JP2006348287A - High-boiling composition and polymeric light-emitting device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-boiling composition so as to be uniform in film thickness when put to film formation, and to provide a polymeric light-emitting device using the composition. <P>SOLUTION: The high-boiling composition comprises two or more organic compounds each ≥100°C in boiling point and one or more polymers with charge transporting tendency or light-emitting tendency in a solid state, wherein at least one of the organic compounds is selected from aliphatic or alicyclic compounds each of which is ≥200°C in boiling point and may have heteroatom(s). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a high-boiling composition and a polymer light-emitting device using the same (hereinafter sometimes referred to as polymer LED).

Various light-emitting elements (polymer LEDs) using a polymer as a light-emitting material have been studied.
As a method for forming a light-emitting layer of a polymer LED, a method of forming a light-emitting element having a large area at a low cost has an advantage that a method of forming a light-emitting element using a solution composition containing a polymer and a solvent by an ink-jet method.

As a solution composition applicable to such an ink jet method, for example, a solution composition containing a polyfluorene derivative and a solvent (Patent Document 1), a solution composition containing a polyarylene vinylene and a solvent (Patent Document 2). It has been known. However, none of the documents describes the use of an aliphatic compound or alicyclic compound having a boiling point of 200 ° C. or higher.
WO00 / 59267 pamphlet WO02 / 96970 brochure

  By the way, when forming a thin film using the composition, there is a problem that the film thickness at the time of film formation is not uniform in a composition containing only a low-boiling solvent or a solvent having a high solubility of a polymer compound. When the film was formed using this method, the non-uniformity of the film thickness was remarkable. Therefore, there has been a demand for a composition that makes the film thickness uniform during film formation.

  As a result of diligent studies to solve the above problems, the present inventors include two or more organic compounds having a boiling point of 100 ° C. or higher, and at least one of the organic compounds is a solvent having a boiling point of 200 ° C. or higher. The present invention has been completed by finding that the film thickness is uniform by performing film formation using a composition containing a solvent in which the solubility of the polymer compound is not so good.

  That is, the present invention is a composition comprising two or more kinds of organic compounds having a boiling point of 100 ° C. or more and one or more kinds of polymers having a charge transporting property or a light emitting property in a solid state, and at least one of the organic compounds. The above composition characterized in that the kind is an organic compound selected from an aliphatic compound optionally having a heteroatom having a boiling point of 200 ° C. or higher or an alicyclic compound optionally having a heteroatom. Is to provide things

  The composition of the present invention has a feature that the film thickness becomes uniform during film formation.

  The composition of the present invention contains one or more aliphatic compounds or alicyclic compounds having a boiling point of 200 ° C. or higher.

  The aliphatic compound having a boiling point of 200 ° C. or higher contained in the composition of the present invention may have a hetero atom, and is an aliphatic hydrocarbon compound, aliphatic alcohol compound, aliphatic glycol compound, aliphatic ester. System compounds, aliphatic compounds containing a nitrogen atom, and aliphatic compounds containing a sulfur atom.

  Examples of the aliphatic hydrocarbon compound include n-dodecane (boiling point 216 ° C.), n-tridecane (boiling point 234 ° C.), n-tetradecane (boiling point 252 to 254 ° C.), and the like.

  Examples of the aliphatic alcohol compounds include 1-nonanol (boiling point 211 ° C.), n-decanol (boiling point 231 ° C.), 2-decanol (boiling point 211 ° C.), n-undecanol (boiling point 241 ° C.), isodecanol (boiling point 220 ° C.). , N-tetradecanol (boiling point 289 ° C.) and the like.

  Aliphatic glycol compounds include diethylene glycol (boiling point 244 ° C.), triethylene glycol (boiling point 287 ° C.), triethylene glycol dimethyl ether (boiling point 216 ° C.), tetraethylene glycol dimethyl ether (boiling point 275 ° C.), ethylene glycol mono-2- Ethyl hexyl ether (boiling point 229 ° C), ethylene glycol monobutyl ether (boiling point 231 ° C), ethylene glycol monohexyl ether (boiling point 208 ° C), ethylene glycol monobenzyl ether (boiling point 256 ° C), dipropylene glycol (boiling point 232 ° C), tri Propylene glycol (boiling point 268 ° C.), 1,3-butanediol (boiling point 208 ° C.), 1,4-butanediol (boiling point 228 ° C.), neopentyl glycol (boiling point 211 ° C.), 1, - pentanediol (boiling point 238~239 ℃), etc. 1,6-hexanediol (boiling point 250 ° C.) and the like.

  Examples of the aliphatic ester compounds include n-octyl acetate (boiling point 208 ° C.), diethyl succinate (boiling point 218 ° C.), and the like.

  Examples of the aliphatic compound containing a nitrogen atom include acetamide (boiling point 222 ° C.).

  Examples of the aliphatic compound containing a sulfur atom include thiodiglycol (boiling point 283 ° C.).

  The aliphatic compound is preferably an aliphatic hydrocarbon compound, an aliphatic alcohol compound, an aliphatic glycol compound, or an aliphatic ester compound from the viewpoint of film-forming properties, and is preferably an aliphatic hydrocarbon compound or an aliphatic alcohol compound. Compounds are more preferred.

  The alicyclic compound having a boiling point of 200 ° C. or higher contained in the composition of the present invention may have a hetero atom, and an alicyclic hydrocarbon compound, an alicyclic ketone compound, an alicyclic lactone compound, an alicyclic ring. Examples thereof include a carbonate compound, an alicyclic compound containing a nitrogen atom, and an alicyclic compound containing a sulfur atom. Examples of the alicyclic hydrocarbon compound include bicyclohexyl (boiling point: 226 to 228 ° C.). Examples of the alicyclic ketone compound include 2- (1-cyclohexenyl) cyclohexanone (boiling point 265 ° C.) and isophorone (boiling point 215 ° C.). Examples of the alicyclic lactone compound include γ-butyrolactone (boiling point 203 to 204 ° C.), δ-valerolactone (boiling point 218 to 220 ° C.), and the like. Examples of the aliphatic carbonate compound include propylene carbonate (boiling point 242 ° C.). Examples of the alicyclic compound containing a nitrogen atom include N-methylpyrrolidone (boiling point 202 ° C.) and 2-pyrrolidone (boiling point 245 ° C.). Examples of the alicyclic compound containing a sulfur atom include sulfolane (boiling point 287 ° C.). From the viewpoint of film formability, a compound containing only carbon, hydrogen, and oxygen atoms is preferable, and bicyclohexyl and 2- (1-cyclohexenyl) cyclohexanone are more preferable.

  The composition of the present invention may include one or more aliphatic compounds or alicyclic compounds having a boiling point of 200 ° C. or higher, but preferably includes 1 to 3 types, and includes 1 to 2 types for ease of production. It is more preferable.

  The aliphatic compound or alicyclic compound having a boiling point of 200 ° C. or higher contained in the composition of the present invention preferably has a boiling point of 220 ° C. or higher from the viewpoint of film uniformity.

  The weight of the aliphatic compound or alicyclic compound having a boiling point of 200 ° C. or higher contained in the composition of the present invention is 30 wt.% With respect to the weight of the composition from the viewpoints of dissolution and viscosity of the polymer, film formability, etc. % Or more is preferable, and 40 wt% or more is more preferable.

The composition of the present invention contains at least one organic compound having a boiling point of 100 ° C. or higher in addition to the aliphatic compound or alicyclic compound having a boiling point of 200 ° C. or higher.
Examples of the organic compound having a boiling point of 100 ° C. or more include aliphatic hydrocarbon compounds, aliphatic alcohol compounds, aliphatic ether compounds, aliphatic glycol compounds, aliphatic ester compounds, aliphatic aldehyde compounds, aliphatic ketones. Compound, aliphatic carboxyl compound, aliphatic compound containing nitrogen atom, aliphatic compound containing sulfur atom, alicyclic compound, alicyclic compound having hetero atom, aromatic hydrocarbon compound, aromatic alcohol compound , Aromatic ester compounds, aromatic aldehyde compounds, aromatic carboxyl compounds and the like. In the present invention, aromatic ether compounds are excluded from organic compounds having a boiling point of 100 ° C. or higher.

