JP2009079092A - Polymer compound and organic electroluminescent element containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound suitably usable for an organic electroluminescent element and the organic electroluminescent element using the compound. <P>SOLUTION: The polymer compound has at least one repeating unit represented by general formula (1) in the polymer chain (wherein Z<SP>1</SP>-Z<SP>4</SP>indicate each a substituent; p<SP>1</SP>and p<SP>2</SP>indicate each an integer of 0-5 and p<SP>3</SP>and p<SP>4</SP>indicate each an integer of 0-4; Z<SP>1</SP>, Z<SP>2</SP>, Z<SP>3</SP>and Z<SP>4</SP>, which exist plurally when p<SP>1</SP>-p<SP>4</SP>are two or more, may be each identical or different; X<SP>1</SP>and X<SP>2</SP>, which may be identical or different, indicate each an unsubstituted or substituted divalent aromatic group; Ar<SP>1</SP>and Ar<SP>2</SP>, which may be identical or different, indicate each an unsubstituted or substituted monovalent aromatic group; Y indicates an unsubstituted or substituted divalent aromatic group; s indicates an integer of 0-1,000; and t indicates an integer of 1-1,000). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polymer compound and an organic electroluminescent device containing the polymer 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 light-emitting organic compound is sandwiched between an anode and a cathode, and excitons (exingtons) are formed by injecting electrons and holes into the thin film and recombining them. ) 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, etc.) can be selected by selecting the type of the luminescent 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, is known.
JP 2000-91081 A International Publication No. 2007/043607 Pamphlet JP 2006-316224 A

  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.

  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 electroluminescence device, and an organic electroluminescence device containing the compound.

  As a result of intensive studies to achieve the above-described problems, the present inventors have found that a polymer compound is soluble in an organic solvent and has no cohesiveness, and can form a homogeneous thin film. As a result, it was found that an organic electroluminescence device with high efficiency and long life can be obtained, and the present invention has been completed.

That is, the present invention provides the following (1) to (13).
(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 an integer of 0~4, p ¹ ~p ⁴ is 2 or more In this case, a plurality of Z ¹ , Z ² , Z ³ and Z ⁴ may be the same or different from each other, and X ¹ and X ² may be the same or different from each other. An unsubstituted or substituted divalent aromatic group, Ar ¹ and Ar ² are the same or different from each other, an unsubstituted or substituted monovalent aromatic group, Y is A substituted or substituted divalent aromatic group, s represents an integer of 0 to 1000, and t represents an integer of 1 to 1000.
A polymer compound having at least one repeating unit represented by the formula:

(2) In general formula (1), the group represented by X ¹ and X ² is a divalent aromatic heterocyclic group having 4 to 30 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. The polymer compound according to (1).

(3) In general formula (1), the groups represented by X ¹ and X ² may be the same or different from each other, and each is a group represented by general formula (a-1) ( The polymer compound according to any one of 1) to (2).

(In the formula, u represents an integer of 0 to 2.)
(4) Z ^{1 to} Z ⁴ may be the same as or different from each other, and each includes a carboxyl group, a hydroxyl group, an amino group, a monosubstituted amino group, a disubstituted amino group, a sulfo group, a phosphoryl group, and a general group. Formulas (1a) to (3a):
-(O) _L -D (1a)
-O (C = O) -D (2a)
-(C = O) OD (3a)
(In the formula, D is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 20 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 high molecular compound as described in.

(5) A group wherein at least one of the substituents of Ar ¹ , Ar ² , X ¹ , X ² and Y and Z ^{1 to} Z ⁴ is selected from the group consisting of a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group The polymer compound according to any one of (1) to (4).

(6) The polymer compound according to (5), wherein at least one of the Ar ¹ , Ar ² , X ¹ , X ² , Y substituent and Z ^{1 to} Z ⁴ is a sulfo group.

(7) An organic electroluminescent material comprising the polymer compound according to any one of (1) to (6).
(8) An organic electroluminescent material obtained by dissolving the polymer compound according to any one of (1) to (6) in an organic solvent.
(9) The organic electroluminescent material according to (8), wherein the organic solvent is a polar solvent.
(10) An organic electroluminescence device comprising at least one layer containing at least one layer containing the polymer compound according to any one of (1) to (6) between a pair of electrodes.
(11) The organic electroluminescence device according to (10), wherein the layer containing the polymer compound according to any one of (1) to (6) is a charge injection transport layer.
(12) The organic electroluminescence device according to (11), wherein the charge injection / transport layer is a hole injection / transport layer.
(13) The organic electroluminescence device according to (12), comprising at least two layers of the hole injecting and transporting layer.

  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. In addition, it is possible to provide a polymer compound suitable for an organic electroluminescence device, and an organic electroluminescence device having a high efficiency and a long lifetime.

  Hereinafter, the present invention will be described in detail.

The polymer compound of the present invention is a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain.
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 an integer of 0~4, p ¹ ~p ⁴ is 2 or more In the case, a plurality of each of Z ¹ , Z ² , Z ³ and Z ⁴ may be the same or different, and X ¹ and X ² may be the same or different from each other. Or a substituted divalent aromatic group, Ar ¹ and Ar ² represent an unsubstituted or substituted monovalent aromatic group which may be the same or different from each other, and Y represents an unsubstituted or And represents a substituted divalent aromatic group, s represents an integer of 0 to 1000, and t represents an integer of 1 to 1000.

In the general formula (1), Ar ¹ and Ar ² 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. 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 4 to 30, and more preferably 4 to 20 carbon atoms. Ar ¹ and Ar ² are preferably the same group, and more preferably the same aromatic hydrocarbon group.

Specific examples of the aromatic hydrocarbon group of Ar ¹ and Ar ² or the aromatic heterocyclic group include, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9 -Anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 2-fluoro-9-phenanthryl 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, 3-pyridyl group, 2-pyridyl group, 2- Rimidyl 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-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, p-terphenyl-4-yl group, p-terphenyl- List 3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group. You can.

Examples of the substituent on the aromatic hydrocarbon group of Ar ¹ and Ar ² or the aromatic heterocyclic group include a carboxyl group, a hydroxyl group, an amino group, a monosubstituted amino group, a disubstituted amino group, a sulfo group, a phosphoryl group, and 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 20 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, and L ′ represents 0 or 1)
And a group represented by the general formula (1′a) is preferable. As the group represented by the general formula (1′a), L ′ is preferably 0.
The substitution position of the substituent on the aromatic hydrocarbon group of Ar ¹ and Ar ² or the aromatic heterocyclic group is not particularly limited. 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an 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-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-propoxy Propyl 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 group, 6-n-hexyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 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-allyloxy-butyl 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-benzyloxypropyl group, 3- (4'-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 2- (Benzyloxymethoxy) ethyl group, 2- (4′-methylbenzyloxymethoxy) ethyl group, phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyl Xymethyl group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxy) Phenyloxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-naphthyl) Oxy) ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-) tert-butylphenyloxy) pentyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 2- (2′-phenyloxyethoxy) group Group, 3- (2'-phenyloxy) propyl group, 4- (2'-phenyloxy ethoxy) 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- N-dithioethyl 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 a phenyl group, 1-naphthyl group, 2-naphthyl group, 15-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-phenyl A phenyl group, 3-phenylphenyl group, 4-phenylphenyl group, etc. can be mentioned.

  Examples of the substituent on the aromatic group of D ′ include a sulfo group, a carboxyl group, a phosphoryl group, a hydroxyl group, a halogen atom, and 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.

  The 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 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, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.

