３）および（１４）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。）

(33)
(In the formulas (31) to (33), R ³⁶ and R ^{36 ′} represent a hydrogen atom or at least one group selected from the group of aromatic groups represented by the general formulas (11) and (12). W ¹ and W ² represent at least one group selected from the group consisting of divalent aromatic groups represented by the general formulas (13) and (14).

  Compound 7 represented by the general formula (7) undergoes a Diels-Alder reaction between the cyclopentadienone group of the general formula (31) and the acetylene group of the general formula (32) and / or the general formula (33). Can be obtained.

  The number average molecular weight (Mn) of compound 7 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 7 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 7 preferably has a polydispersity (Mw / Mn) of less than about 2.5, more preferably less than about 2.3.

1.3. Solvent A
Examples of the solvent A include propylene such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether. Glycol solvents are preferred.

  The boiling point of the solvent A under atmospheric pressure is preferably 100 ° C to 250 ° C, and more preferably 100 ° C to 180 ° C.

1.4. Solvent B
As the solvent B, for example, heptane, cyclohexanone, ethyl ethoxypropionate, ethyl lactate, and γ-butyl lactone are preferably used.

  Further, the boiling point of the solvent B under atmospheric pressure is preferably 30 ° C. to 100 ° C., more preferably 50 ° C. to 90 ° C., and particularly preferably 60 to 80 ° C. For example, when the boiling point is lower than 30 ° C., the solvent may evaporate before the composition is applied to form a coating film, and a uniform coating film may not be formed. On the other hand, when the boiling point of the solvent B is higher than 100 ° C., it is necessary to sufficiently heat.

  Further, the solvent A and the solvent B used in the present invention must be compatible. The compatibility is only required to have such a degree of compatibility that the solvent A and the solvent B are not separated in the specific configuration of the composition.

2. Method for Forming Insulating Film A method for forming an insulating film according to an embodiment of the present invention includes a step of applying the composition to a substrate to form a coating film, and removing solvent A and solvent B from the coating film. And a step of performing a curing process on the coating film.

  In this embodiment, when a composition is applied to a substrate to form a coating film, examples of the coating means include spin coating, dipping method, roll coating method, spray method, and scan coating method.

  The removal of the solvent A and the solvent B from the coating film is specifically performed by evaporating the solvent. Specifically, the solvents A and B can be evaporated by heating as necessary, but the solvent A having a high boiling point is preferably evaporated by heating. Note that the solvent may not be completely removed, and the solvent may remain within a range where the properties as a cured film can be obtained.

  According to the method for forming an insulating film according to the present embodiment, a lower layer in which the polymer A exists at a high density (for example, a lower layer mainly composed of the polymer A having higher compatibility with the solvent A than the solvent B), An insulating film having an upper layer substantially free from the polymer A (for example, an upper layer mainly composed of the polymer B having higher compatibility with the solvent B than the solvent A) can be formed. Here, when the boiling point of the solvent B at atmospheric pressure is lower than that of the solvent A, the solvent A and the solvent B can be efficiently removed.

  Moreover, hardening of a coating film can be performed using at least 1 sort (s) chosen from a heating, ultraviolet irradiation, and electron beam irradiation, and it is preferable to carry out using heating and ultraviolet irradiation simultaneously.

  When the coating is cured by heating, it is preferably performed at 300 to 450 ° C, more preferably 350 to 400 ° C. In this case, the heating time is usually preferably less than 60 minutes, and more preferably 30 minutes. Moreover, when hardening a coating film by ultraviolet irradiation, it is preferable that the wavelength of the ultraviolet-ray used for ultraviolet irradiation is 300 nm or less, and it is more preferable that it is 220-270 nm. In this case, the heating and ultraviolet irradiation time is preferably less than 10 minutes, and more preferably 1 to 5 minutes.

  As the heating means, for example, a hot plate, an oven, a furnace, or the like can be used.

  Examples of constituents of the atmosphere other than oxygen include nitrogen and argon. The pressure is preferably normal pressure.

3. Insulating Film An insulating film according to an embodiment of the present invention is obtained by the above insulating film forming method. When the composition for forming the insulating film described above is applied by a normal method and then the solvent is removed, the composition is separated into two or more layers. Here, examples of the two or more layers include a case where the two or more layers include both “a layer in which polymer A is present at high density” and “a layer in which polymer A is substantially absent”. The insulating film according to the present embodiment includes, for example, two or more layers having different compositions. An insulating film having two or more layers having different compositions can be suitably used as, for example, an insulating film used in a copper damascene wiring structure.