  As the aliphatic hydrocarbon compound, in addition to the aforementioned aliphatic compound having a boiling point of 200 ° C. or higher, n-octane (boiling point 126 ° C.), nonane (boiling point 151 ° C.), n-decane (boiling point 174 ° C.), n- And undecane (boiling point 196 ° C.).

  Examples of the aliphatic alcohol compound include 1-butanol (boiling point 116 to 118 ° C.), 1-pentanol (boiling point 136 to 138 ° C.), 2-pentanol, in addition to the above-described aliphatic compound having a boiling point of 200 ° C. or higher. (Boiling point 118-119 ° C), 1-hexanol (boiling point 157 ° C), 2-hexanol (boiling point 136 ° C), 1-heptanol (boiling point 176 ° C), 2-heptanol (boiling point 160-162 ° C), 1-octanol ( Boiling point 196 ° C), 2-octanol (boiling point 174 to 181 ° C), 2-nonanol (boiling point 193 to 194 ° C), and the like.

  Examples of the aliphatic ether compound include dibutyl ether (boiling point: 137 to 143 ° C.).

  Examples of the aliphatic glycol compounds include ethylene glycol (boiling point 197 ° C.), ethylene glycol monoethyl ether (boiling point 135 ° C.), ethylene glycol diethyl ether (boiling point 124 ° C.), in addition to the above-described aliphatic compounds having a boiling point of 200 ° C. or higher. ), Ethylene glycol monomethyl ether (boiling point 124 ° C.), propylene glycol (boiling point 187 ° C.), propylene glycol monoethyl ether, propylene glycol monomethyl ether (boiling point 119 to 122 ° C.), hexylene glycol (boiling point 198 ° C.) and the like. .

  Examples of the aliphatic ester compounds include n-butyl formate (boiling point 107 ° C.), allyl acetate (boiling point 103 to 104 ° C.), n-butyl acetate (boiling point 120), in addition to the above-described aliphatic compounds having a boiling point of 200 ° C. or higher. -125 ° C), dimethyl succinate (boiling point 195 ° C), diethyl oxalate (boiling point 185 ° C), dimethyl oxalate (boiling point 134-137 ° C), methyl lactate (boiling point 145 ° C), ethyl lactate (boiling point 154 ° C), Examples include methyl pyruvate (boiling point 165 ° C.), ethyl pyruvate (boiling point 156 ° C.), dimethyl malonate (boiling point 181 ° C.), diethyl malonate (boiling point 198 to 199 ° C.).

  Examples of the aliphatic aldehyde compound include furfural (boiling point 161 ° C.).

  Examples of the aliphatic ketone compounds include methyl isobutyl ketone (boiling point 118 ° C.), diisopropyl ketone (boiling point 124 ° C.), diisobutyl ketone (boiling point 163 to 173 ° C.), and the like.

  Examples of the aliphatic carboxyl compounds include formic acid (boiling point 101 ° C.), acetic acid (boiling point 117 to 118 ° C.), propionic acid (boiling point 141 ° C.), and the like.

  Examples of the aliphatic compound containing a nitrogen atom include N, N-dimethylacetamide (boiling point 165 to 166 ° C.), N, N-dimethylformamide (boiling point 153 ° C.) in addition to the above-described aliphatic compound having a boiling point of 200 ° C. or higher. N, N-diisopropylethylamine (boiling point: 127 ° C.) and the like.

  Examples of the aliphatic compound containing a sulfur atom include dimethyl sulfoxide (boiling point 189 ° C.) in addition to the above-described aliphatic compound having a boiling point of 200 ° C. or higher.

  Examples of the alicyclic compound include methylcyclohexane (boiling point 101 ° C.), dimethylcyclohexane (boiling point 120 to 129 ° C.), ethylcyclohexane (boiling point 132 ° C.), cyclohexane, in addition to the above-described alicyclic compound having a boiling point of 200 ° C. or higher. Examples include heptane (boiling point 116 to 118 ° C.) and decalin (boiling point 187 to 195 ° C.).

  Examples of the alicyclic compound having a hetero atom include cyclopentanol (boiling point 139 to 140 ° C.), cyclohexanol (boiling point 160 to 161 ° C.), methylcyclohexane, in addition to the above-described alicyclic compound having a boiling point of 200 ° C. or higher. Hexanol (boiling point 171 to 173 ° C), dimethylcyclohexanol (boiling point 186 ° C), cyclohexenol (boiling point 164 to 166 ° C), cyclohexylmethanol (boiling point 181 ° C), tetrahydrofurfuryl alcohol (boiling point 178 ° C), furfuryl alcohol (Boiling point 170 to 171 ° C), cyclopentanone (boiling point 130 to 131 ° C), cyclohexanone (boiling point 155 ° C), dioxane (boiling point 102 ° C), methylcyclohexanone (boiling point 162 to 171 ° C), and the like. Among the alicyclic compounds having a hetero atom, cyclopentanol, cyclohexanol, methylcyclohexanol, dimethylcyclohexanol, cyclopentanone, and cyclohexanone are preferable from the viewpoint of film formability and the like.

  Aromatic hydrocarbon compounds include toluene (boiling point 111 ° C.), o-xylene (boiling point 143 to 145 ° C.), p-xylene (boiling point 138 ° C.), m-xylene (boiling point 138 to 139 ° C.), mesitylene (162 to 164 ° C), 1,2,4-trimethylbenzene (boiling point 168 ° C), ethylbenzene (boiling point 136 ° C), o-diethylbenzene (boiling point 183 to 184 ° C), m-diethylbenzene (boiling point 181 ° C), p-diethylbenzene (boiling point) 184 ° C), o-ethylmethylbenzene (boiling point 164 to 165 ° C), p-ethylmethylbenzene (boiling point 162 ° C), m-ethylmethylbenzene (boiling point 161 ° C), n-propylbenzene (boiling point 159 ° C), isopropyl Benzene (boiling point 153 ° C), n-butylbenzene (boiling point 183 ° C), s-butylbenzene (boiling point) 73 ° C), isobutylbenzene (boiling point 173 ° C), t-butylbenzene (boiling point 169 ° C), n-pentylbenzene (boiling point 205 ° C), n-hexylbenzene (boiling point 226-227 ° C), n-heptylbenzene (boiling point) 233 ° C.), n-octyl benzene (boiling point 261-263 ° C.), n-nonalbenzene (boiling point 282 ° C.), n-decylbenzene (boiling point 293 ° C.), 1,3-di-isopropylbenzene (boiling point 205 ° C.) 1,4-di-isopropylbenzene (boiling point 205 ° C.), cyclohexylbenzene (boiling point 239 to 240 ° C.), tetralin (boiling point 207 ° C.), biphenyl (boiling point 255 ° C.) and the like.

  Examples of aromatic alcohol compounds include phenol (boiling point 182 ° C), o-cresol (boiling point 190 to 195 ° C), o-ethylphenol (boiling point 195 to 197 ° C), m-cresol (boiling point 202 ° C), p-cresol. (Boiling point 202 ° C), p-ethylphenol (boiling point 218-219 ° C), 4-methoxyphenol (boiling point 246 ° C), on-propylphenol (boiling point 214 ° C), o-isopropylphenol (boiling point 215 ° C), os-butylphenol (boiling point 226-228 ° C), ot-butylphenol (boiling point 224 ° C), mt-butylphenol (boiling point 240 ° C), pt-butylphenol (boiling point 237-239 ° C), benzyl alcohol (Boiling point 206 ° C.).

  Examples of aromatic ester compounds include methyl benzoate (boiling point 199 ° C.), ethyl benzoate (boiling point 212 ° C.), and n-butyl benzoate (boiling point 250 ° C.).

