WO2013146806A1 - 高分子化合物およびそれを用いた発光素子 - Google Patents
高分子化合物およびそれを用いた発光素子 Download PDFInfo
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- WO2013146806A1 WO2013146806A1 PCT/JP2013/058841 JP2013058841W WO2013146806A1 WO 2013146806 A1 WO2013146806 A1 WO 2013146806A1 JP 2013058841 W JP2013058841 W JP 2013058841W WO 2013146806 A1 WO2013146806 A1 WO 2013146806A1
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- 239000007788 liquid Substances 0.000 description 22
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- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 22
- 239000000126 substance Substances 0.000 description 22
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 16
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 16
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- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
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- 229910052751 metal Inorganic materials 0.000 description 13
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
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- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 8
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- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 8
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 7
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- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 6
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
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- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 6
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- 125000004426 substituted alkynyl group Chemical group 0.000 description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 5
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Definitions
- the present invention relates to a polymer compound, a composition containing the polymer compound, an organic thin film, an insolubilized organic thin film, a light emitting element, a planar light source, and a display device.
- a high molecular compound used for manufacturing an organic electroluminescent element for example, a high molecular compound (Patent Document 1) containing a repeating unit derived from arylamine or a benzocyclobutane structure is used.
- a polymer compound containing a repeating unit derived from fluorene (Patent Document 2) and a polymer compound containing a phenylene group having a substituent at a specific position as a repeating unit (Patent Document 3) are known.
- a light emitting device using the above polymer compound does not necessarily have sufficient light emission efficiency.
- the present invention provides the following polymer compound, a composition containing the polymer compound, an organic thin film, an insolubilized organic thin film, a light emitting element, a planar light source, and a display device.
- Ar 5 , Ar 6 and Ar 7 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent heterocyclic group.
- Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 may each be directly bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded.
- R a represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, a halogen atom, or an unsubstituted or substituted monovalent heterocyclic group.
- R a represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, a halogen atom, or an unsubstituted or substituted monovalent heterocyclic group.
- Ar 8 represents a (2 + p) -valent aromatic hydrocarbon group or a (2 + p) -valent heterocyclic group.
- R 1 is alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, oxycarbonyl group, monovalent Represents a heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a hydroxyl group, a nitro group or a cyano group.
- R 1 When a plurality of R 1 are present, they may be the same or different. Note that at least one R 1 substitutes a hydrogen atom directly bonded to a carbon atom adjacent to a carbon atom that forms a bond with another structural unit in the aromatic hydrocarbon group or heterocyclic group.
- p represents an integer of 1 or more.
- na represents an integer of 0 to 3
- nb represents an integer of 0 to 12
- nA represents 0 or 1
- n represents an integer of 1 to 4.
- Ar 10 represents an unsubstituted or substituted (2 + n) -valent aromatic hydrocarbon group or an unsubstituted or substituted (2 + n) -valent heterocyclic group.
- L a and L b each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group.
- La When a plurality of La are present, they may be the same or different.
- L B When a plurality of Lb are present, they may be the same or different.
- L A represents an oxygen atom or a sulfur atom.
- LA When a plurality of LA are present, they may be the same or different.
- Q 1 represents a monovalent crosslinkable group. When a plurality of Q 1 are present, they may be the same or different. Note that the structural unit represented by the formula (3) is different from the structural unit represented by the formula (2).
- Ar 20 and Ar 40 each independently represent an unsubstituted or substituted arylene group or an unsubstituted or substituted divalent heterocyclic group
- Ar 30 ′ represents an unsubstituted or substituted (2 + d) -valent aromatic group.
- Two or more identical or different groups selected from a hydrocarbon group, an unsubstituted or substituted (2 + d) -valent heterocyclic group, or a divalent aromatic hydrocarbon group and a divalent heterocyclic group are linked (2 + d ) -Valent group (the (2 + d) -valent group may have a substituent).
- Q 2 ′, Q 3 ′ and Q 4 ′ represent a monovalent crosslinkable group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent heterocyclic group.
- Q 2 ′, Q 3 ′ and Q 4 ′ are monovalent crosslinkable groups. When a plurality of Q 4 ′ are present, they may be the same or different.
- na represents an integer of 0 to 3
- nb represents an integer of 0 to 12
- nA represents 0 or 1.
- L a and L b each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group.
- L g and L h each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group.
- L g When a plurality of L g are present, they may be the same or different.
- L h When a plurality of L h are present, they may be the same or different.
- L D represents an oxygen atom or a sulfur atom. When a plurality of L D are present, they may be the same or different. Note that the structural unit represented by the formula (4 ′) is different from the structural unit represented by the formula (1).
- An insolubilized organic thin film obtained by insolubilizing the organic thin film according to [3] with a solvent by heating.
- a light emitting device having the organic thin film according to [3] or the insolubilized organic thin film according to [4].
- the present invention it is possible to provide a polymer compound useful for the production of a light emitting device having excellent luminous efficiency. Moreover, according to this invention, the composition containing the said high molecular compound, an organic thin film, an insolubilized organic thin film, a light emitting element, a planar light source, and a display apparatus can be provided.
- Me represents a methyl group
- Et represents an ethyl group
- Ph represents a phenyl group
- t-Bu represents a tert-butyl group
- n-Bu represents a tert-butyl group
- n-Bu represents a tert-butyl group
- n-Hex represents an n-hexyl group
- n-Oct represents an n-octyl group.
- “Structural unit” means a unit structure present in a polymer compound.
- the “structural unit” is preferably contained in the polymer compound as a “repeating unit (that is, a unit structure existing two or more in the polymer compound)”.
- C x -C y indicates that the number of carbon atoms in the partial structure corresponding to the functional group name described immediately after this term is It means x to y. That is, when the organic group described immediately after “C x -C y ” is an organic group named by combining a plurality of functional group names (for example, C x -C y alkoxyphenyl group), This means that the number of carbon atoms in the partial structure corresponding to the functional group name (for example, alkoxy) described immediately after “C x -C y ” among the functional group names is x to y.
- C 1 -C 12 alkyl group means an alkyl group having 1 to 12 carbon atoms
- C 1 -C 12 alkoxyphenyl group means “1 to 12 carbon atoms”. It means a phenyl group having an “alkoxy group”.
- an unsubstituted or substituted means that the functional group described immediately after this term may have a substituent.
- an unsubstituted or substituted alkyl group means “an unsubstituted alkyl group or an alkyl group having a substituent”.
- substituents examples include alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, oxycarbonyl group, 1 Examples thereof include a valent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, imine residue, amide compound residue, acid imide residue, carboxyl group, hydroxy group, nitro group, and cyano group. These groups may further have a substituent selected from the above.
- the “alkyl group” may have a substituent, and may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group (cycloalkyl group).
- the number of carbon atoms of the linear alkyl group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 12, not including the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkyl group and the cyclic alkyl group is preferably 3 to 20, more preferably 3 to 15, and further preferably 3 to 12, not including the number of carbon atoms of the substituent. .
- alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, Examples include octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, and dodecyl group.
- the “alkoxy group” may have a substituent, and may be any of a linear alkoxy group, a branched alkoxy group, and a cyclic alkoxy group (cycloalkoxy group).
- the number of carbon atoms of the linear alkoxy group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12, not including the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkoxy group and the cyclic alkoxy group is preferably 3 to 20, more preferably 3 to 15, and still more preferably 3 to 12, excluding the number of carbon atoms of the substituent. .
- alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyl
- alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyl
- alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyl
- examples thereof include an oxy group, an octyloxy group, a 2-ethylhexyl
- alkylthio group may have a substituent, and may be any of a linear alkylthio group, a molecular chain alkylthio group, and a cyclic alkylthio group (cycloalkylthio group).
- the number of carbon atoms of the linear alkylthio group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12, not including the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkylthio group and the cyclic alkylthio group is preferably 3 to 20, more preferably 3 to 15, and still more preferably 3 to 12, excluding the number of carbon atoms of the substituent. .
- alkylthio group examples include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, Examples include octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, and dodecylthio group.
- aryl group is an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.
- the aryl group may have a substituent, and examples of the aryl group include a group having a benzene ring and a group having a condensed ring.
- the number of carbon atoms of the aryl group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30 without including the number of carbon atoms of the substituent.
- aryl group examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, and a 2-fluorenyl group.
- the “aryloxy group” is a group represented by —O—Ar 11 (Ar 11 represents the above aryl group), and the aryl group in Ar 11 may have a substituent. Unless otherwise specified, the number of carbon atoms of the aryloxy group is preferably 6 to 60, more preferably 6 to 48, and even more preferably 6 to 30 without including the number of carbon atoms of the substituent. Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 2-anthracenyloxy group, a 9-anthracenyloxy group, and 2-fullyloxy group. An oleenyloxy group is mentioned.
- the “arylthio group” is a group represented by —S—Ar 12 (Ar 12 represents the above aryl group), and the aryl group in Ar 12 may have a substituent. Unless otherwise specified, the number of carbon atoms of the arylthio group is preferably 6 to 60, more preferably 6 to 48, and even more preferably 6 to 30 without including the number of carbon atoms of the substituent.
- arylthio group examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 1-anthracenylthio group, a 2-anthracenylthio group, a 9-anthracenylthio group, and a 2-fluorenylthio group.
- the “alkenyl group” may have a substituent, and may be any of a linear alkenyl group, a branched alkenyl group, and a cyclic alkenyl group.
- the number of carbon atoms of the linear alkenyl group is preferably 2 to 20, more preferably 2 to 15, and further preferably 2 to 10, excluding the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkenyl group and the cyclic alkenyl group is preferably 3 to 20, more preferably 3 to 15, and further preferably 3 to 10, excluding the number of carbon atoms of the substituent. .
- alkenyl group examples include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, A 1-octenyl group may be mentioned.
- alkynyl group may have a substituent, and may be any of a linear alkynyl group, a branched alkynyl group, and a cyclic alkynyl group.
- the number of carbon atoms of the linear alkynyl group is preferably 2 to 20, more preferably 2 to 15, and further preferably 2 to 10, excluding the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkynyl group and cyclic alkynyl group is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 10, excluding the number of carbon atoms of the substituent. .
- alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group, 2-hexynyl group, A 1-octynyl group may be mentioned.
- the “amino group” may have a substituent, and is preferably substituted with one or two substituents selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group.
- Amino group hereinafter sometimes referred to as “substituted amino group”.
- the substituent may further have a substituent (hereinafter, the substituent that the organic group further has may be referred to as “secondary substituent”).
- the number of carbon atoms of the substituted amino group is preferably 1 to 60, more preferably 2 to 48, and still more preferably 2 to 40, not including the number of carbon atoms of the secondary substituent.
- substituted amino groups include methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, isopropylamino, diisopropylamino, butylamino, isobutylamino, sec-butylamino Group, tert-butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, dodecylamino group, cyclopentyl amino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C
- the “silyl group” may have a substituent, and is preferably a silyl group substituted with 1 to 3 substituents selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group Group (hereinafter sometimes referred to as “substituted silyl group”).
- the substituent may have a secondary substituent.
- the number of carbon atoms of the substituted silyl group is preferably 1 to 60, more preferably 3 to 48, and still more preferably 3 to 40, not including the number of carbon atoms of the secondary substituent.
- Substituted silyl groups include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-isopropylsilyl, dimethyl-isopropylsilyl, diethyl-isopropylsilyl, tert-butyldimethylsilyl, pentyldimethylsilyl, hexyldimethyl Silyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, phenyl-C 1 ⁇ C 12 alkylsilyl group, C 1 ⁇ C 12 alkoxyphenyl -C 1 ⁇ C 12 alkylsilyl
- halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a fluorine atom is preferable.
- acyl group examples include a group represented by —C ( ⁇ O) —R 44 (R 44 represents the alkyl group, the aryl group, or a monovalent heterocyclic group described later). It is done.
- the alkyl group, aryl group and monovalent heterocyclic group for R 44 may have a substituent. Unless otherwise specified, the number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 18, and even more preferably 2 to 16, not including the number of carbon atoms of the substituent.
- acyl group examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group.
- acyl group having a substituent examples include an acyl group having a halogen atom as a substituent (for example, a trifluoroacetyl group or a pentafluorobenzoyl group).
- the “acyloxy group” is, for example, a group represented by —O—C ( ⁇ O) —R 45 (R 45 represents the alkyl group, the aryl group, or a monovalent heterocyclic group described later). Is mentioned.
- the alkyl group, aryl group and monovalent heterocyclic group for R 45 may have a substituent. Unless otherwise specified, the number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 18, and even more preferably 2 to 16, not including the number of carbon atoms of the substituent.
- acyloxy group examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.
- acyloxy group having a substituent examples include acyloxy groups having a halogen atom as a substituent (for example, a trifluoroacetyloxy group and a pentafluorobenzoyloxy group).
- oxycarbonyl group a group represented by —C ( ⁇ O) —O—R 46 (R 46 represents the above alkyl group, the above aryl group, or a monovalent heterocyclic group described later). Can be mentioned.
- the alkyl group, aryl group and monovalent heterocyclic group for R 46 may have a substituent. Unless otherwise specified, the number of carbon atoms of the oxycarbonyl group is preferably 2 to 20, more preferably 2 to 18, and even more preferably 2 to 16, excluding the number of carbon atoms of the substituent.
- a monovalent heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound.
- the monovalent heterocyclic group may have a substituent, and the monovalent heterocyclic group includes a monocyclic group and a group having a condensed ring.
- the number of carbon atoms of the monovalent heterocyclic group is preferably 2 to 60, more preferably 3 to 30, and still more preferably 4 to 20, not including the number of carbon atoms of the substituent.
- Heterocyclic compounds are not only carbon atoms but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, silicon atoms, selenium atoms as elements constituting the ring among organic compounds having a cyclic structure. , And those containing heteroatoms such as tellurium atoms and arsenic atoms.
- the monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group.
- the monovalent aromatic heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic compound.
- aromatic heterocyclic compounds include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, dibenzofuran.
- Heterocycles containing heteroatoms such as dibenzothiophene exhibit aromaticity
- heterocycles containing heteroatoms such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran themselves are aromatic. Even if not shown, a compound in which an aromatic ring is condensed to the heterocyclic ring can be mentioned.
- the “heterocyclic oxy group” is —O—Ar 13 (Ar 13 represents the above monovalent heterocyclic group), and the monovalent heterocyclic group in Ar 13 may have a substituent. .
- the number of carbon atoms of the heterocyclic oxy group is preferably 2 to 60, more preferably 3 to 30, and still more preferably 4 to 20, not including the number of carbon atoms of the substituent.
- the heterocyclic oxy group include a pyridyloxy group, a pyridazinyloxy group, a pyrimidinyloxy group, a pyrazinyloxy group, and a triazinyloxy group.
- the “heterocyclic thio group” is —S—Ar 14 (Ar 14 represents the above-mentioned monovalent heterocyclic group), and the monovalent heterocyclic group in Ar 14 may have a substituent. .
- the number of carbon atoms of the heterocyclic thio group is preferably 2 to 60, more preferably 3 to 30, and still more preferably 4 to 20, excluding the number of carbon atoms of the substituent.
- the heterocyclic thio group include a pyridylthio group, a pyridazinylthio group, a pyrimidinylthio group, a pyrazinylthio group, and a triazinylthio group.
- the “imine residue” is an imine compound represented by the formula: H—N ⁇ C (R 47 ) 2 or the formula: H—C (R 48 ) ⁇ N—R 49 , and “H” in the formula is Means the residue removed.
- R 47 , R 48 and R 49 each independently represent the alkyl group, the aryl group, the alkenyl group, the alkynyl group or the monovalent heterocyclic group.
- the alkyl group, aryl group, alkenyl group, alkynyl group and monovalent heterocyclic group in R 47 , R 48 and R 49 may have a substituent.
- a plurality of R 47 may be the same as or different from each other, and may be connected to each other to form a ring structure.
- Examples of the imine residue include groups represented by the following structural formulas.
- the “amide compound residue” is an amide compound represented by the formula: HN (R 50 ) —C ( ⁇ O) R 51 or the formula: HC ( ⁇ O) —N (R 52 ) 2 It means a residue excluding “H” in the formula.
- R 50 , R 51 and R 52 each independently represent a hydrogen atom, the alkyl group, the aryl group, the alkenyl group, the alkynyl group or the monovalent heterocyclic group.
- the alkyl group, aryl group, alkenyl group, alkynyl group and monovalent heterocyclic group in R 50 , R 51 and R 52 may have a substituent.
- a plurality of R 52 may be the same as or different from each other, and may be linked to each other to form a ring structure.
- amide compound residues include formamide residues, acetamide residues, propioamide residues, butyroamide residues, benzamide residues, trifluoroacetamide residues, pentafluorobenzamide residues, diformamide residues, diacetamide residues. , Dipropioamide residue, dibutyroamide residue, dibenzamide residue, ditrifluoroacetamide residue, dipentafluorobenzamide residue.
- Acid imide residue means a residue obtained by removing one hydrogen atom directly bonded to the nitrogen atom from an acid imide.
- the number of carbon atoms of the acid imide residue is preferably 4 to 20, more preferably 4 to 18, and still more preferably 4 to 16.
- Examples of the acid imide residue include groups represented by the following structural formulas.
- the “unsubstituted or substituted alkyl group” includes an unsubstituted alkyl group and an alkyl group having the above substituent.
- the alkyl group preferably has a substituent selected from an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom.
- the “unsubstituted or substituted aryl group” includes an unsubstituted aryl group and the above aryl group having the above substituent.
- the aryl group has a substituent selected from an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom. preferable.
- the “unsubstituted or substituted monovalent heterocyclic group” includes an unsubstituted monovalent heterocyclic group and a monovalent heterocyclic group having the above substituent.
- the monovalent heterocyclic group has a substituent selected from an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom. It is preferable that
- the “unsubstituted or substituted arylene group” includes an unsubstituted arylene group and an arylene group having the above-described substituent.
- the arylene group has a substituent selected from an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom. preferable.
- the “arylene group” is an atomic group obtained by removing two hydrogen atoms directly bonded to a carbon atom constituting an aromatic hydrocarbon (preferably an unsubstituted aromatic carbocyclic ring).
- the arylene group may have a substituent, and the arylene group includes a group having a benzene ring and a group having a condensed ring.
- the number of carbon atoms of the arylene group is preferably 6 to 60, more preferably 6 to 48, and even more preferably 6 to 30 without including the number of carbon atoms of the substituent.
- arylene group examples include phenylene groups such as 1,4-phenylene group, 1,3-phenylene group and 1,2-phenylene group; 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2, Naphthalenediyl groups such as 6-naphthalenediyl, 2,7-naphthalenediyl group; 1,4-anthracenediyl group, 1,5-anthracenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group, etc.
- the “unsubstituted or substituted divalent heterocyclic group” includes an unsubstituted divalent heterocyclic group and a divalent heterocyclic group having the above substituent.
- the substituent that the divalent heterocyclic group has is a substituent selected from an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom. It is preferably a group.
- a divalent heterocyclic group is a remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound.
- the divalent heterocyclic group may have a substituent, and the divalent heterocyclic group includes a monocyclic group and a condensed ring group.
- the number of carbon atoms of the divalent heterocyclic group is preferably 2 to 60, more preferably 3 to 30, and still more preferably 4 to 20, not including the carbon atoms of the substituent.
- the divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.
- the divalent aromatic heterocyclic group is a remaining atomic group obtained by removing two hydrogen atoms from an aromatic heterocyclic compound.