  In this case, two layers having different compositions may have different concentrations of specific components (for example, carbon atoms) in the depth direction in each layer. As an insulating film in which the concentration of carbon atoms differs in the depth direction of the insulating film, for example, an insulating film in which the concentration of carbon atoms increases as it approaches the surface, or an insulating film in which the concentration of carbon atoms decreases as it approaches the surface. Can be mentioned. Among these, the insulating film, whose concentration of carbon atoms increases as it approaches the surface of the insulating layer, has a higher concentration of carbon atoms near the surface, and therefore processes such as etching and chemical treatment compared to insulating films with a uniform composition. Excellent resistance.

  An example of the insulating film according to this embodiment is shown in FIG. The insulating film 100 shown in FIG. 1 is obtained by applying the above composition to a base material to form a coating film, and performing a curing treatment on the coating film, and mainly by curing the polymer A. And a second film 10 obtained by curing a coating film mainly containing the polymer B.

4). EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In the examples and comparative examples, “parts” and “%” indicate parts by weight and% by weight, respectively, unless otherwise specified.

4.1. Evaluation method 4.1.1. Contact angle In order to evaluate the hydrophobicity of the polymer film, the contact angle was measured by dropping ultrapure water droplets onto the surface of the polymer film using a contact angle measuring device (DropMaster 500) manufactured by Kyowa Interface Science Co., Ltd. . When the hydrophobicity is high, the resistance to RIE and chemicals is good (good process resistance).

4.1.2. Chemical Solution Resistance An 8-inch wafer on which a polymer film was formed was immersed in a 0.2% dilute hydrofluoric acid aqueous solution at room temperature for 3 minutes, and the change in film thickness before and after the immersion of the polymer film was observed. When the remaining film rate defined below is 99% or more, it is judged that the chemical solution resistance is good (“A”), and when the remaining film rate is less than 99%, the chemical solution resistance is not good (“B”). ).
Remaining film ratio (%) = (film thickness after immersion) / (film thickness before immersion) × 100

4.1.3. Two-layer observation It was confirmed by TEM observation whether the polymer film was separated into two layers by one application. Table 2 shows the case where the two-layer separation was confirmed as “A” and the case where the two-layer separation was not confirmed as “B”.

4.1.4. Solubility The solubility of the polymer in each solvent was measured with x [g / 100 g] as the solubility when the polymer was dissolved in 100 g of the solvent. The results are shown in Table 1.

4.2. Preparation Example 4.2.1. Preparation Example 1 (Preparation of Reaction Solution 1)
After replacing the inside of a 4 L flask with a 4 L capacity equipped with a thermometer, a cooling condenser, a dropping funnel and a stirrer with argon gas, 1.5 L of dry tetrahydrofuran and 71 g of metallic magnesium were charged and bubbled with argon gas. . Thereafter, while stirring at 20 ° C., 500 g of chloromethyltriethoxysilane was slowly added from the dropping funnel. After completion of the dropwise addition, stirring was further continued at 0 ° C. for 12 hours. Hexane was added to the reaction solution, followed by filtration through celite, and the filtrate was dried under vacuum to completely remove the organic solvent in a vacuum oven to obtain a polycarbosilane having a brown solid hydrolyzable group. The weight average molecular weight of the polycarbosilane thus obtained was 420.

  In a quartz separable flask, 40 g of methyltrimethoxysilane, 18 g of tetramethoxysilane, 26 g of polycarbosilane having a hydrolyzable group obtained above, and 17 g of a 20% aqueous solution of tetramethylammonium hydroxide were added to 500 g of ethanol. Then, the mixture was stirred with a three-one motor to stabilize the solution temperature at 55 ° C. Next, a mixed solution of 47 g of ion-exchanged water and 500 g of dipropylene glycol monobutyl ether (boiling point: 230 ° C., hereinafter referred to as “solvent A”) was added to the solution over 1 hour.

