WO2015194429A1 - Solvent for manufacturing organic el elements - Google Patents

Solvent for manufacturing organic el elements Download PDF

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Publication number
WO2015194429A1
WO2015194429A1 PCT/JP2015/066703 JP2015066703W WO2015194429A1 WO 2015194429 A1 WO2015194429 A1 WO 2015194429A1 JP 2015066703 W JP2015066703 W JP 2015066703W WO 2015194429 A1 WO2015194429 A1 WO 2015194429A1
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group
ring
solvent
formula
organic
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PCT/JP2015/066703
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French (fr)
Japanese (ja)
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鈴木陽二
横尾健
赤井泰之
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株式会社ダイセル
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Publication of WO2015194429A1 publication Critical patent/WO2015194429A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources

Definitions

  • the present invention relates to a solvent for producing an organic EL device excellent in solubility of an organic semiconductor material, and a composition for producing an organic EL device comprising the solvent for producing an organic EL device and an organic semiconductor material.
  • Organic electroluminescence (sometimes referred to as “organic EL” in this specification) element is a light emitting device formed of an organic semiconductor material, and emits light by excitons generated by recombination of electrons and holes.
  • a method for forming an organic EL element by applying an organic semiconductor material by ink jet printing, spin coating or the like has attracted attention.
  • the coating method it is possible to easily form a film by applying a coating solution to a substrate and then removing the solvent in the coating solution, so that it is highly productive and energy-saving, and can be easily applied to a large area device. Is excellent.
  • organic semiconductor material used for forming the organic EL element examples include 4,4′-bis (N-carbazolyl) -1,1′-biphenyl (CBP), poly [(9,9-dioctylfluoronyl-2).
  • carbazole biphenyl Since carbazole biphenyl has poor solubility in a solvent, it is not possible to prepare a composition for manufacturing an organic EL device in which an organic semiconductor material is dissolved at a high concentration, and it is difficult to form a thick organic layer. It was.
  • Patent Document 2 describes introducing a solubilization site into an organic semiconductor material
  • Patent Document 3 describes introducing a leaving substituent that imparts solubility to the organic semiconductor material.
  • phase transition and stability decrease occur due to the introduction of the solubilized site.
  • a detachable substituent that imparts solubility is eliminated by heating during dissolution.
  • the object of the present invention is excellent in the solubility of the organic semiconductor material, and by dissolving the organic semiconductor material, a composition for producing an organic EL element for forming an organic EL element by a coating method can be formed. It is in providing the solvent for organic electroluminescent element manufacture.
  • Another object of the present invention is to provide an organic EL device manufacturing composition for forming an organic EL device on a plastic substrate by a coating method by dissolving the organic semiconductor material with excellent solubility of the organic semiconductor material. It is providing the solvent for organic electroluminescent element manufacture which can be formed.
  • Another object of the present invention is to provide a composition for producing an organic EL device capable of forming an organic EL device by a coating method.
  • Another object of the present invention is to provide a composition for producing an organic EL device, which can form an organic EL device on a plastic substrate by a coating method.
  • the following solvent (A) and solvent (B) exhibit high solubility in organic semiconductor materials even at relatively low temperatures, and organic EL containing the solvent.
  • the element manufacturing composition can form an organic EL element by applying a printing method, spin coating method, or the like on a plastic substrate having a lower heat resistance than a glass substrate. It has been found that the material crystallizes by self-organizing action. Furthermore, it discovered that a coating property and a drying property could be improved further if the solvent generally used for an electronic material use was mixed with the said solvent as needed. The present invention has been completed based on these findings.
  • the present invention is a solvent for dissolving an organic semiconductor material, which has the following formula (a): (Wherein R 1 to R 4 are the same or different and are C 1-2 alkyl groups. R 1 and R 4 are bonded to each other to form —N (R 2 ) —C ( ⁇ O) — N (R 3 )-may form a ring) And / or the following formula (b) [Wherein, ring Z represents a ring selected from an aromatic carbocyclic ring, a 5- to 7-membered alicyclic carbocyclic ring, and a 5- to 7-membered heterocyclic ring.
  • R 5 represents an oxo group ( ⁇ O), a thioxy group ( ⁇ S), a —OR a group, a —SR a group, a —O (C ⁇ O) R a group, a —R b O (C ⁇ O) R a group.
  • R a represents a C 1-7 alkyl group, an aryl group, or a group in which the group is bonded via a single bond or a linking group
  • R b represents a C 1-7 alkylene group, an arylene group, or the group described above.
  • R 6 represents a hydrogen atom, a C 1-7 alkyl group, an aryl group, and —OR A group selected from a group (R a is as defined above).
  • R 5 and R 6 may be bonded to each other to form a ring together with the carbon atoms constituting ring Z]
  • the solvent for organic electroluminescent element manufacture containing the solvent (B) represented by these is provided.
  • the solvent (A) is 1,1,3,3-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6.
  • the solvent for producing an organic electroluminescence device which is at least one selected from tetrahydro-2 (1H) pyrimidinone.
  • the solvent (B) may be 2-cyclopentylcyclopentanone, 2-pentylcyclopentanone, 2,3-dihydrobenzofuran, 2,3-dihydro-2-methylbenzofuran, cyclohexyl acetate, 2-methyl
  • the aforementioned is at least one selected from cyclohexyl acetate, 4-t-butylcyclohexyl acetate, 1,2,3,4-tetrahydronaphthalene, 1-oxo-1,2,3,4-tetrahydronaphthalene, and phenylcyclohexane
  • a solvent for producing an organic electroluminescence device is provided.
  • the present invention also provides the organic electroluminescent element manufacturing solvent, wherein the organic semiconductor material is a compound having a structural unit represented by the following formula (1) and / or a compound represented by the following formula (2).
  • the organic semiconductor material is a compound having a structural unit represented by the following formula (1) and / or a compound represented by the following formula (2).
  • Ar 1 may have a substituent, and is a structure selected from an aromatic carbocyclic ring, an aromatic heterocyclic ring, and a ring in which two or more thereof are bonded via a single bond or a linking group.
  • Ar 2 is an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these which may have a substituent, each having a single bond or a linking group.
  • m and n are the same or different and each represents an integer of 1 or more, m Ar 1 and n Ar 2 may be the same or different) (Wherein Ar 3 to Ar 5 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these via a single bond or a linking group.
  • the compound represented by the formula (2) is a compound represented by the following formula (2-1) or a compound represented by the following formula (2-2).
  • a manufacturing solvent is provided.
  • Ar 6 may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these bonded via a single bond or a linking group.
  • a group in which two hydrogen atoms are removed from a structural formula selected from a ring, Ar 7 to Ar 10 are the same or different and may have a substituent, an aromatic carbocycle, an aromatic heterocycle;
  • a group in which one hydrogen atom is removed from a structural formula selected from a ring and a ring in which two or more of these are bonded via a single bond or a linking group is shown.
  • Ar 11 to Ar 13 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these are a single bond or A group obtained by removing two hydrogen atoms from a structural formula selected from a ring bonded through a linking group, Ar 14 to Ar 19 may be the same or different and may have a substituent. A group obtained by removing one hydrogen atom from a structural formula selected from aromatic carbocycles, aromatic heterocycles, and rings in which two or more of these are bonded via a single bond or a linking group)
  • the present invention also provides a compound in which the organic semiconductor material has a structural unit represented by the following formula (1-1), a compound represented by the following formula (2-1-1) to (2-1-5) And the above-mentioned solvent for producing an organic electroluminescence device, which is at least one compound selected from compounds represented by the following formula (2-2-1).
  • the present invention also provides a composition for producing an organic electroluminescence device comprising an organic semiconductor material and the above-mentioned solvent for producing an organic electroluminescence device.
  • the organic semiconductor material is a compound having a structural unit represented by the following formula (1) and / or a compound represented by the following formula (2).
  • Ar 1 may have a substituent, and is a structure selected from an aromatic carbocyclic ring, an aromatic heterocyclic ring, and a ring in which two or more thereof are bonded via a single bond or a linking group.
  • a group in which two hydrogen atoms are removed from the formula, Ar 2 is an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these which may have a substituent, each having a single bond or a linking group.
  • m and n are the same or different and each represents an integer of 1 or more, m Ar 1 and n Ar 2 may be the same or different) (Wherein Ar 3 to Ar 5 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these via a single bond or a linking group.
  • the compound represented by the formula (2) is a compound represented by the following formula (2-1) or a compound represented by the following formula (2-2).
  • a manufacturing composition is provided.
  • Ar 6 may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these bonded via a single bond or a linking group.
  • a group in which two hydrogen atoms are removed from a structural formula selected from a ring, Ar 7 to Ar 10 are the same or different and may have a substituent, an aromatic carbocycle, an aromatic heterocycle;
  • a group in which one hydrogen atom is removed from a structural formula selected from a ring and a ring in which two or more of these are bonded via a single bond or a linking group is shown.
  • Ar 11 to Ar 13 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these are a single bond or A group obtained by removing two hydrogen atoms from a structural formula selected from a ring bonded through a linking group, Ar 14 to Ar 19 may be the same or different and may have a substituent. A group obtained by removing one hydrogen atom from a structural formula selected from aromatic carbocycles, aromatic heterocycles, and rings in which two or more of these are bonded via a single bond or a linking group)
  • the present invention also provides a compound in which the organic semiconductor material has a structural unit represented by the following formula (1-1), a compound represented by the following formula (2-1-1) to (2-1-5) And the above-mentioned composition for producing an organic electroluminescence device, which is at least one compound selected from the compounds represented by the following formula (2-2-1).
  • a solvent for dissolving an organic semiconductor material which comprises a solvent (A) represented by formula (a) and / or a solvent (B) represented by formula (b).
  • the solvent (A) is 1,1,3,3-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-
  • the solvent for producing an organic EL device according to [1] which is at least one selected from 2 (1H) pyrimidinone.
  • the solvent (B) is 2-cyclopentylcyclopentanone, 2-pentylcyclopentanone, 2,3-dihydrobenzofuran, 2,3-dihydro-2-methylbenzofuran, cyclohexyl acetate, 2-methylcyclohexyl acetate, [1] to at least one selected from 4-t-butylcyclohexyl acetate, 1,2,3,4-tetrahydronaphthalene, 1-oxo-1,2,3,4-tetrahydronaphthalene, and phenylcyclohexane [3] The solvent for producing an organic EL device according to any one of [3].
  • a compound in which the organic semiconductor material has a structural unit represented by formula (1-1), compounds represented by formulas (2-1-1) to (2-1-5), and formula (2 -2-1) The composition for producing an organic EL device according to any one of [10] to [12], which is at least one compound selected from the compounds represented by -2-1): [14] The organic EL device according to any one of [10] to [13], wherein the content of the solvent for producing an organic EL device is 50.0 to 99.99% by weight of the total amount of the composition for producing an organic EL device.
  • the solvent for producing an organic EL device of the present invention has high organic semiconductor material solubility even at a relatively low temperature.
  • the composition for organic EL element manufacture of this invention contains the said solvent for organic EL element manufacture, although heat resistance is low compared with a glass substrate, it is a shock-resistant, lightweight and flexible plastic substrate printing method
  • the organic EL element can be directly formed by using a coating method such as spin coating or the like, and a light-weight and flexible display or computer device that is resistant to impact can be formed while greatly reducing costs.
  • the composition for manufacturing an organic EL device of the present invention is applied on a substrate, the organic semiconductor material is crystallized by a self-organizing action, so that an organic semiconductor crystal thin film having high crystallinity is obtained.
  • solvent (A) in the present invention is represented by the above formula (a).
  • R 1 to R 4 are the same or different and are C 1-2 (C 1-2 ) alkyl group. R 1 and R 4 may be bonded to each other to form a ring together with —N (R 2 ) —C ( ⁇ O) —N (R 3 ) — in the formula.
  • the C 1-2 alkyl group in R 1 to R 4 is a methyl group or an ethyl group.
  • Examples of the ring formed by combining R 1 and R 4 together with —N (R 2 ) —C ( ⁇ O) —N (R 3 ) — in the formula include a 2-imidazolidinone ring, 3, Examples include 4,5,6-tetrahydro-2 (1H) pyrimidinone ring.
  • Examples of the solvent (A) in the present invention include 1,1,3,3-tetramethylurea, 1,1,3,3-tetraethylurea, 1,3-dimethyl-2-imidazolidinone, 1,3 -Dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone and the like. These can be used individually by 1 type or in combination of 2 or more types.
  • the solvent for organic EL element production contains the solvent (A) and does not contain the solvent (B) described later
  • the content of the solvent (A) in the total amount of organic EL element production solvent (100% by weight) is, for example, 50% by weight or more (for example, 50 to 100% by weight), preferably 70% by weight or more (for example 70 to 100% by weight), and particularly preferably 80% by weight or more (for example, 80 to 100% by weight), most preferably 90% by weight or more (for example, 90 to 100% by weight).
  • content of a solvent (A) is less than the said range, there exists a tendency for the solubility of an organic-semiconductor material to fall.
  • the solvent (B) in the present invention is a compound containing at least one heteroatom represented by the above formula (b).
  • ring Z represents a ring selected from an aromatic carbocyclic ring, a 5- to 7-membered alicyclic carbocyclic ring, and a 5- to 7-membered heterocyclic ring.
  • the ring examples include an aromatic carbocyclic ring such as a benzene ring; a 5- to 7-membered alicyclic carbocyclic ring (particularly a 5- to 7-membered alkane ring) such as a pentane ring, a hexane ring, and a heptane ring; And 5- to 7-membered heterocycles such as oxolane ring and thiolane ring.
  • aromatic carbocyclic ring such as a benzene ring
  • a 5- to 7-membered alicyclic carbocyclic ring such as a pentane ring, a hexane ring, and a heptane ring
  • 5- to 7-membered heterocycles such as oxolane ring and thiolane ring.
  • R 5 represents an oxo group ( ⁇ O), a thioxy group ( ⁇ S), a —OR a group, a —SR a group, a —O (C ⁇ O) R a group, a —R b O (C ⁇ O) R a group
  • R a represents a C 1-7 alkyl group, an aryl group, or a group in which the group is bonded via a single bond or a linking group
  • R b represents a C 1-7 alkylene group, or An arylene group or a group in which the group is bonded via a single bond or a linking group
  • R 6 represents a group selected from a hydrogen atom, a C 1-7 alkyl group, an aryl group, and an —OR a group (R a is as defined above).
  • Examples of the C 1-7 alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups, and C 3-7 carbon atoms such as cyclopentyl groups.
  • a cycloalkyl group can be mentioned.
  • Examples of the aryl group include a phenyl group.
  • Examples of the C 1-7 alkylene group include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups, 1,2-cyclopentylene groups, , 3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, etc.
  • An alkylene group (including a cycloalkylidene group) and the like can be mentioned.
  • Examples of the arylene group include a phenylene group.
  • linking group examples include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are bonded.
  • Examples of the divalent hydrocarbon group include a linear or branched C 1-18 alkylene group such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group, 2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, etc. And a C 3-18 cycloalkylene group (including a cycloalkylidene group).
  • a linear or branched C 1-18 alkylene group such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group, 2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group
  • substituted or unsubstituted amino group examples include an amino group; a mono- or di (C 1-3 ) alkyl-substituted amino group such as a methylamino group, an ethylamino group, an isopropylamino group, a dimethylamino group, and a diethylamino group. Can be mentioned.
  • Examples of the ring that R 5 and R 6 may be bonded together to form a carbon atom constituting the ring Z include, for example, cyclopentane, cyclohexane, cycloheptane, benzene, methylbenzene, thiophene, methylthiophene, furan, Mention may be made of methylfuran, dihydrofuran, methyldihydrofuran and the like.
  • the weight average molecular weight of the solvent (B) represented by the formula (b) is, for example, about 350 or less, preferably 70 to 250, particularly preferably 80 to 200.
  • Examples of the solvent (B) in the present invention include 2-methylcyclopentanone, 2-methylcyclohexanone, cyclohexylmethyl ether, cyclohexylamine, methoxybenzene, 1,2-dimethoxybenzene, 2,3-dihydrobenzofuran, 2, 3-dihydro-3-methylbenzofuran, 2-cyclopentylcyclopentanone, 2-pentylcyclopentanone, 2,3-dihydro-2-methylbenzofuran, cyclohexyl acetate, 1-methylcyclohexyl acetate, 4-t-butylcyclohexyl acetate 2-methylcyclohexyl acetate, 1,2,3,4-tetrahydronaphthalene, 1-oxo-1,2,3,4-tetrahydronaphthalene, phenylcyclohexane and the like. These can be used alone or in combination of two or more.
  • the solvent for organic EL device production contains the solvent (B) and does not contain the above-mentioned solvent (A)
  • the content of the solvent (B) in the total amount (100% by weight) of the organic EL device production solvent of the present invention ( The total amount in the case of containing two or more in combination is, for example, 50% by weight or more (eg 50 to 100% by weight), preferably 70% by weight or more (eg 70 to 100% by weight), particularly preferably 80% by weight. Or more (for example, 80 to 100% by weight), most preferably 90% by weight or more (for example, 90 to 100% by weight).
  • content of a solvent (B) is less than the said range, there exists a tendency for the solubility of an organic-semiconductor material to fall.
  • the solvent for organic EL element manufacture contains a solvent (A) and a solvent (B)
  • the content of the solvent (A) and the solvent (B) in the total amount (100% by weight) of the solvent for organic EL element manufacture of the present invention The sum of the amounts is, for example, 50% by weight or more (eg 50 to 100% by weight), preferably 70% by weight or more (eg 70 to 100% by weight), particularly preferably 80% by weight or more (eg 80 to 100% by weight), Most preferably, it is 90% by weight or more (for example, 90 to 100% by weight).
  • the solubility of the organic semiconductor material tends to decrease.
  • solvent (C) examples include (mono, di, tri) alkylene glycol monoalkyl ether, (mono, di) alkylene glycol dialkyl ether, (mono, di) alkylene glycol alkyl ether acetate, and (mono, di) alkylene glycol.
  • Rukoto can. These can be used alone or in combination of two or more.
  • Examples of the (mono, di, tri) alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.
  • Examples of the (mono, di) alkylene glycol dialkyl ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, Propylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl n Propyl ether, and dipropylene glycol methyl n- butyl ether.
  • Examples of the (mono, di) alkylene glycol alkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether Acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate and the like
  • Examples of the (mono, di) alkylene glycol diacetate include ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, and dipropylene glycol diacetate.
  • Examples of the (cyclo) alkyl acetate include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate.
  • Examples of the C 3-6 alcohol include n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, and 2-hexyl alcohol. Can be mentioned.
  • Examples of the C 3-6 alkanediol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and the like.
  • Examples of the C 3-6 alkanediol monoalkyl ether include 3-methoxybutanol.
  • Examples of the C 3-6 alkanediol alkyl ether acetate include 3-methoxybutanol acetate.
  • Examples of the C 3-6 alkanediol diacetate include 1,3-butanediol diacetate, 1,4-butanediol diacetate, and 1,6-hexanediol diacetate.
  • hydroxycarboxylic acid ester examples include methyl lactate and ethyl lactate.
  • hydroxycarboxylic acid diester examples include methyl lactate acetate and ethyl lactate acetate.
  • alkoxycarboxylic acid ester examples include methyl methoxypropionate and ethyl ethoxypropionate.
  • Examples of the cyclic ketone include 4-ketoisophorone.
  • lactones examples include ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -acetyl- ⁇ -butyrolactone, and the like.
  • Examples of the cyclic ether include tetrahydrofuran and tetrahydrofurfuryl alcohol.
  • amides examples include dimethylformamide.