  Examples of the substituent of the mono-substituted amino group or the di-substituted amino group include an unsubstituted or substituted linear, branched or cyclic alkyl group, and an unsubstituted or substituted aromatic hydrocarbon group or Aromatic heterocyclic groups can be mentioned.

  Here, as an unsubstituted or substituted linear, branched or cyclic alkyl group, those having 1 to 16 carbon atoms are preferable, and those having 1 to 8 carbon atoms are more preferable. Specific examples of the substituent include those shown as an unsubstituted or substituted linear, branched or cyclic alkyl group for D ′.

  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.

Specific examples of the aromatic hydrocarbon group or aromatic heterocyclic group include those shown as specific examples of the aromatic hydrocarbon group or aromatic heterocyclic group of Ar ¹ and Ar ² .

  Examples of the substituent of the aromatic hydrocarbon group or aromatic heterocyclic group include a sulfo group, a carboxyl group, a phosphoryl group, a hydroxyl group, and an unsubstituted or substituted linear, branched or cyclic alkyl group. Can do. As an unsubstituted or substituted linear, branched or cyclic alkyl group, those having 1 to 16 carbon atoms are preferable, and those having 1 to 8 carbon atoms are more preferable. Specific examples of the substituent include those shown as an unsubstituted or substituted linear, branched or cyclic 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-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— Examples thereof include a bis [4- (1-methylpentyl) phenyl] amino group and an N, N-bis [4- (4-methyl-2-pentyl) phenyl] amino group.

  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) n- (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 n represents an integer of 0 to 2).
n 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 Ar ¹ and Ar ² in the general formula (1), or the aromatic heterocyclic group 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-pyrrolediyl group, 3,4-pyrrolediyl group, 2,5-pyridinediyl 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- Reniru group, 6,12-chrysenyl group, 1,7-perylenyl 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-pyrenyl group, 2,7-carbazolediyl 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, methylene group, ethylene group, propylene group, 1,1-cyclopropylene group, 1,2-cyclopropylene group, 1,1-cyclobutylene group, 1 , 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-hexyl-octyl 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-dimethylcyclohexyl 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-tert-butylcyclohexyl group, 3-tert-butylcyclohexyl Groups, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, cyclotetradecyl group and the like.

  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 aromatic heterocyclic group include those shown as specific examples of Ar ¹ and Ar ² .

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 Ar ¹ and Ar ² 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), X ¹ and X ² 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 divalent Of the aromatic heterocyclic group. Preferably, the group represented by X ¹ and X ² is a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic heterocyclic group having 4 to 30 carbon atoms. X ¹ and X ² are preferably the same group, and more preferably the same aromatic hydrocarbon group.

In the general formula (1), examples of the group represented by X ¹ and X ² include the same divalent aromatic groups as Y in the general formula (1), preferably represented by —Y—. And a group represented by -A- or -AA-, wherein n in the general formula (1b) is an integer of 0 to 1 and B is a single bond.

As the divalent aromatic group for X ¹ and X ² , the general formula (a-1)

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

In the general formula (1), the substituents represented by 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, a monosubstituted amino group, or a disubstituted group. Amino group, sulfo group, phosphoryl group and general formulas (1a) to (3a):
-(O) L-D (1a)
-O (C = O) -D (2a)
-(C = O) OD (3a)
(In the formula, D is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 20 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)
Preferred examples and specific examples of the substituent represented by Z ^{1 to} Z ⁴ are groups selected from the group consisting of the groups represented by the following: aromatic carbonization of Ar ¹ and Ar ² in the general formula (1) Examples thereof are the same as the substituents on the hydrogen group or aromatic heterocyclic group.

In the general formula ^(1), p 1 ~p ⁴ is preferably 0 to 2 integer, more preferably an integer of 0-1. Z ¹ and Z ² and Z ³ and Z ⁴ are preferably the same substituent, and p ¹ and p ² and p ³ and p ⁴ are preferably the same integer.

In the general formula (1), at least one of a substituent represented by Ar ¹ , Ar ² , X ¹ , X ² , Y and a group represented by Z ^{1 to} Z ⁴ is a sulfo group, a carboxyl group, a phosphoryl group, or a hydroxyl group. It is preferably a group selected from the group consisting of and more preferably a sulfo group.

In General formula (1), s is an integer of 0-1000 and t is an integer of 1-1000. Preferably, s is an integer from 0 to 100, and t is an integer from 1 to 100. More preferably, s is an integer of 0-2 and t is an integer of 1-2. Further, when s is 2 or more, each Ar ¹ and Y may be the same or different. When t is 2 or more, each Ar ² , X ¹ and X ² are the same. Or different.

  In the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain, a salt may be formed. 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 weight 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, and is 1,000 to 1,000,000 in terms of polystyrene. Preferably it is 3000-500000. More preferably, it is 4000-200000.

  In addition, the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain has an aromatic hydrocarbon group, a disubstituted amino group, a linear chain in which the terminal group is unsubstituted or substituted. The terminal treatment may be performed by substitution with a branched or cyclic alkyl group, an alkyloxy group having a linear, branched or cyclic alkyl group, a carboxyl group, an alkoxycarbonyl group, a hydroxyl group, or the like.

Specific examples of the polymer compound having at least one repeating unit represented by the general formula (1) of the present invention in the polymer chain are exemplified below, but the present invention is limited to these examples. Is not to be done.
The following formula (R-1) represents a general formula in which Z ^{1 to} Z ⁴ in the general formula (1) are hydrogen atoms, and in Tables 1 to 56 below, specific examples respectively corresponding to Ar ¹ , The combination of Ar ² , Y, X ¹ , X ² , s and t is shown.
Further, ^Ar 1 in the general formula ^{(1), Ar 2, Y} , X 1, X 2, s and t are combinations shown in Tables 1 to 56, and ^{Ar 1, Ar 2, X 1} , X 2 A specific example is a polymer compound in which at least one of the substituents of Y and Z ^{1 to} Z ⁴ is a group selected from the group consisting of a sulfo group, a carboxyl group, a phosphoryl group, and a hydroxyl group.

  Next, the manufacturing method of the high molecular compound which has at least one repeating unit represented by General formula (1) of this invention in a polymer chain is demonstrated.

Examples of the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain include, for example, the general formula (2):
H-N (Ar < ¹ >)-Y-N (Ar < ² >)-H (2)
(In the formula, Ar ¹ , Ar ² and Y are as in the general formula (1).)
And a compound represented by the general formula (3):

(Wherein Q represents a halogen atom, and X ¹ , X ² , Z ^{1 to} Z ⁴ and p ^{1 to} p ⁴ are as described above) are polymerized with a Pd catalyst or the like in the presence of a base. Can be manufactured.

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

The polymer compound according to the present invention, in which Ar ¹ , Ar ² , X ¹ , X ² , Y substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group, is represented by, for example, the general formula (1). It can be produced by sulfonating a polymer compound having at least one repeating unit 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 element material of the present invention will be described.

  The organic electroluminescent element material of the present invention comprises a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain, and is used for a hole injecting and transporting material used for an organic electroluminescent element, It can be used as a light emitting 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 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. As the predetermined solvent, 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.

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

  The organic electroluminescent element of the present invention is obtained by sandwiching at least one layer containing at least one 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 polymer compound of the present invention is preferably used as a constituent component of the charge injection transport layer and / or the light emitting layer, and the hole injection transport layer and the electron injection are used as the charge injection transport layer. Although a transport layer is mentioned, a hole injection transport layer is particularly preferable.

  In the organic electroluminescent element of the present invention, the polymer compound of the present invention may be used alone or in combination.

