JP5372742B2 - Sulfo group-containing polymer compound and intermediate thereof, and organic electroluminescent device containing the compound - Google Patents

Abstract

A sulfonated polymeric compound, and its intermediate, which sulfonated polymeric compound is characterized by having the structure resulting from introduction of a sulfo group in a polymeric compound having, in its polymer chain, at least one of the repeating units represented by the general formula: (1) (wherein each of Z<SUP>1</SUP> to Z<SUP>4</SUP> is a substituent; each of p<SUP>1</SUP> and p<SUP>2</SUP> is an integer of 0 to 5; each of p<SUP>3</SUP> and p<SUP>4</SUP> is an integer of 0 to 4; each of X<SUP>1</SUP> to X<SUP>4</SUP> is a monovalent aromatic group, provided that X<SUP>1</SUP> and X<SUP>2</SUP>, and X<SUP>3</SUP> and X<SUP>4</SUP>, may be bonded with each other to thereby form a ring; Y is a bivalent aromatic group; each of Ar<SUP>1</SUP> to Ar<SUP>4</SUP> independently is a bivalent aromatic group, provided that the bivalent aromatic group may be an aromatic group resulting from bonding of aromatic groups to each other leading to cyclization; each of T<SUP>1</SUP> and T<SUP>2</SUP> independently is a single bond or a group selected from the group consisting of -(CH<SUB>2</SUB>)<SUB>t</SUB>-, -CH=CH-, -C=C-, -O-, -S-, -CQ<SUP>1</SUP>Q<SUP>2</SUP>-, -CO-, -SO-, -SO<SUB>2</SUB>- and -SiE<SUB>2</SUB>-; t is an integer of 1 to 20; each of Q<SUP>1</SUP> and Q<SUP>2</SUP> is an alkyl or an aromatic group, provided that these may be bonded with each other to thereby form a ring; E is a hydrogen atom, an alkyl or an aromatic group; and each of m and n is an integer of 0 to 2).

Description

  The present invention relates to a novel polymer compound containing a sulfo group and an intermediate thereof. Furthermore, this invention relates to the organic electroluminescent element containing this compound.

  In recent years, research and development of functional materials using organic compounds has been actively conducted. Recently, development of an organic electroluminescence element (organic electroluminescence element: organic EL element) using an organic compound as a constituent material of the element has been vigorously advanced.

  An organic electroluminescent device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode. By injecting electrons and holes into the thin film and recombining them, an exciton (Exington) ) And emits light using light emitted when the exciton is deactivated. The organic electroluminescent element can emit light at a low direct current voltage of several volts to several tens of volts, and various colors (for example, red, blue, green) can be selected by selecting the type of the fluorescent organic compound. ) Can be emitted. The organic electroluminescent device having such characteristics is expected to be applied to various light emitting devices and display devices.

  Recently, organic electroluminescence devices using conjugated light-emitting polymers as fluorescent organic compounds (polymer organic electroluminescence) as an advantageous material for large screen TV panels and flexible sheet displays due to the feature of patterning by printing methods. (Device: Polymer organic EL device) has been actively developed.

In an organic electroluminescent device, a light emitting layer is used alone or laminated between electrodes, and a hole transport layer and an electron transport layer are used. However, in order to improve the characteristics and life of the device, a positive layer is adjacent to the anode. It is common to use a hole injection layer. As a material (hole injection material) of the hole injection layer in the polymer organic electroluminescence device, a polythiophene derivative (poly (3,4-ethylenedioxythiophene): hereinafter referred to as PEDOT) which is a conductive polymer. A material (hereinafter, abbreviated as PEDOT / PSS) that is a dispersion containing poly (styrene sulfonic acid) (hereinafter referred to as PSS), which is a high molecular proton acid, and a sulfo group-containing triarylamine A polymer (Patent Document 2) and the like are known.
JP 2000-91081 A Chinese Patent Application No. 1827666

  Said PEDOT / PSS is the state of the dispersion liquid which has poor solubility with respect to an organic solvent, and uses water as a solvent. In organic electroluminescent elements, it is known that moisture causes problems such as short circuiting of the elements. However, since PEDOT / PSS uses water as a solvent, it is pointed out that handling is difficult at the time of element preparation. In addition, since PSS having a high molecular weight is excessively used relative to PEDOT, which is a conductive polymer, it has been pointed out that it is difficult to form a homogeneous thin film that is cohesive. Furthermore, an organic electroluminescent device having a hole injection layer using PEDOT / PSS is desired to be improved in efficiency and lifetime.

  In addition, the sulfo group-containing triarylamine polymer can be used as a solvent prepared by mixing one kind or several kinds of polar solvents such as methanol, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and water. However, the solubility in organic solvents is not always sufficient.

  Further, organic electroluminescent devices using a polymer compound have been desired to be further improved in terms of efficiency and lifetime.

  An object of the present invention is to provide a novel polymer compound suitable for an organic electroluminescent device, an intermediate thereof, and an organic electroluminescent device containing the compound.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that a high molecular compound having a novel tetraphenylthiophene skeleton containing a sulfo group is soluble in an organic solvent, has no cohesiveness, and forms a uniform thin film. It has been found that a long-life organic electroluminescence device can be obtained by using the compound, and the present invention has been completed.

That is, the present invention provides the following (1) to (21).
(1) In the repeating unit represented by the general formula (1), that Yusuke least one of repeating units of at least one of X 1 ^{to X} 4, ^Y and benzene ring is substituted by a sulfo group in the polymer chain sulfo group-containing polymer compound.

^(Wherein, Z 1 to Z ⁴ are ^.p 1 illustrating a substituent, ^{p 2} is an integer of 0 to ^{5, p 3,} p ⁴ is ^.X 1 to X ⁴ represents an integer of 0 to 4 monovalent X ¹ and X ² , X ³ and X ⁴ may be linked to each other to form a ring, Y represents a divalent aromatic group, and Ar ^{1 to} Ar ⁴ represent each other A divalent aromatic group which may be the same or different may be used, and these divalent aromatic groups may be aromatic groups in which aromatic groups are connected to each other to form a ring. ¹ and T ² are a single bond, — (CH ₂ ) _t —, —CH═CH—, —C≡C—, —O—, —S—, —CQ ¹ Q ² —, —CO—, —SO—. , —SO ₂ — and —SiE ₂ —, which may be the same or different from each other, t represents an integer of ¹ to 20. Q ¹ and Q ² are alkyl groups. Ma It represents an aromatic group, .m showing binding to optionally form a ring .E is hydrogen atom, an alkyl group or an aromatic group each other, n represents an integer of 0 to 2.)

（式中、Ｚ^１〜Ｚ^４、ｐ^１〜ｐ^４、Ｘ^１〜Ｘ^４、Ｙおよびｍ、ｎは前記のとおり。）
(2) In the repeating unit represented by the general formula (2), that the repeating units of at least one of X 1 ^{to X} 4, ^Y and benzene ring is substituted by a sulfo group Yusuke least one in the polymer chain ( 1) The sulfo group-containing polymer compound according to ( 1).

(In the formula, Z ^{1 to} Z ⁴ , p ^{1 to} p ⁴ , X ^{1 to} X ⁴ , Y, m, and n are as described above.)

(3) The sulfo group-containing polymer compound according to (1) or (2), wherein the group represented by Y is a group represented by the general formula (a-1).

Wherein Q is a group selected from the group consisting of a single bond, O, S, CH ₂ , CMe ₂ , CO, SO, SO ₂ , SiH ₂ , Si Me ₂ , and k is an integer of 0-2. Represents.)

(4) At least one of the p ^{1 to} p ⁴ is an integer of 1 or more, and the Z ^{1 to} Z ⁴ may be the same as or different from each other, and are each a carboxyl group, a hydroxyl group, an amino group, Monosubstituted amino group, disubstituted amino group, and general formulas (1a) to (3a):
-(O) _L -D (1a)
-O (C = O) -D (2a)
-(C = O) OD (3a)
(Wherein D is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted monovalent aromatic group having 4 to 12 carbon atoms, Any one of (1) to (3), which is a group selected from the group consisting of an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, and L represents 0 or 1) The sulfo group-containing polymer compound described in 1.

(5) The sulfo group-containing polymer compound according to any one of (1) to (3), wherein each of p ^{1 to} p ⁴ is 0.

The present invention also includes the following.
(6) An organic electroluminescent material comprising the sulfo group-containing polymer compound according to any one of (1) to (5).

(7) An organic electroluminescent element material, wherein the sulfo group-containing polymer compound according to any one of (1) to (5) can be used in a state dissolved in an organic solvent.

(8) The organic electroluminescent element material according to (7), wherein the organic solvent is a polar solvent.

(9) An organic electroluminescent device comprising at least one layer containing at least one layer containing the sulfo group-containing polymer compound according to any one of (1) to (5) between a pair of electrodes.

(10) The organic electroluminescent element according to (9), wherein the layer containing the sulfo group-containing polymer compound is a charge injection transport layer.

(11) The organic electroluminescence device according to (10), wherein the charge injection transport layer is a hole injection transport layer.

(12) The organic electroluminescent element according to (11), comprising at least two layers of the hole injecting and transporting layer.

(13) A polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain.

^(Wherein, Z 1 to Z ⁴ are ^.p 1 illustrating a substituent, ^{p 2} is an integer of 0 to ^{5, p 3,} p ⁴ is ^.X 1 to X ⁴ represents an integer of 0 to 4 monovalent X ¹ and X ² , X ³ and X ⁴ may be linked to each other to form a ring, Y represents a divalent aromatic group, and Ar ^{1 to} Ar ⁴ represent each other A divalent aromatic group which may be the same or different may be used, and these divalent aromatic groups may be aromatic groups in which aromatic groups are connected to each other to form a ring. ¹ and T ² are a single bond, — (CH ₂ ) _t —, —CH═CH—, —C≡C—, —O—, —S—, —CQ ¹ Q ² —, —CO—, —SO—. , —SO ₂ — and —SiE ₂ —, which may be the same or different from each other, t represents an integer of ¹ to 20. Q ¹ and Q ² are alkyl groups. Ma It represents an aromatic group, .m showing binding to optionally form a ring .E is hydrogen atom, an alkyl group or an aromatic group each other, n represents an integer of 0 to 2.)

(14) The polymer compound according to (13), wherein the polymer chain has at least one repeating unit represented by the general formula (2).

（式中、Ｚ^１ 〜Ｚ^４、ｐ^１〜ｐ^４、Ｘ^１ 〜Ｘ^４、Ｙおよびｍ、ｎは前記のとおり。）

(In the formula, Z ^{1 to} Z ⁴ , p ^{1 to} p ⁴ , X ^{1 to} X ⁴ , Y, m, and n are as described above.)

(15) An organic electroluminescent element material comprising the polymer compound according to (13) or (14).

(16) An organic electroluminescent element material which can be used in a state where the polymer compound according to (13) or (14) is dissolved in an organic solvent.

(17) An organic electroluminescence device comprising at least one layer containing at least one layer of the polymer compound described in (13) or (14) between a pair of electrodes.

(18) The organic electroluminescence device according to (17), wherein the layer containing the polymer compound is a charge injection transport layer.

(19) The organic electroluminescence device according to (18), wherein the charge injection transport layer is a hole injection transport layer.

(20) The organic electroluminescence device according to (19), comprising at least two layers of the hole injecting and transporting layer.

(21) At least one layer containing at least one sulfo group-containing polymer compound described in (1) is sandwiched, and at least one layer containing at least one polymer compound described in (13) is sandwiched. Organic electroluminescent device.

  According to the present invention, it is possible to provide a polymer compound that is soluble in an organic solvent, has no cohesiveness, and can form a uniform thin film. Further, by using the compound, high efficiency and long life can be obtained. A long-life organic electroluminescent device can be obtained.

  The above-described object and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element.

  Hereinafter, the present invention will be described in detail.

The sulfo group-containing polymer compound of the present invention has a structure in which a sulfo group is introduced into a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain. The polymer compound having at least one repeating unit represented by 1) in the polymer chain is a useful intermediate (hereinafter referred to as “intermediate polymer compound”).
General formula (1):

^(Wherein, Z 1 to Z ⁴ are ^.p 1 illustrating a substituent, ^{p 2} is an integer of 0 to ^{5, p 3,} p ⁴ is ^.X 1 to X ⁴ represents an integer of 0 to 4 monovalent X ¹ and X ² , X ³ and X ⁴ may be linked to each other to form a ring, Y represents a divalent aromatic group, and Ar ^{1 to} Ar ⁴ represent each other A divalent aromatic group which may be the same or different may be used, and these divalent aromatic groups may be aromatic groups in which aromatic groups are connected to each other to form a ring. ¹ and T ² are a single bond, — (CH ₂ ) _t —, —CH═CH—, —C≡C—, —O—, —S—, —CQ ¹ Q ² —, —CO—, —SO—. , —SO ₂ — and —SiE ₂ —, which may be the same or different from each other, t represents an integer of ¹ to 20. Q ¹ and Q ² are alkyl groups. Ma It represents an aromatic group, .m showing binding to optionally form a ring .E is hydrogen atom, an alkyl group or an aromatic group each other, n represents an integer of 0 to 2.)

  The number of sulfo groups is not particularly limited, but the average number of sulfo groups per repeating unit is 0.1 to 20, preferably 0.5 to 10, more preferably 1 to 8. is there.

In the general formula (1), when at least one of p ^{1 to} p ⁴ is an integer of 1 or more, the substituents represented by Z ^{1 to} Z ⁴ may be the same as or different from each other. Carboxyl group, hydroxyl group, amino group, monosubstituted amino group, disubstituted amino group, and general formulas (1a) to (3a):

-(O) _L -D (1a)
-O (C = O) -D (2a)
-(C = O) OD (3a)

(Wherein D is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted monovalent aromatic group having 4 to 12 carbon atoms, An unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, and L represents 0 or 1).

Among the substituents represented by Z ^{1 to} Z ⁴ , D is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and D is an unsubstituted or substituted carbon. Preferable examples and specific examples of the aralkyl group of 7 to 20 include X ^{1 to} X ⁴ in the general formula (1) and Ar ^a1 and Ar ^a2 aromatic hydrocarbon groups in the general formula (a-2), or aromatic And the same as D ′ described later as a substituent on the group heterocyclic group.

  The aromatic group of D includes a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group. These groups may be unsubstituted or substituted. In the case where these groups are unsubstituted or substituted aromatic hydrocarbon groups, the number of carbon atoms constituting the ring of the group is preferably 6 to 12. On the other hand, when these groups are unsubstituted or substituted aromatic heterocyclic groups, the number of carbon atoms constituting the ring of the group is preferably 4 to 12.

  Specific examples of the aromatic hydrocarbon group or aromatic heterocyclic group of D include phenyl group, 1-naphthyl group, 2-naphthyl group, 5-acenaphthylenyl group, 4-quinolyl group, 2-quinolyl group, 4-pyridyl group. Group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrazinyl group, 3-furyl group, 2-furyl group Group, 2-benzofuryl group, 4-dibenzofuranyl group, 2-dibenzofuranyl group, 3-thienyl group, 2-thienyl group, dibenzothiophen-4-yl group, dibenzothiophen-2-yl group, 2-oxazolyl Group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, carbazol-3-yl group, 2-phenyl group Group, 3-phenylphenyl group, 4-phenylphenyl group, and the like.

  Examples of the substituent on the aromatic group of D include a halogen atom, a linear, branched or cyclic alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A linear, branched or cyclic alkyl group may be unsubstituted or substituted. As an alkyl group, a C1-C16 thing is preferable and a C1-C8 thing is more preferable. Specific examples of the unsubstituted or substituted linear, branched or cyclic alkyl group include those shown as the alkyl group of D ′ described later.