  • pyridines examples include pyridine and methylpyridine.
  • aromatic ether examples include veratrol.
  • amines examples include diethylamine and triethylamine.
  • the organic semiconductor material is contained at a high concentration, and coating property, drying property, safety, dispersion
  • the composition for organic EL device manufacture excellent in property, solubility, etc. can be formed.
  • one or more solvents selected from mono C 3-6 alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and C 3-6 alkanediol alkyl ether acetates are used. It is effective to use together.
  • mono C 3-6 alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether
  • mono-C 3-6 alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate
  • C 3-6 One or two solvents selected from alkanediol monoalkyl ether, C 3-6 alkanediol alkyl ether acetate, hydroxycarboxylic acid ester, hydroxycarboxylic acid diester, C 3-6 alcohol, and C 3-6 alkanediol The combined use is effective.
  • (mono, di) C 3 such as propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl n-butyl ether, etc. It is effective to use one or more solvents selected from -6 alkylene glycol C 1-2 alkyl C 3-4 alkyl ether and (cyclo) alkyl acetate.
  • the mixing ratio ([solvent (A) + solvent (B)] / [solvent (C)]; weight ratio) is: For example, it is 95/5 to 50/50, preferably 95/5 to 70/30.
  • the ratio of the solvent (C) is higher than that of the solvent (A) and / or the solvent (B), the solubility of the organic semiconductor material tends to decrease.
  • the solvent for producing the organic EL device of the present invention may contain a conventionally used solvent such as toluene, but the content of toluene or the like is, for example, 10% of the total amount of the solvent for producing the organic EL device of the present invention. % By weight or less, preferably 5% by weight or less, particularly preferably 1% by weight or less. If the content of toluene or the like exceeds the above range, safety is lowered, which is not preferable.
  • the solvent for producing an organic EL device of the present invention contains a solvent (A) and / or a solvent (B), it has a high solubility in organic semiconductor materials even at a relatively low temperature.
  • the solubility of the compound having the structural unit represented by the formula (1) at 100 ° C. is, for example, 0.1 part by weight or more, preferably 1 part by weight or more with respect to 100 parts by weight of the organic EL element production solvent. Preferably it is 2 parts by weight or more.
  • the upper limit of solubility is, for example, 30 parts by weight, preferably 20 parts by weight, particularly preferably 15 parts by weight.
  • solubility is, for example, 0.1 part by weight or more, preferably 1 part by weight or more with respect to 100 parts by weight of the solvent for organic EL device production. Preferably it is 2 parts by weight or more.
  • the upper limit of solubility is, for example, 50 parts by weight, preferably 45 parts by weight, particularly preferably 40 parts by weight.
  • the solvent for producing an organic EL element of the present invention is a solvent for dissolving an organic semiconductor material, more specifically, a composition containing the organic semiconductor material dissolved is applied onto a substrate (for example, printing such as ink jet printing). It is a solvent used for dissolving an organic semiconductor material when forming an organic EL device by applying a method such as a spin coating method or a spin coating method.
  • a method such as a spin coating method or a spin coating method.
  • the compound which has a structural unit represented by following formula (1), and / or the compound represented by following formula (2) is preferable. These can be used alone or in combination of two or more.
  • Ar 1 may have a substituent, and is a structure selected from an aromatic carbocyclic ring, an aromatic heterocyclic ring, and a ring in which two or more thereof are bonded via a single bond or a linking group.
  • a group in which two hydrogen atoms are removed from the formula, Ar 2 is an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these which may have a substituent, each having a single bond or a linking group.
  • m and n are the same or different and each represents an integer of 1 or more, m Ar 1 and n Ar 2 may be the same or different) (Wherein Ar 3 to Ar 5 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these via a single bond or a linking group.
  • aromatic carbocycle examples include two benzene rings, indene rings, naphthalene rings, fluorene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, and triphenylene rings.
  • aromatic carbocycles examples include polycyclic aromatic carbocycles having 9 to 20 carbon atoms in which the above (preferably 2 to 5) rings are condensed.
  • aromatic heterocycle examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, and a pyrrolopyrazole ring.
  • linking group examples include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are bonded.
  • divalent hydrocarbon group examples include, for example, a C 1-4 alkylene group such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group, a 1,2-cyclopentylene group, C 3-18 cycloalkylene such as 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, etc.
  • aromatic carbocycle The aromatic carbocycle, the aromatic heterocycle, or a ring in which two or more of these are bonded through a single bond or a linking group (hereinafter sometimes referred to as “aromatic carbocycle etc.”)
  • Suitable substituents include, for example, C 1-12 (preferably C 1-6 ) alkyl groups such as methyl and ethyl groups; C 2-12 (preferably C 2-6 ) alkenyls such as vinyl groups.
  • C 10-24 (preferably C 12-24 ) N, N-diarylamino group; C 7-36 (preferably C 7-24 ) N-aryl-N-alkylamino group such as phenylmethylamino group
  • An acyl group of C 2-24 such as acetyl group or benzoyl group; a halogen atom such as fluorine atom or chlorine atom; C 1-12 such as trifluoromethyl group (preferably C 1- 6 ) a haloalkyl group; a C 1-24 (preferably C 1-12 ) alkylthio group such as a methylthio group or an ethylthio group; a C 4-36 (preferably C 5-24) such as a phenylthio group, a naphthylthio group or a pyridylthio group.
  • Arylthio group or Roariruchio group trialkylsiloxy group C 1-10 (preferably C 1-5) such as trimethylsiloxy group; a trimethylsilyl group, a silyl group of C 2-36 (preferably C 3-24) such as triphenylsilyl group
  • a hydrocarbon group a C 3-36 (preferably C 4-24 ) aromatic heterocyclic group such as a thienyl group and a pyridyl group.
  • the substituent may further have a substituent (for example, the substituents exemplified above).
  • Substituents possessed by the aromatic carbocycle and the like may be bonded together to form a ring together with carbon atoms constituting the aromatic carbocycle and the like.
  • the molecular weight of the substituent that the aromatic carbocycle or the like may have is preferably 500 or less, particularly preferably 250 or less.
  • Ar 1 is a structural formula of an aromatic carbocycle and / or an aromatic heterocycle, which may have a substituent, in that the hole injection property is increased and the driving voltage of the resulting device is decreased.
  • 2 or more aromatic carbocycles and / or aromatic heterocycles (for example, 2 to 5, preferably 2 to 3) which may have the above-described substituent and a group obtained by removing 2 hydrogen atoms from A group in which two hydrogen atoms are removed from the structural formula formed by bonding, particularly from the structural formula selected from a biphenyl ring, a terphenyl ring, and a fluorene ring, which may have a substituent.
  • a group from which two hydrogen atoms have been removed is preferred because of its excellent solubility.
  • the substituent is preferably a C 1-12 alkyl group or a C 1-12 alkoxy group.
  • Ar 2 is preferably a group in which one hydrogen atom is removed from the structural formula of an aromatic carbocyclic ring (particularly a benzene ring) which may have a substituent, from the viewpoint of excellent solubility.
  • the substituent is preferably a C 1-12 alkyl group or a C 1-12 alkoxy group.
  • m and n are integers of 1 or more (for example, 1 to 3). It is preferable that m is 1 and n is 1 in that the hole injection property to the adjacent hole transport layer or the light emitting layer is increased and the driving voltage of the resulting device is decreased. It is preferable that m is 1 and n is 3 in that radical cations are stably generated, the hole injection property from the electrode is high, and the driving voltage of the resulting device is low.
  • the two structural units enclosed in parentheses in the above formula (1) may be block polymerized or random polymerized.
  • the number of repetitions of the structural unit represented by the above formula (1) is, for example, about 7 to 300, and the structure represented by the above formula (1)
  • the compound having a unit has a weight average molecular weight (in terms of polystyrene by GPC) of, for example, about 5,000 to 200,000, preferably 10,000 to 100,000.
  • Ar 3 to Ar 5 each have a group obtained by removing one hydrogen atom from the structural formula of an aromatic carbocyclic ring (in particular, a benzene ring) which may have a substituent, or a substituent.
  • a group in which one hydrogen atom is removed from the structural formula of an aromatic heterocyclic ring (particularly a carbazole ring) which may be used is preferable.
  • the substituent is preferably a C 1-12 (preferably C 1-6 ) alkyl group and / or a C 10-24 (preferably C 12-24 ) diarylamino group.
  • the substituents may be bonded to each other to form a ring together with the nitrogen atom in the formula (2).
  • the molecular weight of the compound represented by the above formula (2) is, for example, about 300 to 5000, preferably 450 to 3000, particularly preferably 450 to 1000.
  • the compound represented by the formula (2) is preferably a compound selected from a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2).
  • Ar 6 may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these bonded via a single bond or a linking group.
  • a group in which two hydrogen atoms are removed from a structural formula selected from a ring, Ar 7 to Ar 10 are the same or different and may have a substituent, an aromatic carbocycle, an aromatic heterocycle;
  • a group in which one hydrogen atom is removed from a structural formula selected from a ring and a ring in which two or more of these are bonded via a single bond or a linking group is shown.
  • Ar 11 to Ar 13 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these are a single bond or A group obtained by removing two hydrogen atoms from a structural formula selected from a ring bonded through a linking group, Ar 14 to Ar 19 may be the same or different and may have a substituent. A group obtained by removing one hydrogen atom from a structural formula selected from aromatic carbocycles, aromatic heterocycles, and rings in which two or more of these are bonded via a single bond or a linking group)
  • Examples of Ar 6 and Ar 11 to Ar 13 include the same examples as Ar 1 described above.
  • Examples of Ar 7 to Ar 10 and Ar 14 to Ar 19 include the same examples as Ar 3 to Ar 5 described above.
  • Ar 6 is a group in which two hydrogen atoms are removed from the structural formula of an aromatic carbocyclic ring (for example, benzene ring), or two or more (for example 2 Structural formula (for example, biphenyl ring, terphenyl ring structural formula) in which up to 5, preferably 2 to 3 aromatic carbocyclic rings (for example, benzene ring) are bonded via a single bond or a linking group A group in which two hydrogen atoms are removed from is preferable.
  • an aromatic carbocyclic ring for example, benzene ring
  • 2 Structural formula for example, biphenyl ring, terphenyl ring structural formula
  • up to 5, preferably 2 to 3 aromatic carbocyclic rings (for example, benzene ring) are bonded via a single bond or a linking group
  • a group in which two hydrogen atoms are removed from is preferable.
  • Ar 7 to Ar 10 are, among others, a group in which one hydrogen atom is removed from the structural formula of an aromatic carbocyclic ring (in particular, a benzene ring, a phenanthrene ring or an anthracene ring) which may have a substituent, Or the group remove
  • the substituent is preferably a C 1-12 (preferably C 1-6 ) alkyl group and / or a C 6-16 (preferably C 6-10 ) aryl group.
  • Ar 7 and Ar 8 , and Ar 9 and Ar 10 may be bonded to each other to form a ring together with the nitrogen atom to which these Ar groups are bonded.
  • Ar 11 to Ar 13 are particularly preferably groups obtained by removing two hydrogen atoms from the structural formula of an aromatic carbocyclic ring (particularly a benzene ring) which may have a substituent.
  • Ar 14 to Ar 19 are particularly preferably groups in which one hydrogen atom has been removed from the structural formula of an aromatic carbocyclic ring (in particular, a benzene ring) which may have a substituent.
  • the substituent is preferably a C 1-12 (preferably C 1-6 ) alkyl group.
  • Ar 14 and Ar 15 , Ar 16 and Ar 17 , and Ar 18 and Ar 19 may be bonded to each other to form a ring together with the nitrogen atom to which these Ar groups are bonded.
  • organic semiconductor material in the present invention in particular, a compound having a structural unit represented by the following formula (1-1), a compound represented by the following formulas (2-1-1) to (2-1-5), And at least one compound selected from compounds represented by the following formula (2-2-1) is preferred.
  • composition for manufacturing organic EL device is a composition used to form an organic EL device by coating on a substrate (for example, coating by a printing method such as inkjet printing or a spin coating method). And it contains the said organic-semiconductor material and the solvent for organic electroluminescent element manufacture, It is characterized by the above-mentioned.
  • the composition for producing an organic EL device of the present invention is prepared, for example, by mixing the organic semiconductor material and the solvent for producing an organic EL device, and in the atmosphere at a temperature of about 70 to 150 ° C. for 0.1 to 10 hours. It can be prepared by heating to a certain extent.
  • the content of the organic semiconductor material in the composition for producing an organic EL element of the present invention is, for example, when the compound having the structural unit represented by the formula (1-1) is used as the organic semiconductor material.
  • 0.1 part by weight or more preferably 1.0 part by weight or more, and particularly preferably 2.0 part by weight or more with respect to 100 parts by weight of the device manufacturing solvent.
  • the upper limit is, for example, 30 parts by weight, preferably 20 parts by weight, particularly preferably 15 parts by weight.
  • the content of the organic semiconductor material in the composition for manufacturing an organic EL element of the present invention is organic EL element manufacturing.
  • the upper limit is, for example, 30 parts by weight, preferably 20 parts by weight, particularly preferably 15 parts by weight.
  • the content of the organic semiconductor material in the composition for manufacturing an organic EL element of the present invention is organic EL element manufacturing.
  • the upper limit is, for example, 50 parts by weight, preferably 45 parts by weight, particularly preferably 40 parts by weight.
  • the content of the solvent for producing an organic EL element in the composition for producing an organic EL element of the present invention is, for example, 99.99% by weight or less.
  • the lower limit is, for example, 50.0% by weight, preferably 55.0% by weight, particularly preferably 60.0% by weight, and the upper limit is preferably 99.0% by weight, particularly preferably 98.0% by weight. is there.
  • the organic EL device manufacturing solvent content contained in the organic EL device manufacturing composition of the present invention can promote crystallization by the self-organizing action of the organic semiconductor material. It is preferably 1 time (weight) or more, more preferably 1.2 times (weight) or more, and particularly preferably 1.5 times (weight) or more.
  • the upper limit is, for example, 1000 times (weight), preferably 100 times (weight), particularly preferably 50 times (weight).
  • composition for producing an organic EL device of the present invention in addition to the organic semiconductor material and the solvent for producing the organic EL device, components contained in a general composition for producing an organic EL device (for example, epoxy resin, acrylic resin) Resin, cellulose resin, butyral resin, etc.) can be blended as needed.
  • a general composition for producing an organic EL device for example, epoxy resin, acrylic resin
  • Resin for example, cellulose resin, butyral resin, etc.
  • the composition for producing an organic EL device of the present invention can dissolve an organic semiconductor material at a high concentration even at a relatively low temperature. Therefore, although it has lower heat resistance than glass substrates, it can withstand impacts and can directly form organic EL elements on lightweight and flexible plastic substrates, forming impact-resistant, lightweight and flexible displays and computer equipment. can do. Moreover, since the composition for manufacturing an organic EL device of the present invention contains the solvent for manufacturing an organic EL device of the present invention, when applied on a substrate, the organic semiconductor material is crystallized by a self-organizing action and has high crystallinity. A crystal thin film (for example, an organic EL element) is obtained. Furthermore, the organic semiconductor crystal thin film can be easily formed by a simple coating method such as a printing method or a spin coating method, and the cost can be greatly reduced.
  • Example 1 A compound having a structural unit represented by the above formula (1-1) as an organic semiconductor material (poly [(9,9-dioctylfluoronyl-2,7-diyl) -co- (4,4′-N— ( 4-sec-butylphenyl) diphenylamine)], weight average molecular weight: 40000, manufactured by Aldrich Co., Ltd. (hereinafter, sometimes referred to as “TFB”), and 4-t-butyl as a solvent for organic EL device production Cyclohexyl acetate (trade name “BCHXA”, manufactured by Daicel Corporation) was used. Under a 20 ° C.
  • an organic semiconductor material was dispersed in a solvent for producing an organic EL device so that the concentration thereof was 2 wt% to 9 wt%. Then, the composition for organic EL element manufacture was obtained by heating at 100 degreeC for 2 hours under nitrogen atmosphere and light-shielding conditions. The insoluble matter in the obtained composition for manufacturing an organic EL device was visually confirmed, and the solubility of the organic semiconductor material was evaluated according to the following criteria. Evaluation criteria When no insoluble matter is confirmed: ⁇ (Good solubility) When insoluble matter is confirmed: x (poor solubility)
  • Examples 2 to 5 and Comparative Examples 1 to 3 Except having used the solvent for organic EL element manufacture shown in Table 1, the composition for organic EL element manufacture was prepared like Example 1, and the solubility of the organic-semiconductor material was evaluated.
  • BCHXA 4-t-butylcyclohexyl acetate (manufactured by Daicel Corporation)
  • MCHXA 2-methylcyclohexyl acetate (manufactured by Daicel Corporation)
  • THNO 1-oxo-1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
  • PECPAN 2-pentylcyclopentanone (manufactured by Daicel Corporation)
  • CCPPAN 2-cyclopentylcyclopentanone (manufactured by Daicel Corporation)
  • Xyl o-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • ANON cyclohexanone (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Example 6 Compound (4,4 ′, 4 ′′ -tris [phenyl (m-tolyl) amino] triphenylamine represented by the above formula (2-2-1) as an organic semiconductor material, molecular weight: 789, manufactured by Aldrich Co., Ltd. (Hereinafter, sometimes referred to as “TFA”), and 2,3-dihydro-2-methylbenzofuran (trade name “DHMBF”, manufactured by Daicel Corporation) was used as a solvent for producing an organic EL device. Under a 20 ° C. environment, an organic semiconductor material was dispersed in a solvent for producing an organic EL device so that the concentration thereof was 10 wt% to 30 wt%.
  • composition for organic EL element manufacture was obtained by heating at 100 degreeC for 2 hours under nitrogen atmosphere and light-shielding conditions.
  • the insoluble matter in the obtained composition for manufacturing an organic EL device was visually confirmed, and the solubility of the organic semiconductor material was evaluated based on the above criteria.
  • DHMBF 2,3-dihydro-2-methylbenzofuran (manufactured by Daicel Corporation)
  • THN 1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
  • THNO 1-oxo-1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
  • PCH Phenylcyclohexane (manufactured by Daicel Corporation)
  • DMTHP 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (manufactured by Daicel Corporation)
  • CCPPAN 2-cyclopentylcyclopentanone (manufactured by Daicel Corporation)
  • CHXA cyclohexyl acetate (manufactured by Daicel Corporation)
  • DMI 1,3-dimethyl-2-imidazolidinone (manufactured by Daicel Corporation)
  • Example 14 As an organic semiconductor material, a compound represented by the above formula (2-1-1) (4,4′-bis (N-carbazolyl) -1,1′-biphenyl, molecular weight: 485, manufactured by Aldrich Co., Ltd., 1) -oxo-1,2,3,4-tetrahydronaphthalene (trade name “THNO”, manufactured by Daicel Corporation) was used as a solvent for producing organic EL elements. . Under a 20 ° C. environment, an organic semiconductor material was dispersed in a solvent for producing an organic EL element so that its concentration was 2 wt% to 10 wt%.
  • composition for organic EL element manufacture was obtained by heating at 100 degreeC for 2 hours under nitrogen atmosphere and light-shielding conditions.
  • the insoluble matter in the obtained composition for manufacturing an organic EL device was visually confirmed, and the solubility of the organic semiconductor material was evaluated based on the above criteria.
