WO2012133229A1

WO2012133229A1 - Electronic device and polymer compound

Info

Publication number: WO2012133229A1
Application number: PCT/JP2012/057605
Authority: WO
Inventors: 田中　正信; 塁石川; 健作堀江; 顕榊原; 東村　秀之
Original assignee: 住友化学株式会社
Priority date: 2011-03-28
Filing date: 2012-03-23
Publication date: 2012-10-04
Also published as: TW201245267A; JP2012216811A

Abstract

This invention provides an electronic device useful as an electroluminescent element which emits light with high luminance, and provides a polymer compound used in said electronic device. In other words, this invention provides the following inventions: an electronic device which has, as a charge injection layer and / or charge transport layer, a layer containing a polymer compound having a structural unit containing both a group represented by formula (1): -(Q¹)_n1-Y¹(M¹)_a1(Z¹)_b1, and a group represented by the formula (2): -(Q²)_n2-Y², wherein the ratio of the M¹'s in the polymer compound that are H⁺ to the total number of M¹'s in the polymer compound is greater than 0% and less than or equal to 50%; and the polymer compound used in said electronic device.

Description

Electronic devices and polymer compounds

The present invention relates to an electronic device and a polymer compound suitably used for the electronic device.

In order to improve the characteristics of the electroluminescent element, various layers have been studied to be inserted between the light emitting layer and the electrode of the electroluminescent element. For example, an electroluminescent element having a layer made of a non-conjugated polymer compound containing a substituent having a cation and two heteroatoms between a light emitting layer and an electrode is known (Patent Document 1).

Special table 2003-530676 gazette

However, the luminance of the electroluminescent element was not yet sufficient.

An object of the present invention is to provide an electronic device useful as an electroluminescent element that emits light with high luminance, and a polymer compound used in the electronic device.

The present inventors have found that the above object can be achieved by the following electronic device, polymer compound, etc., and have reached the present invention.

The present invention provides the following [1] to [12].
[1] A layer containing a polymer compound having a structural unit containing a group represented by formula (1) and a group represented by formula (2) is provided as a charge injection layer and / or a charge transport layer.
The ratio that M ¹ in the polymer compound is H ⁺ with respect to all M ^{1 in} the polymer compound is greater than 0% and 50% or less.
Electronic devices.
-(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 (1)
(Where
Q ¹ is a divalent organic group.
Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ or —B (R ^α ) ₃ ^— .
M ¹ is H ^{+, a} metal cation, or an ammonium cation which may have a substituent.
Z ¹ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^a ) ₄ ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO. ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ .
n1 is an integer of 0 or more. a1 is an integer of 1 or more. b1 is an integer of 0 or more. However, a1 and b1 are selected so that the charge of the group represented by the formula (1) becomes zero.
R ^α is an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent. Each R ^α may be the same as or different from each other.
R ^a is a monovalent organic group which may have a substituent. When a plurality of R ^a are present, each R ^a may be the same as or different from each other.
When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other.
When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other.
When a plurality of Z ¹ are present, each Z ¹ may be the same as or different from each other. )
-(Q ² ) _n2 -Y ² (2)
(Where
Q ² is a divalent organic group.
Y ² is a cyano group or a group represented by any one of formulas (3) to (11).
n2 is an integer of 0 or more.
When a plurality of Q ² are present, each Q ² may be the same as or different from each other. )
-O- (R'O) _a3 -R '' (3)

-S- (R'S) _a4 -R '' (5)
-C (= O)-(R'-C (= O)) _a4 -R '' (6)
-C (= S)-(R'-C (= S)) _a4 -R '' (7)
-N {(R ′) _a4 R ″} ₂ (8)
—C (═O) O— (R′—C (═O) O) _a4 —R ″ (9)
—C (═O) O— (R′O) _a4 —R ″ (10)
—NHC (═O) — (R′NHC (═O)) _a4 —R ″ (11)
(Where
R ′ is a divalent hydrocarbon group which may have a substituent.
R ″ represents a hydrogen atom, a monovalent hydrocarbon group which may have a substituent, a carboxyl group, a sulfo group, a hydroxyl group, a mercapto group, —NR ^c ₂ , a cyano group or —C (═O). NR ^c ₂ .
R ′ ″ is a trivalent hydrocarbon group which may have a substituent.
a3 is an integer of 1 or more. a4 is an integer of 0 or more.
R ^c is an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 50 carbon atoms, and each R ^c is It may be the same or different.
When a plurality of R ′ are present, each R ′ may be the same as or different from each other.
When a plurality of R ″ are present, each R ″ may be the same as or different from each other.
When a plurality of a4 are present, each a4 may be the same as or different from each other. )

[2] The above [1], wherein the structural unit is one or more structural units selected from the group consisting of the structural unit represented by the formula (12) and the structural unit represented by the formula (14). Electronic devices.

(Where
R ¹ is a monovalent group including a group represented by Formula (13).
Ar ¹ is a (2 + n3) -valent aromatic group that may have a substituent other than R ¹ .
n3 is an integer of 1 or more.
When several R < ¹ > exists, each R < ¹ > may mutually be same or different. )

(Where
R ² is a (1 + m1 + m2) valent organic group.
Q ¹ , Q ² , Y ¹ , M ¹ , Z ¹ , Y ² , n1, a1, b1, and n2 have the same meaning as described above.
m1 and m2 are each independently an integer of 1 or more.
When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other.
When a plurality of Q ² are present, each Q ² may be the same as or different from each other.
When a plurality of Y ¹ are present, each Y ¹ may be the same as or different from each other.
When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other.
When a plurality of Z ¹ are present, each Z ¹ may be the same as or different from each other.
When a plurality of Y ² are present, each Y ² may be the same as or different from each other.
When a plurality of n1 are present, each n1 may be the same as or different from each other.
When a plurality of a1 are present, each a1 may be the same as or different from each other.
When a plurality of b1 are present, each b1 may be the same as or different from each other.
When a plurality of n2 are present, each n2 may be the same as or different from each other. )

(Where
R ³ is a monovalent group including a group represented by the formula (13) or a group represented by the formula (15).
R ⁴ is a monovalent group including a group represented by Formula (16).
Ar ² is a (2 + n4 + n5) -valent aromatic group that may have a substituent other than R ³ and R ⁴ .
n4 and n5 are each independently an integer of 1 or more.
When a plurality of R ³ are present, each R ³ may be the same as or different from each other.
When a plurality of R ⁴ are present, each R ⁴ may be the same as or different from each other. )
-R ⁵ -{(Q ¹ ) _{n 1} -Y ¹ (M ¹ ) a ₁ (Z ¹ ) _{b 1} } _{m 3} (15)
(Where
R ⁵ is a single bond or a (1 + m3) valent organic group.
Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1 and b1 have the same meaning as described above.
m3 represents an integer of 1 or more. However, when R ⁵ is a single bond, m3 is 1.
When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other.
When a plurality of Y ¹ are present, each Y ¹ may be the same as or different from each other.
When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other.
When a plurality of Z ¹ are present, each Z ¹ may be the same as or different from each other.
When a plurality of n1 are present, each n1 may be the same as or different from each other.
When a plurality of a1 are present, each a1 may be the same as or different from each other.
When a plurality of b1 are present, each b1 may be the same as or different from each other. )
-R ⁶ -{(Q ² ) _n2 -Y ² } _m4 (16)
(Where
R ⁶ is a single bond or a (1 + m4) -valent organic group.
Q ² , Y ² and n2 have the same meaning as described above.
m4 is an integer of 1 or more. However, when R ⁶ is a single bond, m4 is 1.
When a plurality of Q ² are present, each Q ² may be the same as or different from each other.
When a plurality of Y ² are present, each Y ² may be the same as or different from each other.
When a plurality of n2 are present, each n2 may be the same as or different from each other. )

[3] The (2 + n3) -valent aromatic group represented by Ar ¹ is represented by the formula 1, 2, 4, 5, 6, ¹³ , ¹⁴ , ¹⁵ , 19, 21, 23, 31, 32, 33, 43, The electronic device according to the above [2], which is a group obtained by removing (2 + n3) hydrogen atoms from the ring represented by 46, 47 or 51.

[4] The (2 + n4 + n5) -valent aromatic group represented by Ar ² is represented by formulas 1, 2, 4, 5, 6, 13, 14, 15, 19, 21, 23, 31, 32, 33, 43, The electronic device according to the above [2] or [3], which is a group obtained by removing (2 + n4 + n5) hydrogen atoms from the ring represented by 46, 47 or 51.

[5] The electronic device according to any one of [1] to [4], wherein the layer containing the polymer compound is provided as an electron injection layer and / or an electron transport layer.
[6] The electronic device according to any one of [1] to [5], which is an electroluminescent element.

[7] having one or more structural units selected from the group consisting of the structural unit represented by formula (12) and the structural unit represented by formula (14);
The ratio in which M ¹ in the polymer compound is H ⁺ is greater than 0% and 50% or less with respect to all M ¹ in the polymer compound.
High molecular compound.

(Where
R ³ is a monovalent group including a group represented by the formula (13) or a group represented by the formula (15).
R ⁴ is a monovalent group including a group represented by Formula (16).
Ar ² is a (2 + n4 + n5) -valent aromatic group that may have a substituent other than R ³ and R ⁴ .
n4 and n5 are each independently an integer of 1 or more.
When a plurality of R ³ are present, each R ³ may be the same as or different from each other.
When a plurality of R ⁴ are present, each R ⁴ may be the same as or different from each other. )
-R ⁵ -{(Q ¹ ) _{n 1} -Y ¹ (M ¹ ) a ₁ (Z ¹ ) _{b 1} } _{m 3} (15)
(Where
R ⁵ is a single bond or a (1 + m3) valent organic group.
Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1 and b1 have the same meaning as described above.
m3 represents an integer of 1 or more. However, when R ⁵ is a single bond, m3 is 1.
When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other.
When a plurality of Y ¹ are present, each Y ¹ may be the same as or different from each other.
When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other.
When a plurality of Z ¹ are present, each Z ¹ may be the same as or different from each other.
When a plurality of n1 are present, each n1 may be the same as or different from each other.
When a plurality of a1 are present, each a1 may be the same as or different from each other.
When a plurality of b1 are present, each b1 may be the same as or different from each other. )
-R ⁶ -{(Q ² ) _n2 -Y ² } _m4 (16)
(Where
R ⁶ is a single bond or a (1 + m4) -valent organic group.
Q ² , Y ² and n2 have the same meaning as described above.
m4 is an integer of 1 or more. However, when R ⁶ is a single bond, m4 is 1.
When a plurality of Q ² are present, each Q ² may be the same as or different from each other.
When a plurality of Y ² are present, each Y ² may be the same as or different from each other.
When a plurality of n2 are present, each n2 may be the same as or different from each other. )
[8] The (2 + n3) -valent aromatic group represented by Ar ¹ is represented by the formula 1, 2, 4, 5, 6, ¹³ , ¹⁴ , ¹⁵ , 19, 21, 23, 31, 32, 33, 43, The polymer compound according to the above [7], which is a group obtained by removing (2 + n3) hydrogen atoms from the ring represented by 46, 47 or 51.

[9] The (2 + n4 + n5) -valent aromatic group represented by Ar ² is represented by the formula 1, 2, 4, 5, 6, 13, 14, 15, 19, 21, 23, 31, 32, 33, 43, The polymer compound according to [7] or [8] above, which is a group obtained by removing (2 + n4 + n5) hydrogen atoms from the ring represented by 46, 47 or 51.

[10] The polymer compound according to any one of [7] to [9] above, wherein Y ² is a group represented by formula (3) or formula (4).
[11] The method for producing a polymer compound according to any one of the above [7] to [10], wherein a raw material containing a compound represented by the formula (21) and containing one or more ions is subjected to condensation polymerization.
Y ³ -A ^a -Y ⁴ (21)
(Where
A ^a is a divalent group including a group represented by the formula (1) and a group represented by the formula (2).
Y ³ and Y ⁴ are each independently a group involved in condensation polymerization. )
[12] Any of the above [7] to [10], wherein a raw material containing a compound not containing ions represented by the formula (21 ′) is subjected to condensation polymerization to synthesize a polymer compound containing ions from the resulting compound A method for producing the polymer compound according to claim 1.
Y ³ -A ^aa -Y ⁴ (21 ')
(Where
A ^aa is a divalent group including a group represented by the formula (22) and a group represented by the formula (2).
Y ³ and Y ⁴ are each independently a group involved in condensation polymerization. )
-R ⁷ -{(Q ³ ) _n6 -Y ⁵ } _m9 (22)
(Where
R ⁷ is a (1 + m9) valent organic group.
Q ³ represents a divalent organic group.
Y ⁵ is —CO ₂ R ^χ , —SO ₃ R ^χ , —SO ₂ R ^χ , —PO ₃ (R ^χ ) _2, or —B (R ^χ ) ₂ .
n6 is an integer of 0 or more.
R ^χ is a hydrogen atom, an ^optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted aryl group having 6 to 50 carbon atoms.
m9 represents an integer of 1 or more.
When a plurality of Q ³ are present, each Q ³ may be the same as or different from each other.
When a plurality of Y ⁵ are present, each Y ⁵ may be the same as or different from each other.
When a plurality of n6 are present, each n6 may be the same as or different from each other.
When a plurality of R ^χ are present, each R ^χ may be the same as or different from each other. )

The electronic device of the present invention can be an electroluminescent element that emits light with high luminance.

Hereinafter, the present invention will be described in detail.

<Polymer compound>
Hereinafter, the structural unit, characteristics, specific examples, production method, ratio in which M ¹ is H ⁺ and a layer containing the polymer compound will be sequentially described.

[1. Structural unit containing group represented by formula (1) and group represented by formula (2)]
The polymer compound of the present invention has a structural unit containing a group represented by the formula (1) and a group represented by the formula (2). The structural unit may contain two or more groups represented by the formula (1), may contain two or more groups represented by the formula (2), and is represented by the formula (1). And two or more groups each represented by formula (2) may be included. The ratio of the total of the structural units to the total structural units contained in the polymer compound is preferably 15 to 100 mol%.

Hereinafter, the group represented by the formula (1) and the group represented by the formula (2) will be sequentially described.

[1.1. Group represented by Formula (1)]
In formula (1), Q ¹ is a divalent organic group. Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ or —B (R ^α ) ₃ ^— . M ¹ is H ^{+, a} metal cation, or an ammonium cation which may have a substituent. Z ¹ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^a ) ₄ ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO. ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ . n1 is an integer of 0 or more. a1 is an integer of 1 or more. b1 is an integer of 0 or more. However, a1 and b1 are selected so that the charge of the group represented by the formula (1) becomes zero. R ^α is an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent. When a plurality of R ^α are present, each R ^α may be the same as or different from each other. R ^a is a monovalent organic group which may have a substituent, and when a plurality of R ^a are present, each R ^a may be the same as or different from each other. When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other. When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other. If the Z ¹ are present, each Z ¹ may be the same or different from each other. When a plurality of groups represented by formula (1) are present in the polymer compound, each group represented by formula (1) may be the same as or different from each other.

In formula (1), Q ¹ is a divalent organic group. Examples of the divalent organic group represented by Q ¹ include the following groups:
Methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-butylene group, 1,4-butylene group, 1,5-pentylene group, 1, Having a substituent such as a 6-hexylene group, a 1,9-nonylene group, a 1,12-dodecylene group, or a group in which at least one hydrogen atom of these groups is substituted with a substituent. A divalent chain saturated hydrocarbon group having 1 to 50 carbon atoms;
Alkenylene group having 2 to 50 carbon atoms which may have a substituent (for example, ethenylene group, propenylene group, 3-butenylene group, 2-butenylene group, 2-pentenylene group, 2-hexenylene group, 2-nonenylene group) A group, a 2-dodecenylene group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, etc.) and / or an ethynylene group, which may have a substituent 2 to 50 divalent chain unsaturated hydrocarbon groups;
A cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclononylene group, a cyclododecylene group, a norbornylene group, an adamantylene group, and at least one hydrogen atom in these groups is substituted with a substituent. A divalent cyclic saturated hydrocarbon group having 3 to 50 carbon atoms which may have a substituent, such as
1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, biphenyl-4,4′-diyl group, among these groups An arylene group having 6 to 50 carbon atoms which may have a substituent, such as a group in which at least one hydrogen atom is substituted with a substituent;
A methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like, An optionally substituted alkyleneoxy group having 1 to 50 carbon atoms, 1,3-phenyleneoxy group, 1,4-phenyleneoxy group, 1,4-naphthyleneoxy group, 1,5-naphthyleneoxy group, An aryleneoxy group having 6 to 50 carbon atoms which may have a substituent such as a 2,6-naphthyleneoxy group or a group in which at least one hydrogen atom of these groups is substituted with a substituent (ie, A divalent organic group represented by the formula: —R ^d —O— (wherein R ^d has an alkylene group having 1 to 50 carbon atoms which may have a substituent or a substituent. Charcoal An arylene group having 1 to 50 atoms, and examples of the alkylene group having 1 to 50 carbon atoms which may have a substituent include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group; Groups, and groups in which at least one hydrogen atom in these groups is substituted with a substituent, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5- A naphthylene group and a 2,6-naphthylene group)));
An imino group having a substituent containing a carbon atom;
A silylene group having a substituent containing a carbon atom.

From the viewpoint of ease of synthesis of a monomer that is a raw material for the polymer compound (hereinafter referred to as “raw material monomer”), the divalent organic group represented by Q ¹ is a divalent chain saturated hydrocarbon. It is preferably a group, an arylene group or an alkyleneoxy group.

As a divalent organic group represented by Q ¹ , a divalent chain saturated hydrocarbon group having 1 to 50 carbon atoms, a divalent chain unsaturated hydrocarbon group having 2 to 50 carbon atoms, carbon, Substituents that may be contained in a divalent cyclic saturated hydrocarbon group having 3 to 50 atoms, an arylene group having 6 to 50 carbon atoms, an alkyleneoxy group having 1 to 50 carbon atoms, an imino group, and a silylene group Are, for example, alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups, arylalkenyl groups, arylalkynyl groups, amino groups, substituted amino groups, Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, hydroxy group, substitution Carboxyl group and a cyano group and a nitro group.
When a plurality of the substituents are present, they may be the same as or different from each other.

Hereinafter, the substituent will be described.
In the present specification, the term “C _m -C _n ” (m, n is a positive integer satisfying m <n) means that the organic group described together with this term has m to n carbon atoms. Represents that. For example, a C _m to C _n alkyl group represents that the alkyl group has m to n carbon atoms, and a C _m to C _n alkyl aryl group represents an alkyl group contained in the alkyl aryl group. This means that the number of carbon atoms is m to n, and in the case of an aryl-C _m to C _n alkyl group, it means that the number of carbon atoms of the alkyl group contained in the arylalkyl group is m to n.

In the present specification, “may have a substituent” means that the hydrogen atom constituting the compound or group described immediately after it is unsubstituted or a part or all of the hydrogen atoms are substituted. Includes both cases where it is substituted.

The alkyl group may be linear or branched, and may be a cycloalkyl group. The alkyl group usually has 1 to 20 carbon atoms (usually 3 to 20 in the case of a cycloalkyl group), and preferably 1 to 10 (3 to 20 in the case of a cycloalkyl group). Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, Nonyl group, decyl group and lauryl group can be mentioned. The hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of such an alkyl group (fluorine atom-substituted alkyl group) include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Examples of the C ₁ to C ₁₂ alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, and a hexyl group. Cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group and lauryl group.

The alkoxy group may be linear or branched, may be a cycloalkyloxy group, and may have a substituent. The number of carbon atoms of the alkoxy group is usually 1 to 20 (usually 3 to 20 for a cycloalkyloxy group), and preferably 1 to 10 (3 to 10 for a cycloalkyloxy group). Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyl Examples thereof include an oxy group, an octyloxy group, a nonyloxy group, a decyloxy group, and a lauryloxy group. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of such an alkoxy group (fluorine atom-substituted alkoxy group) include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group. Examples of the alkoxy group also include a methoxymethyloxy group and a 2-methoxyethyloxy group. Examples of the C ₁ to C ₁₂ alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. Group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group.

The alkylthio group may be linear or branched, may be a cycloalkylthio group, and may have a substituent. The alkylthio group usually has 1 to 20 carbon atoms (usually 3 to 20 for a cycloalkylthio group), and preferably 1 to 10 (3 to 10 for a cycloalkylthio group). Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, An octylthio group, a nonylthio group, a decylthio group, a laurylthio group, etc. are mentioned. A hydrogen atom in the alkylthio group may be substituted with a fluorine atom. Examples of such an alkylthio group (fluorine atom-substituted alkylthio group) include a trifluoromethylthio group.

The aryl group is a remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon. The aryl group includes a group having a benzene ring, a group having a condensed ring, a group in which two or more independent benzene rings and / or condensed rings are single-bonded, and two or more independent benzene rings and / or condensed rings. A divalent organic group (for example, a group bonded via an alkenylene group such as a vinylene group) is also included. The aryl group usually has 6 to 60 carbon atoms, and preferably 6 to 48 carbon atoms. Examples of the aryl group include a phenyl group, a C ₁ to C ₁₂ alkoxyphenyl group, a C ₁ to C ₁₂ alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, and 9- Anthracenyl group etc. are mentioned. A hydrogen atom in the aryl group may be substituted with a fluorine atom. Examples of such an aryl group (fluorine atom-substituted aryl group) include a pentafluorophenyl group. Of the aryl groups, a phenyl group, a C ₁ -C ₁₂ alkoxyphenyl group and a C ₁ -C ₁₂ alkylphenyl group are preferred.

Examples of the C ₁ -C ₁₂ alkoxyphenyl group include a methoxyphenyl group, an ethoxyphenyl group, a propyloxyphenyl group, an isopropyloxyphenyl group, a butoxyphenyl group, an isobutoxyphenyl group, a sec-butoxyphenyl group, and a tert-butoxyphenyl group. Group, pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyl An oxyphenyl group, a lauryloxyphenyl group, etc. are mentioned.

Examples of the C ₁ -C ₁₂ alkylphenyl group include methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, tert -Butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group and dodecylphenyl group.

The aryloxy group usually has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms. Examples of the aryloxy group include a phenoxy group, a C ₁ to C ₁₂ alkoxyphenoxy group, a C ₁ to C ₁₂ alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group. . Of the aryloxy groups, a phenoxy group, a C ₁ -C ₁₂ alkoxyphenoxy group, and a C ₁ -C ₁₂ alkylphenoxy group are preferred.