Specific examples of the monosubstituted amino group and disubstituted amino group of Z ^{1 to} Z ⁴ include, for example, N-methylamino group, N-ethylamino group, N-phenylamino group, N- (1-naphthyl) amino group. N- (2-naphthyl) amino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-diphenylamino group, N, N-di (1-naphthyl) amino group, N, N -Di (2-naphthyl) amino group, 9H-carbazol-9-yl group, 10H-phenothiazin-10-yl group, 10H-phenoxazin-10-yl group, N-phenyl-N- (1-naphthyl) amino Group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N- (1-anthracenyl) amino group, N-phenyl-N- (9-anthracenyl) amino group, N-phenyl-N- (1 Phenanthryl) amino group, N-phenyl-N- (2-phenanthryl) amino group, N-phenyl-N- (3-phenanthryl) amino group, N-phenyl-N- (4-phenanthryl) amino group, N-phenyl -N- (9-phenanthryl) amino group, N-phenyl-N- (1-pyrenyl) amino group, N-phenyl-N- (2-pyrenyl) amino group, N-phenyl-N- (4-pyrenyl) Amino group, N-phenyl-N- (2-fluorenyl) amino group, N-phenyl-N- (5-acenaphthylenyl) amino group, N-phenyl-N- (3-fluoranthenyl) amino group, N-phenyl -N- (1-triphenylenyl) amino group, N-phenyl-N- (2-triphenylenyl) amino group, N-phenyl-N- (1-naphthacenyl) amino group, N Phenyl-N- (2-naphthacenyl) amino group, N-phenyl-N- (9-naphthacenyl) amino group, N-phenyl-N- (3-perylenyl) amino group, N-phenyl-N- (4-quinolyl) ) Amino group, N-phenyl-N- (2-quinolyl) amino group, N-phenyl-N- (2-pyridyl) amino group, N-phenyl-N- (3-pyridyl) amino group, N-phenyl- N- (4-pyridyl) amino group, N-phenyl-N- (2-pyrimidyl) amino group, N-phenyl-N- (3-thienyl) amino group, N-phenyl-N- (2-phenylphenyl) Amino group, N-phenyl-N- (3-phenylphenyl) amino group, N-phenyl-N- (4-phenylphenyl) amino group, N, N-bis [4- (diphenylamino) phenyl] amino group, N, N Bis [3- (diphenylamino) phenyl] amino group, N, N-bis [4- {N′-phenyl-N ′-(2-naphthyl) amino} phenyl] amino group, N, N-bis [3- { N′-phenyl-N ′-(2-naphthyl) amino} phenyl] amino group, N, N-bis [4- {N′-phenyl-N ′-(1-naphthyl) amino} phenyl] amino group, N, N -Bis [3- {N'-phenyl-N '-(1-naphthyl) amino} phenyl] amino group, N, N-bis [4- (9H-carbazol-9-yl) phenyl] amino group, N, N -Bis [3- (9H-carbazol-9-yl) phenyl] amino group, N, N-bis (4-sulfophenyl) amino group, N, N-bis [1- (8-sulfonaphthyl] amino group, N, N-di [2- (8-sulfonaphthyl)] amino group, N- (4-sulfophenyl) -N- [ 1- (8-sulfonaphthyl)] amino group, N- (4-sulfophenyl) -N- [2- (8-sulfonaphthyl)] amino group, 3,6-disulfo-9H-carbazol-9-yl group N, N-bis [4- {bis (4′-sulfophenyl) amino} phenyl] amino group, N, N-bis [4- (3,6-disulfo-9H-carbazol-9-yl) phenyl] amino Group, N, N-bis (4-methylphenyl) amino group, N, N-bis (4-ethylphenyl) amino group, N, N-bis (4-n-propylphenyl) amino group, N, N- Bis (4-iso-propylphenyl) amino group, N, N-bis (4-n-butylphenyl) amino group, N, N-bis (4-iso-butylphenyl) amino group, N, N-bis ( 4-sec-butylphenyl) amino group, N, N-bis (4-tert Butylphenyl) amino group, N, N-bis (4-n-pentylphenyl) amino group, N, N-bis (4-iso-pentylphenyl) amino group, N, N-bis (4-neopentylphenyl) Amino group, N, N-bis (4-tert-pentylphenyl) amino group, N, N-bis (4-n-hexylphenyl) amino group, N, N-bis [4- (1-methylpentyl) phenyl ] Amino group, N, N-bis [4- (4-methyl-2-pentyl) phenyl] amino group, and the like.

p ¹ ~p ⁴ is preferably 0 to 2 integer, more preferably an integer of 0-1. Moreover, it is preferable that Z < ¹ > -Z < ⁴ > is respectively the same substituent, and each of p < ¹ > -p < ⁴ > is the same integer.
Alternatively, p ^{1 to} p ⁴ may be zero.

In the general formula (1), X ^{1 to} X ⁴ independently represent a monovalent aromatic group, and include a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group. These groups may be unsubstituted or substituted, and X ¹ and X ² , X ³ and X ⁴ may be linked to each other to form a ring. In the case where these groups are unsubstituted or substituted aromatic hydrocarbon groups, the number of carbon atoms constituting the ring of the group is preferably 6 to 30, and more preferably 6 to 20 carbon atoms. On the other hand, when these groups are unsubstituted or substituted aromatic heterocyclic groups, the number of carbon atoms constituting the ring of the group is preferably 3 to 30, and more preferably 3 to 20 carbon atoms. X ^{1 to} X ⁴ may be the same group or different groups.

Specific examples of the aromatic hydrocarbon group or aromatic heterocyclic group represented by X ^{1 to} X ⁴ include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, and 9-anthracenyl. Group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 2-fluoro-9-phenanthryl group, 1-biphenyleneyl group, 2-biphenyleneyl group, 1- Pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 5-acenaphthylenyl group, 3-fluoranthenyl group, 1-triphenylenyl group, 2-triphenylenyl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 3-perylenyl group, 4-quinolyl group, 2-quinolyl group, 4-pyridyl group, - pyridyl, 2-pyridyl, 2-pyrimidyl, 4-pyrimidyl group, 5-pyrimidyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrazinyl group,

  3-furyl group, 2-furyl group, 2-benzofuryl group, 4-dibenzofuranyl group, 2-dibenzofuranyl group, 3-thienyl group, 2-thienyl group, dibenzothiophen-4-yl group, dibenzothiophene- 2-yl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzoimidazolyl group, carbazol-3-yl group, 2-phenylphenyl group, 3-phenylphenyl Group, 4-phenylphenyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m- A terphenyl-3-yl group etc. can be mentioned.

X ¹ and X ² , X ³ and X ⁴ may be connected to each other to form a ring. Specific examples of the case where X ¹ and X ² , X ³ and X ⁴ are linked to each other to form a ring include, for example, 9H-carbazol-9-yl group, 10H-phenothiazin-10-yl group, 5H-dibenz [ and b, f] azepine-5-yl group.

In addition, the monovalent aromatic group of X ^{1 to} X ⁴ includes a group represented by the general formula (a-2).

(In the formula, Ar ^a1 and Ar ^a2 represent a monovalent aromatic group and may be linked to each other to form a ring. J represents an integer of 1 to 2)
Ar ^a1 and Ar ^a2 independently represent a monovalent aromatic group, and the monovalent aromatic group may be unsubstituted or substituted.

The monovalent aromatic group for Ar ^a1 and Ar ^a2 includes a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group. These groups may be unsubstituted or substituted, and may be connected to each other to form a ring. In the case where these groups are unsubstituted or substituted aromatic hydrocarbon groups, the number of carbon atoms constituting the ring of the group is preferably 6 to 30, and more preferably 6 to 20 carbon atoms. On the other hand, when these groups are unsubstituted or substituted aromatic heterocyclic groups, the number of carbon atoms constituting the ring of the group is preferably 3 to 30, and more preferably 3 to 20 carbon atoms. Ar ^a1 and Ar ^a2 may be the same group or different groups.

Specific examples of the aromatic hydrocarbon group or the aromatic heterocyclic group of Ar ^a1 and Ar ^a2 include those shown as specific examples of X ^{1 to} X ⁴ . Of these specific examples, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-phenanthryl group are preferable.

Ar ^a1 and Ar ^a2 may be connected to each other to form a ring. Specific examples in the case where Ar ^a1 and Ar ^a2 are linked to each other to form a ring include, for example, 9H-carbazol-9-yl group, 10H-phenothiazin-10-yl group, 5H-dibenz [b, f] azepine- A 5-yl group etc. can be mentioned.

Examples of the substituent on the aromatic hydrocarbon group or aromatic heterocyclic group of X ^{1 to} X ⁴ and the substituent on the aromatic hydrocarbon group or aromatic heterocyclic group of Ar ^a1 and Ar ^a2 include a carboxyl group, Hydroxyl group, amino group, monosubstituted amino group, disubstituted amino group, and general formulas (1′a) to (3′a):

-(O) _L'- D '(1'a)
-O (C = O) -D '(2'a)
-(C = O) OD '(3'a)

(In the formula, D 'is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an unsubstituted or substituted monovalent aromatic group having 4 to 12 carbon atoms. An unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, L ′ represents 0 or 1, and a group represented by the general formula (1′a) Is preferred. As the group represented by the general formula (1′a), L ′ is preferably 0. The substitution positions of the substituents on the aromatic hydrocarbon group or aromatic heterocyclic group of X ^{1 to} X ⁴ and the substituents on the aromatic hydrocarbon group or aromatic heterocyclic group of Ar ^a1 and Ar ^a2 are particularly limited. Not. Moreover, although the number of substitution is not restrict | limited, Preferably it is 0-5.

  Specific examples of the unsubstituted or substituted linear, branched or cyclic alkyl group for D ′ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, s ec -Butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2- Ethylbutyl group, 2-ethylhexyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-propylpentyl group, 2,2-dimethylhexyl group, 2,6-dimethyl- 4-hexyl group, 3,5,5-trimethylpentyl group,

  Cyclohexyl group, cyclohexylmethyl group, cyclopentyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, 1,1-dimethylhexyl group, 1-norbornyl group, 2-norbornanemethyl group, cyclobutyl group, 1-methylcyclopentyl group 4-methylcyclohexyl group, 3-methylcyclohexyl group, 2-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group 3,5-dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group,

  Methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, n-octyloxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-iso-propoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2 -(2'-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2'-ethylhexyloxy) ethyl group, 2-cyclohexyloxyethyl group, 2 -Methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group,

  3-n-propoxypropyl group, 3-iso-propoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- ( 2'-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2'-ethylhexyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group 4-n-propoxybutyl group, 4-iso-propoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 5-methoxypentyl group, 5 -Ethoxypentyl group, 5-n-ethoxypentyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl Le group, 6-n-hexyloxy-hexyl group, 4-methoxy cyclohexyl group, 7-ethoxy-heptyl group, a 7-isopropoxy-heptyl group, 8-methoxy-octyl group, a tetrahydrofurfuryl group,

  2- (2′-methoxyethoxy) ethyl group, 2- (2′-ethoxyethoxy) ethyl group, 2- (2′-n-butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group, 2-allyloxyethyl group, 2- (4′-pentenyloxy) ethyl group, 3-allyloxypropyl group, 3- (2′-hexenyloxy) propyl group, 3- (2′-heptenyloxy) propyl group, 3 -(1'-cyclohexenyloxy) propyl group, 4-allyloxybutyl group, benzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4'-methylbenzyloxy) ethyl group 2- (2′-methylbenzyloxy) ethyl group, 2- (4′-fluorobenzyloxy) ethyl group, 2- (4′-chlorobenzyloxy) ethyl group, 3- Emissions Jill propyl group, 3- (4'-methoxybenzyl) propyl group, 4-benzyloxy-butyl group, 2- (benzyloxy) ethyl group, 2- (4'-methyl-benzyloxy) ethyl group,

  Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyloxymethyl group Group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxyphenyl) Oxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-naphthyloxy) ) Ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyloxy Xylbutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert-butylphenyloxy) pentyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 2- (2′-phenyloxyethoxy) ethyl group, 3- (2′-phenyloxyethoxy) propyl group, 4- (2′-phenyloxyethoxy) butyl group,

  n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octyl Thioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, 2- (2 ′ -Methoxyethylthio) ethyl group, 4- (3'-ethoxypropylthio) butyl group, 2- (2'-ethylthioethylthio) ethyl group, 2-allylthioethyl group, 2 Benzylthioethyl group, 3- (4′-methylbenzylthio) propyl group, 4-benzylthiobutyl group, 2- (2′-benzyloxyethylthio) ethyl group, 3- (3′-benzylthiopropylthio) Propyl group, 2-phenylthioethyl group, 2- (4′-methoxyphenylthio) ethyl group, 2- (2′-phenyloxyethylthio) ethyl group, 3- (2′-phenylthioethylthio) propyl group ,

  2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 6-hydroxyhexyl group, 5-hydroxyheptyl group, 8-hydroxyoctyl group, 2- Examples thereof include a hydroxycyclohexyl group.

  The aromatic group for D ′ includes a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group. These groups may be unsubstituted or substituted. In the case where these groups are unsubstituted or substituted aromatic hydrocarbon groups, the number of carbon atoms constituting the ring of the group is preferably 6 to 12. On the other hand, when these groups are unsubstituted or substituted aromatic heterocyclic groups, the number of carbon atoms constituting the ring of the group is preferably 4 to 12.

  Specific examples of the aromatic hydrocarbon group or aromatic heterocyclic group for D ′ include phenyl group, 1-naphthyl group, 2-naphthyl group, 5-acenaphthylenyl group, 4-quinolyl group, 2-quinolyl group, 4- Pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrazinyl group, 3-furyl group, 2- Furyl group, 2-benzofuryl group, 4-dibenzofuranyl group, 2-dibenzofuranyl group, 3-thienyl group, 2-thienyl group, dibenzothiophen-4-yl group, dibenzothiophen-2-yl group, 2- Oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, carbazol-3-yl group, 2-phenylphenol Examples include an phenyl group, a 3-phenylphenyl group, and a 4-phenylphenyl group.

  Examples of the substituent on the aromatic group of D ′ include a halogen atom, a linear, branched or cyclic alkyl group.

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

  A linear, branched or cyclic alkyl group may be unsubstituted or substituted. As an alkyl group, a C1-C16 thing is preferable and a C1-C8 thing is more preferable. Specific examples of the unsubstituted or substituted linear, branched or cyclic alkyl group include those shown as the unsubstituted or substituted linear, branched or cyclic alkyl group for D ′. Can be mentioned.

  Specific examples of the unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms of D ′ include benzyl group, α-methylbenzyl group, α-ethylbenzyl group, phenethyl group, α-methylphenethyl group, β-methyl. Phenethyl group, α, α-dimethylbenzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl group, 4-ethylbenzyl group, 2 -Ethylbenzyl group, 4-isopropylbenzyl group, 4-tert-butylbenzyl group, 2-tert-butylbenzyl group, 4-tert-pentylbenzyl group, 4-cyclohexylbenzyl group, 4-n-octylbenzyl group, 4 -Tert-octylbenzyl group, 4-allylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4-phenylbenzyl Group, 4- (4′-methylphenyl) benzyl group, 4-methoxybenzyl group, 2-methoxybenzyl group, 2-ethoxybenzyl group, 4-n-butoxybenzyl group, 4-n-heptyloxybenzyl group, 4 -N-decyloxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group,

  3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-isobutoxymethylbenzyl group, 4-allyloxybenzyl group, 4-vinyloxymethylbenzyl group, 4-benzyloxybenzyl group, 4-phenethyloxybenzyl Group, 4-phenyloxybenzyl group, 3-phenyloxybenzyl group, 4-hydroxybenzyl group, 3-hydroxybenzyl group, 2-hydroxybenzyl group, 4-hydroxy-3-methoxybenzyl group, 4-fluorobenzyl group, 2-fluorobenzyl group, 4-chlorobenzyl group, 3-chlorobenzyl group, 2-chlorobenzyl group, 3,4-dichlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthyl A methyl group etc. can be mentioned.

  The substituent of the mono-substituted amino group or the di-substituted amino group is an unsubstituted or substituted linear, branched or cyclic alkyl group. As this alkyl group, a C1-C16 thing is preferable and a C1-C8 thing is more preferable. Specific examples of the alkyl group include those shown as the alkyl group for D ′.

  Specific examples of the mono-substituted amino group and di-substituted amino group include, for example, N-methylamino group, N-ethylamino group, N-phenylamino group, N- (1-naphthyl) amino group, N- (2- Naphthyl) amino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-diphenylamino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) ) Amino group, 9H-carbazol-9-yl group, 10H-phenothiazin-10-yl group, 10H-phenoxazin-10-yl group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl- N- (2-naphthyl) amino group, N-phenyl-N- (1-anthracenyl) amino group, N-phenyl-N- (9-anthracenyl) amino group, N-phenyl-N- (1-phenanthri ) Amino group, N-phenyl-N- (2-phenanthryl) amino group, N-phenyl-N- (3-phenanthryl) amino group, N-phenyl-N- (4-phenanthryl) amino group, N-phenyl- N- (9-phenanthryl) amino group, N-phenyl-N- (1-pyrenyl) amino group, N-phenyl-N- (2-pyrenyl) amino group, N-phenyl-N- (4-pyrenyl) amino group Group, N-phenyl-N- (2-fluorenyl) amino group, N-phenyl-N- (5-acenaphthylenyl) amino group, N-phenyl-N- (3-fluoranthenyl) amino group, N-phenyl- N- (1-triphenylenyl) amino group, N-phenyl-N- (2-triphenylenyl) amino group, N-phenyl-N- (1-naphthacenyl) amino group, N-phenyl-N (2-naphthacenyl) amino group, N-phenyl-N- (9-naphthacenyl) amino group, N-phenyl-N- (3-perylenyl) amino group, N-phenyl-N- (4-quinolyl) amino group, N-phenyl-N- (2-quinolyl) amino group, N-phenyl-N- (2-pyridyl) amino group, N-phenyl-N- (3-pyridyl) amino group, N-phenyl-N- (4 -Pyridyl) amino group, N-phenyl-N- (2-pyrimidyl) amino group, N-phenyl-N- (3-thienyl) amino group, N-phenyl-N- (2-phenylphenyl) amino group, N -Phenyl-N- (3-phenylphenyl) amino group, N-phenyl-N- (4-phenylphenyl) amino group, N, N-bis [4- (diphenylamino) phenyl] amino group, N, N- Screw [3- (Di Phenylamino) phenyl] amino group, N, N-bis [4- {N′-phenyl-N ′-(2-naphthyl) amino} phenyl] amino group, N, N-bis [3- {N′-phenyl-N '-(2-naphthyl) amino} phenyl] amino group, N, N-bis [4- {N'-phenyl-N'-(1-naphthyl) amino} phenyl] amino group, N, N-bis [3- {N′-phenyl-N ′-(1-naphthyl) amino} phenyl] amino group, N, N-bis [4- (9H-carbazol-9-yl) phenyl] amino group, N, N-bis [3- (9H-carbazol-9-yl) phenyl] amino group, N, N-bis (4-sulfophenyl) amino group, N, N-bis [1- (8-sulfonaphthyl] amino group, N, N-di [2- (8-sulfonaphthyl)] amino group, N- (4-sulfophenyl) -N- [1- (8-sulfur) Fonaphthyl)] amino group, N- (4-sulfophenyl) -N- [2- (8-sulfonaphthyl)] amino group, 3,6-disulfo-9H-carbazol-9-yl group, N, N-bis [4- {Bis (4′-sulfophenyl) amino} phenyl] amino group, N, N-bis [4- (3,6-disulfo-9H-carbazol-9-yl) phenyl] amino group, N, N— Bis (4-methylphenyl) amino group, N, N-bis (4-ethylphenyl) amino group, N, N-bis (4-n-propylphenyl) amino group, N, N-bis (4-iso- Propylphenyl) amino group, N, N-bis (4-n-butylphenyl) amino group, N, N-bis (4-iso-butylphenyl) amino group, N, N-bis (4-sec-butylphenyl) ) Amino group, N, N-bis (4-tert-butylpheny) ) Amino group, N, N-bis (4-n-pentylphenyl) amino group, N, N-bis (4-iso-pentylphenyl) amino group, N, N-bis (4-neopentylphenyl) amino group N, N-bis (4-tert-pentylphenyl) amino group, N, N-bis (4-n-hexylphenyl) amino group, N, N-bis [4- (1-methylpentyl) phenyl] amino Group, N, N-bis [4- (4-methyl-2-pentyl) phenyl] amino group, and the like.