Examples of aromatic aldehyde compounds include benzaldehyde (boiling point 178 ° C.).
Examples of aromatic carboxyl compounds include benzoic acid (boiling point 249 ° C.) and phenylacetic acid (boiling point 266 ° C.).

  Among organic compounds having a boiling point of 100 ° C. or higher, from the viewpoint of film-forming properties, aliphatic hydrocarbon compounds, aliphatic alcohol compounds, aliphatic ester compounds, aliphatic ketone compounds, alicyclic compounds, heterocycles An alicyclic compound having an atom, an aromatic hydrocarbon compound, an aromatic alcohol compound, and an aromatic ester compound are preferred.

  When the composition of the present invention contains an aromatic compound (excluding an aromatic ether compound), the boiling point is preferably 250 ° C. or lower, more preferably 220 ° C. or lower, from the viewpoint of film uniformity. Moreover, it is preferable that a boiling point is lower than the aliphatic compound or alicyclic compound which is 200 degreeC or more in boiling point contained in a composition.

  The composition of the present invention is characterized by containing two or more organic compounds having a boiling point of 100 ° C. or higher. From the viewpoint of viscosity, the boiling point is preferably 120 ° C. or higher, and 150 ° C. or higher. Is more preferable, and it is more preferable that it is 170 degreeC or more.

  The composition of the present invention may contain a compound other than an organic compound having a boiling point of 100 ° C. or higher (excluding an aromatic ether compound). Specific examples include compounds having a boiling point of less than 100 ° C. The content of these compounds is preferably 20 wt% or less, more preferably 10 wt% or less, and even more preferably 1 wt% or less based on the weight of the composition of the present invention.

  The composition of the present invention may be liquid or solid, but is preferably liquid at 50 ° C., more preferably liquid at 40 ° C., and liquid at 25 ° C. from the viewpoint of ease of film formation. More preferably. Further, from the viewpoint of storage stability, it is preferable that the solid content does not precipitate at 20 ° C., it is more preferable that the solid content does not precipitate at 10 ° C., and it is more preferable that the solid content does not precipitate at 0 ° C.

  From the viewpoint of storage stability, the aliphatic compound or alicyclic compound having a boiling point of 200 ° C. or higher contained in the composition of the present invention preferably has a melting point of 25 ° C. or lower, and preferably 20 ° C. or lower. More preferably, it is 10 degrees C or less.

The number average molecular weight of the polymer used in the composition of the present invention is preferably 1.0 × 10 ^{3 to} 1.0 × 10 ⁷ from the viewpoint of solubility, viscosity, film formability, etc. It is more preferable that it is * 10 < ³ > -1.0 * 10 < ⁶ >, and it is further more preferable that it is 1.0 * 10 < ⁴ > -2.0 * 10 < ⁵ >.

The weight average molecular weight of the polymer used in the composition of the present invention is preferably 1.0 × 10 ^{3 to} 1.0 × 10 ⁷ from the viewpoint of solubility, viscosity, film formability, etc. It is more preferable that it is * 10 < ⁴ > -2.0 * 10 < ⁶ >, and it is still more preferable that it is 5.0 * 10 < ⁴ > -1.0 * 10 < ⁶ >.

  The weight of the polymer used in the composition of the present invention is more preferably 0.1 to 5 wt% with respect to the weight of the composition from the viewpoint of solubility, viscosity, film production cost, and the like. More preferably, it is ˜2 wt%.

  The viscosity at 25 ° C. of the composition of the present invention is preferably 1 to 20 mPa · s from the viewpoint of film formability and the like.

  The polymer used in the composition of the present invention is not particularly limited as long as it is a charge transporting polymer or a solid light-emitting polymer. A charge transporting polymer is a polymer that transports negative charges (electrons) or positive charges (holes), and may transport both electrons and holes. In order to examine the transport of electric charge, for example, there are a technique of measuring using cyclic voltammetry, a technique of producing and examining an element, and a widely known technique can be used. Electrons and holes may recombine in the charge transporting polymer to emit electroluminescence. Examples of the light-emitting polymer in the solid state include a polymer that emits fluorescence in the solid state and a polymer that emits phosphorescence in the solid state. A polymer that emits light in the solid state may transport charge or emit electroluminescence.

  The thin film produced using the composition of the present invention can be applied to various uses. Polymer electroluminescence, organic transistor, polymer capacitor, secondary battery, solar battery, sensor, thermoelectric conversion element, capacitor, actuator, antistatic agent, gas separation membrane, electromagnetic shield, laser, electrophotographic photoreceptor, organic superconductor The polymer contained in the composition can be appropriately selected depending on the application.

  For polymer LED applications, a light-emitting layer, an electron transport layer, and a hole transport layer can be produced using the composition of the present invention.

  When a light emitting layer is produced using the composition of the present invention, the polymer contained in the composition is an arylene group, a divalent heterocyclic group, a divalent group having a metal complex structure or a divalent fragrance as a repeating unit. It preferably contains at least one group amine group.

As long as the light-emitting property is not impaired, in addition to the above-mentioned repeating units, in the polymer, -CR _a1 = CR _a2- , -C≡C-, -N (R _a3 )-, or (SiR _a4 R _a5 ) _b- You may have the structure shown by these. R _a1 and R _a2 each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R _a3 , R _a4 and R _a5 each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a group containing a substituted amino group. b shows the integer of 1-12. When there are a plurality of R _a1 , R _a2 , R _a3 , R _a4 and R _a5 , they may be the same or different.

Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and those having a condensed ring, two or more independent benzene rings or condensed rings are directly or via a group such as vinylene. Are also included. The arylene group may have a substituent. The type of the substituent is not particularly limited, but from the viewpoint of solubility, fluorescence characteristics, ease of synthesis, characteristics in the case of an element, etc., an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, Arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, Amide groups, acid imide groups, monovalent heterocyclic groups, carboxyl groups, substituted carboxyl groups, and cyano groups are preferred.
Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.
Examples of the arylene group include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (the following formulas 4 to 13), an anthracene-diyl group (the following formulas 14 to 19), and a biphenyl-diyl group (the following formulas 20 to 25). ), Fluorene-diyl group (formula 36-38), terphenyl-diyl group (formula 26-28), condensed ring compound group (formula 29-35), stilbene-diyl (formula AD), Examples include distilbene-diyl (formulas E and F) and indenonaphthalene-diyl (formulas GN).

The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and the group may have a substituent.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable. The type of the substituent is not particularly limited, but from the viewpoint of solubility, fluorescence characteristics, ease of synthesis, characteristics in the case of an element, etc., an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, Arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, Amide groups, acid imide groups, monovalent heterocyclic groups, carboxyl groups, substituted carboxyl groups, and cyano groups are preferred.
Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formula 39 to 44), diazaphenylene group (formula 45 to 48), quinoline diyl group (formula 49 to 63), quinoxalinediyl Groups (formulas 64 to 68), acridinediyl groups (formulas 69 to 72), bipyridyldiyl groups (formulas 73 to 75), phenanthroline diyl groups (formulas 76 to 78),
Groups having a fluorene structure containing oxygen, silicon, nitrogen, selenium, sulfur and the like as heteroatoms (the following formulas 79 to 93),
5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, boron, phosphorus, etc. as a hetero atom (the following formulas 94 to 98, O to Z, AA to AC),
5-membered ring condensed heterocyclic groups containing oxygen, silicon, nitrogen, selenium and the like as a hetero atom (the following formulas 99 to 110),
A 5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, bonded at the α-position of the heteroatom to form a dimer or oligomer (the following formulas 111 to 112), hetero A 5-membered heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as an atom, and a group bonded to the phenyl group at the α-position of the heteroatom (the following formulas 113 to 119);
Groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur or the like as a hetero atom (the following formulas 120 to 125);
A 6-membered heterocyclic group containing oxygen, nitrogen and the like as a hetero atom (the following formulas AD to AG).