The configuration of the organic electroluminescence device of the present invention is not particularly limited. For example, (EL-1) anode 2 / hole injection transport layer 3 / light emitting layer 4 / electron injection transport layer 5 / cathode 6 Type device (FIG. 1), (EL-2) anode 2 / hole injection transport layer 3 / light emitting layer 4 / cathode 6 type device (FIG. 2), (EL-3) anode 2 / light emitting layer 4 / electron injection transport Layer 5 / cathode 6 type element (FIG. 3), (EL-4) anode 2 / light emitting layer 4 / cathode 6 type element (FIG. 4), and the like. Further, (EL-5) anode 2 / hole injection / transport layer 3 / electron injection / transport layer 5 ″ / light-emitting layer 4 / electron injection / transport layer in which the light-emitting layer 4 is sandwiched between electron injection / transport layers 5 ″ and 5 5 / Cathode 6 type element (FIG. 5) can also be used. In addition, the (EL-4) type element configuration includes an element of a type in which a light emitting component is sandwiched between a pair of electrodes as the light emitting layer 4, and (EL-6) hole injection transport as the light emitting layer 4. A device of a type sandwiched between a pair of electrodes in a single layer form in which a component 3a, a light emitting component 4a and an electron injection component 5a are mixed (FIG. 6), (EL-7) as a light emitting layer 4, a hole injection transport component 3a and An element of a type in which a light emitting component 4a is mixed and sandwiched between a pair of electrodes (FIG. 7), (EL-8) as a light emitting layer 4, a light emitting component 4a and an electron injection component 5a are mixed in a single layer form. Any of the elements (FIG. 8) of the type sandwiched between a pair of electrodes may be used.
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 preferred 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. More preferably, it is an (EL-1) type element, an (EL-2) 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, etc. can be mentioned. 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 electroluminescence device of the present invention is composed of the polymer compound of the present invention and / or other compounds having a hole injecting and transporting function (for example, phthalocyanine derivatives, triarylamine derivatives, triarylmethane derivatives, Oxazole derivatives, hydrazone derivatives, stilbene derivatives, pyrazoline derivatives, polysilane derivatives, polyphenylene vinylene and derivatives thereof, polythiophene and derivatives thereof, poly-N-vinylcarbazole and derivatives thereof, and the like. The compounds having a hole injecting and transporting function may be used alone or in combination.

  The organic electroluminescence device of the present invention preferably contains the polymer compound of the present invention in the hole injection transport 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-diamino Benzene, 5,5 "-bis [4- (bis [4-methylphenyl] amino) phenyl-2,2 ', 5', 2" -terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ', 4 "-Tris (9H-carbazole- 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] and the like), polythiophene and its derivatives, poly-N-vinylcarbazole and its derivatives are preferred.

  When the polymer compound of the present invention 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 0.1% by mass or more, More preferably, it is 0.5-99.9 mass%, More preferably, it is 3-97 mass%.

  When the polymer compound of the present invention and another compound having a hole injection / transport function are used in combination, a layer composed of the polymer compound of the present invention and a layer composed of another compound having a hole injection / transport function are laminated. May be.

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 No. 11-283750, FeCl ₃ , and tris (penta) described in JP-A No. 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 polymer compound of the present invention and / or a compound having another 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 (eg hole injection Examples of the compound having a transport function include the aforementioned compounds), organometallic complexes For example, tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, zinc salt of 2- (2′-hydroxyphenyl) benzothiazole, zinc salt of 4-hydroxyacridine, 3-hydroxyflavone Zinc salt, 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, cinnamate derivatives, and the like, and poly-N-vinylcarbazole and derivatives thereof, polythiophene and derivatives thereof, polyphenylene and derivatives thereof. Derivatives of polyfluorene and its derivatives, polyphenylene vinylene and its derivatives, polybiphenylene vinylene and its derivatives, polyterphenylene vinylene and its derivatives, polynaphthylene vinylene and its derivatives, polythienylene vinylene and its derivatives The high molecular compound which has can be mentioned. 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 polymer compound of the present invention in the light emitting layer.

  When the polymer compound of the present invention and another compound having a light emitting function are used in combination, the proportion of these polymer compounds in the light emitting layer is preferably adjusted to 0.001 to 99.999% by 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 polymer compound of the present invention can be used as a host compound for the light emitting layer, and can also be used as a guest compound. When the light emitting layer is formed using the polymer compound of the present invention as a host compound, examples of the guest compound include compounds having other light emitting functions described above, and among them, polycyclic aromatic compounds are preferable.

  When the light emitting layer is formed using the polymer compound of the present invention as a host compound, the guest compound is preferably 0.001 to 40% by mass, more preferably 0.01 to 30% by mass with respect to the host compound. More preferably, 0.1-20 mass% is used. The light emitting layer can be formed using the polymer compound of the present invention as a host material and at least one compound having a light emitting function as a guest material.

  The organic electroluminescent element of the present invention preferably contains the polymer compound of the present invention as a host material in the light emitting layer.

  When the polymer compound of the present invention is used in combination with another compound having a light emitting function as a host material, the polymer compound of the present invention in the light emitting layer is preferably 40.0 to 99.9% by mass. More preferably, it is 60.0-99.9 mass%.

  The usage-amount of a guest material is 0.001-40 mass% with respect to the high molecular compound of this invention, Preferably, it is 0.01-30 mass%, More preferably, it is 0.1-20 mass%. Moreover, a guest material may be used independently and may be used together.

  When the light emitting layer is formed using the polymer compound of the present invention as a guest material, the host material is preferably a polycyclic aromatic compound, a triarylamine derivative, an organometallic complex, or a stilbene derivative, and the polycyclic aromatic compound An organometallic complex is more preferable.

  When the polymer compound of the present invention is used as a guest material, the compound is preferably 0.001 to 40% by mass, more preferably 0.01 to 30% by mass, and still more preferably 0.1 to 20%. Use mass%.

  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).

(G) ₃ -Al (a)
(In the formula, G represents an unsubstituted or substituted 8-quinolinolato ligand.)
(G) 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.)
(G) _2- Al-O-Al- (G) ₂ (c)
(In the formula, G 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-mesh Ru-8-quinolinolato) (4-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8) -Quinolinolate) (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-ki) Linoleate) (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-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,4 5,6-tetramethylphenolate) 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 ( , 4-Dimethyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolato) 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-oxy -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-trifluoromethyl) Mention may be made of -8-quinolinolato) aluminum- [mu] -oxo-bis (2-methyl-5-trifluoromethyl-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,
A plurality of them may be used 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, and a layer adjacent to the hole injecting and transporting layer (for example, a light emitting layer, a light emitting function). 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) to contain, 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 (hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dichloromethane, chloroform, and the like. , 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. The solvent may be used alone,
A plurality of them may be used in combination. 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 polymer compound of the present invention is insoluble in a hydrocarbon-based solvent such as toluene, a layer containing the polymer compound is formed, and then the upper layer is coated by using a hydrocarbon-based solvent. Is possible. 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. Although the density | concentration of a coating liquid is not specifically limited, It can set to the density | concentration range suitable for producing desired thickness with the apply | coating method to implement, Usually, 0.1-50 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 an 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 such as a watch or a liquid crystal panel or illumination), various light-emitting elements (for example, an alternative to a light-emitting element such as an LED), various display elements [for example, It can be used for information display elements (display elements for personal computer monitors, televisions, mobile phones / portable terminals)], various signs, various sensors, and the like.

  In addition, the polymer compound of the present invention includes an organic semiconductor, an organic thin film transistor (TFT), an electrolytic capacitor, a photoelectric conversion element, an electrochromic element (ECD), a conventional conductive polymer material (PEDOT / PSS), It can also be used for applications such as antistatic agents and transparent electrodes.