Examples of the C ₁ -C ₁₂ alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a propyloxyphenoxy group, an isopropyloxyphenoxy group, a butoxyphenoxy group, an isobutoxyphenoxy group, a sec-butoxyphenoxy group, a tert-butoxyphenoxy group. Group, pentyloxyphenoxy group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3,7-dimethyloctyl Examples thereof include an oxyphenoxy group and a lauryloxyphenoxy group.

The arylthio group is, for example, a group in which the aforementioned aryl group is bonded to a sulfur element. The arylthio group may have a substituent on the aromatic ring of the aryl group. The arylthio group usually has 6 to 60 carbon atoms, preferably 6 to 30 carbon atoms. Examples of the arylthio group include a phenylthio group, a C ₁ -C ₁₂ alkoxyphenylthio group, a C ₁ -C ₁₂ alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

The arylalkyl group is, for example, a group in which the aforementioned aryl group is bonded to the aforementioned alkyl group. The arylalkyl group may have a substituent. The arylalkyl group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms. Examples of the arylalkyl group include a phenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group, naphthyl -C ₁ ~ C ₁₂ alkyl group and 2-naphthyl -C ₁ ~ C ₁₂ alkyl group.

The arylalkoxy group is, for example, a group in which the above aryl group is bonded to the above alkoxy group. The arylalkoxy group may have a substituent. The arylalkoxy group usually has 7 to 60 carbon atoms, and preferably 7 to 30 carbon atoms. Examples of the arylalkoxy group include a phenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy group, Examples include ₁ -naphthyl-C ₁ -C ₁₂ alkoxy group and 2-naphthyl-C ₁ -C ₁₂ alkoxy group.

The arylalkylthio group is, for example, a group in which the above aryl group is bonded to the above alkylthio group. The arylalkylthio group may have a substituent. The arylalkylthio group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms. Examples of the arylalkylthio group include a phenyl-C ₁ to C ₁₂ alkylthio group, a C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkylthio group, a C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkylthio group, Examples thereof include a ₁ -naphthyl-C ₁ -C ₁₂ alkylthio group and a 2-naphthyl-C ₁ -C ₁₂ alkylthio group.

The arylalkenyl group is, for example, a group in which the aforementioned aryl group is bonded to the alkenyl group. The arylalkenyl group usually has 8 to 60 carbon atoms, preferably 8 to 30 carbon atoms. Examples of the arylalkenyl group include a phenyl-C ₂ -C ₁₂ alkenyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, a C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkenyl group, Examples include 1-naphthyl-C ₂ -C ₁₂ alkenyl group and 2-naphthyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group or C ₂ -C ₁₂ alkylphenyl A —C ₂ -C ₁₂ alkenyl group is preferred. Examples of the C ₂ -C ₁₂ alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl. Group, 2-hexenyl group and 1-octenyl group.

The arylalkynyl group is, for example, a group in which the aforementioned aryl group is bonded to the alkynyl group. The arylalkynyl group usually has 8 to 60 carbon atoms, preferably 8 to 30 carbon atoms. Examples of the arylalkynyl group include a phenyl-C ₂ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkynyl group, Examples include 1-naphthyl-C ₂ -C ₁₂ alkynyl group and 2-naphthyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group or C ₁ -C ₁₂ alkylphenyl A —C ₂ to C ₁₂ alkynyl group is preferred. Examples of the C ₂ -C ₁₂ alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group. Group, 2-hexynyl group and 1-octynyl group.

As the substituted amino group, at least one hydrogen atom in the amino group is substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The amino group formed is preferred. The alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted amino group is usually 1 to 60, not including the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have. It is preferably 2 to 48. Examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, sec- Butylamino group, tert-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group , lauryl group, a cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, (C ₁ ~ C ₁₂ alkoxy Eniru) amino group, di (C ₁ ~ C ₁₂ alkoxyphenyl) amino group, di (C ₁ ~ C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino Group, pyridazinylamino group, pyrimidylamino group, pyrazinylamino group, triazinylamino group, (phenyl-C ₁ -C ₁₂ alkyl) amino group, (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) Amino group, (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkyl) phenyl -C ₁ ~ C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ ~ C ₁₂ alkylamino groups and 2-naphthyl -C ₁ ~ C ₁₂ alkyl amino group is exemplified et al That.

As the substituted silyl group, at least one hydrogen atom in the silyl group is substituted with 1 to 3 groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group Silyl group formed. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted silyl group is usually 1 to 60, not including the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have. 3 to 48 are preferable. Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, isopropyldimethylsilyl group, isopropyldiethylsilyl group, tert-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group. Group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyldimethylsilyl group, lauryldimethylsilyl group, (phenyl-C _1- (C ₁₂ alkyl) silyl group, (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) silyl group, (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) silyl group, (1-naphthyl- C ₁ ~ C ₁₂ alkyl Silyl group, (2-naphthyl -C ₁ ~ C ₁₂ alkyl) silyl group, (phenyl -C ₁ ~ C ₁₂ alkyl) dimethyl silyl group, a triphenylsilyl group, tri (p- xylyl) silyl group, tribenzylsilyl group , Diphenylmethylsilyl group, tert-butyldiphenylsilyl group and dimethylphenylsilyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The acyl group usually has 2 to 20 carbon atoms, and preferably 2 to 18 carbon atoms. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

The acyloxy group usually has 2 to 20 carbon atoms, and preferably 2 to 18 carbon atoms. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The imine residue means a group in which one hydrogen atom in this structure is removed from an imine compound having a structure represented by at least one of the formula: H—N═C <and the formula: —N═CH—. . As the imine compound, for example, a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine and aldimine is substituted with a substituent (for example, an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, etc.). The compound which is mentioned. The number of carbon atoms in the imine residue is usually 2-20, and preferably 2-18. Examples of the imine residue include a group represented by the formula: —CR ^β = N—R ^γ and a group represented by the formula: —N═C (R ^γ ) ₂ (wherein R ^β represents a hydrogen atom , An alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group, and R ^γ is independently an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group. , When two R ^γ are present, the two R ^γ may be bonded together to form a ring as a divalent group, for example, an ethylene group And alkylene groups having 2 to 18 carbon atoms such as trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc.). Examples of the imine residue include groups represented by the following formulas.

The amide group usually has 1 to 20 carbon atoms and preferably 2 to 18 carbon atoms. Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, Examples include a ditrifluoroacetamide group and a dipentafluorobenzamide group.

The acid imide group is a group obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide. The acid imide group usually has 4 to 20 carbon atoms, and preferably 4 to 18 carbon atoms.
Examples of the acid imide group include groups represented by the following formulas.

The monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from a heterocyclic compound.
Here, the heterocyclic compound is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a silicon atom as an element constituting a ring among organic compounds having a cyclic structure. , An organic compound containing a heteroatom such as a selenium atom, a tellurium atom or an arsenic atom. The monovalent heterocyclic group may have a substituent. The monovalent heterocyclic group usually has 3 to 60 carbon atoms, and preferably 3 to 20 carbon atoms. The number of carbon atoms of the monovalent heterocyclic group does not include the number of carbon atoms of the substituent. Examples of the monovalent heterocyclic group include thienyl group, C ₁ -C ₁₂ alkyl thienyl group, pyrrolyl group, furyl group, pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, Examples thereof include a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group and an isoquinolyl group, among which a thienyl group, a C ₁ to C ₁₂ alkylthienyl group, a pyridyl group, a C ₁ to C ₁₂ alkylpyridyl group and a triazinyl group are preferable. The monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group. The monovalent aromatic heterocyclic group includes an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from a heterocyclic compound in which the heterocyclic ring itself exhibits aromaticity, and the heterocycle Directly from a compound containing an atom but not having aromaticity to a ring in which the aromatic ring is condensed (for example, phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, benzopyran) to the carbon atom constituting the ring It means the remaining atomic group excluding one hydrogen atom to be bonded.

The substituted carboxyl group is a carboxyl group in which a hydrogen atom in the carboxyl group is substituted with one or more groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. is there. That is, the substituted carboxyl group is a group represented by the formula: —C (═O) OR ^* (wherein R ^* is an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group). It is. The substituted carboxyl group usually has 2 to 60 carbon atoms, and preferably 2 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Note that the number of carbon atoms of the substituted carboxyl group does not include the number of carbon atoms of the substituent of the alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group. Examples of the substituted carboxyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, and a pentyloxycarbonyl group. Hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyl Oxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyl Alkoxycarbonyl group, a perfluorooctyl group, phenoxycarbonyl group, and a naphthoxycarbonyl group and pyridyloxycarbonyl group.

In the formula (1), Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ or —B (R ^α ) ₃ ^— . Y ¹ is preferably —CO ₂ ⁻ , —SO ₂ ^— or —PO ₃ ²⁻ from the viewpoint of the acidity of the polymer compound, and more preferably —CO ₂ ^— . Y ¹ is preferably —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ^— or —PO ₃ ²⁻ from the viewpoint of the stability of the polymer compound.

R ^α is an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an aryl group having 6 to 50 carbon atoms which may have a substituent. Examples of the substituent that may be contained in the alkyl group having 1 to 30 carbon atoms and the aryl group having 6 to 50 carbon atoms that may be included in R ^α include the substituents exemplified in the description regarding Q ¹ described above. And the same substituents. When a plurality of substituents are present, they may be the same as or different from each other. R ^α is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, An alkyl having 1 to 20 carbon atoms which may have a substituent, such as a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom of these groups is substituted with a substituent; A phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, and at least one hydrogen atom in these groups is substituted with a substituent. And an aryl group having 6 to 30 carbon atoms which may have a substituent, such as the above-described groups. When a plurality of R ^α are present, each R ^α may be the same as or different from each other.

In formula (1), M ¹ is H ^{+, a} metal cation, or an ammonium cation which may have a substituent. Examples of the metal cation include a monovalent, divalent or trivalent metal cation. Examples of monovalent, divalent or trivalent metal cations include, for example, Li cation, Na cation, K cation, Rb cation, Cs cation, Be cation, Mg cation, Ca cation, Ba Cations, Ag cations, Al cations, Bi cations, Cu cations, Fe cations, Ga cations, Mn cations, Pb cations, Sn cations, Ti cations, V cations, W cations, Examples include a cation of Y, a cation of Yb, a cation of Zn and a cation of Zr, and Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Ag ⁺ , Mg ²⁺ and Ca ²⁺ are preferred. Examples of the substituent that the ammonium cation may have include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a tert-butyl group and the like, having 1 to 10 carbon atoms. And an aryl group having 6 to 60 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

In the formula (1), Z ¹ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^a ) ₄ ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ^−. , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ^-That's it.

R ^a is ^a monovalent organic group which may have ^a substituent. Examples of the organic group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, and at least one hydrogen atom in these groups is a substituent. An alkyl group having 1 to 10 carbon atoms, a phenyl group, a 1-naphthyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, such as a group substituted with And aryl groups having 6 to 30 carbon atoms. Examples of the substituent that the alkyl group having 1 to 10 carbon atoms or the aryl group having 6 to 30 carbon atoms that may be included in R ^a may include the substituents exemplified in the description of Q ¹ described above. Similar substituents can be mentioned. When a plurality of R ^a are present, each R ^a may be the same as or different from each other.

In the formula (1), n1 is an integer of 0 or more. From the viewpoint of the synthesis of the raw material monomer, n1 is preferably an integer of 0 to 8, and more preferably an integer of 0 to 2.

In formula (1), a1 is an integer of 1 or more, and b1 is an integer of 0 or more.

a1 and b1 are selected such that the charge of the group represented by the formula (1) is zero. For example, Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ or —B (R ^α ) ₃ ^— , and M ¹ is H ⁺ or a monovalent metal cation. Or an ammonium cation which may have a substituent, and Z ¹ is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^a ) ₄ ⁻ , R ^a SO ₃ ⁻ , R ^a When it is COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ a1 and b1 are selected to satisfy a1 = b1 + 1. Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ or —B (R ^α ) ₃ ^— , M ¹ is a divalent metal cation, and Z ¹ is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^a ) ₄ ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ , a1 and b1 are selected to satisfy b1 = 2 × a1-1. Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , or —PO ₃ ²⁻ , M ¹ is a trivalent metal cation, Z ¹ is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^a ) ₄ ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , In the case of HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ , a1 and b1 are selected so as to satisfy b1 = 3 × a1-1. Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ or —B (R ^α ) ₃ ^— , and M ¹ is H ⁺ or a monovalent metal cation, When it is an ammonium cation which may have a substituent and Z ¹ is SO ₄ ²⁻ or HPO ₄ ²⁻ , a1 and b1 are selected so as to satisfy a1 = 2 × b1 + 1. In any of the above mathematical expressions representing the relationship between a1 and b1, a1 is preferably an integer of 1 to 5, more preferably 1 or 2.

That is, when a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other. When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other. When a plurality of n2 are present, each n2 may be the same as or different from each other. When a plurality of Z ¹ are present, each Z ¹ may be the same as or different from each other.

Examples of the group represented by the formula (1) include groups represented by the following formulas. In the following formulae, M is H, Li, Na, K, Rb, Cs or N (CH ₃ ) ₄ .

[1.2. Group represented by Formula (2)]
In formula (2), Q ² is a divalent organic group. Y ² is a cyano group or a group represented by any one of formulas (3) to (11). n2 is an integer of 0 or more. When a plurality of Q ² are present, each Q ² may be the same as or different from each other. When a plurality of groups represented by formula (2) are present in the polymer compound, each group represented by formula (2) may be the same as or different from each other.

In formula (2), Q ² is a divalent organic group. Examples of the divalent organic group include the same groups as those exemplified for the divalent organic group represented by Q ¹ described above. From the viewpoint of ease of synthesis of the raw material monomer, Q ² represents a divalent chain saturated hydrocarbon group which may have a substituent, an arylene group or a substituent which may have a substituent. It is preferably an alkyleneoxy group that may have.

Substituents that the divalent chain saturated hydrocarbon group, arylene group, or alkyleneoxy group that may be included in Q ² may have the same substitution as the substituents exemplified in the above description of Q ¹ Groups. When a plurality of substituents are present, they may be the same as or different from each other.

In the formula (2), n2 is an integer of 0 or more, preferably an integer of 0 to 20, and more preferably an integer of 0 to 8.

In the formula (2), Y ² is a cyano group or a group represented by any one of the formulas (3) to (11).

In the formulas (3) to (11), R ′ is a divalent hydrocarbon group which may have a substituent.

Examples of the divalent hydrocarbon group which may have a substituent represented by R ′ include the following groups:
Methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-butylene group, 1,4-butylene group, 1,5-pentylene group, 1, Having a substituent such as a 6-hexylene group, a 1,9-nonylene group, a 1,12-dodecylene group, or a group in which at least one hydrogen atom of these groups is substituted with a substituent. A divalent chain saturated hydrocarbon group having 1 to 50 carbon atoms;
Ethenylene group, propenylene group, 3-butenylene group, 2-butenylene group, 2-pentenylene group, 2-hexenylene group, 2-nonenylene group, 2-dodecenylene group, at least one hydrogen atom in these groups is substituted The number of carbon atoms which may have a substituent, including an alkenylene group having 2 to 50 carbon atoms which may have a substituent and / or an ethynylene group, such as a group substituted by a group 2 to 50 divalent chain unsaturated hydrocarbon groups;
A cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclononylene group, a cyclododecylene group, a norbornylene group, an adamantylene group, and at least one hydrogen atom in these groups is substituted with a substituent. A divalent cyclic saturated hydrocarbon group having 3 to 50 carbon atoms which may have a substituent, such as
1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, biphenyl-4,4′-diyl group, among these groups An arylene group having 6 to 50 carbon atoms which may have a substituent, such as a group in which at least one hydrogen atom is substituted with a substituent.

Divalent chain saturated hydrocarbon group having 1 to 50 carbon atoms, divalent chain unsaturated hydrocarbon group having 2 to 50 carbon atoms, 2 having 3 to 50 carbon atoms, which can be contained in R ′ Examples of the substituent that the valent cyclic saturated hydrocarbon group and the arylene group having 6 to 50 carbon atoms may have include the same substituents as those exemplified in the description of Q ¹ described above. It is done. When a plurality of substituents are present, they may be the same as or different from each other.

In formulas (3) and (5) to (11), R ″ represents a hydrogen atom, a monovalent hydrocarbon group which may have a substituent, a carboxyl group, a sulfo group, a hydroxyl group, a mercapto group, —NR ^c ₂ , a cyano group, or —C (═O) NR ^c ₂ .

Examples of the monovalent hydrocarbon group optionally having a substituent represented by R ″ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom of these groups is substituted with a substituent An alkyl group having 1 to 20 carbon atoms which may have a substituent, and the like, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl Groups, and aryl groups having 6 to 30 carbon atoms which may have a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent.

From the viewpoint of solubility of the polymer compound, the monovalent hydrocarbon group optionally having a substituent represented by R ″ is a methyl group, an ethyl group, a phenyl group, a 1-naphthyl group, 2 -A naphthyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent is preferred.

Examples of the substituent which the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 30 carbon atoms which may be included in R ″ may have the substituents exemplified in the description of Q ¹ above. Examples of the substituent are the same as those of the group. When a plurality of substituents are present, they may be the same as or different from each other.

R ^c of -NR ^c ₂ and -C (= O) in NR ^c ₂ represented by R '' is 1 carbon atoms which may have a substituent group to 30 alkyl group, or a substituent An aryl group having 6 to 50 carbon atoms which may be present. Each R ^c may be the same as or different from each other. Examples of the substituent that the alkyl group having 1 to 30 carbon atoms and the aryl group having 6 to 50 carbon atoms that may be contained in R ^c may include the substituents exemplified in the description of Q ¹ described above. And the same substituents. From the viewpoint of solubility of the polymer compound, R ^c is a methyl group, an ethyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, or at least one hydrogen atom in these groups is a substituent. It is preferably a substituted group.

In formula (4), R ′ ″ is a trivalent hydrocarbon group which may have a substituent.

Examples of the trivalent hydrocarbon group which may have a substituent represented by R ′ ″ include, for example, methanetriyl group, ethanetriyl group, 1,2,3-propanetriyl group, 1,2,4 -Butanetriyl group, 1,2,5-pentanetriyl group, 1,3,5-pentanetriyl group, 1,2,6-hexanetriyl group, 1,3,6-hexanetriyl group, these An alkanetriyl group having 1 to 20 carbon atoms which may have a substituent, such as a group in which at least one hydrogen atom in the group is substituted with a substituent, and 1,2,3 -Benzenetriyl group, 1,2,4-benzenetriyl group, 1,3,5-benzenetriyl group, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. Of 6 to 30 carbon atoms which may have a substituent Riiru group, and the like.

From the viewpoint of the solubility of the polymer compound, the trivalent hydrocarbon group represented by R ′ ″ is methanetriyl group, ethanetriyl group, 1,2,4-benzenetriyl group, 1,3,5- A benzenetriyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent is preferable.

Examples of the substituent that the alkanetriyl group having 1 to 20 carbon atoms and the arenetriyl group having 6 to 30 carbon atoms that may be contained in R ′ ″ may have the above-described explanation regarding Q ¹ Examples thereof include the same substituents as those exemplified above. When a plurality of substituents are present, they may be the same as or different from each other.

In the formulas (3) and (4), a3 is an integer of 1 or more, preferably an integer of 2 to 10.

In the formulas (5) to (11), a4 is an integer of 0 or more. In the formula (5), a4 is preferably an integer of 0 to 30, and more preferably an integer of 3 to 20. In the formulas (6) to (9), a4 is preferably an integer of 0 to 10, and more preferably an integer of 0 to 5. In the formula (10), a4 is preferably an integer of 0 to 20, and more preferably an integer of 3 to 20. In the formula (11), a4 is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.

When a plurality of R ′ are present, each R ′ may be the same as or different from each other. When a plurality of R ″ are present, each R ″ may be the same as or different from each other. When a plurality of a4 are present, each a4 may be the same as or different from each other.

Y ² is a cyano group, a group represented by the formula (3), a group represented by the formula (4), a group represented by the formula (5), or a formula from the viewpoint of ease of synthesis of the raw material monomer. A group represented by (9) or a group represented by formula (10) is preferable, a group represented by formula (3), a group represented by formula (4), and a group represented by formula (5). The group represented by formula (9) is more preferred, and the group represented by formula (3) or group represented by formula (4) is more preferred.

[1.3. For M ^1]
As will be described later, the ratio of M ¹ in the polymer compound of the present invention to H ⁺ is greater than 0% and 50% or less with respect to all M ¹ in the polymer compound. 1% or more and 50% or less. Therefore, in the polymer compound of the present invention, a group represented by the formula (1) in which M ¹ is H ⁺ and a group represented by the formula (1) in which M ¹ is Both groups which are metal cations or ammonium cations which may have a substituent are included. These groups may coexist in the same structural unit, or may exist in different structural units.

[2. Structural unit represented by formula (12) and structural unit represented by formula (14)]
The structural unit containing the group represented by the formula (1) and the group represented by the formula (2) is composed of the structural unit represented by the formula (12) and the structural unit represented by the formula (14). It is preferably one or more structural units selected from the group. That is, the polymer compound used in the present invention preferably has one or more structural units selected from the group consisting of the structural unit represented by formula (12) and the structural unit represented by formula (14). .

The polymer compound used in the present invention may contain only the structural unit represented by the formula (12) as the structural unit, or may contain only the structural unit represented by the formula (14). And the combination of the structural unit represented by Formula (12) and the structural unit represented by Formula (14) may be included. When the polymer compound used in the present invention has one or more structural units selected from the group consisting of the structural unit represented by the formula (12) and the structural unit represented by the formula (14), these structures are used. The ratio of the total of units to the total structural units contained in the polymer compound is preferably 15 to 100 mol%.

[2.1. Structural unit represented by formula (12)]
In Formula (12), R ¹ is a monovalent group including a group represented by Formula (13). Ar ¹ is a (2 + n3) -valent aromatic group that may have a substituent other than R ¹ . n3 is an integer of 1 or more. When a plurality of structural units represented by the formula (12) are present in the polymer compound, each structural unit represented by the formula (12) may be the same as or different from each other.

Hereinafter, R ¹ , Formula (13), Ar ¹ and n3 will be described in this order.

[2.1.1. Description of R ^1]
R ¹ is a monovalent group including a group represented by Formula (13). When several R < ¹ > exists, each R < ¹ > may mutually be same or different.