The divalent group having a metal complex structure is a remaining divalent group obtained by removing two hydrogen atoms from an organic ligand of a metal complex having an organic ligand.
The organic ligand usually has about 4 to 60 carbon atoms. Examples thereof include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, and 2-phenyl-benzo. Examples include thiazole and derivatives thereof, 2-phenyl-benzoxazole and derivatives thereof, porphyrin and derivatives thereof.
Examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.

Specific examples of the divalent group having a metal complex structure include the following (126 to 132).

  In the above formulas 1-132, A-Z, AA-AG, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group. Group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent A heterocyclic group, a carboxyl group, a substituted carboxyl group, a nitro group or a cyano group. Moreover, the carbon atom which the group of Formula 1-132 has may be substituted with the nitrogen atom, the oxygen atom, or the sulfur atom, and the hydrogen atom may be substituted with the fluorine atom. Moreover, adjacent Rs may combine to form a ring.

  Here, the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, and propyl group. Group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3, 7 -Dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, etc., solubility in organic solvents, device characteristics, synthesis From the standpoint of ease and heat resistance, pentyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group Group, decyl group, 3,7-dimethyl octyl group are preferable.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propyloxy group, Isopropyloxy group, butoxy group, isobutoxy 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, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, etc. , Solubility in organic solvents, device characteristics, Easiness standpoint and from the balance between heat resistance such as a, a pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl group, decyloxy group, 3,7-dimethyl octyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, and isopropyl. Thio group, butylthio group, isobutylthio 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, trifluoromethylthio group and the like. From the viewpoint of solubility in organic solvents, device characteristics, ease of synthesis and heat resistance, pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, 3,7-dimethyloctyl Thio group is preferred.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon and having a condensed ring, two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene. Also included. The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl group and a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ have 1 to indicates a 12. the same applies is less.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group, penta A fluorophenyl group and the like are exemplified, and from the viewpoints of solubility in an organic solvent, device characteristics, easiness of synthesis, etc., a C _{1 to} C ₁₂ alkoxyphenyl group and a C _{1 to} C ₁₂ alkylphenyl group are preferable. Specific examples C ₁ -C ₁₂ alkoxy, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ specifically alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, t -Butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like are exemplified.

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include phenoxy group, C _{1 to} C ₁₂ alkoxyphenoxy group, C _{1 to} C ₁₂ alkylphenoxy group, 1 - naphthyloxy group, 2-naphthyloxy group, are exemplified such as pentafluorophenyl group is, solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxy phenoxy group , C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples C ₁ -C ₁₂ alkoxy, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenoxy such as methyl phenoxy groups as group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butylphenoxy Group, isobutylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group and the like.

Arylthio group has a carbon number of usually about 3 to 60, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2 - naphthylthio groups are exemplified such as pentafluorophenyl thio group, solubility in organic solvents, device properties, in terms of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl thio group, C ₁ -C ₁₂ An alkylphenylthio group is preferred.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenyl-C ₁ -C ₁₂ alkyl group and a 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 groups and the like, organic solvents From the viewpoints of solubility in water, device characteristics, easiness of synthesis, etc., C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group Is preferred.

The arylalkoxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenylmethoxy group, a phenylethoxy group, a phenylbutoxy group, a phenylpentyloxy group, and a phenylhexyloxy group. group, phenyl heptene Ciro alkoxy group, a phenyl -C ₁ -C ₁₂ alkoxy groups such as phenyl Ok Ciro 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, are exemplified 2-naphthyl -C ₁ -C ₁₂ alkoxy group, solubility in organic solvents, device properties, synthesis easiness from the point of view, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group preferably .

The arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkylthio group and a C ₁ -C ₁₂ alkoxyphenyl-C _1. -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio groups and the like, From the viewpoint of solubility in organic solvent, device characteristics, easiness of synthesis, etc., C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ Alkylthio groups are preferred.

Arylalkenyl group has a carbon number of usually about 8 to 60, and examples thereof include phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkenyl group, 1-naphthyl-C ₂ -C ₁₂ alkenyl group, 2-naphthyl-C ₂ -C ₁₂ alkenyl group, etc., and solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, a C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl group are preferred.

Arylalkynyl group has a carbon number of usually about 8 to 60, and examples thereof include phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, solubility in organic solvents, device From the viewpoints of characteristics, easiness of synthesis, etc., a C _{1 to} C ₁₂ alkoxyphenyl-C _{2 to} C ₁₂ alkynyl group and a C _{1 to} C ₁₂ alkylphenyl-C _{2 to} C ₁₂ alkynyl group are preferable.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted amino group is usually about 1 to 60, preferably 2 to 48, not including the carbon number of the substituent.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, t-butylamino group Pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxy phenylamino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group , pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkylamino groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl - C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-isopropylsilylsilyl group, diethyl-isopropylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group Hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, Examples thereof include a dimethylphenylsilyl group.

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

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group. Group, pentafluorobenzoyl group and the like.

  The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group. Group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

As the imine residue, an imine compound (refers to an organic compound having —N═C— in the molecule. For example, aldimine, ketimine, and hydrogen atoms on these N are substituted with alkyl groups or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas.

  The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, penta Examples include a fluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzamide group, and the like.

Examples of the acid imide group include residues obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, having about 4 to 20 carbon atoms, and specific examples include the groups shown below. The

The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and silicon in the ring. Say things. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

  Examples of the substituted carboxyl group include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the number of carbons is usually about 2 to 60, preferably 2 to 48. . Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxy Carbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl Group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbo group Group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, and the like. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

（式中、Ａｒ₁、Ａｒ₂、Ａｒ₃及びＡｒ₄はそれぞれ独立に、アリーレン基又は２価の複素環基を表す。Ａｒ₅、Ａｒ₆及びＡｒ₇はそれぞれ独立に、アリール基、又は１価の複素環基を表す。Ａｒ₁〜Ａｒ₇は置換基を有していてもよい。ｘ及びｙはそれぞれ独立に、０又は正の整数を表す。置換基の種類は特には限定されないが、溶解性、蛍光特性、合成の行いやすさ、素子にした場合の特性等の観点から、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、ニトロ基、シアノ基が好ましい。） The divalent aromatic amine group refers to the remaining atomic group obtained by removing two hydrogen atoms from an aromatic amine compound, and the group may have a substituent. The specific structure of the divalent aromatic amine group includes the structure of the following formula (1).

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group or a divalent heterocyclic group. Ar ₅ , Ar ₆ and Ar ₇ each independently represent an aryl group or 1 Represents a valent heterocyclic group, Ar _{1 to} Ar ₇ may have a substituent, x and y each independently represents 0 or a positive integer, and the type of the substituent is not particularly limited; In view of solubility, fluorescence characteristics, ease of synthesis, characteristics in the case of an element, etc., alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group , Arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, Amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, nitro group and cyano group are preferred.)

Examples of the divalent aromatic amine group include those represented by the following (formulas 133 to 140).

In the above formula, R is the same as that in formulas 1-132.
In order to increase the solubility in an organic solvent, it is preferable to have at least one other than a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit including a substituent is small.

  In the above formula, in the substituent in which R contains alkyl, it is preferable that one or more alkyls having a cyclic or branched structure are contained in order to enhance the solubility of the polymer compound in an organic solvent. Furthermore, in the above formula, when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents. Among the structures represented by the above formulas 133 to 140, the structures represented by the above formula 134 and the above formula 137 are preferable from the viewpoint of adjusting the emission wavelength.

In the repeating unit represented by the above formula (1), Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are each independently an arylene group from the viewpoint of adjusting the emission wavelength, device characteristics and the like, and Ar ₅ , Ar It is preferable that ₆ and Ar ₇ each independently represent an aryl group.

Ar ₁ , Ar ₂ , and Ar ₃ are preferably each independently an unsubstituted phenylene group, an unsubstituted biphenyl group, an unsubstituted naphthylene group, or an unsubstituted anthracenediyl group.

