WO2014084188A1

WO2014084188A1 - Fluorine-containing polymerizable monomer and polymer compound using same

Info

Publication number: WO2014084188A1
Application number: PCT/JP2013/081701
Authority: WO
Inventors: 山中　一広; 健資須田; 大樹魚山
Original assignee: セントラル硝子株式会社
Priority date: 2012-11-28
Filing date: 2013-11-26
Publication date: 2014-06-05
Also published as: KR20150046164A; JP2014129339A; JP6268959B2

Abstract

Provided are: an HFIP-group-containing fluorine diamine represented by formula (2) and obtained by introducing an HFIP group to a fluorine diamine compound; and an HFIP-group-containing polymer compound. (In the formula, R¹ represents one type of substituent group selected from a group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C1-4 alkyl group, a C1-4 fluoroalkyl group in which an arbitrary number of hydrogen atoms are replaced with fluorine atoms, a phenyl group, a methoxy group, and a nitro group. R² represents one type of substituent group selected from a group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, a sulfonic acid group, a -C≡C-C(CH₃)₂OH group, a -C≡C-C₆H₅ group, and a -C≡C-Si(CH₃)₃ group. HFIP represents a -C(CF₃)₂OH group. m and n each independently represent an integer of 0-2. 1≤m+n≤4.)

Description

Fluorine-containing polymerizable monomer and polymer compound using the same

The present invention relates to a novel fluorine-containing polymer compound useful as a material for a protective film for an electronic circuit substrate, a protective film for a semiconductor, or a gas separation film. Furthermore, the present invention relates to a fluorine-containing polymerizable monomer for producing the fluorine-containing polymer compound.

The aromatic diamine compound is useful as a raw material for heat resistant polymers represented by polyamide, polyimide, polybenzoxazole and the like. These polymer materials are used in fields such as automobiles, aerospace, and fire protection clothing because of their high heat resistance. However, these polymer materials often have poor solubility in organic solvents and poor moldability. Therefore, in the case of polyimide or polybenzoxazole, after forming into a desired shape using an organic solvent-soluble precursor polymer (polyamide acid, polyamide phenol), dehydration cyclization is performed at a high temperature of 300 ° C. to 350 ° C. The final molded body is modified by polyimide or polybenzoxazole.

However, the molding process as described above is a molding process for use in display members using organic dyes that have relatively low heat resistance and laminated members for semiconductors having different thermal expansion coefficients that are likely to generate residual thermal stress. Unsuitable because the temperature is too high. Therefore, organic solvent-soluble polyimides and polybenzoxazoles that can be molded at a temperature at which the organic solvent is evaporated are attracting attention.

As a method for solubilizing these polymers in an organic solvent, a bent structure such as an ether bond or a methylene bond is introduced into the main chain skeleton, and a bulky structure such as a tert-butyl group or a trifluoromethyl group is used as a side chain. It is known to introduce and destroy the symmetry of the main chain skeleton. Among them, a technique using a fluorene structure is known as a technique for improving the solubility in organic solvents without sacrificing heat resistance.

Polymers having a fluorene structure are not only solubilized in organic solvents, but also have the effect of lowering the dielectric constant and increasing gas permeability due to their unique structure. There are examples of reports as protective films for semiconductors and gas separation films. (Patent Documents 1 and 2).

However, a polymer having a fluorene structure has drawbacks that it is highly hydrophobic and has poor applicability to a hydrophilic substrate and poor mechanical strength due to low intermolecular interaction. There is a report example of trying to eliminate the disadvantage by introducing a hydrophilic group such as phenolic hydroxyl group or carboxyl group into the fluorene skeleton, but a synthesis process for introducing a hydrophilic group such as phenolic hydroxyl group or carboxyl group Is multistage and the operation is complicated (Patent Documents 3, 4, and 8).

Patent Document 3 discloses a method for producing a phenolic hydroxyl group-containing fluorenediamine. In this production method, after introducing a phenolic hydroxyl group into the fluorene skeleton, nitration followed by a hydrogen reduction step yields the objective phenolic hydroxyl group-containing fluorenediamine. According to the description of the examples, each process has a target with a relatively high yield (85 to 90%), but there is a problem of waste due to the use of a large amount of nitric acid, use of an expensive palladium catalyst, high pressure Hydrogen is necessary and it is difficult to say that it is an industrially easy method.

Patent Document 4 discloses a method for producing a carboxyl group-containing fluorenediamine. In this production method, diphenic acid is heated in sulfuric acid to form fluorenone carboxylic acid, and subsequently a target carboxy group-containing fluorenediamine is obtained by a reaction at a high temperature that requires a dehydration step with anilines. This reaction also requires a problem of waste due to the use of a large amount of sulfuric acid, and an additional facility for co-dehydration in the presence of toluene in the dehydration process, which is also not an industrially easy method.

Patent Document 8 discloses a method for producing a phenolic hydroxyl group-containing fluorenediamine in which the substitution positions of a phenolic hydroxyl group and an amino group are reversed as compared with Patent Document 3. In this production method, general-purpose 2-benzoxazoline is used. However, after the reaction, separation and purification operations from by-products by silica gel chromatography are necessary, which is not an industrially easy method.

Thus, it was expected that a phenolic hydroxyl group, a carboxyl group, or a hydrophilic group different from both functional groups would be easily introduced into the fluorene skeleton.

Further, a compound in which a 2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl group is introduced into an aromatic diamine compound having a fluorene structure is not known.

Japanese Patent Laid-Open No. 11-343414 Japanese Unexamined Patent Publication No. 63-190607 JP 2002-105034 A JP 05-194338 A JP 2007-119503 A JP 2007-119504 A JP 2008-150534 A JP 2009-235048 A

The present invention relates to an aromatic diamine compound having a fluorene structure and a 2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl group (hereinafter referred to as “HFIP group” or “—C (CF ₃ ) ₂ OH”. HFIP group-containing fluorenediamine having introduced thereinto), and polyamide compounds, polyimide compounds, and fluorine-containing heterocyclic-containing polymer compounds having a polybenzoxazole-like structure synthesized from HFIP group-containing fluorenediamine. provide.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a hydrophilic group such as a phenolic hydroxyl group or a carboxyl group can be synthesized by a simpler synthesis method than the conventional method of introducing a hydrophilic group such as a phenolic hydroxyl group or a carboxyl group into a fluorene skeleton. It was found that the HFIP group can be introduced into the fluorene skeleton. Furthermore, the present inventors synthesized a fluorine-containing heterocyclic ring-containing polymer compound having a polyamide compound, a polyimide compound, and a polybenzoxazole-like structure from an HFIP group-containing fluorenediamine to complete the present invention.