  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 weight average molecular weight in each Example measured the weight average molecular weight of polystyrene conversion by the 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)

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

(AFM measurement conditions)
Device: Seiko Instruments Scanning Probe Microscope SPI-3800N
Analysis conditions:
Measurement mode DFM
Cantilever SI-DF20
Measurement range 5μm × 5μm

  The average number of sulfo groups per repeating unit of the polymer compound was determined by elemental analysis.

[Example 1]
Production of Exemplified Compound AA-1 N, N′-diphenyl-1,4-phenylenediamine 1.0 g, 2,5-bis [4 ′-(4 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophene 2 To a mixture of .4 g, 1.20 g of sodium tert-butoxide and 70 mL of o-xylene was added a solution of 18 mg of tris (dibenzylideneacetone) dipalladium and 32 mg of tritert-butylphosphine in o-xylene (5 mL) under a nitrogen stream. . The mixture was stirred at 135 degrees for 5 hours in a nitrogen atmosphere. The reaction solution was returned to room temperature and discharged into 460 mL of acetone, and the precipitate was collected by filtration. The obtained solid was washed with water, methanol, and acetone, and dissolved in toluene. This solution was purified by silica gel column chromatography and then discharged into acetone. The precipitate was collected by filtration and dried under reduced pressure to obtain 2.5 g of the polymer compound of Exemplified Compound AA-1.
Weight average molecular weight: 45000

[Example 2]
Production of Exemplified Compound AA-4 In Example 1, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-secbutylphenyl) -1, Except that 1.4 g of 4-phenylenediamine was used, 2.7 g of the polymer compound of Exemplified Compound AA-4 was obtained according to the method described in Example 1.
Weight average molecular weight: 48000

[Example 3]
Production of Exemplified Compound AA-10 N, N′-Diphenyl-1,4-phenylenediamine 1.0 g, 2,5-bis [4 ′-(3 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophenebromo Phenyl) -3,4-diphenylthiophene (2.4 g), sodium tert-butoxide (1.20 g) and o-xylene (70 mL) in a stream of nitrogen, 18 mg of tris (dibenzylideneacetone) dipalladium and 32 mg of tritert-butylphosphine o-Xylene (5 mL) solution was added. The mixture was stirred at 135 degrees for 5 hours in a nitrogen atmosphere. The reaction solution was returned to room temperature and discharged into 300 mL of acetone, and the precipitate was collected by filtration. The obtained solid was washed with water, methanol, and acetone, and dissolved in toluene. This solution was purified by silica gel column chromatography and then discharged into acetone. The precipitate was collected by filtration and dried under reduced pressure to obtain 1.9 g of the polymer compound of Exemplary Compound AA-10.
Weight average molecular weight: 24000

[Example 4]
Production of Exemplified Compound AA-13 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-secbutylphenyl) -1, Except for using 1.4 g of 4-phenylenediamine, 2.4 g of the polymer compound AA-13 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 22000

[Example 5]
Production of Illustrative Compound AB-1 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 1.0 g of N, N′-diphenyl-1,3-phenylenediamine was used. 2.7 g of the polymer compound of Exemplified Compound AB-1 was obtained according to the procedure described in Example 3 except that was used.
Weight average molecular weight: 32000

[Example 6]
Production of Exemplified Compound AB-4 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-secbutylphenyl) -1, Except for using 1.4 g of 3-phenylenediamine, 2.4 g of the polymer compound of Exemplified Compound AB-4 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 42000

[Example 7]
Production of Exemplary Compound AB-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (2-naphthyl) -1,3- Except for using 1.4 g of phenylenediamine, 2.5 g of a polymer compound of Exemplified Compound AB-5 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 20000

[Example 8]
Production of Exemplified Compound AB-6 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (4-phenylphenyl) -1,3 -Except having used 1.6g of phenylenediamines, 2.7g of high molecular compounds of exemplary compound AB-6 were obtained in accordance with the operation as described in Example 3.
Weight average molecular weight: 17000

[Example 9]
Production of Illustrative Compound AB-8 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-diphenylaminophenyl) -1, Except for using 2.3 g of 3-phenylenediamine, 2.7 g of the polymer compound of Exemplified Compound AB-8 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 43000

[Example 10]
Production of Exemplary Compound AB-13 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-secbutylphenyl) benzidine Except that 4 g was used, 2.5 g of the polymer compound of Exemplified Compound AB-13 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 22000

[Example 11]
Preparation of Exemplary Compound AC-1 In Example 3, 1,1-bis [N-phenyl- (4-aminophenyl) was used instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine. In the same manner as described in Example 3 except that 1.6 g of cyclohexane was used, 2.4 g of the polymer compound of Exemplified Compound AC-1 was obtained.
Weight average molecular weight: 60000

[Example 12]
Preparation of Exemplified Compound AC-3 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 1,1-bis [N- (p-sec amylphenyl)- (4-Aminophenyl)] 3.0 g of the polymer compound of Exemplified Compound AC-3 was obtained according to the procedure described in Example 3 except that 2.1 g of cyclohexane was used.
Weight average molecular weight: 47000

[Example 13]
Production of Exemplified Compound AC-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 1,1-bis [N- (2-naphthyl)-(4 -Aminophenyl)] 2.7 g of the polymer compound of Exemplified Compound AC-5 was obtained according to the procedure described in Example 3 except that 2.0 g of cyclohexane was used.
Weight average molecular weight: 39000

[Example 14]
Preparation of Exemplified Compound AC-10 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 1.2 g of N, N′-diphenyl-1,5-naphthalenediamine was used. 2.7 g of the polymer compound of Exemplified Compound AC-10 was obtained according to the procedure described in Example 3 except that was used.
Weight average molecular weight: 25000

[Example 15]
Production of Exemplary Compound AC-14 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (2-naphthyl) -1,5- Except for using 1.6 g of naphthalenediamine, 2.8 g of the polymer compound of Exemplified Compound AC-14 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 29000

[Example 16]
Production of Illustrative Compound AD-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (2-naphthyl) -1,4- Except that 1.6 g of naphthalenediamine was used, 2.7 g of the polymer compound of Exemplified Compound AD-5 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 22000

[Example 17]
Production of Illustrative Compound AD-14 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (2-naphthyl) -4,4 ′ -Except having used 1.7g of diamino diphenyl ether, 2.4g of high molecular compounds of exemplary compound AD-14 were obtained in accordance with the operation as described in Example 3.
Weight average molecular weight: 29000

[Example 18]
Production of Illustrative Compound AE-4 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-secbutylphenyl) -3, Except that 1.8 g of 7-diaminodibenzothiophene was used, 3.0 g of the polymer compound of Exemplified Compound AE-4 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 14000

[Example 19]
Production of Illustrative Compound AE-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (2-naphthyl) -3,7- Except for using 1.8 g of diaminodibenzothiophene, 2.6 g of the polymer compound of Exemplified Compound AE-5 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 19000

[Example 20]
Production of Exemplified Compound AE-10 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-diphenyl-9,9-dioctyl-2,7 -2.8g of high molecular compounds of exemplary compound AE-10 were obtained according to the operation as described in Example 3, except that 2.2g of diaminofluorene was used.
Weight average molecular weight: 30000

[Example 21]
Production of Illustrative Compound AE-14 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-dinaphthyl-9,9-dioctyl-2,7 -Except having used 2.6 g of diaminofluorene, 3.0 g of high molecular compounds of exemplary compound AE-14 were obtained according to the operation as described in Example 3.
Weight average molecular weight: 35000