Ar ₅ , Ar ₆ and Ar ₇ are each preferably an aryl group having three or more substituents independently from the viewpoint of solubility in an organic solvent, device characteristics, and the like. Ar ₅ , Ar ₆ And Ar ₇ is more preferably a phenyl group having 3 or more substituents, a naphthyl group having 3 or more substituents, or an anthranyl group having 3 or more substituents, Ar ₅ , Ar ₆ and Ar ₇ Is more preferably a phenyl group having three or more substituents.

（式中、Ｒe、Ｒf及びＲgは、それぞれ独立に、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、シリルオキシ基、置換シリルオキシ基、１価の複素環基又はハロゲン原子を表す。Ｒe、Ｒf及びＲgに含まれる水素原子はフッ素原子に置換されていてもよい。） Among them, Ar ₅ , Ar ₆ and Ar ₇ are each independently represented by the following formula (9) and preferably x + y ≦ 3, more preferably x + y = 1, and even more preferably x = 1. , Y = 0.

(Wherein, Re, Rf and Rg each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, An arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group, or a halogen atom, and a hydrogen atom contained in Re, Rf, and Rg is a fluorine atom May be substituted.)

  More preferably, in the above formula (9), Re and Rf are each independently an alkyl group having 3 or less carbon atoms, an alkoxy group having 3 or less carbon atoms, or an alkylthio group having 3 or less carbon atoms, and Rg is 3 carbon atoms. Examples thereof include an alkyl group having ˜20, an alkoxy group having 3 to 20 carbon atoms, and an alkylthio group having 3 to 20 carbon atoms.

（ここで、(９−１)、(９−２)で示される構造に含まれるベンゼン環は、それぞれ独立に１個以上４個以下の置換基を有していてもよい。それら置換基は、互いに同一であっても、異なっていてもよい。また、複数の置換基が連結して環を形成していてもよい。さらに、該ベンゼン環に隣接して他の芳香族炭化水素環又は複素環が結合していてもよい。） In the repeating unit represented by the formula (9), Ar ₂ is preferably the following formula (9-1) or (9-2).

(Here, the benzene rings contained in the structures represented by (9-1) and (9-2) may each independently have 1 or more and 4 or less substituents. May be the same or different from each other, and a plurality of substituents may be linked to form a ring, and another aromatic hydrocarbon ring adjacent to the benzene ring or Heterocycle may be bonded.)

As the repeating unit represented by the formula (1), particularly preferred specific examples include those represented by the following (formulas 141 to 142).

（式中、Ａ環及びＢ環はそれぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表し、２つの結合手はそれぞれＡ環及び／又はＢ環上に存在し、Ｒ₁及びＲ₂はそれぞれ独立に置換基を表す。） Preferred polymers for forming the light emitting layer of the polymer LED are represented by the above formula (1) and the following formulas (2) to (8) from the viewpoints of device characteristics, ease of synthesis, fluorescence intensity, and the like. And a polymer containing any of the repeating units.

(In the formula, A ring and B ring each independently represent an aromatic hydrocarbon ring which may have a substituent, and two bonds are present on A ring and / or B ring, respectively. ₁ and R ₂ each independently represents a substituent.)

（式中、Ａ環及びＢ環は前記と同じ意味を表し、２つの結合手はそれぞれＡ環及び／又はＢ環上に存在し、Ｚは−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）（＝Ｏ）−、−Ｎ（Ｒ₃）−、−Ｓｉ（Ｒ₃）（Ｒ₄）−、−Ｐ（＝Ｏ）（Ｒ₃）−、−Ｐ（Ｒ₃）−、−Ｂ（Ｒ₃）−、−Ｃ（Ｒ₃）（Ｒ₄）−Ｏ−、−Ｃ（Ｒ₃）＝Ｎ−又はＳｅ−を表す。Ｒ
₃及びＲ₄はそれぞれ独立に置換基を表す。）

(In the formula, A ring and B ring have the same meaning as described above, and two bonds are present on A ring and / or B ring, respectively, Z is —O—, —S—, —S (═O ) -, - S (= O ) (= O) -, - N (R 3) -, - Si (R 3) (R 4) -, - P (= O) (R 3) -, - P ( _{R 3) -, - B (} R 3) -, - C (R 3) (R 4) -O -, - .R representing a C (R ₃₎ = N- or Se-
₃ and R ₄ each independently represents a substituent. )

（式中、Ｒ₅は、置換基を表す。ｎは０〜４の整数を表す。Ｒ₅が複数存在する場合、それらは同一でも異なっていてもよい。）

(In the formula, R ₅ represents a substituent. N represents an integer of 0 to 4. When a plurality of R ₅ are present, they may be the same or different.)

（式中、Ｒ₆及びＲ₇は、置換基を表す。o及びpはそれぞれ独立に０〜３の整数を表す。Ｒ₆及びＲ₇がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。）

(In the formula, R ₆ and R ₇ each represent a substituent. O and p each independently represent an integer of 0 to 3. When a plurality of R ₆ and R ₇ are present, they are the same or different. May be good.)

（式中、Ｒ₈、Ｒ₉、Ｒ₁₀及びＲ₁₁は置換基を表す。q及びrはそれぞれ独立に０〜４の整数を表す。Ｒ₈及びＲ₉がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。）

(In the formula, R ₈ , R ₉ , R ₁₀ and R ₁₁ each represent a substituent. Q and r each independently represent an integer of 0 to 4. When a plurality of R ₈ and R ₉ are present, They may be the same or different.)

（式中、Ｒ₁₂は置換基を表す。ｕは０〜２の整数を表す。Ａｒ₈及びＡｒ₉はそれぞれ独立にアリーレン基、２価の複素環基又は金属錯体構造を有する２価の基を表す。ｓ及びｔはそれぞれ独立に０又は１を表す。Ｘ₁は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−ＳＯ₂−、−Ｓｅ−，又はＴｅ−を表す。Ｒ₁₂が複数存在する場合、それらは同一でも異なっていてもよい。）

(In the formula, R ₁₂ represents a substituent. U represents an integer of 0 to 2. Ar ₈ and Ar ₉ are each independently an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure. S and t each independently represent 0 or 1. X ₁ represents —O—, —S—, —S (═O) —, —SO ₂ —, —Se—, or Te—. When a plurality of R ₁₂ are present, they may be the same or different.)

（式中、Ａｒ₁₀及びＡｒ₁₁はそれぞれ独立にアリーレン基、２価の複素環基又は金属錯体構造を有する２価の基を表す。ｖ及びｗはそれぞれ独立に０又は１を表す。Ｘ₂は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）（＝Ｏ）−、−Ｓｅ−，−Ｔｅ−、−ＮＲ₁₄−又はＳｉＲ₁₅Ｒ₁₆−を表す。）

(In the formula, Ar ₁₀ and Ar ₁₁ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. V and w each independently represent 0 or 1. X ₂ Represents —O—, —S—, —S (═O) —, —S (═O) (═O) —, —Se—, —Te—, —NR ₁₄ — or SiR ₁₅ R ₁₆ —. .)

In the above formula (2), specific structures include the following formulas (2-1 to 2-17).

（式中、Ｒ₁及びＲ₂は置換基を表し、溶解性や合成の行いやすさ等の観点から、好ましくは、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、ニトロ基又はシアノ基であり、それぞれ前述の基が例示される。これらの置換基の中でも、アルキル基、アルコキシ基、アリール基、アリールオキシ基が好ましい。また、Ｒ₁とＲ₂がそれぞれ互いに結合して環を形成してもよい。）

(In the formula, R ₁ and R ₂ represent a substituent, and from the viewpoints of solubility and ease of synthesis, preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, Arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, An amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a nitro group or a cyano group, each exemplified by the above-mentioned groups, among these substituents, an alkyl group and an alkoxy group , an aryl group, an aryloxy group. in addition, R ₁ and R ₂ are bonded to each other to form a ring Good.)