  • THNO 1-oxo-1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
  • DMTHP 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (manufactured by Daicel Corporation)
  • CCPPAN 2-cyclopentylcyclopentanone (manufactured by Daicel Corporation)
  • THN 1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
  • DHMBF 2,3-dihydro-2-methylbenzofuran (manufactured by Daicel Corporation)
  • DMI 1,3-dimethyl-2-imidazolidinone (manufactured by Daicel Corporation)
  • PCH Phenylcyclohexane (manufactured by Daicel Corporation)
  • Tol Toluene (Tokyo Chemical Industry Co., Ltd.)
  • Xyl o
  • organic semiconductor materials equivalent to or better than toluene, xylene and cyclohexanone for example, compounds represented by the formulas (1) and (2), particularly poly [(9,9-dioctylfluoronyl- 2,7-diyl) -co- (4,4′-N- (4-sec-butylphenyl) diphenylamine)] (compound having a structural unit represented by formula (1-1)), 4,4 ′ -Bis (N-carbazolyl) -1,1′-biphenyl (compound represented by the formula (2-1-1)), 4,4 ′, 4 ′′ -tris [phenyl (m-tolyl) amino] triphenyl Amine (compound represented by the formula (2-2-1)) and the like].
  • organic semiconductor materials equivalent to or better than toluene, xylene and cyclohexanone for example, compounds represented by the formulas (1) and (2), particularly poly [(9,9-diocty
  • the solvent for producing an organic EL device of the present invention has high organic semiconductor material solubility even at a relatively low temperature.
  • the composition for organic EL element manufacture of this invention contains the said solvent for organic EL element manufacture, although heat resistance is low compared with a glass substrate, it is a shock-resistant, lightweight and flexible plastic substrate printing method
  • the organic EL element can be directly formed by using a coating method such as spin coating or the like, and a light-weight and flexible display or computer device that is resistant to impact can be formed while greatly reducing costs.
  • the composition for manufacturing an organic EL device of the present invention is applied on a substrate, the organic semiconductor material is crystallized by a self-organizing action, so that an organic semiconductor crystal thin film having high crystallinity is obtained.

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Abstract

This invention provides the following: a solvent, for manufacturing organic electroluminescent elements, that excels at dissolving an organic semiconductor material; and a composition, for manufacturing organic electroluminescent elements, that contains said organic semiconductor material and the aforementioned solvent for manufacturing organic electroluminescent elements and can be used to form an organic electroluminescent element via a coating method. The aforementioned solvent for manufacturing organic electroluminescent elements is a solvent for dissolving an organic semiconductor material and is characterized by containing a solvent (A) that can be represented by formula (a) and/or a solvent (B) that can be represented by formula (b). (a) (b)

Description

有機ＥＬ素子製造用溶剤Solvent for manufacturing organic EL devices
　本発明は、有機半導体材料の溶解性に優れた有機ＥＬ素子製造用溶剤、及び該有機ＥＬ素子製造用溶剤と有機半導体材料を含む有機ＥＬ素子製造用組成物に関する。本願は、２０１４年６月１７日に日本に出願した、特願２０１４－１２４４３１号、及び２０１５年３月２７日に日本に出願した、特願２０１５－０６５８１４号の優先権を主張し、その内容をここに援用する。 The present invention relates to a solvent for producing an organic EL device excellent in solubility of an organic semiconductor material, and a composition for producing an organic EL device comprising the solvent for producing an organic EL device and an organic semiconductor material. This application claims the priority of Japanese Patent Application No. 2014-124431 filed in Japan on June 17, 2014 and Japanese Patent Application No. 2015-0665814 filed in Japan on March 27, 2015. Is hereby incorporated by reference.
　有機エレクトロルミネッセンス（本明細書では、「有機ＥＬ」と称する場合がある）素子は有機半導体材料によって形成される発光デバイスであり、電子と正孔の再結合によって生じる励起子により発光する。 Organic electroluminescence (sometimes referred to as “organic EL” in this specification) element is a light emitting device formed of an organic semiconductor material, and emits light by excitons generated by recombination of electrons and holes.
　このような有機ＥＬ素子の製造は、従来、ガラス基板上に有機半導体材料を真空蒸着する方法で行われていたが、製造コストが嵩むことや、基板が固く、重く、割れやすいことが問題であった。また、装置の大規模化が容易でないため、大面積デバイスを製造することが困難であることも問題であった。 The manufacture of such an organic EL element has been conventionally performed by a method in which an organic semiconductor material is vacuum-deposited on a glass substrate. However, there are problems in that the manufacturing cost increases and the substrate is hard, heavy, and easy to break. there were. Moreover, since it is not easy to increase the scale of the apparatus, it is also difficult to manufacture a large area device.
　そこで、近年、インクジェット印刷やスピンコート等により有機半導体材料を塗布して有機ＥＬ素子を形成する方法（塗布法）が注目されている。塗布法では、塗布液を基板に塗布し、次いで塗布液中の溶媒を除去することにより容易に成膜できるので、高生産性、省エネルギーであり、大面積デバイスにも容易に対応可能である点で優れている。 Therefore, in recent years, a method (coating method) for forming an organic EL element by applying an organic semiconductor material by ink jet printing, spin coating or the like has attracted attention. In the coating method, it is possible to easily form a film by applying a coating solution to a substrate and then removing the solvent in the coating solution, so that it is highly productive and energy-saving, and can be easily applied to a large area device. Is excellent.
　有機ＥＬ素子の形成に使用される有機半導体材料としては、例えば４，４’－ビス（Ｎ－カルバゾリル）－１，１’－ビフェニル（ＣＢＰ）、ポリ［（９，９－ジオクチルフルオロニル－２，７－ジイル）－ｃｏ－（４，４’－Ｎ－（４－ｓｅｃ－ブチルフェニル）ジフェニルアミン）］（ＴＦＢ）、４，４’，４”－トリス［フェニル（ｍ－トリル）アミノ］トリフェニルアミン（ＴＦＡ）等が知られており、これらをトルエンなどの溶剤に溶かして塗布することにより有機層を形成することができる（特許文献１）。しかし、ＣＢＰに代表される無置換のジカルバゾールビフェニルは溶剤への溶解性が乏しい為、有機半導体材料を高濃度に溶解した有機ＥＬ素子製造用組成物を調製することができず、厚膜の有機層を形成することが困難であった。 Examples of the organic semiconductor material used for forming the organic EL element include 4,4′-bis (N-carbazolyl) -1,1′-biphenyl (CBP), poly [(9,9-dioctylfluoronyl-2). , 7-diyl) -co- (4,4′-N- (4-sec-butylphenyl) diphenylamine)] (TFB), 4,4 ′, 4 ″ -tris [phenyl (m-tolyl) amino] tri Phenylamine (TFA) and the like are known, and an organic layer can be formed by dissolving them in a solvent such as toluene (Patent Document 1) However, an unsubstituted dimer typified by CBP is used. Since carbazole biphenyl has poor solubility in a solvent, it is not possible to prepare a composition for manufacturing an organic EL device in which an organic semiconductor material is dissolved at a high concentration, and it is difficult to form a thick organic layer. It was.
　上記問題を解決する方法として、特許文献２では有機半導体材料に可溶化部位を導入すること、特許文献３では有機半導体材料に可溶性を付与する脱離性置換基を導入することが記載されている。しかし、前者においては、可溶化部位の導入により、相転移や安定性の低下が生じることが問題であった。後者においても、溶解時の加熱により可溶性を付与する脱離性置換基が脱離してしまうことが問題であった。 As a method for solving the above problem, Patent Document 2 describes introducing a solubilization site into an organic semiconductor material, and Patent Document 3 describes introducing a leaving substituent that imparts solubility to the organic semiconductor material. . However, in the former, there has been a problem that phase transition and stability decrease occur due to the introduction of the solubilized site. Even in the latter case, there is a problem in that a detachable substituent that imparts solubility is eliminated by heating during dissolution.
　また、前記特許文献では、有機半導体材料に対して高溶解性を有するトルエンを溶剤として使用することが記載されているが、トルエンは不整脈や脳障害等の原因となる恐れがあり、安全性の点で問題があった。 In addition, the patent document describes that toluene having high solubility in an organic semiconductor material is used as a solvent, but toluene may cause arrhythmia, brain damage, etc. There was a problem in terms.
特開２０１１－０９６７３３号公報JP 2011-096733 A 特開２００８－１６６６２９号公報JP 2008-166629 A 特開２０１３－２０９３５８号公報JP 2013-209358 A
　従って、本発明の目的は、有機半導体材料の溶解性に優れ、有機半導体材料を溶解することにより、塗布法により有機ＥＬ素子を形成するための有機ＥＬ素子製造用組成物を形成することができる有機ＥＬ素子製造用溶剤を提供することにある。
　本発明の他の目的は、有機半導体材料の溶解性に優れ、有機半導体材料を溶解することにより、プラスチック基板上に、塗布法により有機ＥＬ素子を形成するための有機ＥＬ素子製造用組成物を形成することができる有機ＥＬ素子製造用溶剤を提供することにある。
　本発明の他の目的は、塗布法によって有機ＥＬ素子を形成することができる有機ＥＬ素子製造用組成物を提供することにある。
　本発明の他の目的は、プラスチック基板上に、塗布法によって有機ＥＬ素子を形成することができる有機ＥＬ素子製造用組成物を提供することにある。 Therefore, the object of the present invention is excellent in the solubility of the organic semiconductor material, and by dissolving the organic semiconductor material, a composition for producing an organic EL element for forming an organic EL element by a coating method can be formed. It is in providing the solvent for organic electroluminescent element manufacture.
Another object of the present invention is to provide an organic EL device manufacturing composition for forming an organic EL device on a plastic substrate by a coating method by dissolving the organic semiconductor material with excellent solubility of the organic semiconductor material. It is providing the solvent for organic electroluminescent element manufacture which can be formed.
Another object of the present invention is to provide a composition for producing an organic EL device capable of forming an organic EL device by a coating method.
Another object of the present invention is to provide a composition for producing an organic EL device, which can form an organic EL device on a plastic substrate by a coating method.
　本発明者等は上記課題を解決するため鋭意検討した結果、下記溶剤（Ａ）及び溶剤（Ｂ）は、比較的低温でも高い有機半導体材料溶解性を発揮すること、前記溶剤を含有する有機ＥＬ素子製造用組成物は、ガラス基板に比べて耐熱性の低いプラスチック基板上にも印刷法やスピンコート法等の方法で塗布することにより有機ＥＬ素子を形成することができ、塗布後、有機半導体材料が自己組織化作用により結晶化することを見いだした。更に、必要に応じて、前記溶剤に一般的に電子材料用途に使用される溶剤を混合すると、塗布性、乾燥性をさらに向上し得ることを見出した。本発明はこれらの知見に基づいて完成させたものである。 As a result of intensive studies by the present inventors to solve the above problems, the following solvent (A) and solvent (B) exhibit high solubility in organic semiconductor materials even at relatively low temperatures, and organic EL containing the solvent. The element manufacturing composition can form an organic EL element by applying a printing method, spin coating method, or the like on a plastic substrate having a lower heat resistance than a glass substrate. It has been found that the material crystallizes by self-organizing action. Furthermore, it discovered that a coating property and a drying property could be improved further if the solvent generally used for an electronic material use was mixed with the said solvent as needed. The present invention has been completed based on these findings.
　すなわち、本発明は有機半導体材料溶解用の溶剤であって、下記式（ａ）
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ1～Ｒ4は同一又は異なって、Ｃ1-2アルキル基である。Ｒ1とＲ4は互いに結合して式中の－Ｎ（Ｒ2）－Ｃ（＝Ｏ）－Ｎ（Ｒ3）－と共に環を形成していてもよい）
で表される溶剤（Ａ）、及び／又は下記式（ｂ）
Figure JPOXMLDOC01-appb-C000012
 ［式中、環Ｚは芳香族炭素環、５～７員の脂環式炭素環、及び５～７員の複素環から選択される環を示す。Ｒ5はオキソ基（＝Ｏ）、チオキシ基（＝Ｓ）、－ＯＲa基、－ＳＲa基、－Ｏ（Ｃ＝Ｏ）Ｒa基、－ＲbＯ（Ｃ＝Ｏ）Ｒa基（ＲaはＣ1-7アルキル基、又はアリール基、又は前記基が単結合若しくは連結基を介して結合した基を示し、ＲbはＣ1-7アルキレン基、又はアリーレン基、又は前記基が単結合若しくは連結基を介して結合した基を示す）、及び置換又は無置換アミノ基から選択される基を示し、Ｒ6は水素原子、Ｃ1-7アルキル基、アリール基、及び－ＯＲa基（Ｒaは前記に同じ）から選択される基を示す。Ｒ5とＲ6は互いに結合して環Ｚを構成する炭素原子と共に環を形成していてもよい］
で表される溶剤（Ｂ）を含む有機エレクトロルミネッセンス素子製造用溶剤を提供する。 That is, the present invention is a solvent for dissolving an organic semiconductor material, which has the following formula (a):
Figure JPOXMLDOC01-appb-C000011
 (Wherein R 1 to R 4 are the same or different and are C 1-2 alkyl groups. R 1 and R 4 are bonded to each other to form —N (R 2 ) —C (═O) — N (R 3 )-may form a ring)
And / or the following formula (b)
Figure JPOXMLDOC01-appb-C000012
 [Wherein, ring Z represents a ring selected from an aromatic carbocyclic ring, a 5- to 7-membered alicyclic carbocyclic ring, and a 5- to 7-membered heterocyclic ring. R 5 represents an oxo group (═O), a thioxy group (═S), a —OR a group, a —SR a group, a —O (C═O) R a group, a —R b O (C═O) R a group. (R a represents a C 1-7 alkyl group, an aryl group, or a group in which the group is bonded via a single bond or a linking group, and R b represents a C 1-7 alkylene group, an arylene group, or the group described above. Represents a group bonded through a single bond or a linking group), and a group selected from a substituted or unsubstituted amino group, R 6 represents a hydrogen atom, a C 1-7 alkyl group, an aryl group, and —OR A group selected from a group (R a is as defined above). R 5 and R 6 may be bonded to each other to form a ring together with the carbon atoms constituting ring Z]
The solvent for organic electroluminescent element manufacture containing the solvent (B) represented by these is provided.
　本発明は、また、溶剤（Ａ）が、１，１，３，３－テトラメチル尿素、１，３－ジメチル－２－イミダゾリジノン、及び１，３－ジメチル－３，４，５，６－テトラヒドロ－２（１Ｈ）ピリミジノンから選択される少なくとも１種である前記の有機エレクトロルミネッセンス素子製造用溶剤を提供する。 The present invention also provides that the solvent (A) is 1,1,3,3-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6. -Provided is the above-mentioned solvent for producing an organic electroluminescence device, which is at least one selected from tetrahydro-2 (1H) pyrimidinone.
　本発明は、また、溶剤（Ｂ）が、２－シクロペンチルシクロペンタノン、２－ペンチルシクロペンタノン、２，３－ジヒドロベンゾフラン、２，３－ジヒドロ－２－メチルベンゾフラン、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、４－ｔ－ブチルシクロヘキシルアセテート、１，２，３，４－テトラヒドロナフタレン、１－オキソ－１，２，３，４－テトラヒドロナフタレン、及びフェニルシクロヘキサンから選択される少なくとも１種である前記の有機エレクトロルミネッセンス素子製造用溶剤を提供する。 In the present invention, the solvent (B) may be 2-cyclopentylcyclopentanone, 2-pentylcyclopentanone, 2,3-dihydrobenzofuran, 2,3-dihydro-2-methylbenzofuran, cyclohexyl acetate, 2-methyl The aforementioned is at least one selected from cyclohexyl acetate, 4-t-butylcyclohexyl acetate, 1,2,3,4-tetrahydronaphthalene, 1-oxo-1,2,3,4-tetrahydronaphthalene, and phenylcyclohexane A solvent for producing an organic electroluminescence device is provided.
　本発明は、また、有機半導体材料が、下記式（１）で表される構成単位を有する化合物及び／又は下記式（２）で表される化合物である前記の有機エレクトロルミネッセンス素子製造用溶剤を提供する。
Figure JPOXMLDOC01-appb-C000013
 （式中、Ａｒ1は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ2は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。ｍ、ｎは同一又は異なって１以上の整数を示す。ｍ個のＡｒ1、及びｎ個のＡｒ2は、それぞれ同一であってもよく、異なっていてもよい）
Figure JPOXMLDOC01-appb-C000014
 （式中、Ａｒ3～Ａｒ5は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す） The present invention also provides the organic electroluminescent element manufacturing solvent, wherein the organic semiconductor material is a compound having a structural unit represented by the following formula (1) and / or a compound represented by the following formula (2). provide.
Figure JPOXMLDOC01-appb-C000013
 (In the formula, Ar 1 may have a substituent, and is a structure selected from an aromatic carbocyclic ring, an aromatic heterocyclic ring, and a ring in which two or more thereof are bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from the formula, Ar 2 is an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these which may have a substituent, each having a single bond or a linking group. 1 represents a group in which one hydrogen atom is removed from a structural formula selected from a ring bonded to each other, m and n are the same or different and each represents an integer of 1 or more, m Ar 1 and n Ar 2 may be the same or different)
Figure JPOXMLDOC01-appb-C000014
 (Wherein Ar 3 to Ar 5 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these via a single bond or a linking group. A group obtained by removing one hydrogen atom from a structural formula selected from
　本発明は、また、式（２）で表される化合物が、下記式（2-1）で表される化合物又は下記式（2-2）で表される化合物である前記の有機エレクトロルミネッセンス素子製造用溶剤を提供する。
Figure JPOXMLDOC01-appb-C000015
 （式（2-1）中、Ａｒ6は、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ7～Ａｒ10は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。
式（2-2）中、Ａｒ11～Ａｒ13は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ14～Ａｒ19は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す） In the organic electroluminescence device according to the invention, the compound represented by the formula (2) is a compound represented by the following formula (2-1) or a compound represented by the following formula (2-2). A manufacturing solvent is provided.
Figure JPOXMLDOC01-appb-C000015
 (In Formula (2-1), Ar 6 may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from a structural formula selected from a ring, Ar 7 to Ar 10 are the same or different and may have a substituent, an aromatic carbocycle, an aromatic heterocycle; A group in which one hydrogen atom is removed from a structural formula selected from a ring and a ring in which two or more of these are bonded via a single bond or a linking group is shown.
In formula (2-2), Ar 11 to Ar 13 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these are a single bond or A group obtained by removing two hydrogen atoms from a structural formula selected from a ring bonded through a linking group, Ar 14 to Ar 19 may be the same or different and may have a substituent. A group obtained by removing one hydrogen atom from a structural formula selected from aromatic carbocycles, aromatic heterocycles, and rings in which two or more of these are bonded via a single bond or a linking group)
　本発明は、また、有機半導体材料が、下記式（1-1）で表される構成単位を有する化合物、下記式（2-1-1）～（2-1-5）で表される化合物、及び下記式（2-2-1）で表される化合物から選択される少なくとも１種の化合物である前記の有機エレクトロルミネッセンス素子製造用溶剤を提供する。
Figure JPOXMLDOC01-appb-C000016
 The present invention also provides a compound in which the organic semiconductor material has a structural unit represented by the following formula (1-1), a compound represented by the following formula (2-1-1) to (2-1-5) And the above-mentioned solvent for producing an organic electroluminescence device, which is at least one compound selected from compounds represented by the following formula (2-2-1).
Figure JPOXMLDOC01-appb-C000016
　本発明は、また、有機半導体材料と、前記の有機エレクトロルミネッセンス素子製造用溶剤とを含む有機エレクトロルミネッセンス素子製造用組成物を提供する。 The present invention also provides a composition for producing an organic electroluminescence device comprising an organic semiconductor material and the above-mentioned solvent for producing an organic electroluminescence device.