  In the general formula (1), Y is preferably a divalent aromatic group having 4 to 90 carbon atoms.

As the group represented by —Y—, the general formula (1b):
-A- (BA) u- (1b)
(In the formula, A represents a divalent aromatic group, and —B— represents a single bond, an alkylene group, —O—, —S—, —CO—, —SO—, —SO ₂ —, —SiH _2. -And -SiMe _2- , and u represents an integer of 0 to 2.). A may be linked to each other to form a ring.
u is preferably an integer of 0 to 1.

  A is preferably a divalent aromatic group having 4 to 60 carbon atoms, and includes a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group.

  The divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group of A may be unsubstituted or substituted. When the group is an unsubstituted or substituted aromatic hydrocarbon group, the group preferably has 6 to 30 carbon atoms. On the other hand, when the group is an unsubstituted or substituted aromatic heterocyclic group, the group preferably has 4 to 30 carbon atoms.

Examples of the substituent on the substituted divalent aromatic hydrocarbon group or aromatic heterocyclic group of A include the aromatic hydrocarbon group of X ^{1 to} X ⁴ or the aromatic heterocyclic group in the general formula (1) Examples are the same as the above substituents.

  Examples of the divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group represented by A include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, and 2,5-thiophene. Diyl group, 3,4-thiophenediyl group, 2,5-furandiyl group, 3,4-furandiyl group, 2,5-pyrrolidiyl group, 3,4-pyrrolediyl group, 2,5-pyridylyl group, 2, 6-pyridinediyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-fluorenediyl group, 3,6 -Fluorenediyl group, 2,7-carbazolediyl group, 3,6-carbazolediyl group, 4,5-carbazolediyl group, 2,8-dibenzothiophenediyl group, 3,7-dibenzothiophenediyl group, 1, 8-pi Njiiru group, 6,12 Kurisenjiiru group, 1,7-perylenediyl group, 2,8-dibenzofuran-diyl group, 3,7-dibenzofuran-diyl group, the general formula (1b-1),

And a group represented by the general formula (1b-2)

The group etc. which are represented by these can be mentioned.
Examples of the divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group of A include 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthalenediyl group, and 1,5-naphthalenediyl group. Group, 2,7-fluorenediyl group, 9,10-anthracenediyl group, 1,8-pyrenediyl group, 2,7-carbazoldiyl group, 3,7-dibenzothiophenediyl group, 3,7-dibenzofurandiyl group And the general formula (1b-1)

The group represented by these is preferable.
The alkylene group represented by -B- may be unsubstituted or substituted. The unsubstituted or substituted alkylene group is a linear, branched or cyclic alkylene group.

  As an alkylene group, a C1-C6 alkylene group is preferable and a C1-C3 alkylene group is more preferable.

  Specific examples of the unsubstituted or substituted alkylene group include, for example, a methylene group, an ethylene group, a propylene group, a 1,1-cyclopropylene group, a 1,2-cyclopropylene group, a 1,1-cyclobutylene group, , 1-cyclopentylene group, 1,2-cyclopentylene group, 1,1-cyclohexylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 3-methyl-1, 1-cyclohexylene group, 3,3,5-trimethyl-1,1-cyclohexylene group, 1,1-cycloheptylene group, 1,1-diphenylmethylene group, 1,1-dibenzylmethylene group, A 9,9-fluorenylene group can be exemplified.

Examples of the substituent on the alkylene group include an alkyl group, an aromatic group, and an aralkyl group.
The alkyl group on the alkylene group is an unsubstituted or substituted linear, branched or cyclic alkyl group. Specific examples include methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso -Pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, 2-ethylhexyl group, n-heptyl group, 1-methyl Hexyl group, n-octyl group, 1-methylheptyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5- Trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-dodecyl group, 1-methyldecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n Pentadecyl group, 1-hexyloctyl group, n-hexadecyl group, cyclohexyl group, cyclohexylmethyl group, (1-isopropylcyclohexyl) methyl group, (2-isopropylcyclohexyl) ethyl group, cyclopentyl group, 2-ethylbutyl group, 3, 3 -Dimethylbutyl group, 1,1-dimethylhexyl group, bornel group, isobornel group, 1-norbornyl group, 2-norbornanemethyl group, 1-bicyclo [2.2.2] octyl group, 1-adamantyl group, 3- Noradamantyl group, 1-adamantylmethyl group, cyclobutyl group, 1-methylcyclopentyl group, 4-methylcyclohexyl group, 3-methylcyclohexyl group, 2-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethyl Cyclohexyl group, 2,6 -Dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 2,6-diisopropylcyclohexyl group, 4 Examples include -tert-butylcyclohexyl group, 3-tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, and cyclotetradecyl group.

  The aromatic group on the alkylene group includes an unsubstituted or substituted aromatic hydrocarbon group or aromatic heterocyclic group. As the unsubstituted or substituted aromatic hydrocarbon group, those having 6 to 30 carbon atoms constituting the ring are preferable. As the unsubstituted or substituted aromatic heterocyclic group, those having 4 to 30 carbon atoms constituting the ring are preferable.

Examples of the aromatic hydrocarbon group or the aromatic heterocyclic group include those shown as specific examples of X ^{1 to} X ⁴ .

Examples of the substituent on the aromatic hydrocarbon group or aromatic heterocyclic group include those similar to the substituents on the aromatic hydrocarbon group of X ^{1 to} X ⁴ or the aromatic heterocyclic group in the general formula (1). Can be mentioned.

  The aralkyl group on the alkylene group is preferably an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms. Specific examples of the aralkyl group include those shown as the aralkyl group for D ′.

In the general formula (1), Ar ^{1 to} Ar ⁴ represent an unsubstituted or substituted divalent aromatic group which may be the same or different from each other, and represent a divalent aromatic hydrocarbon group or a divalent group. Of the aromatic heterocyclic group. Preferably, the group represented by Ar ^{1 to} Ar ⁴ is a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic heterocyclic group having 4 to 30 carbon atoms. Ar ^{1 to} Ar ⁴ are preferably the same group, and more preferably the same aromatic hydrocarbon group.

In the general formula (1), examples of the group represented by Ar ^{1 to} Ar ⁴ include the same divalent aromatic groups as those in Y in the general formula (1), preferably represented by —Y—. And a group represented by -A- or -AA-, wherein u is an integer of 0 to 1 and B is a single bond and Y in general formula (1b). A may be linked to each other to form a ring.

As the divalent aromatic group for Ar ^{1 to} Ar ⁴ , the general formula (a-3)

(In the formula, v represents an integer of 0 to 2.)
Is more preferable, and it is more preferable that v is an integer of 0 to 1.

In the general formula (1), T ¹ and T ² are a single bond, — (CH ₂ ) _t —, —CH═CH—, —C≡C—, —O—, —S—, —CQ ¹ Q ² —. , —CO—, —SO—, —SO ₂ —, —SiE ₂ —, which may be the same as or different from each other, a single bond, —CH═CH—, — A group represented by C≡C—, —O—, —S—, —CQ ¹ Q ² — is more preferable. t shows the integer of 1-20, and the integer of 1-10 is preferable. Q ¹ and Q ² represent an alkyl group or an aromatic group, and may be bonded to each other to form a ring. E represents a hydrogen atom, an alkyl group or an aromatic group.

Specific examples of the alkyl group of Q ¹ and Q ² include those shown as specific examples of the alkyl group on the alkylene group represented by the above -B-.

The aromatic group of Q ¹ and Q ² includes an unsubstituted or substituted aromatic hydrocarbon group or aromatic heterocyclic group. As the unsubstituted or substituted aromatic hydrocarbon group, those having 6 to 30 carbon atoms constituting the ring are preferable. As the unsubstituted or substituted aromatic heterocyclic group, those having 4 to 30 carbon atoms constituting the ring are preferable.

Examples of the aromatic hydrocarbon group or the aromatic heterocyclic group include those shown as specific examples of X ^{1 to} X ⁴ .

Specific examples of the alkyl group of E can include those shown as specific examples of the alkyl groups of Q ¹ and Q ² , and examples of the aromatic group of E include the specific examples of the aromatic groups of Q ¹ and Q ² The examples given can be mentioned.

Among the sulfo group-containing polymer compounds of the present invention, a polymer compound having at least one repeating unit represented by the general formula (2) in the polymer chain is preferable, and the general formula (2) is useful. It is an intermediate (hereinafter referred to as “intermediate polymer compound”). The sulfo group-containing polymer having at least one repeating unit in which at least one of X ^{1 to} X ⁴ , Y ¹ and the benzene ring of the intermediate polymer compound of the general formula (2) is substituted with a sulfo group in the polymer chain Compounds are preferred.

(Wherein, Z ^{1 to} Z ⁴ , p ^{1 to} p ⁴ , X ^{1 to} X ⁴ , Y, m, and n are as described above).
In general formula (1) or general formula (2), the group represented by Y is preferably a group represented by general formula (a-1).

Wherein Q is a group selected from the group consisting of a single bond, O, S, CH ₂ , CMe ₂ , CO, SO, SO ₂ , SiH ₂ , Si Me ₂ , and k is an integer of 0-2. Represents.)

  The sulfo group-containing polymer compound of the present invention can be obtained, for example, by sulfonating a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain.

  In the sulfo group-containing polymer compound in which a sulfo group is introduced into a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain, a salt may be formed. I do not care. The salt is not particularly limited, and examples thereof include inorganic salts such as lithium, sodium, potassium, calcium, and aluminum, salts with organic amines such as ammonia, trimethylamine, triethylamine, piperidine, morpholine, and amino acids. Can be mentioned.

  Further, the number average molecular weight of the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain is not particularly limited, but is 1000 to 1000000 in terms of polystyrene. Preferably it is 3000-500000. More preferably, it is 4000-200000. The same applies to the number average molecular weight of the sulfo group-containing polymer compound of the present invention.

  In addition, the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain is an aromatic hydrocarbon group in which the terminal functional group which is a polymerization reaction site is unsubstituted or substituted, End-treated by substitution with a substituted amino group, linear, branched or cyclic alkyl group, alkyloxy group having linear, branched or cyclic alkyl group, carboxyl group, alkoxycarbonyl group, hydroxyl group, etc. It doesn't matter.

A sulfo group-containing polymer compound having a structure in which a sulfo group is introduced into a polymer compound having at least one repeating unit represented by the general formula (1) of the present invention in the polymer chain, and the general formula of the present invention Specific examples of the polymer compound having at least one repeating unit represented by (1) in the polymer chain are exemplified below, but the present invention is not limited to these examples. .
The following formula (R-1) shows a general formula in which p ^{1 to} p ⁴ in the general formula (1) are 0 (zero), and in Tables 1 to 53 below, specific examples corresponding respectively to Y , Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , T ¹ , T ² , m, n, X ¹ , X ² , X ³ , X ⁴ .

  Next, a method for producing a compound in which a sulfo group is introduced into a polymer compound having at least one repeating unit represented by the general formula (1) of the present invention in the polymer chain will be described.

  The polymer compound having at least one repeating unit represented by the general formula (1) as a raw material in the polymer chain is, for example, the general formula (3):

(In the formula, X ^{1 to} X ⁴ , Ar ^{1 to} Ar ⁴ , T ¹ , T ² , Y, and m and n are as in the general formula (1).)
And a compound represented by the general formula (4):

(In the formula, X represents a halogen atom, and Z ^{1 to} Z ⁴ and p ^{1 to} p ⁴ are as described above.)
Can be produced by polymerizing with a Pd catalyst or the like in the presence of a base.

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

  The sulfo group-containing polymer compound of the present invention can be produced, for example, by sulfonating a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain.

  Examples of the sulfonating agent used for sulfonation include sulfuric acid, fuming sulfuric acid, sulfur trioxide, sulfur trioxide complex, chlorosulfuric acid, fluorosulfuric acid, and amidosulfuric acid, and the amount of the sulfonating agent to be used is not particularly limited.

  The sulfur trioxide complex is a complex with Lewis acids such as ethers, amines, sulfides, N, N-dimethylformamide / sulfur trioxide complex, dioxane / sulfur trioxide complex, pyridine / sulfur trioxide complex, Examples include triethylamine / sulfur trioxide complex, trimethylamine / sulfur trioxide complex, and the like.

  The reaction can be carried out without solvent or in a solvent. The solvent used in the reaction is not particularly limited as long as it does not affect the reaction, but chlorinated organic solvents such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane; liquid sulfur dioxide, carbon disulfide Acetic acid, acetic anhydride; esters such as ethyl acetate; ethers such as diethyl ether; benzene, toluene, xylene, nitromethane, nitrobenzene, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, acetonitrile, tetrahydrofuran, dioxane Dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like.

  The reaction temperature may be selected from the range of −20 ° C. to 150 ° C. (representing Celsius temperature; hereinafter the same), and the reaction time is several minutes to 96 hours. It can also be obtained by synthesizing sulfonyl chloride with chlorosulfuric acid and hydrolyzing it.

  The method for isolating the polymer compound of the present invention is not particularly limited. If the product is precipitated from the reaction solvent, it can be isolated by filtration or centrifugation, and if dissolved in the reaction solvent, a method of distilling the solvent under reduced pressure or a suitable solvent can be used. In addition, a method of precipitation, filtration, or centrifugation can be employed.

  If the reaction product forms a sulfate salt, the excess sulfonating agent is removed by washing with water after filtration, and the sulfuric acid is removed by neutralizing the resulting sulfate salt with a base. Can do. As the base, hydroxides such as alkali metals and alkaline earth metals, ion exchange resins, and the like can be used.

  When purification is required for the polymer compound of the present invention, a well-known method can be employed. For example, a recrystallization method, a reprecipitation method, a column chromatography method, washing with a solvent ( Sludge), an adsorption treatment using activated carbon, an ion exchange resin treatment, an ion exchange membrane, a dialysis membrane, a reverse osmosis membrane, a treatment method using an ultrafiltration membrane, and the like.

  Next, the organic electroluminescent material of the present invention will be described.

  The organic electroluminescent material of the present invention is a sulfo group-containing polymer compound having a structure in which a sulfo group is introduced into a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain Alternatively, the intermediate polymer compound is composed of a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain, and used for an organic electroluminescent device, a hole injection transport material, light emission It can be used as a material or an electron injecting and transporting material.

  In addition, the organic electroluminescent element material of this invention can be used as an organic electroluminescent element material in the state which melt | dissolved the polymer compound of this invention in the organic solvent. In that case, the solution dissolved in the reaction solvent may be used as it is, or the polymer compound of the present invention may be used after being isolated or purified and dissolved in a predetermined solvent. Specific solvents include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, tetrachloro Halogenated hydrocarbon solvents such as methane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, methanol, propanol, butanol, pentanol , Alcohol solvents such as hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, fluorine-containing alcohol, dibutyl ether Ether solvents such as tetrahydrofuran, dioxane, dimethoxyethane, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl Examples include polar solvents such as sulfoxide. Of these solvents, polar solvents are preferred. When applying using a polar solvent, it becomes possible to laminate | stack the layer which consists of materials soluble in hydrocarbon type solvents, such as toluene, on the layer on it.

  Next, the organic electroluminescent element of the present invention will be described.

  The organic electroluminescent element of the present invention is formed by sandwiching at least one layer containing at least one kind of the sulfo group-containing polymer compound and / or its intermediate polymer compound of the present invention between a pair of electrodes. An organic electroluminescent element is usually formed by sandwiching at least one light emitting layer containing at least one light emitting component between a pair of electrodes. A hole injection / transport layer and / or an electron injection containing a hole injection component as desired, considering the functional level of the hole injection and hole transport, electron injection and electron transport of the compound used in the light emitting layer. An electron injecting and transporting layer containing components can also be provided.

