JP2007173464A - Organic electric field light emitting device, its manufacturing method, and image display medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electric field light emitting device which has a high light emitting intensity, a high light emitting efficiency, and a long device lifetime, and is easily manufactured, to provide its manufacturing method, and to provide an image display medium using the organic electric field light emitting device. <P>SOLUTION: The organic electric field light emitting device comprises one or a plurality of organic compound layers which are sandwiched between a pair of electrodes at least one of which is transparent or semi-transparent. In the organic electric field light emitting device, its manufacturing method, and the image display medium using the organic electric field light emitting device; at least one layer of the organic compound layer contains at least a type of disconjugate system polymer, and at least one terminal group of the disconjugate system polymer has a phosphorescent emitting body. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is an organic electroluminescent element (hereinafter sometimes referred to as an organic EL element) that can be suitably used in the fields of display elements, backlights such as liquid crystals, illumination light sources, electrophotographic exposure apparatuses, signs, signboards, and the like. And a manufacturing method thereof and an image display medium.

An electroluminescent element is a self-luminous all-solid-state element, has high visibility and is resistant to impact, and thus is widely expected to be applied. Currently, those using inorganic phosphors are the mainstream and widely used. However, since driving requires an AC voltage of 200 V or higher and 50 to 1000 Hz, the running cost is high and the luminance is insufficient. Has a problem.
On the other hand, research on electroluminescent devices using organic compounds first started with a single crystal such as anthracene, but the film thickness was as thick as about 1 mm and a driving voltage of 100 V or more was required. For this reason, attempts have been made to reduce the thickness by vapor deposition (see, for example, Non-Patent Document 1).
The light emission of these elements is such that electrons are injected from one of the electrodes and holes are injected from the other electrode, so that the light emitting material in the element is excited to a high energy level, and the excited illuminant becomes the base. This is a phenomenon in which excess energy for returning to the state is emitted as light. However, the driving voltage is still as high as 30 V, the density of electron / hole carriers in the film is low, and the photon generation probability due to carrier recombination is low, so that sufficient luminance cannot be obtained, leading to practical use. There wasn't.

However, in 1987, Tang et al. Sequentially stacked a very thin thin film made of a hole transporting organic low molecular weight compound and a very thin thin film made of a fluorescent organic low molecular weight compound having an electron transporting capability on a transparent substrate by vacuum deposition. The organic electroluminescence device of the function separation type has been reported to obtain high luminance of 1000 cd / m ² or more at a low voltage of about 10 V (for example, see Patent Document 1 or Non-Patent Document 2). Research and development of electroluminescent devices are actively conducted.
These electroluminescent elements having a stacked structure are structures in which an organic light emitter and a charge transporting organic substance (charge transport material) are stacked on an electrode, and each hole and electron moves through the charge transport material and is regenerated. Emits light when bonded. As the organic light emitter, an organic dye emitting fluorescence such as 8-quinolinol aluminum complex or coumarin compound is used. Examples of the charge transport material include diamino compounds such as N, N-di (m-tolyl) N, N′-diphenylbenzidine and 1,1-bis [N, N-di (p-tolyl) aminophenyl] cyclohexane, 4- (N, N-diphenyl) aminobenzaldehyde-N, N-diphenylhydrazone compound and the like.

  However, in terms of these materials, it is left as essential issues to increase the luminous efficiency and to increase the luminous lifetime. In general, when a light-emitting material is excited, fluorescence is emitted (fluorescent compound) and when it is deactivated as phosphorescence via intersystem crossing (phosphorescent compound). The luminous efficiency of the organic electroluminescence device using the fluorescent compound is as low as 5% at the maximum, but the luminous efficiency of the organic electroluminescence device using the phosphorescent compound is said to be 20% at the maximum. There has been a demand for an organic electroluminescent device using the above.

In recent years, since an organic electroluminescent device using an iridium (III) tris (2-phenylpyridine) complex as a phosphorescent compound emitting light at room temperature has been reported (for example, see Non-Patent Document 3 or 4), phosphorous has been actively used. Organic electroluminescence devices using light emission have been developed.
Some organic electroluminescent elements using phosphorescent light emission use low molecular weight materials and high molecular weight materials as well as organic electroluminescent elements using fluorescent compounds. An organic electroluminescent device using a low molecular material is generally manufactured using vacuum deposition. However, since vapor deposition is performed under a high vacuum condition of 10 ⁻⁴ Pa or less, improvement in simplification, workability, large area, cost, etc. is required in production. In particular, since an organic electroluminescent device using phosphorescence is manufactured using a phosphorescent compound as a dopant, it is difficult to manufacture the film uniformly in a large area.

On the other hand, an organic electroluminescent element using a polymer material can be manufactured by a coating process such as spin coating, ink jet, screen printing, spraying or the like. There is a report that a polymer material such as polyvinyl carbazole is mixed with an iridium metal complex (see, for example, Patent Document 2 or Non-Patent Document 5). However, since the crystallinity of the iridium metal complex is high, aggregation occurs and crystallization occurs. It was difficult to dope to the concentration. Moreover, since the charge transportability of the polymer material is inferior, there is a limit to the obtained device characteristics. Furthermore, there is a report of an organic electroluminescent device having a phosphorescent metal complex in a polymer material (see, for example, Patent Document 3). However, in order to increase the efficiency, it is necessary to increase the concentration of the metal complex in the polymer, so the number of metal complex units in the polymer increases, so that the metal complex unit becomes a branch point and the crystallinity increases and the solubility increases. As a result, the heat resistance decreased and there were defects in manufacturing and characteristics.
JP 59-194393 A Japanese Patent Laid-Open No. 2001-257076 JP 2003-171659 A Thin Solid Films, 94, 171 (1982) Appl. Phys. Lett. , 51, 913 (1987) Appl. Phys. Lett. , 75, 4 (1999) J. et al. Am. Chem. Soc. , 123, 4304 (2001) Appl. Phys. Lett. , 80, 2045 (2002)

  It is an object of the present invention to solve the problems in the prior art and achieve the following objects. In other words, non-conjugated polymers having a light-emitting function with excellent thermal stability during storage, storage stability, solubility in solvents and resins, and compatibility, with high emission intensity, high emission efficiency, and device lifetime An object of the present invention is to provide an organic electroluminescence device which is long and easy to produce, a method for producing the same, and an image display medium using the organic electroluminescence device.

In order to achieve the above object, the present inventors have made extensive studies on non-conjugated polymers having light emission. As a result, non-conjugated polymers having a phosphorescent emitter in at least one terminal group are organic electroluminescent elements. As a result, it has been found that the film has suitable charge injection characteristics, charge mobility, thin film forming ability, and light emission characteristics, and the present invention has been completed.
That is, the present invention
<1> In an organic electroluminescent element composed of one or a plurality of organic compound layers sandwiched between a pair of electrodes, at least one of which is transparent or translucent, at least one of the organic compound layers is at least one kind. An organic electroluminescent device comprising: a non-conjugated polymer, wherein at least one terminal group of the non-conjugated polymer has a phosphorescent emitter.

  <2> The organic electroluminescent element according to <1>, wherein the non-conjugated polymer is at least one selected from the group consisting of polyester, polyether and polyurethane.

  <3> The organic electroluminescent element according to <1>, wherein the non-conjugated polymer is a hole transporting polymer.

  <4> The organic electroluminescent element according to <1>, wherein the non-conjugated polymer is a polymer having both hole transporting properties and electron transporting properties.

  <5> The non-conjugated polymer is a polymer composed of a repeating unit containing at least one selected from the structures represented by the following general formulas (I-1) and (I-2) as a partial structure. <1> to <4>, wherein the organic electroluminescent element is characterized in that

(In the general formulas (I-1) and (I-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted, Represents a monovalent condensed aromatic hydrocarbon having 2 to 10 unsubstituted aromatic rings or a substituted or unsubstituted monovalent aromatic heterocyclic ring, and X represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted aromatic Represents a divalent polynuclear aromatic hydrocarbon having 2 to 10 rings, a substituted or unsubstituted divalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, or a substituted or unsubstituted divalent aromatic heterocyclic ring , T represents a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k, i, j are each independently 0 or 1 Represents.)

  <6> The organic compound layer includes at least a light emitting layer, an electron transport layer and / or an electron injection layer, and at least the light emitting layer contains at least one kind of the non-conjugated polymer. It is an organic electroluminescent element as described in <1>.

  <7> The organic compound layer includes at least a hole transport layer and / or a hole injection layer, a light emitting layer, an electron transport layer and / or an electron injection layer, and at least the light emitting layer is the non-conjugated system. The organic electroluminescent element according to <1>, which contains at least one polymer.

