JP2005120209A - Metal complex-containing polymer, organic el element and organic el display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an organic EL (electroluminescent) element that emits phosphorescence, has excellent luminous efficiency, color conversion efficiency, etc., and is suitable for a display, a lighting apparatus, etc. <P>SOLUTION: The organic EL element has an organic thin film layer between a positive electrode and a negative electrode. The organic thin film layer comprises a metal complex-containing polymer that has a metal complex unit having a π electron conjugate part and a π electron conjugate cleavage unit for cleaving the π electron conjugate in the metal complex unit as repeating units. The metal complex-containing polymer is preferably a mode containing repeating units represented by structural formula (1) (A is a π electron conjugate part-containing metal complex unit; B is a π electron conjugate cleavage unit for cleaving the π electron conjugate in the A; x is the mol fraction (mol%) of the A in the whole metal complex-containing polymer; y is the mol fraction (mol%) of the B in the whole metal complex-containing polymer; x+y=100; n is a degree of polymerization). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a metal complex-containing polymer suitably used for various devices such as an organic EL element and a solar cell as a light-emitting material, a color conversion material, and the like, and an organic EL excellent in luminous efficiency using the metal complex-containing polymer. The present invention relates to an element and a high-performance organic EL display using the organic EL element.

The organic EL element can be driven at a lower voltage than an inorganic EL element, and is a solid self-luminous element that can be manufactured without going through a complicated growth process as compared with a conventional inorganic LED. In addition, when considering application to portable displays, organic EL elements are self-luminous, especially when compared to liquid crystal displays (LCDs), so no backlight is required, and lightweight and inexpensive products can be realized. Since the response speed is fast and it is an all-solid-state device, there is an advantage that it is resistant to impact.
Conventionally, monomer materials and polymer materials are known as light emitting materials used for the light emitting layer in the organic EL device. The light emitting layer in the organic EL device is generally formed by vacuum deposition when the monomer material is used, and is formed by a coating method when the polymer material is used, but when the polymer material is used. Is advantageous in that the light emitting layer can be formed in a large area at low cost.

  However, when a full-color organic EL display is manufactured using the polymer material as the light emitting material, the light emitting materials that emit light of the three primary colors of blue (B), green (G), and red (R) are finely coated. There is a problem that it is difficult to form pixels separately. In the past, the polymer material was applied separately by vacuum deposition using a metal mask, but in this case, in addition to the limited processing dimensions of the metal mask, the accuracy of alignment of the metal mask can be improved. As a result of the difficulty, there is a problem that the resolution of color separation is not sufficient and the organic EL display cannot be mass-produced efficiently at low cost.

Therefore, it is also considered to form pixels by finely coating the polymer materials that emit light of three primary colors of blue (B), green (G), and red (R) by an inkjet method. In this case, the polymer material can be used effectively without waste, is low-cost, and a high-definition full-color pixel pattern can be formed more easily than when the metal mask is used for painting by the vacuum deposition method. Thus, the light emitting layer can be formed, and there is an advantage that it is excellent in mass productivity.
Therefore, it is desired to provide the polymer material suitable for forming pixels by the inkjet method.

By the way, light emission by the organic EL element mainly uses fluorescence. That is, when electrons and holes (holes) are injected from both electrodes, they move toward the counter electrode and recombine at a proportion of the light-emitting layer to generate excitons. EL light emission is generated by using energy when returning to the state. The excited state includes a singlet excited state in which the direction of electron spin is antiparallel and a triplet excited state in which the direction of electron spin is parallel, but the fluorescence involves only the singlet excited state. It is a light emission form. From the quantum mechanical reasoning, the generation ratio of singlet excited state (singlet exciton) and triplet excited state (triplet exciton) is 1: 3. Therefore, in the case of an organic EL device using fluorescence, The maximum value of the internal quantum efficiency is 25%. That is, 75% of the excited state is not used for light emission, and at room temperature in particular, the triplet excitons have been thought to be non-light-emitting due to thermal loss.
However, M.M. A. Baldo et al. Obtain an external quantum efficiency of 7.5% (internal quantum efficiency is 37.5% assuming an external extraction efficiency of 20%) even at room temperature by using a platinum complex that exhibits phosphorescence emission from a triplet excited state. It was shown that it exceeds the external quantum efficiency of 5%, which has conventionally been the upper limit (see Patent Document 1 and Non-Patent Document 1). Since the generation probability of the triplet exciton is three times that of the singlet exciton, the quantum efficiency which is three times higher than the conventional EL light emission by fluorescence passing through the singlet exciton is high in EL light emission by phosphorescence emission. It can be expected.
Therefore, it is desired to provide a polymer material that exhibits the phosphorescence emission, has excellent luminous efficiency, and is suitable for an organic EL element, a solar battery, and the like, and an organic EL element and an organic EL display using the polymer material.

International Publication WO00 / 70655 Appl. Phys. Lett. 75, 4 pages, 1999

  An object of the present invention is to solve various problems in the prior art, meet the above demands, and achieve the following objects. That is, the present invention can emit phosphorescence and can be easily formed into a film by an ink jet method or the like, and is suitable for various devices such as an organic EL element and a solar cell as a light emitting material and a color conversion material. A metal complex-containing polymer, an organic EL element that is excellent in light emission efficiency, color conversion efficiency, and the like using the metal complex-containing polymer, and suitable for a display, a lighting device, and the like, and a high-performance organic using the organic EL element An object is to provide an EL display.

  The present invention is based on the following findings obtained as a result of intensive studies by the present inventors in order to achieve the above object. That is, recently, when designing an organic EL element or the like using a monomer material that exhibits phosphorescence and has excellent light emission efficiency, it is not easy to form pixels with high definition and simplicity as described above. On the other hand, when an organic EL element or the like is designed using a polymer material, the pixel can be formed with high definition and simpleness by an ink jet method or the like, but exhibits phosphorescence, has excellent efficiency, and has an organic EL element or the like. It is extremely difficult to design a suitable polymer material. This is because if a structure capable of emitting phosphorescence is simply introduced into the polymer, the polymer does not emit phosphorescence. However, if a triplet exciton confinement structure capable of confining the triplet exciton generated in a unit unit exhibiting phosphorescence emission is introduced into the polymer together with the unit unit, the polymer becomes phosphorous. Can exhibit light emission. And it is the knowledge that the luminous efficiency of the polymer can be improved by introducing the unit unit and the triplet exciton confinement structure into the polymer as repeating units. Means for solving the above-described problems are as described in (Appendix 1) to (Appendix 33) described later.

The metal complex-containing polymer of the present invention comprises, as a repeating unit, a metal complex unit having a π-electron conjugated portion and a π-electron conjugated cleavage unit capable of cleaving π-electron conjugation in the metal complex unit. In the metal complex-containing polymer, when energy (for example, energy generated when a hole and an electron are combined) is applied to the metal complex unit, an exciton such as a triplet exciton is generated by the energy. Is generated and light is emitted when it returns to the ground state. In the metal complex-containing polymer, since the π-electron conjugation in the metal complex unit is cleaved by the π-electron conjugate cleavage unit, the triplet exciton generated in the metal complex unit is the metal complex Since it is trapped in the complex unit and cannot move, it emits light efficiently when returning to the ground state. Since the metal complex polymer is a polymer material, it has excellent handleability and can be easily and highly precisely formed by various coating methods such as an ink jet method. A planar light source, lighting device, segment display device, dot It is suitable as a light emitting material, a color conversion material, etc. in a matrix display device, a backlight of a liquid crystal display device, a solar cell, and the like.
The organic EL device of the present invention has an organic thin film layer between a positive electrode and a negative electrode, and the organic thin film layer cuts a metal complex unit having a π electron conjugated portion and a π electron conjugation in the metal complex unit. It includes a metal complex-containing polymer having a possible π-electron conjugated cleavage unit as a repeating unit. In the organic EL element, since the metal complex-containing polymer of the present invention is used, luminous efficiency, color conversion efficiency, etc. are high, it is thermally and electrically stable, has a long life, and can be mass-produced efficiently. .
The organic EL display of the present invention uses the organic EL element of the present invention. In the organic EL display, since the organic EL element of the present invention is used, the light emission efficiency and the color conversion efficiency are high, it is thermally and electrically stable, has a long life, and has high performance.

  According to the present invention, conventional problems can be solved, the above-mentioned demands can be met, phosphorescence emission is possible, film formation can be easily performed by an ink jet method, etc., a light emitting material, a color conversion material, etc. As an organic EL element, a polymer containing a metal complex suitable for various devices such as a solar cell, and using the metal complex-containing polymer, it is excellent in luminous efficiency, color conversion efficiency, etc., and suitable for a display, a lighting device, etc. An EL element and a high-performance organic EL display using the organic EL element can be provided.

(Metal complex-containing polymer)
The metal complex-containing polymer of the present invention has a metal complex unit having a π-electron conjugated moiety and a π-electron conjugated cleavage unit capable of cleaving π-electron conjugation in the metal complex unit as repeating units, and is further necessary. Depending on the case, it has other units.
The form of the metal complex-containing polymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the metal complex-containing polymer may be linear or branched, but is preferably linear. The triplet exciton generated in the metal complex unit can be confined in the metal complex unit, and the triplet exciton can be any of block copolymers, random copolymers, etc. At least one of the metal complex units and at least one of the π-electron conjugate cleavage units are alternately repeated in that light emission generated when returning from the excited state to the ground state is made efficient and high luminance is obtained. Form is preferred.

The metal complex unit is not particularly limited as long as it has a structure capable of emitting light, and can be appropriately selected according to the purpose. In the present invention, the metal complex unit has a π-electron conjugated moiety. In addition, it is preferable to be capable of binding to the π-electron conjugated cleavage unit, more preferably to be a repeating unit in the metal complex-containing polymer, and to form a repeating unit together with the π-electron conjugated cleavage unit. What is possible is more preferred. Among these metal complex units, those capable of phosphorescence emission are preferable from the viewpoints of light emission efficiency, color conversion efficiency, and the like.
The metal complex unit capable of emitting phosphorescence is not particularly limited and may be appropriately selected depending on the purpose. For example, a central metal and a coordinate bond with the central metal are possible, and a π-electron conjugated moiety is formed. And a metal complex unit having at least a ligand. These metal complex units may be contained alone or in combination of two or more in the metal complex-containing polymer.