（式中、Ｒは、前述のＲが例示されるが、アルキル基、アルコキシ基、アリール基、アリールオキシ基が好ましい。上記式において、図中の複数の水素原子が置換基Ｒで置き換わっていてもよい。Ｒ₃及びＲ₄は置換基を表し、溶解性や合成の行いやすさ等の観点から、好ましくは、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、ニトロ基又はシアノ基であり、それぞれ前述の基が例示される。これらの置換基の中でも、アルキル基、アルコキシ基、アリール基、アリールオキシ基が好ましい。溶解性の観点からは、アルキル基、アルコキシ基、アリール基、アリールオキシ基を１〜３個有することが好ましい。） Examples of the formula (3) include structures represented by the following formulas (3-1 to 3-12).

(In the formula, R is exemplified by the above-mentioned R, but is preferably an alkyl group, an alkoxy group, an aryl group, or an aryloxy group. In the above formula, a plurality of hydrogen atoms in the figure are replaced by a substituent R. R ₃ and R ₄ each represents a substituent, and from the viewpoints of solubility, ease of synthesis, etc., preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group. Group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide Group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, nitro group or cyano group, Among these substituents, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group are preferable, and from the viewpoint of solubility, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group are preferable. It is preferred to have 1 to 3 groups.)

R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R _{16 in the} above formulas (4) to (8) are hydrogen atom, alkyl group, alkoxy group , Alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom , An acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a nitro group, or a cyano group, each of which is exemplified by the aforementioned groups. Among these substituents, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group are preferable. R ₁₀ and R ₁₁ in the above formula (6) are each a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an aryl Alkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group , A substituted carboxyl group, a nitro group, or a cyano group, and the aforementioned groups are exemplified. Among these substituents, a hydrogen atom, an alkyl group, and an aryl group are preferable.

上記式中のＲは、前述のＲが例示されるが、アルキル基、アルコキシ基、アリール基、アリールオキシ基が好ましい。 The following structure is mentioned about said Formula (7).

R in the above formula is exemplified by the above-mentioned R, and is preferably an alkyl group, an alkoxy group, an aryl group, or an aryloxy group.

上記式中のＲは、前述のＲが例示されるが、アルキル基、アルコキシ基、アリール基、アリールオキシ基が好ましい。 As for the formula (8), the following structure is preferable.

R in the above formula is exemplified by the above-mentioned R, and is preferably an alkyl group, an alkoxy group, an aryl group, or an aryloxy group.

  When a hole transport layer of a polymer LED is produced using the composition of the present invention, the polymer contained in the composition is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, an aromatic amine in a side chain or a main chain. Polysiloxane derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, or poly ( 2,5-thienylene vinylene) or a derivative thereof, and a polymer exemplified in the case of producing a light emitting layer are preferably used.

  When an electron transport layer of a polymer LED is produced using the composition of the present invention, the polymer included in the composition is preferably a polymer exemplified in the case of producing a light emitting layer including polyquinoline and polyquinoxaline. It is done.

The polymer used in the composition of the present invention can be produced, for example, by reacting the monomers represented by the general formulas (10) and (11) and the general formulas (12) and / or (13). .
K ₁ -Ar ₁₂ -K ₂ (10)
K ₃ -Ar ₁₃ -K ₄ (11)
K ₅ -L ₁ (12)
K ₆ -L ₂ (13)
(In the formula, Ar ₁₂ and Ar ₁₃ each independently represent an arylene group, a divalent heterocyclic group, a divalent group having a metal complex structure or a divalent aromatic amine group. L ₁ and L ₂ are Each represents a terminal group, and K ₁ , K ₂ , K ₃ , K ₄ , K ₅ and K ₆ each independently represent a leaving group, provided that L ₁ and L ₂ are different from each other.

Examples of the leaving group include a halogen atom, an alkylsulfonyloxy group, an arylsulfonyloxy group, or a group represented by B (OR ₁₇ ) ₂ (wherein R ₁₁ is a hydrogen atom or an alkyl group).

  Here, examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom, a chlorine atom and a bromine atom are preferable, and a bromine atom is most preferable. The alkylsulfonyloxy group may be substituted with a fluorine atom, and examples thereof include a trifluoromethanesulfonyloxy group. The arylsulfonyloxy group may be substituted with an alkyl group, and examples thereof include a phenylsulfonyloxy group and a trisulfonyloxy group.

In the group represented by —B (OR ₁₇ ) ₂ , R ₁₇ is a hydrogen atom or an alkyl group. As an alkyl group, carbon number is about 1-20 normally, and a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group etc. are mentioned. Further, the alkyl groups may be connected to form a ring.

が挙げられ、

が好ましい。 As the group represented by —B (OR ₁₇ ) ₂ , specifically,

Are mentioned,

Is preferred.

  The total amount of monomers charged in general formulas (12) and (13) is generally 0.1 to the total amount of monomers charged in general formulas (10) and (11). It is 10 mol%, 0.2-5 mol% is preferable and 0.5-3 mol% is more preferable.

As a method for producing the polymer used in the present invention, for example, the above-mentioned corresponding monomer is polymerized by Suzuki reaction (Chem. Rev., 95, 2457 (1995)), Polymerization by Grignard reaction (Kyoritsu Shuppan, Polymer Functional Materials Series, Volume 2, Polymer Synthesis and Reaction (2), pages 432-3), Polymerization by Yamamoto Polymerization (Progressive Polymer Science (Prog. Polym) Sci.), 17, 1153-1205, 1992), a method of polymerizing with an oxidizing agent such as FeCl _3, a method of electrochemically oxidatively polymerizing (Maruzen, Experimental Chemistry Course 4th Edition, Volume 28, 339-340 pages).

The case where the Suzuki reaction is used will be described. In this case, for example, K ₁ and K ₂ are each independently a group represented by —B (OR ₁₇ ) ₂ (where R ₁₁ is a hydrogen atom or an alkyl group), and K ₃ and K ₄ are each Independently a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, and K ₅ is a group represented by —B (OR ₁₇ ) ₂ (wherein R ₁₇ is a hydrogen atom or an alkyl group); Monomers in which K ₆ is a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group are reacted in the presence of a Pd (0) catalyst.

In this case, at least one of two or more monomers having two leaving groups used for the reaction is —B (OR ₁₇ ) ₂ (where R ₁₇ is a hydrogen atom or an alkyl group). The reaction that requires a monomer having two halogen atoms, an alkylsulfonyloxy group or an arylsulfonyloxy group is usually represented by the formula (10). And the monomer represented by (11) is reacted for about 1 to 100 hours, and then the monomer (12) is added to the system and reacted for about 0.5 to 50 hours. The body (13) is added to the system and reacted for about 0.5 to 50 hours.

  As the Pd (0) catalyst, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates, etc., inorganic bases such as potassium carbonate, sodium carbonate, barium hydroxide, etc., organic bases such as triethylamine, cesium fluoride, etc. The inorganic salt is added to the monomer in an amount equal to or more than that, preferably 1 to 10 equivalents, and reacted. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

The case where the Yamamoto polymerization method is used will be described. In this case, for example, monomers in which K ₁ , K ₂ , K ₃ , K ₄ , K ₅ and K ₆ are each independently a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group are used. The monomer is reacted in the presence of a Ni (0) complex. The reaction is usually carried out by mixing all the monomers (10) to (13).