  <8> The organic compound layer is composed of at least a hole transport layer and / or a hole injection layer and a light emitting layer, and at least the light emitting layer contains at least one kind of the non-conjugated polymer. The organic electroluminescent element according to <1>, wherein

  <9> The item <1>, wherein the organic compound layer is composed of only one light emitting layer having charge transporting capability, and the light emitting layer contains at least one kind of the non-conjugated polymer. This is an organic electroluminescent element.

  <10> A non-conjugated polymer composed of a repeating unit containing at least one selected from the structures represented by the general formulas (I-1) and (I-2) as a partial structure is represented by the following general formula (II- <1> The organic electroluminescence device according to <5>, which is a polyester represented by 1) or (II-2).

(In General Formulas (II-1) and (II-2), A ₁ represents at least one selected from the structures represented by General Formulas (I-1) and (I-2), and Y ₁ represents 2 Z ₁ represents a divalent carboxylic acid residue, m represents an integer of 1 to 5, and p represents an integer of 5 to 5000.

  <11> A non-conjugated polymer composed of a repeating unit containing at least one selected from the structures represented by the general formulas (I-1) and (I-2) as a partial structure is represented by the following general formula (III- <1> The organic electroluminescence device according to <5>, which is a polyether represented by 1).

(In General Formula (III-1), A ₁ represents at least one selected from the structures represented by General Formulas (I-1) and (I-2), and p represents an integer of 5 to 5,000. To express.)

  <12> A non-conjugated polymer composed of a repeating unit containing at least one selected from the structures represented by the general formulas (I-1) and (I-2) as a partial structure is represented by the following general formula (IV- <1> The organic electroluminescence device according to <5>, which is a polyurethane represented by 1) or (IV-2).

(In Formulas (IV-1) and (IV-2), _{A 1} is the general formula (I-1) and (represents at least one selected from structures represented by I-2), p is 5 to It represents 5,000 integer, _{Y 2} and _{Z 2} each represents a divalent isocyanate, alcohol, or an amine residue.)

  <13> The organic electroluminescent element according to <1>, wherein the phosphorescent emitter is an organic compound.

  <14> The organic electroluminescent element according to <13>, wherein the organic compound is an organometallic complex.

  <15> The organic electroluminescent element according to <14>, wherein the metal contained in the organometallic complex is iridium or platinum.

  <16> The method for producing an organic electroluminescent element according to any one of <1> to <15>, wherein a coating solution for an organic compound layer is prepared by dissolving a component of the organic compound layer in a solvent. It is a manufacturing method of the organic electroluminescent element which has the application | coating process apply | coated by the inkjet method at least.

  <17> An image display medium in which the organic electroluminescent elements according to any one of <1> to <15> are arranged in a matrix form and / or a segment form.

  According to the present invention, an organic electroluminescence device having high brightness, high efficiency, long device life, few defects such as pinholes, and easy to increase in area, and a manufacturing method thereof, and an image display medium using the organic electroluminescence device Can be provided.

Hereinafter, the organic electroluminescent element of the present invention, the manufacturing method thereof, and the image display medium using the organic electroluminescent element will be described in detail.
The organic electroluminescent device of the present invention is an organic electroluminescent device comprising one or a plurality of organic compound layers sandwiched between a pair of electrodes, at least one of which is transparent or translucent. One layer contains at least one kind of non-conjugated polymer, and at least one terminal group of the non-conjugated polymer has a phosphorescent emitter.
In the present invention, “non-conjugated polymer” refers to a polymer having a repeating structure containing at least one σ bond in the main chain skeleton of the polymer.

  In a non-conjugated molecule in which a plurality of luminescent compounds such as phosphorescent emitters are connected, the luminescence intensity of the luminescent compound contained in the molecule may be significantly reduced compared to the case of the luminescent compound alone. From this point, it is preferable to provide a light emitting compound dispersed in the molecule. Since the non-conjugated polymer used in the present invention has a single phosphorescent emitter at the end of the molecular chain, it can prevent the reduction in luminous efficiency as described above and, as a result, obtains sufficient emission intensity. be able to.

In addition, the phosphorescent emitter can be added to any position other than the end of the polymer molecular chain. However, if the phosphorescent emitter is not present at the end, the terminal functional group is , It may adversely affect the light emission of the phosphorescent emitter added to the portion other than the terminal. In addition, when the charge moves between molecules, the charge mobility may be hindered.
However, since the non-conjugated polymer used in the present invention replaces the end of the molecular chain with a phosphorescent emitter instead of a functional group, the phosphorescent emitter alone exhibits sufficient emission characteristics. be able to. In addition, in the case where charges move between molecules, the charge mobility can be further improved. Further, it is easy to synthesize a non-conjugated polymer to replace the terminal functional group with a phosphorescent material.

Furthermore, the non-conjugated polymer used in the present invention may have phosphorescent emitters at both ends. In this case, a non-conjugated polymer having a desired emission color can be easily obtained by making the emission colors of the respective phosphorescent emitters different. Such a non-conjugated polymer can be easily synthesized using copolymerization.
Non-conjugated polymers such as those described above can be synthesized by selecting the structure of the portion other than the phosphorescent emitter and adjusting the molecular weight, so that the desired physical properties (for example, thermal stability, solvent and resin) It is easy to obtain solubility and compatibility, and as a result, a non-conjugated polymer having excellent thermal stability and thin film forming ability can be easily obtained.

  As described above, the non-conjugated polymer used in the present invention has high emission intensity, high emission efficiency, excellent charge transfer characteristics, excellent thermal stability, and easy thin film formation. It is. Therefore, since the organic compound layer of the organic electroluminescent device of the present invention contains the aforementioned non-conjugated polymer, the light emission intensity is high, the light emission efficiency is high, the device life is long, and the manufacture is easy. It is.

  Basic structures of such non-conjugated polymers include polyesters, polyethers, polyurethanes, polyimides, polyamides, polyether ketones, polycarbonates, polysulfides, polyether sulfides, silicon-containing polymers, germanium-containing polymers, and those Among these, at least one selected from the group consisting of polyesters, polyethers, and polyurethanes from the viewpoints of ease of synthesis, thermal stability, solubility in solvents and resins, and compatibility It is preferable that

  The phosphorescent emitter according to the present invention is preferably a material that emits phosphorescence in a solid state. In addition, the phosphorescent emitter according to the present invention may be a substance that generates fluorescence together with phosphorescence.

  The non-conjugated polymer according to the present invention can be a hole-transporting polymer or a polymer having both hole-transporting properties and electron-transporting properties by appropriately selecting the structure described later.

  The non-conjugated polymer according to the present invention is a polymer composed of repeating units containing at least one selected from the structures represented by the following general formulas (I-1) and (I-2) as a partial structure. Is preferred. Such non-conjugated polymers are superior in thermal stability during light emission, solubility in solvents and resins, and phase solubility, so that it is easier to produce organic electroluminescent devices. Reliability such as light emission characteristics and element lifetime as a light emitting element can be improved.

  In the general formulas (I-1) and (I-2), Ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted group. Represents a monovalent condensed aromatic hydrocarbon having 2 to 10 substituted aromatic rings or a substituted or unsubstituted monovalent aromatic heterocyclic ring, and X represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted aromatic ring A divalent polynuclear aromatic hydrocarbon having 2 to 10 carbon atoms, a substituted or unsubstituted aromatic divalent aromatic hydrocarbon having 2 to 10 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic ring; T represents a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k, i and j each independently represents 0 or 1; To express.

In addition, the polynuclear aromatic hydrocarbon and condensed aromatic hydrocarbon selected as one of the structures representing Ar are specifically defined as follows in the present invention.
That is, the “polynuclear aromatic hydrocarbon” refers to a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present and the rings are bonded by a carbon-carbon bond. Specific examples include biphenyl and terphenyl.
“Condensed aromatic hydrocarbon” refers to a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present, and the rings share a pair of carbon atoms. Specific examples include naphthalene, anthracene, phenanthrene and fluorene.

  In addition, the aromatic heterocyclic ring selected as one of the structures representing Ar refers to an aromatic ring including elements other than carbon and hydrogen. Nr = 5 and / or 6 is preferably used as the atom (Nr) constituting the ring skeleton. Further, the type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not particularly limited. For example, a sulfur atom, a nitrogen atom, an oxygen atom and the like are preferably used, and two types are included in the ring skeleton. The above and / or two or more different atoms may be contained. In particular, as a heterocyclic ring having a 5-membered ring structure, thiophene, pyrrole and furan, or a heterocyclic ring in which the carbon at the 3-position and 4-position of the compound is replaced with nitrogen is preferably used. Pyridine is preferably used.