Examples of the central metal include those known as the central metal in a metal complex that emits light, and among them, a metal atom capable of emitting phosphorescence is preferable.
Specific examples of the central metal include rhenium (Re), iridium (Ir), osmium (Os), scandium (Sc), yttrium (Y), platinum (Pt), gold (Au), europium (Eu), and terbium. (Tb), thulium (Tm), dysprosium (Dy), samarium (Sm), praseodymium (Pr), gadolinium (Gd), and the like. Among these, iridium (Ir), platinum (Pt), gold (Au), and europium (Eu) are preferable, and iridium (Ir) is particularly preferable. These may be contained individually by 1 type in the said metal complex containing polymer, and may be contained 2 or more types.

The ligand is not particularly limited as long as it has a coordinate bond with the central metal and has a π-electron conjugated moiety, and can be appropriately selected according to the purpose. For example, a carbonyl ligand, an alkene Ligand, alkyne ligand, amine ligand, imine ligand, nitrile ligand, isonitrile ligand, phosphine ligand, phosphine oxide ligand, phosphite ligand, ether ligand And a sulfone ligand, a sulfoxide ligand, a sulfide ligand; a ligand formed by bonding any of heterocyclics and a benzene ring, and the like.
These ligands may be contained individually by 1 type in the said metal complex containing polymer, and may be contained 2 or more types.

Examples of the carbonyl ligand include ketones such as carbon monoxide, acetone, and benzophenone; diketones such as acetylacetone and acenaphthoquinone; and acetonate coordination such as acetylacetonate, dibenzomethylate, and tenoyltrifluoroacetonate. Child, etc.
Examples of the alkene ligand include ethylene, propylene, butene, hexene, and decene.
Examples of the alkyne ligand include acetylene, phenylacetylene, diphenylacetylene, and the like.
Examples of the amine ligand include triethylamine and tributylamine.
Examples of the imine ligand include benzophenone imine and methyl ethyl ketone imine.
Examples of the nitrile ligand include acetonitrile and benzonitrile.
Examples of the isonitrile ligand include t-butyl isonitrile and phenyl isonitrile.
Examples of the phosphine ligand include triphenylphosphine, tolylphosphine, tricyclohexylphosphine, and tributylphosphine.
Examples of the phosphine oxide ligand include tributyl phosphine oxide, triphenyl phosphine oxide, and the like.
Examples of the phosphite ligand include triphenyl phosphite, tolyl phosphite, tributyl phosphite, triethyl phosphite, and the like.
Examples of the ether ligand include dimethyl ether, diethyl ether, tetrahydrofuran, and the like.
Examples of the sulfone ligand include dimethyl sulfone and dibutyl sulfone.
Examples of the sulfoxide ligand include dimethyl sulfoxide, dibutyl sulfoxide, and the like.
Examples of the sulfide ligand include ethyl sulfide and butyl sulfide.
Examples of the ligand formed by bonding any of the heterocyclic ring (for example, pyridine ring, thiophene ring, benzoxazole ring, etc.) and the benzene ring include phenylpyridine, 2- (paraphenylphenyl) pyridine, 7-bromobenzo [h] quinoline, 2- (4-thiophen-2-yl) pyridine, 2- (4-phenylthiophen-2-yl) pyridine, 2-phenylbenzoxazole, 2- (paraphenylphenyl) benzoxazole 2-phenylbenzothiazole, 2- (paraphenylphenyl) benzothiazole, 2- (benzothiophen-2-yl) pyridine 7,8,12,13,17,18-hexakisethyl-21H, 23H-porphyrin, Etc.

Among the ligands, those represented by the following structural formula are preferable.

  The ligand may be further substituted with a substituent. In this case, the substituent is not particularly limited and may be appropriately selected depending on the purpose. For example, a halogen atom, an alkyl group, Alkylthio group, alkylsilyl group, alkylamino group, aralkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent A heterocyclic group, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. For example, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl Group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, and the like. Among these, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and a 3,7-dimethyloctyl group are preferable.
The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, a methylthio group, an ethylthio group, a propylthio group, an i-propylthio group, a butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, Etc. Among these, a pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, 3,7-dimethyloctylthio group and the like are preferable.

The alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms. For example, a methylsilyl group, an ethylsilyl group, a propylsilyl group, an i-propylsilyl group, a butylsilyl group, i-butylsilyl group, t-butylsilyl group, pentylsilyl group, hexylsilyl group, cyclohexylsilyl group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group Laurylsilyl group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, i-propyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl Group, octyldimethylsilyl group, 2-ethylhexyl - dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, a 3,7-- dimethylsilyl group, lauryldimethylsilyl group, and the like. Among these, pentylsilyl group, hexylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2 -Ethylhexyl-dimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group and the like are preferable.
The alkylamino group may be linear, branched or cyclic, and may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms. , Methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, i-propylamino group, butylamino group, i-butylamino group, t-butylamino group, pentylamino group, hexylamino group, Examples include cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, and the like. Among these, a pentylamino group, hexylamino group, octylamino group, 2-ethylhexylamino group, decylamino group, 3,7-dimethyloctylamino group and the like are preferable.

There is no restriction | limiting in particular as said aralkyl group, According to the objective, it can select suitably, For example, a benzyl group, a phenylethyl group, a phenylpropyl group, etc. are mentioned.
The alkenyl group is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, an octenyl group, Etc.
The alkoxy group may be linear, branched or cyclic, and the carbon number thereof is usually about 1 to 20, and specifically, for example, a methoxy group, an ethoxy group, a propyloxy group I-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy Group, 3,7-dimethyloctyloxy group, lauryloxy group, and the like. Among these, a pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and the like are preferable.
The aryl group usually has about 6 to 60 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

Examples of the aryloxy group, the a is usually about 6 to 60 carbon atoms, for example, a phenoxy _group, C 1 _{-C 12} alkoxy phenoxy _group, C 1 _{-C 12} alkylphenoxy group, 1-naphthyloxy group, 2- A naphthyloxy group, and the like. Among _these, C 1 _{-C 12} alkoxy phenoxy _group, a C 1 _{-C 12} alkylphenoxy group are preferable.
Examples of the arylalkyl group, the carbon number of usually about 7 to 60, for example, phenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkyl _{group, C} 1 ~ C ₁₂ alkylphenyl _-C 1 _{-C 12} alkyl group, 1-naphthyl _-C 1 _{-C 12} alkyl group, 2-naphthyl _-C 1 _{-C 12} alkyl group, and the like. Among _these, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkyl group.
Examples of the aryl alkoxy group, its carbon number of usually about 7 to 60, for example, phenyl _-C 1 _{-C 12} alkoxy _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkoxy _{group, C} 1 ~ C ₁₂ alkylphenyl _-C 1 _{-C 12} alkoxy groups, 1-naphthyl _-C 1 _{-C 12} alkoxy groups, 2-naphthyl _-C 1 _{-C 12} alkoxy group, and the like. Among _these, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkoxy _group, a C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkoxy group are preferred.

The arylalkenyl group usually has about 8 to 60 carbon atoms, such as cis-phenylalkenyl group, trans-phenylalkenyl group, cis-tolylalkenyl group, trans-tolylalkenyl group, cis-1-naphthyl. Examples include an alkenyl group, a trans-1-naphthylalkenyl group, a cis-2-naphthylalkenyl group, a trans-2-naphthylalkenyl group, and the like.
As said aryl alkynyl group, the carbon number is about 8-60 normally, For example, a phenyl alkynyl group, a tolyl alkynyl group, 1-naphthyl alkynyl group, 2-naphthyl alkynyl group, etc. are mentioned.
As the arylamino group, the a is usually about 6 to 60 carbon atoms, e.g., phenylamino group, diphenylamino _group, C 1 _{-C 12} alkoxyphenyl amino group, di _(C 1 _{-C 12} alkoxyphenyl) amino Groups, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino groups, 2-naphthylamino groups, and the like. Among _these, C 1 _{-C 12} alkylphenyl group, such as di _(C 1 _{-C 12} alkylphenyl) amino group are preferable.
The monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms. For example, a thienyl group, C _{1 to} C ₁₂ alkylthienyl group, a pyrrolyl group, a furyl group, a pyridyl _group, C 1 _{-C 12} alkyl pyridyl group, and the like. Among these, a thienyl group, a C _{1 to} C ₁₂ alkyl thienyl group, a pyridyl group, a C _{1 to} C ₁₂ alkyl pyridyl group, and the like are preferable.

なお、前記構造式において、Ｍは、上述した中心金属を表す。Ｌ^２は、Ｍと結合可能な配位子を表す。該配位子については、上述した通りである。ｐは、０〜５の整数を表す。 As a specific example of the metal complex unit, for example, one represented by the following structural formula is preferably exemplified.

In the structural formula, M represents the central metal described above. L ² represents a ligand capable of binding to M. The ligand is as described above. p represents an integer of 0 to 5.

The metal complex unit is preferably included as a repeating unit in the metal complex-containing polymer, and preferably forms one repeating unit together with the π-electron conjugated cleavage unit.
There is no restriction | limiting in particular as a mole fraction in the said whole metal complex containing polymer of the said metal complex unit, Although it can select suitably according to the objective, For example, 1-30 mol% is preferable, and 3-10 mol % Is more preferable.
If the molar fraction of the metal complex unit is less than 1 mol%, light may not be emitted, and if it exceeds 30 mol%, it may be quenched.

  The π-electron conjugate cleavage unit is not particularly limited as long as the π-electron conjugate in the metal complex unit can be cleaved, and can be appropriately selected according to the purpose. It is preferable that a triplet exciton generated in the unit has a structure that can be confined in the metal complex unit. In this case, by confining the triplet exciton generated in the metal complex unit in the metal complex unit, light emission can be efficiently generated when the triplet exciton returns from the excited state to the ground state. This is advantageous.

Specific examples of the π-electron conjugated cleavage unit include (A) an arylene group that can be bonded to the metal complex unit at the meta position, (B) any one selected from an oxygen atom, a silicon atom, and a boron atom; Preferable examples include an arylene group capable of binding to the metal complex unit, (C) an alkylene group having any one selected from an oxygen atom, a silicon atom and a boron atom and capable of binding to the metal complex unit. In the case of (B) and (C), another arylene group or alkylene group is bonded to the oxygen atom, silicon atom or boron atom in place of the arylene group or alkylene group. May be. In addition, the oxygen atom, the silicon atom, or the boron atom may be included in a part of the arylene group or the alkylene group.
These may be contained individually by 1 type in the said metal complex containing polymer, and may be contained 2 or more types.