  For example, when the compound used for the light emitting layer has a good hole injection function, hole transport function and / or electron injection function, and electron transport function, the light emitting layer is a hole injection transport layer and / or electron injection transport. As a type of element configuration that also serves as a layer, a single-layer type element configuration can be adopted. In addition, when the light emitting layer is poor in the hole injection function and / or the hole transport function, a two-layer device configuration in which a hole injection transport layer is provided on the anode side of the light emitting layer can be obtained. When the layer is poor in the electron injection function and / or the electron transport function, a two-layer element configuration in which an electron injection transport layer is provided on the cathode side of the light emitting layer can be obtained. Furthermore, a three-layer device structure in which the light-emitting layer is sandwiched between a hole injecting and transporting layer and an electron injecting and transporting layer can be used.

  In addition, each of the hole injecting and transporting layer, the electron injecting and transporting layer, and the light emitting layer may have a single layer structure or a multilayer structure, and the hole injecting and transporting layer and the electron injecting and transporting layer The layer having an injection function and the layer having a transport function can be separately provided.

  In the organic electroluminescence device of the present invention, the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof is preferably used as a component of the charge injection / transport layer and / or the light emitting layer. Examples include a hole injecting and transporting layer and an electron injecting and transporting layer, and a hole injecting and transporting layer is particularly preferable.

  In the organic electroluminescent device of the present invention, the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof may be used alone or in combination.

The configuration of the organic electroluminescent device of the present invention is not particularly limited. For example, (EL-1) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode type device (FIG. 1). ), (EL-2) anode / hole injection transport layer / light emitting layer / cathode type device (FIG. 2), (EL-3) anode / light emitting layer / electron injection transport layer / cathode type device (FIG. 3), EL-4) Anode / light emitting layer / cathode type element (FIG. 4), and the like. Further, (EL-5) anode 2 / hole injection transport layer 3 / hole injection transport layer 5 ″ / light emission layer in which the light emission layer 4 is sandwiched between the hole injection transport layer 5 ″ and the electron injection transport layer 5 4 / electron injecting and transporting layer 5 / cathode 6 type element (FIG. 5) may be used. The (EL-4) type element structure includes an element of a type in which a light emitting component is sandwiched between a pair of electrodes as a light emitting layer, (EL-6) a hole injection transport component as a light emitting layer, A device of a type in which a light emitting component and an electron injection component are mixed and sandwiched between a pair of electrodes (FIG. 6), (EL-7) a layer in which a hole injection transport component and a light emitting component are mixed as a light emitting layer Type element sandwiched between a pair of electrodes in a form (FIG. 7), (EL-8) type element sandwiched between a pair of electrodes in a single layer form in which a light emitting component and an electron injection component are mixed as a light emitting layer Any of (FIG. 8) may be sufficient.
The hole injection / transport layer 3 may include at least two hole injection / transport layers containing the polymer compound of the present invention.

  The organic electroluminescent device of the present invention is not limited to these device configurations, and each type of device can be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. Further, in each type of device, the hole injection / transport layer is disposed between the light emitting layer, the hole injection / transport component and the light emitting component mixed layer and / or the light emitting layer and the electron injection / transport layer between the light emitting component and the light emitting component. And a mixed layer of electron injecting and transporting components can be provided.

  A preferable configuration of the organic electroluminescent element is an (EL-1) type element, an (EL-2) type element, an (EL-5) type element, an (EL-6) type element, or an (EL-7) type element. Yes, more preferably an (EL-1) type element, an (EL-2) type element, an (EL-5) type element, or an (EL-7) type element.

Hereinafter, the components of the organic electroluminescence device of the present invention will be described in detail.
As an example, (EL-1) anode / hole injection / transport layer / light-emitting layer / electron injection / transport layer / cathode type element shown in FIG. 1 will be described.

  In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection / transport layer, 4 is a light emitting layer, 5 is an electron injection / transport layer, 6 is a cathode, and 7 is a power source.

  The organic electroluminescent element of the present invention is preferably supported by the substrate 1, and the substrate is not particularly limited, but a transparent or translucent substrate is preferable, and the material is soda lime glass, Examples thereof include glass such as borosilicate glass and transparent polymers such as polyester, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethyl methacrylate, polypropylene, and polyethylene. Further, a substrate made of a translucent plastic sheet, quartz, transparent ceramics, or a composite sheet in which these are combined can also be used. Furthermore, for example, a color filter film, a color conversion film, and a dielectric reflection film can be combined with the substrate to control the emission color.

As the anode 2, it is preferable to use a metal, an alloy or a conductive compound having a relatively large work function as an electrode material. Examples of the electrode material used for the anode include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide, ITO ( Indium tin oxide (Indium Tin Oxide), polythiophene, polypyrrole, and the like can be given. These electrode materials may be used alone or in combination. For the anode, these electrode materials can be formed on the substrate by a method such as vapor deposition or sputtering. Further, the anode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the anode is preferably set to several hundred Ω or less, more preferably about 5 to 50 Ω. The thickness of the anode is generally about 5 to 1000 nm, more preferably about 10 to 500 nm, although it depends on the material of the electrode material used.

  The hole injection transport layer 3 is a layer containing a compound having a function of facilitating the injection of holes from the anode and a function of transporting the injected holes.

  The hole injecting and transporting layer of the organic electroluminescent device of the present invention comprises the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof and / or other compounds having a hole injecting and transporting function (for example, phthalocyanine derivatives, tria. At least one kind of reelamine derivative, triarylmethane derivative, oxazole derivative, hydrazone derivative, stilbene derivative, pyrazoline derivative, polysilane derivative, polyphenylenevinylene and its derivative, polythiophene and its derivative, poly-N-vinylcarbazole, etc.) Can be formed. The compounds having a hole injecting and transporting function may be used alone or in combination.

  The organic electroluminescent element of the present invention preferably contains the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof in the hole injecting and transporting layer. In the organic electroluminescence device of the present invention, other compounds having a hole injecting and transporting function that can be used include triarylamine derivatives (for example, 4,4′-bis [N-phenyl-N- (4 ” -Methylphenyl) amino] -1,1'-biphenyl, 4,4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] -1,1'-biphenyl, 4,4'-bis [N-phenyl-N- (3 "-methoxyphenyl) amino] -1,1'-biphenyl, 4,4'-bis [N-phenyl-N- (1" -naphthyl) amino] -1,1 ' -Biphenyl, 3,3'-dimethyl-4,4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] -1,1'-biphenyl, 1,1-bis [4 '-[ N, N-di (4 "-methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N- (4′-methylphenyl) -N- (4 ″ -n-butylphenyl) amino] phenanthrene,

  3,8-bis (N, N-diphenylamino) -6-phenylphenanthridine, 4-methyl-N, N-bis [4 ", 4" '-bis [N', N'-di (4- Methylphenyl) amino] biphenyl-4-yl] aniline, N, N′-bis [4- (diphenylamino) phenyl] -N, N′-diphenyl-1,3-diaminobenzene, N, N′-bis [ 4- (diphenylamino) phenyl] -N, N'-diphenyl-1,4-diaminobenzene, 5,5 "-bis [4- (bis [4-methylphenyl] amino) phenyl-2,2 ': 5 ', 2 "-terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4', 4" -tris (9 H-carbazol-9-yl) triphenylamine, 4,4 ', 4 "-Tris [N, N-bis (4" '-tert-butylbiphenyl-4 " “-Yl) amino] triphenylamine, 1,3,5-tris [N- (4′-diphenylamino) benzene], etc.), polythiophene and its derivatives, poly-N-vinylcarbazole and its derivatives are more preferred.

  When the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof and another compound having a hole injection / transport function are used in combination, the content of these polymer compounds in the hole injection / transport layer is preferably Is 0.1% by mass or more, more preferably 0.5 to 99.9% by mass, and still more preferably 3 to 97% by mass.

  When the sulfo group-containing polymer compound of the present invention or its intermediate polymer compound is used in combination with another compound having a hole injecting and transporting function, the sulfo group-containing polymer compound of the present invention or its intermediate polymer compound is used. You may laminate | stack the layer which consists of a compound which has a layer and another hole injection transport function. In the case of stacking, it is preferable to stack a layer made of another compound having a hole injecting and transporting function on a layer made of the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof.

In the hole injecting and transporting layer, a compound having a hole injecting and transporting function and an electron accepting compound may be used in combination. Examples of the electron-accepting compound include TBPAH (tris (4-bromophenyl) aluminum hexachloroantimonate) described in JP-A-11-283750, FeCl ₃ , and tris (penta) described in JP-A-2003-31365. Lewis acids such as boron compounds such as (fluorophenyl) borane. When using an electron-accepting compound together, it is preferable that content of an electron-accepting compound is 0.1-50 mass% with respect to a positive hole injection transport layer.

  The light emitting layer 4 is a layer containing a compound having a function of injecting holes and electrons, a function of transporting them, and a function of generating excitons by recombination of holes and electrons.

  The light emitting layer can be formed using at least one of the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof and / or another compound having a light emitting function.

  Examples of other compounds having a light emitting function include acridone derivatives, quinacridone derivatives, diketopyrrolopyrrole derivatives, polycyclic aromatic compounds [for example, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenyl Cyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthenyl) benzene, 4,4′-bis (9 "-Ethynylanthracenyl) biphenyl,

  Dibenzo [f, f] diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene derivatives], triarylamine derivatives (for example, the compounds described above as compounds having a hole injecting and transporting function) Organometallic complexes [eg, tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, zinc salt of 2- (2′-hydroxyphenyl) benzothiazole, 4- Zinc salt of hydroxyacridine, zinc salt of 3-hydroxyflavone, beryllium salt of 5-hydroxyflavone, aluminum salt of 5-hydroxyflavone], stilbene derivative [for example, 1,1,4,4-tetraphenyl-1,3 -Butadiene,

  4,4′-bis (2,2-diphenylvinyl) biphenyl, 4,4′-bis [(1,1,2-triphenyl) ethenyl] biphenyl], coumarin derivatives (eg, coumarin 1, coumarin 6, coumarin) 7, Coumarin 30, Coumarin 106, Coumarin 138, Coumarin 151, Coumarin 152, Coumarin 153, Coumarin 307, Coumarin 311, Coumarin 314, Coumarin 334, Coumarin 338, Coumarin 343, Coumarin 500), pyran derivatives (eg, DCM1, DCM2) ), Oxazone derivatives (eg Nile Red), benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamic acid ester derivatives, poly-N-vinylcarbazole and derivatives thereof, polythiophene and derivatives thereof , Polyphenylene and its derivatives, polyfluorene and its derivatives,

  Examples thereof include polyphenylene vinylene and derivatives thereof, polybiphenylene vinylene and derivatives thereof, polyterphenylene vinylene and derivatives thereof, polynaphthylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof. In particular, an acridone derivative, a quinacridone derivative, a polycyclic aromatic compound, a triarylamine derivative, an organometallic complex, and a stilbene derivative are preferable, and a polycyclic aromatic compound and an organometallic complex are more preferable.

  The organic electroluminescent element of the present invention preferably contains the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof in the light emitting layer.

  When the sulfo group-containing polymer compound of the present invention or its intermediate polymer compound and another compound having a light emitting function are used in combination, the proportion of the sulfo group-containing polymer compound of the present invention in the light emitting layer is preferably 0. Adjust to 0.001 to 99.999 mass%.

  The light emitting layer can also be formed from a host compound and a guest compound (dopant) as described in J. Appl. Phys., 65, 3610 (1989) and Japanese Patent Laid-Open No. 5-214332.

  The sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof can be used as a host compound for a light emitting layer, and can also be used as a guest compound. When the light emitting layer is formed using the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof as a host compound, examples of the guest compound include compounds having other light emitting functions described above. Ring aromatic compounds are preferred.

  When the light emitting layer is formed using the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof as a host compound, the guest compound is preferably 0.001 to 40% by mass, more preferably based on the host compound. 0.01 to 30% by mass, more preferably 0.1 to 20% by mass. The light emitting layer can be formed by using the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof as a host material and using at least one compound having another light emitting function as a guest material.

  The organic electroluminescent element of the present invention preferably contains the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof as a host material in the light emitting layer.

  When the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof is used as a host material in combination with another compound having a light emitting function, the sulfo group-containing polymer compound of the present invention or its intermediate The molecular compound is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 99.9% by mass.

  The amount of the guest material used is 0.001 to 40% by mass, preferably 0.01 to 30% by mass, and more preferably 0.001% by mass to the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof. 1 to 20% by mass. Moreover, a guest material may be used independently and may be used together.

  When the light-emitting layer is formed using the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof as a guest material, the host material includes a polycyclic aromatic compound, a triarylamine derivative, an organometallic complex, and stilbene. Derivatives are preferred, and polycyclic aromatic compounds and organometallic complexes are more preferred.

  When the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof is used as a guest material, the compound is preferably 0.001 to 40% by mass, more preferably 0.01 to 30% by mass, More preferably, 0.1-20 mass% is used.

  The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating injection of electrons from the cathode and / or a function of transporting injected electrons.

  Examples of the compound having an electron injecting function used in the electron injecting and transporting layer include organometallic complexes, oxadiazole derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorenones. Derivatives, thiopyrandioxide derivatives and the like. Examples of organometallic complexes include organoaluminum complexes such as tris (8-quinolinolato) aluminum, organic beryllium complexes such as bis (10-benzo [h] quinolinolato) beryllium, beryllium salts of 5-hydroxyflavone, 5- Examples thereof include an aluminum salt of hydroxyflavone. Preferred is an organoaluminum complex, and more preferred is an organoaluminum complex having an unsubstituted or substituted 8-quinolinolate ligand. Examples of the organoaluminum complex having an unsubstituted or substituted 8-quinolylate ligand include compounds represented by general formula (a) to general formula (c).

(F) ₃ -Al (a)
(In the formula, F represents an unsubstituted or substituted 8-quinolinolato ligand.)
(F) ₂ -Al-OM (b)
(In the formula, as described above, OM represents a phenolate ligand, and M represents a hydrocarbon group having 6 to 24 carbon atoms having a phenyl group.)
(F) _2- Al-O-Al- (F) ₂ (c)
(In the formula, F is as described above.)

  Specific examples of organoaluminum complexes having an unsubstituted or substituted 8-quinolinolato ligand include, for example, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl). -8-quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolate) Aluminum, screw (2- Chill-8-quinolinolato) (4-methyl-phenolate) aluminum,

  Bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (4 -Phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) aluminum, bis (2-Methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) ) (3,5-di-tert-butylphenolate) aluminum,

  Bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl -8-quinolinolato) (2,4,6-trimethylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolato) aluminum, bis (2-methyl- 8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2,4-Dimethyl-8-quinolinolate) (3-Phenylphenolate Aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) aluminum ,

  Bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ- Oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8- Quinolinolato) aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoro) Methyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-tri) Fluoromethyl-8-quinolinolato) aluminum.

  A compound having an electron injection function may be used alone or in combination.

  As the cathode 6, it is preferable to use a metal, an alloy or a conductive compound having a relatively small work function as an electrode material. Examples of the electrode material used for the cathode include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium, manganese, yttrium, and aluminum. , Aluminum-lithium alloy, aluminum-calcium alloy, aluminum-magnesium alloy, lithium fluoride, and graphite thin film. These electrode materials may be used alone or in combination.

  For the cathode, these electrode materials can be formed on the electron injecting and transporting layer by, for example, vapor deposition, sputtering, ion vapor deposition, ion plating, or cluster ion beam.

  The cathode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the cathode is preferably several hundred Ω or less. The thickness of the cathode is usually 5 to 1000 nm, preferably 10 to 500 nm, although it depends on the electrode material used. In order to efficiently extract light emitted from the organic electroluminescent device of the present invention, at least one of the anode and the cathode is preferably transparent or translucent, and generally has a transmittance of emitted light of 70% or more. It is preferable to set the material and thickness of the anode or cathode.

  The organic electroluminescent device of the present invention may contain a singlet oxygen quencher in at least one of the hole injection transport layer, the light emitting layer, and the electron injection transport layer. Although it does not specifically limit as a singlet oxygen quencher, For example, rubrene, a nickel complex, diphenylisobenzofuran is mentioned, Preferably it is rubrene.

  The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injection transport layer, and more preferably a hole injection transport layer. When a singlet oxygen quencher is contained in the hole injecting and transporting layer, it may be uniformly contained in the hole injecting and transporting layer. May be contained in the vicinity of the electron injecting and transporting layer). As content of a singlet oxygen quencher, 0.01-50 mass% of the total quantity which comprises the layer (for example, hole injection transport layer) contained, Preferably, 0.05-30 mass%, more Preferably, it is 0.1-20 mass%.

  The formation method of the organic electroluminescent element of this invention is not specifically limited, For example, a vacuum evaporation method, an ionization evaporation method, or a solution coating method can be used.

  When the layer containing the polymer compound of the present invention is a hole injecting and transporting layer, it is preferable to use a solution coating method as a method for forming the hole injecting and transporting layer. Method, casting method, micro gravure coating method, gravure coating method, bar coating method, wire bar coating method, dip coating method, roll coating method, spray coating method, Langmuir-Blodget method, screen printing method, flexographic printing method, offset Examples thereof include a printing method and an inkjet printing method.