  Examples of the substituent related to the phenyl group, polynuclear aromatic hydrocarbon, condensed aromatic hydrocarbon or aromatic heterocycle represented by Ar include a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a substituted amino group, A halogen atom etc. are mentioned. As an alkyl group, a C1-C10 thing is preferable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group etc. are mentioned. As an alkoxy group, a C1-C10 thing is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group etc. are mentioned. As the aryl group, those having 6 to 20 carbon atoms are preferable, and examples thereof include a phenyl group and toluyl group. As the aralkyl group, those having 7 to 20 carbon atoms are preferable, and examples thereof include benzyl group and phenethyl group. Is mentioned. Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, an aralkyl group, and the like, and specific examples are as described above.

  In the present invention, preferred Ar includes a phenyl group, a polynuclear aromatic hydrocarbon, and a condensed aromatic hydrocarbon.

  X is a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted divalent condensed aromatic carbon having 2 to 10 aromatic rings. Represents hydrogen or a substituted or unsubstituted divalent aromatic heterocyclic ring, and specifically includes groups selected from the following formulas (1) to (13).

_Wherein, R 1 _{to R 14} is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group or a halogen atom, A represents 0 or 1, and b represents an integer of 0 to 10. V represents a group selected from the following formulas (13) to (33).

R ₁₅ represents a hydrogen atom, an alkyl group, or a cyano group, and R _{16 to} R ₁₇ represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, A substituted or unsubstituted aralkyl group or a halogen atom is represented, b means the integer of 1-10, c means the integer of 0-10.

  Preferable X includes a phenylene group, a polynuclear aromatic hydrocarbon, and a condensed aromatic hydrocarbon.

  T represents a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, preferably a divalent hydrocarbon group having 2 to 6 carbon atoms. It is selected from a linear hydrocarbon group and a divalent branched hydrocarbon group having 3 to 7 carbon atoms. A specific structure is shown below.

  Specific examples of the structure represented by the general formula (I-1) in the present invention are shown in Tables 1 to 22, and specific examples of the structure represented by the general formula (I-2) are shown in Tables 23 to 43.

  The non-conjugated polymer according to the present invention comprising a repeating unit containing at least one selected from the structures represented by formulas (I-1) and (I-2) as a partial structure is represented by the following formula (II- It may be a polyester represented by 1) or (II-2), a polyether represented by the following general formula (III-1), or a polyurethane represented by the following general formula (IV-1) or (IV-2). .

In General Formulas (II-1) and (II-2), A ₁ represents at least one selected from the structures represented by General Formulas (I-1) and (I-2), and Y ₁ is divalent. Z ₁ represents a divalent carboxylic acid residue, m represents an integer of 1 to 5, and p represents an integer of 5 to 5000.

In General Formula (III-1), A ₁ represents at least one selected from the structures represented by General Formulas (I-1) and (I-2), and p represents an integer of 5 to 5,000. .

In General Formulas (IV-1) and (IV-2), A ₁ represents at least one selected from the structures represented by General Formulas (I-1) and (I-2), and p is 5 to 5 Represents an integer of 1,000, and Y ₂ and Z ₂ represent a divalent isocyanate, alcohol, or amine residue.

In formulas (II-1) and (II-2), Y ₁ represents a divalent alcohol residue, and Z ₁ represents a divalent carboxylic acid residue. Y ₁ and Z ₁ are each independently the following: Groups selected from the formula are preferred.

In the formula, R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, Or a halogen atom, d and e each independently represent an integer of 1 to 10; f independently represents 0, 1 or 2; h and i each independently represents 0 or 1; Is as defined above.

In formulas (IV-1) and (IV-2), Y ₂ and Z ₂ represent a divalent isocyanate, alcohol, or amine residue. Specific examples of Y ₂ and Z ₂ include those represented by Y ₁ and Z ₁ . Examples thereof include the same groups as in the case.

In general formulas (II-1), (II-2), (III-1), (IV-1) and (IV-2), A ₁ represents the above general formulas (I-1) and (I-2). It represents at least one selected from the structure represented by the formula, and two or more types of structures may be contained in one polymer.

A phosphorescent emitter exists in at least one terminal group of the non-conjugated polymer according to the present invention, and the phosphorescent emitter is preferably an organic compound (organic emitter), specifically, substituted or unsubstituted. A compound having a phenyl group, a compound having a monovalent polynuclear aromatic hydrocarbon having 2-10 substituted or unsubstituted aromatic rings, a monovalent condensed aromatic carbonizing having 2-10 substituted or unsubstituted aromatic rings Examples thereof include a compound having hydrogen or a compound having a substituted or unsubstituted monovalent aromatic heterocyclic ring.
Specifically, polyacene derivative compounds such as naphthalene derivatives, anthracene derivatives, tetracene derivatives, perylene derivatives, pyrene derivatives, styrylamine compounds, quinacridone derivative compounds, rubrene derivative compounds, coumarin derivative compounds, porphyrin derivative compounds, and pyran derivative compounds. Can be mentioned. In addition, an organometallic complex is desirable as a material having high emission quantum efficiency and heat resistance.
As the metal contained in the organometallic complex, rhenium, iridium, osmium, scandium, yttrium, platinum, gold, europium, terbium, thulium, dysprosium, samarium, praseodymium, and gatrinium are preferable, and iridium, platinum, and europium are more preferable. Iridium or platinum is particularly preferred. Examples of ligands of such metal complexes include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenylbenzothiazole and derivatives thereof, and 2-phenyl-benzoxazole. And derivatives thereof, 2-phenyl-triazole and derivatives thereof, porphyrin and derivatives thereof, and the like, but are not limited thereto.

  Below, the specific example of the phosphorescence-emitting body based on this invention is shown.

  The non-conjugated polymer according to the present invention preferably has a weight average molecular weight Mw in the range of 5,000 to 500,000.

  Specific examples of polyesters represented by general formula (II-1) or (II-2) are shown in Tables 48 to 50, and specific examples of polyethers represented by general formula (III-1) are shown in Tables 51 to 52. Specific examples of the polyurethane represented by the general formula (IV-1) or (IV-2) are shown in Tables 53 to 54, but the present invention is not limited to these specific examples. The numbers in the monomer column in the table correspond to the structure numbers which are specific examples of the structures represented by the general formulas (I-1) and (I-2). Hereinafter, specific examples (compounds) given respective numbers, for example, specific examples given number 15 are referred to as display compounds (15).

  Next, in the non-conjugated polymer according to the present invention, the polyester represented by the general formula (II-1) or (II-2), the polyether represented by the general formula (III-1), or the general formula (IV- The synthesis method will be described in detail by taking the polyurethane represented by 1) or (IV-2) as an example.

A) Polyester Synthesis Method The polyester of the present invention is a known low molecular weight compound represented by the following structural formula (II-3) described in, for example, the 4th edition Experimental Chemistry Course Vol. 28 (Maruzen, 1992). It can synthesize | combine by polymerizing by the method of.

_{A 1} in Formula (II-3) has the same meaning as _{A 1} in the general formula (II-1) or (II-2). A ′ represents a hydroxyl group, a halogen atom, or a group —O—R ₁₈ , and R ₁₈ represents an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group.

The polyesters represented by the general formulas (II-1) and (II-2) can be synthesized as follows.
1) When A ′ is a hydroxyl group, the compound represented by the general formula (II-3) and the dihydric alcohol represented by HO— (Y ₁ —O) _m —H are mixed in an equivalent amount, Polymerize using a catalyst. As the acid catalyst, those used for usual esterification reaction such as sulfuric acid, toluenesulfonic acid, trifluoroacetic acid and the like can be used, and 1 / 10,000 to 1/10 parts by weight, preferably 1 part by weight of monomer. It is used in the range of 1/1000 to 1/50 parts by mass. In order to remove water generated during the polymerization, it is preferable to use a solvent that can be azeotroped with water, and toluene, chlorobenzene, 1-chloronaphthalene, and the like are effective. It is used in the range of part by mass, preferably 2-50 parts by mass. The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization.

  After completion of the reaction, if the solvent is not used, the polyester is dissolved in a soluble solvent and the solution is used. If the solvent is used, the reaction solution is left as it is, alcohols such as methanol and ethanol, acetone, etc. The polymer is dropped into a poor solvent in which the polymer is difficult to dissolve, the polyester is precipitated, the polyester is separated, washed thoroughly with water or an organic solvent, and dried. Further, if necessary, the reprecipitation treatment in which the polyester is precipitated by dissolving in an appropriate organic solvent and dropping in a poor solvent may be repeated. The reprecipitation treatment is preferably carried out with efficient stirring with a mechanical stirrer or the like. The solvent for dissolving the polyester in the reprecipitation treatment is used in the range of 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 1 part by mass of the polyester. The poor solvent is used in an amount of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, based on 1 part by weight of the polyester.