The arylene group in the π-electron conjugated cleavage unit is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monocyclic aromatic ring group or aromatic rings are bonded to 4 or less rings. Preferred examples include a group having 5 or less condensed aromatic rings and a total number of carbon, oxygen, nitrogen and sulfur atoms of 50 or less.
The monocyclic aromatic ring group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a styryl group, a mesityl group, and a cinnamyl group. , A phenethyl group, a benzhydryl group, and the like, and these may be substituted with a substituent.
The group formed by bonding four or less aromatic rings is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an azulenyl group, A benzanthracenyl group, and the like, which may be substituted with a substituent.
The group having 5 or less condensed aromatic rings and the total number of carbon, oxygen, nitrogen and sulfur atoms is 50 or less is not particularly limited and may be appropriately selected depending on the intended purpose. For example, pyrrolyl group, furyl group, thienyl group, pyridyl group, quinolyl group, isoquinolyl group, imidazolyl group, pyridinyl group, pyrrolopyridinyl group, thiazoyl group, pyrimidinyl group, thiophenyl group, indolyl group, quinolinyl group, pyrinyl group, adenyl group These may be substituted with a substituent.

前記構造式（３）中、ｑは、１〜５の整数を表す。 As the π-electron conjugated cleavage unit, for example, those represented by any of the following structural formulas (3) to (7) are preferable.

In the structural formula (3), q represents an integer of 1 to 5.

前記構造式（４）中、Ａｒは、アリーレン基を表す。Ｒは、アルケン基を表す。ｌ及びｍは、０〜５の整数を表す。ただし、ｌ及びｍは、互いに同時に０であるのは好ましくない。
前記アルケン基としては、直鎖状、分岐状及び環状のいずれでもよく、炭素数は通常１〜１０であり、例えば、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ターシャリーブチレン基、ペンチレン基、イソペンチレン基、ヘキシレン基、イソヘキシレン基、ヘプチレン基、イソヘプチレン基、オクチレン基、イソオクチレン基、ノニレン基、イソノニレン基、デシレン基、イソデシレン基、シクロペンチレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロヘプチレン基、シクロオクチレン基、シクロノニレン基、シクロデシレン基、等が挙げられる。

In the structural formula (4), Ar represents an arylene group. R represents an alkene group. l and m represent the integer of 0-5. However, it is not preferable that l and m are 0 at the same time.
The alkene group may be linear, branched or cyclic, and usually has 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, Tertiary butylene group, pentylene group, isopentylene group, hexylene group, isohexylene group, heptylene group, isoheptylene group, octylene group, isooctylene group, nonylene group, isononylene group, decylene group, isodecylene group, cyclopentylene group, cyclobutylene group, A cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, and the like can be given.

前記構造式（５）から（７）において、Ａｒは、アリーレン基を表す。ｌ及びｍは、０〜５の整数を表す。ただし、ｌ及びｍは、互いに同時に０であるのは好ましくない。

In the structural formulas (5) to (7), Ar represents an arylene group. l and m represent the integer of 0-5. However, it is not preferable that l and m are 0 at the same time.

The π-electron conjugated cleavage unit is preferably included as a repeating unit in the metal complex-containing polymer, and forms one repeating unit together with the metal complex unit.
There is no restriction | limiting in particular as a mole fraction in the said whole metal complex containing polymer of the said (pi) electron conjugate cutting | disconnection unit, According to the objective, it can select suitably, For example, 70-99 mol% is preferable, 90-97 Mole% is more preferable.
If the mole fraction of the π-electron conjugated cleavage unit is less than 70 mol%, it may be quenched, and if it exceeds 99 mol%, it may not emit light.

The total of the mole fraction (mol%) of the π-electron conjugated cleavage unit and the mole fraction (mol%) of the metal complex unit is not particularly limited, and is 90 to 100 mol%. It is more preferable that it is 95-100 mol%, and it is especially preferable that it is 100 mol%.
If the total is less than 90 mol%, the light emission efficiency and luminance of the metal complex-containing polymer may be inferior.

  Among the metal complex-containing polymers, those having a repeating unit represented by the following structural formula (1) are particularly preferable in the present invention.

前記構造式（１）中、Ａは、π電子共役部分を有する前記金属錯体単位を表す。Ｂは、該金属錯体単位Ａにおけるπ電子共役を切断可能な前記π電子共役切断単位を表す。ｘは、前記Ａ（前記金属錯体単位）の金属錯体含有高分子全体におけるモル分率（モル％）を表し、ｙは、前記Ｂ（前記π電子共役切断単位）の金属錯体含有高分子全体におけるモル分率（モル％）を表し、ｘ＋ｙ＝１００である。ｎは、重合度を表す。

In the structural formula (1), A represents the metal complex unit having a π electron conjugated portion. B represents the π electron conjugate cleavage unit capable of cleaving the π electron conjugate in the metal complex unit A. x represents the mole fraction (mol%) of the whole of the metal complex-containing polymer of A (the metal complex unit), and y is the whole of the metal complex-containing polymer of B (the π-electron conjugated cleavage unit). The molar fraction (mol%) is represented, and x + y = 100. n represents the degree of polymerization.

There is no restriction | limiting in particular as said x, Although it can select suitably according to the objective, 1-30 mol% is preferable and 3-10 mol% is more preferable.
If x is less than 1 mol%, light emission may not occur, and if it exceeds 30 mol%, quenching may occur.
There is no restriction | limiting in particular as said y, Although it can select suitably according to the objective, 70-99 mol% is preferable and 90-97 mol% is more preferable.
If y is less than 70 mol%, quenching may occur, and if it exceeds 97 mol%, light emission may not occur.
There is no restriction | limiting in particular as said n, Although it can select suitably according to the objective, 5-2,000 are preferable.
If n is less than 5, the light emission intensity may decrease, and if it exceeds 2,000, it may become insoluble.

  There is no restriction | limiting in particular as said A in the said Structural formula (1), For example, according to the objective, it can select and use suitably from well-known low molecular EL luminescent material. These may be used individually by 1 type and may use 2 or more types together. Among these, from the viewpoint of luminous efficiency, a metal complex unit having a π-electron conjugated moiety and capable of phosphorescence emission is preferable, and for example, those represented by the following structural formula (2) are preferable.

前記構造式（２）中、Ｍは、上述した中心金属を表す。Ｌ^１及びＬ^２は、Ｍと結合可能な配位子を表し、Ｌ^１は、前記構造式（１）におけるＢと結合する配位子を表す。該配位子の具体例については、上述した通りである。ｐは、０〜５の整数を表す。なお、ｐが１以上の場合、Ｌ^１及びＬ^２は、互いに同一であってもよいし、異なっていてもよい。

In the structural formula (2), M represents the central metal described above. L ¹ and L ² represent a ligand that can bind to M, and L ¹ represents a ligand that binds to B in the structural formula (1). Specific examples of the ligand are as described above. p represents an integer of 0 to 5. When p is 1 or more, L ¹ and L ² may be the same as or different from each other.

Among the L ¹ and L ² , those represented by the following structural formula are particularly preferable as described above.

L ¹ and L ² may be further substituted with the above-described substituent. The substituent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the halogen atom described above, the alkyl group described above, the alkylthio group described above, the alkylsilyl group described above, and the alkylamino group described above. , The aralkyl group described above, the alkenyl group described above, the alkoxy group described above, the aryl group described above, the aryloxy group described above, the arylalkyl group described above, the arylalkoxy group described above, the arylalkenyl group described above, the arylalkynyl group described above. , Arylamino groups described above, monovalent heterocyclic groups described above, and the like.

なお、前記各構造式において、Ｍ、Ｌ^２及びｐは、上述の通りである。 As a specific example of A in the structural formula (1), any one represented by the following structural formula is preferable.

In the structural formulas, M, L ² and p are as described above.

  Specific examples of B in the structural formula (1) include (A) an arylene group that can be bonded to the metal complex unit at the meta position, and (B) any one selected from an oxygen atom, a silicon atom, and a boron atom. And an arylene group that can be bonded to the metal complex unit, (C) an alkylene group that has any one selected from an oxygen atom, a silicon atom, and a boron atom and that can bond to the metal complex unit, and the like. It is done. In addition, these arylene groups or alkylene groups are as described above. These may be contained individually by 1 type in the said metal complex containing polymer, and may be contained 2 or more types.

前記構造式（８）中、ｘ及びｙは、モル分率（モル％）を表し、ｘ＋ｙ＝１００である。ｎは、重合度を表す。 Among the metal complex polymers represented by the structural formula (1), those containing a repeating unit represented by the following structural formula (8) are preferable in terms of luminous efficiency.

In the structural formula (8), x and y represent a mole fraction (mol%), and x + y = 100. n represents the degree of polymerization.

The number average molecular weight in the metal complex-containing polymer of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 5,000 or more, and 10,000 to 2,000,000. Is more preferable.
If the number average molecular weight is less than 5,000, the luminous efficiency may not be sufficient.
There is no restriction | limiting in particular as molecular weight dispersion degree (Mw / Mn) of the said metal complex containing polymer | macromolecule, Although it can select suitably according to the objective, 1.0-3.0 are preferable, for example, 1.0 -2.0 is more preferable.
When the molecular weight dispersity (Mw / Mn) exceeds 3.0, an excimer may be formed, resulting in a decrease in luminous efficiency.

  The method for producing the metal complex-containing polymer of the present invention is not particularly limited and may be appropriately selected from known methods according to the purpose. For example, the monomer corresponding to the metal complex unit and the π (1) a method of electrolytic polymerization of a polymerizable oligomer or polymer obtained by combining these two monomers, preferably these two monomers in advance, using a monomer corresponding to an electron conjugate cleavage unit; ) A method of oxidative polymerization with an oxidizing agent such as trivalent iron, (3) a reaction in which the monomer, oligomer or polymer dihalogen compound is converted to Grignard and polymerized, (4) a method of polymerizing using a zero-valent nickel complex, 5) Method of polymerizing by Suzuki coupling reaction, (6) Method of electrochemically oxidative polymerization, (7) Method of decomposing intermediate polymer having appropriate leaving group , And the like.

  In addition, when the metal complex-containing polymer of the present invention is used as a light emitting material, a color conversion material, or the like in a light emitting layer of an organic EL device or a polymer LED, the purity affects the light emitting characteristics. It is desirable to perform a purification process such as fractionation by chromatography.