　本発明は、また、有機半導体材料が、下記式（１）で表される構成単位を有する化合物及び／又は下記式（２）で表される化合物である前記の有機エレクトロルミネッセンス素子製造用組成物を提供する。
Figure JPOXMLDOC01-appb-C000017
 （式中、Ａｒ1は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ2は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。ｍ、ｎは同一又は異なって１以上の整数を示す。ｍ個のＡｒ1、及びｎ個のＡｒ2は、それぞれ同一であってもよく、異なっていてもよい）
Figure JPOXMLDOC01-appb-C000018
 （式中、Ａｒ3～Ａｒ5は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す） In the present invention, the organic semiconductor material is a compound having a structural unit represented by the following formula (1) and / or a compound represented by the following formula (2). I will provide a.
Figure JPOXMLDOC01-appb-C000017
 (In the formula, Ar 1 may have a substituent, and is a structure selected from an aromatic carbocyclic ring, an aromatic heterocyclic ring, and a ring in which two or more thereof are bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from the formula, Ar 2 is an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these which may have a substituent, each having a single bond or a linking group. 1 represents a group in which one hydrogen atom is removed from a structural formula selected from a ring bonded to each other, m and n are the same or different and each represents an integer of 1 or more, m Ar 1 and n Ar 2 may be the same or different)
Figure JPOXMLDOC01-appb-C000018
 (Wherein Ar 3 to Ar 5 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these via a single bond or a linking group. A group obtained by removing one hydrogen atom from a structural formula selected from
　本発明は、また、式（２）で表される化合物が、下記式（2-1）で表される化合物又は下記式（2-2）で表される化合物である前記の有機エレクトロルミネッセンス素子製造用組成物を提供する。
Figure JPOXMLDOC01-appb-C000019
 （式（2-1）中、Ａｒ6は、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ7～Ａｒ10は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。
式（2-2）中、Ａｒ11～Ａｒ13は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ14～Ａｒ19は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す） In the organic electroluminescence device according to the invention, the compound represented by the formula (2) is a compound represented by the following formula (2-1) or a compound represented by the following formula (2-2). A manufacturing composition is provided.
Figure JPOXMLDOC01-appb-C000019
 (In Formula (2-1), Ar 6 may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from a structural formula selected from a ring, Ar 7 to Ar 10 are the same or different and may have a substituent, an aromatic carbocycle, an aromatic heterocycle; A group in which one hydrogen atom is removed from a structural formula selected from a ring and a ring in which two or more of these are bonded via a single bond or a linking group is shown.
In formula (2-2), Ar 11 to Ar 13 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these are a single bond or A group obtained by removing two hydrogen atoms from a structural formula selected from a ring bonded through a linking group, Ar 14 to Ar 19 may be the same or different and may have a substituent. A group obtained by removing one hydrogen atom from a structural formula selected from aromatic carbocycles, aromatic heterocycles, and rings in which two or more of these are bonded via a single bond or a linking group)
　本発明は、また、有機半導体材料が、下記式（1-1）で表される構成単位を有する化合物、下記式（2-1-1）～（2-1-5）で表される化合物、及び下記式（2-2-1）で表される化合物から選択される少なくとも１種の化合物である前記の有機エレクトロルミネッセンス素子製造用組成物を提供する。
Figure JPOXMLDOC01-appb-C000020
 The present invention also provides a compound in which the organic semiconductor material has a structural unit represented by the following formula (1-1), a compound represented by the following formula (2-1-1) to (2-1-5) And the above-mentioned composition for producing an organic electroluminescence device, which is at least one compound selected from the compounds represented by the following formula (2-2-1).
Figure JPOXMLDOC01-appb-C000020
　すなわち、本発明は以下に関する。
［１］　有機半導体材料溶解用の溶剤であって、式（ａ）で表される溶剤（Ａ）、及び／又は式（ｂ）で表される溶剤（Ｂ）を含む有機ＥＬ素子製造用溶剤。
［２］　溶剤（Ａ）が、１，１，３，３－テトラメチル尿素、１，３－ジメチル－２－イミダゾリジノン、及び１，３－ジメチル－３，４，５，６－テトラヒドロ－２（１Ｈ）ピリミジノンから選択される少なくとも１種である［１］に記載の有機ＥＬ素子製造用溶剤。
［３］　溶剤（Ａ）の含有量が、有機ＥＬ素子製造用溶剤全量（１００重量％）の５０～１００重量％である［１］又は［２］に記載の有機ＥＬ素子製造用溶剤。
［４］　溶剤（Ｂ）が、２－シクロペンチルシクロペンタノン、２－ペンチルシクロペンタノン、２，３－ジヒドロベンゾフラン、２，３－ジヒドロ－２－メチルベンゾフラン、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、４－ｔ－ブチルシクロヘキシルアセテート、１，２，３，４－テトラヒドロナフタレン、１－オキソ－１，２，３，４－テトラヒドロナフタレン、及びフェニルシクロヘキサンから選択される少なくとも１種である［１］～［３］の何れか１つに記載の有機ＥＬ素子製造用溶剤。
［５］　溶剤（Ｂ）の含有量が、有機ＥＬ素子製造用溶剤全量（１００重量％）の５０～１００重量％である［１］～［４］の何れか１つに記載の有機ＥＬ素子製造用溶剤。
［６］　溶剤（Ａ）と溶剤（Ｂ）の合計含有量は、有機ＥＬ素子製造用溶剤全量（１００重量％）の５０～１００重量％である［１］～［５］の何れか１つに記載の有機ＥＬ素子製造用溶剤。
［７］　有機半導体材料が、式（１）で表される構成単位を有する化合物及び／又は式（２）で表される化合物である［１］～［６］の何れか１つに記載の有機ＥＬ素子製造用溶剤。
［８］　式（２）で表される化合物が、式（2-1）で表される化合物又は式（2-2）で表される化合物である［７］に記載の有機エレクトロルミネッセンス素子製造用溶剤。
［９］　有機半導体材料が、式（1-1）で表される構成単位を有する化合物、式（2-1-1）～（2-1-5）で表される化合物、及び式（2-2-1）で表される化合物から選択される少なくとも１種の化合物である［１］～［８］の何れか１つに記載の有機ＥＬ素子製造用溶剤。
［１０］　有機半導体材料と、［１］～［９］の何れか１つに記載の有機ＥＬ素子製造用溶剤とを含む有機ＥＬ素子製造用組成物。
［１１］　有機半導体材料が、式（１）で表される構成単位を有する化合物及び／又は式（２）で表される化合物である［１０］に記載の有機ＥＬ素子製造用組成物。
［１２］　式（２）で表される化合物が、式（2-1）で表される化合物又は式（2-2）で表される化合物である［１１］に記載の有機ＥＬ素子製造用組成物。
［１３］　有機半導体材料が、式（1-1）で表される構成単位を有する化合物、式（2-1-1）～（2-1-5）で表される化合物、及び式（2-2-1）で表される化合物から選択される少なくとも１種の化合物である［１０］～［１２］の何れか１つに記載の有機ＥＬ素子製造用組成物。
［１４］　有機ＥＬ素子製造用溶剤の含有量が有機ＥＬ素子製造用組成物全量の５０．０～９９．９９重量％である［１０］～［１３］の何れか１つに記載の有機ＥＬ素子製造用組成物。
［１５］　有機ＥＬ素子製造用溶剤の含有量が有機半導体材料の１～１０００重量倍である［１０］～［１４］の何れか１つに記載の有機ＥＬ素子製造用組成物。 That is, the present invention relates to the following.
[1] A solvent for dissolving an organic semiconductor material, which comprises a solvent (A) represented by formula (a) and / or a solvent (B) represented by formula (b). .
[2] The solvent (A) is 1,1,3,3-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro- The solvent for producing an organic EL device according to [1], which is at least one selected from 2 (1H) pyrimidinone.
[3] The solvent for producing an organic EL device according to [1] or [2], wherein the content of the solvent (A) is 50 to 100% by weight of the total amount (100% by weight) of the solvent for producing an organic EL device.
[4] The solvent (B) is 2-cyclopentylcyclopentanone, 2-pentylcyclopentanone, 2,3-dihydrobenzofuran, 2,3-dihydro-2-methylbenzofuran, cyclohexyl acetate, 2-methylcyclohexyl acetate, [1] to at least one selected from 4-t-butylcyclohexyl acetate, 1,2,3,4-tetrahydronaphthalene, 1-oxo-1,2,3,4-tetrahydronaphthalene, and phenylcyclohexane [3] The solvent for producing an organic EL device according to any one of [3].
[5] The organic EL device according to any one of [1] to [4], wherein the content of the solvent (B) is 50 to 100% by weight of the total amount of the solvent for organic EL device production (100% by weight). Solvent for manufacturing.
[6] The total content of the solvent (A) and the solvent (B) is 50 to 100% by weight of the total amount of the solvent for organic EL device production (100% by weight), and any one of [1] to [5] The solvent for organic electroluminescent element manufacture of description.
[7] The organic semiconductor material according to any one of [1] to [6], wherein the organic semiconductor material is a compound having a structural unit represented by formula (1) and / or a compound represented by formula (2) Solvent for manufacturing organic EL elements.
[8] The organic electroluminescence device production according to [7], wherein the compound represented by the formula (2) is a compound represented by the formula (2-1) or a compound represented by the formula (2-2): Solvent.
[9] A compound in which the organic semiconductor material has a structural unit represented by formula (1-1), compounds represented by formulas (2-1-1) to (2-1-5), and formula (2 -2-1) The solvent for producing an organic EL device according to any one of [1] to [8], which is at least one compound selected from the compounds represented by formula (2-1).
[10] A composition for producing an organic EL device comprising an organic semiconductor material and the solvent for producing an organic EL device according to any one of [1] to [9].
[11] The composition for producing an organic EL device according to [10], wherein the organic semiconductor material is a compound having a structural unit represented by formula (1) and / or a compound represented by formula (2).
[12] The organic EL device production according to [11], wherein the compound represented by the formula (2) is a compound represented by the formula (2-1) or a compound represented by the formula (2-2): Composition.
[13] A compound in which the organic semiconductor material has a structural unit represented by formula (1-1), compounds represented by formulas (2-1-1) to (2-1-5), and formula (2 -2-1) The composition for producing an organic EL device according to any one of [10] to [12], which is at least one compound selected from the compounds represented by -2-1):
[14] The organic EL device according to any one of [10] to [13], wherein the content of the solvent for producing an organic EL device is 50.0 to 99.99% by weight of the total amount of the composition for producing an organic EL device. A composition for device manufacture.
[15] The composition for producing an organic EL device according to any one of [10] to [14], wherein the content of the solvent for producing an organic EL device is 1 to 1000 times the weight of the organic semiconductor material.
　本発明の有機ＥＬ素子製造用溶剤は、比較的低温でも高い有機半導体材料溶解性を有する。そして、本発明の有機ＥＬ素子製造用組成物は、前記有機ＥＬ素子製造用溶剤を含有するため、ガラス基板に比べて耐熱性は低いが、衝撃に強く、軽量且つフレキシブルなプラスチック基板に印刷法やスピンコート法等の塗布法を用いて有機ＥＬ素子を直接形成することができ、衝撃に強く、軽量且つフレキシブルなディスプレイやコンピュータ機器を、コストを大幅に削減しつつ形成することができる。
　さらに、本発明の有機ＥＬ素子製造用組成物を基板上に塗布すると有機半導体材料が自己組織化作用により結晶化するため、高い結晶性を有する有機半導体結晶薄膜が得られる。 The solvent for producing an organic EL device of the present invention has high organic semiconductor material solubility even at a relatively low temperature. And since the composition for organic EL element manufacture of this invention contains the said solvent for organic EL element manufacture, although heat resistance is low compared with a glass substrate, it is a shock-resistant, lightweight and flexible plastic substrate printing method The organic EL element can be directly formed by using a coating method such as spin coating or the like, and a light-weight and flexible display or computer device that is resistant to impact can be formed while greatly reducing costs.
Furthermore, when the composition for manufacturing an organic EL device of the present invention is applied on a substrate, the organic semiconductor material is crystallized by a self-organizing action, so that an organic semiconductor crystal thin film having high crystallinity is obtained.
　（溶剤（Ａ））
　本発明における溶剤（Ａ）は、上記式（ａ）で表される。式（ａ）中、Ｒ1～Ｒ4は同一又は異なって、Ｃ1-2（炭素数１～２）アルキル基である。Ｒ1とＲ4は互いに結合して式中の－Ｎ（Ｒ2）－Ｃ（＝Ｏ）－Ｎ（Ｒ3）－と共に環を形成していてもよい。 (Solvent (A))
The solvent (A) in the present invention is represented by the above formula (a). In formula (a), R 1 to R 4 are the same or different and are C 1-2 (C 1-2 ) alkyl group. R 1 and R 4 may be bonded to each other to form a ring together with —N (R 2 ) —C (═O) —N (R 3 ) — in the formula.
　Ｒ1～Ｒ4におけるＣ1-2アルキル基は、メチル基又はエチル基である。 The C 1-2 alkyl group in R 1 to R 4 is a methyl group or an ethyl group.
　Ｒ1とＲ4が互いに結合して式中の－Ｎ（Ｒ2）－Ｃ（＝Ｏ）－Ｎ（Ｒ3）－と共に形成する環としては、例えば、２－イミダゾリジノン環、３，４，５，６－テトラヒドロ－２（１Ｈ）ピリミジノン環等を挙げることができる。 Examples of the ring formed by combining R 1 and R 4 together with —N (R 2 ) —C (═O) —N (R 3 ) — in the formula include a 2-imidazolidinone ring, 3, Examples include 4,5,6-tetrahydro-2 (1H) pyrimidinone ring.
　本発明における溶剤（Ａ）としては、例えば、１，１，３，３－テトラメチル尿素、１，１，３，３－テトラエチル尿素、１，３－ジメチル－２－イミダゾリジノン、１，３－ジメチル－３，４，５，６－テトラヒドロ－２（１Ｈ）ピリミジノン等を挙げることができる。これらは１種を単独で、又は２種類以上を組み合わせて使用することができる。 Examples of the solvent (A) in the present invention include 1,1,3,3-tetramethylurea, 1,1,3,3-tetraethylurea, 1,3-dimethyl-2-imidazolidinone, 1,3 -Dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone and the like. These can be used individually by 1 type or in combination of 2 or more types.
　有機ＥＬ素子製造用溶剤が溶剤（Ａ）を含有し、後述の溶剤（Ｂ）を含有しない場合、有機ＥＬ素子製造用溶剤全量（１００重量％）における溶剤（Ａ）の含有量（２種以上を組み合わせて含有する場合はその総量）は、例えば５０重量％以上（例えば５０～１００重量％）、好ましくは７０重量％以上（例えば７０～１００重量％）、特に好ましくは８０重量％以上（例えば８０～１００重量％）、最も好ましくは９０重量％以上（例えば９０～１００重量％）である。溶剤（Ａ）の含有量が上記範囲を下回ると、有機半導体材料の溶解性が低下する傾向がある。 When the solvent for organic EL element production contains the solvent (A) and does not contain the solvent (B) described later, the content of the solvent (A) in the total amount of organic EL element production solvent (100% by weight) (two or more types) The total amount thereof is, for example, 50% by weight or more (for example, 50 to 100% by weight), preferably 70% by weight or more (for example 70 to 100% by weight), and particularly preferably 80% by weight or more (for example, 80 to 100% by weight), most preferably 90% by weight or more (for example, 90 to 100% by weight). When content of a solvent (A) is less than the said range, there exists a tendency for the solubility of an organic-semiconductor material to fall.
　（溶剤（Ｂ））
　本発明における溶剤（Ｂ）は、上記式（ｂ）で表される、ヘテロ原子を少なくとも１個含む化合物である。式（ｂ）中、環Ｚは芳香族炭素環、５～７員の脂環式炭素環、及び５～７員の複素環から選択される環を示す。前記環としては、例えば、ベンゼン環等の芳香族炭素環；ペンタン環、ヘキサン環、ヘプタン環等の５～７員の脂環式炭素環（特に、５～７員のアルカン環）；ピロリジン環、オキソラン環、チオラン環等の５～７員の複素環を挙げることができる。 (Solvent (B))
The solvent (B) in the present invention is a compound containing at least one heteroatom represented by the above formula (b). In formula (b), ring Z represents a ring selected from an aromatic carbocyclic ring, a 5- to 7-membered alicyclic carbocyclic ring, and a 5- to 7-membered heterocyclic ring. Examples of the ring include an aromatic carbocyclic ring such as a benzene ring; a 5- to 7-membered alicyclic carbocyclic ring (particularly a 5- to 7-membered alkane ring) such as a pentane ring, a hexane ring, and a heptane ring; And 5- to 7-membered heterocycles such as oxolane ring and thiolane ring.
　式（ｂ）中、Ｒ5はオキソ基（＝Ｏ）、チオキシ基（＝Ｓ）、－ＯＲa基、－ＳＲa基、－Ｏ（Ｃ＝Ｏ）Ｒa基、－ＲbＯ（Ｃ＝Ｏ）Ｒa基（ＲaはＣ1-7アルキル基、又はアリール基、又は前記基が単結合若しくは連結基を介して結合した基を示し、ＲbはＣ1-7アルキレン基、又はアリーレン基、又は前記基が単結合若しくは連結基を介して結合した基を示す）、及び置換又は無置換アミノ基から選択される基を示す。また、Ｒ6は水素原子、Ｃ1-7アルキル基、アリール基、及び－ＯＲa基（Ｒaは前記に同じ）から選択される基を示す。 In the formula (b), R 5 represents an oxo group (═O), a thioxy group (═S), a —OR a group, a —SR a group, a —O (C═O) R a group, a —R b O (C ═O) R a group (R a represents a C 1-7 alkyl group, an aryl group, or a group in which the group is bonded via a single bond or a linking group, and R b represents a C 1-7 alkylene group, or An arylene group or a group in which the group is bonded via a single bond or a linking group), and a group selected from a substituted or unsubstituted amino group. R 6 represents a group selected from a hydrogen atom, a C 1-7 alkyl group, an aryl group, and an —OR a group (R a is as defined above).
　前記Ｃ1-7アルキル基としては、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル基等の直鎖状又は分岐鎖状のアルキル基や、シクロペンチル基等の炭素数３～７のシクロアルキル基を挙げることができる。 Examples of the C 1-7 alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups, and C 3-7 carbon atoms such as cyclopentyl groups. A cycloalkyl group can be mentioned.
　前記アリール基としては、例えば、フェニル基等を挙げることができる。 Examples of the aryl group include a phenyl group.
　前記Ｃ1-7アルキレン基としては、例えば、メチレン、メチルメチレン、ジメチルメチレン、エチレン、プロピレン、トリメチレン基などの直鎖状又は分岐鎖状のアルキレン基や、１，２－シクロペンチレン基、１，３－シクロペンチレン基、シクロペンチリデン基、１，２－シクロヘキシレン基、１，３－シクロヘキシレン基、１，４－シクロヘキシレン基、シクロヘキシリデン基等の炭素数３～７のシクロアルキレン基（シクロアルキリデン基を含む）等を挙げることができる。 Examples of the C 1-7 alkylene group include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups, 1,2-cyclopentylene groups, , 3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, etc. An alkylene group (including a cycloalkylidene group) and the like can be mentioned.
　前記アリーレン基としては、例えば、フェニレン基等を挙げることができる。 Examples of the arylene group include a phenylene group.
　前記連結基としては、例えば、二価の炭化水素基、カルボニル基（－ＣＯ－）、エーテル結合（－Ｏ－）、チオエーテル結合（－Ｓ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＣＯＮＨ－）、カーボネート結合（－ＯＣＯＯ－）、及びこれらが複数個結合した基等を挙げることができる。 Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are bonded.