2) When A ′ is halogen, dihydric alcohols represented by HO— (Y ₁ —O) _m —H are mixed in an approximately equivalent amount and polymerized using an organic basic catalyst such as pyridine or triethylamine. An organic basic catalyst is used in 1-10 equivalent with respect to 1 equivalent of low molecules represented by general formula (II-3), Preferably it is 2-5 equivalent. As the solvent, methylene chloride, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to 1 part by weight of the monomer. Used. The reaction temperature can be arbitrarily set. After the polymerization, reprecipitation treatment is performed as described above, and purification is performed.

  In the case of dihydric alcohols with high acidity such as bisphenol, an interfacial polymerization method can also be used. That is, it can polymerize by adding a dihydric alcohol to water, adding an equivalent base and dissolving it, and then adding a monomer solution equivalent to the dihydric alcohol with vigorous stirring. Under the present circumstances, water is used in 1-1,000 mass parts with respect to 1 mass part of dihydric alcohol, Preferably it is 2-500 mass parts. As the solvent for dissolving the monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene and the like are effective. The reaction temperature can be arbitrarily set, and in order to promote the reaction, it is effective to use a phase transfer catalyst such as an ammonium salt or a sulfonium salt. The phase transfer catalyst is used in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, with respect to 1 part by mass of the monomer.

3) When A ′ is —O—R _18, an excess of a dihydric alcohol represented by HO— (Y ₁ —O) _m —H is added to the monomer represented by the structural formula (II-3). In addition, it can be synthesized by transesterification by heating using inorganic acid such as sulfuric acid and phosphoric acid, titanium alkoxide, acetate or carbonate such as calcium and cobalt, oxide of zinc and lead as a catalyst. The dihydric alcohol is used in the range of 2 to 100 equivalents, preferably 3 to 50 equivalents, with respect to 1 equivalent of the low molecule represented by the general formula (II-3). The catalyst is used in the range of 1 / 10,000 to 1 part by weight, preferably 1 / 1,000 to 1/2 part by weight, based on 1 part by weight of the low molecule represented by the general formula (II-3). . The reaction is carried out at a reaction temperature of 200 to 300 ° C. After completion of the transesterification from the group —O—R ₁₈ to the group —O— (Y ₁ —O) _m —H, HO— (Y ₁ —O) _m —. In order to promote polymerization due to elimination of H, the reaction is preferably performed under reduced pressure. Also, HO- (Y ₁ -O) _m —H is removed azeotropically under normal pressure using a high boiling point solvent such as 1-chloronaphthalene that can be azeotroped with HO— (Y ₁ —O) _m —H. Can also be reacted.

  Further, polyester can be synthesized as follows. In each of the above cases, a compound represented by the following structural formula (II-4) is produced by adding an excess of dihydric alcohols and reacting them, and then using this as a low molecule in the same manner as described above, What is necessary is just to make it react with a bivalent carboxylic acid or a bivalent carboxylic acid halide, and polyester can be obtained by it.

In the formula, A ₁ , Y ₁ and m are as described above.

4) The method for introducing the phosphorescent emitter is not particularly limited, and the following methods are exemplified. That is, when A ′ is a hydroxyl group, it can be introduced by copolymerizing the monocarboxylic acid of the luminescent material or by charging and reacting the monocarboxylic acid of the luminescent material after the polymerization reaction of the polymer. When A ′ is halogen, the monoacid chloride of the luminescent material can be copolymerized, or the monoacid chloride of the luminescent material can be charged and reacted after the polymerization reaction of the polymer. When A ′ is —O—R ₁₈ , the phosphor monoester can be copolymerized, or after the polymer polymerization reaction, the phosphor monoester can be charged and reacted for introduction.

A) Method for Synthesizing Polyether The polyether of the present invention can be easily produced by condensing a compound having a hydroxyl group represented by the following general formula (III-2) between molecules. Here, _{A 1} is the following formula (III-2) is the same as _{A 1} in the general formula (III-1).

Specifically, the polyether can be synthesized, for example, as follows.
1) The above polyether can be synthesized by a method of subjecting a compound represented by the general formula (III-2) (hereinafter abbreviated as a monomer) to heat dehydration condensation. In this case, it is desirable that the monomer be heated and melted without a solvent and reacted under reduced pressure in order to accelerate the polymerization reaction due to the elimination of water. When a solvent is used, a solvent that azeotropes with water, for example, trichloroethane, toluene, chlorobenzene, dichlorobenzene, nitrobenzene, 1-chloronaphthalene, etc. is effective for removing water. 1 to 100 equivalents, preferably 2 to 50 equivalents. The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization. If the polymerization does not proceed, the solvent may be removed from the reaction system and heated and stirred in a viscous state.

  2) The polyether can also be synthesized by a dehydration condensation method using a protonic acid such as p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid, or a Lewis acid such as zinc chloride as an acid catalyst. In this case, the acid catalyst is used in the range of 1 to 1/10000 to 1/10 equivalent, preferably 1/1000 to 1/50 equivalent, per equivalent of monomer. In order to remove water generated during the polymerization, it is preferable to use a solvent azeotropic with water. As the solvent, toluene, chlorobenzene, dichlorobenzene, nitrobenzene, 1-chloronaphthalene and the like are effective, and 1 to 100 equivalents, preferably 2 to 50 equivalents, are used with respect to 1 equivalent of the monomer. The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization.

  3) The above monomers include alkyl isocyanates such as cyclohexyl isocyanate, alkyl isocyanates such as cyclohexyl cyanide, cyanate esters such as p-tolyl cyanate and 2,2-bis (4-cyanatophenyl) propane, and dichloromethane. It can also be synthesized by a method using a condensing agent such as hexylcarbodiimide (DCC) or trichloroacetonitrile. In this case, the condensing agent is used in a range of 1/2 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 equivalent of the monomer. As the solvent, toluene, chlorobenzene, dichlorobenzene, 1-chloronaphthalene and the like are effective, and 1 to 100 equivalents, preferably 2 to 50 equivalents, are used with respect to 1 equivalent of the monomer. Although reaction temperature can be set arbitrarily, it is preferable to make it react from the room temperature to the boiling point of a solvent. Of the synthesis methods 1), 2) and 3), the synthesis method 1) or 3) is preferred because isomerization and side reactions are unlikely to occur. In particular, the synthesis method 3) is more preferable because the reaction conditions are milder.

  After completion of the reaction, if the solvent is not used, dissolve the polyether in a soluble solvent, and if the solvent is used, the solution is used as it is, alcohols such as methanol and ethanol, and non-conjugates such as acetone. The polymer is dropped into a poor solvent in which the polymer is difficult to dissolve, the polyether is precipitated, the polyether is separated, and then thoroughly washed with water or an organic solvent and dried. Further, if necessary, the reprecipitation treatment in which the monomer is precipitated by dissolving in an appropriate organic solvent and dropping in a poor solvent may be repeated. The reprecipitation treatment is preferably carried out with efficient stirring using a mechanical stirrer or the like. The solvent for dissolving the non-conjugated polymer in the reprecipitation treatment is used in the range of 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 1 part by mass of the non-conjugated polymer. The poor solvent is used in an amount of 1 to 1000 parts by mass, preferably 10 to 500 parts by mass with respect to 1 part by mass of the non-conjugated polymer. Furthermore, in the above reaction, a copolymer can be synthesized by using two or more monomers, preferably 2 to 5, more preferably 2 to 3 monomers. By copolymerizing different types of monomers, it is possible to control electrical characteristics, film formability, solubility, and light emission characteristics.

  If the polymerization degree of the polyether is too low, the film formability is inferior, and it is difficult to obtain a strong film. If the polymerization degree is too high, the solubility in the solvent is lowered and the processability is deteriorated. It is set, preferably 10 to 300,000, more preferably 15 to 100,000.

  Moreover, the introduction of the light emitter is not particularly limited, but the following method may be mentioned. That is, polymerization with a phosphor having a hydroxyl group similar to the terminal hydroxyl group, acylation with a monoacid salt compound of the phosphor, and introduction of a urethane residue with monoisocyanate of the phosphor can be applied.

C) Method for Synthesizing Polyurethane The polyurethane of the present invention is prepared by reacting monomers represented by the following general formulas (IV-3) to (IV-6), for example, 4th edition Experimental Chemistry Course Vol. 28 (Maruzen, 1992). The polymer can be synthesized by polymerization by a known method described in New Polymer Experiments Vol. 2 (Kyoritsu Shuppan, 1995), etc. In general formula (IV-3) ~ (IV -6) in, _{A 1} is the same as _{A 1} in the general formula (IV-1) or (IV-2).