R ¹ may be a monovalent group composed of a group represented by Formula (13). That is, the group represented by the formula (13) may be directly bonded to Ar ¹ .

On the other hand, R ¹ may be a group partially including a group represented by the formula (13). That is, the group represented by the formula (13) may be bonded to Ar ¹ through the following group or atom, for example:
Methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, nonylene group, dodecylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group, cyclododecylene group, norbornylene group An adamantylene group, an alkylene group having 1 to 50 carbon atoms which may have a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent;
Methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, nonyleneoxy, dodecyleneoxy, cyclopropyleneoxy, cyclobutyleneoxy, cyclopentyleneoxy, cyclohexene Xyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbornyleneoxy group, adamantyleneoxy group, a group in which at least one hydrogen atom of these groups is substituted with a substituent, etc. An alkyleneoxy group having 1 to 50 carbon atoms which may have a substituent (that is, a divalent organic group represented by the formula: —R ^f —O— (wherein R ^f is a substituent) An alkylene group having 1 to 50 carbon atoms which may have an alkylene group having 1 to 50 carbon atoms which may have a substituent. For example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, nonylene group, dodecylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group. , Cyclododecylene group, norbornylene group, adamantylene group, and a group in which at least one hydrogen atom in these groups is substituted with a substituent));
An imino group optionally having a substituent;
A silylene group optionally having a substituent;
An ethenylene group optionally having a substituent;
An ethynylene group;
Hetero atoms such as oxygen, nitrogen and sulfur atoms.

For example, R ¹ is a group represented by the formula (13) or a formula: —B ¹ — (A ¹ ) _{n * 1} (wherein A ¹ is a group represented by the formula (13)). B ¹ is an alkylene group having 1 to 50 carbon atoms, an alkyleneoxy group having 1 to 50 carbon atoms, an imino group which may have a substituent, a silylene group which may have a substituent, An optionally substituted ethenylene group, an ethynylene group, or a hetero atom, n * 1 is an integer of 1 or more, and when a plurality of A ¹ are present, each A ¹ is They may be the same or different.).

Examples of the substituent that the alkylene group having 1 to 50 carbon atoms, the alkyleneoxy group having 1 to 50 carbon atoms, the imino group, the silylene group, and the ethenylene group that may be contained in R ¹ may have the above-mentioned Examples thereof include the same substituents as those exemplified in the description of Q ¹ . When a plurality of substituents are present, they may be the same as or different from each other.

[2.1.2. Description of group represented by formula (13)]
In formula (13), R ² is a (1 + m1 + m2) valent organic group. Q ¹ , Q ² , Y ¹ , M ¹ , Z ¹ , Y ² , n1, a1, b1, and n2 have the same meaning as described above. m1 and m2 are each independently an integer of 1 or more. When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other. When a plurality of Q ² are present, each Q ² may be the same as or different from each other. When a plurality of Y ¹ are present, each Y ¹ may be the same as or different from each other. When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other. When a plurality of Z ¹ are present, each Z ¹ may be the same as or different from each other. When a plurality of Y ² are present, each Y ² may be the same as or different from each other. When a plurality of n1 are present, each n1 may be the same as or different from each other. When a plurality of a1 are present, each a1 may be the same as or different from each other. When a plurality of b1 are present, each b1 may be the same as or different from each other. When a plurality of n2 are present, each n2 may be the same as or different from each other.

Examples of the (1 + m1 + m2) -valent organic group represented by R ² include the following groups:
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, lauryl Groups (m1 + m2) from an alkyl group having 1 to 20 carbon atoms which may have a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent. Groups excluding hydrogen atoms;
A phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a group in which at least one hydrogen atom of these groups is substituted with a substituent, etc. A group obtained by removing (m1 + m2) hydrogen atoms from an aryl group having 6 to 30 carbon atoms which may have a substituent;
Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy group , A cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a carbon which may have a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent A group in which (m1 + m2) hydrogen atoms are removed from an alkoxy group having 1 to 50 atoms;
A group obtained by removing (m1 + m2) hydrogen atoms from an amino group having a substituent containing a carbon atom; a group obtained by removing (m1 + m2) hydrogen atoms from a silyl group having a substituent containing a carbon atom.

From the viewpoint of ease of synthesis of the raw material monomer, the (1 + m1 + m2) -valent organic group represented by R ² is (m1 + m2) from an alkyl group having 1 to 20 carbon atoms which may have a substituent. A group in which m1 hydrogen atoms are removed from an aryl group having 6 to 30 carbon atoms which may have a substituent, or a carbon atom which may have a substituent A group obtained by removing (m1 + m2) hydrogen atoms from 1 to 50 alkoxy groups is preferable.

A substituent that the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the alkoxy group having 1 to 50 carbon atoms which may be contained in R ² , and amino Examples of the substituent containing a carbon atom that the group and the silyl group may have include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same as or different from each other.

In formula (13), m1 and m2 are each independently an integer of 1 or more.

When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other. When a plurality of Q ² are present, each Q ² may be the same as or different from each other. When a plurality of Y ¹ are present, each Y ¹ may be the same as or different from each other. When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other. When a plurality of Z ¹ are present, each Z ¹ may be the same as or different from each other. When a plurality of Y ² are present, each Y ² may be the same as or different from each other. When a plurality of n1 are present, each n1 may be the same as or different from each other. When a plurality of a1 are present, each a1 may be the same as or different from each other. When a plurality of b1 are present, each b1 may be the same as or different from each other. When a plurality of n2 are present, each n2 may be the same as or different from each other.

[2.1.3. Description of Ar ¹ and n3]
Ar ¹ is a (2 + n3) -valent aromatic group that may have a substituent other than R ¹ .

Ar ¹ may have a substituent other than R ¹ . Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same as or different from each other.

The substituent other than R ¹ possessed by Ar ¹ is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, a substituted carboxyl group or a halogen atom from the viewpoint of ease of synthesis of the raw material monomer. Is preferred.

In the formula (12), n3 is an integer of 1 or more, preferably an integer of 1 to 4, more preferably an integer of 1 to 3.

Examples of the (2 + n3) -valent aromatic group represented by Ar ¹ in the formula (12) include a (2 + n3) -valent aromatic hydrocarbon group and a (2 + n3) -valent aromatic heterocyclic group, (2 + n3) -valent aromatic group consisting of only carbon atoms, or (2 + n3) -valent aromatic group consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms It is preferable that Examples of the (2 + n3) -valent aromatic group include a monocyclic aromatic ring (for example, a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, 1 , 3,5-triazine ring, furan ring, pyrrole ring, pyrazole ring, imidazole ring, oxazole ring, azadiazole ring, etc.), (2 + n3) hydrogen atoms directly bonded to carbon atoms constituting the ring are removed (2 + n3) ) A valent group; (2 + n3) hydrogen atoms directly bonded to the carbon atoms constituting the ring were removed from the condensed polycyclic aromatic ring having a structure in which two or more monocyclic aromatic rings are condensed. (2 + n3) -valent group; a structure in which two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring are connected by a single bond, an ethenylene group or an ethynylene group From the aromatic ring assembly (2 + n3) -valent group obtained by removing (2 + n3) hydrogen atoms directly bonded to the carbon atoms constituting the ring; two selected from the monocyclic aromatic ring, the condensed polycyclic aromatic ring and the aromatic ring assembly Including the above aromatic ring, two adjacent aromatic rings among the aromatic rings have a structure in which they are bridged by a divalent group such as a methylene group, an ethylene group or a carbonyl group, or by a methanetetrayl group. And (2 + n3) -valent groups obtained by removing (2 + n3) hydrogen atoms directly bonded to carbon atoms constituting the ring from the bridged polycyclic aromatic ring.

In the condensed polycyclic aromatic ring, the number of monocyclic aromatic rings to be condensed is preferably 2 to 4, more preferably 2 or 3, from the viewpoint of solubility of the polymer compound. 2 is more preferable. In the aromatic ring assembly, the number of linked aromatic rings is preferably 2 to 4, more preferably 2 or 3, and still more preferably 2, from the viewpoint of solubility. In the bridged polycyclic aromatic ring, the number of bridged aromatic rings is preferably 2 to 4, more preferably 2 or 3, from the viewpoint of solubility of the polymer compound. 2 is more preferable.

Examples of the monocyclic aromatic ring include rings represented by the following formulas.

Examples of the condensed polycyclic aromatic ring include rings represented by the following formulas.

Examples of the aromatic ring assembly include a ring represented by the following formula.

Examples of the bridged polycyclic aromatic ring include rings represented by the following formulas.

From the viewpoint of the conductivity of the polymer compound and the ease of synthesis of the raw material monomer, the (2 + n3) -valent aromatic group represented by Ar ¹ is represented by the formulas 1 to 15, 19 to 25, 31 to 35, 43, 46. It is preferably a (2 + n3) -valent group obtained by removing (2 + n3) hydrogen atoms directly bonded to carbon atoms constituting the ring from the ring represented by ˜48 or 51. , 6, 13, 14, 15, 19, 21, 23, 31, 32, 33, 43, 46, 47 or 51, a hydrogen atom directly bonded to a carbon atom constituting the ring is (2 + n3 It is more preferable that the number is a (2 + n3) -valent group, and the ring is selected from the ring represented by the formula 1, 5, 6, 13, 14, 15, 21, 23, 33, 43, 46 or 47. (2 + n3) hydrogen atoms directly bonded to constituting carbon atoms were removed ( Further preferably + n3) valent group.

Ar ¹ is preferably a group obtained by removing n3 hydrogen atoms from a divalent group represented by the following formulas 52 to 63.

[2.2. Structural unit represented by formula (14)]
In Formula (14), R ³ is a monovalent group including a group represented by Formula (13) or a group represented by Formula (15). R ⁴ is a monovalent group including a group represented by Formula (16). Ar ² is a (2 + n4 + n5) -valent aromatic group that may have a substituent other than R ³ and R ⁴ . n4 and n5 are each independently an integer of 1 or more. When a plurality of structural units represented by the formula (14) are present in the polymer compound, each structural unit represented by the formula (14) may be the same as or different from each other.

[2.1.1. Description of R ^3]
R ³ is a monovalent group including a group represented by the formula (13) or a group represented by the formula (15). When a plurality of R ³ are present, they may be the same as or different from each other.

R ³ may be a monovalent group composed of a group represented by the formula (13) or a group represented by the formula (15). That is, the group represented by the formula (13) or the group represented by the formula (15) may be directly bonded to Ar ² .

On the other hand, R ³ may be a group partially including a group represented by Formula (13) or a group represented by Formula (15). That is, the group represented by the formula (13) or the group represented by the formula (15) may be bonded to Ar ² through, for example, the following groups or atoms:
Methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, nonylene group, dodecylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group, cyclododecylene group, norbornylene group An adamantylene group, an alkylene group having 1 to 50 carbon atoms which may have a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent;
Methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, nonyleneoxy, dodecyleneoxy, cyclopropyleneoxy, cyclobutyleneoxy, cyclopentyleneoxy, cyclohexene Xyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbornyleneoxy group, adamantyleneoxy group, groups in which at least one hydrogen atom of these groups is substituted with a substituent, etc. An alkyleneoxy group having 1 to 50 carbon atoms which may have a substituent (that is, a divalent organic group represented by the formula: —R ^g —O— (wherein R ^g is a substituent) An alkylene group having 1 to 50 carbon atoms which may have an alkylene group having 1 to 50 carbon atoms which may have a substituent. For example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, nonylene group, dodecylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group. , Cyclododecylene group, norbornylene group, adamantylene group, and a group in which at least one hydrogen atom in these groups is substituted with a substituent));
An imino group optionally having a substituent;
A silylene group optionally having a substituent;
An ethenylene group optionally having a substituent;
An ethynylene group;
Hetero atoms such as oxygen, nitrogen and sulfur atoms.

For example, R ³ is a group represented by the formula (13), a group represented by the formula (15), or a formula: —B ² — (A ² ) _{n * 2} (wherein A ² represents the formula (13) Or a group represented by formula (15).
B ² has the same meaning as B ¹ . n * 2 is an integer of 1 or more. When a plurality of A ² are present, each A ² may be the same as or different from each other. ).

Examples of the substituent that may be contained in the alkylene group having 1 to 50 carbon atoms, the alkyleneoxy group having 1 to 50 carbon atoms, the imino group, the silylene group, and the ethenylene group that may be included in R ³ are as described above. Examples thereof include the same substituents as those exemplified in the description of Q ¹ . When a plurality of substituents are present, they may be the same as or different from each other.

[2.1.2. Description of R ^4]
R ⁴ is a monovalent group including a group represented by Formula (16). When a plurality of R ⁴ are present, each R ⁴ may be the same as or different from each other.

R ⁴ may be a monovalent group composed of a group represented by Formula (16). That is, the group represented by the formula (16) may be directly bonded to Ar ² .

On the other hand, R ⁴ may be a group partially including a group represented by the formula (16). That is, the group represented by the formula (16) may be bonded to Ar ² through a group (same as the substituent) exemplified in the description of R ³ described above or an atom.

For example, R ⁴ is a group represented by the formula (16) or a formula: —B ³ — (A ³ ) _{n * 3} (wherein A ³ is a group represented by the formula (16); ³ is the same as B ¹ , n * 3 is an integer of 1 or more, and when a plurality of A ³ are present, each A ³ may be the same as or different from each other. It is a group.

[2.3. Description of group represented by formula (15)]
In Formula (15), R ⁵ is a single bond or a (1 + m3) -valent organic group. Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1, and b1 have the same meaning as described above. m3 is an integer of 1 or more. However, when R ⁵ is a single bond, m3 is 1. When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other. When a plurality of Y ¹ are present, each Y ¹ may be the same as or different from each other. When a plurality of M ¹ are present, each M ¹ may be the same as or different from each other. When a plurality of Z ¹ are present, each Z ¹ may be the same as or different from each other. When a plurality of n1 are present, each n1 may be the same as or different from each other. When a plurality of a1 are present, each a1 may be the same as or different from each other. When a plurality of b1 are present, each b1 may be the same as or different from each other.

In formula (15), examples of the (1 + m3) -valent organic group represented by R ⁵ include the following groups:
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, lauryl M3 hydrogen atoms from an alkyl group having 1 to 20 carbon atoms which may have a substituent, such as a group or a group in which at least one hydrogen atom in these groups is substituted with a substituent A group excluding
A phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a group in which at least one hydrogen atom of these groups is substituted with a substituent, etc. A group obtained by removing m3 hydrogen atoms from an aryl group having 6 to 30 carbon atoms which may have a substituent;
Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy group , A cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a carbon which may have a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent A group in which m3 hydrogen atoms have been removed from an alkoxy group having 1 to 50 atoms; a group in which m3 hydrogen atoms have been removed from an amino group having a substituent containing a carbon atom;
A group obtained by removing m3 hydrogen atoms from a silyl group having a substituent containing a carbon atom.

From the viewpoint of ease of synthesis of the raw material monomer, the (1 + m3) -valent organic group represented by R ⁵ is an m3 hydrogen atom from an optionally substituted alkyl group having 1 to 20 carbon atoms. A group excluding atoms, a group obtained by removing m3 hydrogen atoms from an aryl group having 6 to 30 carbon atoms which may have a substituent, or a carbon atom having 1 substituent which may have a substituent A group obtained by removing m3 hydrogen atoms from ˜50 alkoxy groups is preferred.

A substituent that the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the alkoxy group having 1 to 50 carbon atoms which may be contained in R ⁵ , and amino Examples of the substituent containing a carbon atom that the group and the silyl group may have include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same as or different from each other.

In formula (15), m3 is an integer of 1 or more. However, when R ⁵ is a single bond, m3 is 1.

[2.4. Description of group represented by formula (16)]
In Formula (16), R ⁶ is a single bond or a (1 + m4) valent organic group. Y ² and n2 have the same meaning as described above. m4 is an integer of 1 or more. However, when R ⁶ is a single bond, m4 is 1. When a plurality of Q ² are present, each Q ² may be the same as or different from each other. When a plurality of Y ² are present, each Y ² may be the same as or different from each other. When a plurality of n2 are present, each n2 may be the same as or different from each other.

In the formula (16), examples of the (1 + m4) -valent organic group represented by R ⁶ include the following groups:
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, lauryl M4 hydrogen atoms from an alkyl group having 1 to 20 carbon atoms which may have a substituent, such as a group or a group in which at least one hydrogen atom in these groups is substituted with a substituent A group excluding
A phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a group in which at least one hydrogen atom of these groups is substituted with a substituent, etc. A group in which an m4 hydrogen atom is removed from an aryl group having 6 to 30 carbon atoms which may have a substituent;
Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy group , A cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a carbon which may have a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent A group obtained by removing m4 hydrogen atoms from an alkoxy group having 1 to 50 atoms;
A group in which m4 hydrogen atoms have been removed from an amino group having a substituent containing a carbon atom;
A group obtained by removing m4 hydrogen atoms from a silyl group having a substituent containing a carbon atom.

From the viewpoint of ease of synthesis of the raw material monomer, the (1 + m4) valent organic group represented by R ⁶ is m4 from an alkyl group having 1 to 20 carbon atoms which may have a substituent. A group excluding a hydrogen atom, a group having 6 to 30 carbon atoms which may have a substituent, a group having m4 hydrogen atoms removed from an aryl group having 1 to 30 carbon atoms, and a group having 1 to 1 carbon atoms which may have a substituent Groups in which m4 hydrogen atoms have been removed from 50 alkoxy groups are preferred.

A substituent that the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the alkoxy group having 1 to 50 carbon atoms that may be contained in R ⁶ ; Examples of the substituent containing a carbon atom that the group and the silyl group may have include the same substituents as those exemplified in the description of Q ¹ described above. When there are a plurality of substituents that the (1 + m4) -valent organic group represented by R ⁶ may have, they may be the same as or different from each other.

In formula (16), m4 is an integer of 1 or more. However, when R ⁶ is a single bond, m4 is 1.

[2.5. Description of Ar ² ]
In Formula (14), Ar ² is a (2 + n4 + n5) -valent aromatic group that may have a substituent other than R ³ and R ⁴ .

Ar ² may have a substituent other than R ³ and R ⁴ . Examples of the substituent include the same substituent exemplified in the description of substituents exemplified in the description with respect to Q ^1. When a plurality of the substituents are present, they may be the same as or different from each other.

As the substituent other than R ³ and R ⁴ possessed by Ar ² , an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, a substituted carboxyl group, or a halogen atom from the viewpoint of ease of synthesis of the raw material monomer It is preferable that

In the formula (14), n4 is an integer of 1 or more, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

In the formula (14), n5 is an integer of 1 or more, preferably an integer of 1 to 4, more preferably an integer of 1 to 3.

Examples of the (2 + n4 + n5) -valent aromatic group represented by Ar ² in the formula (14) include a (2 + n4 + n5) -valent aromatic hydrocarbon group and a (2 + n4 + n5) -valent aromatic heterocyclic group, (2 + n4 + n5) -valent aromatic group consisting of only carbon atoms, or (2 + n4 + n5) -valent aromatic group consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms It is preferable that Examples of the (2 + n4 + n5) -valent aromatic group include monocyclic aromatic rings (eg, benzene ring, pyridine ring, 1,2-diazine ring, 1,3-diazine ring, 1,4-diazine ring, furan (2 + n4 + n5) -valent group obtained by removing (2 + n4 + n5) hydrogen atoms directly bonded to carbon atoms constituting the ring from a ring, pyrrole ring, pyrazole ring, imidazole ring, etc .; two or more monocyclic aromatic rings A (2 + n4 + n5) -valent group in which (2 + n4 + n5) hydrogen atoms directly bonded to carbon atoms constituting the ring are removed from a condensed polycyclic aromatic ring having a structure in which the monocyclic aromatic ring and the monocyclic aromatic ring A hydrogen atom in which two or more aromatic rings selected from the group consisting of condensed polycyclic aromatic rings are directly bonded to carbon atoms constituting the ring from an aromatic ring assembly in which a single bond, ethenylene group or ethynylene group is connected. A (2 + n4 + n5) -valent group in which (2 + n4 + n5) are removed; including two or more aromatic rings selected from the monocyclic aromatic ring, the condensed polycyclic aromatic ring, and the aromatic ring assembly, Carbon atoms constituting a ring from a bridged polycyclic aromatic ring having a bridge in which two adjacent aromatic rings are bridged by a divalent group such as a methylene group, an ethylene group, a carbonyl group or the like, or a methanetetrayl group And (2 + n4 + n5) -valent groups obtained by removing (2 + n4 + n5) hydrogen atoms directly bonded to.

In the condensed polycyclic aromatic ring, the number of monocyclic aromatic rings to be condensed is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2 from the viewpoint of the solubility of the polymer compound. In the aromatic ring assembly, the number of linked aromatic rings is preferably 2 to 4, more preferably 2 or 3, and still more preferably 2 from the viewpoint of solubility. In the bridged polycyclic aromatic ring, the number of bridged aromatic rings is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2 from the viewpoint of solubility of the polymer compound.

Examples of the monocyclic aromatic ring include rings represented by Formulas 1 to 5 and Formulas 7 to 10 exemplified in the description of the structural unit represented by Formula (12).

Examples of the condensed polycyclic aromatic ring include rings represented by formulas 13 to 33 exemplified in the description of the structural unit represented by formula (12).

Examples of the aromatic ring assembly include rings represented by formulas 34 to 42 exemplified in the description of the structural unit represented by formula (12).

Examples of the bridged polycyclic aromatic ring include rings represented by Formulas 43 to 51 exemplified in the description of the structural unit represented by Formula (12).

The (2 + n4 + n5) -valent aromatic group represented by Ar ² is represented by formulas 1 to 5, 7 to 10, formulas 13 to 15, 19 to 19 from the viewpoint of the conductivity of the polymer compound and the ease of synthesis of the raw material monomer. A group in which (2 + n4 + n5) hydrogen atoms directly bonded to the carbon atoms constituting the ring are removed from the ring represented by 25, 31 to 35, 43, 46 to 48 or 51 is preferable. From the ring represented by 5, 6, 13, 14, 15, 19, 21, 23, 31, 32, 33, 43, 46, 47 or 51, a hydrogen atom directly bonded to the carbon atom constituting the ring ( (2 + n4 + n5) groups are more preferable, and a hydrogen atom directly bonded to a carbon atom constituting the ring from the ring represented by the formula 1, 13, 14, 15, 21, 23, 33, 43, 46, or 47 A group in which (2 + n4 + n5) is removed is more preferable.