Here, for example, the metal complex-containing polymer represented by the following structural formula (9) can be synthesized as follows. First, methoxyphenylpyridine (MeOPPy) is synthesized according to a conventional method. That is, as shown in the following reaction formula (1), 3-methoxyphenylmagnesium bromide is synthesized using Mg in dehydrated THF (tetrahydrofuran). Next, 2-bromopyridine, [1,2-bis (diphenylphosphino) ethane] dichloronickel (0) (Ni (dppe) Cl ₂ ) dissolved in dehydrated THF was added to the previously obtained 3- Methoxyphenylmagnesium bromide is added and reacted at room temperature to give colorless and transparent 3-methoxyphenylpyridine (MeOPPy). Identification can be performed by C, H, N elemental analysis, NMR, and IR.

次いで、このＭｅＯＰＰｙとトリス（アセチルアセトナト）イリジウム(ＩＩＩ)（Ｉｒ（ａｃａｃ）_３）を下記反応式（２）で示すように、高温で反応させ、トリス（３−メトキシフェニルピリジン）イリジウム(ＩＩＩ)（Ｉｒ（ＭｅＯＰＰｙ）_３）を合成した。即ち、ＭｅＯＰＰｙとＩｒ（ａｃａｃ）_３をグリセロール中で反応させ、カラムで精製することにより、蛍光性黄色粉末としてＩｒ（ＭｅＯＰＰｙ）_３を得る。同定はＣ、Ｈ、Ｎ及びＩｒ元素分析、ＩＲで行うことができる。これらの操作を８回繰り返すことにより、Ｉｒ（ＭｅＯＰＰｙ）_３を得ることができる。

Next, this MeOPPy and tris (acetylacetonato) iridium (III) (Ir (acac) ₃ ) are reacted at a high temperature as shown in the following reaction formula (2) to obtain tris (3-methoxyphenylpyridine) iridium (III ) (Ir (MeOPPy) ₃ ) was synthesized. That is, MeOPPy and Ir (acac) ₃ are reacted in glycerol and purified by a column to obtain Ir (MeOPPy) ₃ as a fluorescent yellow powder. Identification can be performed by C, H, N and Ir elemental analysis and IR. Ir (MeOPPy) ₃ can be obtained by repeating these operations eight times.

This Ir (MeOPPy) ₃ is hydrolyzed to form an OH group in an aqueous hydrochloric acid solution as shown in the following reaction formula (3) according to a conventional method, and tris (3-hydroxyphenylpyridine) iridium (III ) (Ir (HOPPy) ₃ ).

The resulting tris (3-hydroxyphenylpyridine) iridium (III) (Ir (HOPPy) ₃ ) is reacted with HCl in the presence of water to obtain tris (phenylpyridine) iridium (III) (Ir (PPy) ₃ ) Can be obtained. Next, a metal complex-containing polymer represented by the following structural formula (9) is synthesized by a polymerization reaction using the tris (phenylpyridine) iridium (III) (Ir (PPy) ₃ ) and benzene as monomer units. can do.

Since the metal complex-containing polymer of the present invention is a polymer material, when forming a thin film or the like using the metal complex-containing polymer, the ink-jet method or the like can be easily used regardless of complicated and expensive methods such as vapor deposition. A low-cost method can be adopted, and in this case, high-definition painting can be performed, so that high-definition pixels and the like can be easily formed using the metal complex-containing polymer. Suitable for a display or the like. Further, in the metal complex-containing polymer, regions (dots or blocks) due to the metal complex unit exhibiting phosphorescence are present at regular intervals through the π-electron conjugated cleavage unit. When a thin film or the like is formed using a metal complex-containing polymer, the problem of “concentration quenching” that occurs when the metal complex units can be uniformly dispersed in the thin film and the metal complex units are close to each other. Can be effectively avoided. The “concentration quenching” is noticeable when a metal complex is used as a monomer.
The metal complex-containing polymer of the present invention can emit phosphorescence, and can be easily formed into a film by an ink jet method or the like, and can be suitably used as a light emitting material, a color conversion material, etc. It can be suitably used as a flat fluorescent lamp, planar light source, lighting device, segment display device, dot matrix display device, backlight of liquid crystal display device, organic EL element, polymer LED, solar cell, etc. It can be particularly suitably used for the organic EL device and the organic EL display of the invention.

(Organic EL device)
The organic EL device of the present invention has an organic thin film layer between a positive electrode and a negative electrode, and the organic thin film layer has the metal complex-containing polymer of the present invention, that is, a metal complex unit having a π-electron conjugated portion. And a metal complex-containing polymer comprising, as a repeating unit, a π-electron conjugated cleavage unit capable of cleaving π-electron conjugation in the metal complex unit, and other layers or members appropriately selected according to the purpose You may have. The organic thin film layer includes, for example, a light emitting layer, a light emitting layer / hole transport layer, a light emitting layer / electron transport layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like.

In the organic EL device of the present invention, the metal complex-containing polymer of the present invention is contained in the organic thin film layer, but is contained in the light emitting layer, the light emitting layer / hole transport layer, the light emitting layer / electron transport layer, and the like. It is preferable that it is contained alone in the light emitting layer. In this case, it is advantageous in that the light emitting layer can be easily formed by a coating method such as an ink jet method.
In addition, formation of the said light emitting layer by the inkjet method can be performed by, for example, drying suitably after ejecting the inkjet ink containing the said metal complex containing polymer of this invention using a nozzle head. At this time, when the light emitting layer to be formed is separately applied to at least a red light emitting layer, a green light emitting layer, and a blue light emitting layer, for example, the red light emitting layer, the green light emitting layer, and the blue light emitting layer are patterned in a single pixel. It can be made. Suitable examples of the pattern include a lattice shape and a checkered shape.

-Positive electrode-
The positive electrode is not particularly limited and may be appropriately selected depending on the purpose. However, in the organic thin film layer, specifically, when the organic thin film layer has only the light emitting layer, the light emitting layer In the case where the organic thin film layer further has the hole transport layer, the hole transport layer, and in the case where the organic thin film layer further has the hole injection layer, the hole injection layer has a hole ( Those capable of supplying a carrier are preferred.

  The material for the positive electrode is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Among these, A material having a work function of 4 eV or more is preferable.

  Specific examples of the material of the positive electrode include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and conductivity with these metals. Examples thereof include mixtures or laminates with metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene and polypyrrole, and laminates of these with ITO. These may be used individually by 1 type and may use 2 or more types together. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  There is no restriction | limiting in particular as thickness of the said positive electrode, Although it can select suitably with materials etc., 30-500 nm is preferable and 50-200 nm is more preferable.

The positive electrode is usually formed on a substrate such as soda lime glass or non-alkali glass, or a transparent resin.
When the glass is used as the substrate, the soda-lime glass provided with a barrier coating such as the alkali-free glass or silica is preferable from the viewpoint of reducing the eluted ions from the glass.

  The thickness of the substrate is not particularly limited as long as the thickness is sufficient to maintain mechanical strength. However, when glass is used as the substrate, it is usually 0.2 mm or more and 0.7 mm or more. preferable.

  The positive electrode may be formed by, for example, vapor deposition, wet film formation, electron beam method, sputtering method, reactive sputtering method, MBE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high frequency excitation). It is preferably formed by the above-described methods such as ion plating method, molecular lamination method, LB method, printing method, transfer method, and chemical reaction method (sol-gel method, etc.). be able to.

  The positive electrode can be subjected to washing and other treatments to reduce the driving voltage of the organic EL element and increase the light emission efficiency. As said other process, when the raw material of the said positive electrode is ITO, UV-ozone process, a plasma process, etc. are mentioned suitably, for example.

-Negative electrode-
The negative electrode is not particularly limited and may be appropriately selected depending on the purpose. However, in the organic thin film layer, specifically, when the organic thin film layer has only the light emitting layer, the light emitting layer When the organic thin film layer further has the electron transport layer, electrons are supplied to the electron transport layer, and when the organic thin film layer has an electron injection layer between the organic thin film layer and the negative electrode, electrons are supplied to the electron injection layer. What can do is preferable.

  The material of the negative electrode is not particularly limited and can be appropriately selected depending on the adhesion, ionization potential, stability, and the like of the electron transport layer, the light-emitting layer, and other layers or molecules adjacent to the negative electrode. Examples thereof include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof.

Specific examples of the material of the negative electrode include alkali metals (for example, Li, Na, K, Cs, etc.), alkaline earth metals (for example, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys or the like. Mixed metals, lithium-aluminum alloys or mixed metals thereof, magnesium-silver alloys or mixed metals thereof, rare earth metals such as indium and ytterbium, and alloys thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a material having a work function of 4 eV or less is preferable, and aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, and the like are more preferable.

  There is no restriction | limiting in particular as thickness of the said negative electrode, Although it can select suitably according to the material of this negative electrode, etc., 1-10000 nm is preferable and 20-200 nm is more preferable.

The negative electrode may be, for example, a vapor deposition method, a wet film formation method, an electron beam method, a sputtering method, a reactive sputtering method, an MBE (molecular beam epitaxy) method, a cluster ion beam method, an ion plating method, a plasma polymerization method (high frequency excitation). (Ion plating method), molecular lamination method, LB method, printing method, transfer method, etc.
When two or more types are used together as the negative electrode material, the two or more types of materials may be vapor-deposited at the same time to form an alloy electrode or the like, or an alloy prepared in advance may be vapor-deposited to form an alloy electrode or the like May be.

  The resistance value of the positive electrode and the negative electrode is preferably low, and is preferably several hundred Ω / □ or less.

-Hole injection layer-
The hole injection layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the hole injection layer preferably has a function of injecting holes from the positive electrode when an electric field is applied. .
The material for the hole injection layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, PEDOT: PSS (poly-3,4-ethylenedioxythiophene doped with poly (styrene sulfonate) or Examples include starburstamine (4,4 ′, 4 ″ -tris [3-methylphenyl (phenyl) amino] triphenylamine: m-MTDATA) represented by the formula, copper phthalocyanine, polyaniline, and the like.