Specifically, for example, in the case of the monomers represented by the general formulas (IV-3) and (IV-4), the polyurethane can be synthesized as follows. Diisocyanate monomer in the case of a dihydric alcohol represented by the general formula (IV-3) is, _OCN-Y 2 equivalents of mixed and diisocyanates represented by -NCO, also the monomers represented by the general formula (IV-4) In the case of an alcohol, an equivalent mixture with a dihydric alcohol represented by HO—Z ₂ —OH is mixed and polyadded. As a catalyst, what is used for the polyurethane synthesis reaction by normal polyaddition, such as organometallic compounds, such as dibutyltin (II) dilaurate, dibutyltin diacetate, and lead naphthenate, can be used. Further, when an aromatic diisocyanate is used for the synthesis of polyurethane, a tertiary amine such as triethylenediamine can be used as a catalyst. These organometallic compounds and tertiary amines may be mixed and used as a catalyst. The amount of the catalyst is used in the range of 1 / 10,000 to 1/10 parts by mass, preferably 1 / 1,000 to 1/50 parts by mass, with respect to 1 part by mass of the monomer. As the solvent, any solvent can be used as long as it can dissolve the monomer and diisocyanate or dihydric alcohol. However, a solvent having low polarity and a solvent that does not cause hydrogen bonding with the alcohol from the viewpoint of reactivity. It is preferable to use toluene, chlorobenzene, dichlorobenzene, 1-chloronaphthalene and the like are effective. The amount of the solvent is used in the range of 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 1 part by mass of the monomer. The reaction temperature can be arbitrarily set.

  After completion of the reaction, the reaction solution is dropped as it is into a poor solvent in which alcohols such as methanol and ethanol and polymers such as acetone are difficult to dissolve, and after polyurethane is precipitated and separated, it is sufficiently washed with water or an organic solvent. And dry. Further, if necessary, the reprecipitation treatment may be repeated for dissolving in an appropriate organic solvent and dropping in a poor solvent to precipitate polyurethane. The reprecipitation treatment is preferably carried out with efficient stirring with a mechanical stirrer or the like. The solvent for dissolving the polyurethane during the reprecipitation treatment is used in the range of 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 1 part by mass of the polyurethane. The poor solvent is used in an amount of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, based on 1 part by weight of polyurethane.

In the case of the low molecules represented by the general formulas (IV-5) and (IV-6), the polyurethane can be synthesized as follows. When the low molecule is a bischloroformate represented by the general formula (IV-5), it is mixed with an equivalent amount of a diamine represented by ₂ HN—Y ₂ —NH ₂ and the monomer is represented by the general formula (IV-6). In the case of diamines represented by the formula ( ₂ ), they are mixed in an equivalent amount with the bischloroformates represented by ClOCO-Z ₂ -OCOCl and subjected to polycondensation. As the solvent, methylene chloride, dichloroethane, trichloroethane, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to 1 part by weight of monomer. Used in the range of parts. The reaction temperature can be arbitrarily set. After the polymerization, purification is performed by reprecipitation as described above.

In addition, when the diamine represented by ₂ HN—Y ₂ —NH ₂ has a high basicity, an interfacial polymerization method can also be used. That is, after adding diamines to water and adding an equivalent amount of acid to dissolve, polymerization can be performed by adding the diamines and an equivalent monomer solution represented by the above general formula (IV-5) with vigorous stirring. Under the present circumstances, water is used in 1-1000 mass parts with respect to 1 mass part of diamines, Preferably it is 10-500 mass parts. As the solvent for dissolving the monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene and the like are effective. The reaction temperature can be arbitrarily set, and in order to promote the reaction, it is effective to use a phase transfer catalyst such as an ammonium salt or a sulfonium salt. The phase transfer catalyst is used in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, with respect to 1 part by mass of the monomer.

Moreover, the introduction of the light emitter is not particularly limited, but the following method may be mentioned. In the case of (IV-3), the monohydric alcohol of the luminescent material can be copolymerized or introduced after the polymerization reaction of the polymer is charged and reacted with the monohydric alcohol of the luminescent material. In the case of (IV-4), the monoisocyanate of the luminescent material can be copolymerized or introduced after the polymerization reaction of the polymer is charged and reacted with the monoisocyanate of the luminescent material.
In the case of (IV-5), the monovalent carboxylic acid of the luminescent material can be copolymerized or introduced after the polymerization reaction of the polymer is charged and reacted with the monovalent carboxylic acid of the luminescent material. In the case of (IV-6), the monoamine of the luminescent material can be copolymerized or introduced after the polymerization reaction of the polymer is charged and reacted with the monoamine of the luminescent material.

Next, the layer structure of the organic EL element of the present invention will be described in detail.
The organic EL device of the present invention comprises a pair of electrodes, at least one of which is transparent or translucent, and one or more organic compound layers including a light-emitting layer sandwiched between the electrodes. The layer structure is not particularly limited as long as it contains at least one non-conjugated polymer as described above in the light emitting layer.

  In the organic EL device of the present invention, when the organic compound layer is one layer, the organic compound layer means a light emitting layer having charge transporting ability, and the light emitting layer contains the non-conjugated polymer. On the other hand, when the organic compound layer has a plurality of layers (that is, in the case of a function separation type in which each layer has a different function), at least one of the layers is a light emitting layer, and this light emitting layer is a light emitting layer having a charge transporting ability. May be.

In this case, as a specific example of the layer structure composed of the light emitting layer or the light emitting layer having the charge transporting capability and other layers,
(1) A layer configuration comprising a light emitting layer, an electron transport layer and / or an electron injection layer,
(2) A layer configuration including a hole transport layer and / or a hole injection layer, a light emitting layer, an electron transport layer and / or an electron injection layer,
(3) Layer structure formed from a hole transport layer and / or a hole injection layer, and a light emitting layer,
The layers other than the light-emitting layer having the layer constitutions (1) to (3) and the light-emitting layer having charge transport ability have a function as a charge transport layer or a charge injection layer.

  In any one of the layer configurations (1) to (3), any layer may contain a non-conjugated polymer, but in any layer configuration, the light-emitting layer has a non-conjugated system. It is preferable that a polymer is contained.

  In the organic EL device of the present invention, the light-emitting layer having a charge transport function, the hole transport layer, the hole injection layer, the electron transport layer, and the electron injection layer are formed of a charge transport compound other than a non-conjugated polymer ( Hole transport material, electron transport material) may be further included. Details of such a charge transporting compound will be described later.

Hereinafter, although it demonstrates in detail, referring drawings, it is not necessarily limited to these.
1 to 4 are schematic cross-sectional views for explaining the layer structure of the organic EL element of the present invention. In the case of FIGS. 1, 2, and 3, the organic compound layer has a plurality of layers. FIG. 4 shows an example, and an example in which the number of organic compound layers is one is shown. In FIG. 1 to FIG. 4, components having similar functions are described with the same reference numerals.

The organic EL element shown in FIG. 1 is formed by sequentially laminating a transparent electrode 2, a light emitting layer 4, an electron transport layer and / or an electron injection layer 5, and a back electrode 7 on a transparent insulator substrate 1. This corresponds to 1). However, when the layer denoted by reference numeral 5 is composed of an electron transport layer and an electron injection layer, the electron transport layer, the electron injection layer, and the back electrode 7 are laminated in this order on the back electrode 7 side of the light emitting layer 4. .
2 includes a transparent electrode 2, a hole transport layer and / or a hole injection layer 3, a light emitting layer 4, an electron transport layer and / or an electron injection layer 5, and a back surface. The electrodes 7 are sequentially stacked and correspond to the layer configuration (2). However, when the layer denoted by reference numeral 3 is composed of a hole transport layer and a hole injection layer, the hole injection layer, the hole transport layer, and the light emitting layer 4 are provided on the back electrode 7 side of the transparent electrode 2. Laminated sequentially.

The organic EL element shown in FIG. 3 is obtained by sequentially laminating a transparent electrode 2, a hole transport layer and / or a hole injection layer 3, a light emitting layer 4 and a back electrode 7 on a transparent insulator substrate 1. This corresponds to the configuration (3). However, when the layer indicated by reference numeral 3 is composed of a hole transport layer and a hole injection layer, the hole injection layer, the hole transport layer, and the light emitting layer 4 are provided on the back electrode 7 side of the transparent electrode 2. They are stacked in this order.
The organic EL element shown in FIG. 4 is obtained by sequentially laminating a transparent electrode 2, a light emitting layer 6 having a charge transporting capability, and a back electrode 7 on a transparent insulator substrate 1.
In addition, when the top emission structure and the cathode / anode are both transmissive using transparent electrodes, it is also possible to have a structure in which the layer configuration of FIGS.