  Moreover, as a formation method of a light emitting layer, a vacuum evaporation method, an ionization evaporation method, or a solution coating method can be used. When the light emitting layer contains the polymer compound of the present invention or when it contains a polymer compound having a light emitting function, the light emitting layer is preferably formed using a solution coating method. When the light emitting layer contains a compound having a light emitting function, it can be formed by using a vacuum vapor deposition method, an ionization vapor deposition method, or a solution coating method. Furthermore, as a method for forming the electron injecting and transporting layer, a vacuum deposition method, an ionization deposition method or a solution coating method can be used.

  When each layer is formed by a solution coating method, a component for forming each layer or its component and a binder resin are dissolved or dispersed in a solvent to obtain a coating solution. Examples of the solvent include organic solvents (hexane solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, etc. , Halogenated hydrocarbon solvents such as tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, methanol, propanol, butanol , Alcohol solvents such as pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, fluorine-containing alcohol, Ether solvents such as tilether, tetrahydrofuran, dioxane, dimethoxyethane, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, And polar solvents such as dimethyl sulfoxide) and water. A solvent may be used independently and may be used together. When the components of the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer are dispersed in a solvent, for example, a ball mill, a sand mill, a paint shaker, an attritor, or a homogenizer is used as a dispersion method. Can be used.

  When the sulfo group-containing polymer compound of the present invention or an intermediate polymer compound thereof is insoluble in a hydrocarbon solvent such as toluene, after forming a layer containing the polymer compound, the upper layer is composed of a hydrocarbon-based compound. It can laminate | stack by apply | coating using a solvent. In particular, when the polymer compound is used as a hole injecting and transporting layer, the light emitting layer can be laminated by coating, which is advantageous in the organic electroluminescent element configuration (EL-2).

  Examples of the binder resin that can be used in each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer include poly-N-vinyl carbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl methacrylate, poly Methyl acrylate, polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, Examples thereof include polymer compounds such as polythienylene vinylene and its derivatives. Binder resins may be used alone or in combination.

  The concentration of the coating solution is not particularly limited, but can be set to a concentration range suitable for producing a desired thickness by a coating method to be carried out, usually 0.1 to 50% by mass, preferably , 0.5 to 30% by mass. When the binder resin is used, the amount used is not particularly limited, but it is usually based on the total amount of the binder resin and the components forming each layer such as the hole injection transport layer, the light emitting layer, and the electron injection transport layer. The binder resin is used so that the content of the binder resin is 5 to 99.9% by mass, preferably 10 to 99% by mass (relative to the total amount of each component when a single-layer element is formed).

  The thickness of each layer such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited, but is usually 5 nm to 5 μm.

In addition, the organic electroluminescent device of the present invention produced under the above conditions is provided with a protective layer (sealing layer) for the purpose of preventing contact with oxygen, moisture, etc. For example, it can be protected by enclosing it in paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite-containing fluorocarbon oil). Examples of the material used for the protective layer include organic polymer materials (for example, fluorine resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, Polyphenylene oxide), inorganic materials (for example, diamond thin film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide, metal sulfide), and photocurable resin. The material used for the protective layer may be used alone or in combination.
The protective layer may have a single layer structure or a multilayer structure.

  Moreover, the organic electroluminescent element of this invention can also provide a metal oxide film (for example, aluminum oxide film) and a metal fluoride film as a protective film in an electrode.

The organic electroluminescent element of the present invention can also be provided with an interface layer (intermediate layer) on the surface of the anode.
Examples of the material for the interface layer include organic phosphorus compounds, polysilanes, aromatic amine derivatives, and phthalocyanine derivatives.

  Furthermore, the surface of an electrode, for example, an anode, can be used by treating the surface with acid, ammonia / hydrogen peroxide, or plasma.

  The organic electroluminescent element of the present invention can be usually used as a DC drive type element, but can also be used as an AC drive type element. Further, the organic electroluminescence device of the present invention may be a segment type, a passive drive type such as a simple matrix drive type, or an active drive type such as a TFT (thin film transistor) type or a MIM (metal-insulator-metal) type. It may be. The driving voltage is usually 2 to 30V. The organic electroluminescent element of the present invention includes a panel-type light source (for example, a backlight for a clock, a liquid crystal panel, etc.), various light emitting elements (for example, an alternative to a light emitting element such as an LED), and various display elements (for example, information display Element (PC monitor, mobile phone / mobile terminal display element)], various signs, various sensors, and the like.

  In addition, the sulfo group-containing polymer compound of the present invention or the intermediate polymer compound thereof is an organic semiconductor, organic thin film transistor (TFT), electrolytic capacitor, photoelectric conversion using a conventional conductive polymer material (PEDOT / PSS). It can also be used for applications such as devices, electrochromic devices (ECD), and antistatic agents.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example.

In addition, the molecular weight in each Example measured the number average molecular weight of polystyrene conversion by gel permeation chromatography (GPC).

(GPC analysis conditions)
Apparatus: Gel permeation chromatograph GPC 101 (manufactured by Shodex)
Detector: differential refractometer column: GPC K-806LX3 (8.0 mm I.D. × 30 cm, manufactured by Shodex)
Column temperature: 40 ° C Solvent: Chloroform Injection volume: 100 μl
Flow rate: 1ml / min
Standard substance: Monodispersed polystyrene (manufactured by Shodex)
The ultraviolet absorption spectrum was measured using the following apparatus, and the absorption maximum wavelength (λmax) was determined.

(UV (λmax))
It measured using Shimadzu UV-visible spectrophotometer UV-2500PC.

Evaluation of film formability was confirmed by observing the surface roughness with an atomic force microscope (AFM).

(AFM measurement conditions)
Apparatus: Seiko Instruments scanning probe microscope SPI-3800N
Analysis conditions:
Measurement mode DFM
Cantilever SI-DF20
Measurement range 5μm × 5μm

The number of sulfo groups was determined by elemental analysis.

[Example 1]
Production of Illustrative Compound A1-1
N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine 1.30 g, 2,5-bis (4′-bromophenyl) -3,4-diphenylthiophene To a mixture of 1.19 g, 0.61 g of sodium tert-butoxide and 25 mL of o-xylene under a nitrogen stream, tris (dibenzylideneacetone) dipalladium A solution of 8 mg and 17.3 mg of tritert-butylphosphine in o-xylene (2 mL) was added. The mixture was stirred at 135 degrees for 4 hours in a nitrogen atmosphere. The reaction solution is returned to room temperature, purified by silica gel column chromatography, and then discharged into acetone. The precipitate is collected by filtration and dried under reduced pressure, and the repeating unit of (Exemplary Compound A1-1) is contained in the polymer chain. 1.45 g of a compound having at least one of the following was obtained as a yellow solid.
Molecular weight: 21000
UV (λmax): 346 nm (toluene)

[Example 2]
Production of Illustrative Compound A1-3 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.26 g of N′-bis [p- (N, N-diphenylamino) phenyl] -1,4-phenylenediamine was used, the polymer of Exemplified Compound A1-3 1.39 g of compound was obtained.
Number average molecular weight: 25000

[Example 3]
Production of Illustrative Compound A1-4 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified according to the method described in Example 1, except that 2.10 g of N′-bis [p- (3,6-dihexyl-9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine was used. 1.91 g of a polymer compound A1-4 was obtained.
Number average molecular weight: 21600

[Example 4]
Production of Exemplified Compound A1-5 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example 1 except that 2.10 g N'-bis [p- {N- (p-octylphenyl) -N- (p-hexylphenyl) amino} phenyl] -1,4-phenylenediamine was used. According to the method, 1.91 g of the polymer compound of Exemplified Compound A1-5 was obtained.
Number average molecular weight: 18800

[Example 5]
Production of Exemplary Compound A1-8 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified according to the method described in Example 1, except that 1.59 g of N′-bis [p- {N-phenyl-N- (4-phenylphenyl) amino} phenyl] -1,4-phenylenediamine was used. 1.51 g of a polymer compound of Compound A1-8 was obtained.
Number average molecular weight: 17300

[Example 6]
Production of Illustrative Compound A1-9 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified compounds according to the method described in Example 1, except that 1.91 g of N′-bis [p- {N, N-di (4-phenylphenyl) amino} phenyl] -1,4-phenylenediamine was used. 1.83 g of a polymer compound of A1-9 was obtained.
Number average molecular weight: 15600

[Example 7]
Production of Exemplary Compound A1-10 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.97 g of N′-bis [p- {N-phenyl-N- (4-diphenylaminophenyl) amino} phenyl] -1,4-phenylenediamine was used. 1.72 g of the polymer compound of Exemplified Compound A1-10 was obtained.
Number average molecular weight: 24100

[Example 8]
Production of Exemplified Compound A1-11 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified according to the method described in Example 1, except that 2.69 g of N′-bis [p- {N, N-di (4-diphenylaminophenyl) amino} phenyl] -1,4-phenylenediamine was used. 2.29 g of a polymer compound of Compound A1-11 was obtained.
Number average molecular weight: 27200

[Example 9]
Production of Exemplary Compound A1-12 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example except that 1.97 g of N′-bis [p- [N-phenyl-N- {p- (9H-carbazol-9-yl) phenyl} amino] phenyl] -1,4-phenylenediamine was used According to the method described in 1, 1.76 g of the polymer compound of Exemplified Compound A1-12 was obtained.
Number average molecular weight: 14300

[Example 10]
Production of Exemplary Compound A1-13 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example 1 except that 2.67 g of N′-bis [p- [N, N-di {p- (9H-carbazol-9-yl) phenyl} amino] phenyl] -1,4-phenylenediamine was used. According to the method described in 2., 2.24 g of the polymer compound of Exemplified Compound A1-13 was obtained.
Number average molecular weight: 25800

[Example 11]
Production of Exemplified Compound A1-14 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Except for using 2.19 g of N′-bis [p- {N-phenyl-N- (4- (N-phenyl-N-1-naphthyl) aminophenyl) amino} phenyl] -1,4-phenylenediamine. According to the method described in Example 1, 1.97 g of the polymer compound of Exemplified Compound A1-14 was obtained.
Number average molecular weight: 22100

[Example 12]
Production of Exemplary Compound A1-15 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Except for using 2.19 g of N′-bis [p- {N-phenyl-N- (4- (N-phenyl-N-2-naphthyl) aminophenyl) amino} phenyl] -1,4-phenylenediamine. According to the method described in Example 1, 1.88 g of the polymer compound of Exemplified Compound A1-15 was obtained.
Number average molecular weight: 21100

[Example 13]
Production of Exemplary Compound A1-17 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified compound according to the method described in Example 1 except that 1.69 g of N′-bis [p- {N-phenyl-N- (9-phenanthryl) amino} phenyl] -1,4-phenylenediamine was used. 1.70 g of a polymer compound of A1-17 was obtained.
Number average molecular weight: 16200

[Example 14]
Production of Exemplary Compound A1-18 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified compound according to the method described in Example 1, except that 1.69 g of N′-bis [p- {N-phenyl-N- (9-anthracenyl) amino} phenyl] -1,4-phenylenediamine was used. 1.68 g of a polymer compound of A1-18 was obtained.
Number average molecular weight: 13300

[Example 15]
Production of Illustrative Compound A2-2 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 2.304 g of N′-bis [p- (3,6-dihexyl-9H-carbazol-9-yl) phenylphenyl] -1,4-phenylenediamine was used. 2.02 g of the polymer compound of the exemplary compound A2-2 was obtained.
Number average molecular weight: 23100

[Example 16]
Production of Illustrative Compound A2-6 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.80 g of N′-bis [4- {pN-phenyl-N- (1-naphthyl) amino} phenylphenyl] -1,4-phenylenediamine was used. Then, 1.72 g of the polymer compound of Exemplified Compound A2-6 was obtained.
Number average molecular weight: 21100

[Example 17]
Production of Exemplified Compound A2-7 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.8 g of N′-bis [4- {pN-phenyl-N- (2-naphthyl) amino} phenylphenyl] -1,4-phenylenediamine was used. Then, 1.75 g of the polymer compound of Exemplified Compound A2-7 was obtained.
Number average molecular weight: 14100

[Example 18]
Production of Illustrative Compound A3-1 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.76 g of N′-bis {2- (7-N, N-diphenylamino-9,9-dimethyl) fluorenyl} -1,4-phenylenediamine was used. 1.71 g of the polymer compound of Exemplified Compound A3-1 was obtained.
Number average molecular weight: 20600

[Example 19]
Production of Illustrative Compound A3-2 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 2.59 g of N′-bis {2- (7-N, N-diphenylamino-9,9-dioctyl) fluorenyl} -1,4-phenylenediamine was used. 2.17 g of the polymer compound of Exemplified Compound A3-2 was obtained.
Number average molecular weight: 24100

[Example 20]
Production of Exemplary Compound A3-4 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, As described in Example 1, except that 1.75 g of N′-bis [2- {7- (9H-carbazol-9-yl) -9,9-dimethyl} fluorenyl] -1,4-phenylenediamine was used. According to the method, 1.66 g of the polymer compound of Exemplified Compound A3-4 was obtained.
Number average molecular weight: 26100

[Example 21]
Production of Illustrative Compound A3-6 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Except for using 2.54 g of N′-bis [2- {7- (3,6-dihexyl-9H-carbazol-9-yl) -9,9-dimethyl} fluorenyl] -1,4-phenylenediamine, According to the method described in Example 1, 2.11 g of the polymer compound of Exemplified Compound A3-6 was obtained.
Number average molecular weight: 27800

[Example 22]
Production of Illustrative Compound A3-7 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, N'-bis [2- {7- (N- (p-octylphenyl) -N- (p-hexylphenyl) amino) -9,9-dimethyl} fluorenyl] -1,4-phenylenediamine (2.58 g) Except for the use, according to the method described in Example 1, 2.32 g of the polymer compound of Exemplified Compound A3-7 was obtained.
Number average molecular weight: 32100

[Example 23]
Production of Exemplary Compound B1-1 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified compound according to the method described in Example 1, except that 1.98 g of N′-bis [p- {N, N-di (4-hexylphenyl) amino} phenyl] -1,3-phenylenediamine was used. 1.87 g of the polymer compound of B1-1 was obtained.
Number average molecular weight: 19400

[Example 24]
Production of Exemplified Compound B1-2 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Except for using 1.43 g of N′-bis [p- (N, N-diphenylamino) phenyl] -3,3′-diaminobiphenyl, according to the method described in Example 1, 1.45 g of molecular compound was obtained.
Number average molecular weight: 15600

[Example 25]
Production of Exemplified Compound B1-5 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, N , N′-bis [p-{(N- (p-octylphenyl) -N- (p-hexylphenyl) amino} phenyl] -1,5-naphthalenediamine, except that 2.20 g was used. According to the method described in 1., 1.95 g of the polymer compound of Exemplified Compound B1-5 was obtained.
Number average molecular weight: 22000

[Example 26]
Production of Exemplary Compound B1-6 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1 except that 1.37 g of N′-bis [p- (N, N-diphenylamino) phenyl] -1,4-naphthalenediamine was used, the polymer of Exemplified Compound B1-6 1.40 g of compound was obtained.
Number average molecular weight: 23800

[Example 27]
Production of Exemplified Compound B1-7 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Polymer of Exemplified Compound B1-7 according to the method described in Example 1 except that 1.53 g of N′-bis [p- (N, N-diphenylamino) phenyl] -3,6-pyrenediamine is used. 1.51 g of compound was obtained.
Number average molecular weight: 21600

[Example 28]
Production of Exemplified Compound B1-8 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Polymer of Exemplified Compound B1-8 according to the method described in Example 1 except that 1.58 g of N′-bis [p- (N, N-diphenylamino) phenyl] -6,12-chrysenediamine was used. 1.53 g of compound was obtained.
Number average molecular weight: 14700

[Example 29]
Preparation of Exemplary Compound B1-9 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Polymer of Exemplified Compound B1-9 according to the method described in Example 1 except that 1.46 g of N′-bis [p- (N, N-diphenylamino) phenyl] -3,7-dibenzofuranamine was used. 1.42 g of compound was obtained.
Number average molecular weight: 28400

[Example 30]
Preparation of Exemplified Compound B1-10 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.49 g of N′-bis [p- (N, N-diphenylamino) phenyl] -2,8-dibenzothiophenediamine was used, 1.45 g of molecular compound was obtained.
Number average molecular weight: 16200

[Example 31]
Preparation of Exemplary Compound B1-11 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified Compound B1-11 according to the method described in Example 1 except that 1.49 g of N′-bis [p- (N, N-diphenylamino) phenyl] -4,4′-thiobisbenzenamine was used. 1.50 g of the polymer compound was obtained.
Number average molecular weight: 12300

[Example 32]
Production of Exemplified Compound B1-12 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example 1 except that 1.86 g of (9,9-dimethylfluorenyl) -N, N′-bis [p- (N, N-diphenylamino) phenyl] -3,7-carbazolediamine was used. According to the method of description, 1.68g of high molecular compounds of exemplary compound B1-12 were obtained.
Number average molecular weight: 11400

[Example 33]
Production of Exemplified Compound B1-13 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified compound according to the method described in Example 1 except that 1.51 g of 4 ′-(1-methylethylidene) -bis [N- {p- (N, N-diphenylamino) phenyl} benzeneamine] was used. 1.55 g of the polymer compound B1-13 was obtained.
Number average molecular weight: 13800