That is, the present invention is as follows.

[Invention 1]
A fluorine-containing fluorenediamine represented by the formula (2).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH ₃ ) ₂ OH group, —C≡C—C ₆ H ₅ group, —C≡C—Si (CH ₃ ) ₃ group Represents a substituent, HFIP represents a —C (CF ₃ ) ₂ OH group, m and n each independently represents an integer of 0 to 2, and m + n is from 1 to 4.

[Invention 2]
The fluorine-containing fluorenediamine according to invention 1 represented by formula (3-1):

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH ₃ ) ₂ OH group, —C≡C—C ₆ H ₅ group, —C≡C—Si (CH ₃ ) ₃ group Represents a substituent, and HFIP represents a —C (CF ₃ ) ₂ OH group.)

[Invention 3]
The fluorine-containing fluorenediamine according to invention 1 or 2 represented by formula (2B).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) And represents one kind of substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and HFIP represents a —C (CF ₃ ) ₂ OH group.)

[Invention 4]
The fluorine-containing diamine according to any one of the inventions 1 to 3 is a dicarboxylic acid or dicarboxylic acid derivative represented by the formula (10) or (11), or a tetracarboxylic dianhydride represented by the formula (14). A polymer compound obtained by contacting with and reacting with.

(In Formula (10), A is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom, Any number of hydrogen atoms may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group, and each R ⁴ is independently a hydrogen atom or a carbon number of 1 to 10 In formula (11), A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and is an oxygen atom, a sulfur atom, or a nitrogen atom. Any number of hydrogen atoms may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group, and X is Tsu atom, a chlorine atom, a bromine atom or an iodine atom.)

(In the formula (14), R ⁵ is a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom and a nitrogen atom. And any number of hydrogen atoms may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, or a cyano group.)

[Invention 5]
A polymer compound containing at least a repeating unit represented by formula (6).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH ₃ ) ₂ OH group, —C≡C—C ₆ H ₅ group, —C≡C—Si (CH ₃ ) ₃ group A represents a substituent, A is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom; Several hydrogen atoms are alkyl, fluorine, chlorine, fluoro Kill group, a carboxyl group, may .HFIP be substituted by a hydroxy group or a cyano group is -C (CF ₃₎ ₂ .m and n represents an OH group each independently represents an integer of 0 to 2 M + n is 1 or more and 4 or less.)

[Invention 6]
The polymer compound according to invention 5, comprising at least a repeating unit represented by formula (19).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH ₃ ) ₂ OH group, —C≡C—C ₆ H ₅ group, —C≡C—Si (CH ₃ ) ₃ group A represents a substituent, A is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom; Several hydrogen atoms are alkyl, fluorine, chlorine, fluoro Kill group, a carboxyl group, may .HFIP be substituted by a hydroxy group or a cyano group is -C (CF ₃₎ ₂ OH group.)

[Invention 7]
The polymer compound according to invention 5 or 6, comprising at least a repeating unit represented by formula (6A).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) 1 represents a substituent selected from the group consisting of phenyl group, methoxy group and nitro group, A is a divalent organic group containing one or more selected from alicyclic, aromatic and alkylene groups, and oxygen May contain atoms, sulfur atoms, or nitrogen atoms, and any number of hydrogen atoms may be substituted with alkyl groups, fluorine atoms, chlorine atoms, fluoroalkyl groups, carboxyl groups, hydroxy groups, or cyano groups HFIP represents a —C (CF ₃ ) ₂ OH group.)

[Invention 8]
A polymer compound containing at least a repeating unit represented by formula (9).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) 1 represents a substituent selected from the group consisting of a group, a phenyl group, a methoxy group, and a nitro group, and R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, or a biphenyl group. , Sulfonic acid group, —C≡C—C (CH ₃ ) ₂ OH group, —C≡C—C ₆ H ₅ group, —C≡C—Si (CH ₃ ) ₃ group A represents a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom; The number of hydrogen atoms is an alkyl group, a fluorine atom, a chlorine atom, Kill group, a carboxyl group, may be substituted by a hydroxy group or a cyano group.)

[Invention 9]
The polymer compound according to invention 8, which contains at least a repeating unit represented by formula (9B).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) 1 represents a substituent selected from the group consisting of a group, a phenyl group, a methoxy group, and a nitro group, A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, It may contain oxygen, sulfur, or nitrogen atoms, and any number of hydrogen atoms are substituted with alkyl, fluorine, chlorine, fluoroalkyl, carboxyl, hydroxy or cyano groups May be good.)

[Invention 10]
A polymer compound containing at least a repeating unit represented by formula (7).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH ₃ ) ₂ OH group, —C≡C—C ₆ H ₅ group, —C≡C—Si (CH ₃ ) ₃ group R ⁵ represents a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Any number of hydrogen atoms may be alkyl groups, fluoroalkyl Optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF ₃ ) ₂ OH group, m and n each independently represents an integer of 0 to 2; m + n is 1 or more and 4 or less.)

[Invention 11]
The polymer compound according to invention 10, comprising at least a repeating unit represented by formula (7A).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH ₃ ) ₂ OH group, —C≡C—C ₆ H ₅ group, —C≡C—Si (CH ₃ ) ₃ group R ⁵ represents a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Any number of hydrogen atoms may be alkyl groups, fluoroalkyl And optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF ₃ ) ₂ OH group.)

[Invention 12]
The polymer compound according to invention 10 or 11, comprising at least a repeating unit represented by formula (7B).

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) R ⁵ represents a tetravalent organic group containing one or more substituents selected from the group consisting of a phenyl group, a methoxy group and a nitro group, wherein R ⁵ is one or more selected from an alicyclic ring, an aromatic ring and an alkylene group; Fluorine atom, chlorine atom, oxygen atom, sulfur atom, nitrogen atom may be contained, and any number of hydrogen atoms may be substituted with alkyl group, fluoroalkyl group, carboxyl group, hydroxy group or cyano group HFIP represents a —C (CF ₃ ) ₂ OH group.)

[Invention 13]
A polymer compound containing at least a repeating unit represented by formula (8).

[Invention 14]
The polymer compound according to invention 13, comprising at least a repeating unit represented by formula (8A).

[Invention 15]
The polymer compound according to invention 13 or 14, comprising at least a repeating unit represented by formula (8B).

[Invention 16]
The polymer compound according to any one of Inventions 5 to 9, wherein the divalent organic group A is at least one selected from the formulas (25) to (29).