There is no restriction | limiting in particular as thickness of the said positive hole injection layer, Although it can select suitably according to the objective, For example, about 50-150 nm is preferable and 70-100 nm is more preferable.
The hole injection layer is formed by, for example, a vapor deposition method, a wet film forming method, an electron beam method, a sputtering method, a reactive sputtering method, an MBE (molecular beam epitaxy) method, a cluster ion beam method, an ion plating method, a plasma polymerization method. It can be suitably formed by the above-described methods such as (high frequency excitation ion plating method), molecular lamination method, LB method, printing method, transfer method and the like.

-Other layers or members-
The organic EL device of the present invention may have other layers or members appropriately selected according to the purpose. Examples of the other layers include a protective layer, a color conversion layer, and a sealing material. It is mentioned in.

The protective layer is not particularly limited and may be appropriately selected depending on the purpose. For example, molecules or substances that promote deterioration of the organic EL element such as moisture or oxygen may enter the organic EL element. Those that can be suppressed are preferred.
Examples of the material of the protective layer include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, and BaO. , Fe ₂ O ₃ , Y ₂ O ₃ , TiO _{2 and} other metal oxides, SiN, SiN _x O _{y and} other nitrides, MgF ₂ , LiF, AlF ₃ , CaF _{2 and} other metal fluorides, polyethylene, polypropylene, Contains polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer Copolymer obtained by copolymerizing the monomer mixture, into the copolymer backbone Fluorine-containing copolymer having a Jo structure, 1% by weight of the water absorbing material water absorption, such as moisture-proof material water absorption rate of 0.1% or less and the like.

  The protective layer may be, for example, a vapor deposition method, a wet film forming method, a sputtering method, a reactive sputtering method, an MBE (molecular beam epitaxy) method, a cluster ion beam method, an ion plating method, a plasma polymerization method (high frequency excitation ion plating). Method), printing method, transfer method, and the like.

There is no restriction | limiting in particular as said color conversion layer, Although it can select suitably according to the objective, It is preferable to contain the said metal complex containing polymer of this invention.
By the way, in general, an organic molecule excited by light of a certain wavelength emits light from an excited state and transitions to the ground state before the transition of the excitation energy within the molecule or by interaction with other molecules. It is known that the wavelengths of excitation light and emission do not match because a part of the energy is lost non-radiatively in the form of thermal energy. The energy difference between excitation light and light emission is called Stokes shift. The color conversion material that has been used for the color conversion layer so far has been a fluorescent light-emitting material in which only light emission from a singlet is observed due to the wide range of material selection. Light emission is observed on the long-wavelength side of the strongest absorption band in the visible range with a small shift (<100 nm) .For example, blue light emission is efficiently absorbed and converted to red color. Can not do it. On the other hand, since the metal complex desired effective molecule of the present invention is a phosphorescent material, when it is excited by light of a certain wavelength and a singlet excited state is generated, it rapidly enters a triplet excited state that is a lower energy state. The Stokes shift is larger than that of fluorescent materials because the phosphor can emit phosphorescence. (In the case of ordinary organic materials, the triplet state should be about 0.1 to 2 eV lower than the energy of the singlet excited state. It has been known). For example, in applications that convert blue light emission as an excitation source into red, the color conversion layer using a phosphorescent material has a higher absorption rate of blue light than when a fluorescent material is used. The color conversion rate per one becomes high. In other words, since the color conversion layer using the fluorescent light emitting material does not absorb blue light, more blue light is transmitted through the color conversion layer. To compensate for this, increasing the thickness of the color conversion layer without changing the dispersion concentration increases the amount of blue light absorption and can increase the intensity of red light. However, leaching from the color conversion layer occurs when an organic EL device is manufactured. For example, the material constituting the organic EL element is deteriorated by a residue of moisture or an organic solvent and a non-light-emitting region is generated. Therefore, it is preferable to make the color conversion layer as thin as possible.

The position where the color conversion layer is provided is not particularly limited and may be appropriately selected depending on the purpose. For example, when performing full color display, it is preferably provided on the pixel.
The color conversion layer is preferably one that can convert light in the wavelength region of ultraviolet light to blue light into red light.
The method for forming the color conversion layer is not particularly limited and may be appropriately selected depending on the purpose. However, when the metal complex-containing polymer of the present invention is used as a color conversion material, for example, A coating method, for example, an ink jet method is preferable.
A known color filter or the like may be used as the color conversion layer.

The structure of the organic EL device of the present invention is not particularly limited and may be appropriately selected depending on the purpose. Examples of the layer structure thereof include the following layer structures (1) to (13): , (1) positive electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / negative electrode, (2) positive electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / Negative electrode, (3) Positive electrode / Hole transport layer / Light emitting layer / Electron transport layer / Electron injection layer / Negative electrode, (4) Positive electrode / Hole transport layer / Light emitting layer / Electron transport layer / Negative electrode, (5) Positive electrode / Hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / negative electrode, (6) positive electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / negative electrode, (7) Positive electrode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / negative electrode, (8) positive electrode / hole transport layer / light emitting layer / electron transport layer / negative electrode, (9) positive electrode / hole injection layer / positive Hole transport layer / light emitting layer / electron transport layer / electric Child injection layer / negative electrode, (10) positive electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / negative electrode, (11) positive electrode / hole transport layer / light emitting layer / electron transport layer / electron injection layer Preferred examples include: / negative electrode, (12) positive electrode / hole transport layer / light emitting layer / electron transport layer / negative electrode, and (13) positive electrode / hole transport layer / light emitting layer / electron transport layer / negative electrode.
When the organic EL element has the hole blocking layer, in (1) to (13), the layer in which the hole blocking layer is disposed between the light emitting layer and the electron transport layer. A structure is mentioned suitably.

The organic EL element may be a single color light emitting element, a multicolor emitting element, or a full color type element.
For example, as described in “Monthly Display”, September 2000 issue, pages 33 to 37, the organic EL element is a full color type, as described in the three primary colors (blue (B), green). (G), red light (R)), a three-color light emitting method in which organic EL elements that emit light corresponding to red (R) are arranged on a substrate, and white light emitted by a white light emitting organic EL element into three primary colors through a color filter. And a color conversion method in which blue light emitted by an organic EL element for blue light emission is converted into red (R) and green (G) through a fluorescent dye layer, etc. are known. Can be particularly preferably employed.

  There is no restriction | limiting in particular as a drive aspect of the said organic EL element, Although it can select suitably according to the objective, For example, "Nikkei Electronics", No. 765, March 13, 2000 issue, pages 55-62 Examples of driving modes such as a passive matrix panel and an active matrix panel as described in (1) are preferable.

There is no restriction | limiting in particular as the luminescent color of the organic EL element of this invention, It can be set as a desired luminescent color by selecting suitably the material of the said light emitting layer according to the objective. In addition, it is preferable that light emission of this organic EL element is phosphorescence emission from viewpoints, such as luminous efficiency.
From the viewpoint of the applied voltage in the organic EL device of the present invention, it is desired to emit light at a voltage of 10 V or less, preferably 7 V or less, more preferably 5 V or less.
The light emission luminance of the organic EL device of the present invention is preferably 100 cd / m ² or more, more preferably 500 cd / m ² or more at an applied voltage of 10 V, more preferably 500 cd / m ² from a practical viewpoint. ^It is particularly preferable that the number is ² or more.

  The organic EL element of the present invention includes, for example, a lighting device, a computer, a vehicle-mounted display, a field display, a household device, a business device, a household appliance, a traffic display, a clock display, a calendar display, a lumi Although it can be suitably used in various fields including nescent screens and acoustic devices, it can be particularly suitably used for the organic EL display of the present invention described below.

(Organic EL display)
The organic EL display of the present invention is not particularly limited except that at least the organic EL element of the present invention is used, and a known configuration can be appropriately employed.

The organic EL display may be monochromatic, multicolor, or full color.
As a method for making the organic EL display of a full color type, as described in, for example, “Monthly Display”, September 2000, pages 33 to 37, the three primary colors (blue (B), green (G), red light (R)), a three-color light emitting method in which organic EL elements that emit light corresponding to red (R) are arranged on a substrate, and white light emitted by a white light emitting organic EL element into three primary colors through a color filter. And a color conversion method in which blue light emission by an organic EL element for blue light emission is converted into red (R) and green (G) through a fluorescent dye layer are known.

  When a full-color type organic EL display is manufactured by the three-color light emission method, an organic EL element for blue light emission, an organic EL element for red light emission, and an organic EL element for green light emission are required. The organic EL element of each color is not particularly limited except that the metal complex-containing polymer of the present invention is used as the light emitting material of the light emitting layer, and can be appropriately selected from known ones. Preferred examples include (positive electrode) / light emitting layer / Al-Li (negative electrode).

  There is no restriction | limiting in particular as an aspect of the said organic EL display, Although it can select suitably according to the objective, For example, "Nikkei Electronics", No. 765, March 13, 2000 issue, pages 55-62 Preferred examples include a passive matrix panel and an active matrix panel as described.

  For example, as shown in FIG. 1, the passive matrix panel has strip-like positive electrodes 14 (for example, ITO electrodes) arranged in parallel with each other on a glass substrate 12, and in parallel with each other in order on the positive electrode 14. And an organic thin film layer 24 for blue light emission, an organic thin film layer 26 for green light emission, and an organic thin film layer 28 for red light emission disposed in a direction substantially orthogonal to the positive electrode 14, and an organic thin film layer for blue light emission. 24. On the organic thin film layer 26 for green light emission and the organic thin film layer 28 for red light emission, the negative electrode 22 having the same shape as these is provided.

  In the passive matrix panel, for example, as shown in FIG. 2, a positive line 30 made up of a plurality of positive electrodes 14 and a negative line 32 made up of a plurality of negative electrodes 22 intersect each other in a substantially perpendicular direction to form a circuit. ing. The organic thin film layers 24, 26 and 28 for blue light emission, green light emission and red light emission located at each intersection function as pixels, and a plurality of organic EL elements 34 exist corresponding to each pixel. In the passive matrix panel, when a current is applied to one of the positive electrodes 14 in the positive electrode line 30 and one of the negative electrodes 22 in the negative electrode line 32 by the constant current source 36, the organic thin film layer located at the intersection is applied to the current. A current is applied, and the organic light emitting thin film layer at the position emits light. By controlling the light emission for each pixel, a full color image can be easily formed.