[Example 34]
Production of Exemplified Compound B1-14 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, 3, Exemplified compound according to the method described in Example 1 except that 1.51 g of 3 ′-(1-methylethylidene) -bis [N- {p- (N, N-diphenylamino) phenyl} benzeneamine] was used. 1.49 g of a polymer compound of B1-14 was obtained.
Number average molecular weight: 12900

[Example 35]
Production of Exemplified Compound B1-15 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified Compound B1 according to the method described in Example 1 except that 1.60 g of 1-bis [{N-4- (4′-N, N-diphenylamino) phenyl} -4-aminophenyl] cyclohexane was used. As a result, 1.59 g of a polymer compound of −15 was obtained.
Number average molecular weight: 21200

[Example 36]
Preparation of Exemplary Compound B1-17 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified compound according to the method described in Example 1 except that 1.93 g of N′-bis [p- (N, N-diphenylamino) phenyl] -9,9-dioctyl-2,7-fluorenediamine was used. 1.76 g of the polymer compound of B1-17 was obtained.
Number average molecular weight: 34800

[Example 37]
Preparation of Exemplified Compound B1-18 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.77 g of 4 ′-(9H-fluorene-9-ylidene) -bis [N- {p- (N, N-diphenylamino) phenyl} benzeneamine] was used. 1.63 g of the polymer compound of Exemplified Compound B1-18 was obtained.
Number average molecular weight: 21100

[Example 38]
Production of Illustrative Compound B1-20 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1 except that 1.27 g of N′-bis [p- (N, N-diphenylamino) phenyl] -2,6-pyridinediamine was used, the polymer of Exemplified Compound B1-20 1.36 g of compound was obtained.
Number average molecular weight: 12000

[Example 39]
Production of Exemplary Compound B1-21 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.49 g of N′-bis [p- (N, N-diphenylamino) phenyl] -4,4′-diaminobenzophenone was used, 1.46 g of molecular compound was obtained.
Number average molecular weight: 18200

[Example 40]
Preparation of Exemplified Compound B1-22 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified Compound B1-22 according to the method described in Example 1 except that 1.56 g of N′-bis [p- (N, N-diphenylamino) phenyl] -4,4′-sulfonylbisbenzenamine was used. 1.59 g of the polymer compound was obtained.
Number average molecular weight: 22000

[Example 41]
Production of Exemplified Compound B2-2 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, The method described in Example 1 except that 2.30 g of N′-bis [4- {4′-N, N-di (4-hexylphenyl) aminophenyl} phenyl] -1,3-phenylenediamine was used. As a result, 2.02 g of the polymer compound of Exemplified Compound B2-2 was obtained.
Number average molecular weight: 19500

[Example 42]
Production of Exemplified Compound B2-15 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example 1 except that 2.64 g of 1-bis [{N-4- (4′-N, N-di (4-hexylphenyl) aminophenyl) phenyl} -4-aminophenyl] cyclohexane was used. According to the method, 2.20 g of the polymer compound of Exemplified Compound B2-15 was obtained.
Number average molecular weight: 13700

[Example 43]
Production of Illustrative Compound B2-17 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example except that 2.97 g of N′-bis [4- {pN, N-di (4-hexylphenyl) amino} phenylphenyl] -9,9-dioctyl-2,7-fluorenediamine was used. According to the method described in 1., 2.34 g of the polymer compound of Exemplified Compound B2-17 was obtained.
Number average molecular weight: 32100

[Example 44]
Production of Exemplified Compound B2-18 Instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine in Example 1, 4,4 Implemented except using 2.81 g of '-(9H-fluorene-9-ylidene) -bis [N- {4- (pN, N-di (4-hexylphenyl) amino) phenylphenyl} benzeneamine]. According to the method described in Example 1, 2.21 g of the polymer compound of Exemplified Compound B2-18 was obtained.
Number average molecular weight: 18600

[Example 45]
Production of Illustrative Compound B3-2 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example except that 2.47 g of N′-bis [7- {N, N-di (4-hexylphenyl) amino} -9,9-dimethyl-2-fluorenyl] -1,3-phenylenediamine was used. According to the method described in 1, 2.03 g of the polymer compound of Exemplified Compound B3-2 was obtained.
Number average molecular weight: 22000

[Example 46]
Production of Exemplary Compound B3-16 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, 2.81 g of 1-bis [{N-9,9-dimethyl-7- (4′-N, N-di (4-hexylphenyl) amino) -2-fluorenyl} -4-aminophenyl] cyclohexane was used. Except for the above, according to the method described in Example 1, 2.33 g of the polymer compound of Exemplified Compound B3-16 was obtained.
Number average molecular weight: 28400
[Example 47]
Production of Exemplified Compound B3-18 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, N'-bis [9,9-dimethyl-7- {N, N-di (4-hexylphenyl) amino} -2-fluorenyl] -9,9-dioctyl-2,7-fluorenediamine 3.14 g used Except for the above, according to the method described in Example 1, 2.71 g of the polymer compound of Exemplified Compound B3-18 was obtained.
Number average molecular weight: 24600

[Example 48]
Production of Exemplified Compound B3-19 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, 4 ′-(9H-Fluorene-9-ylidene) -bis [N- {9,9-dimethyl-7- (N, N-di (4-hexylphenyl) amino) -2-fluorenyl} benzeneamine] 2.98 g According to the method described in Example 1 except that was used, 2.47 g of the polymer compound of Exemplified Compound B3-19 was obtained.
Number average molecular weight: 11800

[Example 49]
Production of Exemplified Compound B4-1 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.26 g of N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,3-phenylenediamine was used, 1.38 g of molecular compound was obtained.
Number average molecular weight: 13500

[Example 50]
Preparation of Exemplified Compound B4-16 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified according to the method described in Example 1, except that 1.92 g of N′-bis [p- (9H-carbazol-9-yl) phenyl] -9,9-dioctyl-2,7-fluorenediamine was used. 1.87 g of the polymer compound B4-16 was obtained.
Number average molecular weight: 28400

[Example 51]
Production of Illustrative Compound B4-17 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example 1 except that 2.63 g of N′-bis [p- (3,6-dihexyl-9H-carbazol-9-yl) phenyl] -9,9-dioctyl-2,7-fluorenediamine was used. According to the method of description, 2.32g of high molecular compounds of exemplary compound B4-17 were obtained.
Number average molecular weight: 31200

[Example 52]
Production of Exemplary Compound B5-1 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 1.5 ′ g of N′-bis [4- (9H-carbazol-9-yl) phenylphenyl] -1,3-phenylenediamine was used, 1.44 g of a polymer compound was obtained.
Number average molecular weight: 29200

[Example 53]
Production of Exemplified Compound B5-16 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, According to the method described in Example 1, except that 2.24 g of N′-bis [4- (9H-carbazol-9-yl) phenylphenyl] -9,9-dioctyl-2,7-fluorenediamine was used. 1.99 g of the polymer compound of Exemplified Compound B5-16 was obtained.
Number average molecular weight: 24000

[Example 54]
Production of Exemplified Compound B5-17 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Example 1 except that 2.96 g of N′-bis [4- (3,6-dihexyl-9H-carbazol-9-yl) phenylphenyl] -9,9-dioctyl-2,7-fluorenediamine was used. According to the method described in the above, 2.57 g of the polymer compound of Exemplified Compound B5-17 was obtained.
Number average molecular weight: 19500

[Example 55]
Production of Illustrative Compound B6-1 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, The method described in Example 1 except that 1.75 g of N′-bis [9,9-dimethyl-7- (9H-carbazol-9-yl) -2-fluorenyl] -1,3-phenylenediamine was used. As a result, 1.65 g of the polymer compound of Exemplified Compound B6-1 was obtained.
Number average molecular weight: 21300

[Example 56]
Production of Exemplified Compound B6-2 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Implemented except that 2.46 g N'-bis [9,9-dimethyl-7- (3,6-dihexyl-9H-carbazol-9-yl) -2-fluorenyl] -1,3-phenylenediamine was used. According to the method described in Example 1, 2.22 g of the polymer compound of Exemplified Compound B6-2 was obtained.
Number average molecular weight: 24800

[Example 57]
Preparation of Exemplified Compound B6-16 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Except for using 2.80 g of 1-bis [{N-9,9-dimethyl-7- (3,6-dihexyl-9H-carbazol-9-yl) -2-fluorenyl} -4-aminophenyl] cyclohexane According to the method described in Example 1, 2.46 g of the polymer compound of Exemplified Compound B6-16 was obtained.
Number average molecular weight: 21500

[Example 58]
Preparation of Exemplary Compound B6-17 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Implemented except that 2.41 g of N′-bis [9,9-dimethyl-7- (9H-carbazol-9-yl) -2-fluorenyl] -9,9-dioctyl-2,7-fluorenediamine was used. According to the method described in Example 1, 2.10 g of the polymer compound of Exemplified Compound B6-17 was obtained.
Number average molecular weight: 30100

[Example 59]
Production of Exemplified Compound B6-18 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, 3.13 g of N′-bis [9,9-dimethyl-7- (3,6-dihexyl-9H-carbazol-9-yl) -2-fluorenyl] -9,9-dioctyl-2,7-fluorenediamine Except for the use, according to the method described in Example 1, 2.61 g of the polymer compound of Exemplified Compound B6-18 was obtained.
Number average molecular weight: 28500

[Example 60]
Production of Exemplified Compound B6-19 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Except for using 2.26 g of 4 ′-(9H-fluorene-9-ylidene) -bis [N- {9,9-dimethyl-7- (9H-carbazol-9-yl) -2-fluorenyl} benzeneamine] According to the method described in Example 1, 1.98 g of the polymer compound of Exemplified Compound B6-19 was obtained.
Number average molecular weight: 19400

[Example 61]
Production of Exemplified Compound C1-20 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, The method described in Example 1 except that 2.54 g of N′-bis [4- (3′-N, N-di (4-octylphenyl) aminophenyl) phenyl] -1,4-phenylenediamine was used. As a result, 2.11 g of the polymer compound of Exemplified Compound C1-20 was obtained.
Number average molecular weight: 13900

[Example 62]
Production of Exemplified Compound D1-5 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Except for using 2.49 g of N′-bis [4- {4′-N- (4-octylphenyl) -N- (4-hexylphenyl) aminophenyloxy} phenyl] -1,4-phenylenediamine, According to the method described in Example 1, 2.20 g of the polymer compound of Exemplified Compound D1-5 was obtained.
Number average molecular weight: 31000

[Example 63]
Preparation of Exemplified Compound D1-6 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, As described in Example 1, except that 1.87 g of N′-bis [4- {4′-N-phenyl-N- (1-naphthyl) aminophenyloxy} phenyl] -1,4-phenylenediamine was used. According to the method, 1.77 g of the polymer compound of Exemplified Compound D1-6 was obtained.
Number average molecular weight: 24500

[Example 64]
Production of Exemplified Compound D1-7 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, As described in Example 1, except that 1.87 g of N′-bis [4- {4′-N-phenyl-N- (2-naphthyl) aminophenyloxy} phenyl] -1,4-phenylenediamine was used. According to the method, 1.69 g of the polymer compound of Exemplified Compound D1-7 was obtained.
Number average molecular weight: 24100

[Example 65]
Production of Exemplified Compound E1-6 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Except for using 2.60 g of N′-bis [4- {4′-N- (4-octylphenyl) -N- (4-hexylphenyl) aminophenyloxy} phenyl] -1,5-naphthalenediamine, According to the method described in Example 1, 2.31 g of the polymer compound of Exemplified Compound E1-6 was obtained.
Number average molecular weight: 25000

[Example 66]
Production of Exemplified Compound G1-1 In Example 1, instead of using 1.30 g of N, N′-bis [p- (9H-carbazol-9-yl) phenyl] -1,4-phenylenediamine, Exemplified compound G1 according to the method described in Example 1, except that 1.72 g of N′-bis [4- {4′-N, N-diphenylaminophenylthio} phenyl] -1,4-phenylenediamine was used. 1.68 g of a polymer compound of -1.
Number average molecular weight: 16200

[Example 67]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Illustrative Compound A1-1. 1.35 g of a polymer compound having at least one repeating unit represented by the exemplified compound A1-1 in the polymer chain was dissolved in 43.7 g of chloroform, and charged with 20 g of 98% sulfuric acid under a nitrogen stream. And stirred at room temperature for 1.5 hours. The reaction solution was discharged into 200 ml of acetonitrile, and the precipitate was collected by filtration. The obtained solid was washed with acetonitrile until the pH of the filtrate became 5, and dried under reduced pressure at 70 degrees for 8 hours to obtain 1.57 g of a crude product as a brown solid. 1.57 g of the crude product was dissolved in 90 ml of 50% aqueous methanol, 160 ml of an anion exchange resin (Amberlite IRA400-OHAG from Organo) was added, and the mixture was stirred at room temperature for 5 hours. After the ion exchange resin was removed by filtration, the filtrate was concentrated to dryness and dried under reduced pressure at 70 degrees for 7 hours. The obtained solid was dissolved in 30 ml of methanol and reprecipitated with 80 ml of toluene to obtain 1 g of the objective compound 1.5 as a brown solid. The compound was dissolved in methanol and insoluble in toluene. Further, the compound was not observed to be cohesive in the solution state.

The average number of sulfo groups per repeating unit was calculated from the following formula.
Average number of sulfo groups = {Repeating unit molecular weight of (Exemplary Compound A1-1) × Sulfur Element Analysis Value (%) − Sulfur Number in Repeating Unit of Exemplified Compound A1-1 × Sulfur Atom Weight × 100} ÷ {Sulfur Atom Weight × 100-elemental analysis value of sulfur (%) x (sulfo group molecular weight-hydrogen atom weight)}
Elemental sulfur analysis value 13.6%
Average number of sulfo groups per repeating unit: 5.3 UV (λmax): 341 nm (MeOH)

[Example 68]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one benzene ring is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A1-3 In Example 67, Except for using 1.35 g of the polymer compound of Example Compound A1-1 obtained in Example 2, instead of using 1.35 g of the polymer compound of Example Compound A1-1 obtained in Example 1, The operation described in Example 67 was performed to obtain 1.60 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 3.5

[Example 69]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A1-10. Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Exemplified Compound A1-10 obtained in Example 7 was used, The operation described in Example 67 was performed to obtain 1.51 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.5

[Example 70]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A1-11. Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Illustrated Compound A1-11 obtained in Example 8 was used, The operation described in Example 67 was performed to obtain 1.57 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.9

[Example 71]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A1-13 In Example 67, Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Exemplified Compound A1-13 obtained in Example 10 was used, The procedure described in Example 67 was performed to obtain 1.58 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 6.0

[Example 72]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A1-17. Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Illustrative Compound A1-17 obtained in Example 13 was used, The operation described in Example 67 was performed to obtain 1.43 g of the objective polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 4.9

[Example 73]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A2-6 In Example 67, Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Illustrative Compound A2-6 obtained in Example 16 was used, The operation described in Example 67 was performed to obtain 1.49 g of the objective polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.2

[Example 74]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A2-7. Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Illustrative Compound A2-7 obtained in Example 17 was used, The operation described in Example 67 was performed to obtain 1.47 g of the objective polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.1

[Example 75]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A3-1. Except for using 1.35 g of the polymer compound of Example Compound A3-1 obtained in Example 18, instead of using 1.35 g of the polymer compound of Example Compound A1-1 obtained in Example 1, The operation described in Example 67 was performed to obtain 1.44 g of the objective polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 4.7

[Example 76]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound A3-4. Except for using 1.35 g of the polymer compound of Example Compound A3-4 obtained in Example 20, instead of using 1.35 g of the polymer compound of Example Compound A1-1 obtained in Example 1, The operation described in Example 67 was performed to obtain 1.55 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.0

[Example 77]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound B1-6 In Example 67, Except for using 1.35 g of the polymer compound of Exemplified Compound B1-6 obtained in Example 26 instead of using 1.35 g of the polymer compound of Illustrative Compound A1-1 obtained in Example 1, The procedure described in Example 67 was performed to obtain 1.46 g of the objective polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.0

[Example 78]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound B1-9 In Example 67, Except for using 1.35 g of the polymer compound of Example Compound B1-9 obtained in Example 29 instead of using 1.35 g of the polymer compound of Example Compound A1-1 obtained in Example 1, The procedure described in Example 67 was performed to obtain 1.46 g of the objective polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 4.9

[Example 79]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound B1-12 In Example 67, Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Illustrative Compound B1-12 obtained in Example 32 was used, The procedure described in Example 67 was performed to obtain 1.67 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 6.2

[Example 80]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound B1-13. Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Exemplified Compound B1-13 obtained in Example 33 was used, The operation described in Example 67 was performed to obtain 1.50 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.2

[Example 81]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound B1-14. Except for using 1.35 g of the polymer compound of Exemplified Compound B1-14 obtained in Example 34 instead of using 1.35 g of the polymer compound of Illustrative Compound A1-1 obtained in Example 1, The operation described in Example 67 was performed to obtain 1.51 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.3

[Example 82]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one benzene ring is substituted with a sulfo group in the repeating unit represented by Exemplary Compound B1-15 In Example 67, Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Exemplified Compound B1-15 obtained in Example 35 was used, The operation described in Example 67 was performed to obtain 1.52 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.4