Using a Ni (0) complex (zero-valent nickel complex), as a nickel complex, a method in which zero-valent nickel is used as it is, a nickel salt is reacted in the presence of a reducing agent, and zero-valent nickel is generated in the system. There is a method of reacting.
Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, Bis (1,5-cyclooctadiene) nickel (0) is preferred from the viewpoint of versatility and low cost. Moreover, it is preferable from a viewpoint of a yield improvement to add a neutral ligand. Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Nitrogen-containing ligands such as triphenylphosphine, tolylphosphine, tributylphosphine, triphenoxyphosphine, and the like, and nitrogen-containing ligands are preferred in terms of versatility and low cost. 2,2′-bipyridyl is particularly preferable in terms of high reactivity and high yield. In particular, from the viewpoint of improving the yield of the polymer, a system in which 2,2′-bipyridyl is added as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0) is preferable.
In the method of reacting zero-valent nickel in the system, nickel chloride, nickel acetate or the like is used as the nickel salt. As the reducing agent, zinc, sodium hydride, hydrazine and derivatives thereof, lithium aluminum hydride, and the like are used. As the additive, ammonium iodide, lithium iodide, potassium iodide, and the like are used as necessary. The polymerization solvent is not particularly limited as long as it does not inhibit the polymerization, but preferably contains one or more aromatic hydrocarbon solvents and / or ether solvents. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, butylbenzene, naphthalene, and tetralin, and toluene, xylene, tetralin, and tetramethylbenzene are preferable. Examples of the ether solvent include diisopropyl ether, tetrahydrofuran, 1,4-dioxane, diphenyl ether, ethylene glycol dimethyl ether, tert-butyl methyl ether, and the like. 4-dioxane and the like are preferable. Of the solvents, tetrahydrofuran is most preferred. In addition, from the viewpoint of improving the polymerizability and solubility, the solvent may be an aromatic hydrocarbon solvent and / or an ether solvent, an aromatic hydrocarbon solvent and an ether solvent as long as it does not inhibit the polymerization reaction. A mixed solvent with a solvent other than the above may be used.

  Reaction operation etc. can be performed according to the method as described in Unexamined-Japanese-Patent No. 2000-44544, for example. In the Yamamoto polymerization method, for example, the polymerization reaction is usually performed in an inert gas atmosphere such as argon or nitrogen, in a tetrahydrofuran solvent at a temperature of 60 ° C., in the presence of a zero-valent nickel complex or a neutral ligand. Is called. The polymerization time is usually about 0.5 to 100 hours, but is preferably within 10 hours from the viewpoint of production cost. The polymerization temperature is usually about 0 to 200 ° C, but 20 to 100 ° C is preferable from the viewpoint of high yield and low heating cost.

  Moreover, when using a neutral ligand, the usage-amount is preferable about 0.5-10 mol with respect to 1 mol of zerovalent nickel complexes from the point of reaction yield and cost. 8-1.5 mol is more preferable, and 0.9-1.1 mol is still more preferable.

  The amount of the zero-valent nickel complex is not particularly limited as long as it does not inhibit the polymerization reaction, but if the amount used is too small, the molecular weight tends to be low, and if it is too large, the post-treatment is complicated. Tend to be. Therefore, 0.1-10 mol is preferable with respect to 1 mol of monomers, 1-5 mol is more preferable, and 2-3.5 mol is more preferable.

  When a polymer is used as a light emitting material for polymer LED, it is preferable to polymerize after purifying the monomer before polymerization by distillation, sublimation purification, recrystallization, etc., and after synthesis, reprecipitation purification, fractionation by chromatography Or the like.

  The polymer contained in the composition of the present invention may be one type or two or more types. When two or more kinds of polymers are included, a polymer that does not transport charges or a polymer that does not emit light in a solid state may be included.

  Regarding the storage stability of the composition of the present invention, the viscosity change after 30 days from the preparation is preferably within ± 5% of the viscosity at the time of preparation, and the viscosity change after 90 days from the preparation is prepared. More preferably within ± 5% of the viscosity at the time.

  As a method for producing a thin film from the composition of the present invention, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method Further, film forming methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet method can be used. Among these methods, the composition of the present invention is particularly suitable for forming a film using an inkjet method.

  The ink jet method is a method in which a polymer is dissolved in a solvent and the solution is discharged by an ink jet apparatus or the like. When preparing a solution, an additive and a dopant may be included. The advantage is that it can be used in different colors and can be used effectively with little material loss.

  The optimum thickness of the thin film varies depending on the material used and the application, but is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  The composition of the present invention is characterized in that a thin film having a uniform thickness is formed when a film is formed. When used as a light emitting layer of a polymer LED, light emission unevenness is small if the film thickness is uniform, and the luminance half-life is prolonged when it is made into an element. Here, as the uniformity of the film, it is preferable that the central part of the film has a flat shape. Even if the shape of the film is slightly convex or concave, there is little problem with light emission and there is no problem. On the other hand, a thin film having a large degree of concave shape has a large unevenness in light emission, and the luminance half-life is shortened when it is formed into an element. Various methods are known for measuring the shape of a thin film. For example, a liquid composition is taken into a syringe, a high-definition needle is attached, discharged onto a glass substrate, dried, and then used with an interference microscope. There is a technique for measuring the shape of a dried and thin film. As a drying method, drying may be performed at room temperature or a temperature may be applied, and may be performed at normal pressure or reduced pressure.

The shape of the thin film can be determined visually, but can also be determined from the ratio of the film thickness of the thickest part to the film thickness of the central part of the film. That is,
The value of (thickness of the thickest part) / (film thickness of the central part of the film) is preferably 1.50 or less, more preferably 1.35 or less, from the viewpoint of reducing unevenness in light emission. .20 or less is further preferable, 1.10 or less is more preferable, and 1.05 or less is more preferable.

  The polymer LED of the present invention has a light-emitting layer between electrodes composed of an anode and a cathode, and the light-emitting layer is produced using the composition of the present invention. The polymer LED of the present invention includes a polymer light-emitting device in which a layer containing a conductive polymer is provided adjacent to the electrode between at least one electrode and the light-emitting layer. Also included is a polymer light emitting device in which an insulating layer having an average film thickness of 2 nm or less is provided adjacent to the electrode.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.

Specific examples of the structure of the polymer LED of the present invention include the following structures a) to d).
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

  Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. It is. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin insulating layer may be inserted at the interface between the charge transport layer and the light emitting layer. The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned. For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / electron transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having an ionization potential of a value, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ or less, and the leakage current between the light emitting pixels is reduced. In order to achieve this, 10 ⁻⁵ S / cm to 10 ² is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ is more preferable.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm. Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ or less, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like. The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon .

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  As the film thickness of the light emitting layer, the optimum value varies depending on the material to be used, and it may be selected so that the drive voltage and the light emission efficiency are appropriate values. For example, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm-200 nm.

  The light emitting layer can also be produced using the composition of the present invention.

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain. , Pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thieni Lembinylene) or a derivative thereof is exemplified.

  Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Polymeric hole transport materials such as polythiophene or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof are preferred, more preferably polyvinyl carbazole or derivatives thereof, Polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of polysilane or derivatives thereof include compounds described in Chem. Rev., 89, 1359 (1989), and GB 2300196 published specification. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include those used in the solution composition of the present invention.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an ink jet method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  A positive hole transport layer can also be produced using the composition of the present invention.

  When the polymer LED of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its Derivatives, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or Examples thereof include polyfluorene or a derivative thereof.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  Although there is no particular limitation on the method for forming the electron transport layer, in the case of a low molecular electron transport material, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is used. Each method is exemplified by film formation from a molten state. When forming a film from a solution or a molten state, a polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an ink jet method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

  The film thickness of the electron transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  The electron transport layer can also be produced using the composition of the present invention.

  The substrate on which the polymer LED of the present invention is formed may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

  Usually, it is preferable that at least one of the electrode composed of the anode and the cathode is transparent or translucent, and the anode side is transparent or translucent. As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used. The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. is there. In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

  As a material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or graphite or graphite intercalation compound Etc. are used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers. The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to stably use the polymer LED for a long period of time, it is preferable to attach a protective layer and / or protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If the space is maintained by using the spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It is easy to suppress damage to the element. Among these, it is preferable to take any one or more measures.

  The polymer light emitting device of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like.