  In the active matrix panel, for example, as shown in FIG. 3, scanning lines, data lines, and current supply lines are formed on a glass substrate 12 in a grid pattern. The TFT circuit 40 is connected and arranged on each grid, and can be driven by the TFT circuit 40, and has a positive electrode 14 (for example, an ITO electrode) arranged in each grid. The organic thin film layer 24 for blue light emission, the organic thin film layer 26 for green light emission, and the organic thin film layer 28 for red light emission are arranged in parallel in order, and the organic thin film layer 24 for blue light emission, green light emission On the organic thin film layer 26 for red light and the organic thin film layer 28 for red light emission, the negative electrode 22 is disposed so as to cover them all. The organic thin film layer 24 for blue light emission, the organic thin film layer 26 for green light emission, and the organic thin film layer 28 for red light emission have the hole transport layer 16, the light emitting layer 18, and the electron transport layer 20, respectively.

  In the active matrix panel, for example, as shown in FIG. 4, a plurality of scanning lines 46, a plurality of parallel data lines 42 and a current supply line 44 are orthogonal to each other. A switching TFT 48 and a driving TFT 50 are connected to each grid to form a circuit. When a current is applied from the driving circuit 38, the switching TFT 48 and the driving TFT 50 can be driven for each grid. In each grid, the organic thin film elements 24, 26, and 28 for blue light emission, green light emission, and red light emission function as pixels, and in the active matrix panel, the scanning lines 46 arranged in the horizontal direction are arranged. When a current is applied from one drive circuit 38 to one and the current supply line 44 arranged in the vertical direction, at that time, the switching TFT 48 located at the intersection is driven, and accordingly the driving TFT 50 is driven, The organic EL element 52 at the position emits light. By controlling the light emission for each pixel, a full color image can be easily formed.

In addition, when using the said metal complex containing polymer of this invention as a color conversion material, the said color conversion method can be employ | adopted especially suitably.
As a specific example of the organic EL display of the present invention by the color conversion method, for example, as shown in FIG. 5, this organic EL display is an organic EL for blue light emission on an electrode 25 arranged corresponding to a pixel. The thin film layer 30 is provided on one surface, and further has the transparent electrode 20 thereon. On the transparent electrode 20, a laminate of a red color conversion layer 60 and a red color filter 65, a green color conversion layer 70, and a green color filter 80 are disposed via a protective layer (planarization layer) 15. The laminate is arranged. And the glass substrate 10 is provided on these.
When a voltage is applied between the electrode 25 and the transparent electrode 21 in this organic EL display, the organic thin film layer 55 for blue light emission emits blue light. A part of the blue light is transmitted through the transparent electrode 20, passes through the protective layer 15 and the glass substrate 10 as it is, and is emitted to the outside. On the other hand, in the portion where the color conversion layer 60 for red and the color conversion layer 70 for green exist, the blue emission light is converted into red and green in these color conversion layers, respectively, and further the red color filter 65. By passing through the green color filter 80, red light emission light and green light emission light are transmitted through the glass substrate 10, respectively. As a result, full color display is possible in the organic EL display.
When the color conversion layers 60 and 70 are formed of the metal complex-containing polymer (phosphorescent material) of the present invention, the metal complex-containing polymer can be made into a single thin film and manufactured. In addition, the color conversion efficiency is extremely excellent.

  The organic EL display of the present invention includes, for example, a computer, an on-vehicle display, an outdoor display, a household device, a business device, a household appliance, a traffic display, a clock display, a calendar display, and a luminescent screen. It can be suitably used in various fields including acoustic equipment.

  Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.

-Synthesis of polymer containing metal complex-
Methoxyphenylpyridine (MeOPPy) was synthesized according to a conventional method. That is, as shown in the following reaction formula (1), 3-methoxyphenylmagnesium bromide was synthesized using 8.98 g (48 mmol) of 3-bromoanisole in 60 ml of dehydrated THF (tetrahydrofuran). Next, a solution in which 6.32 g (40 mmol) of 2-bromopyridine and 0.74 g of [1,2-bis (diphenylphosphino) ethane] dichloronickel (0) (Ni (dppe) Cl ₂ ) are dissolved in 40 ml of dehydrated THF The 3-methoxyphenylmagnesium bromide obtained above was added and reacted at room temperature for 12 hours to obtain 6.03 g (32.4 mmol) of colorless and transparent 3-methoxyphenylpyridine (MeOPPy). Identification was performed by C, H, N elemental analysis, NMR, and IR.

Next, this MeOPPy and tris (acetylacetonato) iridium (III) (Ir (acac) ₃ ) are reacted at a high temperature as shown in the following reaction formula (2) to obtain tris (3-methoxyphenylpyridine) iridium (III ) (Ir (MeOPPy) ₃ ) was synthesized.
That is, MeOPPy 5.00 g (27.0 mmol) and Ir (acac) ₃
2.0 g (4.1 mmol) was reacted in 200 ml of glycerol for 9 hours at 250 ° C. and purified by a column to obtain 0.400 g (0.54 mmol) of Ir (MeOPPy) ₃ as a fluorescent yellow powder. . Identification was performed by C, H, N and Ir elemental analysis and IR.
By repeating these operations 8 times, a total of 3.20 g (4.32 mmol) of Ir (MeOPPy) ₃ was obtained.

This Ir (MeOPPy) ₃ is hydrolyzed to form an OH group in an aqueous hydrochloric acid solution as shown in the following reaction formula (3) according to a conventional method, and tris (3-hydroxyphenylpyridine) iridium (III ) (Ir (HOPPy) ₃ ) was obtained.

The resulting tris (3-hydroxyphenylpyridine) iridium (III) (Ir (HOPPy) ₃ ) is reacted with HCl in the presence of water to obtain tris (phenylpyridine) iridium (III) (Ir (PPy) ₃ )
Next, the tris (phenylpyridine) iridium (III) (Ir (PPy) ₃ )
Using 10 g and 90 g of benzene as monomer units, a metal complex-containing polymer represented by the following structural formula (9) (number average molecular weight = 7,000) was synthesized by a polymerization reaction.

-Production of organic EL elements-
ITO (indium tin oxide) as a positive electrode (lower electrode) was formed on a glass substrate by sputtering so as to have a thickness of 2000 mm (200 nm). Next, ITO was processed into a stripe shape by photolithography and wet etching.
On the ITO, a solution prepared by dissolving the metal complex-containing polymer (number average molecular weight = 7,000) represented by the following structural formula (9) synthesized in Example 1 in chloroform was spin-coated to have a thickness of 1500 mm (150 nm). ) To form a light emitting layer.

Thereafter, an MgAg layer having a mass ratio of Mg and Ag (Mg: Ag = 10: 1) as a negative electrode (upper electrode) is formed by co-evaporation using a metal mask so that the thickness becomes 3000 mm (300 nm). Formed on top.
When an electric current was applied to the organic EL device of Example 2 manufactured as described above so that the MgAg side was a negative electrode and the ITO side was a positive electrode, red light emission was observed from the ITO side.

Comparative Example 1

-Production of organic EL elements-
In Example 1, the organic EL element of Comparative Example 1 was produced in the same manner as in Example 1 except that the polymer represented by the following structural formula (number average molecular weight = 21,000) as the light emitting layer was used. .

  With respect to the organic EL element of Comparative Example 1 manufactured as described above, when the MgAg side was a negative electrode and the ITO side was a positive electrode, and current was passed, red light emission was observed from the ITO side.

Next, when the luminous efficiency of the obtained organic EL elements of Example 1 and Comparative Example 1 was measured using a luminance meter (manufactured by Topcon), the luminous efficiency of the organic EL element of Example 1 was 15 lm / W. Met. On the other hand, the luminous efficiency of the organic EL element of Comparative Example 1 is 2
lm / W, about 1 / 7.5 of Example 1.
As a result, a metal complex-containing polymer containing a repeating unit composed of a metal complex unit having a π-electron conjugated moiety and a π-electron conjugated cleavage unit capable of cleaving π-electron conjugation in the metal complex unit is used as the light-emitting material of the light-emitting layer As a result, it was found that the π-electron conjugation in the metal complex unit is cleaved by the π-electron conjugated cleavage unit, the quantum efficiency of phosphorescence emission can be increased, and the light emission efficiency is greatly improved.

前記構造式（１）中、Ａは、π電子共役部分を有する金属錯体単位を表す。Ｂは、前記Ａにおけるπ電子共役を切断可能なπ電子共役切断単位を表す。ｘは、前記Ａの金属錯体含有高分子全体におけるモル分率（モル％）を表し、ｙは、前記Ｂの金属錯体含有高分子全体におけるモル分率（モル％）を表し、ｘ＋ｙ＝１００である。ｎは、重合度を表す。
（付記５） 構造式（１）におけるＡが、下記構造式（２）で表される付記４に記載の有機ＥＬ素子。

前記構造式（２）中、Ｍは、中心金属を表す。Ｌ^１及びＬ^２は、Ｍと結合可能な配位子を表し、Ｌ^１は、構造式（１）におけるＢと結合する２価の配位子を表す。ｐは、０〜５の整数を表す。ｐが１以上の場合、Ｌ^１及びＬ^２は、互いに同一であってもよいし、異なっていてもよい。
（付記６） Ｌ^１及びＬ^２が、中心金属に単座又は２座以上で配位結合可能な原子を一部に有し、該原子が炭素原子、窒素原子、酸素原子、硫黄原子、セレン原子、テルル原子、ポロニウム原子及びリン原子から選択される付記５に記載の有機ＥＬ素子。
（付記７） Ｌ^１及びＬ^２が、カルボニル配位子、アルケン配位子、アルキン配位子、アミン配位子、イミン配位子、ニトリル配位子、イソニトリル配位子、ホスフィン配位子、ホスフィンオキシド配位子、ホスファイト配位子、エーテル配位子、スルホン配位子、スルホキシド配位子、スルフィド配位子、並びに、複素環及びベンゼン環のいずれかが結合して形成された配位子から選択される付記５から６のいずれかに記載の有機ＥＬ素子。
（付記８） Ｌ^１及びＬ^２が、下記構造式のいずれかで表される付記５から７のいずれかに記載の有機ＥＬ素子。