Each will be described in detail below.
The organic compound layer containing the non-conjugated polymer in the present invention functions as the light emitting layer 4 and the electron transport layer 5 in the case of the layer structure of the organic EL element shown in FIG. In the case of the organic EL element layer configuration shown in FIG. 2, any of the hole transport layer 3, the light emitting layer 4, and the electron transport layer 5 can function, and the organic layer shown in FIG. In the case of the layer configuration of the EL element, both can act as the hole transport layer 3 and the light emitting layer 4, and in the case of the layer configuration of the organic EL element shown in FIG. can do.

  In the case of the layer structure of the organic EL element shown in FIGS. 1 to 4, the transparent insulator substrate 1 is preferably transparent in order to extract emitted light, and glass, plastic film, etc. are used, but are not limited thereto. . Further, the transparent electrode 2 is preferably transparent to extract emitted light in the same manner as the transparent insulator substrate, and preferably has a high work function for injecting holes. Indium tin oxide (ITO), tin oxide (NESA) ), Oxide films such as indium oxide and zinc oxide, and vapor deposited or sputtered gold, platinum, palladium and the like are used, but not limited thereto.

  In the case of the layer structure of the organic EL element shown in FIGS. 1 and 2, the electron transport layer 5 is formed from an electron transport material imparted with a function (electron transport ability) according to the purpose. As such an electron transporting material, an oxadiazole derivative, a nitro-substituted fluorenone derivative, a diphenoquinone derivative, a thiopyrandioxide derivative, a fluorenylidenemethane derivative, and the like are preferable. Preferable specific examples include the following exemplary compounds (VII-1) to (VII-3), but are not limited thereto. Moreover, you may combine with several electron transport material instead of single.

  In the case of the layer configuration of the organic EL element shown in FIGS. 2 and 3, the hole transport layer 3 is composed of a hole transport material provided with a function (hole transport ability) according to the purpose. Examples of such hole transporting materials include tetraphenylenediamine derivatives, triphenylamine derivatives, carbazole derivatives, stilbene derivatives, aryl hydrazone derivatives, porphyrin compounds, and the like, as exemplified by the following exemplified compounds (VIII-1) to ( VIII-9), but is not limited thereto. Moreover, you may combine not with single but with several hole transportable material. Here, n and x represent an integer of 1 or more.

In the case of the layer structure of the organic EL element shown in FIGS. 1 to 4, the light emitting layer 4 and the light emitting layer 6 having charge transporting ability contain at least one non-conjugated polymer.
In the present invention, the light emitting layer 4 is a positive electrode for adjusting the hole mobility with respect to the non-conjugated polymer used in the present invention for the purpose of improving the durability of the organic electroluminescent device or improving the light emitting efficiency. The hole transport material may be mixed and dispersed in the range of 0.1% by mass to 50% by mass. In addition, the light emitting layer 6 having a charge transporting ability is formed by mixing and dispersing a hole transporting material for adjusting hole mobility in a range of 0.1 mass% to 50 mass%. Examples of such hole transporting materials include tetraphenylenediamine derivatives, triphenylamine derivatives, carbazole derivatives, stilbene derivatives, aryl hydrazone derivatives, and porphyrin compounds, but have good compatibility with the nonconjugated polymer. Therefore, a tetraphenylenediamine derivative and a triphenylamine derivative are preferable.

In addition, the light emitting layer 4 has an electron transporting material for adjusting the electron mobility of the non-conjugated polymer used in the present invention as a similar object when the hole transporting material is mixed and dispersed. It may be formed by mixing and dispersing in the range of 1% by mass to 50% by mass. The light emitting layer 6 having charge transporting ability is formed by mixing and dispersing an electron transporting material for adjusting electron mobility in a range of 0.1 mass% to 50 mass%. Examples of such electron transport materials include oxadiazole derivatives, nitro-substituted fluorenone derivatives, diphenoquinone derivatives, thiopyran dioxide oxide derivatives, fluorenylidenemethane derivatives, and the like.
In addition, when both the hole mobility and the electron mobility need to be adjusted, both the hole transport material and the electron transport material may be mixed together in the non-conjugated polymer.

In addition, the light emitting layer 4 and the light emitting layer 6 having charge transporting ability may be doped with a different dye compound as a guest material for improving the light emission intensity, adjusting the color purity, and the light emission spectrum. The dye compound to be doped may be an organic low molecule or an organic polymer.
Preferable examples when the dye compound to be doped is a low-molecular-weight organic compound include chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, coumarin derivatives, styrylarylene derivatives, silole derivatives, oxazole derivatives, oxathiazoles Preferable examples in the case where the derivative, the oxadiazole derivative, or the like is a polymer include polyparaphenylene derivatives, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyacetylene derivatives, and the like. As preferred specific examples, the following compounds (IX-1) to (IX-17) are used, but are not limited thereto.

  In Structural Formulas (IX-1) to (IX-17), n and x represent an integer of 1 or more, and y represents 0 or 1. In Structural Formulas (IX-16) and (IX-17), Ar represents a substituted or unsubstituted monovalent or divalent aromatic group. In Structural Formula (IX-17), X represents substituted or unsubstituted. Represents a substituted divalent aromatic group.

  Actually, doping is performed by mixing in a non-conjugated polymer solution or dispersion. The doping ratio of the dye compound in the light emitting layer is about 0.001% by mass to 40% by mass, preferably about 0.01% by mass to 10% by mass. As the coloring compound used for such doping, an organic compound that is compatible with the light emitting material and does not interfere with the formation of a good thin film of the light emitting layer is used, preferably a DCM derivative, a quinacridone derivative, a rubrene derivative. And porphyrin-based compounds. As preferred specific examples, the following compounds (X-1) to (X-4) are used, but are not limited thereto.

In the case of the layer structure of the organic EL element shown in FIGS. 1 to 4, the back electrode 7 is made of a metal that can be vacuum-deposited and has a low work function for performing electron injection. Silver, indium and alloys thereof, metal halide compounds such as lithium fluoride and lithium oxide, and metal oxides. Further, a protective layer may be provided on the back electrode 7 in order to prevent the element from being deteriorated by moisture or oxygen.
Specific examples of the protective layer material include metals such as In, Sn, Pb, Au, Cu, Ag, and Al, metal oxides such as MgO, SiO ₂ , and TiO ₂ , polyethylene resins, polyurea resins, and polyimide resins. Resin. For forming the protective layer, a vacuum deposition method, a sputtering method, a plasma polymerization method, a CVD method, or a coating method can be applied.

  The organic electroluminescent elements shown in FIGS. 1 to 4 are manufactured by sequentially forming individual layers on the transparent electrode 2 according to the layer structure of each organic electroluminescent element. Note that the hole transport layer and / or hole injection layer 3, the light-emitting layer 4, the electron transport layer and / or the electron injection layer 5, or the light-emitting layer 6 having a charge transport function is obtained by using the above-described materials by vacuum deposition, Or it melt | dissolves or disperses | distributes in a suitable organic solvent, and it forms with the spin coating method, the casting method, the dip method etc. on the said transparent electrode using the obtained coating liquid.

In the manufacturing method of the organic electroluminescent element of this invention, it is preferable to have at least the application | coating process which apply | coats the coating liquid for organic compound layers by the inkjet method. That is, an image forming technique based on ink jet recording that is used in an ink jet printer can be used to form an organic compound layer.
In the case of using the inkjet method, the organic compound layer coating liquid is used instead of the ink, and the droplet-shaped organic compound layer coating liquid is ejected from the nozzle of the droplet ejection head, thereby obtaining a desired position on the substrate. In addition, an organic compound layer having a desired film thickness and shape can be formed.
In addition, as a droplet discharge head, the same basic configuration and principle as those of a recording head used in an ink jet printer can be used. That is, by applying an external stimulus such as pressure or heat to the organic compound layer coating liquid, a method of discharging the organic compound layer coating liquid from a nozzle in a droplet form (piezo ink jet method using a piezoelectric element, heat A thermal ink jet method using a boiling phenomenon) can be used.

However, in the production of the organic electroluminescent device of the present invention, the external stimulus is more preferably pressure than heat. When the external stimulus is heat, the inkjet printing process involves the formation (solidification) of a coating film by discharging the organic compound layer coating liquid from the nozzle and volatilizing the solvent of the organic compound layer coating liquid that has landed on the substrate. In this case, since the viscosity of the coating solution for organic compound layer is largely changed by heat, it may be difficult to control the leveling property and patterning accuracy.
Moreover, as an apparatus used for manufacturing the organic electroluminescent element of the present invention using the inkjet method, in addition to the above-described liquid droplet ejection head, for example, an organic electroluminescent element is formed as necessary. A fixing or conveying means for the substrate or the like, or a droplet discharge head scanning means for scanning the droplet discharge head with respect to the substrate plane direction may be provided.