  In order to obtain planar light emission using the polymer LED of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Furthermore, in order to obtain a dot matrix element, both the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymeric fluorescent substances having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  Furthermore, the planar light emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

  Moreover, the pigment | dye layer for lasers, the material for organic solar cells, the organic semiconductor for organic transistors, and the material for electroconductive thin films can be produced using the solution composition of this invention.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Here, the number average molecular weight and the weight average molecular weight are determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation: LC-10Avp (trade name)) in terms of polystyrene, Z average molecular weight, number average molecular weight and weight average molecular weight. Asked. The polymer to be measured was dissolved in tetrahydrofuran so as to have a concentration of about 0.5 wt%, and 50 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (trade name, manufactured by Tosoh) and one TSKgel SuperH2000 (trade name, manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A (trade name)) was used as the detector.
The shape of the thin film is measured by taking 3 mL of the composition into a syringe, attaching a high-definition needle FN-002N (trade name, 20 μm pore size) (manufactured by Musashi Engineering) onto a glass substrate, forming a thin film, After drying under reduced pressure for 10 minutes at room temperature, the shape of the dried thin film was measured using an interference microscope Micromap 557N (trade name, manufactured by Micromap).
Moreover, in the viscosity measurement, it measured using LVDV-II + Pro (brand name) by BROOKFIELD.

Synthesis example 1
<Synthesis of Polymer 1>
In a nitrogen atmosphere, 195.37 g of the following compound A, 239.44 g of the following compound B, and 232.89 g of 2,2′-bipyridyl were dissolved in 46.26 kg of dehydrated tetrahydrofuran, and the temperature was raised to 60 ° C. , Bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } 410.15 g was added and reacted for 5 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25% ammonia water 8.52 kg / methanol 16.88 kg / ion exchanged water 31.98 kg and stirred for 2 hours, and then the deposited precipitate was filtered. And dried under reduced pressure. After drying, the precipitate was dissolved in 16.22 kg of toluene. After dissolution, 830 g of radiolite was added and the insoluble matter was filtered. The obtained filtrate was purified through an alumina column, then the purified solution was added to a mixed solution of ion-exchanged water 13.52 kg / 25% ammonia water 2.04 kg, stirred for 0.5 hour, and then the aqueous layer was removed. . Further, 13.52 kg of ion-exchanged water was added to the organic layer and stirred for 0.5 hour, and then the aqueous layer was removed. A portion of the obtained organic layer was concentrated under reduced pressure, and then the organic layer was poured into 34.18 kg of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer 1) was 234.54 g. The number average molecular weight and weight-average molecular weight in terms of polystyrene were respectively ^{Mn = 1.2x10 4, Mw = 7.7x10} 4.

Example 1
<Production of Composition 1>
A composition 1 was produced by dissolving 0.10 g of the polymer 1 in a mixed solution of 7.0 g of tetralin (boiling point 207 ° C.) and 3.0 g of bicyclohexyl (boiling point 226 to 228 ° C.).

Production Example 1
<Production of Composition 2>
A composition 2 was produced by dissolving 0.10 g of the polymer 1 in a mixed solution of 3.0 g of anisole and 7.0 g of xylene.

Example 2
<Preparation of thin film>
A thin film was prepared using Composition 1 by the above-described method. The shape of the thin film was a shape close to a planar shape as shown in FIG. The value of (thickness of the thickest part) / (film thickness of the central part of the film) was 1.14.

Example 3
<Measurement of viscosity of composition 1>
It was 4.0 mPa * s when the viscosity measurement of the composition 1 was performed.

Comparative Example 1
<Preparation of thin film>
A thin film was prepared using Composition 2 by the above-described method. The shape of the thin film was concave as shown in FIG. The value of (thickness of the thickest part) / (film thickness of the central part of the film) was 2.38.

Measurement example 1
<Measurement of viscosity of composition 2>
It was 1.1 mPa * s when the viscosity measurement of the composition 2 was performed.

Example 4
<Production of Composition 3>
0.10 g of polymer 1 was dissolved in a mixed solution of 3.0 g of tetralin (boiling point 207 ° C.) and 7.0 g of 2- (1-cyclohexenyl) cyclohexanone (boiling point 265 ° C.) to prepare composition 3.

Example 5
<Measurement of viscosity of composition 3>
It was 8.8 mPa * s when the viscosity measurement of the composition 3 was performed.

Example 6
<Production of Composition 4>
0.10 g of the polymer 1 was dissolved in a mixed solution of 3.0 g of methyl benzoate (boiling point 199 ° C.) and 7.0 g of bicyclohexyl (boiling point 226 to 228 ° C.) to prepare a composition 4.

Example 7
<Measurement of viscosity of composition 4>
When the viscosity of the composition 4 was measured, it was 3.6 mPa · s.

Example 8
<Fluorescence characteristic evaluation of composition 4>
The composition 4 was spin-coated on a quartz plate to prepare a polymer compound thin film. The fluorescence spectrum of this thin film was measured using a fluorescence spectrophotometer (Fluorolog (trade name) manufactured by JOBINYVON-SPEX) at an excitation wavelength of 350 nm.
Composition 4 had a fluorescence peak wavelength of 464 nm.

The shape of a film formed using the composition 1 is shown. The horizontal axis represents the distance (μm) of the thin film, and the vertical axis represents the film thickness (μm) of the thin film. The shape of the film | membrane formed into a film using the composition 2 is shown. The horizontal axis represents the distance (μm) of the thin film, and the vertical axis represents the film thickness (μm) of the thin film.

Claims (19)

  A composition comprising two or more kinds of organic compounds having a boiling point of 100 ° C. or more and one or more kinds of polymers that are charge-transporting or light-emitting in a solid state, wherein at least one of the organic compounds has a boiling point The said composition characterized by being the organic compound chosen from the aliphatic compound which may have a hetero atom which is 200 degreeC or more, or the alicyclic compound which may have a hetero atom.   The composition according to claim 1, wherein the organic compound selected from an aliphatic compound or an alicyclic compound having a boiling point of 200 ° C or higher has a melting point of 25 ° C or lower.   The composition according to claim 1 or 2, wherein the alicyclic compound contains a carbon 6-membered ring structure.   The composition according to any one of claims 1 to 3, wherein the weight of the aliphatic compound or alicyclic compound having a boiling point of 200 ° C or higher is 30 wt% or more with respect to the total weight of the composition. The composition according to any one of claims 1 to 4, wherein the polymer has a weight-average molecular weight in terms of polystyrene of 1.0 x 10 ^{3 to} 5.0 x 10 ⁶ .   The composition according to any one of claims 1 to 5, wherein the weight of the polymer is 0.1 to 5.0 wt% with respect to the weight of the entire composition.   The composition according to claim 1, which has a viscosity of 1 to 20 mPa · s.   The composition according to any one of claims 1 to 7, which does not contain an aromatic ether compound.   A thin film produced using the composition according to any one of claims 1 to 8.   The thin film according to claim 9, wherein the value of (thickness of the thickest part) / (film thickness of the central part of the film) is 1.50 or less.   A composition comprising at least a light-emitting layer between electrodes composed of an anode and a cathode, wherein the light-emitting layer contains one or more kinds of light-emitting polymers in a solid state according to any one of claims 1 to 8. A polymer light-emitting device manufactured by using a polymer.   It has at least a light emitting layer and a hole transport layer between electrodes composed of an anode and a cathode, and the hole transport layer is one kind of the charge transporting polymer according to any one of claims 1 to 8. A polymer light-emitting device manufactured using the above-described composition.   It has at least a light emitting layer and an electron transport layer between electrodes composed of an anode and a cathode, and the electron transport layer contains one or more kinds of charge transporting polymers according to any one of claims 1 to 8. A polymer light-emitting device produced using a composition.   The method for producing a polymer light-emitting device according to claim 11, wherein the polymer light-emitting device is produced using a printing method.   The method for producing a polymer light-emitting device according to claim 11, wherein the polymer light-emitting device is produced using an inkjet method.   A planar light source comprising the polymer light emitting device according to any one of claims 11 to 13.   A segment display device comprising the polymer light-emitting device according to claim 11.   A dot matrix display device comprising the polymer light-emitting device according to claim 11. A liquid crystal display device comprising the polymer light-emitting device according to claim 11 as a backlight.

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