(In the formula, the line that intersects the wavy line represents the coupling position.)

[Invention 17]
The polymer compound according to any one of Inventions 10 to 15, wherein R ⁵ is one or more selected from formulas (30) to (35).

According to the present invention, it is possible to provide an HFIP group-containing fluorenediamine. Furthermore, according to the present invention, it is possible to provide a polyamide compound, a polyimide compound, and a fluorine-containing heterocyclic-containing polymer compound having a polybenzoxazole-like structure synthesized from HFIP group-containing fluorenediamine.

Hereinafter, the present invention will be described, but the present invention is not limited to the following embodiments.

In the present specification, among aromatic diamine compounds having a fluorene structure, 9,9-bis (4-aminophenyl) fluorene represented by the following formula (1) is referred to as “fluor orange amine”. It may have a substituent.

However, when it has a HFIP group as a substituent, it distinguishes and calls as "HFIP group containing fluorene amine".

HFIP group-containing fluoreneamine according to the present invention, HFIP group-containing fluoreneamine as monomers, polyamide compound obtained by polymerization reaction, polyimide compound, fluorine-containing heterocyclic ring-containing polymer compound having a polybenzoxazole-like structure in this order It explains along.

<HFIP group-containing full orange amine>
The HFIP group-containing fluorenediamine according to the present invention is represented by the formula (2).

Of the HFIP group-containing fluorenediamine represented by the formula (2) (hereinafter sometimes referred to as “HFIP group-containing fluorenediamine (2)”), the compounds represented by the formulas (3-1) and (3-2) HFIP group-containing fluorenediamine is preferred.

(In the formula, R ¹ , R ² and HFIP have the same meaning as in formula (2).)

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl Group, perfluoro tert-butyl group and the like.

Specific examples of the HFIP group-containing fluorenediamine include compounds represented by the following formulas (4-1) to (4-12).

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Me represents a methyl group. Ph represents a phenyl group. HFIP has the same meaning as in formula (2).)
Among them, the HFIP group-containing fluorenediamines represented by the general formulas (4-1) and (4-2) are particularly preferable because of the availability of fluoreneamine as a raw material for synthesizing the HFIP group-containing fluorenediamine.

The HFIP group-containing fluorenediamine (2) according to the present invention is obtained by replacing fluorediamine represented by the formula (5) (hereinafter sometimes referred to as “fluorangeamine” (5)) with hexafluoroacetone or hexafluoroacetone. -It is obtained by making it react with a trihydrate (refer patent document 5, 6, 7).

(In formula (5), R ¹ and R ² have the same meaning as in formula (2).)

This reaction can be carried out without solvent, but a solvent can also be used. The solvent used is not particularly limited as long as it does not participate in the reaction, but is preferably an aromatic hydrocarbon such as xylene, toluene, benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, or water. The amount of the solvent to be used is not particularly limited, but it is not preferable to use a large amount because the yield per volume decreases.

In this reaction, the reactor to be used is not particularly limited. However, when a sealed reactor (autoclave) is used, the mode differs depending on whether hexafluoroacetone or hexafluoroacetone trihydrate is used. . In the case of using hexafluoroacetone, first, fluorenediamine (5) and, if necessary, a catalyst and / or a solvent are charged into the reactor. Subsequently, it is preferable to introduce hexafluoroacetone successively while raising the temperature so that the internal pressure of the reactor does not exceed 0.5 MPa.

When hexafluoroacetone trihydrate is used, it is possible to initially charge fluorenediamine (5) and the required amount of hexafluoroacetone trihydrate, and if necessary, a catalyst and / or The reaction can be carried out by charging the solvent into the reactor.

The reaction time of this reaction is not particularly limited, but the optimum reaction time varies depending on the temperature and the amount of catalyst used. Therefore, it is preferable to complete this step after confirming that the raw material has been sufficiently consumed by carrying out the reaction while measuring the progress of the reaction by a general-purpose analysis means such as gas chromatography. After completion of the reaction, the HFIP group-containing fluorenediamine (2) can be obtained by ordinary means such as extraction, distillation, and crystallization. Moreover, it can also refine | purify by column chromatography, recrystallization, etc. as needed.

<Polymer compound>
Next, using a HFIP group-containing fluorenediamine (2) as a monomer, a polyamide compound (hereinafter referred to as “polyamide compound (6)”) containing at least a repeating unit represented by the general formula (6) obtained by a polymerization reaction A polyamide compound containing at least the repeating unit represented by the general formula (7) (hereinafter sometimes referred to as “polyamide compound (7)”) and the general formula (8). A polymer compound such as a polyimide compound containing at least a repeating unit (hereinafter sometimes referred to as “polyimide compound (8)”) will be described in order. Furthermore, the fluorine-containing heterocyclic ring-containing polymer compound having a polybenzoxazole-like structure containing at least the repeating unit represented by the general formula (9) (hereinafter referred to as “fluorinated heterocyclic ring-containing polymer compound (9)”) )).

[Polyamide compound (6)]
Among the HFIP group-containing fluorenediamine polymer compounds according to the present invention, the polyamide compound (6) is an HFIP-containing fluorenediamine (2), a carboxylic acid or a carboxylic acid represented by formula (10) or formula (11). It can be obtained by reacting with a derivative.

(Wherein R ¹ , R ² , HFIP, m and n are as defined in formula (2). R ⁴ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a benzyl group. It is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group, may contain an oxygen atom, a sulfur atom or a nitrogen atom, and any number of hydrogen atoms is an alkyl group, (It may be substituted with a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group, and X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)

As the dicarboxylic acid or dicarboxylic acid derivative represented by the general formulas (10) and (11), any of aliphatic dicarboxylic acid, aromatic dicarboxylic acid, or these dicarboxylic acid derivatives may be used.

Examples of the aliphatic dicarboxylic acid and derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dicarboxylic acid compounds of sebacic acid or their dicarboxylic acid derivatives. It is done.