　上記二価の炭化水素基としては、例えば、メチレン基、メチルメチレン基、ジメチルメチレン基、エチレン基、プロピレン基、トリメチレン基等の直鎖又は分岐鎖状のＣ1-18アルキレン基や、１，２－シクロペンチレン基、１，３－シクロペンチレン基、シクロペンチリデン基、１，２－シクロヘキシレン基、１，３－シクロヘキシレン基、１，４－シクロヘキシレン基、シクロヘキシリデン基等のＣ3-18シクロアルキレン基（シクロアルキリデン基を含む）等を挙げることができる。 Examples of the divalent hydrocarbon group include a linear or branched C 1-18 alkylene group such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group, 2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, etc. And a C 3-18 cycloalkylene group (including a cycloalkylidene group).
　前記置換又は無置換アミノ基としては、例えば、アミノ基；メチルアミノ基、エチルアミノ基、イソプロピルアミノ基、ジメチルアミノ基、ジエチルアミノ基等のモノ又はジ（Ｃ1-3）アルキル置換アミノ基等を挙げることができる。 Examples of the substituted or unsubstituted amino group include an amino group; a mono- or di (C 1-3 ) alkyl-substituted amino group such as a methylamino group, an ethylamino group, an isopropylamino group, a dimethylamino group, and a diethylamino group. Can be mentioned.
　Ｒ5とＲ6が互いに結合して環Ｚを構成する炭素原子と共に形成していてもよい環としては、例えば、シクロペンタン、シクロヘキサン、シクロヘプタン、ベンゼン、メチルベンゼン、チオフェン、メチルチオフェン、フラン、メチルフラン、ジヒドロフラン、メチルジヒドロフラン等を挙げることができる。 Examples of the ring that R 5 and R 6 may be bonded together to form a carbon atom constituting the ring Z include, for example, cyclopentane, cyclohexane, cycloheptane, benzene, methylbenzene, thiophene, methylthiophene, furan, Mention may be made of methylfuran, dihydrofuran, methyldihydrofuran and the like.
　式（ｂ）で表される溶剤（Ｂ）の重量平均分子量としては、例えば３５０以下程度、好ましくは７０～２５０、特に好ましくは８０～２００である。 The weight average molecular weight of the solvent (B) represented by the formula (b) is, for example, about 350 or less, preferably 70 to 250, particularly preferably 80 to 200.
　本発明における溶剤（Ｂ）としては、例えば、２－メチルシクロペンタノン、２－メチルシクロヘキサノン、シクロヘキシルメチルエーテル、シクロヘキシルアミン、メトキシベンゼン、１，２－ジメトキシベンゼン、２，３－ジヒドロベンゾフラン、２，３－ジヒドロ－３－メチルベンゾフラン、２－シクロペンチルシクロペンタノン、２－ペンチルシクロペンタノン、２，３－ジヒドロ－２－メチルベンゾフラン、シクロヘキシルアセテート、１－メチルシクロヘキシルアセテート、４－ｔ－ブチルシクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、１，２，３，４－テトラヒドロナフタレン、１－オキソ－１，２，３，４－テトラヒドロナフタレン、フェニルシクロヘキサン等を挙げることができる。これらは１種を単独で、又は２種以上を組み合わせて使用することができる。 Examples of the solvent (B) in the present invention include 2-methylcyclopentanone, 2-methylcyclohexanone, cyclohexylmethyl ether, cyclohexylamine, methoxybenzene, 1,2-dimethoxybenzene, 2,3-dihydrobenzofuran, 2, 3-dihydro-3-methylbenzofuran, 2-cyclopentylcyclopentanone, 2-pentylcyclopentanone, 2,3-dihydro-2-methylbenzofuran, cyclohexyl acetate, 1-methylcyclohexyl acetate, 4-t-butylcyclohexyl acetate 2-methylcyclohexyl acetate, 1,2,3,4-tetrahydronaphthalene, 1-oxo-1,2,3,4-tetrahydronaphthalene, phenylcyclohexane and the like. These can be used alone or in combination of two or more.
　有機ＥＬ素子製造用溶剤が溶剤（Ｂ）を含有し、前述の溶剤（Ａ）を含有しない場合、本発明の有機ＥＬ素子製造用溶剤全量（１００重量％）における溶剤（Ｂ）の含有量（２種以上を組み合わせて含有する場合はその総量）は、例えば５０重量％以上（例えば５０～１００重量％）、好ましくは７０重量％以上（例えば７０～１００重量％）、特に好ましくは８０重量％以上（例えば８０～１００重量％）、最も好ましくは９０重量％以上（例えば９０～１００重量％）である。溶剤（Ｂ）の含有量が上記範囲を下回ると、有機半導体材料の溶解性が低下する傾向がある。 When the solvent for organic EL device production contains the solvent (B) and does not contain the above-mentioned solvent (A), the content of the solvent (B) in the total amount (100% by weight) of the organic EL device production solvent of the present invention ( The total amount in the case of containing two or more in combination is, for example, 50% by weight or more (eg 50 to 100% by weight), preferably 70% by weight or more (eg 70 to 100% by weight), particularly preferably 80% by weight. Or more (for example, 80 to 100% by weight), most preferably 90% by weight or more (for example, 90 to 100% by weight). When content of a solvent (B) is less than the said range, there exists a tendency for the solubility of an organic-semiconductor material to fall.
　また、有機ＥＬ素子製造用溶剤が溶剤（Ａ）と溶剤（Ｂ）を含有する場合、本発明の有機ＥＬ素子製造用溶剤全量（１００重量％）における溶剤（Ａ）と溶剤（Ｂ）の含有量の和は、例えば５０重量％以上（例えば５０～１００重量％）、好ましくは７０重量％以上（例えば７０～１００重量％）、特に好ましくは８０重量％以上（例えば８０～１００重量％）、最も好ましくは９０重量％以上（例えば９０～１００重量％）である。溶剤（Ａ）と溶剤（Ｂ）の含有量の和が上記範囲を下回ると、有機半導体材料の溶解性が低下する傾向がある。 Moreover, when the solvent for organic EL element manufacture contains a solvent (A) and a solvent (B), the content of the solvent (A) and the solvent (B) in the total amount (100% by weight) of the solvent for organic EL element manufacture of the present invention The sum of the amounts is, for example, 50% by weight or more (eg 50 to 100% by weight), preferably 70% by weight or more (eg 70 to 100% by weight), particularly preferably 80% by weight or more (eg 80 to 100% by weight), Most preferably, it is 90% by weight or more (for example, 90 to 100% by weight). When the sum of the contents of the solvent (A) and the solvent (B) is less than the above range, the solubility of the organic semiconductor material tends to decrease.
　（溶剤（Ｃ））
　本発明の有機ＥＬ素子製造用溶剤は、上記溶剤（Ａ）、溶剤（Ｂ）以外にも、一般的に電子材料用途に使用される溶剤であって、上記溶剤（Ａ）及び／又は溶剤（Ｂ）と相溶する溶剤（＝溶剤（Ｃ））を併用してもよい。 (Solvent (C))
The solvent for producing an organic EL device of the present invention is a solvent generally used for electronic materials in addition to the solvent (A) and the solvent (B), and the solvent (A) and / or the solvent ( A solvent (= solvent (C)) compatible with B) may be used in combination.
　溶剤（Ｃ）としては、例えば、（モノ，ジ，トリ）アルキレングリコールモノアルキルエーテル、（モノ，ジ）アルキレングリコールジアルキルエーテル、（モノ，ジ）アルキレングリコールアルキルエーテルアセテート、（モノ，ジ）アルキレングリコールジアセテート、（シクロ）アルキルアセテート、Ｃ3-6アルコール、Ｃ3-6アルカンジオール、Ｃ3-6アルカンジオールモノアルキルエーテル、Ｃ3-6アルカンジオールアルキルエーテルアセテート、Ｃ3-6アルカンジオールジアセテート、グリセリントリアセテート、ヒドロキシカルボン酸エステル、ヒドロキシカルボン酸ジエステル、アルコキシカルボン酸エステル、環状ケトン、ラクトン、環状エーテル、アミド類、ピリジン類、芳香族アセテート、芳香族エーテル、アミン類等を挙げることができる。これらは１種を単独で、又は２種以上を組み合わせて使用することができる。 Examples of the solvent (C) include (mono, di, tri) alkylene glycol monoalkyl ether, (mono, di) alkylene glycol dialkyl ether, (mono, di) alkylene glycol alkyl ether acetate, and (mono, di) alkylene glycol. Diacetate, (cyclo) alkyl acetate, C 3-6 alcohol, C 3-6 alkanediol, C 3-6 alkanediol monoalkyl ether, C 3-6 alkanediol alkyl ether acetate, C 3-6 alkanediol diacetate Glycerin triacetate, hydroxycarboxylic acid ester, hydroxycarboxylic acid diester, alkoxycarboxylic acid ester, cyclic ketone, lactone, cyclic ether, amides, pyridines, aromatic acetate, aromatic ether, amines, etc. Rukoto can. These can be used alone or in combination of two or more.
　前記（モノ，ジ，トリ）アルキレングリコールモノアルキルエーテルとしては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールｎ－プロピルエーテル、エチレングリコールｎ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールｎ－プロピルエーテル、ジエチレングリコールｎ－ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールｎ－プロピルエーテル、プロピレングリコールｎ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールｎ－プロピルエーテル、ジプロピレングリコールｎ－ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールｎ－ブチルエーテル等を挙げることができる。 Examples of the (mono, di, tri) alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di Propylene glycol - propyl ether, and dipropylene glycol n- butyl ether, tripropylene glycol monomethyl ethers, tripropylene glycol n- butyl ether.
　前記（モノ，ジ）アルキレングリコールジアルキルエーテルとしては、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、プロピレングリコールメチルエチルエーテル、プロピレングリコールメチルｎ－プロピルエーテル、プロピレングリコールメチルｎ－ブチルエーテル、ジプロピレングリコールメチルエチルエーテル、ジプロピレングリコールメチルｎ－プロピルエーテル、ジプロピレングリコールメチルｎ－ブチルエーテル等を挙げることができる。 Examples of the (mono, di) alkylene glycol dialkyl ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, Propylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl n Propyl ether, and dipropylene glycol methyl n- butyl ether.
　前記（モノ，ジ）アルキレングリコールアルキルエーテルアセテートとしては、例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノプロピルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノプロピルエーテルアセテート、ジプロピレングリコールモノブチルエーテルアセテート等を挙げることができる。 Examples of the (mono, di) alkylene glycol alkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether Acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate and the like.
　前記（モノ，ジ）アルキレングリコールジアセテートとしては、例えば、エチレングリコールジアセテート、ジエチレングリコールジアセテート、プロピレングリコールジアセテート、ジプロピレングリコールジアセテート等を挙げることができる。 Examples of the (mono, di) alkylene glycol diacetate include ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, and dipropylene glycol diacetate.
　前記（シクロ）アルキルアセテートとしては、例えば、メチルアセテート、エチルアセテート、ｎ－プロピルアセテート、イソプロピルアセテート、ブチルアセテート等を挙げることができる。 Examples of the (cyclo) alkyl acetate include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate.
　前記Ｃ3-6アルコールとしては、例えば、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、ｓｅｃ－ブチルアルコール、ｔｅｒｔ－ブチルアルコール、ｎ－ペンチルアルコール、ｎ－ヘキシルアルコール、２－ヘキシルアルコール等を挙げることができる。 Examples of the C 3-6 alcohol include n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, and 2-hexyl alcohol. Can be mentioned.
　前記Ｃ3-6アルカンジオールとしては、例えば、１，３－ブタンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール等を挙げることができる。 Examples of the C 3-6 alkanediol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and the like.
　前記Ｃ3-6アルカンジオールモノアルキルエーテルとしては、例えば、３－メトキシブタノール等を挙げることができる。 Examples of the C 3-6 alkanediol monoalkyl ether include 3-methoxybutanol.
　前記Ｃ3-6アルカンジオールアルキルエーテルアセテートとしては、例えば、３－メトキシブタノールアセテート等を挙げることができる。 Examples of the C 3-6 alkanediol alkyl ether acetate include 3-methoxybutanol acetate.
　前記Ｃ3-6アルカンジオールジアセテートとしては、例えば、１，３－ブタンジオールジアセテート、１，４－ブタンジオールジアセテート、１，６－ヘキサンジオールジアセテート等を挙げることができる。 Examples of the C 3-6 alkanediol diacetate include 1,3-butanediol diacetate, 1,4-butanediol diacetate, and 1,6-hexanediol diacetate.
　前記ヒドロキシカルボン酸エステルとしては、例えば、乳酸メチル、乳酸エチル等を挙げることができる。 Examples of the hydroxycarboxylic acid ester include methyl lactate and ethyl lactate.
　前記ヒドロキシカルボン酸ジエステルとしては、例えば、乳酸メチルアセテート、乳酸エチルアセテート等を挙げることができる。 Examples of the hydroxycarboxylic acid diester include methyl lactate acetate and ethyl lactate acetate.
　前記アルコキシカルボン酸エステルとしては、例えば、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル等を挙げることができる。 Examples of the alkoxycarboxylic acid ester include methyl methoxypropionate and ethyl ethoxypropionate.
　前記環状ケトンとしては、例えば、４－ケトイソホロン等を挙げることができる。 Examples of the cyclic ketone include 4-ketoisophorone.
　前記ラクトン類としては、例えば、β－ブチロラクトン、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、γ－バレロラクトン、α－アセチル－γ－ブチロラクトン等を挙げることができる。 Examples of the lactones include β-butyrolactone, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, α-acetyl-γ-butyrolactone, and the like.
　前記環状エーテルとしては、例えば、テトラヒドロフラン、テトラヒドロフルフリルアルコール等を挙げることができる。 Examples of the cyclic ether include tetrahydrofuran and tetrahydrofurfuryl alcohol.
　前記アミド類としては、例えば、ジメチルホルムアミド等を挙げることができる。 Examples of the amides include dimethylformamide.
　前記ピリジン類としては、例えば、ピリジン、メチルピリジン等を挙げることができる。 Examples of the pyridines include pyridine and methylpyridine.
　前記芳香族エーテルとしては、例えば、ベラトロール等を挙げることができる。 Examples of the aromatic ether include veratrol.
　前記アミン類としては、例えば、ジエチルアミン、トリエチルアミン等を挙げることができる。 Examples of the amines include diethylamine and triethylamine.
　本発明では、上記溶剤（Ａ）及び／又は溶剤（Ｂ）と溶剤（Ｃ）とを併用することにより、有機半導体材料を高濃度に含有し、且つ、塗布性、乾燥性、安全性、分散性、溶解性等に優れた有機ＥＬ素子製造用組成物を形成することができる。 In the present invention, by using the solvent (A) and / or the solvent (B) and the solvent (C) in combination, the organic semiconductor material is contained at a high concentration, and coating property, drying property, safety, dispersion The composition for organic EL device manufacture excellent in property, solubility, etc. can be formed.
　塗布性をより向上するためには、前記（モノ，ジ，トリ）アルキレングリコールモノアルキルエーテル、（モノ，ジ）アルキレングリコールジアルキルエーテル、（モノ，ジ）アルキレングリコールアルキルエーテルアセテート、（モノ，ジ）アルキレングリコールジアセテート、及びアルコキシカルボン酸エステルから選択される溶剤を１種又は２種以上併用することが効果的である。 In order to further improve the coating properties, the (mono, di, tri) alkylene glycol monoalkyl ether, (mono, di) alkylene glycol dialkyl ether, (mono, di) alkylene glycol alkyl ether acetate, (mono, di) It is effective to use one or more solvents selected from alkylene glycol diacetate and alkoxycarboxylic acid ester in combination.
　分散性をより向上するためには、プロピレングリコールモノメチルエーテルアセテート等のモノＣ3-6アルキレングリコールアルキルエーテルアセテート、及びＣ3-6アルカンジオールアルキルエーテルアセテートから選択される溶剤を１種又は２種以上併用することが効果的である。 To further improve dispersibility, one or more solvents selected from mono C 3-6 alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and C 3-6 alkanediol alkyl ether acetates are used. It is effective to use together.
　染料溶解性をより向上するためには、プロピレングリコールモノメチルエーテル等のモノＣ3-6アルキレングリコールモノアルキルエーテル、プロピレングリコールモノメチルエーテルアセテート等のモノＣ3-6アルキレングリコールアルキルエーテルアセテート、Ｃ3-6アルカンジオールモノアルキルエーテル、Ｃ3-6アルカンジオールアルキルエーテルアセテート、ヒドロキシカルボン酸エステル、ヒドロキシカルボン酸ジエステル、Ｃ3-6アルコール、及びＣ3-6アルカンジオールから選択される溶剤を１種又は２種以上併用することが効果的である。 To further improve the dye solubility, mono C 3-6 alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, mono-C 3-6 alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, C 3-6 One or two solvents selected from alkanediol monoalkyl ether, C 3-6 alkanediol alkyl ether acetate, hydroxycarboxylic acid ester, hydroxycarboxylic acid diester, C 3-6 alcohol, and C 3-6 alkanediol The combined use is effective.
　エポキシ樹脂やアクリル樹脂の溶解性をより向上するためには、（モノ，ジ，トリ）アルキレングリコールモノアルキルエーテル、（モノ，ジ）アルキレングリコールジアルキルエーテル、（モノ，ジ）アルキレングリコールアルキルエーテルアセテート、（モノ，ジ）アルキレングリコールジアセテート、環状ケトン、ラクトン類、環状エーテル、アミド類、ピリジン類、芳香族アセテート、及びアミン類から選択される溶剤を１種又は２種以上併用することが効果的である。 In order to further improve the solubility of epoxy resin and acrylic resin, (mono, di, tri) alkylene glycol monoalkyl ether, (mono, di) alkylene glycol dialkyl ether, (mono, di) alkylene glycol alkyl ether acetate, It is effective to use one or more solvents selected from (mono, di) alkylene glycol diacetates, cyclic ketones, lactones, cyclic ethers, amides, pyridines, aromatic acetates, and amines in combination. It is.
　乾燥性をより向上するためには、プロピレングリコールメチルｎ－プロピルエーテル、プロピレングリコールメチルｎ－ブチルエーテル、ジプロピレングリコールメチルｎ－プロピルエーテル、ジプロピレングリコールメチルｎ－ブチルエーテル等の（モノ，ジ）Ｃ3-6アルキレングリコールＣ1-2アルキルＣ3-4アルキルエーテル、及び（シクロ）アルキルアセテートから選択される溶剤を１種又は２種以上併用することが効果的である。 In order to further improve the drying property, (mono, di) C 3 such as propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl n-butyl ether, etc. It is effective to use one or more solvents selected from -6 alkylene glycol C 1-2 alkyl C 3-4 alkyl ether and (cyclo) alkyl acetate.
　溶剤（Ａ）及び／又は溶剤（Ｂ）と溶剤（Ｃ）とを併用する場合、その混合比（［溶剤（Ａ）＋溶剤（Ｂ）］／［溶剤（Ｃ）］；重量比）は、例えば９５／５～５０／５０、好ましくは９５／５～７０／３０である。溶剤（Ａ）及び／又は溶剤（Ｂ）に比べ溶剤（Ｃ）の割合が多くなると、有機半導体材料の溶解性が低下する傾向がある。 When the solvent (A) and / or the solvent (B) and the solvent (C) are used in combination, the mixing ratio ([solvent (A) + solvent (B)] / [solvent (C)]; weight ratio) is: For example, it is 95/5 to 50/50, preferably 95/5 to 70/30. When the ratio of the solvent (C) is higher than that of the solvent (A) and / or the solvent (B), the solubility of the organic semiconductor material tends to decrease.