[Example 22]
Production of Exemplified Compound AF-4 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-secbutylphenyl) -3, Except that 7 g of 7-diaminodibenzofuran was used, 3.2 g of the polymer compound of Exemplified Compound AF-4 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 17000

[Example 23]
Production of Exemplary Compound AF-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (2-naphthyl) -3,7- Except for using 1.7 g of diaminodibenzofuran, 3.1 g of the polymer compound of Exemplified Compound AF-5 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 23000

[Example 24]
Production of Exemplified Compound AF-12 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-sec amylphenyl) -4, Except for using 2.0 g of 4′-diaminodiphenyl sulfide, 3.0 g of the polymer compound of Exemplified Compound AF-12 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 18000

[Example 25]
Production of Exemplified Compound AF-14 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (2-naphthyl) -4,4 ′ -According to the operation described in Example 3, except that 1.8 g of diaminodiphenyl sulfide was used, 2.9 g of the polymer compound of Exemplified Compound AF-14 was obtained.
Weight average molecular weight: 17000

[Example 26]
Production of Exemplary Compound AG-4 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 4,4 ′-(1-methylethylidene) -bis [N— 2.7 g of the polymer compound of Exemplified Compound AG-4 was obtained in accordance with the procedure described in Example 3 except that (4-sec butylphenyl) benzeneamine] was used in an amount of 1.9 g.
Weight average molecular weight: 24000

[Example 27]
Production of Exemplified Compound AG-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 4,4 ′-(1-methylethylidene) -bis [N— 2.6 g of the polymer compound of Exemplified Compound AG-5 was obtained according to the procedure described in Example 3, except that 1.8 g of (2-naphthyl) benzeneamine] was used.
Weight average molecular weight: 14000

[Example 28]
Production of Exemplified Compound AG-12 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 4,4 ′-[1,3-phenylene-bis (1- Methylethylidene)]-bis [N- (4-sec amylphenyl) benzeneamine] was used in accordance with the procedure described in Example 3 except that 2.4 g of 2.9 g of the polymer compound of Exemplified Compound AG-12 was used. Obtained.
Weight average molecular weight: 20000

[Example 29]
Production of Exemplified Compound AG-14 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 4,4 ′-[1,3-phenylene-bis (1- Methyl ethylidene)]-bis [N- (2-naphthyl) benzenamine] was used in the same manner as described in Example 3 except that 2.3 g of the polymer compound of Exemplified Compound AG-14 was obtained. .
Weight average molecular weight: 35000

[Example 30]
Production of Exemplified Compound AH-4 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-bis (4-sec amylphenyl) -3, Except that 1.7 g of 3′-diaminobiphenyl was used, 2.9 g of the polymer compound of Exemplified Compound AH-4 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 40000

[Example 31]
Production of Exemplary Compound AH-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N, N′-di (2-naphthyl) -3,3 ′ -According to the operation described in Example 3, except that 1.7 g of diaminobiphenyl was used, 2.9 g of the polymer compound of Exemplified Compound AH-5 was obtained.
Weight average molecular weight: 29000

[Example 32]
Production of Exemplified Compound AH-12 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 4,4 ′-(9H-fluorene-9-ylidene) -bis [ Except for using 2.5 g of N- (4-sec amylphenyl) benzeneamine], 3.1 g of the polymer compound of Exemplified Compound AH-12 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 34000

[Example 33]
Production of Exemplified Compound AH-14 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 4,4 ′-(9H-fluorene-9-ylidene) -bis [ 3.3 g of the polymer compound of Exemplified Compound AH-14 was obtained according to the procedure described in Example 3 except that 2.3 g of N- (2-naphthyl) benzeneamine] was used.
Weight average molecular weight: 18000

[Example 34]
Production of Illustrative Compound AI-4 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 2,5-bis [4′-N- (4-secbutyl) According to the procedure described in Example 3 except that 2.6 g of (phenyl) aminophenyl] -3,4-diphenylthiophene was used, 3.3 g of the polymer compound of Exemplified Compound AI-4 was obtained.
Weight average weight average molecular weight: 39000

[Example 35]
Preparation of Exemplified Compound AI-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 2,5-bis [4′-N- (2-naphthyl) Except for using 2.6 g of aminophenyl] -3,4-diphenylthiophene, 3.4 g of the polymer compound of Exemplified Compound AI-5 was obtained according to the procedure described in Example 3.
Weight average weight average molecular weight: 48000

[Example 36]
Preparation of Exemplified Compound AI-10 In Example 1, instead of using 2.4 g of 2,5-bis [4 ′-(4 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophene, Instead of using 3.0 g of bis [4 ′-(4 ″ -chlorobiphenyl) phenyl] -3,4-diphenylthiophene instead of 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N , N′-bis (4-secbutylphenyl) -1,3-phenylenediamine was used in accordance with the procedure described in Example 1 except that 1.4 g of the polymer compound of Exemplified Compound AI-10 was 2.9 g. Obtained.
Weight average molecular weight: 43000

[Example 37]
Preparation of Exemplified Compound AI-14 In Example 1, instead of using 2.4 g of 2,5-bis [4 ′-(4 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophene, Instead of using 2.8 g of bis [4 ′-(4 ″ -chloronaphthalenyl) phenyl] -3,4-diphenylthiophene, 1.0 g of N, N′-diphenyl-1,4-phenylenediamine Except that 1.4 g of N, N′-bis (4-secbutylphenyl) -1,3-phenylenediamine was used, the polymer compound of Exemplified Compound AI-14 was 3 according to the procedure described in Example 1. 0.0 g was obtained.
Weight average molecular weight: 25000

[Example 38]
Preparation of Exemplary Compound AJ-1 In Example 1, instead of using 2.4 g of 2,5-bis [4 ′-(4 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophene, Instead of using 3.0 g of bis [4 ′-(4 ″ -chlorobiphenyl) phenyl] -3,4-diphenylthiophene instead of 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N , N′-bis (4-secbutylphenyl) -1,5-naphthalenediamine was used in the same manner as described in Example 1 except that 1.6 g of the polymer compound of Exemplified Compound AJ-1 was 2.7 g. Obtained.
Weight average molecular weight: 15000

[Example 39]
Preparation of Exemplary Compound AK-9 In Example 1, instead of using 2.4 g of 2,5-bis [4 ′-(4 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophene, Instead of using 3.0 g of bis [4 ′-(4 ″ -chlorobiphenyl) phenyl] -3,4-diphenylthiophene instead of 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N , N′-di (2-naphthyl) -1,3-phenylenediamine was used in accordance with the procedure described in Example 1 to obtain 2.9 g of the polymer compound of Exemplified Compound AK-9. .
Weight average molecular weight: 27000

[Example 40]
Production of Illustrative Compound AM-1 In Example 1, instead of using 2.4 g of 2,5-bis [4 ′-(4 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophene, Instead of using 3.0 g of bis [4 ′-(4 ″ -chlorobiphenyl) phenyl] -3,4-diphenylthiophene instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, , 1-bis [N- (2-naphthyl)-(4-aminophenyl)] cyclohexane 2.0 g was used according to the procedure described in Example 1, except that 3 0.0 g was obtained.
Weight average molecular weight: 47000

[Example 41]
Production of Exemplary Compound BA-1 In Example 1, in place of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 0.4 g of aniline was used instead of 1.0 g. According to the operation, 1.8 g of a polymer compound of Exemplified Compound BA-1 was obtained.
Weight average molecular weight: 51000

[Example 42]
Production of Exemplified Compound BA-10 In Example 3, in place of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, 0.4 g of aniline was used instead of 1.0 g. According to the operation, 1.6 g of the polymer compound of Exemplified Compound BA-10 was obtained.
Weight average molecular weight: 49000