（付記９） 構造式（２）におけるＭが、レニウム（Ｒｅ）、イリジウム（Ｉｒ）、オスミウム（Ｏｓ）、スカンジウム（Ｓｃ）、イットリウム（Ｙ）、白金（Ｐｔ）、金（Ａｕ）、ユーロピウム（Ｅｕ）、テルビウム（Ｔｂ）、ツリウム（Ｔｍ）、ディスプロシウム（Ｄｙ）、サマリウム（Ｓｍ）、プラセオジウム（Ｐｒ）及びガドリニウム（Ｇｄ）から選択される付記５から８のいずれかに記載の有機ＥＬ素子。
（付記１０） π電子共役切断単位が、金属錯体単位とメタ位で結合可能なアリーレン基と、酸素原子、ケイ素原子及びホウ素原子から選択されるいずれかを有しかつ金属錯体単位と結合可能なアリーレン基と、酸素原子、ケイ素原子及びホウ素原子から選択されるいずれかを有しかつ金属錯体単位と結合可能なアルキレン基と、のいずれかである付記１から９のいずれかに記載の有機ＥＬ素子。
（付記１１） π電子共役切断単位が、下記構造式（３）から（７）のいずれかで表される付記１から１０のいずれかに記載の有機ＥＬ素子。

前記構造式（３）中、ｑは、１以上の整数を表す。

前記構造式（４）中、Ａｒは、アリーレン基を表す。Ｒは、アルケン基を表す。ｌ及びｍは、０〜５の整数を表す。 The preferred embodiments of the present invention are as follows.
(Additional remark 1) It has an organic thin film layer between a positive electrode and a negative electrode, and this organic thin film layer can cut | disconnect the pi electron conjugation in the metal complex unit which has a pi electron conjugated part, and the π electron conjugation in this metal complex unit An organic EL device comprising a metal complex-containing polymer having a conjugated cleavage unit as a repeating unit.
(Additional remark 2) The organic electroluminescent element of Additional remark 1 in which an organic thin film layer contains a metal complex containing polymer as a luminescent material at least.
(Supplementary note 3) The organic EL according to any one of Supplementary notes 1 to 2, wherein the metal complex-containing polymer has a repeating unit composed of a metal complex unit and a π-electron conjugate cleavage unit bonded to the metal complex unit. element.
(Appendix 4) The organic EL device according to any one of appendices 1 to 3, wherein the metal complex-containing polymer has a repeating unit represented by the following structural formula (1).

In the structural formula (1), A represents a metal complex unit having a π electron conjugated portion. B represents a π electron conjugate cutting unit capable of cutting the π electron conjugate in A. x represents a mole fraction (mol%) in the entire metal complex-containing polymer of A, y represents a mole fraction (mol%) in the entire metal complex-containing polymer of B, and x + y = 100 is there. n represents the degree of polymerization.
(Supplementary note 5) The organic EL element according to supplementary note 4, wherein A in the structural formula (1) is represented by the following structural formula (2).

In the structural formula (2), M represents a central metal. L ¹ and L ² represent a ligand that can bind to M, and L ¹ represents a divalent ligand that binds to B in the structural formula (1). p represents an integer of 0 to 5. When p is 1 or more, L ¹ and L ² may be the same as or different from each other.
(Supplementary Note 6) L ¹ and L ^2, in a portion of the coordinate bond an atom to the central metal in the monodentate or bidentate or higher, the atom carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom Item 5. The organic EL device according to appendix 5, selected from a tellurium atom, a polonium atom, and a phosphorus atom.
(Appendix 7) L ¹ and L ² are carbonyl ligand, alkene ligand, alkyne ligand, amine ligand, imine ligand, nitrile ligand, isonitrile ligand, phosphine ligand. , Phosphine oxide ligand, phosphite ligand, ether ligand, sulfone ligand, sulfoxide ligand, sulfide ligand, and any of heterocyclic ring and benzene ring The organic EL device according to any one of supplementary notes 5 to 6, which is selected from ligands.
(Supplementary note 8) The organic EL element according to any one of supplementary notes 5 to 7, wherein L ¹ and L ² are represented by any of the following structural formulas.

(Supplementary Note 9) M in the structural formula (2) is rhenium (Re), iridium (Ir), osmium (Os), scandium (Sc), yttrium (Y), platinum (Pt), gold (Au), europium ( The organic EL according to any one of supplementary notes 5 to 8, selected from Eu), terbium (Tb), thulium (Tm), dysprosium (Dy), samarium (Sm), praseodymium (Pr) and gadolinium (Gd) element.
(Supplementary Note 10) The π-electron conjugated cleavage unit has an arylene group that can be bonded to the metal complex unit at the meta position, and is selected from an oxygen atom, a silicon atom, and a boron atom, and can be bonded to the metal complex unit The organic EL according to any one of appendices 1 to 9, which is any one of an arylene group and an alkylene group having any one selected from an oxygen atom, a silicon atom, and a boron atom and capable of binding to a metal complex unit. element.
(Supplementary note 11) The organic EL device according to any one of Supplementary notes 1 to 10, wherein the π-electron conjugate cleavage unit is represented by any one of the following structural formulas (3) to (7).

In the structural formula (3), q represents an integer of 1 or more.

In the structural formula (4), Ar represents an arylene group. R represents an alkene group. l and m represent the integer of 0-5.

前記構造式（５）から（７）において、Ａｒは、アリーレン基を表す。ｌ及びｍは、０〜５の整数を表す。
（付記１２） 金属錯体含有高分子が、下記構造式（８）で表される繰り返し単位を有する付記１から１１のいずれかに記載の有機ＥＬ素子。

前記構造式（８）中、ｘ及びｙは、モル分率（モル％）を表し、ｘ＋ｙ＝１００である。ｎは、重合度を表す。
（付記１３） 金属錯体含有高分子の数平均分子量が５,０００以上である付記１から１２のいずれかに記載の有機ＥＬ素子。
（付記１４） リン光発光を示す付記１から１３のいずれかに記載の有機ＥＬ素子。
（付記１５） 有機薄膜層が発光層を有してなり、該発光層が、少なくとも赤色発光層、緑色発光層及び青色発光層に塗り分けられた付記１から１４のいずれかに記載の有機ＥＬ素子。
（付記１６） 発光層が、塗り分けにより、赤色発光層、緑色発光層及び青色発光層が単一画素内でパターン化された付記１から１５のいずれかに記載の有機ＥＬ素子。
（付記１７） パターン化が格子状及び市松状のいずれかにされた付記１６に記載の有機ＥＬ素子。
（付記１８） π電子共役部分を有する金属錯体単位と、該金属錯体単位におけるπ電子共役を切断可能なπ電子共役切断単位とを繰り返し単位として有してなることを特徴とする金属錯体含有高分子。
（付記１９） 発光材料として用いられる付記１８に記載の金属錯体含有高分子。
（付記２０） 金属錯体単位と、該金属錯体単位に結合したπ電子共役切断単位とからなる繰り返し単位を有してなる付記１８から１９のいずれかに記載の金属錯体含有高分子。
（付記２１） 下記構造式（１）で表される繰り返し単位を有してなる付記１８から２０のいずれかに記載の金属錯体含有高分子。

前記構造式（１）中、Ａは、π電子共役部分を有する金属錯体単位を表す。Ｂは、前記Ａにおけるπ電子共役を切断可能なπ電子共役切断単位を表す。ｘは、前記Ａの金属錯体含有高分子全体におけるモル分率（モル％）を表し、ｙは、前記Ｂの金属錯体含有高分子全体におけるモル分率（モル％）を表し、ｘ＋ｙ＝１００である。ｎは、重合度を表す。
（付記２２） 構造式（１）におけるＡが、下記構造式（２）で表される付記２１に記載の金属錯体含有高分子。

前記構造式（２）中、Ｍは、中心金属を表す。Ｌ^１及びＬ^２は、Ｍと結合可能な配位子を表し、Ｌ^１は、構造式（１）におけるＢと結合する２価の配位子を表す。ｐは、０〜５の整数を表す。ｐが１以上の場合、Ｌ^１及びＬ^２は、互いに同一であってもよいし、異なっていてもよい。
（付記２３） Ｌ^１及びＬ^２が、中心金属に単座又は２座以上で配位結合可能な原子を一部に有し、該原子が炭素原子、窒素原子、酸素原子、硫黄原子、セレン原子、テルル原子、ポロニウム原子及びリン原子から選択される付記２２に記載の金属錯体含有高分子。
（付記２４） Ｌ^１及びＬ^２が、カルボニル配位子、アルケン配位子、アルキン配位子、アミン配位子、イミン配位子、ニトリル配位子、イソニトリル配位子、ホスフィン配位子、ホスフィンオキシド配位子、ホスファイト配位子、エーテル配位子、スルホン配位子、スルホキシド配位子、スルフィド配位子、並びに、複素環及びベンゼン環のいずれかが結合して形成された配位子から選択される付記２２から２３のいずれかに記載の金属錯体含有高分子。
（付記２５） Ｌ^１及びＬ^２が、下記構造式のいずれかで表される付記２２から２４のいずれかに記載の金属錯体含有高分子。

（付記２６） 構造式（２）におけるＭが、レニウム（Ｒｅ）、イリジウム（Ｉｒ）、オスミウム（Ｏｓ）、スカンジウム（Ｓｃ）、イットリウム（Ｙ）、白金（Ｐｔ）、金（Ａｕ）、ユーロピウム（Ｅｕ）、テルビウム（Ｔｂ）、ツリウム（Ｔｍ）、ディスプロシウム（Ｄｙ）、サマリウム（Ｓｍ）、プラセオジウム（Ｐｒ）及びガドリニウム（Ｇｄ）から選択される付記２２から２５のいずれかに記載の金属錯体含有高分子。
（付記２７） π電子共役切断単位が、金属錯体単位とメタ位で結合可能なアリーレン基と、酸素原子、ケイ素原子及びホウ素原子から選択されるいずれかを有しかつ金属錯体単位と結合可能なアリーレン基と、酸素原子、ケイ素原子及びホウ素原子から選択されるいずれかを有しかつ金属錯体単位と結合可能なアルケン基と、のいずれかである付記１８から２６のいずれかに記載の金属錯体含有高分子。
（付記２８） π電子共役切断単位が、下記構造式（３）から（７）のいずれかで表される付記２７に記載の金属錯体含有高分子。

前記構造式（３）中、ｑは、１以上の整数を表す。

前記構造式（４）中、Ａｒは、アリーレン基を表す。Ｒは、アルケン基を表す。ｌ及びｍは、０〜５の整数を表す。

In the structural formulas (5) to (7), Ar represents an arylene group. l and m represent the integer of 0-5.
(Supplementary note 12) The organic EL device according to any one of Supplementary notes 1 to 11, wherein the metal complex-containing polymer has a repeating unit represented by the following structural formula (8).