　また、本発明の有機ＥＬ素子製造用溶剤はトルエン等の従来使用されていた溶剤を含有していても良いが、トルエン等の含有量は、本発明の有機ＥＬ素子製造用溶剤全量の例えば１０重量％以下、好ましくは５重量％以下、特に好ましくは１重量％以下である。トルエン等の含有量が上記範囲を上回ると、安全性が低下するため好ましくない。 The solvent for producing the organic EL device of the present invention may contain a conventionally used solvent such as toluene, but the content of toluene or the like is, for example, 10% of the total amount of the solvent for producing the organic EL device of the present invention. % By weight or less, preferably 5% by weight or less, particularly preferably 1% by weight or less. If the content of toluene or the like exceeds the above range, safety is lowered, which is not preferable.
　本発明の有機ＥＬ素子製造用溶剤は溶剤（Ａ）及び／又は溶剤（Ｂ）を含有するため、比較的低温でも高い有機半導体材料溶解性を有する。１００℃における前記式（１）で表される構成単位を有する化合物の溶解度は、有機ＥＬ素子製造用溶剤１００重量部に対して、例えば０．１重量部以上、好ましくは１重量部以上、特に好ましくは２重量部以上である。溶解度の上限は例えば３０重量部、好ましくは２０重量部、特に好ましくは１５重量部である。１００℃における前記式（２）で表される構成単位を有する化合物の溶解度は、有機ＥＬ素子製造用溶剤１００重量部に対して、例えば０．１重量部以上、好ましくは１重量部以上、特に好ましくは２重量部以上である。溶解度の上限は例えば５０重量部、好ましくは４５重量部、特に好ましくは４０重量部である。 Since the solvent for producing an organic EL device of the present invention contains a solvent (A) and / or a solvent (B), it has a high solubility in organic semiconductor materials even at a relatively low temperature. The solubility of the compound having the structural unit represented by the formula (1) at 100 ° C. is, for example, 0.1 part by weight or more, preferably 1 part by weight or more with respect to 100 parts by weight of the organic EL element production solvent. Preferably it is 2 parts by weight or more. The upper limit of solubility is, for example, 30 parts by weight, preferably 20 parts by weight, particularly preferably 15 parts by weight. The solubility of the compound having the structural unit represented by the formula (2) at 100 ° C. is, for example, 0.1 part by weight or more, preferably 1 part by weight or more with respect to 100 parts by weight of the solvent for organic EL device production. Preferably it is 2 parts by weight or more. The upper limit of solubility is, for example, 50 parts by weight, preferably 45 parts by weight, particularly preferably 40 parts by weight.
　（有機半導体材料）
　本発明の有機ＥＬ素子製造用溶剤は、有機半導体材料溶解用の溶剤、より具体的には、有機半導体材料が溶解した状態で含まれる組成物を基板上に塗布（例えば、インクジェット印刷等の印刷法やスピンコート法等の方法で塗布）して有機ＥＬ素子を形成する際に、有機半導体材料を溶解するために使用される溶剤である。前記有機半導体材料としては特に限定されないが、本発明においては、下記式（１）で表される構成単位を有する化合物、及び／又は下記式（２）で表される化合物が好ましい。これらは１種を単独で、又は２種以上を組み合わせて使用することができる。 (Organic semiconductor materials)
The solvent for producing an organic EL element of the present invention is a solvent for dissolving an organic semiconductor material, more specifically, a composition containing the organic semiconductor material dissolved is applied onto a substrate (for example, printing such as ink jet printing). It is a solvent used for dissolving an organic semiconductor material when forming an organic EL device by applying a method such as a spin coating method or a spin coating method. Although it does not specifically limit as said organic-semiconductor material, In this invention, the compound which has a structural unit represented by following formula (1), and / or the compound represented by following formula (2) is preferable. These can be used alone or in combination of two or more.
Figure JPOXMLDOC01-appb-C000021
 （式中、Ａｒ1は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ2は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。ｍ、ｎは同一又は異なって１以上の整数を示す。ｍ個のＡｒ1、及びｎ個のＡｒ2は、それぞれ同一であってもよく、異なっていてもよい）
Figure JPOXMLDOC01-appb-C000022
 （式中、Ａｒ3～Ａｒ5は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す）
Figure JPOXMLDOC01-appb-C000021
 (In the formula, Ar 1 may have a substituent, and is a structure selected from an aromatic carbocyclic ring, an aromatic heterocyclic ring, and a ring in which two or more thereof are bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from the formula, Ar 2 is an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these which may have a substituent, each having a single bond or a linking group. 1 represents a group in which one hydrogen atom is removed from a structural formula selected from a ring bonded to each other, m and n are the same or different and each represents an integer of 1 or more, m Ar 1 and n Ar 2 may be the same or different)
Figure JPOXMLDOC01-appb-C000022
 (Wherein Ar 3 to Ar 5 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these via a single bond or a linking group. A group obtained by removing one hydrogen atom from a structural formula selected from
　前記芳香族炭素環としては、例えば、ベンゼン環や、インデン環、ナフタレン環、フルオレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環等の２個以上（好ましくは、２～５個）の環が縮合した、炭素数９～２０の多環芳香族炭素環を挙げることができる。 Examples of the aromatic carbocycle include two benzene rings, indene rings, naphthalene rings, fluorene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, and triphenylene rings. Examples thereof include polycyclic aromatic carbocycles having 9 to 20 carbon atoms in which the above (preferably 2 to 5) rings are condensed.
　前記芳香族複素環としては、例えば、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シンノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環等の、５～６員芳香族複素単環、又は２個以上（好ましくは、２～４個）の環が縮合した多環芳香族複素環を挙げることができる。 Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, and a pyrrolopyrazole ring. , Pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, A quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, or the like, or two or more (preferably 2 to 4) Rings) And a polycyclic aromatic heterocycle fused.
　前記連結基としては、例えば、二価の炭化水素基、カルボニル基（－ＣＯ－）、エーテル結合（－Ｏ－）、チオエーテル結合（－Ｓ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＣＯＮＨ－）、カーボネート結合（－ＯＣＯＯ－）、及びこれらが複数個結合した基等を挙げることができる。 Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are bonded.
　上記二価の炭化水素基としては、例えば、メチレン基、メチルメチレン基、ジメチルメチレン基、エチレン基、プロピレン基、トリメチレン基等のＣ1-4アルキレン基や、１，２－シクロペンチレン基、１，３－シクロペンチレン基、シクロペンチリデン基、１，２－シクロヘキシレン基、１，３－シクロヘキシレン基、１，４－シクロヘキシレン基、シクロヘキシリデン基等のＣ3-18シクロアルキレン基（シクロアルキリデン基を含む）等を挙げることができる。 Examples of the divalent hydrocarbon group include, for example, a C 1-4 alkylene group such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group, a 1,2-cyclopentylene group, C 3-18 cycloalkylene such as 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, etc. Group (including a cycloalkylidene group) and the like.
　前記芳香族炭素環、芳香族複素環、又はこれらの２個以上が単結合又は連結基を介して結合した環（以後、「芳香族炭素環等」と称する場合がある）が有していてもよい置換基としては、例えば、メチル基、エチル基等のＣ1-12（好ましくはＣ1-6）のアルキル基；ビニル基等のＣ2-12（好ましくはＣ2-6）のアルケニル基；エチニル基等のＣ2-12（好ましくはＣ2-6）のアルキニル基；メトキシ基、エトキシ基等のＣ1-12（好ましくはＣ1-6）のアルコキシ基；フェノキシ基、ナフトキシ基、ピリジルオキシ基等のＣ6-16（好ましくはＣ6-10）のアリールオキシ基；メトキシカルボニル基、エトキシカルボニル基等のＣ2-12（好ましくはＣ2-6）のアルコキシカルボニル基；Ｎ，Ｎ－ジメチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基等のＣ2-12（好ましくはＣ2-6）のＮ，Ｎ－ジアルキルアミノ基；Ｎ，Ｎ－ジフェニルアミノ基、Ｎ，Ｎ－ジトリルアミノ基、Ｎ－（９－フェナントレニル）－Ｎ－フェニルアミノ基、Ｎ－カルバゾリル基等のＣ10-24（好ましくはＣ12-24）のＮ，Ｎ－ジアリールアミノ基；フェニルメチルアミノ基等のＣ7-36（好ましくはＣ7-24）のＮ－アリール－Ｎ－アルキルアミノ基；アセチル基、ベンゾイル基等のＣ2-24（好ましくはＣ2-12）のアシル基；フッ素原子、塩素原子等のハロゲン原子；トリフルオロメチル基等のＣ1-12（好ましくはＣ1-6）のハロアルキル基；メチルチオ基、エチルチオ基等のＣ1-24（好ましくはＣ1-12）のアルキルチオ基；フェニルチオ基、ナフチルチオ基、ピリジルチオ基等のＣ4-36（好ましくはＣ5-24）のアリールチオ基又はヘテロアリールチオ基；トリメチルシリル基、トリフェニルシリル基等のＣ2-36（好ましくはＣ3-24）のシリル基；トリメチルシロキシ基等のＣ1-10（好ましくはＣ1-5）のトリアルキルシロキシ基；トリフェニルシロキシ基等のＣ6-36（好ましくはＣ6-24）のトリアリールシロキシ基；シアノ基；フェニル基、ナフチル基等のＣ6-36（好ましくはＣ6-24）の芳香族炭化水素基；チエニル基、ピリジル基等のＣ3-36（好ましくはＣ4-24）の芳香族複素環基等を挙げることができる。前記置換基は、さらに置換基（例えば、上記例示されている置換基等）を有していてもよい。前記芳香族炭素環等が有する置換基同士は、互いに結合して前記芳香族炭素環等を構成する炭素原子と共に環を形成していてもよい。 The aromatic carbocycle, the aromatic heterocycle, or a ring in which two or more of these are bonded through a single bond or a linking group (hereinafter sometimes referred to as “aromatic carbocycle etc.”) Suitable substituents include, for example, C 1-12 (preferably C 1-6 ) alkyl groups such as methyl and ethyl groups; C 2-12 (preferably C 2-6 ) alkenyls such as vinyl groups. Group: C 2-12 (preferably C 2-6 ) alkynyl group such as ethynyl group; C 1-12 (preferably C 1-6 ) alkoxy group such as methoxy group, ethoxy group; phenoxy group, naphthoxy group C 6-16 (preferably C 6-10 ) aryloxy group such as pyridyloxy group; C 2-12 (preferably C 2-6 ) alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; N , N-dimethylamino group, N, N-diethylamino group and the like C 2-12 ( Preferably C 2-6 ) N, N-dialkylamino group; N, N-diphenylamino group, N, N-ditolylamino group, N- (9-phenanthrenyl) -N-phenylamino group, N-carbazolyl group, etc. C 10-24 (preferably C 12-24 ) N, N-diarylamino group; C 7-36 (preferably C 7-24 ) N-aryl-N-alkylamino group such as phenylmethylamino group An acyl group of C 2-24 (preferably C 2-12 ) such as acetyl group or benzoyl group; a halogen atom such as fluorine atom or chlorine atom; C 1-12 such as trifluoromethyl group (preferably C 1- 6 ) a haloalkyl group; a C 1-24 (preferably C 1-12 ) alkylthio group such as a methylthio group or an ethylthio group; a C 4-36 (preferably C 5-24) such as a phenylthio group, a naphthylthio group or a pyridylthio group. ) Arylthio group or Roariruchio group; trialkylsiloxy group C 1-10 (preferably C 1-5) such as trimethylsiloxy group; a trimethylsilyl group, a silyl group of C 2-36 (preferably C 3-24) such as triphenylsilyl group A C 6-36 (preferably C 6-24 ) triarylsiloxy group such as a triphenylsiloxy group; a cyano group; a C 6-36 (preferably C 6-24 ) aromatic group such as a phenyl group or a naphthyl group; A hydrocarbon group; a C 3-36 (preferably C 4-24 ) aromatic heterocyclic group such as a thienyl group and a pyridyl group. The substituent may further have a substituent (for example, the substituents exemplified above). Substituents possessed by the aromatic carbocycle and the like may be bonded together to form a ring together with carbon atoms constituting the aromatic carbocycle and the like.
　前記芳香族炭素環等が有してもよい置換基の分子量は、５００以下が好ましく、特に好ましくは２５０以下である。 The molecular weight of the substituent that the aromatic carbocycle or the like may have is preferably 500 or less, particularly preferably 250 or less.
　Ａｒ1としては、正孔の注入性が高くなり、得られる素子の駆動電圧が低くなる点で、置換基を有していてもよい、芳香族炭素環及び／又は芳香族複素環の構造式から２個の水素原子を除いた基、及び前記置換基を有していてもよい、芳香族炭素環及び／又は芳香族複素環が２個以上（例えば２～５個、好ましくは２～３個）結合してなる構造式から２個の水素原子を除いた基が好ましく、特に、置換基を有していてもよい、ビフェニル環、ターフェニル環、及びフルオレン環から選択される構造式から２個の水素原子を除いた基が溶解性に優れる点で好ましい。前記置換基としてはＣ1-12アルキル基又はＣ1-12アルコキシ基が好ましい。 Ar 1 is a structural formula of an aromatic carbocycle and / or an aromatic heterocycle, which may have a substituent, in that the hole injection property is increased and the driving voltage of the resulting device is decreased. 2 or more aromatic carbocycles and / or aromatic heterocycles (for example, 2 to 5, preferably 2 to 3) which may have the above-described substituent and a group obtained by removing 2 hydrogen atoms from A group in which two hydrogen atoms are removed from the structural formula formed by bonding, particularly from the structural formula selected from a biphenyl ring, a terphenyl ring, and a fluorene ring, which may have a substituent. A group from which two hydrogen atoms have been removed is preferred because of its excellent solubility. The substituent is preferably a C 1-12 alkyl group or a C 1-12 alkoxy group.
　Ａｒ2としては、溶解性に優れる点で、置換基を有していてもよい芳香族炭素環（特に、ベンゼン環）の構造式から１個の水素原子を除いた基が好ましい。前記置換基としてはＣ1-12アルキル基又はＣ1-12アルコキシ基が好ましい。 Ar 2 is preferably a group in which one hydrogen atom is removed from the structural formula of an aromatic carbocyclic ring (particularly a benzene ring) which may have a substituent, from the viewpoint of excellent solubility. The substituent is preferably a C 1-12 alkyl group or a C 1-12 alkoxy group.
　前記式（１）中のｍ、ｎは１以上の整数（例えば１～３）を示す。隣接する正孔輸送層や発光層への正孔の注入性が高くなり、得られる素子の駆動電圧が低くなる点では、ｍは１、ｎは１であることが好ましい。ラジカルカチオンを安定に生成し、電極からの正孔注入性が高く、得られる素子の駆動電圧が低くなる点では、ｍは１、ｎは３であることが好ましい。 In the formula (1), m and n are integers of 1 or more (for example, 1 to 3). It is preferable that m is 1 and n is 1 in that the hole injection property to the adjacent hole transport layer or the light emitting layer is increased and the driving voltage of the resulting device is decreased. It is preferable that m is 1 and n is 3 in that radical cations are stably generated, the hole injection property from the electrode is high, and the driving voltage of the resulting device is low.
　上記式（１）中の丸括弧でくくられた２つの構成単位は、ブロック重合されていても良く、ランダム重合されていても良い。 The two structural units enclosed in parentheses in the above formula (1) may be block polymerized or random polymerized.
　上記式（１）で表される構成単位（大括弧（＝角括弧）でくくられた構成単位）の繰り返し数としては、例えば７～３００程度であり、前記式（１）で表される構成単位を有する化合物の重量平均分子量（ＧＰＣによる、ポリスチレン換算）は、例えば５０００～２０００００程度、好ましくは１００００～１０００００である。 The number of repetitions of the structural unit represented by the above formula (1) (the structural unit enclosed by square brackets (= square brackets)) is, for example, about 7 to 300, and the structure represented by the above formula (1) The compound having a unit has a weight average molecular weight (in terms of polystyrene by GPC) of, for example, about 5,000 to 200,000, preferably 10,000 to 100,000.
　また、Ａｒ3～Ａｒ5としては、置換基を有していてもよい芳香族炭素環（特に、ベンゼン環）の構造式から１個の水素原子を除いた基、又は置換基を有していてもよい芳香族複素環（特に、カルバゾール環）の構造式から１個の水素原子を除いた基が好ましい。前記置換基としてはＣ1-12（好ましくはＣ1-6）のアルキル基及び／又はＣ10-24（好ましくはＣ12-24）のジアリールアミノ基が好ましい。Ａｒ3～Ａｒ5から選択される２つの基は、前記置換基同士が互いに結合して式（２）中の窒素原子と共に環を形成していてもよい。 Ar 3 to Ar 5 each have a group obtained by removing one hydrogen atom from the structural formula of an aromatic carbocyclic ring (in particular, a benzene ring) which may have a substituent, or a substituent. A group in which one hydrogen atom is removed from the structural formula of an aromatic heterocyclic ring (particularly a carbazole ring) which may be used is preferable. The substituent is preferably a C 1-12 (preferably C 1-6 ) alkyl group and / or a C 10-24 (preferably C 12-24 ) diarylamino group. In the two groups selected from Ar 3 to Ar 5 , the substituents may be bonded to each other to form a ring together with the nitrogen atom in the formula (2).
　上記式（２）で表される化合物の分子量としては、例えば３００～５０００程度、好ましくは４５０～３０００、特に好ましくは４５０～１０００である。 The molecular weight of the compound represented by the above formula (2) is, for example, about 300 to 5000, preferably 450 to 3000, particularly preferably 450 to 1000.
　前記式（２）で表される化合物としては、下記式（2-1）で表される化合物及び下記式（2-2）で表される化合物から選択される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000023
 （式（2-1）中、Ａｒ6は、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ7～Ａｒ10は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。
式（2-2）中、Ａｒ11～Ａｒ13は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ14～Ａｒ19は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す） The compound represented by the formula (2) is preferably a compound selected from a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2).
Figure JPOXMLDOC01-appb-C000023
 (In Formula (2-1), Ar 6 may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from a structural formula selected from a ring, Ar 7 to Ar 10 are the same or different and may have a substituent, an aromatic carbocycle, an aromatic heterocycle; A group in which one hydrogen atom is removed from a structural formula selected from a ring and a ring in which two or more of these are bonded via a single bond or a linking group is shown.
In formula (2-2), Ar 11 to Ar 13 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these are a single bond or A group obtained by removing two hydrogen atoms from a structural formula selected from a ring bonded through a linking group, Ar 14 to Ar 19 may be the same or different and may have a substituent. A group obtained by removing one hydrogen atom from a structural formula selected from aromatic carbocycles, aromatic heterocycles, and rings in which two or more of these are bonded via a single bond or a linking group)
　Ａｒ6、Ａｒ11～Ａｒ13としては、上記Ａｒ1と同様の例を挙げることができる。 Examples of Ar 6 and Ar 11 to Ar 13 include the same examples as Ar 1 described above.
　Ａｒ7～Ａｒ10、Ａｒ14～Ａｒ19としては、上記Ａｒ3～Ａｒ5と同様の例を挙げることができる。 Examples of Ar 7 to Ar 10 and Ar 14 to Ar 19 include the same examples as Ar 3 to Ar 5 described above.