Examples of aromatic dicarboxylic acids and derivatives thereof include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-dicarboxybiphenyl, 3,3′-dicarboxybiphenyl, 3,3′-dicarboxyldiphenyl ether, 3, 4'-dicarboxyldiphenyl ether, 4,4'-dicarboxyldiphenyl ether, 3,3'-dicarboxyldiphenylmethane, 3,4'-dicarboxyldiphenylmethane, 4,4'-dicarboxyldiphenylmethane, 3,3'-dicarboxyl Diphenyldifluoromethane, 3,4'-dicarboxyldiphenyldifluoromethane, 4,4'-dicarboxyldiphenyldifluoromethane, 3,3'-dicarboxyldiphenylsulfone, 3,4'-dicarboxyldiphenylsulfone, 4,4 ' Dicarboxyl diphenyl sulfone, 3,3′-dicarboxyl diphenyl sulfide, 3,4′-dicarboxyl diphenyl sulfide, 4,4′-dicarboxyl diphenyl sulfide, 3,3′-dicarboxyl diphenyl ketone, 3,4′- Dicarboxyl diphenyl ketone, 4,4'-dicarboxyl diphenyl ketone, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (3,4'-dicarboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2-bis (3,4'-dicarboxyphenyl) hexafluoropropane, 2,2-bis (4- Carboxyphenyl) hexafluoropropane, 1,3-bis (3-carboxy Boxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 1,4-bis (4-carboxyphenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene) ) Bisbenzoic acid, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid 2,2-bis (4- (3-carboxyphenoxy) phenyl) propane, 2,2-bis (4- (4-carboxyphenoxy) phenyl) propane, 2,2-bis (4- (3-carboxyphenoxy) ) Phenyl) hexafluoropropane, 2,2-bis (4- (4-carboxyphenoxy) phenyl) hexafluoropropane, bis (4- (3-carboxy) Ciphenoxy) phenyl) sulfide, bis (4- (4-carboxyphenoxy) phenyl) sulfide, bis (4- (3-carboxyphenoxy) phenyl) sulfone or bis (4- (4-carboxyphenoxy) phenyl) sulfone, per 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid, 2- (perfluorononenyloxy) terephthalic acid or 4-methoxy which is a dicarboxylic acid containing a fluorononenyloxy group -5- (perfluorononenyloxy) isophthalic acid, a dicarboxylic acid containing a perfluorohexenyloxy group, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) phthalic acid, 2- ( Perfluorohexenyloxy) tele Tal acid or 4-methoxy-5- (perfluoroalkyl hexenyloxy) isophthalic acid, 2,2'-di-trifluoromethyl-4,4'-dicarboxylate biphenyl or their dicarboxylic acid derivatives.

Among these, terephthalic acid, isophthalic acid, 4,4′-dicarboxybiphenyl, 2,2′-ditrifluoromethyl-4 are easy to obtain, easy to polycondensation reaction, and excellent in transparency. 4,4′-dicarboxybiphenyl and 2,2-bis (4-carboxyphenyl) hexafluoropropane are preferred.

Of the polyamide compounds (6), a polyamide compound containing at least a repeating unit represented by any of the following formulas (12-1) to (12-5) is preferable.

(In the formula, R ¹ , R ² and HFIP have the same meaning as in formula (2).)
Specifically, a polyamide compound containing at least a repeating unit represented by any of the following formulas (13-1) to (13-10) can be given.

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Me represents a methyl group. Ph represents a phenyl group. HFIP has the same meaning as in formula (2).)

Among these, a polyamide compound containing at least a repeating unit represented by any one of the formulas (13-1) to (13-5) is particularly preferred because of the availability of fluoreneamine as a raw material for the synthesis of HFIP group-containing fluoreneamine. preferable.

The weight average molecular weight of the polyamide compound (6) is preferably 10,000 or more, more preferably 20,000 or more. The upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less. When the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor. When the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult. The weight average molecular weight here is determined as a converted value based on standard polystyrene by gel permeation chromatography (hereinafter sometimes referred to as “GPC”) analysis (the same applies hereinafter). Detailed analysis conditions for the analysis are described in the examples of the present application.

The method for synthesizing the polyamide compound (6) is not particularly limited, and a known method for synthesizing a polyamide compound from a diamine compound and a carboxylic acid compound or a derivative thereof can be employed. For example, a composition having HFIP group-containing fluorenediamine (2) and a dicarboxylic acid or dicarboxylic acid derivative represented by the general formulas (10) and (11) is melted together at 150 ° C. or higher and condensed without solvent. Examples thereof include a polymerization reaction method, a condensation polymerization reaction in a solvent at 150 ° C. or higher, and a polymerization reaction in a solvent at a temperature of −20 to 80 ° C.

In the synthesis of the polyamide compound (6), a solvent can be used. The solvent to be used is not particularly limited as long as the reaction substrate dissolves and does not freeze at the reaction temperature, and examples thereof include amides, aromatics, halogens, lactones and the like. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile , Chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ- Butyrolactone can be used. These solvents may be used alone or as a mixture of two or more.

Furthermore, it is effective to carry out the reaction in the presence of acid acceptors such as pyridine and triethylamine together with these solvents.

[Polyamide compound (7)]
Furthermore, among the HFIP group-containing fluorinated amine polymer compounds according to the present invention, the polyamide compound (7) reacts the HFIP-containing fluorenediamine (2) with the tetracarboxylic dianhydride represented by the formula (14). Can be obtained.

(Wherein R ¹ , R ² , HFIP, m and n are as defined in formula (2). R ⁵ is a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group. Yes, it may contain fluorine atom, chlorine atom, oxygen atom, sulfur atom, nitrogen atom, and any number of hydrogen atoms are substituted with alkyl group, fluoroalkyl group, carboxyl group, hydroxy group or cyano group May be.)

As the tetracarboxylic dianhydride represented by the general formula (14), those having any of aliphatic, alicyclic and aromatic structures in R ⁵ can be used. Specifically, benzenetetracarboxylic dianhydride (pyromellitic dianhydride), trifluoromethylbenzenetetracarboxylic dianhydride, bistrifluoromethylbenzenetetracarboxylic dianhydride, difluorobenzenetetracarboxylic dianhydride , Naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, terphenyltetracarboxylic dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ketonic dianhydride, oxydiphthalic acid Anhydride, bicyclo (2,2,2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid Dianhydride, 2,3,4,5-thiophenetetracarboxylic dianhydride, 2,5,6,2≡, 5≡, 6≡ Hexafluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfonic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride Anhydrides may be mentioned, and two or more of these may be used in combination.

Of the polyamide compounds (7), polyamide compounds containing at least any of the repeating units represented by the following formulas (15-1) to (15-6) are preferable.

(In the formula, R ¹ , R ² and HFIP have the same meaning as in formula (2).)
Specific examples include polyamide compounds containing at least any of the repeating units represented by the following formulas (16-1) to (16-12).

Among these, polyamide compounds containing at least any one of the repeating units represented by the formulas (16-1) to (16-6) are obtained because of the availability of fluorenediamine as a raw material for the synthesis of HFIP group-containing fluorenediamine, Particularly preferred.