In the formula (14), Ar ² represents a hydrogen atom (n4 + n5) from the divalent groups represented by the formulas 52, 53, and 55 to 63 exemplified in the description of the structural unit represented by the formula (12). It is preferable that the group is removed.

[2.3. For M ^1]
As will be described later, the proportion of M ¹ in the polymer compound of the present invention being H ⁺ is greater than 0% and 50% or less with respect to all M ¹ in the polymer compound. 1% or more and 50% or less. Therefore, when the polymer compound of the present invention has one or more structural units selected from the group consisting of the structural unit represented by formula (12) and the structural unit represented by formula (14), A group in which M ¹ is H ⁺ , a group in which M ¹ is a metal cation, or a group that is an ammonium cation that may have a substituent. And both are included.

[2.4. Example of each structural unit)
[2.4.1. Example of structural unit represented by formula (12)]
Examples of the structural unit represented by the formula (12) include structural units that may have a substituent represented by the following formula. From the viewpoint of ease of synthesis of the polymer compound and electron transport properties. Are preferably structural units represented by the formulas 52a ¹ , 55a ¹ , 55b ¹ , 55c ¹ , 56b ¹ , 57b ¹ , 58a ¹ , 59b ¹ , 60b ¹ , 61a ¹ , 61b ¹ , 61c ¹ , 63b ^1. . In the following formulas, R ² , Q ¹ , n 1, Y ¹ , M ¹ , Z ¹ , a 1, m 1, Q ² , n 2, Y ² and m ² have the same meaning as described above. When there are a plurality of each of R ² , Q ¹ , n 1, Y ¹ , M ¹ , Z ¹ , a 1, m 1, Q ² , n 2, Y ² and m ² , each of the plurality is the same or different. It may be.

In the above formula, from the viewpoint of ease of synthesis, R ² is an (m1 + m2) number of (m1 + m2) atoms directly bonded to a carbon atom constituting the ring from an optionally substituted aryl group having 6 to 30 carbon atoms. A group excluding a hydrogen atom is preferred.
The aryl group having 6 to 30 carbon atoms which may have a substituent is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, or these A group in which at least one hydrogen atom in the group is substituted with a substituent is preferable.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, each of the plurality may be the same as or different from each other.

Examples of the structural unit represented by the formula (12) include structural units that may have a substituent represented by the following formula. In the following formulas, M has the same meaning as described above.

[2.4.2. Example of structural unit represented by formula (14)]
Examples of the structural unit represented by the formula (14) include structural units that may have a substituent represented by the following formula. From the viewpoint of ease of synthesis of the polymer compound and electron transport properties. Are preferably structural units represented by the formulas 52a ² , 55a ² , 55b ² , 55c ² , 56b ² , 57b ² , 58a ² , 59a ² , 60b ² , 61a ² , 61c ² or 63a ² . In the following formulas, R ² , Q ¹ , n 1, Y ¹ , M ¹ , Z ¹ , a 1, m 1, Q ² , n 2, Y ² , m ² , R ⁵ , m 3, R ⁶ and m 4 are the same as described above. Meaning. When there are a plurality of each of R ² , Q ¹ , n 1, Y ¹ , M ¹ , Z ¹ , a 1, m 1, Q ² , n 2, Y ² , m ² , R ⁵ , m 3, R ⁶ and m 4 Each of the plurality may be the same as or different from each other.

In the above formula, from the viewpoint of ease of synthesis, R ² is an (m1 + m2) number of (m1 + m2) atoms directly bonded to a carbon atom constituting the ring from an optionally substituted aryl group having 6 to 30 carbon atoms. A group excluding a hydrogen atom is preferred.
In the above formula, from the viewpoint of ease of synthesis, R ⁵ is an m 3 hydrogen atom directly bonded to the carbon atom constituting the ring from the aryl group having 6 to 30 carbon atoms which may have a substituent. It is preferable that it is group remove | excluding.
In the above formula, from the viewpoint of ease of synthesis, R ⁶ is an m4 hydrogen atom directly bonded to a carbon atom constituting the ring from an optionally substituted aryl group having 6 to 30 carbon atoms. It is preferable that it is group remove | excluding. The aryl group having 6 to 30 carbon atoms which may have a substituent is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, or these A group in which at least one hydrogen atom in the group is substituted with a substituent is preferable.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same as or different from each other.

Examples of the structural unit represented by the formula (14) include structural units that may have a substituent represented by the following formula. In the following formulas, M has the same meaning as described above.

[3. Other structural units)
The polymer compound used in the present invention may further have a structural unit represented by the formula (17).

(In formula (17), Ar ³ is a divalent aromatic group which may have a substituent or a divalent aromatic amine residue which may have a substituent, and X ′ is a substituted group. An imino group which may have a group, a silylene group which may have a substituent, an ethenylene group or an ethynylene group which may have a substituent, and m5 and m6 are each independently 0 or 1 Provided that at least one of m5 and m6 is 1.)

Ar ⁸ in the formula (24) is a divalent aromatic group which may have a substituent or a divalent aromatic amine residue which may have a substituent.

Examples of the divalent aromatic group represented by Ar ³ in the formula (17) include a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group. Examples of the divalent aromatic group include a monocyclic aromatic ring (for example, a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, 1,3 , 5-triazine ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, oxadiazole ring, azadiazole ring, etc.) and two hydrogen atoms directly bonded to the carbon atoms constituting the ring 2 divalent groups removed; 2 hydrogen atoms directly bonded to carbon atoms constituting the ring are removed from a condensed polycyclic aromatic ring having a structure in which two or more monocyclic aromatic rings are condensed. A valent group; two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring, from an aromatic ring assembly connected by a single bond, an ethenylene group or an ethynylene group, Directly attached to the carbon atoms constituting the ring A divalent group in which two hydrogen atoms are removed; two aromatic rings selected from the monocyclic aromatic ring, the condensed polycyclic aromatic ring, and the aromatic ring assembly, and two adjacent aromatic rings A ring is composed of a bridged polycyclic aromatic ring having a structure in which two aromatic rings are bridged by a divalent group such as a methylene group, an ethylene group, a carbonyl group, an imino group, or a methanetetrayl group A divalent group in which two hydrogen atoms directly bonded to the carbon atom to be removed are removed.

Examples of the Aribashi polycyclic aromatic ring include the following rings.

From one or both of the electron accepting property and hole accepting property of the polymer compound, the divalent aromatic group represented by Ar ³ is represented by the formulas 52 to 67, 68 to 83, 89 to 93, A divalent group obtained by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the ring represented by 104 to 106, 108 or 109 is preferably represented by the formulas 52 to 57, 66, 67, It is more preferably a divalent group obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting the ring from the ring represented by 89, 91, 93, 104, 105, 108 or 109.

The above divalent aromatic group may have a substituent. Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above.

Examples of the divalent aromatic amine residue represented by Ar ³ in formula (17) include a group represented by formula (18).

(In the formula (18), Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently an arylene group which may have a substituent or a divalent heterocyclic ring which may have a substituent. Ar ⁸ , Ar ⁹ and Ar ¹⁰ are each independently an aryl group which may have a substituent or a monovalent heterocyclic group which may have a substituent, and m7 and m8 is each independently 0 or 1.)

Examples of the substituent that the arylene group, aryl group, divalent heterocyclic group and monovalent heterocyclic group may have include, for example, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, Aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue , Substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkyloxycarbonyl group, aryl Oxycarbonyl group, arylalkyloxycarbo Group, include heteroaryl aryloxycarbonyl group and a carboxyl group. Examples of the substituent include a vinyl group, acetylene group, butenyl group, acrylic group, acrylate group, acrylamide group, methacryl group, methacrylate group, methacrylamide group, vinyl ether group, vinylamino group, silanol group, and small ring (cyclohexane). A propyl group, a cyclobutyl group, an epoxy group, an oxetane group, a diketene group, an episulfide group, etc.), a lactone group, a lactam group, or a cross-linking group such as a group containing a structure of a siloxane derivative.

When m7 is 0, the carbon atom in Ar ⁴ and the carbon atom in Ar ⁶ may be directly bonded. The carbon atom in Ar ⁴ and the carbon atom in Ar ⁶ may be bonded via a divalent group such as —O— or —S—.

Ar ⁸ , Ar ⁹ and Ar ¹⁰ are each independently an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. Examples of the aryl group include the same groups as the aryl groups exemplified in the description of Q ¹ described above. As the monovalent heterocyclic group, examples of the monovalent aromatic group include the same groups as the monovalent heterocyclic group exemplified in the above description of Q ¹ . Examples of the substituent include the same groups as the monovalent heterocyclic group exemplified in the description of Q ¹ described above.

Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Examples of the arylene group include the remaining atomic groups obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting an aromatic ring from an aromatic hydrocarbon. The arylene group is selected from a group having a benzene ring, a group having a condensed ring, a group in which two or more selected from an independent benzene ring and a condensed ring are single-bonded, and an independent benzene ring and condensed ring. Examples include a group in which two or more are bonded via a divalent organic group (for example, an alkenylene group such as a vinylene group). The arylene group usually has 6 to 60 carbon atoms, and preferably 7 to 48 carbon atoms. Examples of arylene groups include phenylene groups, biphenylene groups, C ₁ -C ₁₇ alkoxyphenylene groups, C ₁ -C ₁₇ alkylphenylene groups, 1-naphthylene groups, 2-naphthylene groups, 1-anthracenylene groups, 2-anthracenylene groups. And 9-anthracenylene group. A hydrogen atom in the arylene group may be substituted with a fluorine atom. Examples of the corresponding arylene group (fluorine atom-substituted aryl group) include a tetrafluorophenylene group. Among the arylene groups, a phenylene group, a biphenylene group, a C ₁ to C ₁₂ alkoxyphenylene group, and a C ₁ to C ₁₂ alkylphenylene group are preferable.

The divalent heterocyclic group represented by Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ includes the remaining atomic group obtained by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the heterocyclic compound. Is mentioned. Here, the heterocyclic compound is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a silicon atom as an element constituting a ring among organic compounds having a cyclic structure. , An organic compound containing a heteroatom such as a selenium atom, a tellurium atom or an arsenic atom. The divalent heterocyclic group may have a substituent. The divalent heterocyclic group usually has 4 to 60 carbon atoms, and preferably 4 to 20 carbon atoms. The number of carbon atoms of the divalent heterocyclic group does not include the number of carbon atoms of the substituent. Examples of the divalent heterocyclic group include a thiophene diyl group, a C ₁ -C ₁₂ alkylthiophene diyl group, a pyrrole diyl group, a furandiyl group, a pyridinediyl group, a C ₁ -C ₁₂ alkylpyridine diyl group, a pyridazine diyl group, pyrimidinediyl group, pyrazinediyl group, a triazine-diyl group, pyrrolidinediyl group, piperidine-diyl group, quinolinediyl group, and include isoquinolinediyl group, among others, a thiophene-diyl group, C ₁ ~ C ₁₂ alkyl thiophenediyl group, and pyridinediyl group More preferred are C ₁ -C ₁₂ alkylpyridinediyl groups.

Examples of the substituent that the arylene group and the divalent heterocyclic group may have include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same as or different from each other.

The divalent aromatic amine residue represented by the formula (18) is a group obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting the ring from the aromatic amine represented by the following formulas 115 to 124. Is exemplified. From the viewpoint of the stability to the hole current of the polymer compound, the divalent aromatic amine residue represented by the formula (18) is a ring formed from the aromatic amine represented by the formula 115, 116, 117, or 120. A group obtained by removing two hydrogen atoms directly bonded to the constituting carbon atom is preferred.

The aromatic amines represented by formulas 115 to 124 may have a substituent as long as a divalent aromatic amine residue can be generated. Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ and the group represented by the formula (2), and the group represented by the formula (2). It is preferable that When a plurality of substituents are present, they may be the same as or different from each other.

In formula (17), X ′ represents an imino group which may have a substituent, a silylene group which may have a substituent, an ethenylene group or an ethynylene group which may have a substituent. Examples of the substituent that the imino group, silyl group or ethenylene group may have include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, An alkyl group having 1 to 20 carbon atoms such as a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a 3,7-dimethyloctyl group, a lauryl group; Examples thereof include aryl groups having 6 to 30 carbon atoms such as phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group and 9-anthracenyl group.

When a plurality of substituents are present in the imino group, the silylene group, and the ethenylene group, they may be the same or different from each other.

From the viewpoint of stability of the polymer compound against air, moisture or heat, X ′ is preferably an imino group, an ethenylene group or an ethynylene group.

M5 and m6 are each independently 0 or 1, and at least one of m5 and m6 is 1. From the viewpoint of electron transport properties of the polymer compound, it is preferable that m5 is 1 and m6 is 0.

[4. Content ratio of structural units)
The polymer compound of the present invention preferably contains a structural unit represented by the formula (12) and a structural unit represented by the formula (14). The ratio of the total of these structural units to the total structural units (excluding the terminal structural units) contained in the polymer compound is 30 to 100 mol% from the viewpoint of the luminous efficiency of the electroluminescent device. More preferred.

[5. (Terminal structural unit)
Examples of the terminal structural unit (terminal group) of the polymer compound of the present invention include a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- Butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group , Lauryloxy group, methylthio group, ethylthio Group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, laurylthio group Methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, sec-butoxyphenyl group, tert-butoxyphenyl group, pentyloxyphenyl group, hexyloxyphenyl group, Cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group 3,7-dimethyloctyloxyphenyl group, lauryloxyphenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group Tert-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group, methylamino group, dimethylamino group, ethylamino group , Diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, sec-butylamino group, tert-butylamino group Pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, Dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ ~ C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyrazinylamino group, tri Jiniruamino group, (phenyl -C ₁ ~ C ₁₂ alkyl) amino group, (C ₁ ~ C ₁₂ alkoxyphenyl -C ₁ ~ C ₁₂ alkyl) amino group, (C ₁ ~ C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkyl ) Amino group, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, isopropyldimethylsilyl group, isopropyldiethylsilyl group, tert-butyl Dimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethyl Silyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, a 3,7-dimethyl silyl group, lauryl dimethyl silyl group, (phenyl -C ₁ ~ C ₁₂ alkyl) silyl group, (C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl) silyl group, (C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl) silyl group, (1-naphthyl-C ₁ to C ₁₂ alkyl) silyl group (2-naphthyl-C ₁ -C ₁₂ alkyl) silyl group, (phenyl-C ₁ -C ₁₂ alkyl) dimethylsilyl group, triphenylsilyl group, tri (p-xylyl) silyl group, tribenzylsilyl group, diphenyl Methylsilyl group, tert-butyldiphenylsilyl group, dimethylphenylsilyl group, thienyl group, C ₁ -C ₁₂ alkylthieni Group, pyrrolyl group, furyl group, pyridyl group, C ₁ -C ₁₂ alkylpyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group, isoquinolyl group, hydroxyl group, mercapto group , Fluorine atom, chlorine atom, bromine atom and iodine atom.

When there are a plurality of the terminal structural units, they may be the same as or different from each other.

[6. Characteristics of polymer compounds)
Hereinafter, the characteristics of the polymer compound of the present invention will be described.

[6.1. (Molecular weight)
The polymer compound refers to a compound having a polystyrene-equivalent weight average molecular weight of 1 × 10 ³ or more.

From the viewpoint of film formability by application of the polymer compound of the present invention, the lower limit of the weight average molecular weight in terms of polystyrene of the polymer compound is preferably 1 × 10 ³ or more, and preferably 2 × 10 ³ or more. Is more preferably 3 × 10 ³ or more, and particularly preferably 5 × 10 ³ or more. From the same viewpoint, the upper limit of the weight average molecular weight in terms of polystyrene of the polymer compound is preferably 1 × 10 ⁸ or less, and more preferably 1 × 10 ⁷ or less. The range of the weight average molecular weight in terms of polystyrene of the polymer compound is preferably 1 × 10 ³ to 1 × 10 ⁸ , more preferably 2 × 10 ³ to 1 × 10 ⁷ , and more preferably 3 × 10 ^3. ~ still more preferably from 1 × 10 ^7, particularly preferably ^{5 × 10 3 ~ 1 × 10} 7.

From the viewpoint of the purity of the polymer compound of the present invention, the polymer compound preferably has a polystyrene-equivalent number average molecular weight of 1 × 10 ³ or more. From the same viewpoint, the upper limit of the polystyrene-equivalent number average molecular weight of the polymer compound is preferably 5 × 10 ⁷ or less, more preferably 1 × 10 ⁷ or less, and 5 × 10 ⁶ or less. More preferably. The range of the number average molecular weight in terms of polystyrene of the polymer compound is preferably 1 × 10 ³ to 5 × 10 ⁷ , more preferably 1 × 10 ³ to 1 × 10 ⁷ , and more preferably 1 × 10 ^3. More preferably, it is ˜5 × 10 ⁶ .

From the viewpoint of solubility of the polymer compound of the present invention, the lower limit of the weight average molecular weight in terms of polystyrene of the polymer compound is preferably 1 × 10 ³ or more. From the same viewpoint, the upper limit of the polystyrene equivalent weight average molecular weight of the polymer compound is preferably 5 × 10 ⁵ or less, more preferably 5 × 10 ⁴ or less, and 3 × 10 ³ or less. More preferably. Range of weight average molecular weight in terms of polystyrene of the polymer compound is preferably ^{1 × 10 3 ~ 5 × 10} 5, more preferably ^{1 × 10 3 ~ 5 × 10} 4, 1 × 10 3 More preferably, it is ˜3 × 10 ³ .

The polystyrene-equivalent number average molecular weight and weight average molecular weight of the polymer compound of the present invention can be determined, for example, using gel permeation chromatography (GPC).

[6.2. Characteristics as a conjugated polymer compound)
The polymer compound used in the present invention is preferably a conjugated polymer compound. When the polymer compound of the present invention is a conjugated polymer compound, the polymer compound has one unshared electron pair possessed by multiple bonds and / or atoms such as nitrogen atoms and oxygen atoms in the main chain. It means that it includes a region that is continuous across a single bond. In the case where the polymer compound is a conjugated polymer compound, from the viewpoint of electron transport properties of the conjugated polymer compound, {(multiple bonds in the polymer compound and / or atoms such as nitrogen atom and oxygen atom have Calculated by the number of atoms on the main chain included in the region where the unshared electron pairs are connected across one single bond) / (number of all atoms on the main chain in the polymer compound)} × 100 The ratio (%) is preferably 50% or more, more preferably 60% or more, further preferably 70% or more, particularly preferably 80% or more, and 90% or more. Particularly preferred.

[6.3. Orbital energy)
From the viewpoint of electron acceptability and hole acceptability of the polymer compound of the present invention, the lower limit of the minimum unoccupied molecular orbital (LUMO) orbital energy of the polymer compound is preferably −5.0 eV or more, and −4 More preferable is 5 eV or more. From the same viewpoint, the upper limit of the LUMO orbital energy of the polymer compound is preferably −2.0 eV or less. The range of the LUMO orbital energy of the polymer compound is preferably from −5.0 eV to −2.0 eV, more preferably from −4.5 eV to −2.0 eV.

From the same viewpoint, the lower limit of the orbital energy of the highest occupied molecular orbital (HOMO) of the polymer compound of the present invention is preferably −6.0 eV or more, more preferably −5.5 eV or more. From the same viewpoint, the upper limit of the HOMO orbital energy of the polymer compound is preferably −3.0 eV or less. The range of the orbital energy of HOMO of the polymer compound is preferably from -6.0 eV to -3.0 eV, more preferably from -5.5 eV to -3.0 eV.
The orbital energy of HOMO is usually lower than that of LUMO.

The orbital energy of the HOMO of the polymer compound can be obtained by measuring the ionization potential of the polymer compound and using the obtained ionization potential as the orbital energy. The orbital energy of LUMO of a polymer compound can be obtained by calculating the energy difference between HOMO and LUMO and using the sum of the value and the ionization potential measured above as the orbital energy. A photoelectron spectrometer can be used to measure the ionization potential. The energy difference between HOMO and LUMO is determined from the absorption terminal by measuring the absorption spectrum of the polymer compound using an ultraviolet spectrophotometer, visible spectrophotometer, or near infrared spectrophotometer.

[7. Specific examples of polymer compounds]
Examples of the polymer compound of the present invention include polymer compounds represented by the following formulas. In the present specification, in a polymer compound having a structural unit represented by a formula in which a plurality of structures are separated by a slash “/”, these structural units are randomly arranged. When the two structures are separated by a slash “/”, the proportion of the right structural unit is (100-p) mol%. p is preferably from 30 to 99, more preferably from 50 to 99. In the polymer compound represented by the formula in which three types of structures are separated by a slash “/”, the proportion of the structural unit on the left is p mol%, the proportion of the central structural unit is q mol%, and the structural unit on the right The ratio of is (100-pq) mol%. p is preferably from 1 to 50, and more preferably from 1 to 30. q is preferably 1 to 50, and more preferably 1 to 30. In addition, structural units other than the structural unit represented by the following formula may be further included, and in this case, it can be expressed in the same manner as below. These structural units are arranged at random. In the following formulae, M has the same meaning as described above, n is the degree of polymerization, and any hydrogen atom in the formula may be replaced with a substituent within a synthesizable range. Examples of the substituent include the same groups as the substituents exemplified in the description regarding Q ¹ described above.

[7. Method for producing polymer compound)
The method for producing the polymer compound of the present invention will be described below. As a preferred embodiment of the method for producing the polymer compound of the present invention, a compound containing ions is used as a raw material, and this is subjected to condensation polymerization, and a compound containing no ions in the first step is used as a raw material. A method of synthesizing a polymer compound by synthesizing a polymer compound and synthesizing a polymer compound containing ions from the polymer compound in the second step can be mentioned.

For example, a method of selecting and using a compound represented by the following formula (21) as the raw material can be mentioned.

Y ³ -A ^a -Y ⁴ (21)
(In Formula (21), A ^a is ^a divalent group including a group represented by Formula (1) and a group represented by Formula (2), and Y ³ and Y ⁴ are each independently And represents a group involved in condensation polymerization.)

Further, for example, a method of selecting and using a compound represented by the following formula (21 ′) as the raw material can be mentioned.