　Ａｒ6としては、なかでも、前記置換基を有していてもよい、芳香族炭素環（例えば、ベンゼン環）の構造式から２個の水素原子を除いた基、又は２個以上（例えば２～５個、好ましくは２～３個）の芳香族炭素環（例えば、ベンゼン環）が単結合又は連結基を介して結合してなる構造式（例えば、ビフェニル環、ターフェニル環の構造式）から２個の水素原子を除いた基が好ましい。 Ar 6 is a group in which two hydrogen atoms are removed from the structural formula of an aromatic carbocyclic ring (for example, benzene ring), or two or more (for example 2 Structural formula (for example, biphenyl ring, terphenyl ring structural formula) in which up to 5, preferably 2 to 3 aromatic carbocyclic rings (for example, benzene ring) are bonded via a single bond or a linking group A group in which two hydrogen atoms are removed from is preferable.
　Ａｒ7～Ａｒ10としては、なかでも、置換基を有していてもよい芳香族炭素環（特に、ベンゼン環、フェナントレン環、アントラセン環）の構造式から１個の水素原子を除いた基、又は置換基を有していてもよい芳香族複素環（特に、カルバゾール環）の構造式から１個の水素原子を除いた基が好ましい。前記置換基としてはＣ1-12（好ましくはＣ1-6）のアルキル基及び／又はＣ6-16（好ましくはＣ6-10）のアリール基が好ましい。Ａｒ7とＡｒ8、Ａｒ9とＡｒ10は、前記置換基同士が互いに結合して、これらのＡｒ基が結合する窒素原子と共に環を形成していてもよい。 Ar 7 to Ar 10 are, among others, a group in which one hydrogen atom is removed from the structural formula of an aromatic carbocyclic ring (in particular, a benzene ring, a phenanthrene ring or an anthracene ring) which may have a substituent, Or the group remove | excluding one hydrogen atom from the structural formula of the aromatic heterocyclic ring (especially carbazole ring) which may have a substituent is preferable. The substituent is preferably a C 1-12 (preferably C 1-6 ) alkyl group and / or a C 6-16 (preferably C 6-10 ) aryl group. Ar 7 and Ar 8 , and Ar 9 and Ar 10 may be bonded to each other to form a ring together with the nitrogen atom to which these Ar groups are bonded.
　Ａｒ11～Ａｒ13としては、なかでも、置換基を有していてもよい芳香族炭素環（特に、ベンゼン環）の構造式から２個の水素原子を除いた基が好ましい。 Ar 11 to Ar 13 are particularly preferably groups obtained by removing two hydrogen atoms from the structural formula of an aromatic carbocyclic ring (particularly a benzene ring) which may have a substituent.
　Ａｒ14～Ａｒ19としては、なかでも、置換基を有していてもよい芳香族炭素環（特に、ベンゼン環）の構造式から１個の水素原子を除いた基が好ましい。前記置換基としてはＣ1-12（好ましくはＣ1-6）のアルキル基が好ましい。Ａｒ14とＡｒ15、Ａｒ16とＡｒ17、Ａｒ18とＡｒ19は、前記置換基同士が互いに結合して、これらのＡｒ基が結合する窒素原子と共に環を形成していてもよい。 Ar 14 to Ar 19 are particularly preferably groups in which one hydrogen atom has been removed from the structural formula of an aromatic carbocyclic ring (in particular, a benzene ring) which may have a substituent. The substituent is preferably a C 1-12 (preferably C 1-6 ) alkyl group. Ar 14 and Ar 15 , Ar 16 and Ar 17 , and Ar 18 and Ar 19 may be bonded to each other to form a ring together with the nitrogen atom to which these Ar groups are bonded.
　本発明における有機半導体材料としては、特に下記式（1-1）で表される構成単位を有する化合物、下記式（2-1-1）～（2-1-5）で表される化合物、及び下記式（2-2-1）で表される化合物から選択される少なくとも１種の化合物が好ましい。
Figure JPOXMLDOC01-appb-C000024
 As the organic semiconductor material in the present invention, in particular, a compound having a structural unit represented by the following formula (1-1), a compound represented by the following formulas (2-1-1) to (2-1-5), And at least one compound selected from compounds represented by the following formula (2-2-1) is preferred.
Figure JPOXMLDOC01-appb-C000024
　［有機ＥＬ素子製造用組成物］
　本発明の有機ＥＬ素子製造用組成物は、基板上に塗布（例えば、インクジェット印刷等の印刷法やスピンコート法等の方法で塗布）して有機ＥＬ素子を形成するのに使用される組成物であって、上記有機半導体材料と有機ＥＬ素子製造用溶剤とを含むことを特徴とする。 [Composition for manufacturing organic EL device]
The composition for producing an organic EL device of the present invention is a composition used to form an organic EL device by coating on a substrate (for example, coating by a printing method such as inkjet printing or a spin coating method). And it contains the said organic-semiconductor material and the solvent for organic electroluminescent element manufacture, It is characterized by the above-mentioned.
　本発明の有機ＥＬ素子製造用組成物は、例えば、上記有機半導体材料と、上記有機ＥＬ素子製造用溶剤とを混合し、大気下で、７０～１５０℃程度の温度で０．１～１０時間程度加熱することにより調製することができる。 The composition for producing an organic EL device of the present invention is prepared, for example, by mixing the organic semiconductor material and the solvent for producing an organic EL device, and in the atmosphere at a temperature of about 70 to 150 ° C. for 0.1 to 10 hours. It can be prepared by heating to a certain extent.
　本発明の有機ＥＬ素子製造用組成物中の有機半導体材料の含有量は、例えば、有機半導体材料として前記式（1-1）で表される構成単位を有する化合物を使用する場合は、有機ＥＬ素子製造用溶剤１００重量部に対して、例えば０．１重量部以上、好ましくは１．０重量部以上、特に好ましくは２．０重量部以上である。上限は、例えば３０重量部、好ましくは２０重量部、特に好ましくは１５重量部である。 The content of the organic semiconductor material in the composition for producing an organic EL element of the present invention is, for example, when the compound having the structural unit represented by the formula (1-1) is used as the organic semiconductor material. For example, 0.1 part by weight or more, preferably 1.0 part by weight or more, and particularly preferably 2.0 part by weight or more with respect to 100 parts by weight of the device manufacturing solvent. The upper limit is, for example, 30 parts by weight, preferably 20 parts by weight, particularly preferably 15 parts by weight.
　本発明の有機ＥＬ素子製造用組成物中の有機半導体材料の含有量は、例えば、有機半導体材料として前記式（2-1-1）で表される化合物を使用する場合は、有機ＥＬ素子製造用溶剤１００重量部に対して、例えば０．１重量部以上、好ましくは１．０重量部以上、特に好ましくは２．０重量部以上である。上限は、例えば３０重量部、好ましくは２０重量部、特に好ましくは１５重量部である。 For example, when the compound represented by the formula (2-1-1) is used as the organic semiconductor material, the content of the organic semiconductor material in the composition for manufacturing an organic EL element of the present invention is organic EL element manufacturing. For example, 0.1 part by weight or more, preferably 1.0 part by weight or more, and particularly preferably 2.0 part by weight or more with respect to 100 parts by weight of the solvent. The upper limit is, for example, 30 parts by weight, preferably 20 parts by weight, particularly preferably 15 parts by weight.
　本発明の有機ＥＬ素子製造用組成物中の有機半導体材料の含有量は、例えば、有機半導体材料として前記式（2-2-1）で表される化合物を使用する場合は、有機ＥＬ素子製造用溶剤１００重量部に対して、例えば１．０重量部以上、好ましくは３．０重量部以上、特に好ましくは５．０重量部以上である。上限は、例えば５０重量部、好ましくは４５重量部、特に好ましくは４０重量部である。 For example, when the compound represented by the formula (2-2-1) is used as the organic semiconductor material, the content of the organic semiconductor material in the composition for manufacturing an organic EL element of the present invention is organic EL element manufacturing. For example, 1.0 part by weight or more, preferably 3.0 parts by weight or more, and particularly preferably 5.0 parts by weight or more with respect to 100 parts by weight of the solvent. The upper limit is, for example, 50 parts by weight, preferably 45 parts by weight, particularly preferably 40 parts by weight.
　本発明の有機ＥＬ素子製造用組成物中の有機ＥＬ素子製造用溶剤の含有量は、例えば９９．９９重量％以下である。その下限は、例えば５０．０重量％、好ましくは５５．０重量％、特に好ましくは６０．０重量％であり、上限は、好ましくは９９．０重量％、特に好ましくは９８．０重量％である。 The content of the solvent for producing an organic EL element in the composition for producing an organic EL element of the present invention is, for example, 99.99% by weight or less. The lower limit is, for example, 50.0% by weight, preferably 55.0% by weight, particularly preferably 60.0% by weight, and the upper limit is preferably 99.0% by weight, particularly preferably 98.0% by weight. is there.
　本発明の有機ＥＬ素子製造用組成物に含まれる有機ＥＬ素子製造用溶剤含有量は、有機半導体材料の自己組織化作用による結晶化を促進することができる点で、有機半導体材料に対し、例えば１倍（重量）以上が好ましく、更に好ましくは１．２倍（重量）以上、特に好ましくは１．５倍（重量）以上である。上限は、例えば１０００倍（重量）、好ましくは１００倍（重量）、特に好ましくは５０倍（重量）である。 The organic EL device manufacturing solvent content contained in the organic EL device manufacturing composition of the present invention can promote crystallization by the self-organizing action of the organic semiconductor material. It is preferably 1 time (weight) or more, more preferably 1.2 times (weight) or more, and particularly preferably 1.5 times (weight) or more. The upper limit is, for example, 1000 times (weight), preferably 100 times (weight), particularly preferably 50 times (weight).
　本発明の有機ＥＬ素子製造用組成物には、上記有機半導体材料と上記有機ＥＬ素子製造用溶剤以外にも、一般的な有機ＥＬ素子製造用組成物に含まれる成分（例えば、エポキシ樹脂、アクリル樹脂、セルロース樹脂、ブチラール樹脂等）を必要に応じて適宜配合することができる。 In the composition for producing an organic EL device of the present invention, in addition to the organic semiconductor material and the solvent for producing the organic EL device, components contained in a general composition for producing an organic EL device (for example, epoxy resin, acrylic resin) Resin, cellulose resin, butyral resin, etc.) can be blended as needed.
　本発明の有機ＥＬ素子製造用組成物は、比較的低温でも有機半導体材料を高濃度に溶解することができる。そのため、ガラス基板に比べて耐熱性は低いが、衝撃に強く、軽量且つフレキシブルなプラスチック基板にも有機ＥＬ素子を直接形成することができ、衝撃に強く、軽量且つフレキシブルなディスプレイやコンピュータ機器を形成することができる。また、本発明の有機ＥＬ素子製造用組成物は本発明の有機ＥＬ素子製造用溶剤を含むため、基板上に塗布すると有機半導体材料が自己組織化作用により結晶化し、高い結晶性を有する有機半導体結晶薄膜（例えば、有機ＥＬ素子）が得られる。更に、印刷法、スピンコート法等の簡便な塗布法で容易に前記有機半導体結晶薄膜の形成が可能であり、コストの大幅な削減が可能である。 The composition for producing an organic EL device of the present invention can dissolve an organic semiconductor material at a high concentration even at a relatively low temperature. Therefore, although it has lower heat resistance than glass substrates, it can withstand impacts and can directly form organic EL elements on lightweight and flexible plastic substrates, forming impact-resistant, lightweight and flexible displays and computer equipment. can do. Moreover, since the composition for manufacturing an organic EL device of the present invention contains the solvent for manufacturing an organic EL device of the present invention, when applied on a substrate, the organic semiconductor material is crystallized by a self-organizing action and has high crystallinity. A crystal thin film (for example, an organic EL element) is obtained. Furthermore, the organic semiconductor crystal thin film can be easily formed by a simple coating method such as a printing method or a spin coating method, and the cost can be greatly reduced.
　以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
　実施例１
　有機半導体材料として上記式（1-1）で表される構成単位を有する化合物（ポリ［（９，９－ジオクチルフルオロニル－２，７－ジイル）－ｃｏ－（４，４’－Ｎ－（４－ｓｅｃ－ブチルフェニル）ジフェニルアミン）］、重量平均分子量：４００００、アルドリッチ（株）製、以後、「ＴＦＢ」と称する場合がある）を使用し、有機ＥＬ素子製造用溶剤として４－ｔ－ブチルシクロヘキシルアセテート（商品名「ＢＣＨＸＡ」、（株）ダイセル製）を使用した。
　２０℃環境下で、有機ＥＬ素子製造用溶剤中に有機半導体材料を、その濃度が２重量％～９重量％となる様に分散した。その後、窒素雰囲気、遮光条件下、１００℃で２時間加熱して有機ＥＬ素子製造用組成物を得た。得られた有機ＥＬ素子製造用組成物中の不溶物を目視で確認し、有機半導体材料の溶解性を下記基準で評価した。
　評価基準
　不溶物が確認されなかった場合：○（溶解性良好）
　不溶物が確認された場合：×（溶解性不良） Example 1
A compound having a structural unit represented by the above formula (1-1) as an organic semiconductor material (poly [(9,9-dioctylfluoronyl-2,7-diyl) -co- (4,4′-N— ( 4-sec-butylphenyl) diphenylamine)], weight average molecular weight: 40000, manufactured by Aldrich Co., Ltd. (hereinafter, sometimes referred to as “TFB”), and 4-t-butyl as a solvent for organic EL device production Cyclohexyl acetate (trade name “BCHXA”, manufactured by Daicel Corporation) was used.
Under a 20 ° C. environment, an organic semiconductor material was dispersed in a solvent for producing an organic EL device so that the concentration thereof was 2 wt% to 9 wt%. Then, the composition for organic EL element manufacture was obtained by heating at 100 degreeC for 2 hours under nitrogen atmosphere and light-shielding conditions. The insoluble matter in the obtained composition for manufacturing an organic EL device was visually confirmed, and the solubility of the organic semiconductor material was evaluated according to the following criteria.
Evaluation criteria When no insoluble matter is confirmed: ○ (Good solubility)
When insoluble matter is confirmed: x (poor solubility)
　実施例２～５、比較例１～３
　表１に示した有機ＥＬ素子製造用溶剤を使用した以外は実施例１と同様にして有機ＥＬ素子製造用組成物を調製し、有機半導体材料の溶解性を評価した。 Examples 2 to 5 and Comparative Examples 1 to 3
Except having used the solvent for organic EL element manufacture shown in Table 1, the composition for organic EL element manufacture was prepared like Example 1, and the solubility of the organic-semiconductor material was evaluated.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
　ＢＣＨＸＡ：４－ｔ－ブチルシクロヘキシルアセテート（（株）ダイセル製）
　ＭＣＨＸＡ：２－メチルシクロヘキシルアセテート（（株）ダイセル製）
　ＴＨＮＯ：１－オキソ－１，２，３，４－テトラヒドロナフタレン（（株）ダイセル製）
　ＰＥＣＰＡＮ：２－ペンチルシクロペンタノン（（株）ダイセル製）
　ＣＰＣＰＡＮ：２－シクロペンチルシクロペンタノン（（株）ダイセル製）
　Ｔｏｌ：トルエン（東京化成工業（株）製）
　Ｘｙｌ：ｏ－キシレン（東京化成工業（株）製）
　ＡＮＯＮ：シクロヘキサノン（東京化成工業（株）製） BCHXA: 4-t-butylcyclohexyl acetate (manufactured by Daicel Corporation)
MCHXA: 2-methylcyclohexyl acetate (manufactured by Daicel Corporation)
THNO: 1-oxo-1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
PECPAN: 2-pentylcyclopentanone (manufactured by Daicel Corporation)
CCPPAN: 2-cyclopentylcyclopentanone (manufactured by Daicel Corporation)
Tol: Toluene (Tokyo Chemical Industry Co., Ltd.)
Xyl: o-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.)
ANON: cyclohexanone (manufactured by Tokyo Chemical Industry Co., Ltd.)
　実施例６
　有機半導体材料として上記式（2-2-1）で表される化合物（４，４’，４”－トリス［フェニル（ｍ－トリル）アミノ］トリフェニルアミン、分子量：７８９、アルドリッチ（株）製、以後「ＴＦＡ」と称する場合がある）を使用し、有機ＥＬ素子製造用溶剤として２，３－ジヒドロ－２－メチルベンゾフラン（商品名「ＤＨＭＢＦ」、（株）ダイセル製）を使用した。
　２０℃環境下で、有機ＥＬ素子製造用溶剤中に有機半導体材料を、その濃度が１０重量％～３０重量％となる様に分散した。その後、窒素雰囲気、遮光条件下、１００℃で２時間加熱して有機ＥＬ素子製造用組成物を得た。得られた有機ＥＬ素子製造用組成物中の不溶物を目視で確認し、有機半導体材料の溶解性を上記基準で評価した。 Example 6
Compound (4,4 ′, 4 ″ -tris [phenyl (m-tolyl) amino] triphenylamine represented by the above formula (2-2-1) as an organic semiconductor material, molecular weight: 789, manufactured by Aldrich Co., Ltd. (Hereinafter, sometimes referred to as “TFA”), and 2,3-dihydro-2-methylbenzofuran (trade name “DHMBF”, manufactured by Daicel Corporation) was used as a solvent for producing an organic EL device.
Under a 20 ° C. environment, an organic semiconductor material was dispersed in a solvent for producing an organic EL device so that the concentration thereof was 10 wt% to 30 wt%. Then, the composition for organic EL element manufacture was obtained by heating at 100 degreeC for 2 hours under nitrogen atmosphere and light-shielding conditions. The insoluble matter in the obtained composition for manufacturing an organic EL device was visually confirmed, and the solubility of the organic semiconductor material was evaluated based on the above criteria.
　実施例７～１３、比較例４～６
　表２に示した有機ＥＬ素子製造用溶剤を使用した以外は実施例６と同様にして有機ＥＬ素子製造用組成物を調製し、有機半導体材料の溶解性を評価した。 Examples 7 to 13 and Comparative Examples 4 to 6
Except having used the solvent for organic EL element manufacture shown in Table 2, the composition for organic EL element manufacture was prepared like Example 6, and the solubility of the organic-semiconductor material was evaluated.
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
　ＤＨＭＢＦ：２，３－ジヒドロ－２－メチルベンゾフラン（（株）ダイセル製）
　ＴＨＮ：１，２，３，４－テトラヒドロナフタレン（（株）ダイセル製）
　ＴＨＮＯ：１－オキソ－１，２，３，４－テトラヒドロナフタレン（（株）ダイセル製）
　ＰＣＨ：フェニルシクロヘキサン（（株）ダイセル製）
　ＤＭＴＨＰ：１，３－ジメチル－３，４，５，６－テトラヒドロ－２（１Ｈ）－ピリミジノン（（株）ダイセル製）
　ＣＰＣＰＡＮ：２－シクロペンチルシクロペンタノン（（株）ダイセル製）
　ＣＨＸＡ：シクロヘキシルアセテート（（株）ダイセル製）
　ＤＭＩ：１，３－ジメチル－２－イミダゾリジノン（（株）ダイセル製）
　Ｔｏｌ：トルエン（東京化成工業（株）製）
　Ｘｙｌ：ｏ－キシレン（東京化成工業（株）製）
　ＡＮＯＮ：シクロヘキサノン（東京化成工業（株）製） DHMBF: 2,3-dihydro-2-methylbenzofuran (manufactured by Daicel Corporation)
THN: 1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
THNO: 1-oxo-1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
PCH: Phenylcyclohexane (manufactured by Daicel Corporation)
DMTHP: 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (manufactured by Daicel Corporation)
CCPPAN: 2-cyclopentylcyclopentanone (manufactured by Daicel Corporation)
CHXA: cyclohexyl acetate (manufactured by Daicel Corporation)
DMI: 1,3-dimethyl-2-imidazolidinone (manufactured by Daicel Corporation)
Tol: Toluene (Tokyo Chemical Industry Co., Ltd.)