The composition and properties of the organic compound layer coating solution are not particularly limited, but the viscosity of the organic compound layer coating solution is preferably within a range of 0.01 to 1000 cps at 25 ° C. , Preferably in the range of 1-100 cps.
When the viscosity is less than 0.01 cps, the coating solution for the organic compound layer that has landed on the substrate tends to spread in the plane direction of the substrate, making it difficult to control the film thickness, and patterning accuracy may deteriorate. . Moreover, when the viscosity exceeds 1000 cps, the viscosity of the organic compound layer coating solution is too high, and it may be liable to cause ejection failure.

  The viscosity of the coating solution for the organic compound layer is controlled by controlling the content of the non-conjugated polymer, the content of other additive components added as necessary, the molecular weight of the non-conjugated polymer, etc. It can be adjusted to a desired value.

  The film thicknesses of the hole transport layer and / or hole injection layer 3, the light-emitting layer 4, the electron transport layer and / or the electron injection layer 5, and the light-emitting layer 6 having a charge transport function are each 10 μm or less, particularly A range of 0.001 to 5 μm is preferred. The dispersion state of each of the above materials (non-conjugated polymer, light emitting material, etc.) may be a molecular dispersion state or a fine particle state such as a microcrystal. In the case of a film forming method using a coating solution, it is necessary to select a dispersion solvent in consideration of the dispersibility and solubility of each material in order to obtain a molecular dispersion state. In order to disperse into fine particles, a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer, an ultrasonic method, or the like can be used.

  Finally, in the case of the organic electroluminescence device shown in FIGS. 1 and 2, the back electrode 7 is formed on the electron transport layer and / or the electron injection layer 5 by vacuum deposition, sputtering, or the like. The organic electroluminescent element of the present invention is completed. In the case of the organic electroluminescent element shown in FIG. 3, the back electrode 7 is provided on the light emitting layer 4, and in the case of the organic electroluminescent element shown in FIG. 4, on the light emitting layer 6 having a charge transport function. By forming the back electrode 7 by a vacuum deposition method, a sputtering method or the like, the organic electroluminescence device of the present invention is completed.

The organic EL device of the present invention can emit light by applying a DC voltage of ^{2 to} 20 V and a current density of 1 to 200 mA / cm ² between a pair of electrodes.

The image display medium of the present invention is characterized in that the organic electroluminescent elements of the present invention are arranged in a matrix form and / or a segment form.
In the present invention, when the organic electroluminescent elements are arranged in a matrix, only the electrodes may be arranged in a matrix, or both the electrodes and the organic compound layer may be arranged in a matrix. . In the present invention, when organic electroluminescent elements are arranged in segments, only the electrodes may be arranged in segments, or both electrodes and organic compound layers may be arranged in segments. Also good.
A matrix-like or segment-like organic compound layer can be easily formed by using the ink jet method described above.
A conventionally known device can be used as a driving device and a driving method for the matrix organic electroluminescent device and the segment organic electroluminescent device.

Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.
First, the non-conjugated polymer used in the examples was synthesized as follows, for example.
(Synthesis Example 1)
Monomer structure [44] having dicarboxylic acid [44] Compound 0.08 g and phosphor 586 having monocarboxylic acid 0.05 g ethylene glycol 8.0 ml and tetrabutoxy titanium 0.02 g were placed in a 50 ml three-necked eggplant flask, and nitrogen was added. The mixture was heated and stirred at 210 ° C. for 8 hours under an air stream. Thereafter, the pressure was reduced to 0.5 mmHg and the mixture was heated to 200 ° C. while distilling off ethylene glycol, and the reaction was continued for 4 hours. Thereafter, the mixture was cooled to room temperature, dissolved in 50 ml of monochlorobenzene, insoluble matter was filtered through a 0.5 μm PTFE filter, and the filtrate was dropped into 500 ml of stirring methanol to precipitate a polymer. The obtained polymer was filtered, thoroughly washed with methanol, and dried to obtain 0.9 g of a polymer [Compound 15].

(Synthesis Example 2)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the monomer structure [88] compound having a dicarboxylic acid and the phosphor 585 having a monocarboxylic acid were used in Synthesis Example 1 to obtain 0.8 g of a polymer [Compound 25]. It was.

(Synthesis Example 3)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the monomer structure [176] compound having a dicarboxylic acid and the phosphor 585 having a monocarboxylic acid were used in Synthesis Example 1 to obtain 0.8 g of a polymer [Compound 35]. It was.

(Synthesis Example 4)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the monomer structure [207] compound having a dicarboxylic acid and the phosphor 586 having a monocarboxylic acid were used in Synthesis Example 1. Thus, 0.8 g of a polymer [Compound 41] was obtained. It was.

(Synthesis Example 5)
The monomer structure [44] compound having two hydroxyalkyl groups [1.0] and the phosphor 586 having one hydroxyalkyl group were reduced to 0.5 mmHg and heated to 200 ° C., and the reaction was continued for 6 hours. Thereafter, the mixture was cooled to room temperature, dissolved in 50 ml of monochlorobenzene, insoluble matter was filtered through a 0.5 μm PTFE filter, and the filtrate was dropped into 500 ml of stirring methanol to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with methanol, and then dried to obtain 0.8 g of a polymer [Compound 88].

(Synthesis Example 6)
Synthesis was performed in the same manner as in Synthesis Example 5 except that the monomer structure [176] compound having two hydroxyalkyl groups and the phosphor 585 having one hydroxyalkyl group were used. Compound 100] was obtained.

(Synthesis Example 7)
In Synthesis Example 5, the compound was synthesized in the same manner as in Synthesis Example 5 except that the monomer structure [207] compound having two hydroxyalkyl groups and the phosphor 600 having one hydroxyalkyl group were used. Compound 105] was obtained.

(Synthesis Example 8)
Synthesis was performed in the same manner as in Synthesis Example 5 except that the monomer structure [285] compound having two hydroxyalkyl groups and the phosphor 586 having one hydroxyalkyl group were used. Compound 115] was obtained.

(Synthesis Example 9)
Monomer structure having diisocyanate [44] 1.0 g of compound and 0.05 g of phosphor 586 having one hydroxyalkyl were placed in 10 ml of hexadiol and 0.05 g of dibutyltin dilaurate in a 100 ml three-necked eggplant flask, and nitrogen was added. The mixture was heated and stirred at 180 ° C. for 8 hours under an air stream. Thereafter, the mixture was cooled to room temperature, dissolved in 50 ml of monochlorobenzene, insoluble matter was filtered through a 0.5 μm PTFE filter, and the filtrate was dropped into 500 ml of stirring methanol to precipitate a polymer. The obtained polymer was filtered, washed thoroughly with methanol, and then dried to obtain 0.6 g of a polymer [Compound 158].

Example 1
ITO (manufactured by Sanyo Vacuum Co., Ltd.) formed on the transparent insulating substrate was patterned by photolithography using a strip-shaped photomask and further etched to form a strip-shaped ITO electrode (width 2 mm). Next, the ITO glass substrate was washed with neutral detergent, pure water, acetone (for electronics industry, manufactured by Kanto Chemical) and isopropanol (for electronics industry, manufactured by Kanto Chemical) for 5 minutes each, and then spinned. It was dried with a coater. Thereafter, ultraviolet ozone cleaning was performed. A non-conjugated polymer [Exemplary Compound (15)] as a light emitting layer is prepared on a 5% by mass chlorobenzene solution on the substrate, filtered through a 0.5 μm PTFE filter, and then 0.100 μm thick by a spin coater method. A thin film was formed. After fully drying, use a metallic mask with strip-shaped holes, and finally install this mask. The back surface is 2 mm wide with LiF 0.005 μm and Al 0.15 μm thick. The electrode was formed so as to cross the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Example 2)
Using a solution prepared by preparing a 10% by mass chlorobenzene solution containing 1 part by mass of a non-conjugated polymer [Exemplary Compound (25)] and 4 parts by mass of poly (N-vinylcarbazole), and filtering with a 0.5 μm PTFE filter. In the same manner as in Example 1, a thin film having a thickness of about 0.110 μm was formed by a spin coater method on a glass substrate on which a 2 mm wide strip-type ITO electrode was formed by etching. After sufficiently drying, a back electrode having a width of 2 mm, Ca of 0.04 μm and Al of 0.15 μm was formed so as to cross the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Example 3)
A non-conjugated polymer [Exemplary Compound (35)] having a thickness of 0.050 μm was formed on the ITO glass substrate etched and washed in the same manner as in Example 1 as a hole transporting layer and a light emitting layer in the same manner as in Example 1. As the electron transport layer, the exemplary compound (VII-1) having a thickness of 0.030 μm was formed. Subsequently, a back electrode having a width of 2 mm and a thickness of LiF of 0.005 μm and Al of 0.15 μm was formed so as to intersect the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

Example 4
An organic electroluminescent device was produced in the same manner as in Example 1 except that the exemplified compound (41) was used instead of the exemplified compound (15) used in Example 1.