[Example 43]
Production of Exemplified Compound BA-13 In Example 3, except that 1.0 g of N, N′-diphenyl-1,4-phenylenediamine was used, 0.6 g of 4-secbutylaniline was used. According to the operation described in 3, 1.7 g of the polymer compound of Exemplified Compound BA-13 was obtained.
Weight average molecular weight: 37000

[Example 44]
Production of Illustrative Compound BA-14 In Example 3, Example 3 was repeated except that 0.5 g of 2-naphthylamine was used instead of 1.0 g of N, N′-diphenyl-1,4-phenylenediamine. 1.7 g of a polymer compound of Exemplified Compound BA-14 was obtained according to the operation described.
Weight average molecular weight: 42000

[Example 45]
Preparation of Exemplified Compound BC-1 In Example 1, instead of using 2.4 g of 2,5-bis [4 ′-(4 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophene, Instead of using 3.0 g of bis [4 ′-(4 ″ -chlorobiphenyl) phenyl] -3,4-diphenylthiophene instead of 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, aniline Except that 0.4 g was used, 2.2 g of the polymer compound of Exemplified Compound BC-1 was obtained according to the procedure described in Example 1.
Weight average molecular weight: 37000

[Example 46]
Production of Exemplified Compound CA-1 In Example 1, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N1, N4-diphenyl-N1- [4- (phenylamino) phenyl ] According to the operation described in Example 1 except that 1.6 g of 1,4-diaminobenzene was used, 2.6 g of the polymer compound of Exemplified Compound CA-1 was obtained.
Weight average molecular weight: 28000

[Example 47]
Production of Exemplified Compound CA-13 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N1, N4-bis (4-secbutylphenyl) -N1- [ Except for using 2.3 g of 4- (4-secbutylphenylamino) phenyl] -1,4-diaminobenzene, 3.0 g of the polymer compound of Exemplified Compound CA-13 was prepared according to the procedure described in Example 3. Obtained.
Weight average molecular weight: 17000

[Example 48]
Preparation of Exemplary Compound CB-1 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N1, N3-diphenyl-N1- [3- (phenylamino) phenyl 2.7 g of the polymer compound of Exemplified Compound CB-1 was obtained according to the procedure described in Example 3 except that 1.6 g of 1,3-diaminobenzene was used.
Weight average molecular weight: 30000

[Example 49]
Production of Exemplary Compound CB-4 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N1, N3-bis (4-secbutylphenyl) -N1- [ Except for using 2.3 g of 3- (4-secbutylphenylamino) phenyl] -1,3-diaminobenzene, 3.0 g of the polymer compound of Exemplified Compound CB-4 was prepared according to the procedure described in Example 3. Obtained.
Weight average molecular weight: 22000

[Example 50]
Production of Exemplified Compound CB-5 In Example 3, instead of using 1.0 g of N, N′-diphenyl-1,4-phenylenediamine, N1, N3-di (2-naphthyl) -N1- [3- Except for using 2.2 g of (2-naphthylamino) phenyl] -1,3-diaminobenzene, 3.2 g of the polymer compound of Exemplified Compound CB-5 was obtained according to the procedure described in Example 3.
Weight average molecular weight: 27000

[Example 51]
Production of Exemplified Compound DB-4 4-sec Butylaniline 0.5 g, 2,5-bis [4 ′-(3 ″ -chlorophenyl) phenyl] -3,4-diphenylthiophene 8.4 g, sodium tert-butoxide 6 To a mixture of 0.1 g and o-xylene 250 mL, a solution of 15 mg tris (dibenzylideneacetone) dipalladium and 27 mg tritert-butylphosphine in o-xylene (17 mL) was added under a nitrogen stream. The mixture was stirred at 135 degrees for 5 hours in a nitrogen atmosphere. The reaction mixture was cooled to room temperature, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. This was concentrated and then purified by silica gel column chromatography to obtain 3.5 g of the following dichloro compound (DB-4A).

To a mixture of 2.5 g of the obtained dichloro compound, 0.7 g of N, N′-bis (4-secbutylphenyl) -1,3-phenylenediamine, 0.58 g of sodium tert-butoxide and 75 mL of o-xylene, nitrogen was added. Under an air stream, 9 mg of tris (dibenzylideneacetone) dipalladium and 16 mg of tritert-butylphosphine in o-xylene (5 mL) were added. The mixture was stirred at 135 degrees for 5 hours in a nitrogen atmosphere. The reaction solution was returned to room temperature and discharged into 300 mL of acetone, and the precipitate was collected by filtration. The obtained solid was washed with water, methanol, and acetone, and dissolved in toluene. This solution was purified by silica gel column chromatography and then discharged into acetone. The precipitate was collected by filtration and dried under reduced pressure to obtain 2.2 g of the polymer compound of Exemplary Compound DB-4.
Weight average molecular weight: 25000

[Example 52]
Production of Exemplified Compound DB-5 In Example 51, instead of using 2.5 g of the dichloro compound (DB-4A), 2.5 g of the following dichloro compound (DB-5A) was used,

Instead of using 0.7 g of N, N′-bis (4-secbutylphenyl) -1,3-phenylenediamine, 0.7 g of N, N′-di (2-naphthyl) -1,3-phenylenediamine Except that was used, 2.3 g of the polymer compound of Exemplified Compound DB-5 was obtained according to the procedure described in Example 51.
Weight average molecular weight: 18000

[Example 53]
Production of Exemplary Compound EB-4 In Example 51, instead of using 0.7 g of N, N′-bis (4-secbutylphenyl) -1,3-phenylenediamine, N1, N3-di (4-sec According to the procedure described in Example 51 except that 1.1 g of (butylphenyl) -N1- [3- (4-secbutylphenylamino) phenyl] -1,3-diaminobenzene was used, 2.1 g of a polymer compound was obtained.
Weight average molecular weight: 22000

[Example 54]
Production of Exemplified Compound EB-5 In Example 51, instead of using 2.5 g of the dichloro compound (DB-4A), 2.5 g of the dichloro compound (DB-5A) was used, and N, N′-di Instead of using 0.7 g of (4-sec butylphenyl) -1,3-phenylenediamine, N1, N3-di (2-naphthyl) -N1- [3- (2-naphthylamino) phenyl] -1, Except that 1.1 g of 3-diaminobenzene was used, 2.3 g of a polymer compound of Exemplified Compound EB-5 was obtained according to the procedure described in Example 51.
Weight average molecular weight: 14000

[Example 55]
Production of polymer compound in which repeating unit of exemplary compound AA-1 is Ar ¹ , Ar ² , X ¹ , X ² , Y substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group The polymer compound 1.4 g of the obtained exemplary compound AA-1 was dissolved in 44 g of chloroform, charged with 20 g of 98% sulfuric acid under a nitrogen stream, and stirred at room temperature for 6 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 reached 5, and dried under reduced pressure at 70 degrees for 8 hours to obtain 1.6 g of a crude product as a brown solid. 1.6 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 1.5 g of the objective compound 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 AA-1) × Sulfur Element Analysis Value (%) − Sulfur Number in Repeating Unit of (Exemplary Compound AA-1) × Sulfur Atom Weight × 100} ÷ {Sulfur Atom Weight × 100-elemental analysis value of sulfur (%) x (sulfo group molecular weight-hydrogen atom weight)}
Average number of sulfo groups per repeating unit: 2.1

[Example 56]
In the repeating unit of Exemplified Compound AA-10, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AA-10 obtained in Example 3 was used, The operation described in Example 55 was performed to obtain 1.5 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 1.9

[Example 57]
In the repeating unit of Exemplified Compound AB-1, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AB-1 obtained in Example 5 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.0