- divalent heterocyclic group examples include pyridinediyl groups such as 2,5-pyridinediyl group and 2,6-pyridinediyl group; quinolinediyl groups such as 2,6-quinolinediyl group; 1,4-isoquinolinediyl group , 1,5-isoquinolinediyl group such as 1,5-isoquinolinediyl group; quinoxalinediyl group such as 5,8-quinoxalinediyl group; 2,1,3-benzoyldiazole group such as 2,1,3-benzothiadiazole-4,7-diyl group Benzothiadiazole group; benzothiazole diyl group such as 4,7-benzothiazole diyl group; dibenzosilol diyl group such as 2,7-dibenzosilol diyl group; dibenzofuran-4,7-diyl group, dibenzofuran-3,8-diyl Group such as dibenzofuranyl
- Examples of the “divalent group in which two or more identical or different groups selected from an arylene group and a divalent heterocyclic group are linked” include biphenylylene groups such as 2,7-biphenylylene group and 3,6-biphenylylene group And a divalent group in which two groups selected from an arylene group and a divalent heterocyclic group are linked by a single bond.
- the divalent group may have a substituent, and the substituent that the divalent group has is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group unless otherwise specified. And a substituent selected from a heterocyclic oxy group and a halogen atom.
- the polymer compound according to this embodiment includes a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), and / or And a structural unit represented by the following formula (4 ′).
- the polymer compound is useful for the production of a light emitting device having excellent luminous efficiency.
- the polymer compound according to this embodiment is preferably a conjugated polymer compound.
- the “conjugated polymer compound” is a polymer compound in which a conjugated system spreads on the main chain skeleton, and a polyarylene having an arylene group such as polyfluorene or polyphenylene as a repeating unit; polythiophene, polydibenzofuran, etc.
- a hetero atom or the like is included in the main chain in the structural unit, it is only required that conjugation is substantially achieved.
- a structural unit derived from triarylamine may be included as the structural unit. .
- the first structural unit contained in the polymer compound of the present invention is a structural unit represented by the following formula (1).
- Ar 1 and Ar 3 each independently represent an unsubstituted or substituted arylene group or an unsubstituted or substituted divalent heterocyclic group.
- Ar 2 and Ar 4 are each independently two or more selected from an unsubstituted or substituted arylene group, an unsubstituted or substituted divalent heterocyclic group, or an arylene group and a divalent heterocyclic group Represents a divalent group to which these groups are linked (the group may have a substituent).
- Ar 5 , Ar 6 and Ar 7 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent heterocyclic group.
- Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 may each be directly bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded.
- R a represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, a halogen atom, or an unsubstituted or substituted monovalent heterocyclic group.
- Ar 5 , Ar 6 and Ar 7 are preferably unsubstituted or substituted aryl groups, and the formula (1) is more preferably the following formula (1A).
- R 5 , R 6 and R 7 are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group , Halogen atom, acyl group, acyloxy group, oxycarbonyl group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, imine residue, amide compound residue, acid imide residue, carboxyl group, hydroxy group Represents a nitro group or a cyano group. When a plurality of R 5 are present, they may be the same or different.
- R 6 When a plurality of R 6 are present, they may be the same or different, and a plurality of R 7 are present. They may be the same or different. In addition, this group may have said substituent.
- R 5 , R 6 and R 7 are preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group.
- h, i and j each independently represents an integer of 0 to 5.
- h, i, and j are preferably integers of 0 to 3, more preferably integers of 1 to 3.
- the number of carbon atoms of the arylene group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 is usually 6 to 60, preferably 6 to 48, not including the number of carbon atoms of the substituent, More preferably, it is 6-20, and more preferably 6-14.
- arylene group examples include a phenylene group (for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group), a naphthalenediyl group (for example, 1,4-naphthalenediyl group, 2, 6-naphthalenediyl group, 2,7-naphthalenediyl group), anthracenediyl group (for example, 2,6-anthracenediyl group, 9,10-anthracenediyl group), phenanthenediyl group (for example, 2,7-phenanthenediyl group) Group), dihydrophenanthrene diyl group (for example, 9,10-dihydrophenanthrene-2,7-diyl group), naphthacene diyl group (for example, 5,12-naphthacene diyl group), fluorenediyl group (for example, 2,7-full group) Orangeyl group, 3,6-fluorenediyl group), spiro
- Examples of the divalent heterocyclic group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 include a 2,5-pyrroldiyl group, a 2,1,3-benzothiadiazole-4,7-diyl group, Examples thereof include a dibenzofurandiyl group, a dibenzothiophenediyl group, and a dibenzosilolediyl group, and these groups optionally have the above-described substituent.
- Examples of the divalent group in which two or more identical or different groups selected from an arylene group and a divalent heterocyclic group represented by Ar 2 and Ar 4 are linked include the following formula (B-1), And groups represented by formula (B-2), formula (B-3), formula (B-4), formula (B-5), formula (B-6) and formula (B-7), A group represented by the formula (B-1) is preferable. These groups may have the above-described substituent. In addition, the groups represented by formula (B-1), formula (B-2), and formula (B-3) may be referred to as a biphenylylene group.
- substituents include the above-mentioned substituents, and preferably an alkyl group, an alkoxy group or an aryl group. And more preferably an alkyl group.
- Ar 1 and Ar 3 are preferably an unsubstituted or substituted arylene group, more preferably an unsubstituted or substituted phenylene group, and still more preferably an unsubstituted or substituted 1,4-phenylene group. is there.
- Ar 2 or Ar 4 is preferably an unsubstituted or substituted arylene group, or a divalent group in which two or more identical or different groups selected from an arylene group and a divalent heterocyclic group are linked (the group May have a substituent.), More preferably, an unsubstituted or substituted phenylene group, an unsubstituted or substituted biphenylylene group, an unsubstituted or substituted spirofluorenediyl group, an unsubstituted or A substituted phenanthrene diyl group, an unsubstituted or substituted dihydrophenanthrene diyl group or an unsubstituted or substituted fluorenediyl group, more preferably an unsubstituted or substituted fluorenediyl group, and the polymer compound of the present embodiment Since the lifetime characteristics of the light emitting device manufactured using the It is a 2,7-fluorenediyl group.
- the groups represented by Ar 1 and Ar 3 are preferably unsubstituted or substituted phenylene groups, since the light emitting device produced using the polymer compound of the present embodiment is more excellent in luminous efficiency. More preferably, it is a substituted or substituted 1,4-phenylene group.
- the groups represented by Ar 2 and Ar 4 are more excellent in luminous efficiency of a light-emitting device produced using the polymer compound of the present embodiment, and therefore are unsubstituted or substituted phenylene groups, unsubstituted or substituted biphenylylenes.
- Preferred is a group, an unsubstituted or substituted spirofluorangeyl group, an unsubstituted or substituted phenanthrene diyl group, an unsubstituted or substituted dihydrophenanthrene diyl group, or an unsubstituted or substituted fluorenediyl group.
- an unsubstituted or substituted fluorenediyl group is more preferable, and an unsubstituted or substituted 2,7-fluorenediyl group is more preferable. More preferably.
- the group represented by R a is preferably a hydrogen atom, an unsubstituted alkyl group, an unsubstituted alkoxy group, an unsubstituted aryl group, a halogen atom or an unsubstituted monovalent heterocyclic group.
- Definitions and examples of the unsubstituted or substituted alkyl group, the unsubstituted or substituted alkoxy group, the unsubstituted or substituted aryl group, the halogen atom, the unsubstituted or substituted monovalent heterocyclic group represented by R a are as follows: These are the same as the definitions and examples of the alkyl group, alkoxy group, aryl group, halogen atom and monovalent heterocyclic group described as the substituent.
- Ar 8 is a fluorenediyl group
- the structural unit represented by the formula (1) has excellent characteristics (for example, luminance life) of a light emitting device manufactured using the polymer compound of the present embodiment, the following formula (9a) and formula (9b) , A structural unit represented by the formula (9c), the formula (9d), the formula (9e) or the formula (9f) is preferable, and is represented by the formula (9c), the formula (9d) or the formula (9e). A structural unit is more preferable, and a structural unit represented by Formula (9c) or Formula (9e) is even more preferable.
- R 41 represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, a halogen atom Atom, acyl group, acyloxy group, oxycarbonyl group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, imine residue, amide compound residue, acid imide residue, carboxyl group, hydroxy group, nitro Group or cyano group, preferably a hydrogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted amino group, acyl group or cyano group, more preferably A hydrogen atom, an alkyl group, an alkoxy group or an aryl group; A
- the formulas (9a) to (9f) are usually structural units represented by the following formulas (9-001) to (9-086), and the formulas (9-001) to (9-005) And structural units represented by formula (9-012) to formula (9-059), formula (9-070) to formula (9-086) are preferred, and the formula (9-012) to formula (9 -059), and structural units represented by the formulas (9-071) to (9-078) are more preferable, and the characteristics of the light emitting device produced using the polymer compound of the present embodiment (for example, Since the luminance life is excellent, it is more preferably a structural unit represented by formula (9-020) to formula (9-059) or formula (9-071) to formula (9-078). -036) to formula (9-059) and formula (9-071) to formula (9-074) Particularly preferred.
- the polymer compound of the present embodiment may have only one of the above structural units as the first structural unit, or may have a plurality of different structural units among the above structural units.
- the second structural unit contained in the polymer compound of the present invention is a structural unit represented by the following formula (2).
- Ar 8 represents a (2 + p) -valent aromatic hydrocarbon group or a (2 + p) -valent heterocyclic group.
- R 1 is alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, oxycarbonyl group, monovalent Represents a heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a hydroxyl group, a nitro group or a cyano group.
- R 1 When a plurality of R 1 are present, they may be the same or different. Note that at least one R 1 substitutes a hydrogen atom directly bonded to a carbon atom adjacent to a carbon atom that forms a bond with another structural unit in the aromatic hydrocarbon group or heterocyclic group. p represents an integer of 1 or more.
- the (2 + p) -valent aromatic hydrocarbon group represented by Ar 8 or the (2 + p) -valent heterocyclic group is an arylene group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 and a divalent group. It is the same as the heterocyclic group of In addition to R 1 , the group represented by Ar 8 may have the above-described substituent.
- the “other structural unit” may be a structural unit represented by the formula (2) (that is, the structural unit represented by the formula (2) may be continuously bonded). .)
- the number of carbon atoms of the (2 + p) -valent aromatic hydrocarbon group represented by Ar 8 is usually 6 to 60, preferably 6 to 48, more preferably 6 to 20, and further preferably 6 to 14 It is.