(Example 5)
An organic electroluminescent device was produced in the same manner as in Example 2 except that the exemplified compound (88) was used instead of the exemplified compound (25) used in Example 2.

(Example 6)
An organic electroluminescent device was produced in the same manner as in Example 3 except that the exemplified compound (100) was used instead of the exemplified compound (35) used in Example 3.

(Example 7)
An organic electroluminescent device was produced in the same manner as in Example 3, except that the exemplified compound (105) was used instead of the exemplified compound (35) used in Example 3.

(Example 8)
An organic electroluminescent device was produced in the same manner as in Example 3 except that the exemplified compound (115) was used instead of the exemplified compound (35) used in Example 3.

Example 9
An organic electroluminescent device was produced in the same manner as in Example 3 except that the exemplified compound (158) was used instead of the exemplified compound (35) used in Example 3.

(Comparative Example 1)
A dichloroethane solution containing 2% by mass of iridium (III) tris (2-phenylpyridine) complex as a luminescent material in polyvinyl carbazole (PVK) with respect to PVK was prepared and filtered through a 0.5 μm PTFE filter. Using this solution, an organic compound layer having a film thickness of 0.1 μm was formed on a glass substrate on which a 2 mm-wide strip-shaped ITO electrode was formed by etching, and was sufficiently dried. Thereafter, a back electrode having a width of 2 mm and a thickness of LiF of 0.005 μm and Al of 0.15 μm was formed so as to intersect the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Comparative Example 2)
In polyvinyl carbazole (PVK), iridium (III) tris (2-phenylpyridine) complex as a light emitting material is 2% by mass with respect to PVK, and the compound (VII-1) is 30% by mass with respect to PVK as an electron transporting material. After mixing, a 10% by mass dichloroethane solution was prepared and filtered through a 0.5 μm PTFE filter. Using this solution, an organic compound layer having a film thickness of 0.1 μm was formed on a glass substrate on which a 2 mm-wide strip-shaped ITO electrode was formed by etching, and was sufficiently dried. Thereafter, a back electrode having a width of 2 mm and a thickness of LiF of 0.005 μm and Al of 0.15 μm was formed so as to intersect the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

The organic EL device manufactured as described above is bonded to a glass sealing plate with epoxy resin under dry nitrogen, and then DC driving is performed by applying a DC voltage with the ITO electrode side plus and the Al back electrode minus at room temperature. Light was emitted by the method (DC drive). At this time, the drive current density was adjusted so that the initial luminance was 800 cd / m ² . Table 55 shows the drive current density of each organic EL element.
Next, the time (drive time) required for the luminance of each organic EL element to be half of the initial luminance was measured. Table 55 shows the relative value of the driving time of each organic EL element when the driving time of the organic EL element of Comparative Example 1 is 1.0. Table 55 shows values V / V ₀ obtained by dividing the applied voltage (V) when the luminance of each EL element is half of the initial luminance by the initial applied voltage (V ₀ ).

It is the schematic block diagram which showed an example of the laminated constitution of the organic electroluminescent element of this invention. It is the schematic block diagram which showed an example of the laminated constitution of the organic electroluminescent element of this invention. It is the schematic block diagram which showed an example of the laminated constitution of the organic electroluminescent element of this invention. It is the schematic block diagram which showed an example of the laminated constitution of the organic electroluminescent element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent insulator board | substrate 2 Transparent electrode 3 Hole transport layer and / or hole injection layer 4 Light emitting layer 5 Electron transport layer and / or electron injection layer 6 Light emitting layer 7 with charge transport ability Back electrode

Claims (17)

In an organic electroluminescent element composed of one or more organic compound layers sandwiched between a pair of electrodes at least one of which is transparent or translucent,
Organic electroluminescence characterized in that at least one of the organic compound layers contains at least one non-conjugated polymer, and at least one terminal group of the non-conjugated polymer has a phosphorescent emitter. element.   The organic electroluminescent element according to claim 1, wherein the non-conjugated polymer is at least one selected from the group consisting of polyester, polyether, and polyurethane.   The organic electroluminescent device according to claim 1, wherein the non-conjugated polymer is a hole transporting polymer.   2. The organic electroluminescent device according to claim 1, wherein the non-conjugated polymer is a polymer having both hole transport properties and electron transport properties. The non-conjugated polymer is a polymer comprising a repeating unit containing at least one selected from the structures represented by the following general formulas (I-1) and (I-2) as a partial structure. The organic electroluminescent element according to any one of claims 1 to 4.

(In the general formulas (I-1) and (I-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted, Represents a monovalent condensed aromatic hydrocarbon having 2 to 10 unsubstituted aromatic rings or a substituted or unsubstituted monovalent aromatic heterocyclic ring, and X represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted aromatic Represents a divalent polynuclear aromatic hydrocarbon having 2 to 10 rings, a substituted or unsubstituted divalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, or a substituted or unsubstituted divalent aromatic heterocyclic ring , T represents a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k, i, j are each independently 0 or 1 Represents.)   The organic compound layer is composed of at least a light emitting layer, an electron transport layer and / or an electron injection layer, and at least the light emitting layer contains at least one kind of the non-conjugated polymer. Item 2. The organic electroluminescent device according to Item 1.   The organic compound layer includes at least a hole transport layer and / or a hole injection layer, a light emitting layer, an electron transport layer and / or an electron injection layer, and at least the light emitting layer includes the non-conjugated polymer. The organic electroluminescent element according to claim 1, comprising at least one kind.   The organic compound layer is composed of at least a hole transport layer and / or a hole injection layer and a light emitting layer, and at least the light emitting layer contains at least one kind of the non-conjugated polymer. The organic electroluminescent element according to claim 1.   2. The organic electric field according to claim 1, wherein the organic compound layer is composed of only one light emitting layer having charge transporting ability, and the light emitting layer contains at least one kind of the non-conjugated polymer. Light emitting element. A non-conjugated polymer comprising a repeating unit containing at least one selected from the structures represented by the general formulas (I-1) and (I-2) as a partial structure is represented by the following general formula (II-1) or The organic electroluminescent element according to claim 5, which is a polyester represented by (II-2).

(In General Formulas (II-1) and (II-2), A ₁ represents at least one selected from the structures represented by General Formulas (I-1) and (I-2), and Y ₁ represents 2 Z ₁ represents a divalent carboxylic acid residue, m represents an integer of 1 to 5, and p represents an integer of 5 to 5000. A non-conjugated polymer composed of a repeating unit containing at least one selected from the structures represented by the general formulas (I-1) and (I-2) as a partial structure is represented by the following general formula (III-1). The organic electroluminescent device according to claim 5, wherein the organic electroluminescent device is a polyether as shown.

(In General Formula (III-1), A ₁ represents at least one selected from the structures represented by General Formulas (I-1) and (I-2), and p represents an integer of 5 to 5,000. To express.) A non-conjugated polymer composed of a repeating unit containing at least one selected from the structures represented by the general formulas (I-1) and (I-2) as a partial structure is represented by the following general formula (IV-1) or The organic electroluminescent element according to claim 5, which is a polyurethane represented by (IV-2).

(In Formulas (IV-1) and (IV-2), _{A 1} is the general formula (I-1) and (represents at least one selected from structures represented by I-2), p is 5 to It represents 5,000 integer, _{Y 2} and _{Z 2} each represents a divalent isocyanate, alcohol, or an amine residue.)   2. The organic electroluminescent element according to claim 1, wherein the phosphorescent emitter is an organic compound.   The organic electroluminescent element according to claim 13, wherein the organic compound is an organometallic complex.   The organic electroluminescent element according to claim 14, wherein the metal contained in the organometallic complex is iridium or platinum. A method for producing an organic electroluminescent element according to any one of claims 1 to 15,
The manufacturing method of the organic electroluminescent element which has an application | coating process which apply | coats the coating liquid for organic compound layers which dissolved the structural component of the said organic compound layer in the solvent by the inkjet method.   An image display medium comprising the organic electroluminescent elements according to any one of claims 1 to 15 arranged in a matrix and / or a segment.

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