Y ³ -A ^aa -Y ⁴ (21 ')
(In the formula (21 ′),
A ^aa is a divalent group including a group represented by the formula (22) and a group represented by the formula (2).
Y ³ and Y ⁴ are each independently a group involved in condensation polymerization. )
-R ⁷ -{(Q ³ ) _n6 -Y ⁵ } _m9 (22)
(In the formula (22),
R ⁷ is a (1 + m9) valent organic group.
Q ³ represents a divalent organic group.
Y ⁵ is —CO ₂ R ^χ , —SO ₃ R ^χ , —SO ₂ R ^χ , —PO ₃ (R ^χ ) _2, or —B (R ^χ ) ₂ .
n6 is an integer of 0 or more.
R ^χ is a hydrogen atom, an ^optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted aryl group having 6 to 50 carbon atoms.
m9 represents an integer of 1 or more.
When a plurality of Q ³ are present, each Q ³ may be the same as or different from each other.
When a plurality of Y ⁵ are present, each Y ⁵ may be the same as or different from each other.
When a plurality of n6 are present, each n6 may be the same as or different from each other.
When there are a plurality of ^Rχ , each ^Rχ compound may be the same as or different from each other. )

In the polymer compound of the present invention, -A ^a in the above formula (21) - together with a structural unit represented by the -A ^a - In case of containing other structural units other than the above -A ^a A compound having two groups involved in condensation polymerization, which is a structural unit other than-, may be used together with the compound represented by the above formula (21) for condensation polymerization. In addition, you may use the compound represented by the said Formula (21 ') instead of the compound represented by Formula (21).

Examples of the compound having two groups involved in condensation polymerization include compounds represented by formula (19) and formula (20).

Y ⁶ -A ^b -Y ⁷ (19)
(In the formula (19), ^Ab is a divalent aromatic group optionally having a substituent represented by Ar ³ or a divalent aromatic amine residue optionally having a substituent. Y ⁶ and Y ⁷ each independently represent a group involved in condensation polymerization.)

Y ⁸ -A ^c -Y ⁹ (20)
(In the formula (20), ^Ac is a structural unit represented by a divalent aromatic group having a group represented by the formula (2) or a divalent aromatic amine residue, and the divalent aromatic Examples of the group and the divalent aromatic amine residue include the same groups as those described above for Ar ³ , and Y ⁸ and Y ⁹ each independently represent a group involved in condensation polymerization. )

Thus, in addition to the compound represented by the formula (21) (Y ³ -A ^a -Y ⁴ ), the compound represented by the formula (19) and / or the compound represented by the formula (20) Can be polymerized to produce a polymer compound further having a structural unit represented by -A ^b- and / or a structural unit represented by -A ^c- . In addition, you may use the compound represented by the said Formula (21 ') instead of the compound represented by Formula (21).

Examples of the groups (Y ³ , Y ⁴ , Y ⁶ , Y ⁷ , Y ⁸ and Y ⁹ ) involved in the condensation polymerization in the formulas (21), (21 ′), (19) and (20) include, for example, hydrogen Atoms, halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, boric acid ester residues, sulfonium methyl groups, phosphonium methyl groups, phosphonate methyl groups, monohalogenated methyl groups, -B (OH) ₂ , formyl Groups, cyano groups and vinyl groups.

Examples of the halogen atom that can be selected as a group involved in the condensation polymerization include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl sulfonate group that can be selected as a group involved in the condensation polymerization include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.

Examples of the aryl sulfonate group that can be selected as a group involved in the condensation polymerization include a benzene sulfonate group and a p-toluene sulfonate group.

Examples of the arylalkyl sulfonate group that can be selected as a group involved in the condensation polymerization include a benzyl sulfonate group.

Examples of the boric acid ester residue that can be selected as a group involved in the condensation polymerization include groups represented by the following formulae.

Examples of the sulfonium methyl group that can be selected as a group involved in the condensation polymerization include the following formula:
_{^{_{^{-CH 2 S + Me 2 E -}}}} , _{^{_{or, -CH 2 S + Ph 2 E}}} -
(In the formula, E represents a halogen atom. Ph represents a phenyl group, and the same shall apply hereinafter.)
The group represented by these is illustrated.

Examples of the phosphonium methyl group that can be selected as a group involved in the condensation polymerization include the following formula:
-CH ₂ P ⁺ Ph ₃ E ^-
(In the formula, E has the same meaning as described above.)
The group represented by these is illustrated.

Examples of the phosphonate methyl group that can be selected as the group involved in the condensation polymerization include the following formula:
-CH ₂ PO (OR ^j ) ₂
(In the formula, R ^j represents an alkyl group, an aryl group, or an arylalkyl group.)
The group represented by these is illustrated.

Examples of the monohalogenated methyl group that can be selected as the group involved in the condensation polymerization include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

A group suitable as a group involved in the condensation polymerization varies depending on the type of polymerization reaction. In the case of a reaction using a zerovalent nickel complex such as a Yamamoto coupling reaction, for example, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and an aryl alkyl sulfonate group can be mentioned. In the case of a reaction using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, for example, an alkyl sulfonate group, a halogen atom, a boric acid ester residue, and —B (OH) ₂ can be mentioned. In the case of oxidative polymerization using an oxidizing agent or electrochemically, for example, a hydrogen atom is used.

When the polymer compound of the present invention is produced, for example, the compound (monomer) represented by the formula (21) having a plurality of groups involved in condensation polymerization is converted into the formula (19) or ( 20) In addition to the compound (monomer) represented by 20), if necessary, a polymerization method in which the compound is dissolved in an organic solvent and reacted at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point using an alkali or an appropriate catalyst is employed. May be. As the polymerization method, for example, “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis” (Organic Syntheses) ", Collective Volume 6 (Collective Volume VI), pages 407-411, John Wiley & Sons, Inc., 1988, Method, Chemical Review (Chem. Rev.), Vol. 95, 2457 (1995), Journal of Organometallic Chem., 576. The method according to p. 147 (1999), Macromolecular Chemistry Macromolecular Symposium (Macromol.Chem., Macromol.Symp.), Vol. 12, include a method described in page 229 (1987). In addition, instead of the compound represented by the formula (21), the compound represented by the formula (21 ′) may be used.

In producing the polymer compound of the present invention, a known condensation polymerization reaction may be employed depending on the group involved in the condensation polymerization. Examples of the condensation polymerization reaction include a method of polymerizing a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing a corresponding monomer by a Grignard reaction, a method of polymerizing by a Ni (0) complex, and an oxidizing agent such as FeCl _3. A method of polymerizing the monomer to be polymerized, a method of electrochemically oxidizing the corresponding monomer, and a method of decomposing an intermediate polymer having an appropriate leaving group. Among condensation polymerization reactions, a method of polymerizing by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, and a method of polymerizing a corresponding monomer by a nickel zero-valent complex are preferable because the structure of the resulting polymer compound can be easily controlled. .

Another preferred embodiment of the method for producing the polymer compound of the present invention is a group selected from the group consisting of a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and an aryl alkyl sulfonate group as a group involved in condensation polymerization. And a method of producing a polymer compound by condensation polymerization in the presence of a nickel zero-valent complex using a raw material monomer containing
Examples of the raw material monomer used in such a method include dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds, halogen-alkyl sulfonate compounds, and halogen-aryl sulfonates. Compounds, halogen-aryl alkyl sulfonate compounds, alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds and aryl sulfonate-aryl alkyl sulfonate compounds.

In another preferred embodiment of the method for producing the polymer compound of the present invention, as a group involved in condensation polymerization, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, —B (OH) ₂ , And the total number (J) of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, and arylalkyl sulfonate groups, which have a group selected from the group consisting of boric acid ester residues, and all the raw material monomers have, A raw material monomer in which the ratio of the total number of moles (K) of —B (OH) ₂ and boric acid ester residues (K) is substantially 1 (usually, K / J is in the range of 0.7 to 1.2), Examples include a method of condensation polymerization in the presence of a nickel catalyst or a palladium catalyst.

An organic solvent can be used when producing the polymer compound. Generally, it is preferable to use an organic solvent that has been sufficiently deoxygenated to suppress side reactions, although it varies depending on the compound or reaction used. When producing a polymer compound using an organic solvent, the reaction is preferably allowed to proceed under an inert atmosphere. In the organic solvent, it is preferable to perform a dehydration treatment in the same manner as the deoxygenation treatment. However, this is not the case in the case of reaction in a two-phase system with water such as Suzuki coupling reaction.

Examples of the organic solvent include the following organic solvents:
Saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane;
Unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, xylene;
Alcohols such as methanol, ethanol, propanol, isopropanol, butanol and tert-butyl alcohol; carboxylic acids such as formic acid, acetic acid and propionic acid;
Ethers such as dimethyl ether, diethyl ether, methyl-tert-butyl ether, tetrahydrofuran (hereinafter referred to as “THF”), tetrahydropyran, dioxane;
Amines such as trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, pyridine;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and N-methylmorpholine oxide.

These organic solvents may be used alone or in combination of two or more. Among organic solvents, ethers are preferable from the viewpoint of reactivity, and THF and diethyl ether are more preferable. From the viewpoint of reaction rate, toluene and xylene are preferred.

In producing the polymer compound, it is preferable to add an alkali or a catalyst to the reaction solution in order to react the raw material monomers. What is necessary is just to select an alkali and a catalyst according to the superposition | polymerization method etc. to employ | adopt. It is preferable that the alkali and the catalyst are sufficiently dissolved in the solvent used for the reaction. As a method of mixing the alkali and catalyst into the reaction solution, a method of slowly adding an alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon gas or nitrogen gas, and an alkali or catalyst A method of slowly adding the reaction solution to the solution is exemplified.

In the polymer compound of the present invention, the terminal group may be protected with a stable group. If the polymerization active group remains as it is at the terminal group, the light emission characteristics and life characteristics of the obtained electroluminescent device may be deteriorated. When the polymer compound of the present invention is a conjugated polymer compound and the terminal group is protected with a stable group as described above, it has a conjugated bond continuous with the conjugated structure of the main chain of the polymer compound. It is preferable. Examples of the conjugated structure include a structure bonded to an aryl group or a heterocyclic group via a carbon-carbon bond. Examples of the stable group for protecting the end group include a monovalent aromatic group.

As a preferred method for producing the polymer compound of the present invention, the polymer compound containing no ions is synthesized in the first step, and the polymer compound containing ions is synthesized from the polymer compound in the second step. The synthesis method will be described below.

A more preferred embodiment of the method includes a method of polymerizing a polymer compound having no cation in the first step and producing a polymer compound containing a cation from the polymer compound in the second step. Examples of the reaction in the first step include a method of polymerizing a polymer compound having no cation by the above-described condensation polymerization reaction. As the reaction in the second step, for example, the polymer compound obtained in the first step, metal hydroxide, metal carbonate, alkylammonium hydroxide, etc. are dissolved in water or an organic solvent as necessary, Examples thereof include a method of reacting at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point, and a method of converting a cation to H ⁺ with hydrochloric acid, sulfuric acid, acetic acid or the like as necessary after the reaction. In addition, the method of selecting and using the compound represented by said Formula (21 ') can be utilized suitably.

[8. Ratio in which M ^{1 of} polymer compound is H ⁺ ]
In the polymer compound of the present invention, from the viewpoint of heat resistance and solubility of the polymer compound, the ratio of M ¹ in the polymer compound to H ⁺ is relative to all M ¹ in the polymer compound. Therefore, it is preferably 0.1% or more and 30% or less, and more preferably 0.1% or more and 20% or less.

The proportion of M ¹ in the polymer compound of the present invention being H ⁺ can be measured by NMR spectrum.

[9. Layer containing polymer compound)
The layer containing the polymer compound of the present invention is preferably substantially non-luminescent when used in an electroluminescent device. Here, the fact that a layer containing a certain polymer compound is substantially non-luminous means as follows. First, in Example 2 below, an electroluminescent element E is produced in the same manner as in Example 2 except that the target polymer compound is used instead of the conjugated polymer compound 1. On the other hand, the electroluminescent element C1 is manufactured as described in Comparative Example 1 below. The electroluminescent element E has a layer containing a polymer compound, but the electroluminescent element C1 is different from the electroluminescent element E and the electroluminescent element C1 only in that it does not have a layer containing a polymer compound. Next, a forward voltage of 10 V is applied to the electroluminescent element E and the electroluminescent element C1, and an emission spectrum is measured. The wavelength λ that gives the maximum peak in the emission spectrum obtained for the electroluminescent element C1 is obtained. The emission spectrum obtained for the electroluminescent element C1 is normalized by setting the emission intensity at the wavelength λ to 1, and the normalized emission amount S ₀ is calculated by integrating the wavelength. On the other hand, assuming that the emission intensity at the wavelength λ is 1, the emission spectrum obtained for the electroluminescent element E is also normalized, and the normalized emission amount S is calculated by integrating the wavelength. When the value calculated by (S−S ₀ ) / S ₀ × 100% is 30% or less, that is, compared with the normalized light emission amount of the electroluminescent element C1 having no layer containing a polymer compound. When the increase in the normalized light emission amount of the electroluminescent element E having a layer containing a molecular compound is 30% or less, the layer containing the polymer compound used is usually substantially non-luminescent, and (S The value calculated by −S ₀ ) / S ₀ × 100 is preferably 15% or less, and more preferably 10% or less.

<Electronic device>
Next, the electronic device of the present invention will be described.

The electronic device of the present invention includes a layer containing a polymer compound having a structural unit containing a group represented by the formula (1) and a group represented by the formula (2) as a charge injection layer and / or a charge transport layer. The proportion of M ¹ in the polymer compound being H ⁺ is 0.1% to 50% with respect to all M ¹ in the polymer compound. The electronic device of the present invention usually includes a first electrode, a second electrode, and a light emitting layer or a charge separation layer in addition to the layer containing the polymer compound. The light emitting layer or the charge separation layer is located between the first electrode and the second electrode.

The electronic device of the present invention can be used for elements such as electroluminescent elements and photoelectric conversion elements. When an electronic device is used for an electroluminescent element (hereinafter sometimes referred to as “electroluminescent element of the present invention”), the electronic device has a light emitting layer. When an electronic device is used for a photoelectric conversion element (hereinafter sometimes referred to as “the photoelectric conversion element of the present invention”), the electronic device has a charge separation layer.

<Electroluminescent device>
The electroluminescent element of the present invention will be described below. The electroluminescent element of the present invention is an electroluminescent element having a layer containing the above-described polymer compound.

The electroluminescent element of the present invention is used in the present invention, for example, located in the cathode, the anode, the light emitting layer located between the cathode and the anode, and between the light emitting layer and the cathode or the anode. It has a layer containing a polymer compound. The electroluminescent element of the present invention can have a substrate as an optional component, and on the surface of the substrate, the cathode, the anode, the light emitting layer, the layer containing the polymer compound used in the present invention, and an optional It can be set as the structure which provided the component.

Examples of the layer structure of the electroluminescent device of the present invention include the following embodiments:
(1) A mode in which an anode is provided on a substrate, a light emitting layer is laminated thereon, a layer containing the polymer compound of the present invention is laminated thereon, and a cathode is laminated thereon.
(2) A mode in which an anode is provided on a substrate, a layer containing the polymer compound of the present invention is laminated thereon, a light emitting layer is laminated, and a cathode is laminated further thereon.
(3) An anode is provided on the substrate, a layer containing the polymer compound of the present invention is laminated thereon, a light emitting layer is laminated thereon, a layer containing the polymer compound of the present invention is laminated thereon, and A mode in which a cathode is laminated on the upper layer;
(4) A mode in which a cathode is provided on a substrate, a layer containing the polymer compound of the present invention is laminated thereon, a light emitting layer is laminated thereon, and an anode is laminated thereon.
(5) A mode in which a cathode is provided on a substrate, a light emitting layer is laminated thereon, a layer containing the polymer compound of the present invention is laminated thereon, and an anode is laminated thereon.
(6) A cathode is provided on a substrate, a layer containing the polymer compound of the present invention is laminated thereon, a light emitting layer is laminated thereon, and a layer containing the polymer compound of the present invention is laminated thereon. Further, an aspect in which an anode is further laminated thereon

In each of the above aspects (1) to (6), a layer having another function such as a protective layer, a buffer layer, a reflective layer, or a hole blocking layer may be further provided. The configuration of the electroluminescent element will be described in detail later. Further, when the sealing film or the sealing substrate is covered with the electroluminescent element, a light emitting device in which the electroluminescent element is blocked from the outside air is formed.

[1. Layer containing the polymer compound of the present invention]
In the layer containing the polymer compound of the present invention, the polymer compound may be mixed with a known material. For example, high molecular charge transport materials, low molecular charge transport materials, conductive carbon such as graphene, fullerene, and carbon nanotubes, electrically conductive compounds such as metals, alloys, metal oxides, metal sulfides, and mixtures thereof Is mentioned. As the charge transport material, a material constituting the hole transport layer or a material constituting the electron transport layer may be used. As the metal, alloy, metal oxide, and metal sulfide, a material constituting the anode or a material constituting the cathode may be used. Furthermore, an organic material that does not have a light emitting function and a charge transporting function may be mixed as long as the light emitting function as the light emitting element is not impaired.

The electroluminescent element of the present invention may be any of an electroluminescent element of a so-called bottom emission type in which light is taken from the substrate side, a so-called top emission type in which light is taken from the side opposite to the substrate, and a double-sided light-emitting type.

Examples of a method for forming a layer containing the polymer compound of the present invention include a method of forming a film using a solution containing the polymer compound.

Examples of the solvent used for film formation from a solution include water, alcohols, ethers, esters, nitrile compounds, nitro compounds, alkyl halides, aryl halides, thiols, sulfides, and sulfoxides. , Thioketones, amides, carboxylic acids, one kind of solvent, and two or more kinds of mixed solvents selected from these. The solubility parameter of the solvent is preferably 9.3 or more. Examples of the solvent having a solubility parameter of 9.3 or more (values in parentheses represent the solubility parameter values of each solvent) include water (21.0), methanol (12.9), ethanol (11 .2), 2-propanol (11.5), 1-butanol (9.9), tert-butyl alcohol (10.5), acetonitrile (11.8), 1,2-ethanediol (14.7) N, N-dimethylformamide (11.5), dimethyl sulfoxide (12.8), acetic acid (12.4), nitrobenzene (11.1), nitromethane (11.0), 1,2-dichloroethane (9. 7), dichloromethane (9.6), chlorobenzene (9.6), bromobenzene (9.9), dioxane (9.8), propylene carbonate (13.3), pyridine (10.4), disulfur Carbon (10.0), and include mixed solvents of these solvents. (Refer to Solvent Handbook, 14th printing, Kodansha Co., Ltd., for the solubility parameter values).

The solubility parameter (δ _m ) of a mixed solvent of two kinds of solvents (referred to as solvent 1 and solvent 2) can be obtained by δ _m = δ ₁ × φ ₁ + δ ₂ × φ ₂ (δ ₁ is the value of solvent 1). The solubility parameter, φ ₁ is the volume fraction of solvent 1, δ ₂ is the solubility parameter of solvent 2, and φ ₂ is the volume fraction of solvent 2.)

Examples of the film forming method from a solution include a coating method and a printing method. Specifically, for example, a spin coating method, a casting method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method. Method, slit coating method, cap coating method, spray coating method, capillary coating method, nozzle coating method, micro gravure printing method, gravure printing method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing method And a reverse printing method.

The thickness of the layer containing the polymer compound of the present invention may be selected so that the optimum value varies depending on the polymer compound used, and the driving voltage and the light emission efficiency are moderate values, preferably 1 nm to 1 μm, preferably 2 nm to 500 nm is more preferable, and 2 nm to 200 nm is still more preferable. From the viewpoint of protecting the light emitting layer, the thickness is preferably 5 nm to 1 μm.

[2. Layer structure of electroluminescent element]
An electroluminescent element generally has a cathode, an anode, and a light emitting layer positioned between the cathode and the anode. Furthermore, you may provide the component.

For example, one or more of a hole injection layer and a hole transport layer can be provided between the anode and the light emitting layer. When the hole injection layer is present, a hole transport layer can be provided between the light emitting layer and the hole injection layer.

Meanwhile, one or more of an electron injection layer and an electron transport layer can be provided between the cathode and the light emitting layer. When an electron injection layer is present, an electron transport layer can be provided between the light emitting layer and the electron injection layer.

The layer containing the polymer compound of the present invention can be used as a layer such as a hole injection layer, a hole transport layer, an electron injection layer, or an electron transport layer. When the layer containing the polymer compound is used as one or two layers selected from a hole injection layer and a hole transport layer, the first electrode is an anode and the second electrode is a cathode. When the layer containing the polymer compound is used as one or two layers selected from an electron injection layer and an electron transport layer, the first electrode is a cathode and the second electrode is an anode.

The anode is an electrode that supplies holes to layers such as a hole injection layer, a hole transport layer, and a light emitting layer. The cathode is an electrode that supplies electrons to layers such as an electron injection layer, an electron transport layer, and a light emitting layer.

The light emitting layer is a function that receives holes from the layer adjacent to the anode side and receives electrons from the layer adjacent to the cathode side when an electric field is applied, and moves the received charges (electrons and holes) by the force of the electric field. And a layer having a function of providing a field for recombination of electrons and holes and connecting recombination to light emission.

The electron injection layer is a layer adjacent to the cathode and has a function of receiving electrons from the cathode, and if necessary, a function of transporting electrons, a function of blocking holes injected from the anode, and light emission. A layer having any function of supplying electrons to the layer. The electron transport layer is a layer mainly having a function of transporting electrons, and if necessary, a function of receiving electrons from the cathode, a function of blocking holes injected from the anode, and supplying electrons to the light emitting layer. A layer having any of the functions.

The hole injection layer is a layer adjacent to the anode and is a layer having a function of receiving holes from the anode, and if necessary, a function of transporting holes, a function of supplying holes to the light emitting layer, and A layer having any function of blocking electrons injected from the cathode. The hole transport layer is a layer mainly having a function of transporting holes, and if necessary, a function of receiving holes from the anode, a function of supplying holes to the light emitting layer, and electrons injected from the cathode. A layer having any of the functions of blocking the above.

Note that the electron transport layer and the hole transport layer may be collectively referred to as a charge transport layer. The electron injection layer and the hole injection layer may be collectively referred to as a charge injection layer.

That is, the electroluminescent element of the present invention can have the following layer configuration (a), or any of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer from the layer configuration (a). It is also possible to have a layer structure in which one or more layers are omitted. In the layer structure (a), the layer containing the polymer compound of the present invention may be used as one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer. it can.