- the (2 + p) -valent aromatic hydrocarbon group is preferably a trivalent, tetravalent or pentavalent aromatic hydrocarbon group, and since the synthesis of the monomer as a raw material becomes easy, the trivalent or tetravalent aromatic hydrocarbon group is preferred. It is more preferably an aromatic hydrocarbon group, and particularly preferably tetravalent.
- the “(2 + p) valent aromatic hydrocarbon group” includes (2 + p) number of (2 + p) bonded directly from an aromatic hydrocarbon (preferably an unsubstituted aromatic carbocycle) to a carbon atom constituting the ring.
- the remaining atomic group excluding a hydrogen atom means a group having a benzene ring and a group having a condensed ring.
- the group represented by Ar 8 is preferably a (2 + p) valent aromatic hydrocarbon group.
- the group represented by Ar 8 is more excellent in luminous efficiency of a light-emitting device produced using the polymer compound of the present embodiment, so that a phenylene group, naphthalenediyl group, phenanthrene diyl group, dihydrophenanthrene diyl group or full An orangeyl group is preferable, a phenylene group or a fluorenediyl group is more preferable, and a 1,4-phenylene group or a 2,7-fluorenediyl group is further preferable.
- the group represented by R 1 is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group, or a cyano group, more preferably An alkyl group, an alkoxy group or an aryl group;
- p represents an integer of 1 or more, preferably an integer of 1 to 4, and is more preferably 1 or 2, more preferably 2, because synthesis of a monomer as a raw material becomes easy. is there.
- the groups represented by the formula (2) are preferred as those where Ar 8 is a (2 + p) -valent aromatic hydrocarbon group, Since the characteristics (for example, luminance lifetime) of the light emitting device manufactured using the polymer compound of the present embodiment are excellent, the formula (10a), the formula (10b), the formula (10h), the formula (10i), the formula (10j) ) Or a group represented by formula (10k) is more preferred, and a group represented by formula (10a), formula (10h), formula (10j) or formula (10k) is more preferred.
- R 14 and R 15 are a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group Group, halogen atom, acyl group, acyloxy group, oxycarbonyl group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, imine residue, amide compound residue, acid imide residue, carboxyl group, hydroxy group Group, nitro group or cyano group, preferably a hydrogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted amino group, acyl group or cyano group, and more A hydrogen atom, an alkyl group, an alkoxy group, or an aryl group is preferable.
- a plurality of R 14 may be the same or different.
- a plurality of R 15 may be the same or different.
- adjacent R 14s may be bonded to each other to form a ring structure with the carbon atoms to which they are bonded, and adjacent R 15s are bonded to each other to have a ring structure with the carbon atoms to which they are bonded.
- R 14 and R 15 adjacent to each other may be bonded to each other to form a ring structure together with the carbon atom to which they are bonded.
- At least one of R 14 represents a group other than a hydrogen atom (that is, the R 1 ).
- R 8 represents a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen Atom, acyl group, acyloxy group, oxycarbonyl group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, imine residue, amide compound residue, acid imide residue, carboxyl group, hydroxy group, nitro Represents a group or a cyano group, preferably a hydrogen atom, an alkyl group, an alkoxy group or an aryl group.
- a plurality of R 8 may be the same or different, and may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.
- the structural units represented by the formula (2) are usually structural units represented by the following formulas (10-1) to (10-173), and the formulas (10-1) to (10-18) ), And structural units represented by formulas (10-41) to (10-173) are preferred, and formulas (10-1) to (10-18), (10-41) to (10 10-76), Formula (10-85) to Formula (10-128), and Formula (10-154) to Formula (10-173) are more preferable. Since the characteristics (for example, luminance lifetime) of the light emitting device manufactured using the molecular compound are excellent, the formula (10-1) to the formula (10-18), the formula (10-59) to the formula (10-68), These are structural units represented by formula (10-85) to formula (10-128) and formula (10-154) to formula (10-168).
- the structural unit represented by 168) is particularly preferable.
- the polymer compound of the present embodiment may have only one type of the above structural unit as the second structural unit, or may have a plurality of different structural units among the above structural units.
- the third structural unit contained in the polymer compound of the present invention is a structural unit selected from a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4 ′).
- na represents an integer of 0 to 3
- nb represents an integer of 0 to 12
- nA represents 0 or 1
- n represents an integer of 1 to 4.
- Ar 10 represents an unsubstituted or substituted (2 + n) -valent aromatic hydrocarbon group or an unsubstituted or substituted (2 + n) -valent heterocyclic group.
- L a and L b each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group. When a plurality of La are present, they may be the same or different. When a plurality of Lb are present, they may be the same or different.
- L A represents an oxygen atom or a sulfur atom.
- Q 1 represents a monovalent crosslinkable group. When a plurality of Q 1 are present, they may be the same or different. Note that the structural unit represented by the formula (3) is different from the structural unit represented by the formula (2).
- na represents an integer of 0 to 3, and it is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0 because synthesis of a monomer as a raw material becomes easy.
- nb represents an integer of 0 to 12, and is preferably 0 to 10, more preferably 0 to 8, because synthesis of a monomer as a raw material becomes easy.
- nA is 0 or 1, and is preferably 0 because the light-emitting element produced using the polymer compound of this embodiment has excellent hole transportability and durability. Note that durability means, for example, luminance life.
- n is an integer of 1 to 4, but the light-emitting device manufactured using the polymer compound of the present embodiment has excellent hole transportability and durability, so that an integer of 1 to 3 is used. It is preferable that 2 is more preferable.
- the number of carbon atoms of the unsubstituted or substituted (2 + n) -valent aromatic hydrocarbon group represented by Ar 10 is usually 6 to 60, preferably 6 to 48, more preferably 6 to 20, more preferably 6 to 14.
- the (2 + n) -valent aromatic hydrocarbon group is preferably a divalent, trivalent, tetravalent or pentavalent aromatic hydrocarbon group, and is preferably a trivalent or tetravalent aromatic hydrocarbon group. Is more preferable.
- the “(2 + n) -valent aromatic hydrocarbon group” refers to (2 + n) number of (2 + n) atoms bonded to a carbon atom constituting a ring from an aromatic hydrocarbon (preferably an unsubstituted aromatic carbocyclic ring).
- the remaining atomic group excluding a hydrogen atom means a group having a benzene ring and a group having a condensed ring.
- the number of carbon atoms does not include the number of carbon atoms of the substituent.
- aromatic hydrocarbon examples include benzene, naphthalene, anthracene, 1-tetracene, pyrene, perylene, fluorene, benzofluorene, phenanthrene, dihydrophenanthrene, chrysene, coronene, and the like, and the stability of the polymer compound of this embodiment Benzene, naphthalene, anthracene, pyrene, fluorene, benzofluorene, phenanthrene, and dihydrophenanthrene are preferable, and benzene, naphthalene is preferable. More preferred is fluorene.
- the number of carbon atoms of the unsubstituted or substituted (2 + n) -valent heterocyclic group represented by Ar 10 is usually 3 to 60, preferably 3 to 20.
- the (2 + n) -valent heterocyclic group is preferably a divalent, trivalent, tetravalent or pentavalent heterocyclic group, and more preferably a divalent, trivalent or tetravalent heterocyclic group.
- the (2 + n) -valent heterocyclic group is preferably a (2 + n) -valent aromatic heterocyclic group.
- (2 + n) -valent heterocyclic group means a remaining atomic group obtained by removing (2 + n) hydrogen atoms bonded to a carbon atom constituting a ring from a heterocyclic compound.
- a group having a ring or a condensed ring is included.
- the number of carbon atoms does not include the number of carbon atoms of the substituent.
- the heterocyclic compound include pyridine, pyrimidine, triazine, quinoline, isoquinoline, quinoxaline, dibenzofuran, dibenzothiophene, carbazole, phenoxazine, phenothiazine, benzothiadiazole, dibenzosilole, and the like.
- the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group.
- Arylalkynyl group amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, cyano group, more preferably alkyl group, alkoxy group, aryl group , An aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group and a cyano group, more preferably an alkyl group, an alkoxy group and an aryl group.
- Ar 10 is an unsubstituted or substituted (2 + n) -valent aromatic, because the hole-transport property and durability of the light-emitting device produced using the polymer compound of this embodiment are excellent.
- a hydrocarbon group is preferred.
- the alkylene group represented by L a and L b may be linear, branched or cyclic, and may have a substituent.
- a straight-chain alkylene group is preferable because synthesis of a monomer as a raw material becomes easy.
- the number of carbon atoms in the linear alkylene group and the branched alkylene group is usually 1 to 20, preferably 1 to 10, and more preferably 1 to 6.
- the number of carbon atoms in the cyclic alkylene group is usually 3 to 20, preferably 3 to 10, and more preferably 3 to 6.
- alkylene group examples include a methylene group, 1,2-ethylene group, 1,3-propylene group, 1,3-butylene group, 1,3-pentylene group, 1,4-pentylene group, 1,5-pentylene group, Examples include 1,4-hexylene group, 1,6-hexylene group, 1,7-heptylene group, 1,6-octylene group, 1,8-octylene group and the like.
- the phenylene group represented by L a and L b may have a substituent.
- the phenylene group include o-phenylene, m-phenylene, and p-phenylene.
- the substituent that the phenylene group may have include an alkyl group, an alkoxy group, a halogen atom, and a cyano group.
- L a because the monomer synthesis as a raw material is facilitated, it is preferable that a phenylene group.
- L b because the monomer synthesis as a raw material is facilitated, is preferably an alkylene group.
- L A represents an oxygen atom or a sulfur atom, for monomer synthesis as a raw material is facilitated, is preferably an oxygen atom.
- Q 1 represents a monovalent crosslinkable group.
- Q 1 includes, for example, an unsubstituted or substituted aziridinyl group, an unsubstituted or substituted azetidinyl group, an azide group, an unsubstituted or substituted epoxy group, an unsubstituted or substituted oxetanyl group, an unsubstituted or substituted alkenyl group, An unsubstituted or substituted alkynyl group, a group having a cyclobutene structure, etc.