[Example 58]
In the repeating unit of Exemplified Compound AB-5, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y, and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AB-5 obtained in Example 7 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.0

[Example 59]
In the repeating unit of Exemplified Compound AB-6, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group In Example 55, Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 1.4 g of the polymer compound of Example Compound AB-6 obtained in Example 8 was used. The operation described in Example 55 was performed to obtain 1.5 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.2

[Example 60]
In the repeating unit of Exemplified Compound AB-8, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group In Example 55, Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.3 g of the polymer compound of Example Compound AB-8 obtained in Example 9 was used, The operation described in Example 55 was performed to obtain 1.5 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 4.2

[Example 61]
In the repeating unit of exemplary compound AC-1, production of a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y, and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AC-1 obtained in Example 11 was used, The operation described in Example 55 was performed to obtain 1.5 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 1.9

[Example 62]
In the repeating unit of Exemplified Compound AC-5, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group In Example 55, Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AC-5 obtained in Example 13 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.3

[Example 63]
In the repeating unit of Exemplified Compound AC-10, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 1.4 g of the polymer compound of Example Compound AC-10 obtained in Example 14 was used. The operation described in Example 55 was performed to obtain 1.4 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.2

[Example 64]
In the repeating unit of Exemplified Compound AC-14, Production of Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 1.4 g of the polymer compound of Example Compound AC-14 obtained in Example 15 was used. The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.1

[Example 65]
In the repeating unit of Exemplified Compound AD-5, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AD-5 obtained in Example 16 was used, The operation described in Example 55 was performed to obtain 1.5 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.8

[Example 66]
In the repeating unit of Exemplified Compound AD-14, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group In Example 55, Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AD-14 obtained in Example 17 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.3

[Example 67]
In the repeating unit of Exemplified Compound AE-5, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 1.0 g of the polymer compound of Example Compound AE-5 obtained in Example 19 was used. The operation described in Example 55 was performed to obtain 1.2 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.7

[Example 68]
In the repeating unit of Exemplified Compound AE-10, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AE-10 obtained in Example 20 was used, The operation described in Example 55 was performed to obtain 1.5 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.0

[Example 69]
In the repeating unit of Exemplified Compound AE-14, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y, and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AE-14 obtained in Example 21 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.7

[Example 70]
In the repeating unit of Exemplified Compound AF-5, Production of Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group In Example 55, Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 1.0 g of the polymer compound of Example Compound AF-5 obtained in Example 23 was used. The operation described in Example 55 was performed to obtain 1.3 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.0

[Example 71]
In the repeating unit of Exemplified Compound AF-14, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AF-14 obtained in Example 25 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.9

[Example 72]
In the repeating unit of Exemplified Compound AG-5, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 1.0 g of the polymer compound of Example Compound AG-5 obtained in Example 27 was used. The operation described in Example 55 was performed to obtain 1.2 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.1

[Example 73]
In the repeating unit of Exemplified Compound AG-14, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.35 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 1.0 g of the polymer compound of Example Compound AG-14 obtained in Example 29 was used. The procedure described in Example 55 was performed to obtain 1.1 g of the objective polymer compound.
Average number of sulfo groups per repeating unit: 3.1

[Example 74]
In the repeating unit of Exemplified Compound AH-5, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AH-5 obtained in Example 31 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.0

[Example 75]
In the repeating unit of Exemplified Compound AH-14, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Exemplified Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Illustrative Compound AH-14 obtained in Example 33 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.8

[Example 76]
In the repeating unit of Exemplified Compound AI-5, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Except for using 1.4 g of the polymer compound of Exemplified Compound AI-5 obtained in Example 35 instead of using 1.4 g of the polymer compound of Illustrative Compound AA-1 obtained in Example 1, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.9

[Example 77]
In the repeating unit of Exemplified Compound AK-9, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AK-9 obtained in Example 39 was used, The operation described in Example 55 was performed to obtain 1.5 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.1

[Example 78]
In the repeating unit of the exemplary compound AM-1, production of a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y, and at least one of Z ^{1 to} Z ⁴ is a sulfo group. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound AM-1 obtained in Example 40 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.9

[Example 79]
In the repeating unit of the exemplary compound BA-1, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 2.0 g of the polymer compound of Example Compound BA-1 obtained in Example 41 was used. The operation described in Example 55 was performed to obtain 2.2 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.1

[Example 80]
In the repeating unit of Exemplified Compound BA-10, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group In Example 55, Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 2.0 g of the polymer compound of Example Compound BA-10 obtained in Example 42 was used, The operation described in Example 55 was performed to obtain 2.3 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.2

[Example 81]
In the repeating unit of Exemplified Compound BA-14, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 2.0 g of the polymer compound of Example Compound BA-14 obtained in Example 44 was used. The operation described in Example 55 was performed to obtain 2.4 g of the objective polymer compound.
Average number of sulfo groups per repeating unit: 3.0

[Example 82]
In the repeating unit of Exemplified Compound BC-1, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 2.0 g of the polymer compound of Example Compound BC-1 obtained in Example 45 was used. The operation described in Example 55 was performed to obtain 2.2 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.1

[Example 83]
In the repeating unit of exemplary compound CA-1, production of a polymer compound in which at least one of substituents of Ar ¹ , Ar ² , X ¹ , X ² , Y and at least one of Z ^{1 to} Z ⁴ is a sulfo group Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound CA-1 obtained in Example 46 was used, The operation described in Example 55 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 2.0

[Example 84]
In the repeating unit of Exemplary Compound CB-1, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound CB-1 obtained in Example 48 was used, The operation described in Example 54 was performed to obtain 1.6 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 1.9

[Example 85]
In the repeating unit of Exemplified Compound CB-5, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound CB-5 obtained in Example 50 was used, The operation described in Example 55 was performed to obtain 1.7 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 3.9

[Example 86]
In the repeating unit of Exemplified Compound DB-5, Production of a Polymer Compound in which Ar ¹ , Ar ² , X ¹ , X ² , Y Substituent and at least one of Z ^{1 to} Z ⁴ is a sulfo group In Example 55, Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, except that 1.4 g of the polymer compound of Example Compound DB-5 obtained in Example 52 was used, The procedure described in Example 55 was performed to obtain 1.8 g of the intended polymer compound.
Average number of sulfo groups per repeating unit: 5.7

[Example 87]
In the repeating unit of Exemplified Compound EB-5, a polymer compound in which Ar ¹ , Ar ² , X ¹ , X ² , a substituent of Y ² and at least one of Z ^{1 to} Z ⁴ is a sulfo group is produced. Instead of using 1.4 g of the polymer compound of Example Compound AA-1 obtained in Example 1, 1.0 g of the polymer compound of Example Compound EB-5 obtained in Example 54 was used. The operation described in Example 55 was performed to obtain 1.3 g of the target polymer compound.
Average number of sulfo groups per repeating unit: 6.1

[Example 88] Evaluation of film formability Using a methanol solution of the polymer compound obtained in Example 55 (solution obtained by dissolving 20 mg of a polymer compound in 4 mL of methanol) on a glass substrate, a film having a thickness of 60 nm was formed by spin coating. The film was formed with a thickness. 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 57 shows the results of surface roughness measurement by AFM.

[Example 89] to [Example 120] Evaluation of film-forming property Instead of the polymer compound obtained in Example 55, the polymer compound obtained in Example 56 to Example 87 was used in the same manner as in Example 88. When the film was formed by the method and observed, a uniform film was formed. Table 57 shows the results of surface roughness measurement by AFM.