The weight average molecular weight of the polyamide compound (7) is preferably 10,000 or more, more preferably 20,000 or more. The upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less. When the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor. When the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult.

The method for synthesizing the polyamide compound (7) is not particularly limited, and for example, a composition having a HFIP group-containing fluorenediamine (2) and a dicarboxylic acid derivative represented by the general formula (14) at 150 ° C. or higher. Examples thereof include a method in which they are melted together and subjected to a polycondensation reaction without solvent, a method in which a polycondensation reaction is performed at 150 ° C. or higher in a solvent, and a method in which a polymerization reaction is performed in a solvent at a temperature of −20 to 80 ° C.

In addition, a solvent can be used in the synthesis of the polyamide compound (7). The solvent to be used is not particularly limited as long as the reaction substrate dissolves and does not freeze at the reaction temperature, and examples thereof include amides, aromatics, halogens, lactones and the like. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile , Chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ- Butyrolactone can be used. These solvents may be used alone or as a mixture of two or more.

[Polyimide compound]
Among the HFIP group-containing fluorenediamine polymer compounds according to the present invention, the polyimide compound represented by the formula (8) is synthesized from the polyamide compound (7).

Of the polyimide compound (8), a polyimide compound containing at least any one of the repeating units represented by the following formulas (17-1) to (17-6) is preferable.

(In the formula, R ¹ , R ² and HFIP have the same meaning as in formula (2).)
Specific examples include polyimide compounds containing at least one of the repeating units represented by the following formulas (18-1) to (18-12).

Among these, polyimide compounds containing at least any one of the repeating units represented by formulas (18-1) to (18-6) are particularly preferred because of the availability of fluoreneamine as a raw material for the synthesis of HFIP group-containing fluoreneamine. preferable.

The weight average molecular weight of the polyimide compound (8) is preferably 10,000 or more, more preferably 20,000 or more. The upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less. When the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor. When the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult.

The synthesis reaction of the polyimide (8), that is, the dehydration cyclization reaction of the polyamide compound (7) is carried out under the condition that the reaction is promoted only by heating or by the combined use of an additive such as acid or base and heat.

Generally, the polyamide compound (7) solution can be imidized at a high temperature of 150 ° C. or higher and 250 ° C. or lower to prepare a polyimide solution containing an HFIP group. At that time, pyridine, triethylamine, acetic anhydride or the like may be used as an additive. The concentration of the polyimide containing HFIP groups in the solution is preferably 5% by mass or more and 50% by mass or less. If it is less than 5% by mass, it is too thin to be industrially practical. If it exceeds 50% by mass, it is difficult to dissolve. Furthermore, it is preferably 10% by mass or more and 40% by mass or less.

The solvent used in preparing the solution of the polyamide compound (7) is not particularly limited as long as the reaction substrate dissolves. For example, N, N-dimethylformamide, N, N-dimethylacetamide, hexa Methylphosphoric triamide or N-methyl-2-pyrrolidone, aromatic solvents benzene, anisole, diphenyl ether, nitrobenzene or benzonitrile, halogenated solvents chloroform, dichloromethane, 1,2-dichloroethane or 1,1,2 , 2-tetrachloroethane, lactones γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone or α-methyl-γ-butyrolactone. These solvents may be used alone or as a mixed solvent of two or more.

As a method for synthesizing the polyimide (8), a method in which the reaction solution immediately after the synthesis of the polyamide compound (7) is directly subjected to a dehydration cyclization reaction is also applicable. In this case, the above-mentioned temperature range, additive, concentration and solvent can be used.

[Fluorine-containing heterocyclic ring-containing polymer compound]
Among the HFIP group-containing fluoreneamine polymer compounds according to the present invention, the fluorine-containing heterocyclic ring-containing polymer compound (9) is a polyamide compound containing at least a repeating unit represented by the formula (19) (hereinafter “polyamide”). Compound (19) ”may be obtained by dehydrating cyclization.

(In the formula, R ¹ , R ² and HFIP are as defined in formula (2). A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group, It may contain a sulfur atom or a nitrogen atom, and any number of hydrogen atoms may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group. )

Specifically, the dehydration cyclization reaction shown in the following reaction formula proceeds to form a heterocyclic ring.

(In the formula, A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and any number The hydrogen atom may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group, and the line segment intersecting with the wavy line represents the bonding position.)

Of the fluorine-containing heterocyclic ring-containing polymer compound (9), a fluorine-containing heterocyclic ring-containing polymer compound containing at least any one of the repeating units represented by the following formulas (20-1) to (20-5) is preferable. .

(In the formula, R ¹ , R ² and HFIP have the same meaning as in formula (2).)
Specific examples include fluorine-containing heterocyclic ring-containing polymer compounds containing at least any one of the repeating units represented by the following formulas (21-1) to (21-10).

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Me represents a methyl group. Ph represents a phenyl group.)

Among these, a fluorine-containing heterocyclic ring containing at least any one of the repeating units represented by formulas (21-1) to (21-5) because of the availability of fluoreneamine as a raw material for the synthesis of HFIP group-containing fluorenediamine. The containing polymer compound is particularly preferable.

The weight average molecular weight of the fluorine-containing heterocyclic ring-containing polymer compound (9) is preferably 10,000 or more, more preferably 20,000 or more. The upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less. When the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor. When the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult.

As a synthesis method of the fluorine-containing heterocyclic-containing polymer compound (9) by dehydration cyclization of the polyamide compound (19), reaction conditions such as heating, use of an acid catalyst, and a base catalyst can be selected.

For example, the reaction conditions in the similar dehydration cyclization reaction disclosed in Patent Documents 6 and 7 can be applied mutatis mutandis.

As another example, the polyamide compound (19) is heated in a solvent at 150 to 250 ° C., whereby the dehydration cyclization of the polyamide compound (19) proceeds, and the fluorine-containing heterocyclic ring-containing polymer compound (9) Produces. At that time, pyridine, triethylamine, acetic anhydride and the like may be added for the purpose of allowing the reaction to proceed efficiently.

In the synthesis of the fluorine-containing heterocyclic ring-containing polymer compound (9), a solvent can be used. The solvent to be used is not particularly limited as long as the reaction substrate dissolves and does not freeze at the reaction temperature, and examples thereof include amides, aromatics, halogens, lactones and the like. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile , Chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ- Butyrolactone can be used. These solvents may be used alone or as a mixture of two or more. Furthermore, it is effective to carry out the reaction in the presence of acid acceptors such as pyridine and triethylamine together with these solvents.