- an unsubstituted or substituted alkenyl group An unsubstituted or substituted aryl group having a clobutene structure, an unsubstituted or substituted monovalent heterocyclic group having a cyclobutene structure is more preferred, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group having a cyclobutene structure Is more preferable.
- examples of Q 1 include groups represented by the following formulas (Q-1), (Q-2), and (Q-01) to (Q-19), which are used as raw materials. Since monomer synthesis is facilitated, formulas (Q-1), (Q-2), (Q-01), (Q-03), (Q-04), (Q-06) to (Q-18) Groups represented by formula (Q-1), (Q-2), (Q-09) to (Q-18) are more preferred, and groups represented by formula (Q-1) or (Q -2) is more preferable.
- the benzocyclobutene ring may have a substituent.
- substituents in formula (Q-1) include an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted alkylthio group, an unsubstituted or substituted aryl group, an unsubstituted or substituted group, Aryloxy group, unsubstituted or substituted arylthio group, unsubstituted or substituted amino group, unsubstituted or substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, non Examples thereof include a substituted or substituted monovalent heterocyclic group, an unsubstituted or substituted carboxyl group, a cyano group, and a nitro group.
- ne and nf each independently represent 0 or 1.
- L X1 represents an oxygen atom, a sulfur atom, a carbonyl group or a group represented by —O—CO—.
- R 21 , R 22 , R 23 , R 24 and R 25 are each independently a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted alkylthio group, unsubstituted or A substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an unsubstituted or substituted monovalent heterocyclic group, an unsubstituted or substituted amino group, an unsubstituted or substituted silyl group, An unsubstituted or substituted acyl group, an unsubstituted or substituted acyloxy group, a
- the compound having a double bond with a wavy line may be any of E-form, Z-form, or a mixture of E-form and Z-form.
- R X represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted alkylthio group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, unsubstituted or Substituted arylthio group, unsubstituted or substituted amino group, unsubstituted or substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, unsubstituted or substituted monovalent complex It represents a cyclic group, an unsubstituted or substituted carboxyl group, a cyano group or a nitro group.
- R X represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted acyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent heterocyclic group.
- R X is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy, because the raw material monomer is easily synthesized.
- an unsubstituted or substituted monovalent heterocyclic group is preferred, and a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, and an unsubstituted or substituted aryl group are more preferred.
- the R N since the monomer synthesis as a raw material is facilitated, an alkyl group substituted with an aryl group, an unsubstituted or substituted acyl group, monovalent heterocyclic group unsubstituted or substituted is preferred.
- “*” represents a bond.
- Examples of the formula (Q-1) include the following formula (Q-1-1) or (Q-1-2), which facilitates the synthesis of the monomer used as a raw material. Preferably there is.
- R Y represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted alkylthio group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, unsubstituted or Substituted arylthio group, unsubstituted or substituted amino group, unsubstituted or substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, unsubstituted or substituted monovalent complex It represents a cyclic group, an unsubstituted or substituted carboxyl group, a cyano group or a nitro group.
- R Y is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy, because synthesis of the starting monomer is facilitated.
- Group or an unsubstituted or substituted monovalent heterocyclic group more preferably a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, or an unsubstituted or substituted aryl group. And more preferably a hydrogen atom or an unsubstituted or substituted alkyl group.
- “*” represents a bond.
- ne represents 0 or 1
- 0 is preferable because the hole transport property and durability of the light-emitting device produced using the polymer compound of this embodiment are excellent.
- nf is 0 or 1
- 0 is preferable because synthesis of a monomer as a raw material becomes easy.
- L X1 represents an oxygen atom, a sulfur atom, a carbonyl group or a group represented by —O—CO—, which facilitates the synthesis of a monomer as a raw material.
- a group represented by —CO— is preferred.
- R 21 , R 22 , R 23 , R 24 , and R 25 are excellent in the hole transport property and durability of the light emitting device manufactured using the polymer compound of this embodiment.
- the structural unit represented by the formula (3) is represented by the following formula (3-1) because the light-emitting element produced using the polymer compound of the present embodiment has excellent hole transportability and durability. Are preferred.
- nc represents an integer of 0 to 3
- nd represents an integer of 0 to 12
- nB represents 0 or 1
- L c and L d each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group.
- L c represents an integer of 0 to 3
- nd represents an integer of 0 to 12
- nB represents 0 or 1
- L c and L d each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group.
- L B represents an oxygen atom or a sulfur atom.
- Q 1 has the same meaning as described above.
- a plurality of Q 1 are present, they may be the same or different.
- R 80 is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted monovalent heterocyclic ring A group or an unsubstituted or substituted heterocyclic oxy group;
- m represents 1 or 2, and includes the viewpoints of hole transportability and durability of the light-emitting device produced using the polymer compound of the present embodiment, and the polymer compound. From the viewpoint of converting an organic thin film into an insolubilized organic thin film, 2 is preferable.
- L c are as defined above L a, it is identical to the illustrative and preferred ranges of the L a.
- L d has the same meaning as L b, and is the same as the exemplified and preferred ranges in L b .
- L B has the same meaning as L A, and is the same as the examples and preferred ranges in L A.
- Q 1 represents the same meaning as Q 1 in the formula (3), and is the same as the exemplified and preferred range in the formula (3).
- R 80 is excellent in hole transportability and durability of the light-emitting device using the polymer compound of the present embodiment, so that an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group It is preferably a group, more preferably a substituted aryl group, and further preferably an aryl group substituted with an alkyl group.
- the fluorene ring may have a substituent, and the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an aryl group.
- the structural unit represented by the formula (3) is represented by the following formula (3-2) because the hole transport property and durability of the light emitting device manufactured using the polymer compound of the present embodiment are excellent. Are preferred.
- nc represents an integer of 0 to 3
- nd represents an integer of 0 to 12
- nB represents 0 or 1
- k represents an integer of 1 to 4.
- L c and L d each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group.
- L B represents an oxygen atom or a sulfur atom.
- Q 1 has the same meaning as described above. When a plurality of Q 1 are present, they may be the same or different.
- R 90 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted monovalent heterocyclic ring A group or an unsubstituted or substituted heterocyclic oxy group; When a plurality of R 90 are present, they may be the same or different. ]
- k represents an integer of 1 to 4, and the light-emitting element produced using the polymer compound of the present embodiment is more excellent in hole transportability and durability, and this embodiment From the viewpoint of converting an organic thin film containing the above polymer compound into an insolubilized organic thin film, it is preferably 1 or 2, and more preferably 2.
- R 90 is excellent in the hole transport property and durability of the light-emitting device using the polymer compound of the present embodiment, so that a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or A substituted aryl group is preferable, and a hydrogen atom is more preferable because synthesis of a monomer as a raw material becomes easy.
- Examples of the structural unit represented by the formula (3) include structural units represented by the following formulas (3-101) to (3-155), and the formulas (3-101) to (3-107) , (3-111), (3-114), (3-116) to (3-119), (3-125), (3-132) to (3-143), (3-147) to (3- 3-149) and (3-155) are preferred, and the structural units represented by formulas (3-101) to (3-105), (3-107), (3-111), (3-114), (3-117) to (3-119), (3-132), (3-134), (3-136), (3-137), (3-140) to (3-143), (3 -147) to (3-149) are more preferable, and the structural units represented by formulas (3-103), (3-105), (3-132), (3-1 7), more preferably a structural unit represented by (3-140), the formula (3-131), particularly preferably a structural unit represented by (3-140).
- the polymer compound of the present embodiment may have only one structural unit represented by the formula (3) as the third structural unit, and among the structural units represented by the formula (3) It may have a plurality of different structural units, but from the viewpoint of converting an organic thin film into an insolubilized organic thin film, it contains at least one monovalent crosslinkable group represented by the above formula (Q-1), Containing at least one monovalent crosslinkable group represented by the formula (Q-2), or a monovalent crosslinkable group represented by the formula (Q-1) and the formula (Q-2). At least one type is preferably included, and more preferably one or more types of monovalent crosslinkable groups represented by the formula (Q-1) and the formula (Q-2).
- c represents 0 or 1
- d represents an integer of 0 to 4
- Ar 20 and Ar 40 each independently represent an unsubstituted or substituted arylene group or an unsubstituted or substituted divalent heterocyclic group
- Ar 30 ′ represents an unsubstituted or substituted (2 + d) -valent aromatic group.
- Q 2 ′, Q 3 ′ and Q 4 ′ are each independently a monovalent crosslinkable group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent heterocyclic ring
- at least one of Q 2 ′, Q 3 ′ and Q 4 ′ is a monovalent crosslinkable group.
- Q 4 ′ When a plurality of Q 4 ′ are present, they may be the same or different.
- na represents an integer of 0 to 3
- nb represents an integer of 0 to 12
- nA represents 0 or 1.
- L a and L b each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group.
- La When a plurality of La are present, they may be the same or different.
- Lb When a plurality of Lb are present, they may be the same or different.
- L A represents an oxygen atom or a sulfur atom.
- LA When a plurality of LA are present, they may be the same or different.
- ng represents an integer of 0 to 3
- nh represents an integer of 0 to 12
- nD represents 0 or 1.
- L g and L h each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group.
- L g When a plurality of L g are present, they may be the same or different. When a plurality of L h are present, they may be the same or different.
- L D represents an oxygen atom or a sulfur atom. When a plurality of L D are present, they may be the same or different. Note that the structural unit represented by the formula (4 ′) is different from the structural unit represented by the formula (1).
- na and ng each independently represent an integer of 0 to 3, which facilitates synthesis of the starting monomer, and is preferably an integer of 0 to 2, more preferably 0 or 1. 0 is more preferable.
- nb and nh each independently represent an integer of 0 to 12, and the synthesis of the starting monomer is facilitated. Therefore, an integer of 0 to 10 is preferable, and an integer of 0 to 8 is more preferable. preferable.
- nA and nD each independently represent 0 or 1, and the hole transportability and durability (particularly the luminance lifetime) of the light-emitting device produced using the polymer compound of the present embodiment. ) Is excellent, it is preferably 0.