Xyl: o-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.)
ANON: cyclohexanone (manufactured by Tokyo Chemical Industry Co., Ltd.)
　実施例１４
　有機半導体材料として上記式（2-1-1）で表される化合物（４，４’－ビス（Ｎ－カルバゾリル）－１，１’－ビフェニル、分子量：４８５、アルドリッチ（株）製、以後、「ＣＢＰ」と称する場合がある）を使用し、有機ＥＬ素子製造用溶剤として１－オキソ－１，２，３，４－テトラヒドロナフタレン（商品名「ＴＨＮＯ」、（株）ダイセル製）を使用した。
　２０℃環境下で、有機ＥＬ素子製造用溶剤中に有機半導体材料を、その濃度が２重量％～１０重量％となる様に分散した。その後、窒素雰囲気、遮光条件下、１００℃で２時間加熱して有機ＥＬ素子製造用組成物を得た。得られた有機ＥＬ素子製造用組成物中の不溶物を目視で確認し、有機半導体材料の溶解性を上記基準で評価した。 Example 14
As an organic semiconductor material, a compound represented by the above formula (2-1-1) (4,4′-bis (N-carbazolyl) -1,1′-biphenyl, molecular weight: 485, manufactured by Aldrich Co., Ltd., 1) -oxo-1,2,3,4-tetrahydronaphthalene (trade name “THNO”, manufactured by Daicel Corporation) was used as a solvent for producing organic EL elements. .
Under a 20 ° C. environment, an organic semiconductor material was dispersed in a solvent for producing an organic EL element so that its concentration was 2 wt% to 10 wt%. Then, the composition for organic EL element manufacture was obtained by heating at 100 degreeC for 2 hours under nitrogen atmosphere and light-shielding conditions. The insoluble matter in the obtained composition for manufacturing an organic EL device was visually confirmed, and the solubility of the organic semiconductor material was evaluated based on the above criteria.
　実施例１５～２０、比較例７～９
　表３に示した有機ＥＬ素子製造用溶剤を使用した以外は実施例１４と同様にして有機ＥＬ素子製造用組成物を調製し、有機半導体材料の溶解性を評価した。 Examples 15 to 20, Comparative Examples 7 to 9
Except having used the solvent for organic EL element manufacture shown in Table 3, the composition for organic EL element manufacture was prepared like Example 14, and the solubility of the organic-semiconductor material was evaluated.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　ＴＨＮＯ：１－オキソ－１，２，３，４－テトラヒドロナフタレン（（株）ダイセル製）
　ＤＭＴＨＰ：１，３－ジメチル－３，４，５，６－テトラヒドロ－２（１Ｈ）－ピリミジノン（（株）ダイセル製）
　ＣＰＣＰＡＮ：２－シクロペンチルシクロペンタノン（（株）ダイセル製）
　ＴＨＮ：１，２，３，４－テトラヒドロナフタレン（（株）ダイセル製）
　ＤＨＭＢＦ：２，３－ジヒドロ－２－メチルベンゾフラン（（株）ダイセル製）
　ＤＭＩ：１，３－ジメチル－２－イミダゾリジノン（（株）ダイセル製）
　ＰＣＨ：フェニルシクロヘキサン（（株）ダイセル製）
　Ｔｏｌ：トルエン（東京化成工業（株）製）
　Ｘｙｌ：ｏ－キシレン（東京化成工業（株）製）
　ＡＮＯＮ：シクロヘキサノン（東京化成工業（株）製） THNO: 1-oxo-1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
DMTHP: 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (manufactured by Daicel Corporation)
CCPPAN: 2-cyclopentylcyclopentanone (manufactured by Daicel Corporation)
THN: 1,2,3,4-tetrahydronaphthalene (manufactured by Daicel Corporation)
DHMBF: 2,3-dihydro-2-methylbenzofuran (manufactured by Daicel Corporation)
DMI: 1,3-dimethyl-2-imidazolidinone (manufactured by Daicel Corporation)
PCH: Phenylcyclohexane (manufactured by Daicel Corporation)
Tol: Toluene (Tokyo Chemical Industry Co., Ltd.)
Xyl: o-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.)
ANON: cyclohexanone (manufactured by Tokyo Chemical Industry Co., Ltd.)
　本発明の有機ＥＬ素子製造用溶剤は、トルエン、キシレン、シクロヘキサノンに比べて安全性に優れる。また、上記実施例から、トルエン、キシレン、シクロヘキサノンと同等若しくはより優れた有機半導体材料［例えば式（１）、（２）で表される化合物、特に、ポリ［（９，９－ジオクチルフルオロニル－２，７－ジイル）－ｃｏ－（４，４’－Ｎ－（４－ｓｅｃ－ブチルフェニル）ジフェニルアミン）］（式（1-1）で表される構成単位を有する化合物）、４，４’－ビス（Ｎ－カルバゾリル）－１，１’－ビフェニル（式（2-1-1）で表される化合物）、４，４’，４”－トリス［フェニル（ｍ－トリル）アミノ］トリフェニルアミン（式（2-2-1）で表される化合物）等］の溶解性を有する。 The solvent for producing the organic EL device of the present invention is superior in safety compared with toluene, xylene and cyclohexanone. Further, from the above examples, organic semiconductor materials equivalent to or better than toluene, xylene and cyclohexanone [for example, compounds represented by the formulas (1) and (2), particularly poly [(9,9-dioctylfluoronyl- 2,7-diyl) -co- (4,4′-N- (4-sec-butylphenyl) diphenylamine)] (compound having a structural unit represented by formula (1-1)), 4,4 ′ -Bis (N-carbazolyl) -1,1′-biphenyl (compound represented by the formula (2-1-1)), 4,4 ′, 4 ″ -tris [phenyl (m-tolyl) amino] triphenyl Amine (compound represented by the formula (2-2-1)) and the like].
　本発明の有機ＥＬ素子製造用溶剤は、比較的低温でも高い有機半導体材料溶解性を有する。そして、本発明の有機ＥＬ素子製造用組成物は、前記有機ＥＬ素子製造用溶剤を含有するため、ガラス基板に比べて耐熱性は低いが、衝撃に強く、軽量且つフレキシブルなプラスチック基板に印刷法やスピンコート法等の塗布法を用いて有機ＥＬ素子を直接形成することができ、衝撃に強く、軽量且つフレキシブルなディスプレイやコンピュータ機器を、コストを大幅に削減しつつ形成することができる。
　さらに、本発明の有機ＥＬ素子製造用組成物を基板上に塗布すると有機半導体材料が自己組織化作用により結晶化するため、高い結晶性を有する有機半導体結晶薄膜が得られる。 The solvent for producing an organic EL device of the present invention has high organic semiconductor material solubility even at a relatively low temperature. And since the composition for organic EL element manufacture of this invention contains the said solvent for organic EL element manufacture, although heat resistance is low compared with a glass substrate, it is a shock-resistant, lightweight and flexible plastic substrate printing method The organic EL element can be directly formed by using a coating method such as spin coating or the like, and a light-weight and flexible display or computer device that is resistant to impact can be formed while greatly reducing costs.
Furthermore, when the composition for manufacturing an organic EL device of the present invention is applied on a substrate, the organic semiconductor material is crystallized by a self-organizing action, so that an organic semiconductor crystal thin film having high crystallinity is obtained.

Claims (10)

  1. 　有機半導体材料溶解用の溶剤であって、下記式（ａ）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1～Ｒ4は同一又は異なって、Ｃ1-2アルキル基である。Ｒ1とＲ4は互いに結合して式中の－Ｎ（Ｒ2）－Ｃ（＝Ｏ）－Ｎ（Ｒ3）－と共に環を形成していてもよい）
    で表される溶剤（Ａ）、及び／又は下記式（ｂ）
    Figure JPOXMLDOC01-appb-C000002
     ［式中、環Ｚは芳香族炭素環、５～７員の脂環式炭素環、及び５～７員の複素環から選択される環を示す。Ｒ5はオキソ基（＝Ｏ）、チオキシ基（＝Ｓ）、－ＯＲa基、－ＳＲa基、－Ｏ（Ｃ＝Ｏ）Ｒa基、－ＲbＯ（Ｃ＝Ｏ）Ｒa基（ＲaはＣ1-7アルキル基、又はアリール基、又は前記基が単結合若しくは連結基を介して結合した基を示し、ＲbはＣ1-7アルキレン基、又はアリーレン基、又は前記基が単結合若しくは連結基を介して結合した基を示す）、及び置換又は無置換アミノ基から選択される基を示し、Ｒ6は水素原子、Ｃ1-7アルキル基、アリール基、及び－ＯＲa基（Ｒaは前記に同じ）から選択される基を示す。Ｒ5とＲ6は互いに結合して環Ｚを構成する炭素原子と共に環を形成していてもよい］
    で表される溶剤（Ｂ）を含む有機エレクトロルミネッセンス素子製造用溶剤。     A solvent for dissolving an organic semiconductor material having the following formula (a)
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 to R 4 are the same or different and are C 1-2 alkyl groups. R 1 and R 4 are bonded to each other to form —N (R 2 ) —C (═O) — N (R 3 )-may form a ring)
    And / or the following formula (b)
    Figure JPOXMLDOC01-appb-C000002
     [Wherein, ring Z represents a ring selected from an aromatic carbocyclic ring, a 5- to 7-membered alicyclic carbocyclic ring, and a 5- to 7-membered heterocyclic ring. R 5 represents an oxo group (═O), a thioxy group (═S), a —OR a group, a —SR a group, a —O (C═O) R a group, a —R b O (C═O) R a group. (R a represents a C 1-7 alkyl group, an aryl group, or a group in which the group is bonded via a single bond or a linking group, and R b represents a C 1-7 alkylene group, an arylene group, or the group described above. Represents a group bonded through a single bond or a linking group), and a group selected from a substituted or unsubstituted amino group, R 6 represents a hydrogen atom, a C 1-7 alkyl group, an aryl group, and —OR A group selected from a group (R a is as defined above). R 5 and R 6 may be bonded to each other to form a ring together with the carbon atoms constituting ring Z]
    The solvent for organic electroluminescent element manufacture containing the solvent (B) represented by these.
  2. 　溶剤（Ａ）が、１，１，３，３－テトラメチル尿素、１，３－ジメチル－２－イミダゾリジノン、及び１，３－ジメチル－３，４，５，６－テトラヒドロ－２（１Ｈ）ピリミジノンから選択される少なくとも１種である請求項１に記載の有機エレクトロルミネッセンス素子製造用溶剤。 Solvent (A) is 1,1,3,3-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H The solvent for producing an organic electroluminescence device according to claim 1, wherein the solvent is at least one selected from pyrimidinone.
  3. 　溶剤（Ｂ）が、２－シクロペンチルシクロペンタノン、２－ペンチルシクロペンタノン、２，３－ジヒドロベンゾフラン、２，３－ジヒドロ－２－メチルベンゾフラン、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、４－ｔ－ブチルシクロヘキシルアセテート、１，２，３，４－テトラヒドロナフタレン、１－オキソ－１，２，３，４－テトラヒドロナフタレン、及びフェニルシクロヘキサンから選択される少なくとも１種である請求項１又は２に記載の有機エレクトロルミネッセンス素子製造用溶剤。 Solvent (B) is 2-cyclopentylcyclopentanone, 2-pentylcyclopentanone, 2,3-dihydrobenzofuran, 2,3-dihydro-2-methylbenzofuran, cyclohexyl acetate, 2-methylcyclohexyl acetate, 4-t The at least one selected from the group consisting of -butylcyclohexyl acetate, 1,2,3,4-tetrahydronaphthalene, 1-oxo-1,2,3,4-tetrahydronaphthalene, and phenylcyclohexane. Solvent for producing organic electroluminescence elements.
  4. 　有機半導体材料が、下記式（１）で表される構成単位を有する化合物及び／又は下記式（２）で表される化合物である請求項１～３の何れか１項に記載の有機エレクトロルミネッセンス素子製造用溶剤。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ａｒ1は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ2は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。ｍ、ｎは同一又は異なって１以上の整数を示す。ｍ個のＡｒ1、及びｎ個のＡｒ2は、それぞれ同一であってもよく、異なっていてもよい）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ａｒ3～Ａｒ5は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す）     The organic electroluminescence according to any one of claims 1 to 3, wherein the organic semiconductor material is a compound having a structural unit represented by the following formula (1) and / or a compound represented by the following formula (2). Solvent for device manufacturing.
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, Ar 1 may have a substituent, and is a structure selected from an aromatic carbocyclic ring, an aromatic heterocyclic ring, and a ring in which two or more thereof are bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from the formula, Ar 2 is an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these which may have a substituent, each having a single bond or a linking group. 1 represents a group in which one hydrogen atom is removed from a structural formula selected from a ring bonded to each other, m and n are the same or different and each represents an integer of 1 or more, m Ar 1 and n Ar 2 may be the same or different)
    Figure JPOXMLDOC01-appb-C000004
     (Wherein Ar 3 to Ar 5 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these via a single bond or a linking group. A group obtained by removing one hydrogen atom from a structural formula selected from
  5. 　式（２）で表される化合物が、下記式（2-1）で表される化合物又は下記式（2-2）で表される化合物である請求項４に記載の有機エレクトロルミネッセンス素子製造用溶剤。
    Figure JPOXMLDOC01-appb-C000005
     （式（2-1）中、Ａｒ6は、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ7～Ａｒ10は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。
    式（2-2）中、Ａｒ11～Ａｒ13は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ14～Ａｒ19は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す）     The compound represented by the formula (2) is a compound represented by the following formula (2-1) or a compound represented by the following formula (2-2). solvent.
    Figure JPOXMLDOC01-appb-C000005
     (In Formula (2-1), Ar 6 may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from a structural formula selected from a ring, Ar 7 to Ar 10 are the same or different and may have a substituent, an aromatic carbocycle, an aromatic heterocycle; A group in which one hydrogen atom is removed from a structural formula selected from a ring and a ring in which two or more of these are bonded via a single bond or a linking group is shown.
    In formula (2-2), Ar 11 to Ar 13 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these are a single bond or A group obtained by removing two hydrogen atoms from a structural formula selected from a ring bonded through a linking group, Ar 14 to Ar 19 may be the same or different and may have a substituent. A group obtained by removing one hydrogen atom from a structural formula selected from aromatic carbocycles, aromatic heterocycles, and rings in which two or more of these are bonded via a single bond or a linking group)
  6. 　有機半導体材料が、下記式（1-1）で表される構成単位を有する化合物、下記式（2-1-1）～（2-1-5）で表される化合物、及び下記式（2-2-1）で表される化合物から選択される少なくとも１種の化合物である請求項１～３の何れか１項に記載の有機エレクトロルミネッセンス素子製造用溶剤。
    Figure JPOXMLDOC01-appb-C000006
         The organic semiconductor material includes a compound having a structural unit represented by the following formula (1-1), a compound represented by the following formula (2-1-1) to (2-1-5), and the following formula (2 The solvent for producing an organic electroluminescence device according to any one of claims 1 to 3, which is at least one compound selected from compounds represented by -2-1).
    Figure JPOXMLDOC01-appb-C000006
  7. 　有機半導体材料と、請求項１～６の何れか１項に記載の有機エレクトロルミネッセンス素子製造用溶剤とを含む有機エレクトロルミネッセンス素子製造用組成物。 A composition for producing an organic electroluminescence device comprising an organic semiconductor material and the solvent for producing an organic electroluminescence device according to any one of claims 1 to 6.
  8. 　有機半導体材料が、下記式（１）で表される構成単位を有する化合物及び／又は下記式（２）で表される化合物である請求項７に記載の有機エレクトロルミネッセンス素子製造用組成物。
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ａｒ1は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ2は置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。ｍ、ｎは同一又は異なって１以上の整数を示す。ｍ個のＡｒ1、及びｎ個のＡｒ2は、それぞれ同一であってもよく、異なっていてもよい）
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ａｒ3～Ａｒ5は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す）     The composition for manufacturing an organic electroluminescence device according to claim 7, wherein the organic semiconductor material is a compound having a structural unit represented by the following formula (1) and / or a compound represented by the following formula (2).
    Figure JPOXMLDOC01-appb-C000007
     (In the formula, Ar 1 may have a substituent, and is a structure selected from an aromatic carbocyclic ring, an aromatic heterocyclic ring, and a ring in which two or more thereof are bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from the formula, Ar 2 is an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these which may have a substituent, each having a single bond or a linking group. 1 represents a group in which one hydrogen atom is removed from a structural formula selected from a ring bonded to each other, m and n are the same or different and each represents an integer of 1 or more, m Ar 1 and n Ar 2 may be the same or different)
    Figure JPOXMLDOC01-appb-C000008
     (Wherein Ar 3 to Ar 5 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these via a single bond or a linking group. A group obtained by removing one hydrogen atom from a structural formula selected from
  9. 　式（２）で表される化合物が、下記式（2-1）で表される化合物又は下記式（2-2）で表される化合物である請求項８に記載の有機エレクトロルミネッセンス素子製造用組成物。
    Figure JPOXMLDOC01-appb-C000009
     （式（2-1）中、Ａｒ6は、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ7～Ａｒ10は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す。
    式（2-2）中、Ａｒ11～Ａｒ13は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から２個の水素原子を除いた基を示し、Ａｒ14～Ａｒ19は、同一又は異なって、置換基を有していてもよい、芳香族炭素環、芳香族複素環、及びこれらの２個以上が単結合又は連結基を介して結合した環から選択される構造式から１個の水素原子を除いた基を示す）     The compound represented by the formula (2) is a compound represented by the following formula (2-1) or a compound represented by the following formula (2-2), for producing an organic electroluminescence device according to claim 8. Composition.
    Figure JPOXMLDOC01-appb-C000009
     (In Formula (2-1), Ar 6 may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these bonded via a single bond or a linking group. A group in which two hydrogen atoms are removed from a structural formula selected from a ring, Ar 7 to Ar 10 are the same or different and may have a substituent, an aromatic carbocycle, an aromatic heterocycle; A group in which one hydrogen atom is removed from a structural formula selected from a ring and a ring in which two or more of these are bonded via a single bond or a linking group is shown.
    In formula (2-2), Ar 11 to Ar 13 are the same or different and each may have a substituent, an aromatic carbocyclic ring, an aromatic heterocyclic ring, and two or more of these are a single bond or A group obtained by removing two hydrogen atoms from a structural formula selected from a ring bonded through a linking group, Ar 14 to Ar 19 may be the same or different and may have a substituent. A group obtained by removing one hydrogen atom from a structural formula selected from aromatic carbocycles, aromatic heterocycles, and rings in which two or more of these are bonded via a single bond or a linking group)
  10. 　有機半導体材料が、下記式（1-1）で表される構成単位を有する化合物、下記式（2-1-1）～（2-1-5）で表される化合物、及び下記式（2-2-1）で表される化合物から選択される少なくとも１種の化合物である請求項７に記載の有機エレクトロルミネッセンス素子製造用組成物。
    Figure JPOXMLDOC01-appb-C000010
         The organic semiconductor material includes a compound having a structural unit represented by the following formula (1-1), a compound represented by the following formula (2-1-1) to (2-1-5), and the following formula (2 The composition for producing an organic electroluminescence device according to claim 7, which is at least one compound selected from the compounds represented by -2-1).
    Figure JPOXMLDOC01-appb-C000010
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