[Polymerization component]
Further, for the purpose of improving the heat resistance of the polymer compound and obtaining solubility in a desired organic solvent, a polyamide compound (6), a polyamide compound (7), a polyimide obtained from the HFIP group-containing fluorenediamine (2) In the synthesis of the compound (8) and the fluorine-containing heterocyclic ring-containing polymer compound (9), a diamine compound not containing an HFIP group may be added as a polymerization component.

Specifically, the diamine compound includes 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, 3,3′-bistrifluoromethyl-4,4′-diaminobiphenyl, 2,2′- Bistrifluoromethyl-4,4′-diaminobiphenyl, 3,3′-bistrifluoromethyl-5,5′-diaminobiphenyl, bis (trifluoromethyl) -4,4′-diaminobiphenyl, bis (fluorinated alkyl) -4,4'-diaminobiphenyl, dichloro-4,4'-diaminobiphenyl, dibromo-4,4'-diaminobiphenyl, bis (fluorinated alkoxy) -4,4'-diaminobiphenyl, diphenyl-4,4 ' -Diaminobiphenyl, 4,4'-bis (4-aminotetrafluorophenoxy) tetrafluorobe Zen, 4,4′-bis (4-aminotetrafluorophenoxy) octafluorobiphenyl, 4,4′-binaphthylamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 1,4-xylylenediamine, dimethyl-4,4′-diaminobiphenyl, dialkyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, dimethoxy-4,4′-diaminobiphenyl, diethoxy-4,4′-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,4'- Aminodiphenylmethane, 3,3'-dimethyl-diaminodiphenylmethane, 3,3'-diethyl-diaminodiphenylmethane, 9,9-bis (4-aminophenyl) fluorene, 4,4'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, 2,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4 ' -Diaminobenzophenone, 3,3'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene 4,4′-bis (4-aminophen Enoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-amino) Phenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-amino-2-trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3-amino-5-tri) Fluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2 2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane 4,4′-bis (4-aminophenoxy) octafluorobiphenyl, 4,4′-diaminobenzanilide, etc., and two or more of these may be used in combination.

<Aspect in Use of Polymer Compound>
The polymer compound of the present invention can be used in a varnish state, a powder state, a film state, or a solid state dissolved in an organic solvent. At that time, the obtained polymer compound may contain additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, and a sensitizer as necessary. Absent.

When using in varnish, apply it on a substrate such as glass, silicon wafer, metal, metal oxide, ceramics, resin, etc. by usual methods such as spin coating, spray coating, flow coating, impregnation coating, brush coating. Can do.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

The physical property evaluation of the polymer compound using the HFIP group-containing fluorenediamine and the HFIP group-containing fluorenediamine obtained in the present invention was performed by the following methods.

[NMR (nuclear magnetic resonance) measurement]
The structure of the compound was confirmed by ¹ H-NMR and ¹⁹ F-NMR measurements using an NMR (nuclear magnetic resonance) apparatus (JNM-AL400 or JNM-ECA400; manufactured by JEOL Ltd.) having a resonance frequency of 400 MHz.

[Weight average molecular weight measurement]
The weight average molecular weight (hereinafter sometimes referred to as “Mw”) is a value determined by gel permeation chromatography (HLC-8320 manufactured by Tosoh Corporation, tetrahydrofuran is used) with polystyrene as a standard product.

[Example 1]
<Synthesis of HFIP group-containing fluorenediamine represented by formula (22) (HFIP-FL)>
9,9-bis (4-aminophenyl) fluorene (25 g, 0.072 mol, Tokyo Chemicals), hexafluoroacetone trihydrate (70 g, 0.32 mol), paratoluenesulfonic acid monohydrate in a 300 mL autoclave (0.68 g, 3.6 mmol) was added, the autoclave was sealed, and the mixture was stirred in an oil bath at 130 ° C. for 17 hours. After cooling to room temperature (especially the ambient temperature without heating or cooling, usually about 15 to 30 ° C., the same applies hereinafter), toluene (50 g) is added to the reaction solution, and the resulting solid is filtered and washed with water. Further, it was washed with chloroform (100 ml). The obtained solid was filtered and dried under reduced pressure to obtain a white powder (11.6 g, 0.017 mol, yield 25%). From the NMR analysis, it was confirmed that the white powder was a HFIP group-containing fluorenediamine represented by the formula (22) (hereinafter sometimes referred to as “HFIP-FL”).
[NMR measurement]
¹ H-NMR (DMSO-d ₆ ): δ 9.19 (brs, 2H), 7.87 (d, J = 7.6 Hz, 2H), 7.35 (m, 2H), 7.26 (m, 4H), 7.02 (s, 2H), 6.80 (dd, J = 8.5, 1.7 Hz, 2H), 6.60 (d, J = 8.5 Hz, 2H), 5.55 ( brs, 4H);
¹⁹ F-NMR (DMSO-d ₆ ): δ-72.65 (s)

[Example 2]
<Synthesis of HFIP group-containing fluorenediamine represented by formula (23) (HFIP-MeFL)>
In a 300 mL autoclave, 9,9-bis (4-amino-3-methylphenyl) fluorene (70 g, 0.186 mol), hexafluoroacetone trihydrate (220 g, 1.000 mol), paratoluenesulfonic acid monohydrate The product (1.77 g, 9.3 mmol) was added, the autoclave was sealed, and the mixture was stirred in an oil bath at 130 ° C. for 24 hours. After cooling to room temperature, methanol (200 mL) was added to the reaction solution, and the resulting solid was filtered and further washed with chloroform (100 ml). The obtained solid was filtered and dried under reduced pressure to obtain a white powder (15.2 g, 0.022 mol, yield 20%). From the NMR analysis, it was confirmed that the white powder was a HFIP group-containing fluorenediamine represented by the formula (23) (hereinafter sometimes referred to as “HFIP-MeFL”).
[NMR measurement]
¹ H-NMR (DMSO-d ₆ ): δ 10.11 (brs, 2H), 7.86 (d, J = 7.2 Hz, 2H), 7.35 (m, 2H), 7.26 (m, 4H), 6.97 (s, 2H), 6.79 (s, 2H), 5.24 (brs, 4H), 1.98 (s, 6H);
¹⁹ F-NMR (DMSO-d ₆ ): δ-72.92 (s)

[Example 3]
<Synthesis of polymer P1 by polymerization reaction of HFIP-FL and 6FDA>
In a 300-mL three-neck flask, HFIP-FL (10.01 g, 14.7 mmol), 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter sometimes referred to as “6FDA”) ( 6.533 g (14.7 mmol) and N, N-dimethylacetamide (38.57 g) were added, and the mixture was stirred at room temperature for 18 hours under a nitrogen atmosphere. The obtained reaction liquid was thrown into water and methanol mixed solvent (mixing volume ratio is 1: 1), and white precipitation was obtained. The obtained white precipitate was filtered, collected, and then vacuum dried at room temperature for 12 hours to obtain polymer P1 (yield 14.89 g, yield 90%). As a result of GPC measurement, Mw was 51,000. In the following formula, n represents the number of repeating units (the same applies to the Examples section).