- d is an integer of 0 to 4.
- an integer of 0 to 3 is used. Is preferable, and an integer of 0 to 2 is more preferable.
- examples of the arylene group in Ar 20 and Ar 40 include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthalenediyl group, 2 , 6-Naphthalenediyl group, 2,7-naphthalenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group, 2,7-phenanthenediyl group, 5,12-naphthacenediyl group, 2,7- Examples include fluorenediyl group, 3,6-fluorenediyl group, 1,6-pyrene diyl group, 2,7-pyrene diyl group and 3,8-perylene diyl group, 1,4-phenylene group, 2,7-fullyl group Orangeyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group, 2,7-phenanthrene diyl group or 1,6-pyrene diyl group Preferably, 1,
- examples of the divalent heterocyclic group for Ar 20 and Ar 40 include 2,5-pyrroldiyl group, dibenzofurandiyl group, dibenzothiophenediyl group and 2,1,3-benzothiadiazole-4 , 7-diyl group. In addition, these groups may have the said substituent.
- Ar 20 and Ar 40 are each an unsubstituted or substituted arylene group because the hole transport property and durability of the light-emitting device produced using the polymer compound of this embodiment are excellent. Preferably there is.
- the number of carbon atoms of the unsubstituted or substituted (2 + d) -valent aromatic hydrocarbon group represented by Ar 30 ′ is usually 6 to 60, not including the number of carbon atoms of the substituent. Preferably, it is 6 to 48, more preferably 6 to 20, and still more preferably 6 to 14.
- the (2 + d) -valent aromatic hydrocarbon group is preferably a divalent, trivalent, tetravalent or pentavalent aromatic hydrocarbon group, and is preferably a trivalent or tetravalent aromatic hydrocarbon group. Is more preferable.
- the “(2 + d) -valent aromatic hydrocarbon group” means (2 + d) groups bonded directly from an aromatic hydrocarbon (preferably an unsubstituted aromatic carbocyclic ring) to carbon atoms constituting the ring. This means the remaining atomic group excluding the hydrogen atom, and includes a group having a benzene ring and a group having a condensed ring.
- aromatic hydrocarbon examples include benzene, naphthalene, anthracene, 1-tetracene, pyrene, perylene, fluorene, benzofluorene, phenanthrene, dihydrophenanthrene, chrysene, coronene, and the stability of the polymer compound of the present embodiment.
- benzene, naphthalene, anthracene, pyrene, fluorene, benzofluorene, phenanthrene or dihydrophenanthrene is preferable, More preferred is benzene, naphthalene or fluorene.
- the number of carbon atoms of the unsubstituted or substituted (2 + d) -valent heterocyclic group represented by Ar 30 ′ is usually 3 to 60, not including the number of carbon atoms of the substituent. Is 3-20.
- the (2 + d) -valent heterocyclic group is preferably a divalent, trivalent, tetravalent or pentavalent heterocyclic group, and more preferably a divalent, trivalent or tetravalent heterocyclic group. .
- the (2 + d) -valent heterocyclic group is preferably a (2 + d) -valent aromatic heterocyclic group.
- the “(2 + d) -valent heterocyclic group” means the remaining atomic group obtained by removing (2 + d) hydrogen atoms directly bonded to the carbon atoms constituting the ring from the heterocyclic compound, A monocyclic group and a group having a condensed ring are included.
- the heterocyclic compound include pyridine, pyrimidine, triazine, quinoline, isoquinoline, quinoxaline, dibenzofuran, dibenzothiophene, carbazole, phenoxazine, phenothiazine, benzothiadiazole, and dibenzosilole.
- the (2 + d) -valent group having a structure in which two or more of the same or different rings selected from the aromatic ring and heterocycle represented by Ar 30 ′ are linked is represented by the formula (B-1), A group represented by formula (B-2), formula (B-3), formula (B-4), formula (B-5), formula (B-6) or formula (B-7) is preferred,
- the group represented by (B-1) is more preferable. In addition, these groups may have the said substituent.
- the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group.
- Ar 30 ′ has excellent hole transportability and durability of the light-emitting device produced using the polymer compound of the present embodiment, and therefore has an unsubstituted or substituted (2 + d) value.
- Aromatic hydrocarbon groups are preferred.
- the alkylene group represented by L a , L b , L g and L h may be linear, branched or cyclic, and may have a substituent.
- a straight-chain alkylene group is preferable because synthesis of a monomer as a raw material becomes easy.
- the number of carbon atoms in the linear alkylene group and the branched alkylene group is usually 1 to 20, preferably 1 to 10, and more preferably 1 to 6.
- the number of carbon atoms in the cyclic alkylene group is usually 3 to 20, preferably 3 to 10, and more preferably 3 to 6.
- alkylene group examples include a methylene group, 1,2-ethylene group, 1,3-propylene group, 1,3-butylene group, 1,3-pentylene group, 1,4-pentylene group, 1,5-pentylene group, Examples include 1,4-hexylene group, 1,6-hexylene group, 1,7-heptylene group, 1,6-octylene group, 1,8-octylene group and the like.
- the phenylene group represented by L a , L b , L g and L h may have a substituent.
- the phenylene group include o-phenylene, m-phenylene, and p-phenylene.
- the substituent that the phenylene group may have include an alkyl group, an alkoxy group, a halogen atom, and a cyano group.
- L a and L g are preferably a phenylene group because synthesis of a monomer as a raw material becomes easy.
- L b and L h are preferably alkylene groups because synthesis of monomers as raw materials is facilitated.
- L A and L D represent an oxygen atom or a sulfur atom, and since it is easy to synthesize a monomer as a raw material, an oxygen atom is preferable.
- Q 2 ′, Q 3 ′ and Q 4 ′ each independently represent a monovalent crosslinkable group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or Although it represents a substituted monovalent heterocyclic group, at least one of Q 2 ′, Q 3 ′ and Q 4 ′ represents a monovalent crosslinkable group.
- examples of the monovalent crosslinkable group represented by Q 2 ′, Q 3 ′ and Q 4 ′ include an unsubstituted or substituted aziridinyl group, an unsubstituted or substituted azetidinyl group, an azide group, Examples include an unsubstituted or substituted epoxy group, an unsubstituted or substituted oxetanyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, and a group having a cyclobutene structure.
- the substituted or substituted aryl group is an unsubstituted or substituted monovalent having a cyclobutene structure.
- the heterocyclic group is preferably an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group having a cyclobutene structure, and an unsubstituted or substituted monovalent heterocyclic group having a cyclobutene structure, more preferably unsubstituted or substituted. And an unsubstituted or substituted aryl group having a cyclobutene structure is more preferable.
- examples of the monovalent crosslinkable group represented by Q 2 ′, Q 3 ′ and Q 4 ′ include, for example, the above formulas (Q-1), (Q-2), (Q-01) Monovalent crosslinkable groups represented by (Q-19), (Q-1-1), and (Q-1-2) can be mentioned, and the monomer as a raw material can be easily synthesized.
- (Q-1), (Q-2), (Q-01), (Q-03), (Q-04), (Q-06) to (Q-18), (Q-1-1), (Q -1-2) is preferably a monovalent crosslinkable group represented by formulas (Q-1), (Q-2), (Q-09) to (Q-19), (Q-1-1), A monovalent crosslinkable group represented by (Q-1-2) is more preferred, represented by the formula (Q-1), (Q-1-1), (Q-1-2) or (Q-2) More preferred are monovalent crosslinkable groups.
- Q 2 ′, Q 3 ′ or Q 4 ′ is a group other than a monovalent crosslinkable group
- Q 2 ′, Q 3 ′ or Q 4 ′ is an unsubstituted or substituted aryl group Is preferable, and an unsubstituted or substituted phenyl group is more preferable.
- the hole transportability and durability of the light emitting device produced using the polymer compound of this embodiment are excellent.
- the unsubstituted or substituted alkyl group represented by Q 2 ′, Q 3 ′ and Q 4 ′ is the same as the “alkyl group” described as the above-mentioned substituent. 1 to C 20 alkyl group.
- the unsubstituted or substituted aryl group represented by Q 2 ′, Q 3 ′ and Q 4 ′ is the same as the “aryl group” described as the substituent, but preferably phenyl Group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group or 2-fluorenyl group.
- the unsubstituted or substituted monovalent heterocyclic group represented by Q 2 ′, Q 3 ′ and Q 4 ′ is the same as the “monovalent heterocyclic group” described as the substituent. However, it is preferably a pyridyl group, a pyrimidyl group, a triazyl group or a quinolyl group.
- the structural unit represented by the formula (4 ′) is preferably a structural unit represented by the following formula (4′-1) because the synthesis of the monomer as a raw material becomes easy.
- Ar 20 , Ar 30 ′, Ar 40 , La, Lb, LA, na, nb and nA represent the same meaning as in formula (4 ′).
- d1 represents an integer of 1 to 4
- Ar 50 and Ar 60 each independently represent an unsubstituted or substituted aryl group or an unsubstituted or substituted monovalent heterocyclic group.
- Q 4 represents a monovalent crosslinkable group.
- d1 is an integer of 1 to 4.
- 1 to 3 Is preferably an integer of 2 and more preferably 2.
- Ar 50 and Ar 60 each independently represent an unsubstituted or substituted aryl group or an unsubstituted or substituted monovalent heterocyclic group, and the polymer compound of the present embodiment Since a hole-transport property and durability of a light-emitting element produced using the compound are excellent, an unsubstituted or substituted aryl group is preferable.
- the unsubstituted or substituted aryl group represented by Ar 50 and Ar 60 is the same as the “aryl group” described as the substituent, but is preferably a phenyl group, 1- A naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group or a 2-fluorenyl group;
- the unsubstituted or substituted monovalent heterocyclic group represented by Ar 50 and Ar 60 is the same as the “monovalent heterocyclic group” described as the substituent.
- a pyridyl group, a pyrimidyl group, a triazyl group or a quinolyl group is preferable.
- examples of the monovalent crosslinkable group represented by Q 4 include an unsubstituted or substituted aziridinyl group, an unsubstituted or substituted azetidinyl group, an azide group, an unsubstituted or substituted epoxy group. , An unsubstituted or substituted oxetanyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, and a group having a cyclobutene structure.