  Then, after making it react at 55 degreeC for 4 hours, 24 g of 10% propylene glycol monopropyl ether solutions of acetic acid were added, it was made to react for 30 minutes, and the reaction liquid was cooled to room temperature. A solution containing methanol and water was removed from the reaction solution at 50 ° C. by evaporation to obtain a reaction solution 1 (solid content concentration 10%) in which the polymer A was dissolved in the solvent A.

4.2.2. Preparation Example 2 (Preparation of Reaction Solution 2)
-Preparation of film-forming composition (2) for organic film 1000 ml three-necked flask equipped with thermometer, argon gas inlet tube, stirring device 120 ml tetrahydrofuran, 3.46 g dichlorobistriphenylphosphine palladium, copper iodide 1.44 g, piperidine 20 ml, 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 methanol, then dissolved in cyclohexanone, washed twice with ultrapure water, further reprecipitated with 5 liters of methanol, the precipitate was filtered and dried, and the weight average molecular weight 35,000 polymer B was obtained. 2 g of polymer B and 0.05 g of polyvinyl methoxysiloxane having a weight average molecular weight of 500 were dissolved in 18 g of cyclohexanone (boiling point 155 ° C., hereinafter referred to as “solvent B”), and 0.2 μm pore size polytetrafluoroethylene (manufactured by DuPont) And filtration with a filter made of Teflon (registered trademark) to obtain a reaction solution 2 containing the polymer B.

4.3. Example 4.3.1. Example 1
The reaction solution 1 and the reaction solution 2 were blended so that the weight ratio of the polymer was 50:50, 0.1 phr of dimethylpolysiloxane was added as a leveling agent, and the mixture was stirred for 30 minutes with a mix rotor. A forming composition was obtained.

4.3.2. Comparative Example 1
To 50 g of the reaction solution 1, 5 g of polymer B and 45 g of dipropylene glycol monobutyl ether (solvent A) are added and blended, 0.1 phr of dimethylpolysiloxane is added as a leveling agent, and the mixture is stirred for 30 minutes with a mix rotor. The film forming composition of Comparative Example 1 was obtained. However, polymer precipitation was observed with this composition.

4.3.3. Film Formation The composition for film formation of Example 1 and the reaction solution 2 were respectively applied to an 8-inch silicon wafer by using a spin coating method, and were heated on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. After drying the substrate for 3 minutes, the substrate was baked on a hot plate at 420 ° C. for 30 minutes to form the polymer films (film thickness 0.5 μm) of Example 1 and Reference Example 1, respectively.

  According to Table 2, the film obtained using the film-forming composition of Example 1 has high hydrophobicity, excellent chemical resistance, a lower layer in which polymer A is present in high density, and polymer A is substantially It consists of two layers with the upper layer that does not exist. This is clear when compared with the membrane of Reference Example 1 obtained using only Polymer B.

FIG. 1 is a diagram schematically showing an insulating film according to an embodiment of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... 2nd film | membrane (upper layer), 20 ... 1st film | membrane (lower layer), 100 ... Insulating film

Claims (4)

Hydrolyzing and condensing at least one 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 polycarbosilane having a hydrolyzable group. A polymer A composed of the hydrolyzed condensate obtained by
R ¹ _a Si (OR ² ) _4-a (1)
(In the formula, R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 2.)
_{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ··· (2)
(In the formula, R ^{3 to} R ⁶ independently represent a monovalent organic group, b and c independently represent a number of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or (CH ₂ ) Represents a group represented by _m- (wherein m is an integer of 1 to 6), and d represents 0 or 1.)
Polymer B comprising at least one polymer selected from polyarylene, polyarylene ether, polybenzoxazole, and polyimide;
Solvent A and solvent B having a boiling point lower than solvent A at atmospheric pressure;
It includes, and meets the following formula (i) and (ii),
A composition for forming an insulating film, which is used for forming an insulating film having two layers having different compositions.
Solubility of the polymer A in the solvent A> Solubility of the polymer A in the solvent B (i)
Solubility of the polymer B in the solvent A <Solubility of the polymer B in the solvent B (ii)   The composition according to claim 1, wherein the difference between the boiling point of the solvent A and the boiling point of the solvent B is 40 ° C. or more. Applying the composition according to claim 1 or 2 to a substrate to form a coating film;
Removing the solvent A and the solvent B from the coating film;
A step of curing the coating film;
An insulating film forming method including: An insulating film obtained by the method for forming an insulating film according to claim 3 and having two layers having different compositions.

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