[Example 4]
<Synthesis of polymer P1-1 by imidization of polymer P1, and solvent solubility of P1-1>
In a 100 mL eggplant flask, polymer P1 (5 g), acetic anhydride (0.998 g, 9.78 mmol) and triethylamine (1.08 g, 10.66 mmol) were added and dissolved in N, N-dimethylacetamide (20 g). And then reacted at 110 ° C. for 24 hours. The obtained reaction liquid was thrown into water and methanol mixed solvent (mixing volume ratio is 1: 1), and white precipitation was obtained. The resulting white precipitate was filtered, collected, and then vacuum dried at room temperature for 12 hours to obtain polymer P1-1 (yield 4.11 g, yield 85%). As a result of GPC measurement, Mw was 31,000. From IR measurement, 1,780 cm ^-1, from that confirmed the absorption of the specific imide group to 1,720 cm ^-1, it was found that a polymer P1-1. The obtained polymer P1-1 was soluble in tetrahydrofuran and N, N-dimethylformamide (the polymer solid was stirred at room temperature in a solvent at a concentration of 5 wt% at the room temperature, the same applies hereinafter).

[Example 5]
<Film-forming experiment of polymer P1-1>
The polymer P1-1 (3 g) obtained in Example 4 was dissolved in N, N-dimethylacetamide (12 g), and then the obtained solution was spin-coated on a glass substrate to obtain N, N-dimethyl. The upper limit temperature was 180 ° C. close to the boiling point of acetamide, and heating was performed at 100 ° C. for 1 hour and 180 ° C. for 1 hour. On the glass substrate, no peeling or cracking was observed visually, and a uniform film having a thickness of 25 μm was obtained.

[Example 6]
<Synthesis of polymer P2 by polymerization reaction of HFIP-MeFL and isophthalic acid chloride>
In a 300-mL three-necked flask, HFIP-MeFL (9.00 g, 12.7 mmol), isophthalic acid chloride (2.52 g, 12.7 mmol), N, N-dimethylacetamide (46 g) were added, and under a nitrogen atmosphere, Stir at room temperature for 18 hours. The obtained reaction liquid was thrown into water and methanol mixed solvent (mixing volume ratio is 1: 1), and white precipitation was obtained. The obtained white precipitate was filtered, collected, and then vacuum dried at room temperature for 12 hours to obtain polymer P2 (yield 8.73 g, yield 83%). As a result of GPC measurement, Mw was 25,000.

[Example 7]
<Synthesis of Polymer P2-1 by Heat Dehydration Reaction of Polymer P2 and Solvent Solubility of P2-1>
Polymer P2 (5 g) was dissolved in N-methylpyrrolidone (20 g), and the resulting solution was stirred at 200 ° C. for 12 hours. The obtained reaction liquid was thrown into water and methanol mixed solvent (mixing volume ratio is 1: 1), and white precipitation was obtained. The obtained white precipitate was filtered, collected, and then vacuum dried at room temperature for 12 hours to obtain polymer P2-1 (yield 3.83 g, yield 80%). As a result of GPC measurement, Mw was 23,000. From IR measurement, absorption peculiar to C (= N) group could be confirmed at 1,650 cm ^−1, and it was found to be polymer P2-1. The obtained polymer P2-1 was soluble in N-methylpyrrolidone.

[Example 8]
<Film-forming experiment of polymer P2-1>
After the polymer P2-1 (3 g) obtained in Example 7 was dissolved in N-methylpyrrolidone (12 g), the obtained solution was spin-coated on a glass substrate and was close to the boiling point of N-methylpyrrolidone. 200 ° C. was the upper limit temperature, and heating was performed at 100 ° C. for 1 hour and at 200 ° C. for 1 hour. On the glass substrate, no peeling or cracking was observed visually, and a uniform film having a thickness of 23 μm was obtained.

[Examples 9 to 13]
<Synthesis of polymers P3 to P7>
In the same manner as in Example 3, HFIP-FL or HFIP-MeFL and the following various tetracarboxylic dianhydrides, PMDA, BPDA, BTDA, DSDA, and ODPA, were polymerized to form the following polymer: P3 to P7 were obtained. The results are shown in Table 1.

[Examples 14 to 17]
<Synthesis of polymers P8 to P11>
Polymerization reaction of HFIP-FL or HFIP-MeFL with the following various dicarboxylic acid dichlorides, TPC, BPDC, 6FDC, 6FBDC, was performed in the same manner as in Example 6 to obtain the following polymers P8 to P11. It was. The results are shown in Table 2.

[Examples 18 to 22]
<Synthesis of polymers P3-1 to P7-1 and their solvent solubility>
In the same manner as in Example 4, the following polymers P3-1 to P7-1, which are polyimide compounds, were obtained from the polymers P3 to P7, which were polyamic acids, respectively. The results are shown in Table 3. The obtained P3-1 to P7-1 were all soluble in tetrahydrofuran and N, N-dimethylacetamide.

[Examples 23 to 26]
<Synthesis of polymers P8-1 to P11-1 and their solvent solubility>
In the same manner as in Example 7, the following polymers P8-1 to P11-1 were obtained from the polymers P8 to P11, which are polyamides containing HFIP groups, respectively by a dehydration ring-closing reaction. The results are shown in Table 4. The obtained P8-1 to P11-1 were all soluble in N-methylpyrrolidone.

[Examples 27 to 35]
<Film formation experiment of polymers P3-1 to P11-1>
The polymers P3-1 to P7-1 were spin-coated on the glass substrate by the same method as in Example 5, and the polymers P8-1 to P11-1 were formed by the same method as in Example 8. The results are shown in Table 5.

The coating film of the HFIP group-containing polymer compound according to the present invention can be used as a coating material for a flat panel display, a protective film for a substrate body for an electronic circuit, a protective film for a semiconductor, and the like.