[Comparative Example 1] Evaluation of film formability A film was formed and observed in the same manner as in Example 88 using PEDOT / PSS (formula (4)) instead of the polymer compound obtained in Example 55. The film thickness was found to be more varied than that formed using the polymer compound obtained in Example 55. Table 57 shows the results of surface roughness measurement by AFM.

  As is clear from Table 57, the polymer compound of the present invention showed a very excellent film formability as compared with PEDOT / PSS.

[Example 121] (Creation of organic electroluminescence device)
Ultrasonic cleaning of patterned glass substrate with 150 nm thick ITO transparent electrode (sputtered film; sheet resistance 15Ω) 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 polymer compound obtained in Example 55 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. Formed.

  Next, a xylene solution (2.0% by weight) of a polymer compound ADS259BE (formula 5) 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 6) 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 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 6.1 V and luminance of 140 cd / cm ² was confirmed. When continuous driving was performed for 200 hours from an initial luminance of 500 cd / cm ² , the luminance reduction rate was 22%. The results are shown in Table 58.

[Example 122] to [Example 153]
In Example 121, when forming the hole injecting and transporting layer, instead of using the polymer compound obtained in Example 55, the polymer compound obtained in Examples 56 to 87 was used. In accordance with the operation described in 121, an organic electroluminescent element was produced. Further, a direct current voltage was applied to the device in the same manner as in Example 121, the characteristics of the device were measured, and the results are shown in Table 58.

[Comparative Example 2]
In Example 121, instead of using the polymer compound obtained in Example 55 when forming the first hole injecting and transporting layer, it is represented by the formula (7) described in International Publication No. 2007/043607. According to the procedure described in Example 121, an organic electric field was used except that a sulfo group-containing polymer compound having at least one repeating unit in which at least one benzene ring was substituted with a sulfo group in the repeating unit in the polymer chain was used. A light emitting element was manufactured. Further, a direct current voltage was applied to the device in the same manner as in Example 121, the characteristics of the device were measured, and the results are shown in Table 58.

[Example 154]
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 wt%) of the polymer compound synthesized in Example 2 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 5.7 V and a luminance of 153 cd / cm ² was confirmed. When continuous driving was performed for 200 hours from an initial luminance of 500 cd / cm ² , the luminance reduction rate was 28%. The results are shown in Table 59.

[Example 155] to [Example 173]
In Example 154, instead of using the polymer compound obtained in Example 2 in forming the second hole injecting and transporting layer, Examples 4, 6, 10, 12, 18, 22, 24, 26 , 28, 30, 32, 34, 36, 37, 38, 43, 47, 49, 51, and 53 except that the polymer compound obtained in accordance with the procedure described in Example 154 was used. Was made. Further, a direct current voltage was applied to the device in the same manner as in Example 154, the characteristics of the device were measured, and the results are shown in Table 59.

[Comparative Example 3]
In Example 154, in forming the second hole injecting and transporting layer, it is described in Example 154 except that the ADS259BE (formula 5) is used instead of using the polymer compound obtained in Example 2. 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 154, the characteristics of the device were measured, and the results are shown in Table 59.

[Comparative Example 4]
In Example 154, when forming the second hole injecting and transporting layer, instead of using the polymer compound obtained in Example 2, it is represented by the formula (8) described in JP-A-2006-316224. An organic electroluminescent device was produced according to the procedure described in Example 154 except that the polymer compound composed of the above repeating units was used. Further, a direct current voltage was applied to the device in the same manner as in Example 154, the characteristics of the device were measured, and the results are shown in Table 59.

[Example 174]
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 polymer compound obtained in Example 58 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. A first hole injecting and transporting layer was formed. Next, a toluene solution (1.5% by weight) of the polymer compound obtained in Example 2 was formed into a film with 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 5.2 V and a luminance of 155 cd / cm ² was confirmed. When continuous driving was performed for 200 hours from an initial luminance of 500 cd / cm ² , the luminance reduction rate was 23%. The results are shown in Table 60.

[Example 175] to [Example 194]
In Example 174, instead of using the polymer compound obtained in Example 2 in forming the hole injecting and transporting layer, Examples 4, 6, 10, 12, 18, 22, 24, 26, 28, An organic electroluminescent device was produced according to the procedure described in Example 174 except that the polymer compound obtained in 30, 32, 34, 36, 37, 38, 43, 47, 49, 51, 53 was used. . Further, a direct current voltage was applied to the device in the same manner as in Example 174, the characteristics of the device were measured, and the results are shown in Table 60.

  As is apparent from Table 58 to Table 60, the organic EL device of the present invention using the polymer compound of the present invention as a hole injecting and transporting material has high emission luminance, excellent luminous efficiency, and low luminance reduction rate. It was excellent in terms of life.

  The organic electroluminescent element obtained by using the polymer compound of the present invention can be used as a panel-type light source, various light-emitting elements, display elements, labels, and sensors.

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.

Explanation of symbols

1: substrate 2: anode 3: hole injection transport layer 3a: hole injection transport component 4: light emitting layer 4a: light emission component 5: electron injection transport layer 5 ": electron injection transport layer 5a: electron injection transport component 6: cathode 7: Power supply

Claims (13)

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 an integer of 0~4, p ¹ ~p ⁴ is 2 or more In the case, a plurality of each of Z ¹ , Z ² , Z ³ and Z ⁴ may be the same or different, and X ¹ and X ² may be the same or different from each other. Or a substituted divalent aromatic group, Ar ¹ and Ar ² represent an unsubstituted or substituted monovalent aromatic group which may be the same or different from each other, and Y represents an unsubstituted or And represents a substituted divalent aromatic group, s represents an integer of 0 to 1000, and t represents an integer of 1 to 1000.
A polymer compound having at least one repeating unit represented by the formula: In general formula (1), the group represented by X ¹ and X ² is a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic heterocyclic group having 4 to 30 carbon atoms. Item 1. The polymer compound according to item 1. The group represented by X ¹ and X ² in the general formula (1) is a group represented by the general formula (a-1), respectively. ^3. The polymer compound according to claim 1.

(In the formula, u represents an integer of 0 to 2.) 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, a monosubstituted amino group, a disubstituted amino group, a sulfo group, a phosphoryl group, and a general formula (1a). ) To (3a):
-(O) _L -D (1a)
-O (C = O) -D (2a)
-(C = O) OD (3a)
(In the formula, D is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted monovalent aromatic group having 4 to 12 carbon atoms, 4. An unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, wherein L represents 0 or 1, and is a group selected from the group consisting of groups represented by any one of claims 1 to 3. High molecular compound. The Ar ¹ , Ar ² , X ¹ , X ² , Y substituent and at least one of Z ^{1 to} Z ⁴ is a group selected from the group consisting of a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group. Item 5. The polymer compound according to any one of Items 1 to 4 The polymer compound according to claim 5, wherein at least one of the substituent of Ar ¹ , Ar ² , X ¹ , X ² , Y and Z ^{1 to} Z ⁴ is a sulfo group. The organic electroluminescent element material which consists of a high molecular compound in any one of Claims 1-6.   An organic electroluminescent element material comprising the polymer compound according to claim 1 dissolved in an organic solvent.   The organic electroluminescent element material according to claim 8, wherein the organic solvent is a polar solvent.   An organic electroluminescence device comprising at least one layer containing at least one layer of the polymer compound according to any one of claims 1 to 6 between a pair of electrodes.   The organic electroluminescent device according to claim 10, wherein the layer containing the polymer compound according to claim 1 is a charge injection transport layer.   The organic electroluminescence device according to claim 11, wherein the charge injection transport layer is a hole injection transport layer.   The organic electroluminescence device according to claim 12, comprising at least two hole injection transport layers.

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