- an unsubstituted or substituted alkenyl group an unsubstituted or substituted aryl group having a cyclobutene structure, an unsubstituted or substituted monovalent heterocyclic group having a cyclobutene structure, an unsubstituted or substituted alkenyl group, a cyclobutene structure More preferred is an unsubstituted or substituted aryl group having
- examples of the monovalent crosslinkable group represented by Q 4 include the formulas (Q-1), (Q-2), (Q-01) to (Q-19), Monovalent crosslinkable groups represented by (Q-1-1) and (Q-1-2) are mentioned, and the synthesis of monomers as raw materials is facilitated, so that the formulas (Q-1), (Q-2) ), (Q-01), (Q-03), (Q-04), (Q-06) to (Q-18), (Q-1-1), (Q-1-2) Monovalent crosslinkable groups are preferred, and in the formulas (Q-1), (Q-2), (Q-09) to (Q-19), (Q-1-1), (Q-1-2)
- the monovalent crosslinkable group represented by formula (Q-1), (Q-1-1), (Q-1-2) or (Q-2) is more preferred. Further preferred.
- Formula (4 ′) is preferably Formula (4) above because synthesis of a monomer as a raw material becomes easy.
- c, Ar 20 and Ar 40 represent the same meaning as described above.
- Ar 30 is a divalent group in which two or more identical or different groups selected from an unsubstituted or substituted arylene group, an unsubstituted or substituted divalent heterocyclic group, or an arylene group and a divalent heterocyclic group are linked. A group (the group may have a substituent).
- Q 2 represents a monovalent crosslinkable group
- Q 3 represents a monovalent crosslinkable group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent heterocyclic group. Show.
- c is 0 because synthesis of the monomer as a raw material is easy and the hole transport property and durability of the light-emitting device produced using the polymer compound of this embodiment are excellent. Preferably there is.
- the groups represented by Ar 20 , Ar 30, and Ar 40 are unsubstituted or substituted arylene groups. It is preferable because of its excellent hole transportability and durability.
- examples of the arylene group in Ar 20 , Ar 30 and Ar 40 include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a 1,4-naphthalenediyl group.
- a rangeyl group is preferred, and a 1,4-phenylene group is more preferred. These may have the above substituents.
- examples of the divalent heterocyclic group in Ar 20 , Ar 30 and Ar 40 include 2,5-pyrrolediyl group, dibenzofurandiyl group, dibenzothiophenediyl group and 2,1,3-benzothiadiazole. And a -4,7-diyl group, which may have the above-described substituent.
- the divalent group in which two or more identical or different groups selected from an arylene group and a divalent heterocyclic group in Ar 30 are linked includes the formulas (B-1) and (B-2). ), (B-3), (B-4), (B-5), (B-6) or (B-7), preferably the group represented by the formula (B-1). More preferably, it is a group. In addition, these groups may have the said substituent.
- examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, and an arylalkoxy group.
- examples of the monovalent crosslinkable group represented by Q 2 include those represented by the above formulas (Q-1), (Q-2), (Q-01) to (Q-19). Since the hole transport property and durability of the light emitting device produced using the polymer compound of this embodiment are excellent, the formulas (Q-1), (Q-2), (Q-01) ), (Q-03), (Q04), (Q-06) to (Q-18) are preferred, and the groups represented by formulas (Q-1), (Q-2), (Q-07) are preferred. ) To (Q-18) are more preferable, and a group represented by the formula (Q-1) is more preferable.
- examples of the monovalent crosslinkable group represented by Q 3 include those represented by the above formulas (Q-1), (Q-2), (Q-01) to (Q-19). Since the hole transport property and durability of the light emitting device produced using the polymer compound of this embodiment are excellent, the formulas (Q-1), (Q-2), (Q-01) ), (Q-03), (Q04), (Q-06) to (Q-18) are preferred, and the groups represented by formulas (Q-1), (Q-2), (Q-07) are preferred. ) To (Q-18) are more preferable, and a group represented by the formula (Q-1) is more preferable.
- the unsubstituted or substituted alkyl group represented by Q 3 is the same as the “alkyl group” described as the substituent, but is preferably a C 1 -C 20 alkyl group.
- the unsubstituted or substituted aryl group represented by Q 3 is the same as the “aryl group” described as the substituent, but is preferably a phenyl group, 1-naphthyl group, 2-naphthyl group. Group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group or 2-fluorenyl group.
- the unsubstituted or substituted monovalent heterocyclic group represented by Q 3 is the same as the “monovalent heterocyclic group” described as the substituent, but preferably a pyridyl group, A pyrimidyl group, a triazyl group or a quinolyl group;
- Q 3 is preferably the same monovalent crosslinkable group as Q 1 because the synthesis of the raw material monomer is facilitated.
- the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group.
- Arylalkynyl group amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, cyano group, more preferably alkyl group, alkoxy group, aryl group , An aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group and a cyano group, more preferably an alkyl group, an alkoxy group and an aryl group.
- Examples of the structural unit represented by the formula (4 ′) include structural units represented by the formulas (4-101) to (4-127), and include the formula (4-101) to the formula (4-110). Or structural units represented by formulas (4-115) to (4-127) are preferred, and formula (4-101), formula (4-105) to formula (4-108), formula (4-115) Alternatively, structural units represented by formulas (4-117) to (4-124) are more preferable, and are represented by formulas (4-101), (4-105), (4-107), and (4-115). And a structural unit represented by formula (4-118), formula (4-120), or formula (4-124) is more preferred. Formula (4-101), formula (4-115), formula (4-118) ) Or a structural unit represented by the formula (4-120) is particularly preferable.
- the polymer compound of the present invention includes a structural unit represented by the formula (1), a structural unit represented by the formula (2), a structural unit represented by the formula (3), and / or the following formula: A high molecular compound containing a structural unit represented by (4 ′), The structural unit represented by the formula (1), the structural unit represented by the formula (2), the structural unit represented by the formula (3), and the structural unit represented by the formula (4 ′).
- the polymer compound includes at least two types of structural units selected from the group consisting of: A polymer compound comprising a structural unit represented by the formula (1), a structural unit represented by the formula (2), and at least two types of structural units represented by the formula (3).
- the structural unit represented by the formula (1), the structural unit represented by the formula (2), and two types It is more preferable that the polymer compound includes a structural unit represented by the formula (3): The structural unit represented by the formula (1), the structural unit represented by the formula (2), the structural unit represented by the formula (3-103), and the structural unit represented by the formula (3-105). Selected from the structural unit represented by formula (3-132), the structural unit represented by formula (3-137), and the structural unit represented by formula (3-140).
- the polymer compound of the present invention may contain a constituent unit other than the first constituent unit, the second constituent unit, and the third constituent unit.
- first structural unit, the second structural unit, and the third structural unit of the polymer compound of the present invention may be linked by a non-conjugated structure (that is, other structural unit).
- a non-conjugated structure that is, other structural unit.
- R is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, oxycarbonyl group, It represents a monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, imine residue, amide compound residue, acid imide residue, carboxyl group, hydroxyl group, nitro group or cyano group.
- Ar represents an aromatic hydrocarbon group having 6 to 60 carbon atoms which may contain a hetero atom.
- examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a boron atom, a phosphorus atom, and a selenium atom.
- the content (total content) of the first structural unit is superior to the luminous efficiency of the light-emitting device manufactured using the polymer compound of the present embodiment, and therefore is based on the total structural units contained in the polymer compound. 0.1 to 99.9 mol%, preferably 1 to 99 mol%, more preferably 5 to 70 mol%, particularly preferably 10 to 50 mol%. preferable.
- the content (total content) of the second structural unit is superior to the luminous efficiency of the light-emitting device manufactured using the polymer compound of the present embodiment, and thus is based on the total structural units contained in the polymer compound. 0.1 to 99.9 mol%, preferably 1 to 99.9 mol%, more preferably 10 to 99 mol%, and further preferably 30 to 70 mol%. Is particularly preferred.
- the content of the third structural unit is excellent in thermal crosslinkability when producing a light emitting device using the polymer compound of the present embodiment.
- it is preferably from 0.1 to 99.9 mol%, more preferably from 1 to 99 mol%, further preferably from 2 to 50 mol%, more preferably from 3 to 30 mol%. Is particularly preferred.
- the energy gap calculated from the absorption edge obtained by absorption spectrum measurement is 2.9 eV or more.
- the terminal group is preferably a stable group (for example, an aryl group, a monovalent aromatic heterocyclic group, etc.).
- the polymer compound of the present embodiment may be any copolymer, for example, any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.
- the polymer compound of the present embodiment is useful as a light-emitting material, a charge transport material, and a charge injection material, and when used, may be used in combination with other compounds as a composition described later.
- the number average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound of the present embodiment is preferably 1 ⁇ 10 3 to 1 ⁇ 10 7 , more preferably 1 ⁇ 10 7. 4 to 5 ⁇ 10 6 .
- the weight average molecular weight in terms of polystyrene of the polymer compound of the present embodiment is preferably 1 ⁇ 10 4 to 5 ⁇ 10 7 , and more preferably 5 ⁇ 10 4 to 1 ⁇ 10 7 .
- the glass transition temperature of the polymer compound of this embodiment is 70 ° C. or higher. It is preferable.
- the light emitting device manufactured using the polymer compound of the present embodiment is a high performance light emitting device that can be driven with excellent luminous efficiency. Therefore, the light emitting element is useful for a backlight of a liquid crystal display, a curved or flat light source for illumination, a segment display device, a dot matrix display device, and the like.
- the polymer compound of the present embodiment includes a laser dye, an organic solar cell material, an organic semiconductor for an organic transistor, a conductive thin film, a conductive thin film material such as an organic semiconductor thin film, and a light emitting property that emits fluorescence or phosphorescence. It can also be used as a thin film material.
- the polymer compound of the present embodiment includes, for example, a compound represented by the following formula (1M) (hereinafter, sometimes referred to as “compound 1M”) and a compound represented by the following formula (2M) (hereinafter, depending on circumstances).