Claims

A fluorine-containing fluorenediamine represented by the formula (2).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—Si (CH 3 ) 3 group Represents a substituent, HFIP represents a —C (CF 3 ) 2 OH group, m and n each independently represents an integer of 0 to 2, and m + n is from 1 to 4.
The fluorine-containing fluorenediamine according to claim 1, which is represented by the formula (3-1).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—SI (CH 3 ) 3 group Represents a substituent, and HFIP represents a —C (CF 3 ) 2 OH group.)
The fluorine-containing fluorenediamine according to claim 1 or 2 represented by the formula (2B).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) And represents one kind of substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and HFIP represents a —C (CF 3 ) 2 OH group.)
The fluorinated diamine according to any one of claims 1 to 3, wherein the dicarboxylic acid or dicarboxylic acid derivative represented by the formula (10) or (11) or the tetracarboxylic dianhydride represented by the formula (14) is used. A polymer compound obtained by contacting and reacting with a product.

(In Formula (10), A is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom, Any number of hydrogen atoms may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group, and each R 4 is independently a hydrogen atom or a carbon number of 1 to 10 In formula (11), A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and is an oxygen atom, a sulfur atom, or a nitrogen atom. Any number of hydrogen atoms may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group, and X is Tsu atom, a chlorine atom, a bromine atom or an iodine atom.)

(In the formula (14), R 5 is a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom and a nitrogen atom. And any number of hydrogen atoms may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, or a cyano group.)
A polymer compound containing at least a repeating unit represented by formula (6).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—Si (CH 3 ) 3 group A represents a substituent, A is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom; Several hydrogen atoms are alkyl, fluorine, chlorine, fluoro Kill group, a carboxyl group, may .HFIP be substituted by a hydroxy group or a cyano group is -C (CF 3) 2 .m and n represents an OH group each independently represents an integer of 0 to 2 M + n is 1 or more and 4 or less.)
The polymer compound according to claim 5, comprising at least a repeating unit represented by formula (19).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—Si (CH 3 ) 3 group A represents a substituent, A is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom; Several hydrogen atoms are alkyl, fluorine, chlorine, fluoro Kill group, a carboxyl group, may .HFIP be substituted by a hydroxy group or a cyano group is -C (CF 3) 2 OH group.)
The polymer compound according to claim 5 or 6, comprising at least a repeating unit represented by formula (6A).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) 1 represents a substituent selected from the group consisting of phenyl group, methoxy group and nitro group, A is a divalent organic group containing one or more selected from alicyclic, aromatic and alkylene groups, and oxygen May contain atoms, sulfur atoms, or nitrogen atoms, and any number of hydrogen atoms may be substituted with alkyl groups, fluorine atoms, chlorine atoms, fluoroalkyl groups, carboxyl groups, hydroxy groups, or cyano groups HFIP represents a —C (CF 3 ) 2 OH group.)
A polymer compound containing at least a repeating unit represented by formula (9).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) 1 represents a substituent selected from the group consisting of a group, a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, or a biphenyl group. , Sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—Si (CH 3 ) 3 group A represents a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom; The number of hydrogen atoms is an alkyl group, a fluorine atom, a chlorine atom, Kill group, a carboxyl group, may be substituted by a hydroxy group or a cyano group.)
The high molecular compound of Claim 8 containing the repeating unit represented by Formula (9B) at least.

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) 1 represents a substituent selected from the group consisting of a group, a phenyl group, a methoxy group, and a nitro group, A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, It may contain oxygen, sulfur, or nitrogen atoms, and any number of hydrogen atoms are substituted with alkyl, fluorine, chlorine, fluoroalkyl, carboxyl, hydroxy or cyano groups May be good.)
A polymer compound containing at least a repeating unit represented by formula (7).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—Si (CH 3 ) 3 group R 5 represents a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Any number of hydrogen atoms may be alkyl groups, fluoroalkyl Optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF 3 ) 2 OH group, m and n each independently represents an integer of 0 to 2; m + n is 1 or more and 4 or less.)
The polymer compound according to claim 10, comprising at least a repeating unit represented by formula (7A).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—Si (CH 3 ) 3 group R 5 represents a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Any number of hydrogen atoms may be alkyl groups, fluoroalkyl And optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF 3 ) 2 OH group.)
The polymer compound according to claim 10 or 11, comprising at least a repeating unit represented by formula (7B).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) R 5 represents a tetravalent organic group containing one or more substituents selected from the group consisting of a phenyl group, a methoxy group and a nitro group, wherein R 5 is one or more selected from an alicyclic ring, an aromatic ring and an alkylene group; Fluorine atom, chlorine atom, oxygen atom, sulfur atom, nitrogen atom may be contained, and any number of hydrogen atoms may be substituted with alkyl group, fluoroalkyl group, carboxyl group, hydroxy group or cyano group HFIP represents a —C (CF 3 ) 2 OH group.)
A polymer compound containing at least a repeating unit represented by formula (8).

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—Si (CH 3 ) 3 group R 5 represents a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Any number of hydrogen atoms may be alkyl groups, fluoroalkyl Optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF 3 ) 2 OH group, m and n each independently represents an integer of 0 to 2; m + n is 1 or more and 4 or less.)
The high molecular compound of Claim 13 containing the repeating unit represented by Formula (8A) at least.

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C≡C—C (CH 3 ) 2 OH group, —C≡C—C 6 H 5 group, —C≡C—Si (CH 3 ) 3 group R 5 represents a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Any number of hydrogen atoms may be alkyl groups, fluoroalkyl And optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF 3 ) 2 OH group.)
The high molecular compound of Claim 13 or 14 containing the repeating unit represented by Formula (8B) at least.

(Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) R 5 represents a tetravalent organic group containing one or more substituents selected from the group consisting of a phenyl group, a methoxy group and a nitro group, wherein R 5 is one or more selected from an alicyclic ring, an aromatic ring and an alkylene group; Fluorine atom, chlorine atom, oxygen atom, sulfur atom, nitrogen atom may be contained, and any number of hydrogen atoms may be substituted with alkyl group, fluoroalkyl group, carboxyl group, hydroxy group or cyano group HFIP represents a —C (CF 3 ) 2 OH group.)
10. The polymer compound according to claim 5, wherein the divalent organic group A is one or more selected from formulas (25) to (29). .

(In the formula, the line that intersects the wavy line represents the coupling position.)
The polymer compound according to any one of claims 10 to 15, wherein R 5 is one or more selected from the formulas (30) to (35).

(In the formula, the line that intersects the wavy line represents the coupling position.)