In the structural formula (8), x and y represent a mole fraction (mol%), and x + y = 100. n represents the degree of polymerization.
(Supplementary note 13) The organic EL device according to any one of Supplementary notes 1 to 12, wherein the metal complex-containing polymer has a number average molecular weight of 5,000 or more.
(Supplementary note 14) The organic EL element according to any one of supplementary notes 1 to 13, which exhibits phosphorescence.
(Supplementary note 15) The organic EL according to any one of Supplementary notes 1 to 14, wherein the organic thin film layer has a light emitting layer, and the light emitting layer is separately applied to at least a red light emitting layer, a green light emitting layer, and a blue light emitting layer. element.
(Supplementary note 16) The organic EL element according to any one of supplementary notes 1 to 15, wherein the light-emitting layer is patterned so that a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer are patterned in a single pixel.
(Supplementary note 17) The organic EL element according to supplementary note 16, wherein the patterning is in a lattice shape or a checkered shape.
(Supplementary Note 18) A metal complex-containing high composition comprising a metal complex unit having a π-electron conjugated moiety and a π-electron conjugated cleavage unit capable of cleaving π-electron conjugation in the metal complex unit as a repeating unit. molecule.
(Additional remark 19) Metal complex containing polymer of Additional remark 18 used as a luminescent material.
(Supplementary note 20) The metal complex-containing polymer according to any one of supplementary notes 18 to 19, comprising a repeating unit comprising a metal complex unit and a π-electron conjugate cleavage unit bonded to the metal complex unit.
(Supplementary note 21) The metal complex-containing polymer according to any one of supplementary notes 18 to 20, comprising a repeating unit represented by the following structural formula (1).

In the structural formula (1), A represents a metal complex unit having a π electron conjugated portion. B represents a π electron conjugate cutting unit capable of cutting the π electron conjugate in A. x represents a mole fraction (mol%) in the entire metal complex-containing polymer of A, y represents a mole fraction (mol%) in the entire metal complex-containing polymer of B, and x + y = 100 is there. n represents the degree of polymerization.
(Supplementary note 22) The metal complex-containing polymer according to supplementary note 21, wherein A in the structural formula (1) is represented by the following structural formula (2).

In the structural formula (2), M represents a central metal. L ¹ and L ² represent a ligand that can bind to M, and L ¹ represents a divalent ligand that binds to B in the structural formula (1). p represents an integer of 0 to 5. When p is 1 or more, L ¹ and L ² may be the same as or different from each other.
(Supplementary Note 23) L ¹ and L ² partially have atoms that can be coordinated to a central metal in a monodentate or bidentate manner, and the atoms are carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms. 24. The metal complex-containing polymer according to supplement 22, wherein the polymer is selected from a tellurium atom, a polonium atom and a phosphorus atom.
(Supplementary Note 24) L ¹ and L ² are carbonyl ligand, alkene ligand, alkyne ligand, amine ligand, imine ligand, nitrile ligand, isonitrile ligand, phosphine ligand. , Phosphine oxide ligand, phosphite ligand, ether ligand, sulfone ligand, sulfoxide ligand, sulfide ligand, and any of heterocyclic ring and benzene ring 24. The metal complex-containing polymer according to any one of appendices 22 to 23, which is selected from ligands.
(Supplementary Note 25) The metal complex-containing polymer according to any one of Supplementary Notes 22 to 24, wherein L ¹ and L ² are represented by any of the following structural formulas.

(Supplementary Note 26) M in the structural formula (2) is rhenium (Re), iridium (Ir), osmium (Os), scandium (Sc), yttrium (Y), platinum (Pt), gold (Au), europium ( Eu), terbium (Tb), thulium (Tm), dysprosium (Dy), samarium (Sm), praseodymium (Pr) and gadolinium (Gd) Containing polymer.
(Supplementary Note 27) The π-electron conjugated cleavage unit has an arylene group that can be bonded to the metal complex unit at the meta position, and is selected from an oxygen atom, a silicon atom, and a boron atom, and can be bonded to the metal complex unit 27. The metal complex according to any one of appendices 18 to 26, wherein the metal complex is any one of an arylene group and an alkene group having any one selected from an oxygen atom, a silicon atom, and a boron atom and capable of binding to a metal complex unit. Containing polymer.
(Supplementary note 28) The metal complex-containing polymer according to supplementary note 27, wherein the π-electron conjugate cleavage unit is represented by any one of the following structural formulas (3) to (7).

In the structural formula (3), q represents an integer of 1 or more.

In the structural formula (4), Ar represents an arylene group. R represents an alkene group. l and m represent the integer of 0-5.

前記構造式（５）から（７）において、Ａｒは、アリーレン基を表す。ｌ及びｍは、０〜５の整数を表す。
（付記２９） 下記構造式（８）で表される繰り返し単位を有する付記１８から２８のいずれかに記載の金属錯体含有高分子。

前記構造式（８）中、ｘ及びｙは、モル分率（モル％）を表し、ｘ＋ｙ＝１００である。ｎは、重合度を表す。
（付記３０） 数平均分子量が５,０００以上である付記１８から２９のいずれかに記載の金属錯体含有高分子。
（付記３１） リン光発光を示す付記１８から３０のいずれかに記載の金属錯体含有高分子。
（付記３２） 付記１から１７のいずれかに記載の有機ＥＬ素子を用いたことを特徴とする有機ＥＬディスプレイ。
（付記３３） パッシブマトリクスパネル及びアクティブマトリクスパネルのいずれかである付記３２に記載の有機ＥＬディスプレイ。

In the structural formulas (5) to (7), Ar represents an arylene group. l and m represent the integer of 0-5.
(Appendix 29) The metal complex-containing polymer according to any one of appendices 18 to 28, having a repeating unit represented by the following structural formula (8).

In the structural formula (8), x and y represent a mole fraction (mol%), and x + y = 100. n represents the degree of polymerization.
(Supplementary note 30) The metal complex-containing polymer according to any one of supplementary notes 18 to 29, wherein the number average molecular weight is 5,000 or more.
(Supplementary note 31) The metal complex-containing polymer according to any one of supplementary notes 18 to 30, which exhibits phosphorescence.
(Additional remark 32) The organic EL display using the organic EL element in any one of Additional remark 1 to 17 characterized by the above-mentioned.
(Supplementary note 33) The organic EL display according to supplementary note 32, which is either a passive matrix panel or an active matrix panel.

Since the metal complex-containing polymer of the present invention is a polymer material, it has excellent handleability and can be easily and precisely formed by various coating methods such as an ink jet method. A planar light source, lighting device, segment display It can be suitably used as a light emitting material, a color conversion material, and the like in a device, a dot matrix display device, a backlight of a liquid crystal display device, an organic EL element, a solar cell, a polymer LED, and the like.
The organic EL device of the present invention uses the metal complex-containing polymer of the present invention as a luminescent material, a color conversion material, etc., and thus exhibits high luminous efficiency, color conversion efficiency, etc., and a coating method is used. Because it is possible, it is excellent in productivity. For this reason, the organic EL element includes, for example, a lighting device, a computer, a vehicle-mounted display, an outdoor display, a household device, a commercial device, a household appliance, a traffic-related display, a clock display, a calendar display, It can be suitably used in various fields including luminescent screens, audio equipment and the like.
Since the organic display of the present invention uses the organic EL element of the present invention, it has high luminance and high luminous efficiency, has a long element life, can be easily manufactured, and can be manufactured at low cost. For this reason, the organic EL display includes, for example, a computer, an on-vehicle display, an outdoor display, a household device, a commercial device, a home appliance, a traffic display, a clock display, a calendar display, a luminescent It can be suitably used in various fields including screens and audio equipment.

FIG. 1 is a schematic explanatory diagram for explaining one structural example of a passive matrix organic EL display (passive matrix panel). FIG. 2 is a schematic explanatory diagram for explaining a circuit in the passive matrix type organic EL display (passive matrix panel) shown in FIG. FIG. 3 is a schematic explanatory diagram for explaining a structural example of an active matrix organic EL display (active matrix panel). FIG. 4 is a schematic explanatory diagram for explaining a circuit in the active matrix type organic EL display (active matrix panel) shown in FIG. FIG. 5 is a schematic explanatory diagram for explaining one structural example of the organic EL display.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic EL display 10 Glass substrate 12 Glass substrate 14 Positive electrode 15 Protective layer (flattening layer)
16 Hole injection layer / transport layer 20 Light emission layer / electron transport layer 21 Transparent electrode 22 Negative electrode 24 Organic thin film layer for blue light emission 25 Electrode 26 Organic thin film layer for green light emission 28 Organic thin film layer for red light emission 30 Positive electrode line 32 Negative electrode line 34 Organic EL element 36 Constant current source 38 Drive circuit 40 TFT circuit 42 Data line 44 Power supply line 46 Scan line 48 TFT for switching
50 Driving TFT
55 Organic thin film layer for blue light emission 60 Color conversion layer for red 65 Red color filter 70 Color conversion layer for green 80 Green color filter

Claims (5)

  An organic thin film layer is provided between the positive electrode and the negative electrode, and the organic thin film layer includes a metal complex unit having a π electron conjugated portion, and a π electron conjugated cutting unit capable of cutting π electron conjugation in the metal complex unit. An organic EL device comprising a metal complex-containing polymer having a repeating unit as a repeating unit. The organic EL device according to claim 1, wherein the metal complex-containing polymer has a repeating unit represented by the following structural formula (1).

In the structural formula (1), A represents a metal complex unit having a π electron conjugated portion. B represents a π electron conjugate cutting unit capable of cutting the π electron conjugate in A. x represents a mole fraction (mol%) in the entire metal complex-containing polymer of A, y represents a mole fraction (mol%) in the entire metal complex-containing polymer of B, and x + y = 100 is there. n represents the degree of polymerization. The organic EL device according to claim 2, wherein A in the structural formula (1) is represented by the following structural formula (2).

In the structural formula (2), M represents a central metal. L ¹ and L ² represent a ligand that can bind to M, and L ¹ represents a divalent ligand that binds to B. p represents an integer of 0 to 5. When p is 1 or more, L ¹ and L ² may be the same as or different from each other.   A metal complex-containing polymer comprising a metal complex unit having a π-electron conjugated moiety and a π-electron conjugated cleavage unit capable of cleaving π-electron conjugation in the metal complex unit as repeating units. An organic EL display using the organic EL element according to claim 1.

Images