(A) Anode-hole injection layer- (hole transport layer) -emission layer- (electron transport layer) -electron injection layer-cathode

The sign “-” indicates that each layer is laminated adjacently. “(Hole transport layer)” indicates a layer structure including one or more hole transport layers. “(Electron transport layer)” indicates a layer structure including one or more electron transport layers. The same applies to the description of the layer structure below.

The electroluminescent element of the present invention can have two light emitting layers in one laminated structure. In this case, the electroluminescent element can have the following layer configuration (b), or from the layer configuration (b), one of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and an electrode. It is also possible to have a layer structure in which more layers are omitted. In the layer structure (b), the layer containing the polymer compound of the present invention is used as a layer existing between the anode and the light emitting layer closest to the anode, or between the cathode and the light emitting layer closest to the cathode. Used as an existing layer.

(B) Anode-hole injection layer- (hole transport layer) -emission layer- (electron transport layer) -electron injection layer-electrode-hole injection layer- (hole transport layer) -emission layer- (electron transport) Layer)-electron injection layer-cathode

The electroluminescent element of the present invention can have three or more light emitting layers in one laminated structure. In this case, the electroluminescent device may have the following layer configuration (c), or from the layer configuration (c), among the hole injection layer, the hole transport layer, the electron transport layer, the electron injection layer, and the electrode. It is also possible to have a layer structure in which one or more layers are omitted. In the layer structure (c), the layer containing the polymer compound of the present invention is used as a layer existing between the anode and the light emitting layer closest to the anode, or between the cathode and the light emitting layer closest to the cathode. Used as an existing layer.

(C) Anode-hole injection layer- (hole transport layer) -emission layer- (electron transport layer) -electron injection layer-repeat unit A-repeat unit A ...- cathode

Here, “repeating unit A” indicates a unit of a layer configuration of electrode—hole injection layer— (hole transport layer) —light emitting layer— (electron transport layer) —electron injection layer.

Preferred layer configurations of the electroluminescent device of the present invention include the following layer configurations (d) to (n). In the following layer configuration, the layer containing the polymer compound of the present invention can be used as one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

(D) Anode-hole injection layer-light emitting layer-cathode (e) Anode-light emitting layer-electron injection layer-cathode (f) Anode-hole injection layer-light emitting layer-electron injection layer-cathode (g) anode- Hole injection layer-hole transport layer-light emitting layer-cathode (k) anode-hole injection layer-hole transport layer-light emitting layer-electron injection layer-cathode (l) anode-light emitting layer-electron transport layer-electrons Injection layer-cathode (m) anode-hole injection layer-emission layer-electron transport layer-electron injection layer-cathode (n) anode-hole injection layer-hole transport layer-emission layer-electron transport layer-electron injection Layer-cathode

The layer containing the polymer compound of the present invention is preferably an electron injection layer or an electron transport layer.
When the layer containing the polymer compound is an electron injection layer or an electron transport layer, the first electrode is a cathode.

In the electroluminescent device of the present invention, an insulating layer may be provided adjacent to the electrode in order to improve adhesion with the electrode and / or improve injection of charge from the electrode. A thin buffer layer may be inserted at the interface of the charge transport layer or the light emitting layer for the purpose of improving the adhesion of the interface and preventing mixing. The order of the layers to be stacked, the number of layers to be stacked, and the thickness of each layer can be determined in consideration of light emission efficiency and element lifetime.

[3. Each layer constituting the electroluminescent element]
Next, the material and forming method of each layer constituting the electroluminescent element of the present invention will be described in more detail.

[3.1. substrate〕
The substrate constituting the electroluminescent element of the present invention may be any substrate that does not chemically change when the electrodes are formed and when the organic layer is formed. As the substrate, for example, glass, plastic, polymer film, metal film, silicon substrate, or a substrate in which these are laminated is used. A commercially available product may be used as the substrate, or a substrate manufactured by a known method may be used.

When the electroluminescent element of the present invention constitutes a pixel of a display device, a circuit for driving a pixel may be provided on the substrate, or a planarization film may be provided on the drive circuit. Good. The center line average roughness (Ra) of the planarizing film preferably satisfies Ra <10 nm.

Ra can be measured with reference to JIS-B0651 to JIS-B0656, JIS-B0671-1, etc. based on JIS-B0601-2001 of Japanese Industrial Standards JIS.

[3.2. anode〕
The work function of the light emitting layer side surface of the anode constituting the electroluminescent device of the present invention is a viewpoint of the ability to supply holes to organic semiconductor materials used in hole injection layers, hole transport layers, interlayers, light emitting layers, etc. Therefore, it is preferably 4.0 eV or more.

As the material constituting the anode, for example, metals, alloys, conductive compounds (for example, metal oxides, metal sulfides, etc.), and mixtures thereof can be used. Specifically, for example, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), molybdenum oxide, and gold, silver, chromium, nickel, etc. And mixtures of these conductive metal oxides and these metals.

The anode may have a single layer structure composed of one or more of these materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. In the case of a multilayer structure, the work function of the material constituting the anode of the outermost surface layer on the light emitting layer side is more preferably 4.0 eV or more.

A known method can be used as a method for producing the anode. For example, a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and a method by film formation from a solution (a mixed solution with a polymer binder may be used).

The thickness of the anode is usually 10 nm to 10 μm, preferably 40 nm to 500 nm.

From the viewpoint of preventing poor electrical connection such as a short circuit, the center line average roughness (Ra) of the light emitting layer side surface of the anode preferably satisfies Ra <10 nm, and more preferably satisfies Ra <5 nm.

After the anode is prepared by the above method, an electron accepting compound such as UV ozone, a silane coupling agent, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, etc. Surface treatment with a solution such as a solution containing The surface treatment can improve the electrical connection with the layer in contact with the anode.

When the anode is used as a light reflecting electrode in the electroluminescent element of the present invention, the anode includes a light reflecting layer made of a highly light reflecting metal and a high work function material layer containing a material having a work function of 4.0 eV or more. A multi-layer structure in which is combined is preferable.

Examples of the configuration of the anode include the following configurations.
(I) Ag-MoO ₃
(Ii) (Ag—Pd—Cu alloy) — (ITO and / or IZO)
(Iii) (Al—Nd alloy) — (ITO and / or IZO)
(Iv) (Mo—Cr alloy) — (ITO and / or IZO)
(V) (Ag—Pd—Cu alloy) — (ITO and / or IZO) —MoO ₃

In order to obtain a sufficient light reflectivity, the thickness of the light reflection layer made of a highly light reflective metal (for example, Al, Ag, Al alloy, Ag alloy, Cr alloy, etc.) is preferably 50 nm or more, and 80 nm. More preferably. The thickness of the high work function material layer including a material having a work function of 4.0 eV or more (for example, ITO, IZO, MoO _3, etc.) is usually in the range of 5 nm to 500 nm.

[3.3. (Hole injection layer)
In addition to the polymer compound of the present invention, examples of the material constituting the hole injection layer include the following materials:
Carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorene derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, starburst amines, phthalocyanine derivatives, amino-substituted chalcones Derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) ) Derivatives, organosilane derivatives, and polymers containing them;
Conductive metal oxides such as vanadium oxide, tantalum oxide, tungsten oxide, molybdenum oxide, ruthenium oxide, aluminum oxide;
Conductive polymers and oligomers such as polyaniline, aniline-based copolymer, thiophene oligomer, polythiophene;
Organic conductive materials such as poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid, polypyrrole, and polymers containing them;
Amorphous carbon;
Acceptors such as tetracyanoquinodimethane derivatives (for example, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), 1,4-naphthoquinone derivatives, diphenoquinone derivatives, polynitro compounds, etc. Organic compounds;
Silane coupling agents such as octadecyltrimethoxysilane.

The material may be a single component or a composition composed of a plurality of components. The hole injection layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or a plurality of layers having different compositions. . The material illustrated as a material which comprises a positive hole transport layer can be used as a material which comprises a positive hole injection layer.

As a method for preparing the hole injection layer, a known method can be used. When the hole injection material used for the hole injection layer is an inorganic material, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used. For a low molecular organic material, a vacuum deposition method or a transfer method can be used. (For example, laser transfer, thermal transfer, etc.), a method of film formation from a solution (a mixed solution with a polymer binder may be used), and the like can be used. When the hole injection material is a polymer organic material, a method of film formation from a solution can be used.

When the hole injection material is a low molecular organic material such as a pyrazoline derivative, an arylamine derivative, a stilbene derivative, or a triphenyldiamine derivative, it is preferable to form the hole injection layer using a vacuum deposition method.

The hole injection layer can also be formed using a mixed solution in which a polymer compound binder and the low molecular organic material are dispersed.

It is preferable that the polymer compound binder to be mixed does not extremely inhibit charge transport. A compound that does not strongly absorb visible light is preferred. Examples of the polymer compound binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof , Polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

The solvent used for film formation from a solution may be any solvent that can dissolve the hole injection material. Examples of the solvent include water, chlorine-containing solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as THF, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, butyl acetate and ethyl. An ester solvent such as cellosolve acetate is exemplified.

Examples of the film forming method from a solution include a printing method and a coating method, and specifically, for example, a spin coating method, a casting method, a micro gravure printing method, a gravure printing method, a bar coating method, a roll coating method. Method, wire bar coating method, dip coating method, slit coating method, cap coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing method, nozzle coating method, capillary coating method And a reverse printing method. In terms of easy pattern formation, it is preferable to use a printing method (for example, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, an inkjet printing method, or the like) or a nozzle coating method.

When forming both the hole injection layer and the organic layer by a coating method when forming an organic layer such as a hole transport layer and a light-emitting layer following the hole injection layer, it was applied first. A layer (lower layer) may be dissolved in a solvent contained in a solution of a layer to be applied later, making it impossible to produce a laminated structure. In this case, a method of insolubilizing the lower layer can be used. Solvent insolubilization methods include, for example, a method of adding a crosslinking group to a polymer compound and crosslinking to insolubilize, or mixing a low molecular compound having a crosslinking group having an aromatic ring typified by aromatic bisazide as a crosslinking agent. , A method of crosslinking and insolubilization, a method of mixing a low molecular compound having a crosslinking group not having an aromatic ring represented by an acrylate group as a crosslinking agent, crosslinking and insolubilizing, and exposing the lower layer to ultraviolet light to crosslink And a method of insolubilizing in an organic solvent used for the production of the upper layer, and a method of insolubilizing the organic solvent used in the production of the upper layer by heating and crosslinking the lower layer. When the lower layer is heated, the heating temperature is usually 100 ° C. to 300 ° C., and the time is usually 1 minute to 1 hour.

Other methods of laminating without dissolving the lower layer other than by cross-linking include, for example, a method using different polar solutions for the production of adjacent layers. Specific examples of the method include a method in which a water-soluble polymer compound is used for the lower layer and an oil-soluble polymer compound is used for the upper layer so that the lower layer does not dissolve even when applied.

The thickness of the hole injection layer varies depending on the material used, and may be selected so that the driving voltage and the light emission efficiency are appropriate. Usually, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 10 nm to 100 nm.

[3.4. Hole transport layer)
In the electroluminescent device of the present invention, examples of the material constituting the hole transport layer include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorene derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolones. Derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrins Compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, organic silane derivatives, and polymers containing these structures; aniline copolymers, thiophene It includes organic conductive materials such as polypyrrole; oligomers, conductive polymers and oligomers such as polythiophene.

The material may be a single component or a composition comprising a plurality of components.
The hole transport layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or a plurality of layers having different compositions. .
The material illustrated as a material which comprises a positive hole injection layer can be used as a material which comprises a positive hole transport layer.

Examples of the method for producing the hole transport layer and the like include the same methods as those for producing the hole injection layer. Examples of the method by film formation from a solution include a printing method and a coating method. Specifically, for example, a spin coating method, a casting method, a bar coating method, a roll coating method, a wire bar coating method, a dip method, and the like. Coating method, slit coating method, cap coating method, spray coating method, capillary coating method, nozzle coating method, micro gravure printing method, gravure printing method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing And reversal printing. When a sublimable compound material is used as the material for the hole transport layer, a vacuum deposition method and a transfer method are usually used.

Examples of the solvent used for film formation from a solution include the solvents exemplified in the film formation method of the hole injection layer.

When an organic layer such as a light-emitting layer is formed by a coating method following the hole transport layer, if the previously applied layer (lower layer) is dissolved in the solvent contained in the solution of the layer to be applied later, The lower layer can be insolubilized by the same method as exemplified in the film formation method of the hole injection layer.

The thickness of the hole transport layer differs depending on the material used, and may be selected so that the driving voltage and the light emission efficiency are appropriate. Usually, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm to 100 nm.

[3.5. (Light emitting layer)
In the electroluminescent device of the present invention, when the light emitting layer contains a polymer compound, examples of the polymer compound include polyfluorene derivatives, polyparaphenylene vinylene derivatives, polyphenylene derivatives, polyparaphenylene derivatives, polythiophene derivatives, polydialkylfluorenes, Conjugated polymer compounds such as polyfluorene benzothiadiazole and polyalkylthiophene can be preferably used.

The light emitting layer containing the polymer compound may be a polymer dye compound such as a perylene dye, a coumarin dye, or a rhodamine dye, and / or rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, or Nile Red. , Coumarin 6, quinacridone and other low molecular dye compounds may be contained. The light emitting layer containing the polymer compound includes naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, dyes such as polymethine, xanthene, coumarin, and cyanine, metal complexes of 8-hydroxyquinoline and derivatives thereof, A metal complex emitting phosphorescence such as aromatic amine, tetraphenylcyclopentadiene and derivatives thereof, and tetraphenylbutadiene and derivatives thereof, and tris (2-phenylpyridine) iridium may be contained.

The light emitting layer may be composed of a composition of a non-conjugated polymer compound and a compound selected from light emitting organic compounds such as the organic dye and the metal complex. Non-conjugated polymer compounds include, for example, polyethylene, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone Examples thereof include resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicon resins. The non-conjugated polymer compound is a carbazole derivative, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, fluorene derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative in the side chain. Selected from the group consisting of amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, and organosilane derivatives It may have the structure of one or more derivatives or compounds.

When the light emitting layer contains a low molecular compound, examples of the low molecular compound include low molecular dye compounds such as rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, nile red, coumarin 6, carbazole, quinacridone, Naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine, xanthene, coumarin, cyanine, and indigo dyes, metal complexes of 8-hydroxyquinoline and derivatives thereof, metal complexes of phthalocyanine and derivatives thereof , Aromatic amines, tetraphenylcyclopentadiene and derivatives thereof, and tetraphenylbutadiene and derivatives thereof.

The light emitting layer may contain a metal complex that emits phosphorescence. Examples of the phosphorescent-emitting metal complex include tris (2-phenylpyridine) iridium, thienylpyridine ligand-containing iridium complex, phenylquinoline ligand-containing iridium complex, and triazacyclononane skeleton-containing terbium complex.

The material may be a single component or a composition comprising a plurality of components.
The light emitting layer may have a single-layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or a plurality of layers having different compositions.

Examples of the method for forming the light emitting layer include the same method as that for forming the hole injection layer. Examples of the film forming method from a solution include a printing method and a coating method, and specifically, for example, a spin coating method, a casting method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating. Method, slit coating method, cap coating method, spray coating method, capillary coating method, nozzle coating method, micro gravure printing method, gravure printing method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing method And a reverse printing method. When a sublimable compound material is used as the light emitting layer material, a vacuum deposition method or a transfer method is usually used.

Examples of the solvent used for film formation from a solution include the solvents exemplified in the method for forming a hole injection layer.

When an organic layer such as an electron transport layer is formed by a coating method subsequent to the light emitting layer, the layer previously applied (lower layer) is dissolved in the solvent contained in the solution of the layer to be applied later. The lower layer can be insolubilized in the same manner as exemplified in the method for forming the hole injection layer.

The thickness of the light emitting layer varies depending on the material used, and may be selected so that the driving voltage and the light emission efficiency are appropriate values. Usually, the thickness is 5 nm to 1 μm, preferably 10 nm to 500 nm. Preferably, it is 30 nm to 200 nm.

[3.6. (Electron transport layer)
In the electroluminescent device of the present invention, as a material constituting the electron transport layer, a known material can be used in addition to the polymer compound of the present invention. For example, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, fluorene derivative, benzoquinone and its derivative, naphthoquinone and its derivative, anthraquinone and its derivative, tetracyanoanthraquinodimethane and its derivative, fluorenone derivative, diphenyldicyanoethylene And its derivatives, diphenoquinone derivatives, anthraquinodimethane derivatives, anthrone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic rings (eg naphthalene, perylene, etc.) tetracarboxylic anhydride Products, phthalocyanine derivatives, metal complexes (eg, metal complexes of 8-quinolinol derivatives, metal complexes with metal phthalocyanine ligands, benzo Metal complexes with xazole ligands, metal complexes with benzothiazole ligands), organosilane derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene And derivatives thereof. Among these, triazole derivatives, oxadiazole derivatives, benzoquinone and derivatives thereof, anthraquinone and derivatives thereof, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof Derivatives are preferred.

The material may be a single component or a composition comprising a plurality of components.
The electron transport layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or a plurality of layers having different compositions.
The material illustrated as a material which comprises an electron injection layer can be used as a material which comprises an electron carrying layer.

As a method for forming the electron transport layer, the same method as that for forming the hole injection layer may be used. Examples of the film forming method from a solution include a printing method and a coating method, and specifically, for example, a spin coating method, a casting method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating. Method, slit coating method, cap coating method, spray coating method, capillary coating method, nozzle coating method, micro gravure printing method, gravure printing method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing method And a reverse printing method. When a sublimable compound material is used for the electron transport layer, a vacuum deposition method or a transfer method is usually used.

When an organic layer such as an electron injection layer is formed by a coating method following the electron transport layer, when the previously applied layer (lower layer) is dissolved in the solvent contained in the solution of the layer to be applied later, The lower layer can be insolubilized by the same method as exemplified in the film formation method of the hole injection layer.

The thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. Usually, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm to 100 nm.

[3.7. Electron injection layer
In the electroluminescent device of the present invention, as a material constituting the electron injection layer, a known material can be used in addition to the polymer compound of the present invention. For example, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, fluorene derivative, benzoquinone and its derivative, naphthoquinone and its derivative, anthraquinone and its derivative, tetracyanoanthraquinodimethane and its derivative, fluorenone derivative, diphenyldicyanoethylene And derivatives thereof, diphenoquinone derivatives, anthraquinodimethane derivatives, anthrone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic rings (naphthalene, perylene, etc.) tetracarboxylic acid anhydrides, Phthalocyanine derivatives, various metal complexes (for example, metal complexes of 8-quinolinol derivatives, metal phthalocyanine, benzoxazole) Metal complexes, metal complexes of benzothiazole as a ligand) and organic silane derivatives.

The material may be a single component or a composition comprising a plurality of components.
The electron injection layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or a plurality of layers having different compositions.
The material illustrated as a material which comprises an electron carrying layer can be used as a material which comprises an electron injection layer.

As a method for forming the electron injection layer, the same method as that for forming the hole injection layer may be used. Examples of the film forming method from a solution include a printing method and a coating method, and specifically, for example, a spin coating method, a casting method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating. Method, slit coating method, cap coating method, spray coating method, capillary coating method, nozzle coating method, micro gravure printing method, gravure printing method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing method And a reverse printing method. When a sublimable compound material is used as the material for the electron injection layer, a vacuum deposition method or a transfer method is usually used.

The thickness of the electron injection layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. Usually, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm to 100 nm.

[3.8. cathode〕
The cathode may have a single layer structure made of one or more materials, or may have a multilayer structure made of a plurality of layers having the same composition or a plurality of layers having different compositions.

When the cathode has a single layer structure, the material constituting the cathode is selected from, for example, low resistance metals such as gold, silver, copper, aluminum, chromium, tin, lead, nickel, titanium, and these low resistance metals Alloys including one or more, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), conductive metal oxides such as molybdenum oxide, and these conductive metal oxides and metals And a mixture thereof.

When the cathode has a multilayer structure, it is preferably a two-layer structure of a first cathode layer and a cover cathode layer, or a three-layer structure of a first cathode layer, a second cathode layer, and a cover cathode layer. Here, the first cathode layer refers to the layer closest to the light emitting layer in the cathode, and the cover cathode layer refers to the layer covering the first cathode layer in the case of the two-layer structure, and in the case of the three-layer structure. A layer covering the first cathode layer and the second cathode layer. From the viewpoint of the electron supply capability, the work function of the material constituting the first cathode layer is preferably 3.5 eV or less. The material constituting the first cathode layer is preferably a metal having a work function of 3.5 eV or less, an oxide of the metal, a fluoride of the metal, a carbonate of the metal, or a composite oxide of the metal. Used. As a material for the cover cathode layer, a material having low resistivity and high corrosion resistance to moisture (for example, metal, metal oxide) is preferably used.

Examples of the material constituting the first cathode layer include metals such as alkali metals and alkaline earth metals, alloys containing one or more of the metals, oxides of the metals, halides of the metals, and carbonates of the metals. , One or more materials selected from the group consisting of the composite oxides of metals and mixtures thereof. Examples of alkali metal, alkali metal oxides, alkali metal halides, alkali metal carbonates and alkali metal composite oxides include lithium, sodium, potassium, rubidium, cesium, lithium oxide, sodium oxide, potassium oxide , Rubidium oxide, cesium oxide, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, potassium molybdate, potassium titanate, Examples include potassium tungstate and cesium molybdate. Examples of alkaline earth metals, alkaline earth metal oxides, alkaline earth metal halides, alkaline earth metal carbonates and alkaline earth metal composite oxides include magnesium, calcium, strontium, barium, Magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, barium molybdate, barium tungstate It is done. Examples of alloys containing at least one alkali metal or alkaline earth metal include Li—Al alloys, Mg—Ag alloys, Al—Ba alloys, Mg—Ba alloys, Ba—Ag alloys, and Ca—Bi—Pb—Sn. An alloy is mentioned. A composition of the material exemplified as the material constituting the first cathode layer and the material exemplified as the material constituting the electron injection layer can also be used as the material constituting the first cathode layer. Examples of the material constituting the second cathode layer include the same materials as the material of the first cathode layer.

Examples of the material constituting the cover cathode layer include low resistance metals such as gold, silver, copper, aluminum, chromium, tin, lead, nickel, titanium, alloys containing one or more of these low resistance metals, and metal nanoparticles. , Metal nanowires, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), conductive metal oxides such as molybdenum oxide, and mixtures of these conductive metal oxides and metals , Conductive metal oxide nanoparticles, graphene, fullerene, carbon nanotubes and other conductive carbon.