[Example 83]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound B1-18. Instead of using 1.35 g of the polymer compound of Exemplified Compound A1-1 obtained in Example 1, except that 1.35 g of the polymer compound of Exemplified Compound B1-18 obtained in Example 37 was used, The operation described in Example 67 was performed to obtain 1.60 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 6.1

[Example 84]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound B4-1 In Example 67, Except for using 1.35 g of the polymer compound of Example Compound B4-1 obtained in Example 49 instead of using 1.35 g of the polymer compound of Example Compound A1-1 obtained in Example 1, The operation described in Example 67 was performed to obtain 1.44 g of the objective polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 4.9

[Example 85]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain, in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound D1-6 In Example 67, Except for using 1.35 g of the polymer compound of Exemplified Compound D1-6 obtained in Example 63 instead of using 1.35 g of the polymer compound of Illustrative Compound A1-1 obtained in Example 1, The operation described in Example 67 was performed to obtain 1.49 g of the objective polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.2

[Example 86]
Production of a sulfo group-containing polymer compound having at least one repeating unit in the polymer chain in which at least one of the benzene rings is substituted with a sulfo group in the repeating unit represented by Exemplary Compound D1-7. Except for using 1.35 g of the polymer compound of Example Compound D1-7 obtained in Example 64 instead of using 1.35 g of the polymer compound of Example Compound A1-1 obtained in Example 1, The operation described in Example 67 was performed to obtain 1.51 g of the target polymer compound.
The average number of sulfo groups per repeating unit was calculated based on the method described in Example 67.
Average number of sulfo groups per repeating unit: 5.3

[Example 87] (Production of organic electroluminescent device)
A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 nm was subjected to ultrasonic cleaning using a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and ethanol. The substrate was dried with nitrogen gas and further UV / ozone cleaned. First, on the ITO transparent electrode, by using a methanol solution of the sulfo group-containing polymer compound obtained in Example 67 as a hole injection material (a solution in which 20 mg of a polymer compound is dissolved in 4 mL of methanol), by spin coating, A film was formed to a thickness of 20 nm, and dried under reduced pressure (100 degrees, 30 minutes) on a hot plate to form a layer. Next, this glass substrate was fixed to a substrate holder of a vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 −4 Pa. N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine was deposited at a deposition rate of 0.2 nm / sec to a thickness of 40 nm, and then tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0. Vapor deposition was performed at a thickness of 50 nm at 2 nm / sec. Further, lithium fluoride was deposited at a thickness of 0.5 nm at 0.2 nm / sec. Aluminum was vapor-deposited thereon as a cathode to produce an organic electroluminescent element (organic EL element-1).

In addition, vapor deposition was implemented, maintaining the pressure reduction state of a vapor deposition tank. A direct current voltage was applied to the produced organic electroluminescent element, and it was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at 50 degrees. Initially, green light emission of 4.05 V and luminance of 288 cd / m ² was confirmed. The device was allowed to stand at 100 degrees for 1 hour, and it was confirmed that there was no significant change in light emission characteristics.

  Table 54 shows the results of measurement of the time taken for the emission luminance to decay by 20% and 50% with respect to the initial luminance.

Comparative Example 1 Life Evaluation of Organic Electroluminescent Device In Example 87, the sulfo group-containing polymer compound obtained in Example 67 was used as the hole injection material in the PEDOT / PSS (Bayer, trade name BaytronP) formula (7 ), An organic electroluminescence device was prepared in the same manner as in Example 87 (organic EL device-2), and the light emission lifetimes of the devices were compared.

Table 54 shows the time until the light emission luminance attenuates by 20% and 50% with respect to the initial luminance as a relative value when the organic EL element-1 is 100.

  As is apparent from Table 54, the organic EL device-1 of the present invention using the sulfo group-containing polymer compound of the present invention as the hole injection material showed a longer emission lifetime than the organic EL device-2.

[Example 88] Evaluation of film formability Using a methanol solution of the polymer compound obtained in Example 67 (solution obtained by dissolving 20 mg of a polymer compound in 4 mL of methanol) on a glass substrate, a thickness of 60 nm was obtained by spin coating. The film was formed. When the surface of the film obtained by drying under reduced pressure (100 degrees, 30 minutes) on a hot plate was observed, a uniform film was formed. Table 55 shows the measurement results of surface roughness by AFM.

[Comparative Example 2] Evaluation of film formability In place of the polymer compound obtained in Example 67, the PEDOT / PSS (Bayer, trade name BaytronP) formula (7) was used in the same manner as in Example 88. When the film was observed, the film thickness was found to be more varied than that formed using the polymer compound obtained in Example 67. Table 55 shows the measurement results of surface roughness by AFM.

[Comparative Example 3] Evaluation of film formability Instead of the polymer compound obtained in Example 67, a commercially available polymer represented by the formula (8) (molecular weight 28000: ADS254BE manufactured by ADS) was sulfonated. Using the resulting sulfo group-containing triarylamine polymer (hereinafter referred to as “substituted sulfonic acid of formula (8)”), an attempt was made to form a film in the same manner as in Example 88, but it was hardly soluble in methanol. Yes, the film could not be formed.

  The sulfonic acid substitution product of formula (8) was synthesized by the following method.

  0.400 g of the polymer represented by the formula (8) was dissolved in 13.0 g of chloroform, charged with 6 g of 98% sulfuric acid under a nitrogen stream, and stirred at room temperature for 48 hours. The reaction solution was discharged into 60 ml of acetonitrile, and the precipitate was collected by filtration. The obtained solid was washed with acetonitrile until the pH of the filtrate became 5, and dried under reduced pressure at 70 degrees for 8 hours to obtain 0.38 g of the objective compound as a brown solid.

The average number of sulfo groups per repeating unit was calculated in the same manner as in Example 67.
Elemental sulfur analysis value 1.0%
Average number of sulfo groups per repeating unit: 0.2

  As is clear from Table 55, the sulfo group-containing polymer compound of the present invention showed very good film forming properties as compared with BaytronP and the sulfonic acid substitution product of formula (8).

[Example 89] to [Example 107] Evaluation of film formability Instead of the polymer compound obtained in Example 67, the sulfo group-containing polymer compound obtained in Example 68 to Example 86 was replaced with Example 88. When a film was formed and observed by the same method as described above, a uniform film was formed. Table 56 shows the measurement results of surface roughness by AFM.

  As is clear from Table 56, the sulfo group-containing polymer compound of the present invention showed very good film formability as compared with BaytronP and the sulfonic acid substitution product of formula (8).

[Example 108] (Preparation of organic electroluminescent device) (Evaluation of sulfo body)
Ultrasonic cleaning of patterned glass substrate with 150 nm thick ITO transparent electrode (sputtered film product; sheet resistance 15 Ω) with neutral detergent, semi-coclean (Furuuchi Chemical), ultrapure water, acetone, isopropyl alcohol After washing in this order, it was dried with nitrogen blow, and finally ultraviolet ozone cleaning was performed. Next, a methanol solution (2.0% by weight) of the sulfo group-containing polymer compound obtained in Example 67 was formed into a film having a thickness of 65 nm by spin coating, and dried under reduced pressure (100 ° C., 1 hour) on a hot plate. ) To form a first hole injecting and transporting layer.
Next, a xylene solution (2.0% by weight) of a polymer compound ADS259BE (formula 14) manufactured by American DyeSource is formed to a thickness of 50 nm by spin coating, and heat treatment is performed in a nitrogen atmosphere on a hot plate. (180 degree | times, 1 hour), the 2nd positive hole injection transport layer was formed.

  Next, after rinsing the second hole injecting and transporting layer with xylene, a xylene solution (1.2 wt%) of polyfluorene (formula 15) is formed to a thickness of 60 nm by spin coating, and hot A light emitting layer was formed by drying under reduced pressure (140 degrees, 30 minutes) on the plate.

  Next, the glass substrate is fixed to the substrate holder of the vapor deposition apparatus, lithium fluoride (LiF) is deposited on the light emitting layer, and the film thickness is 0.5 nm at a vapor deposition rate of 0.2 nm / second using a molybdenum boat. Then, aluminum (Al) was heated by a tungsten boat to form an aluminum layer having a film thickness of 100 nm at a deposition rate of 2.0 nm / sec to complete the cathode. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. In this organic electroluminescence device, light emission was observed through a glass substrate by applying a direct current voltage using ITO as an anode and LiF / Al as a cathode. The luminance was measured with a Topcon luminance meter BM-8.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, blue light emission of 5.1 V and luminance of 162 cd / m ² was confirmed. When continuous driving was performed for 200 hours from an initial luminance of 500 cd / m ² , the luminance reduction rate was 22%. The results are shown in Table 57.

[Example 109] to [Example 127]
In Example 108, instead of using the sulfo group-containing polymer compound obtained in Example 67 when forming the hole injection transport layer, the sulfo group-containing polymer compound obtained in Example 68 to Example 86 was used. An organic electroluminescent element was produced according to the procedure described in Example 108 except that was used. Further, a direct current voltage was applied to the device in the same manner as in Example 108, the characteristics of the device were measured, and the results are shown in Table 57.

[Comparative Example A-1]
In Example 108, instead of using the polymer compound obtained in Example 67 when forming the first hole injecting and transporting layer, the PEDOT / PSS (Bayer, trade name BaytronP) formula (7) is used. An organic electroluminescent element was produced according to the procedure described in Example 108 except that it was used. Further, a direct current voltage was applied to the device in the same manner as in Example 108, the characteristics of the device were measured, and the results are shown in Table 57.

[Example 128]
Ultrasonic cleaning of patterned glass substrate with 150 nm thick ITO transparent electrode (sputtered film product; sheet resistance 15 Ω) with neutral detergent, semi-coclean (Furuuchi Chemical), ultrapure water, acetone, isopropyl alcohol After washing in this order, it was dried with nitrogen blow, and finally ultraviolet ozone cleaning was performed. Next, the PEDOT / PSS was formed into a film having a thickness of 65 nm by a spin coating method, and dried under reduced pressure (200 ° C., 1 hour) on a hot plate to form a first hole injection / transport layer. Next, a toluene solution (1.5% by weight) of the polymer compound synthesized in Example 3 was formed into a film having a thickness of 50 nm by spin coating, and heat treatment was performed in a nitrogen atmosphere on a hot plate (180 1 hour), a second hole injection transport layer was formed.

  Next, after rinsing the second hole injecting and transporting layer with toluene, the xylene solution of polyfluorene (1.2 wt%) was formed into a film with a thickness of 60 nm by a spin coating method, A light emitting layer was formed by drying under reduced pressure (140 degrees, 30 minutes). Next, the glass substrate is fixed to the substrate holder of the vapor deposition apparatus, lithium fluoride (LiF) is deposited on the light emitting layer, and the film thickness is 0.5 nm at a vapor deposition rate of 0.2 nm / second using a molybdenum boat. Then, aluminum (Al) was heated with a tungsten boat to form an aluminum layer having a thickness of 100 nm at a deposition rate of 2.0 nm / sec to complete the cathode. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. In this organic electroluminescence device, light emission was observed through a glass substrate by applying a direct current voltage using ITO as an anode and LiF / Al as a cathode. The luminance was measured with a Topcon luminance meter BM-8.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, blue light emission of 5.4 V and a luminance of 151 cd / m ² was confirmed. When continuous driving was performed for 200 hours from an initial luminance of 500 cd / m ² , the luminance reduction rate was 28%. The results are shown in Table 58.

[Example 129] to [Example 153]
In Example 128, instead of using the polymer compound obtained in Example 3 in forming the second hole injecting and transporting layer, Examples 4, 8, 10, 15, 19, 21, 22, 23 25, 41, 42, 43, 44, 45, 46, 47, 48, 51, 54, 56, 57, 59, 61, 62, 65, except that the polymer compound obtained in Example 65 was used. An organic electroluminescent element was produced according to the operation described in 1. Further, a direct current voltage was applied to the device in the same manner as in Example 128, the characteristics of the device were measured, and the results are shown in Table 58.

[Comparative Example B-1]
In Example 128, in forming the second hole injecting and transporting layer, it is described in Example 128 except that the ADS259BE (formula 14) was used instead of using the polymer compound obtained in Example 3. The organic electroluminescent element was produced according to the above operations. Further, a direct current voltage was applied to the device in the same manner as in Example 128, the characteristics of the device were measured, and the results are shown in Table 58.

[Comparative Example B-2]
In Example 128, when forming the second hole injecting and transporting layer, instead of using the polymer compound obtained in Example 3, it is represented by the formula (16) described in JP-A-2006-316224. An organic electroluminescent device was produced according to the procedure described in Example 128 except that a polymer compound composed of repeating units was used. Further, a direct current voltage was applied to the device in the same manner as in Example 128, the characteristics of the device were measured, and the results are shown in Table 58.

[Example 155]
Ultrasonic cleaning of patterned glass substrate with 150 nm thick ITO transparent electrode (sputtered film product; sheet resistance 15 Ω) with neutral detergent, semi-coclean (Furuuchi Chemical), ultrapure water, acetone, isopropyl alcohol After washing in this order, it was dried with nitrogen blow, and finally ultraviolet ozone cleaning was performed. Next, a methanol solution (2.0% by weight) of the sulfo group-containing polymer obtained in Example 67 was formed into a film with a thickness of 65 nm by spin coating, and dried under reduced pressure (100 ° C., 1 hour) on a hot plate. ) To form a first hole injecting and transporting layer. Next, a toluene solution (1.5% by weight) of the polymer compound obtained in Example 3 was formed into a film having a thickness of 50 nm by spin coating, and heat treatment was performed on a hot plate in a nitrogen atmosphere ( 180 ° C., 1 hour), a second hole injection transport layer was formed.

  Next, after rinsing the second hole injecting and transporting layer with toluene, the above xylene solution of polyfluorene (1.2% by weight) was formed into a film having a thickness of 60 nm by spin coating, And dried under reduced pressure (140 degrees, 30 minutes) to form a light emitting layer. Next, the glass substrate is fixed to the substrate holder of the vapor deposition apparatus, lithium fluoride (LiF) is deposited on the light emitting layer, and the film thickness is 0.5 nm at a vapor deposition rate of 0.2 nm / second using a molybdenum boat. Then, aluminum (Al) was heated with a tungsten boat to form an aluminum layer with a film thickness of 100 nm at a deposition rate of 2.0 nm / sec to complete the cathode. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. In this organic electroluminescence device, light emission was observed through a glass substrate by applying a direct current voltage using ITO as an anode and LiF / Al as a cathode. The luminance was measured with a Topcon luminance meter BM-8.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, blue light emission of 5.3 V and luminance of 165 cd / m ² was confirmed. When continuous driving was performed for 200 hours from an initial luminance of 500 cd / m ² , the luminance reduction rate was 26%. The results are shown in Table 59.

[Example 156] to [Example 180]
In Example 155, instead of using the polymer compound obtained in Example 3 in forming the hole injection transport layer, Examples 4, 8, 10, 15, 19, 21, 22, 23, 25, 41, 42, 43, 44, 45, 46, 47, 48, 51, 54, 56, 57, 59, 61, 62, except that the polymer compound obtained in Example 65 was used. According to the operation, an organic electroluminescent device was produced. Further, in the same manner as in Example 155, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 59.

  As is clear from Tables 57 to 59, the organic EL device using the sulfo group-containing polymer compound of the present invention and the polymer compound of the present invention as an intermediate thereof as a hole injecting and transporting material has an emission luminance. The light emission efficiency was high and the luminance reduction rate was low, and the device life was excellent.