Examples of the configuration when the cathode has a multilayer structure include Mg / Al, Ca / Al, Ba / Al, NaF / Al, KF / Al, RbF / Al, CsF / Al, Na ₂ CO ₃ / Al, K ₂ Two-layer structure of the first cathode layer and the cover cathode layer, such as CO ₃ / Al, Cs ₂ CO ₃ / Al, and LiF / Ca / Al, NaF / Ca / Al, KF / Ca / Al, RbF / Ca First cathode layer, second cathode layer and cover cathode such as / Al, CsF / Ca / Al, Ba / Al / Ag, KF / Al / Ag, KF / Ca / Ag, K ₂ CO ₃ / Ca / Ag A three-layer structure of layers may be mentioned. Here, the symbol “/” indicates that each layer is adjacent. Note that the material constituting the second cathode layer preferably has a reducing action on the material constituting the first cathode layer. Here, the presence / absence and degree of the reducing action between the materials can be estimated from, for example, the bond dissociation energy (ΔrH °) between the compounds. That is, in the case of a combination in which the bond dissociation energy is positive in the reduction reaction of the material constituting the second cathode layer to the material constituting the first cathode layer, the material constituting the second cathode layer changes the first cathode layer. It can be said that it has a reducing action on the constituent materials. The bond dissociation energy can be referred to, for example, in “Electrochemical Handbook 5th Edition” (Maruzen, published in 2000) and “Thermodynamic Database MALT” (Science and Technology, published in 1992).

As a method for producing the cathode, known methods can be used, and examples thereof include a vacuum deposition method, a sputtering method, an ion plating method, and a method of film formation from a solution (a mixed solution with a polymer binder may be used). . When using metals, metal oxides, fluorides, and carbonates, vacuum evaporation is often used, and high-boiling metal oxides, high-boiling metal composite oxides, conductive metal oxides such as indium tin oxide (ITO) In the case of using the sputtering method, a sputtering method and an ion plating method are frequently used. When forming a film using two or more kinds of metals, metal oxides, fluorides, carbonates, high boiling point metal oxides, metal composite oxides, and conductive metal oxides, a co-evaporation method, a sputtering method, An ion plating method or the like is used. In the case of metal nanoparticles, metal nanowires, and conductive metal oxide nanoparticles, a method of film formation from a solution is frequently used. In particular, a co-evaporation method is suitable for forming a film of a low molecular organic compound and a metal or metal oxide, fluoride, or carbonate.

The optimum thickness of the cathode varies depending on the material and the layer structure used, and the driving voltage, light emission efficiency, and element lifetime may be selected to be appropriate values. Usually, the thickness of the first cathode layer is 0.5 nm to 20 nm. The thickness of the cover cathode layer is usually 10 nm to 1 μm. For example, when Ba or Ca is used for the first cathode layer and Al is used for the cover cathode layer, the thickness of Ba or Ca is preferably 2 nm to 10 nm, and the thickness of Al is 10 nm to 500 nm. Is preferred. For example, when NaF or KF is used for the first cathode layer and Al is used for the cover cathode layer, the thickness of NaF or KF is preferably 1 nm to 8 nm, and the thickness of Al is preferably 10 nm to 500 nm.

In the electroluminescent device of the present invention, when the cathode is used as the light transmissive electrode, the visible light transmittance of the cover cathode layer is preferably 40% or more, and more preferably 50% or more. This visible light transmittance is easily achieved by using a transparent conductive metal oxide such as indium tin oxide (ITO), indium zinc oxide (IZO), or molybdenum oxide as the cover cathode layer material. Alternatively, it can be easily achieved by setting the thickness of the cover cathode layer using a low resistance metal such as gold, silver, copper, aluminum, chromium, tin, lead and the like and an alloy containing these metals to 30 nm or less.

For the purpose of improving the light transmittance from the cathode side, an antireflection layer can be provided on the cover cathode layer of the cathode. The material constituting the antireflection layer preferably has a refractive index of 1.8 to 3.0. Examples of the material satisfying this refractive index include ZnS, ZnSe, and WO ₃ . The thickness of the antireflection layer varies depending on the material used, but is usually 10 nm to 150 nm.

[3.9. Insulating layer
The insulating layer is a layer having functions such as improving adhesion with the electrode, improving charge injection from the electrode, and preventing mixing with an adjacent layer. Examples of the material constituting the insulating layer include metal fluorides, metal oxides, and organic insulating materials (for example, polymethyl methacrylate). The thickness of the insulating layer is usually 5 nm or less. Examples of the installation position of the insulating layer (for example, an insulating layer having a thickness of 5 nm or less) include a position adjacent to the cathode and a position adjacent to the anode.

[3.10. Other components
The electroluminescent element can have a sealing member. The position of the sealing member is usually on the side opposite to the substrate across the light emitting layer or the like. The electroluminescent element can have arbitrary components for configuring a display device, such as a filter such as a color filter and a fluorescence conversion filter, a circuit and wiring necessary for driving a pixel, and the like.

[4. Method for manufacturing electroluminescent element]
The electroluminescent element of the present invention can be produced, for example, by sequentially laminating each layer constituting the electroluminescent element on a substrate. For example, an anode is provided on a substrate, a layer such as a hole injection layer and a hole transport layer is sequentially provided thereon, a light emitting layer is provided thereon, and an electron transport layer, an electron injection layer, and the like are provided thereon. The electroluminescent element can be manufactured by providing the above layer and further laminating the cathode thereon. As another example, a cathode is provided on a substrate, and an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, etc. are sequentially provided thereon, and further, an anode is provided thereon. By laminating, an electroluminescent element can be manufactured. To give another example, electroluminescence is obtained by joining an anode or a substrate on the anode side laminated with each layer on the anode, and a cathode or substrate on the cathode side laminated with each layer on the cathode. An element can be manufactured.

[5. Application of electroluminescent device)
A display device can be manufactured using the electroluminescent element of the present invention. The display device includes an electroluminescent element as a pixel unit. The arrangement mode of the pixel unit can be an arrangement normally employed in a display device such as a television, and can be an aspect in which a large number of pixels are arranged on a common substrate. In the display device of the present invention, the pixels arranged on the substrate can be formed in a pixel region defined by the bank.

The electroluminescent element of the present invention can be used for a planar illumination device or a curved illumination device.

<Photoelectric conversion element>
The photoelectric conversion element of the present invention will be described below. The photoelectric conversion element of the present invention is a photoelectric conversion element having a layer containing the polymer compound of the present invention.

The photoelectric conversion element of the present invention includes, for example, a cathode, an anode, a charge separation layer located between the cathode and the anode, and a charge separation layer located between the charge separation layer and the cathode or the anode. It has a layer containing a polymer compound. The photoelectric conversion element of the present invention can have a substrate as an optional component, and on the surface of the substrate, the cathode, the anode, the charge separation layer, the layer containing the polymer compound of the present invention, and an optional configuration It can be set as the structure which provided the element.

Examples of the layer configuration of the photoelectric conversion element of the present invention include the following embodiments:
(1) A mode in which an anode is provided on a substrate, a charge separation layer is laminated thereon, a layer containing the polymer compound of the present invention is laminated thereon, and a cathode is laminated thereon.
(2) A mode in which an anode is provided on a substrate, a layer containing the polymer compound of the present invention is laminated thereon, a charge separation layer is laminated, and a cathode is laminated further thereon.
(3) An anode is provided on the substrate, a layer containing the polymer compound of the present invention is laminated thereon, a charge separation layer is laminated, and a layer containing the polymer compound of the present invention is laminated thereon. A mode in which a cathode is further laminated on the upper layer;
(4) A mode in which a cathode is provided on a substrate, a layer containing the polymer compound of the present invention is laminated thereon, a charge separation layer is laminated thereon, and an anode is further laminated thereon;
(5) A mode in which a cathode is provided on a substrate, a charge separation layer is laminated thereon, a layer containing the polymer compound of the present invention is laminated thereon, and an anode is laminated thereon.
(6) A cathode is provided on a substrate, a layer containing the polymer compound of the present invention is laminated thereon, a charge separation layer is laminated thereon, and a layer containing the polymer compound of the present invention is laminated thereon. And an anode is laminated on the upper layer;

In each of the above aspects (1) to (6), a layer other than the layer containing the polymer compound of the present invention and the charge separation layer may be further provided. The configuration of the photoelectric conversion element will be separately described in detail below.

[1. Layer containing the polymer compound of the present invention (organic thin film of the present invention)]
In the layer containing the polymer compound of the present invention, the polymer compound may be mixed with a known material. Examples of known materials include electron donating compounds, electron accepting compounds, metal nanoparticles, and metal oxide nanoparticles.

Examples of the method for forming the layer containing the polymer compound of the present invention include a method of forming a film using a solution containing the polymer compound of the present invention.

Examples of the solvent used for film formation from a solution include water, alcohols, ethers, esters, carboxylic acids, alkyl halides, heterocyclic aromatic compounds, thiols, sulfides, thioketones, and sulfoxides. , One kind of solvent selected from nitro compounds and nitrile compounds, and two or more kinds of mixed solvents selected from these. It is preferable that the solubility parameter of a solvent is 9.3 or more. Examples of the solvent having a solubility parameter of 9.3 or more (the values in parentheses represent the solubility parameter values of the respective solvents) and the solubility parameter values are as described above.

A solubility parameter (δ _m ) of a mixed solvent obtained by mixing two kinds of solvents (solvent 1 and solvent 2) can be obtained by δ _m = δ ₁ × φ ₁ + δ ₂ × φ ₂ (δ ₁ Is the solubility parameter of solvent 1, φ ₁ is the volume fraction of solvent 1, δ ₂ is the solubility parameter of solvent 2, and φ ₂ is the volume fraction of solvent 2.

Examples of the film forming method from a solution include a printing method and a coating method, and specifically, for example, a spin coating method, a casting method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating. Method, slit coating method, cap coating method, spray coating method, capillary coating method, nozzle coating method, micro gravure printing method, gravure printing method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing method And a reverse printing method.

The thickness of the layer containing the polymer compound of the present invention may be selected so that the optimum value varies depending on the polymer compound used and the photoelectric conversion efficiency is an appropriate value, preferably 1 nm to 1 μm, and preferably 2 nm to 500 nm. More preferred is 2 nm to 200 nm.

[2. Layer structure of photoelectric conversion element]
The photoelectric conversion element of the present invention has a cathode, an anode, a charge separation layer located between the cathode and the anode, and a layer containing the polymer compound of the present invention. The position of the layer containing the polymer compound of the present invention is preferably between the charge separation layer and the cathode and / or between the charge separation layer and the cathode, and between the cathode and the charge separation layer. It is more preferable.

[3. Each layer constituting the photoelectric conversion element]
[3.1. (Charge separation layer)
The charge separation layer of the photoelectric conversion element of the present invention preferably contains an electron donating compound and an electron accepting compound.

The charge separation layer may contain an electron donating compound alone or in combination of two or more. The charge separation layer may contain an electron accepting compound alone or in combination of two or more. The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

Examples of the electron donating compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and conjugated polymer compounds. Examples of the conjugated polymer compound include oligothiophene and derivatives thereof, polyfluorene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline, and Examples thereof include polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

Examples of the electron accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone derivatives. , diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, fullerenes and derivatives thereof such as C _60, bathocuproine Phenanthrene derivatives such as titanium oxide, metal oxides such as titanium oxide, and carbon nanotubes. The electron-accepting compound is preferably titanium oxide, carbon nanotube, fullerene, or fullerene derivative, and more preferably fullerene or fullerene derivative.

The thickness of the charge separation layer is usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and still more preferably 20 nm to 200 nm.

Any method may be used for producing the charge separation layer. For example, a method by film formation from a solution and a vacuum deposition method can be mentioned.

Examples of the film forming method from a solution include spin coating, casting, micro gravure printing, gravure printing, bar coating, roll coating, wire bar coating, dip coating, slit coating, and cap coating. Coating methods such as spin coating, flexographic printing, spray coating, screen printing, flexographic printing, offset printing, inkjet printing, dispenser printing, nozzle coating, capillary coating, etc. The gravure printing method, the ink jet printing method, and the dispenser printing method are preferable.

[3.2. substrate〕
The photoelectric conversion element of the present invention is usually formed on a substrate. This substrate may be any substrate that does not change when the electrode is formed and when the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, the opposite electrode (that is, the electrode farther from the substrate) is preferably transparent or translucent.

[3.3. electrode〕
Examples of the material constituting the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, for example, indium oxide, zinc oxide, tin oxide, a composite thereof (for example, indium / tin / oxide (ITO), indium / zinc / oxide, etc.), NESA, gold, platinum, silver, and copper are included. Can be mentioned. Of these, ITO, indium / zinc / oxide, and tin oxide are preferable.

Examples of the electrode manufacturing method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like.

As the material constituting the electrode, an organic transparent conductive film such as polyaniline and derivatives thereof, polythiophene and derivatives thereof may be used. As a material constituting the electrode, a metal, a conductive polymer, or the like can be used. One of the pair of electrodes is preferably a material having a low work function. Examples of the material constituting the electrode include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. An alloy of two or more metals selected from the group consisting of those metals; one or more metals selected from those metals; and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and Alloys with one or more selected from the group consisting of tin; graphite; graphite intercalation compounds. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

[3.4. (Middle layer)
As a means for improving the photoelectric conversion efficiency of the photoelectric conversion element of the present invention, an intermediate layer may be included in the photoelectric conversion element in addition to the layer containing the polymer compound and the charge separation layer used in the present invention. Examples of the material constituting the intermediate layer include alkali metal halides (for example, lithium fluoride), alkali metal oxides, alkaline earth metal halides, and alkaline earth metal oxides. Examples of the material constituting the intermediate layer include fine particles of inorganic semiconductor such as titanium oxide and PEDOT (poly-3,4-ethylenedioxythiophene).

[4. Use of photoelectric conversion element)
The photoelectric conversion element of the present invention can be operated as an organic thin film solar cell by irradiating light such as sunlight from a transparent or translucent electrode to generate a photovoltaic force between the electrodes. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

By irradiating light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes or in a state where no voltage is applied, a photocurrent flows and the organic light sensor can be operated.
It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

[5. (Solar cell module)
The organic thin film solar cell can basically have the same module structure as a conventional solar cell module. In general, a solar cell module has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin, protective glass, or the like, and light is taken in from the opposite side of the support substrate. On the other hand, a transparent material such as tempered glass may be used for the support substrate of the solar cell module, and a cell may be formed thereon to take in light from the transparent support substrate side. Specifically, as a structure of the solar cell module, for example, a module structure called a super straight type, a substrate type, or a potting type, and a substrate integrated module structure used in an amorphous silicon solar cell or the like are known. The organic thin film solar cell of the present invention can take a structure appropriately selected from these module structures depending on the purpose of use, the place of use and the environment.

In typical super straight type and substrate type module structures, cells are arranged at regular intervals between support substrates that are transparent on one or both sides and have been subjected to antireflection treatment. Adjacent cells are connected by metal leads or flexible wiring. A collecting electrode is disposed on the outer edge, and the generated electric power is taken out to the outside. Depending on the purpose, various types of plastic materials such as ethylene vinyl acetate (EVA) may be placed between the substrate and the cell in the form of a film or a filled resin in order to protect the cell and / or improve the current collection efficiency. Good. When used in places where it is not necessary to cover the surface with a hard material, such as a place where there is little impact from the outside, the protective function is achieved by configuring the surface protective layer with a transparent plastic film or curing the above filling resin. It is possible to dispense with the support substrate on one side. In order to seal the inside and to secure the rigidity of the module, the periphery of the support substrate is fixed in a sandwich shape with a metal frame, and the support substrate and the frame are hermetically sealed with a sealing material. If a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.

In the case of a solar cell in which a flexible support such as a polymer film is used, for example, cells are sequentially formed while feeding a roll-shaped support, cut into a desired size, and then the peripheral portion is flexible and moisture-proof. A battery body can be produced by sealing with a material.
A solar cell using a flexible support may have a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391. A solar cell using a flexible support can be used by being bonded and fixed to curved glass or the like.

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer compound were determined by using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation: HLC-8220 GPC). Calculated as molecular weight. The sample to be measured was dissolved in THF to a concentration of about 0.5% by weight, and 50 μL was injected into GPC. As the mobile phase of GPC, THF was used and allowed to flow at a flow rate of 0.5 mL / min.

The structural analysis of the compound and the polymer compound was performed by ¹ H-NMR analysis using a 300 MHz NMR spectrometer manufactured by Varian. The measurement was performed by dissolving the sample in a soluble heavy solvent (a solvent in which a hydrogen atom in a solvent molecule was replaced with a deuterium atom) so as to have a concentration of 20 mg / mL.

The HOMO orbital energy of the polymer compound was determined by measuring the ionization potential of the polymer compound of the present invention and using the obtained ionization potential as the orbital energy. Specifically, a sample in which a polymer compound was formed on a quartz substrate to a thickness of about 100 nm was used.

The orbital energy of LUMO of the polymer compound was determined by calculating the energy difference between HOMO and LUMO and using the sum of the value and the ionization potential measured above as the orbital energy. For measurement of the ionization potential, a photoelectron spectrometer (manufactured by Riken Keiki Co., Ltd .: AC-2) was used. The energy difference between HOMO and LUMO was obtained from the absorption terminal by measuring the absorption spectrum of the polymer compound of the present invention using an ultraviolet / visible / near infrared spectrophotometer (Varian: Cary 5E). Specifically, a sample in which a polymer compound was formed on a quartz substrate to a thickness of about 100 nm was used.

[Production Example 1]
Synthesis of 2,7-dibromo-9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (compound A) 2,7-dibromo -9-fluorenone (52.5 g), ethyl salicylate (154.8 g) and mercaptoacetic acid (1.4 g) were placed in a 300 mL flask, and the gas in the flask was replaced with nitrogen gas. Thereto was added methanesulfonic acid (630 mL) and the mixture was stirred at 75 ° C. overnight. The mixture was allowed to cool, added to ice water and stirred for 1 hour to produce a solid. The resulting solid was filtered off and washed with heated acetonitrile. The washed solid was dissolved in acetone, and the solid was recrystallized from the obtained acetone solution and filtered. The resulting solid (62.7 g), 2- [2- (2-methoxyethoxy) ethoxy] ethyl p-toluenesulfonate (86.3 g), potassium carbonate (62.6 g), and 1,4,7, 10,13,16-hexaoxacyclooctadecane (sometimes referred to as “18-crown-6”) (7.2 g) was dissolved in N, N-dimethylformamide (670 mL) and the solution was transferred to a flask. Stir at 105 ° C. overnight. The obtained mixture was allowed to cool to room temperature, added to ice water, and stirred for 1 hour. Thereafter, chloroform is added to the reaction solution, liquid separation extraction is performed, and the solution is concentrated, whereby 2,7-dibromo-9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2- Methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Compound A) (51.2 g) was obtained.

[Production Example 2]
2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-bis [3-ethoxycarbonyl-4- [2- [2- ( Synthesis of 2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Compound B) After the gas in the flask was placed in a nitrogen gas atmosphere, Compound A (15 g), bis (pinacolato) diboron (8.9 g), [ 1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (0.8 g), 1,1′-bis (diphenylphosphino) ferrocene (0.5 g), potassium acetate (9.4 g) ) And dioxane (400 mL), heated to 110 ° C., and heated to reflux for 10 hours. The reaction liquid was filtered after standing_to_cool and the filtrate was concentrate | evaporated under reduced pressure. The reaction mixture was washed 3 times with methanol. The precipitate was dissolved in toluene, and activated carbon was added to the solution and stirred. Thereafter, the mixture was filtered and the filtrate was concentrated under reduced pressure to give 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-bis [ 3-Ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Compound B) (11.7 g) was obtained.

[Production Example 3]
Synthesis of poly [9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene] (polymer compound A) by Suzuki coupling In flask Into an inert gas atmosphere, Compound A (0.55 g), Compound B (0.61 g), Triphenylphosphine palladium (0.01 g), Methyltrioctylammonium chloride (manufactured by Sigma-Aldrich, product) Name Aliquat 336®) (0.20 g) and toluene (10 mL) were mixed and heated to 105 ° C. To the reaction solution, 2M aqueous sodium carbonate solution (6 mL) was added dropwise and refluxed for 8 hours. 4-tert-butylphenylboronic acid (0.01 g) was added to the reaction solution, and the mixture was refluxed for 6 hours. Then, a sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g / mL) was added, and the mixture was stirred for 2 hours. The mixed solution was dropped into methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in THF. The obtained solution was dropped into a mixed solvent of methanol and 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in THF. The obtained solution was added dropwise to methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in THF and purified by passing through an alumina column and a silica gel column.
The THF solution collected from the column was concentrated and then added dropwise to methanol, and the precipitated solid was filtered and dried. The yield of the obtained poly [9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene] (polymer compound A) was 520 mg. there were.

The number average molecular weight in terms of polystyrene of the polymer compound A was 5.2 × 10 ⁴ . The high molecular compound A consists of a structural unit represented by the formula (A).

[Production Example 4]
Synthesis of poly [9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene] (polymer compound A) by Yamamoto polymerization After bringing the gas under an inert gas atmosphere, Compound A (1.31 g), 2,2′-bipyridine (0.48 g), bis (1,5-cyclooctadiene) nickel (0.84 g), and THF (150 mL) was mixed and stirred at 55 ° C. for 5 hours. After the mixture was cooled to room temperature, the reaction solution was added dropwise to a mixture of methanol (200 mL), water (200 mL), and 15% by weight aqueous ammonia (50 mL) to form a precipitate. The resulting precipitate was collected by filtration, dried under reduced pressure, and redissolved in THF. The solution was filtered through celite, and the filtrate was concentrated under reduced pressure. Methanol was added dropwise to the concentrated solution, and the resulting precipitate was collected by filtration, and then dried under reduced pressure to obtain polymer compound A (970 mg). The number average molecular weight in terms of polystyrene of the polymer compound A was 1.5 × 10 ⁵ .

[Example 1]
Synthesis of cesium salt of polymer compound A (conjugated polymer compound 1) Polymer compound A (200 mg) synthesized in Production Example 3 was placed in a 100 mL flask, and the gas in the flask was replaced with nitrogen gas. THF (20 mL) and ethanol (20 mL) were added and the mixture was warmed to 55 ° C. An aqueous solution dissolved in cesium hydroxide monohydrate (120 mg) water (2 mL) was added thereto, and the mixture was stirred at 55 ° C. for 6 hours. Then, after cooling a mixture to room temperature, the reaction solvent was depressurizingly distilled. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (150 mg). The obtained cesium salt of polymer compound A is referred to as “conjugated polymer compound 1”. The conjugated polymer compound 1 is composed of a structural unit represented by the formula (B).

From the NMR spectrum, in the conjugated polymer compound 1, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer compound A completely disappeared and the signal derived from the carboxyl group was generated. The ratio of H ⁺ of the conjugated polymer compound 1 estimated from the integral value of ¹ H NMR was 26% with respect to the total of the cesium salt of the carboxyl group and the carboxyl group. The conjugated polymer compound 1 had an orbital energy of HOMO of −5.5 eV and an orbital energy of LUMO of −2.7 eV.

[Reference Example 1]
Synthesis of polyurethane sodium salt (non-conjugated polymer compound 1) After the gas in the 100 mL flask was put under an inert gas atmosphere, 1,3-butanediol (1.0 g), dibutyltin dilaurate (7.5 mg), and Dimethylolpropionic acid (0.5 g) was placed in a 100 mL flask, N, N-dimethylformamide (50 mL) was added, and the mixture was stirred at 90 ° C. for 30 min. Isophorone diisocyanate (3.3 g) was added and heated at 90 ° C. for 3 hours. The solution containing the polymer compound obtained at this stage was subjected to GPC measurement according to the method described above, and the molecular weight of the polymer compound was measured. The number average molecular weight in terms of polystyrene was 1.9 × 10 ³ , which was in terms of polystyrene. The weight average molecular weight was 3.0 × 10 ³ . Thereafter, the temperature of the reaction solution was lowered to 60 ° C. and neutralized by adding a 1M aqueous sodium hydroxide solution. After stirring at 60 ° C. for 1 hour, the solvent was distilled off from the reaction solution to obtain a white solid (2.0 g). The obtained polyurethane sodium salt is referred to as “non-conjugated polymer compound 1”. The non-conjugated polymer compound 1 is composed of a structural unit represented by the formula (V).

[Example 2]
Production of electroluminescent element 1 A hole injecting material solution is applied onto an ITO anode (thickness: 45 nm) patterned on the surface of a glass substrate, and holes are injected by spin coating so that the thickness is 60 nm. Layers were deposited. The glass substrate on which the hole injection layer was formed was heated in a nitrogen atmosphere at 200 ° C. for 10 minutes to insolubilize the hole injection layer, the substrate was naturally cooled to room temperature, and the substrate on which the hole injection layer was formed was Obtained.

Here, AQ-1200, a polythiophene / sulfonic acid hole injection material obtained from Plextronics, was used as the hole injection material solution.

Next, a hole transporting polymer material and xylene were mixed to obtain a composition for forming a hole transporting layer containing 0.7 wt% of the hole transporting polymer material.

Here, the hole transporting polymer material was synthesized by the following method.
After making the gas in the flask under an inert gas atmosphere, 2,7-dibromo-9,9-di (octyl) fluorene (1.4 g), 2,7-bis (4,4,5,5-tetra Methyl-1,3,2-dioxaborolan-2-yl) -9,9-di (octyl) fluorene (6.4 g), N, N-bis (4-bromophenyl) -N ′, N′-bis ( 4-butylphenyl) -1,4-phenylenediamine (4.1 g), bis (4-bromophenyl) benzocyclobutenamine (0.6 g), tetraethylammonium hydroxide (1.7 g), palladium acetate (4. 5 mg), tri (2-methoxyphenyl) phosphine (0.03 g), and toluene (100 mL) were mixed, and the mixture was heated and stirred at 100 ° C. for 2 hours. Phenylboronic acid (0.06 g) was then added and the resulting mixture was stirred for 10 hours. After allowing to cool, the aqueous layer was removed, an aqueous sodium diethyldithiocarbamate solution was added and stirred, the aqueous layer was removed, and the organic layer was washed with water and 3% by weight acetic acid. The organic layer was poured into methanol to precipitate a solid, and then the filtered solid was again dissolved in toluene and passed through a silica gel and alumina column. The eluted toluene solution containing the solid was recovered, and the recovered toluene solution was poured into methanol to precipitate the solid. The precipitated solid was collected by filtration and vacuum dried at 50 ° C. to obtain a hole transporting polymer material. The weight average molecular weight in terms of polystyrene of the hole transporting polymer material was 3.0 × 10 ⁵ .

On the hole injection layer of the substrate on which the hole injection layer obtained above was formed, the composition for forming a hole transport layer was applied by a spin coating method to obtain a coating film having a thickness of 20 nm. The substrate provided with this coating film was heated at 180 ° C. for 60 minutes in a nitrogen atmosphere to insolubilize the coating film, and then naturally cooled to room temperature to obtain a substrate on which a hole transport layer was formed.

Next, the light emitting polymer material and xylene were mixed to obtain a light emitting layer forming composition containing 1.4% by weight of the light emitting polymer material.

Here, the light emitting polymer material was synthesized by the following method.
After making the gas in the flask under an inert gas atmosphere, 2,7-dibromo-9,9-di (octyl) fluorene (9.0 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) 1,4-phenylenediamine (1.3 g), 2,7-bis (4,4,5,5-tetramethyl-1,3 , 2-Dioxaborolan-2-yl) -9,9-di (4-hexylphenyl) fluorene (13.4 g), tetraethylammonium hydroxide (43.0 g), palladium acetate (8 mg), tri (2-methoxyphenyl) ) Phosphine (0.05 g) and toluene (200 mL) were mixed, and the mixture was heated and stirred at 90 ° C. for 8 hours. Phenylboronic acid (0.22 g) was then added and the resulting mixture was stirred for 14 hours. After allowing to cool, the aqueous layer was removed, an aqueous sodium diethyldithiocarbamate solution was added and stirred, the aqueous layer was removed, and the organic layer was washed with water and 3 wt% aqueous acetic acid. The organic layer was poured into methanol to precipitate a solid, and then the collected solid was dissolved again in toluene and passed through a silica gel and alumina column. The eluted toluene solution containing the solid was recovered, and the recovered toluene solution was poured into methanol to precipitate the solid. The precipitated solid was vacuum dried at 50 ° C. to obtain a light emitting polymer material (12.5 g). According to gel permeation chromatography, the obtained light-emitting polymer material had a polystyrene-equivalent weight average molecular weight of 3.1 × 10 ⁵ .

On the hole transport layer of the substrate on which the hole transport layer obtained above was formed, the composition for forming a light emitting layer was applied by a spin coat method to obtain a coating film having a thickness of 80 nm. The substrate provided with this coating film was heated at 130 ° C. for 10 minutes in a nitrogen atmosphere to evaporate the solvent and then naturally cooled to room temperature to obtain a substrate on which a light emitting layer was formed.

Methanol and conjugated polymer compound 1 were mixed to obtain a solution containing 0.2% by weight of conjugated polymer compound 1. On the light emitting layer of the board | substrate with which the light emitting layer obtained above was formed, the said solution was apply | coated by the spin coat method, and the coating film with a thickness of 10 nm was obtained. The substrate provided with this coating film was heated at 130 ° C. for 10 minutes in a nitrogen atmosphere to evaporate the solvent, and then naturally cooled to room temperature to obtain a substrate on which a layer containing the conjugated polymer compound 1 was formed.

The substrate on which the layer containing the conjugated polymer compound 1 obtained above was formed was inserted into a vacuum apparatus, and an Al film was formed on the layer by vacuum vapor deposition to form a cathode, thereby forming a laminated structure. 1 was produced.

The laminated structure 1 obtained above was taken out from the vacuum apparatus, and sealed with sealing glass and a two-component mixed epoxy resin in a nitrogen atmosphere to obtain an electroluminescent element 1.

[Comparative Example 1]
Production of Electroluminescent Element A Electroluminescent element A was obtained in the same manner as in Example 2, except that non-conjugated polymer compound 1 was used instead of conjugated polymer compound 1.

[Measurement]
A forward voltage of 10 V was applied to the electroluminescent elements 1 and A obtained above, and the light emission luminance and the light emission efficiency were measured. The results are shown in Table 1.

As is apparent from Table 1, the electroluminescent device 1 of the present invention is superior in light emission luminance and luminous efficiency as compared to the electroluminescent device A not provided with the layer containing the polymer compound of the present invention.

Claims

A layer containing a polymer compound having a structural unit containing a group represented by formula (1) and a group represented by formula (2) as a charge injection layer and / or a charge transport layer;
The ratio that M 1 in the polymer compound is H + with respect to all M 1 in the polymer compound is greater than 0% and 50% or less.
Electronic devices.
-(Q 1 ) n1 -Y 1 (M 1 ) a1 (Z 1 ) b1 (1)
(Where
Q 1 is a divalent organic group.
Y 1 is —CO 2 − , —SO 3 − , —SO 2 − , —PO 3 2− or —B (R α ) 3 — .
M 1 is H +, a metal cation, or an ammonium cation which may have a substituent.
Z 1 represents F − , Cl − , Br − , I − , OH − , B (R a ) 4 − , R a SO 3 − , R a COO − , ClO − , ClO 2 − , ClO 3 − , ClO. 4 − , SCN − , CN − , NO 3 − , SO 4 2− , HSO 4 − , PO 4 3− , HPO 4 2− , H 2 PO 4 − , BF 4 − or PF 6 − .
n1 is an integer of 0 or more. a1 is an integer of 1 or more. b1 is an integer of 0 or more. However, a1 and b1 are selected so that the charge of the group represented by the formula (1) becomes zero.
R α is an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent. Each R α may be the same as or different from each other.
R a is a monovalent organic group which may have a substituent. When a plurality of R a are present, each R a may be the same as or different from each other.
When a plurality of Q 1 are present, each Q 1 may be the same as or different from each other.
When a plurality of M 1 are present, each M 1 may be the same as or different from each other.
When a plurality of Z 1 are present, each Z 1 may be the same as or different from each other. )
-(Q 2 ) n2 -Y 2 (2)
(Where
Q 2 is a divalent organic group.
Y 2 is a cyano group or a group represented by any one of formulas (3) to (11).
n2 is an integer of 0 or more.
When a plurality of Q 2 are present, each Q 2 may be the same as or different from each other. )
-O- (R'O) a3 -R '' (3)

-S- (R'S) a4 -R '' (5)
-C (= O)-(R'-C (= O)) a4 -R '' (6)
-C (= S)-(R'-C (= S)) a4 -R '' (7)
-N {(R ′) a4 R ″} 2 (8)
—C (═O) O— (R′—C (═O) O) a4 —R ″ (9)
—C (═O) O— (R′O) a4 —R ″ (10)
—NHC (═O) — (R′NHC (═O)) a4 —R ″ (11)
(Where
R ′ is a divalent hydrocarbon group which may have a substituent.
R ″ represents a hydrogen atom, a monovalent hydrocarbon group which may have a substituent, a carboxyl group, a sulfo group, a hydroxyl group, a mercapto group, —NR c 2 , a cyano group or —C (═O). NR c 2 .
R ′ ″ is a trivalent hydrocarbon group which may have a substituent.
a3 is an integer of 1 or more. a4 is an integer of 0 or more.
R c is an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 50 carbon atoms, and each R c is It may be the same or different.
When a plurality of R ′ are present, each R ′ may be the same as or different from each other.
When a plurality of R ″ are present, each R ″ may be the same as or different from each other.
When a plurality of a4 are present, each a4 may be the same as or different from each other. )
The electronic device according to claim 1, wherein the structural unit is one or more structural units selected from the group consisting of a structural unit represented by formula (12) and a structural unit represented by formula (14).

(Where
R 1 is a monovalent group including a group represented by Formula (13).
Ar 1 is a (2 + n3) -valent aromatic group that may have a substituent other than R 1 .
n3 is an integer of 1 or more.
When several R < 1 > exists, each R < 1 > may mutually be same or different. )

(Where
R 2 is a (1 + m1 + m2) valent organic group.
Q 1 , Q 2 , Y 1 , M 1 , Z 1 , Y 2 , n1, a1, b1, and n2 have the same meaning as described above.
m1 and m2 are each independently an integer of 1 or more.
When a plurality of Q 1 are present, each Q 1 may be the same as or different from each other.
When a plurality of Q 2 are present, each Q 2 may be the same as or different from each other.
When a plurality of Y 1 are present, each Y 1 may be the same as or different from each other.
When a plurality of M 1 are present, each M 1 may be the same as or different from each other.
When a plurality of Z 1 are present, each Z 1 may be the same as or different from each other.
When a plurality of Y 2 are present, each Y 2 may be the same as or different from each other.
When a plurality of n1 are present, each n1 may be the same as or different from each other.
When a plurality of a1 are present, each a1 may be the same as or different from each other.
When a plurality of b1 are present, each b1 may be the same as or different from each other.
When a plurality of n2 are present, each n2 may be the same as or different from each other. )

(Where
R 3 is a monovalent group including a group represented by the formula (13) or a group represented by the formula (15).
R 4 is a monovalent group including a group represented by Formula (16).
Ar 2 is a (2 + n4 + n5) -valent aromatic group that may have a substituent other than R 3 and R 4 .
n4 and n5 are each independently an integer of 1 or more.
When a plurality of R 3 are present, each R 3 may be the same as or different from each other.
When a plurality of R 4 are present, each R 4 may be the same as or different from each other. )
-R 5 -{(Q 1 ) n 1 -Y 1 (M 1 ) a 1 (Z 1 ) b 1 } m 3 (15)
(Where
R 5 is a single bond or a (1 + m3) valent organic group.
Q 1 , Y 1 , M 1 , Z 1 , n1, a1 and b1 have the same meaning as described above.
m3 represents an integer of 1 or more. However, when R 5 is a single bond, m3 is 1.
When a plurality of Q 1 are present, each Q 1 may be the same as or different from each other.
When a plurality of Y 1 are present, each Y 1 may be the same as or different from each other.
When a plurality of M 1 are present, each M 1 may be the same as or different from each other.
When a plurality of Z 1 are present, each Z 1 may be the same as or different from each other.
When a plurality of n1 are present, each n1 may be the same as or different from each other.
When a plurality of a1 are present, each a1 may be the same as or different from each other.
When a plurality of b1 are present, each b1 may be the same as or different from each other. )
-R 6 -{(Q 2 ) n2 -Y 2 } m4 (16)
(Where
R 6 is a single bond or a (1 + m4) -valent organic group.
Q 2 , Y 2 and n2 have the same meaning as described above.
m4 is an integer of 1 or more. However, when R 6 is a single bond, m4 is 1.
When a plurality of Q 2 are present, each Q 2 may be the same as or different from each other.
When a plurality of Y 2 are present, each Y 2 may be the same as or different from each other.
When a plurality of n2 are present, each n2 may be the same as or different from each other. )
The (2 + n3) -valent aromatic group represented by Ar 1 is represented by the formula 1, 2, 4, 5, 6, 13 , 14 , 15 , 19, 21, 23, 31, 32, 33, 43, 46, 47. The electronic device according to claim 2, wherein the electronic device is a group obtained by removing (2 + n3) hydrogen atoms from the ring represented by 51.
The (2 + n4 + n5) -valent aromatic group represented by Ar 2 is represented by the formula 1, 2, 4, 5, 6, 13, 14, 15, 19, 21, 23, 31, 32, 33, 43, 46, 47. The electronic device according to claim 2, wherein the electronic device is a group obtained by removing (2 + n4 + n5) hydrogen atoms from the ring represented by 51.
The electronic device according to claim 1, comprising a layer containing the polymer compound as an electron injection layer and / or an electron transport layer.
The electronic device according to claim 1, which is an electroluminescent element.
Having one or more structural units selected from the group consisting of the structural unit represented by formula (12) and the structural unit represented by formula (14),
The ratio in which M 1 in the polymer compound is H + is greater than 0% and 50% or less with respect to all M 1 in the polymer compound.
High molecular compound.

(Where
R 1 is a monovalent group including a group represented by Formula (13).
Ar 1 is a (2 + n3) -valent aromatic group that may have a substituent other than R 1 .
n3 is an integer of 1 or more.
When several R < 1 > exists, each R < 1 > may mutually be same or different. )

(Where
R 2 is a (1 + m1 + m2) valent organic group.
Q 1 is a divalent organic group.
Q 2 is a divalent organic group.
Y 1 is —CO 2 − , —SO 3 − , —SO 2 − , —PO 3 2− or —B (R α ) 3 — .
M 1 is H +, a metal cation, or an ammonium cation which may have a substituent.
Z 1 represents F − , Cl − , Br − , I − , OH − , B (R a ) 4 − , R a SO 3 − , R a COO − , ClO − , ClO 2 − , ClO 3 − , ClO. 4 − , SCN − , CN − , NO 3 − , SO 4 2− , HSO 4 − , PO 4 3− , HPO 4 2− , H 2 PO 4 − , BF 4 − or PF 6 − .
Y 2 is a cyano group or a group represented by any one of formulas (3) to (11).
n1 is an integer of 0 or more. a1 is an integer of 1 or more. b1 is an integer of 0 or more. However, a1 and b1 are selected so that the charge of the group represented by the formula (1) becomes zero.
R α is an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent. Each R α may be the same as or different from each other.
R a is a monovalent organic group which may have a substituent. When a plurality of R a are present, each R a may be the same as or different from each other.
n2 is an integer of 0 or more.
m1 and m2 are each independently an integer of 1 or more.
When a plurality of Q 1 are present, each Q 1 may be the same as or different from each other.
When a plurality of Q 2 are present, each Q 2 may be the same as or different from each other.
When a plurality of Y 1 are present, each Y 1 may be the same as or different from each other.
When a plurality of M 1 are present, each M 1 may be the same as or different from each other.
When a plurality of Z 1 are present, each Z 1 may be the same as or different from each other.
When a plurality of Y 2 are present, each Y 2 may be the same as or different from each other.
When a plurality of n1 are present, each n1 may be the same as or different from each other.
When a plurality of a1 are present, each a1 may be the same as or different from each other.
When a plurality of b1 are present, each b1 may be the same as or different from each other.
When a plurality of n2 are present, each n2 may be the same as or different from each other. )

(Where
R 3 is a monovalent group including a group represented by the formula (13) or a group represented by the formula (15).
R 4 is a monovalent group including a group represented by Formula (16).
Ar 2 is a (2 + n4 + n5) -valent aromatic group that may have a substituent other than R 3 and R 4 .
n4 and n5 are each independently an integer of 1 or more.
When a plurality of R 3 are present, each R 3 may be the same as or different from each other.
When a plurality of R 4 are present, each R 4 may be the same as or different from each other. )
-R 5 -{(Q 1 ) n 1 -Y 1 (M 1 ) a 1 (Z 1 ) b 1 } m 3 (15)
(Where
R 5 is a single bond or a (1 + m3) valent organic group.
Q 1 , Y 1 , M 1 , Z 1 , n1, a1 and b1 have the same meaning as described above.
m3 represents an integer of 1 or more. However, when R 5 is a single bond, m3 is 1.
When a plurality of Q 1 are present, each Q 1 may be the same as or different from each other.
When a plurality of Y 1 are present, each Y 1 may be the same as or different from each other.
When a plurality of M 1 are present, each M 1 may be the same as or different from each other.
When a plurality of Z 1 are present, each Z 1 may be the same as or different from each other.
When a plurality of n1 are present, each n1 may be the same as or different from each other.
When a plurality of a1 are present, each a1 may be the same as or different from each other.
When a plurality of b1 are present, each b1 may be the same as or different from each other. )
-R 6 -{(Q 2 ) n2 -Y 2 } m4 (16)
(Where
R 6 is a single bond or a (1 + m4) -valent organic group.
Q 2 , Y 2 and n2 have the same meaning as described above.
m4 is an integer of 1 or more. However, when R 6 is a single bond, m4 is 1.
When a plurality of Q 2 are present, each Q 2 may be the same as or different from each other.
When a plurality of Y 2 are present, each Y 2 may be the same as or different from each other.
When a plurality of n2 are present, each n2 may be the same as or different from each other. )
The (2 + n3) -valent aromatic group represented by Ar 1 is represented by the formula 1, 2, 4, 5, 6, 13 , 14 , 15 , 19, 21, 23, 31, 32, 33, 43, 46, 47. The polymer compound according to claim 7, which is a group obtained by removing (2 + n3) hydrogen atoms from the ring represented by 51.
The (2 + n4 + n5) -valent aromatic group represented by Ar 2 is represented by the formula 1, 2, 4, 5, 6, 13, 14, 15, 19, 21, 23, 31, 32, 33, 43, 46, 47. The polymer compound according to claim 7, which is a group obtained by removing (2 + n4 + n5) hydrogen atoms from the ring represented by 51.
The high molecular compound of Claim 7 whose Y < 2 > is group represented by Formula (3) or Formula (4).
The method for producing a polymer compound according to claim 7, wherein a raw material containing a compound represented by the formula (21) and containing one or more ions is subjected to condensation polymerization.
Y 3 -A a -Y 4 (21)
(Where
A a is a divalent group including a group represented by the formula (1) and a group represented by the formula (2).
Y 3 and Y 4 are each independently a group involved in condensation polymerization. )
The method for producing a polymer compound according to claim 7, wherein a raw material containing a compound represented by the formula (21 ') and containing no ions is subjected to condensation polymerization, and a polymer compound containing ions is synthesized from the obtained compound.
Y 3 -A aa -Y 4 (21 ')
(Where
A aa is a divalent group including a group represented by the formula (22) and a group represented by the formula (2).
Y 3 and Y 4 are each independently a group involved in condensation polymerization. )
-R 7 -{(Q 3 ) n6 -Y 5 } m9 (22)
(Where
R 7 is a (1 + m9) valent organic group.
Q 3 represents a divalent organic group.
Y 5 is —CO 2 R χ , —SO 3 R χ , —SO 2 R χ , —PO 3 (R χ ) 2, or —B (R χ ) 2 .
n6 is an integer of 0 or more.
R χ is a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted aryl group having 6 to 50 carbon atoms.
m9 represents an integer of 1 or more.
When a plurality of Q 3 are present, each Q 3 may be the same as or different from each other.
When a plurality of Y 5 are present, each Y 5 may be the same as or different from each other.
When a plurality of n6 are present, each n6 may be the same as or different from each other.
When a plurality of R χ are present, each R χ may be the same as or different from each other. )