（式中、Ｚ ^１ 〜Ｚ ^４ は置換基を示す。ｐ ^１ 、ｐ ^２ は０〜５の整数、ｐ ^３ 、ｐ ^４ は０〜４の整数を示す。Ｘ ^１ 〜Ｘ ^４ は一価の芳香族基を示し、Ｘ ^１ とＸ ^２ 、Ｘ ^３ とＸ ^４ は、互いに連結して環を形成してもよい。Ｙは二価の芳香族基を示し、Ａｒ ^１ 〜Ａｒ ^４ は互いに同一であっても異なっていても良い二価の芳香族基を示す。また、これらの二価の芳香族基は、芳香族基が互いに連結して環を形成した芳香族基でもよい。Ｔ ^１ とＴ ^２ は単結合、−（ＣＨ _２ ） _ｔ −、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＱ ^１ Ｑ ^２ −、−ＣＯ−、−ＳＯ−、−ＳＯ _２ −、−ＳｉＥ _２ −からなる群から選ばれる基であり、互いに同一であっても異なっていても良い。ｔは１〜２０の整数を示す。Ｑ ^１ およびＱ ^２ はアルキル基または芳香族基を示し、互いに結合して環を形成していてもよい。Ｅは水素原子、アルキル基または芳香族基を示す。ｍ、ｎは０〜２の整数を示す。）
で表される繰り返し単位を高分子鎖中に少なくとも一つ有する高分子化合物に対してスルホ基を導入した構造であるスルホ基含有高分子化合物。
２．一般式（２）：

（式中、Ｚ ^１ 〜Ｚ ^４ 、ｐ ^１ 〜ｐ ^４ 、Ｘ ^１ 〜Ｘ ^４ 、Ｙおよびｍ、ｎは前記のとおり。）
で表される繰り返し単位を高分子鎖中に少なくとも一つ有する高分子化合物に対してスルホ基を導入した構造である１に記載のスルホ基含有高分子化合物。
３．前記Ｙで表される基が一般式（ａ−１）で表される基である１または２に記載のスルホ基含有高分子化合物。

（式中、Ｑは単結合、Ｏ、Ｓ、ＣＨ _２ 、ＣＭｅ _２ 、ＣＯ、ＳＯ、ＳＯ _２ 、ＳｉＨ _２ 、ＳｉＭｅ _２ からなる群から選ばれる基であり、ｋは０〜２の整数を表す。）
４．前記ｐ ^１ 〜ｐ ^４ の少なくとも一つが１以上の整数であり、前記Ｚ ^１ 〜Ｚ ^４ は、互いに同一であっても異なっていてもよく、それぞれカルボキシル基、ヒドロキシル基、アミノ基、一置換アミノ基、二置換アミノ基、および一般式（１ａ）〜（３ａ）：
−（Ｏ） _Ｌ −Ｄ （１ａ）
−Ｏ（Ｃ＝Ｏ）−Ｄ （２ａ）
−（Ｃ＝Ｏ）Ｏ−Ｄ （３ａ）
（式中、Ｄは無置換または置換された直鎖状、分岐鎖状または環状の炭素数１〜８のアルキル基、無置換または置換された炭素数４〜１２の一価の芳香族基、無置換または置換された炭素数７〜２０のアラルキル基を示し、Ｌは０または１を示す）
で表される基からなる群から選択される基である１〜３のいずれかに記載のスルホ基含有高分子化合物。
５．前記ｐ ^１ 〜ｐ ^４ がそれぞれ０である１〜３のいずれかに記載のスルホ基含有高分子化合物。
６．１〜５のいずれかに記載のスルホ基含有高分子化合物からなる有機電界発光素子材料。
７．１〜５のいずれかに記載のスルホ基含有高分子化合物を有機溶媒に溶解させた状態で用いることができることを特徴とする有機電界発光素子材料。
８．前記有機溶媒が極性溶媒である７の記載の有機電界発光素子材料。
９．一対の電極間に、１〜５のいずれかに記載のスルホ基含有高分子化合物を少なくとも一種含有する層を、少なくとも一層挟持してなる有機電界発光素子。
１０．前記スルホ基含有高分子化合物を含有する層が、電荷注入輸送層である９に記載の有機電界発光素子。
１１．前記電荷注入輸送層が正孔注入輸送層である１０に記載の有機電界発光素子。
１２．前記正孔注入輸送層を少なくとも二層備える１１に記載の有機電界発光素子。
１３．一般式（１）で表される繰り返し単位を高分子鎖中に少なくとも一つ有する高分子化合物。

（式中、Ｚ ^１ 〜Ｚ ^４ は置換基を示す。ｐ ^１ 、ｐ ^２ は０〜５の整数、ｐ ^３ 、ｐ ^４ は０〜４の整数を示す。Ｘ ^１ 〜Ｘ ^４ は一価の芳香族基を示し、Ｘ ^１ とＸ ^２ 、Ｘ ^３ とＸ ^４ は、互いに連結して環を形成していてもよい。Ｙは二価の芳香族基を示し、Ａｒ ^１ 〜Ａｒ ^４ は互いに同一であっても異なっていても良い二価の芳香族基を示す。また、これらの二価の芳香族基は、芳香族基が互いに連結して環を形成した芳香族基でもよい。Ｔ ^１ とＴ ^２ は単結合、−（ＣＨ _２ ） _ｔ −、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＱ ^１ Ｑ ^２ −、−ＣＯ−、−ＳＯ−、−ＳＯ _２ −、−ＳｉＥ _２ −からなる群から選ばれる基であり、互いに同一であっても異なっていても良い。ｔは１〜２０の整数を示す。Ｑ ^１ およびＱ ^２ はアルキル基または芳香族基を示し、互いに結合して環を形成していてもよい。Ｅは水素原子、アルキル基または芳香族基を示す。ｍ、ｎは０〜２の整数を示す。）
１４．一般式（２）で表される繰り返し単位を高分子鎖中に少なくとも一つ有する１３に記載の高分子化合物。

（式中、Ｚ ^１ 〜Ｚ ^４ 、ｐ ^１ 〜ｐ ^４ 、Ｘ ^１ 〜Ｘ ^４ 、Ｙおよびｍ、ｎは前記のとおり。）
１５．１３または１４に記載の高分子化合物からなる有機電界発光素子材料。
１６．１３または１４に記載の高分子化合物を有機溶媒に溶解させた状態で用いることができることを特徴とする有機電界発光素子材料。
１７．一対の電極間に、１３または１４に記載の高分子化合物を少なくとも一種含有する層を、少なくとも一層挟持してなる有機電界発光素子。
１８．前記高分子化合物を含有する層が、電荷注入輸送層である１７記載の有機電界発光素子。
１９．前記電荷注入輸送層が正孔注入輸送層である１８に記載の有機電界発光素子。
２０．前記正孔注入輸送層を少なくとも二層備える１９に記載の有機電界発光素子。
２１．１に記載のスルホ基含有高分子化合物を少なくとも一種含有する層を少なくとも一層挟持し、１３に記載の高分子化合物を少なくとも一種含有する層を少なくとも一層挟持してなる有機電界発光素子。
The organic electroluminescent device obtained using the sulfo group-containing polymer compound of the present invention and the polymer compound of the present invention as an intermediate thereof is used as a panel-type light source, various light-emitting devices, display devices, labels, and sensors. can do.
Hereinafter, examples of the reference form will be added.
1. General formula (1):

^(Wherein, Z 1 to Z ⁴ are ^.p 1 illustrating a substituent, ^{p 2} is an integer of 0 to ^{5, p 3,} p ⁴ is ^.X 1 to X ⁴ represents an integer of 0 to 4 monovalent X ¹ and X ² , X ³ and X ⁴ may be linked to each other to form a ring, Y represents a divalent aromatic group, and Ar ^{1 to} Ar ⁴ are the same as each other It shows the a and may be different divalent aromatic groups in. also, these divalent aromatic groups may be an aromatic group aromatic groups are linked to each other to form a ring .T ¹ And T ² are a single bond, — (CH ₂ ) _t —, —CH═CH—, —C≡C—, —O—, —S—, —CQ ¹ Q ² —, —CO—, —SO—, -SO ₂ -, - SiE ₂ - a group selected from the group consisting of, the .Q ¹ and ^{Q 2} represents an .t an integer of from 1 to 20 also being the same or different or an alkyl group It represents an aromatic group, .m showing binding to optionally form a ring .E is hydrogen atom, an alkyl group or an aromatic group each other, n represents an integer of 0 to 2.)
A sulfo group-containing polymer compound having a structure in which a sulfo group is introduced into a polymer compound having at least one repeating unit represented by the formula:
2. General formula (2):

^{(Wherein, Z 1 ~Z 4, p 1} ~p 4, X 1 ~X 4, Y and m, n are as above.)
2. The sulfo group-containing polymer compound according to 1, which has a structure in which a sulfo group is introduced into a polymer compound having at least one repeating unit represented by the formula:
3. The sulfo group-containing polymer compound according to 1 or 2, wherein the group represented by Y is a group represented by formula (a-1).

(In the formula, Q is a group selected from the group consisting of a single bond, O, S, CH ₂ , CMe ₂ , CO, SO, SO ₂ , SiH ₂ , and SiMe ₂ , and k represents an integer of 0 to 2. .)
4). Wherein at least one is an integer of 1 or more of p ¹ ~p ^4, wherein Z ¹ to Z ⁴ may be the being the same or different, each a carboxyl group, a hydroxyl group, an amino group, monosubstituted amino Groups, disubstituted amino groups, and general formulas (1a) to (3a):
-(O) _L -D (1a)
-O (C = O) -D (2a)
-(C = O) OD (3a)
(Wherein D is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted monovalent aromatic group having 4 to 12 carbon atoms, An unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, and L represents 0 or 1)
The sulfo group-containing polymer compound according to any one of 1 to 3, which is a group selected from the group consisting of groups represented by:
5. Sulfo group-containing polymer compound according to any one of 1 to 3 the ^p 1 ~p ⁴ is zero, respectively.
The organic electroluminescent element material which consists of a sulfo group containing high molecular compound in any one of 6.1-5.
7. An organic electroluminescent element material, wherein the sulfo group-containing polymer compound according to any one of 7 to 5 can be used in a state dissolved in an organic solvent.
8). 8. The organic electroluminescent element material according to 7, wherein the organic solvent is a polar solvent.
9. An organic electroluminescence device comprising at least one layer containing at least one kind of the sulfo group-containing polymer compound according to any one of 1 to 5 between a pair of electrodes.
10. 10. The organic electroluminescence device according to 9, wherein the layer containing the sulfo group-containing polymer compound is a charge injection / transport layer.
11. 11. The organic electroluminescence device according to 10, wherein the charge injection / transport layer is a hole injection / transport layer.
12 12. The organic electroluminescent device according to 11, comprising at least two hole injection transport layers.
13. A polymer compound having at least one repeating unit represented by the general formula (1) in a polymer chain.

^(Wherein, Z 1 to Z ⁴ are ^.p 1 illustrating a substituent, ^{p 2} is an integer of 0 to ^{5, p 3,} p ⁴ is ^.X 1 to X ⁴ represents an integer of 0 to 4 monovalent X ¹ and X ² , X ³ and X ⁴ may be linked to each other to form a ring, Y represents a divalent aromatic group, and Ar ^{1 to} Ar ⁴ represent each other The divalent aromatic group may be the same or different, and these divalent aromatic groups may be aromatic groups in which aromatic groups are connected to each other to form a ring. ¹ and T ² are a single bond, — (CH ₂ ) _t —, —CH═CH—, —C≡C—, —O—, —S—, —CQ ¹ Q ² —, —CO—, —SO—. _{, -SO 2 -, - SiE 2} - a group selected from the group consisting of, the .Q ¹ and ^{Q 2} represents an .t an integer of from 1 to 20 also being the same or different alkyl Or an aromatic group, a bond optionally to form a ring .E hydrogen atom, .m represents an alkyl group or an aromatic group, n represents an integer of 0 to 2 to each other.)
14 14. The polymer compound according to 13, having at least one repeating unit represented by the general formula (2) in the polymer chain.

^{(Wherein, Z 1 ~Z 4, p 1} ~p 4, X 1 ~X 4, Y and m, n are as above.)
15. An organic electroluminescent element material comprising the polymer compound according to 15.13 or 14.
16. An organic electroluminescent device material, wherein the polymer compound according to 16.13 or 14 can be used in a state dissolved in an organic solvent.
17. An organic electroluminescence device comprising at least one layer containing at least one polymer compound described in 13 or 14 between a pair of electrodes.
18. 18. The organic electroluminescence device according to 17, wherein the layer containing the polymer compound is a charge injection / transport layer.
19. 19. The organic electroluminescence device according to 18, wherein the charge injection / transport layer is a hole injection / transport layer.
20. 20. The organic electroluminescence device according to 19, comprising at least two hole injection / transport layers.
2. An organic electroluminescent device comprising at least one layer containing at least one sulfo group-containing polymer compound according to 21.1 and at least one layer containing at least one polymer compound according to 13.

Claims (21)

General formula (1):

^(Wherein, Z 1 to Z ⁴ are ^.p 1 illustrating a substituent, ^{p 2} is an integer of 0 to ^{5, p 3,} p ⁴ is ^.X 1 to X ⁴ represents an integer of 0 to 4 monovalent X ¹ and X ² , X ³ and X ⁴ may be linked to each other to form a ring, Y represents a divalent aromatic group, and Ar ^{1 to} Ar ⁴ are the same as each other It shows the a and may be different divalent aromatic groups in. also, these divalent aromatic groups may be an aromatic group aromatic groups are linked to each other to form a ring .T ¹ And T ² are a single bond, — (CH ₂ ) _t —, —CH═CH—, —C≡C—, —O—, —S—, —CQ ¹ Q ² —, —CO—, —SO—, -SO ₂ -, - SiE ₂ - a group selected from the group consisting of, the .Q ¹ and ^{Q 2} represents an .t an integer of from 1 to 20 also being the same or different or an alkyl group It represents an aromatic group, .m showing binding to optionally form a ring .E is hydrogen atom, an alkyl group or an aromatic group each other, n represents an integer of 0 to 2.)
In the repeating unit represented by, ^X 1 ~X 4, ^Y and at least one of Yusuke least one repeating unit substituted with a sulfo group in the polymer chain absence sulfo group-containing polymer compound of the benzene ring. General formula (2):

(In the formula, Z ^{1 to} Z ⁴ , p ^{1 to} p ⁴ , X ^{1 to} X ⁴ , Y, m, and n are as described above.)
In in represented by repeating units, ^X 1 ~X 4, ^Y and sulfo according repeating units at least one is substituted by a sulfo group 請 Motomeko 1 that Yusuke least one in the polymer chain of the benzene ring Group-containing polymer compound. The sulfo group-containing polymer compound according to claim 1 or 2, wherein the group represented by Y is a group represented by formula (a-1).

(In the formula, Q is a group selected from the group consisting of a single bond, O, S, CH ₂ , CMe ₂ , CO, SO, SO ₂ , SiH ₂ , and SiMe ₂ , and k represents an integer of 0 to 2. .) At least one of the p ^{1 to} p ⁴ is an integer of 1 or more, and the Z ^{1 to} Z ⁴ may be the same as or different from each other, and are each a carboxyl group, a hydroxyl group, an amino group, or a monosubstituted amino group. Groups, disubstituted amino groups, and general formulas (1a) to (3a):
-(O) _L -D (1a)
-O (C = O) -D (2a)
-(C = O) OD (3a)
(Wherein D is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted monovalent aromatic group having 4 to 12 carbon atoms, An unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, and L represents 0 or 1)
The sulfo group-containing polymer compound according to any one of claims 1 to 3, which is a group selected from the group consisting of groups represented by: Sulfo group-containing polymer compound according to any one of claims 1 to 3 wherein p ¹ ~p ⁴ is zero, respectively.   The organic electroluminescent element material which consists of a sulfo group containing polymer compound in any one of Claims 1-5.   An organic electroluminescent element material, wherein the sulfo group-containing polymer compound according to any one of claims 1 to 5 can be used in a state dissolved in an organic solvent.   The organic electroluminescent element material according to claim 7, wherein the organic solvent is a polar solvent.   An organic electroluminescence device comprising at least one layer containing at least one layer containing the sulfo group-containing polymer compound according to any one of claims 1 to 5 between a pair of electrodes.   The organic electroluminescent element according to claim 9, wherein the layer containing the sulfo group-containing polymer compound is a charge injection transport layer.   The organic electroluminescent device according to claim 10, wherein the charge injection transport layer is a hole injection transport layer.   The organic electroluminescence device according to claim 11, comprising at least two hole injection transport layers. A polymer compound having at least one repeating unit represented by the general formula (1) in a polymer chain.

^(Wherein, Z 1 to Z ⁴ are ^.p 1 illustrating a substituent, ^{p 2} is an integer of 0 to ^{5, p 3,} p ⁴ is ^.X 1 to X ⁴ represents an integer of 0 to 4 monovalent X ¹ and X ² , X ³ and X ⁴ may be linked to each other to form a ring, Y represents a divalent aromatic group, and Ar ^{1 to} Ar ⁴ represent each other The divalent aromatic group may be the same or different, and these divalent aromatic groups may be aromatic groups in which aromatic groups are connected to each other to form a ring. ¹ and T ² are a single bond, — (CH ₂ ) _t —, —CH═CH—, —C≡C—, —O—, —S—, —CQ ¹ Q ² —, —CO—, —SO—. _{, -SO 2 -, - SiE 2} - a group selected from the group consisting of, the .Q ¹ and ^{Q 2} represents an .t an integer of from 1 to 20 also being the same or different alkyl Or an aromatic group, a bond optionally to form a ring .E hydrogen atom, .m represents an alkyl group or an aromatic group, n represents an integer of 0 to 2 to each other.) The polymer compound according to claim 13, wherein the polymer chain has at least one repeating unit represented by the general formula (2).

(In the formula, Z ^{1 to} Z ⁴ , p ^{1 to} p ⁴ , X ^{1 to} X ⁴ , Y, m, and n are as described above.)   The organic electroluminescent element material which consists of a high molecular compound of Claim 13 or Claim 14.   An organic electroluminescent element material, wherein the polymer compound according to claim 13 or 14 can be used in a state dissolved in an organic solvent.   An organic electroluminescent device comprising at least one layer containing at least one layer of the polymer compound according to claim 13 or 14 between a pair of electrodes.   The organic electroluminescent element according to claim 17, wherein the layer containing the polymer compound is a charge injection transport layer.   The organic electroluminescent device according to claim 18, wherein the charge injection transport layer is a hole injection transport layer.   The organic electroluminescent device according to claim 19, comprising at least two hole injection transport layers. The claim 1 sulfo group-containing polymer compound according to at least one layer sandwiching the layers contains at least one, is formed by at least a Sokyo lifting a layer that contains at least one polymeric compound according to claim 13, wherein the organic electroluminescent device .

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