- Compound 2M a compound represented by the following formula (3M) (hereinafter, sometimes referred to as “Compound 3M”) and / or a compound represented by the following formula (4'M) (hereinafter, the case).
- the compound 1M, the compound 2M, the compound 3M, and the compound 4′M are sometimes collectively referred to as “monomer”.
- Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , x and y are as defined above, and Z 1 and Z 2 are each independently the following:
- the group selected from the group selected from the substituent group A or the following substituent group B is represented.
- Ar 8 , R 1 and p are as defined above, and Z 3 and Z 4 each independently represent a group selected from the following substituent group A or the following substituent group B.
- Ar 10 , L a , L b , L A , na, nb, nA, n and Q 1 are as defined above, and Z 5 and Z 6 are each independently the following substituent A Or a group selected from the following substituent group B.
- Ar 20 , Ar 30 ′ , Ar 40 , c, d, Q 2 ′, Q 3 ′, Q 4 ′, L a , L b , L A , L g , L h , L D 1 , na, nb, nA, ng, nh and nD are as defined above, and Z 7 and Z 8 each independently represent a group selected from the following substituent group A or the following substituent group B.
- ⁇ Substituent group A> A chlorine atom, a bromine atom, an iodine atom, —O—S ( ⁇ O) 2 R 31 (R 31 may be substituted with an alkyl group, or an alkyl group, an alkoxy group, a nitro group, a fluorine atom, or a cyano group) Represents a good aryl group).
- R 32 represents a hydrogen atom or an alkyl group, and a plurality of R 32 may be the same as or different from each other, and are bonded to each other to form a ring structure together with the oxygen atoms to which they are bonded.
- -BF 3 Q 10 Q 10 represents a monovalent cation selected from the group consisting of Li + , Na + , K + , Rb + and Cs +.
- a group represented by —MgY 1 (Y 1 represents a chlorine atom, a bromine atom or an iodine atom), a group represented by —ZnY 2 (Y 2 represents a chlorine atom, a bromine atom or an iodine atom) And -Sn (R 33 ) 3 (R 33 represents a hydrogen atom or an alkyl group, and a plurality of R 33 may be the same or different from each other, and Each joins And may form a ring structure together with
- a compound having a group selected from Substituent Group A and a compound having a group selected from Substituent Group B may be subjected to condensation polymerization by a known coupling reaction, and carbon atoms bonded to the group may be bonded to each other.
- condensation polymerization by a known coupling reaction, and carbon atoms bonded to the group may be bonded to each other.
- a compound having a group selected only from the substituent group A is also, for example, a method of polymerizing with a Ni (0) catalyst (Yamamoto polymerization) (Progress in Polymer Science, Vol. 17, 1153-1205. Page, 1992), condensation polymers can be obtained.
- the first structural unit is derived from the compound 1M and the second structural unit is derived from the compound 2M.
- the third structural unit is derived from at least one compound selected from the group consisting of compound 3M and compound 4'M.
- condensation polymerization method examples include a polymerization method by Suzuki coupling reaction (Chem. Rev., Vol. 95, pages 2457-2483 (1995)), a polymerization method by Grignard reaction (Bull. Chem. Soc. Jpn., 51, 2091 (1978)), a method of polymerizing with Ni (0) catalyst (Progress in Polymer Science, 17, 173-1205, 1992). And a method using a Stille coupling reaction (European Polymer Journal, Vol. 41, pages 2923-2933 (2005)).
- a method of polymerizing by Suzuki coupling reaction and a method of polymerizing by Ni (0) catalyst are preferable, and the structure of the polymer compound
- a method of polymerizing by an aryl-aryl cross-coupling reaction such as a Suzuki coupling reaction, a Grignard reaction, or a Stille coupling reaction is more preferable, and a reaction of polymerizing by a Suzuki coupling reaction is particularly preferable.
- condensation polymerization method examples include a method in which each of the above compounds is reacted with an appropriate catalyst or base as necessary.
- the total number of moles of groups selected from the substituent group A possessed by each compound, and the substituent group B The ratio with the total number of moles of the group selected from the above may be adjusted.
- the ratio of the latter mole number to the former mole number is preferably 0.95 to 1.05, more preferably 0.98 to 1.02, and 0.99 to 1.01. More preferably.
- the monomer may be synthesized and isolated in advance, or may be synthesized in a reaction system and used as it is.
- these monomers are preferably purified by a method such as distillation, chromatography, sublimation purification, recrystallization, or a combination thereof.
- a catalyst As the catalyst, when polymerized by Suzuki coupling reaction, palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, dichlorobistriphenylphosphine palladium, dichlorobis [tris (2-methoxy Phenyl) phosphine] palladium, dichlorobis [tri-t-butylphosphine] palladium and other transition metal complexes, and these transition metal complexes include triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, and the like. Examples thereof include a complex coordinated with a ligand.
- the Ni (0) catalyst may be nickel [tetrakis (triphenylphosphine)], [1,3-bis (diphenylphosphino) propane] dichloronickel, [bis (1 , 4-cyclooctadiene)] nickel and other transition metal complexes, and these transition metal complexes include triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, diphenylphosphinopropane, substituted or unsubstituted Or a complex in which a ligand such as substituted or unsubstituted phenanthroline is coordinated.
- a previously synthesized catalyst may be used, or a catalyst prepared in a reaction system may be used as it is.
- these catalysts may be used individually by 1 type, or may use 2 or more types together.
- the amount of the catalyst used may be an effective amount as a catalyst.
- it is usually 0.0001 to 300 mol% in terms of the number of moles of transition metal with respect to 100 mol% of all monomers in the polymerization reaction,
- the amount is preferably 0.001 to 50 mol%, more preferably 0.01 to 20 mol%.
- a base inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, hydroxide
- organic bases such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
- the amount of the base used is usually 50 to 2000 mol%, preferably 100 to 1000 mol%, based on 100 mol% of all monomers in the polymerization reaction.
- the polymerization reaction may be performed in the absence of a solvent or in the presence of a solvent, but is usually performed in the presence of an organic solvent.
- organic solvent include toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
- An organic solvent may be used individually by 1 type, or may use 2 or more types together.
- the amount of the organic solvent used is preferably such that the total concentration of all monomers in the polymerization reaction is 0.1 to 90% by weight, more preferably 1 to 50% by weight. More preferably, the amount is 30% by weight.
- the reaction temperature of the polymerization reaction is preferably ⁇ 100 to 200 ° C., more preferably ⁇ 80 to 150 ° C., and further preferably 0 to 120 ° C.
- the reaction time is usually 1 hour or longer, preferably 2 to 500 hours.
- a compound represented by the following formula (1T) is used as a chain terminator to avoid leaving a polymerizable group (for example, Z 1 , Z 2 ) at the terminal of the polymer compound of the present embodiment. May be.
- a polymerizable group for example, Z 1 , Z 2
- Ar T represents an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent
- Z T represents the above-mentioned substituent group A And a group selected from the group consisting of the above-mentioned substituent group B.
- aryl group and monovalent aromatic heterocyclic group in Ar T include the same aryl groups and monovalent aromatic heterocyclic groups exemplified as R 1 described above.
- the post-treatment of the polymerization reaction can be carried out by a known method, for example, a method of removing water-soluble impurities by liquid separation, or a precipitate precipitated by adding the reaction solution after the polymerization reaction to a lower alcohol such as methanol.
- the method of filtering and drying can be performed alone or in combination.
- the polymer compound of this embodiment may be purified by ordinary methods such as recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, etc.
- a purification treatment such as reprecipitation purification and fractionation by chromatography after condensation polymerization.
- the compound of the present embodiment is a compound represented by the following formula (4-1) useful for the production of the above polymer compound.
- Z 7 , Z 8 Ar 20 , Ar 30 ′ , Ar 40 , d 1, Q 4 , L a , L b , L A , na, nb and nA are as defined above.
- a preferred form of the compound represented by the formula (4-1) is a compound represented by the following formula (4-2).
- Z 7 , Z 8 , Ar 20 , Ar 40 , Ar 50 , Ar 60 , Q 4 , nb and L b represent the same meaning as described above.
- a preferred form of the compound represented by the formula (4-2) is a compound represented by the following formula (4-3).
- R x is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted alkylthio group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted Or substituted arylthio group, unsubstituted or substituted amino group, unsubstituted or substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, unsubstituted or substituted monovalent It represents a heterocyclic group, an unsubstituted or substituted carboxyl group, a cyano group, or a nitro group.
- a plurality of R x may be the same or different.
- the compound represented by the formula (4-3) can be synthesized by, for example, the following scheme A (Scheme A).
- the compound represented by the formula (4-3a) is a palladium compound typified by a base such as sodium-tert-butoxide, [tris (dibenzylideneacetone)] dipalladium in an organic solvent
- the compound represented by the formula (4-3b) can be derived by a Buchwald reaction or the like using the compound represented by the formula (4-3a ′).
- the compound represented by the formula (4-3b) includes a base such as sodium-tert-butoxide, a palladium compound typified by [tris (dibenzylideneacetone)] palladium, and a compound represented by the formula (4-3b) in an organic solvent.
- the compound represented by the formula (4-3c) can be derived by the Buchwald reaction with the compound represented by ').
- the compound represented by the formula (4-3c) can be derived into a compound represented by the formula (4-3Br) by reacting with a brominating agent such as N-bromosuccinimide in an organic solvent.
- a brominating agent such as N-bromosuccinimide in an organic solvent.
- the group represented by Z 7 and Z 8 is selected from the substituent group (a) or the substituent group (b) excluding the bromine atom by a known method. It can be derived into a compound represented by the formula (4-3) converted into a group. Further, the compound represented by the formula (4-3Br) can be used as it is as the compound represented by the formula (4-3).
- a preferred form of the compound represented by the formula (4-3) is a compound represented by the following formula (4-4).
- R x is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted alkylthio group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted Or substituted arylthio group, unsubstituted or substituted amino group, unsubstituted or substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, unsubstituted or substituted monovalent It represents a heterocyclic group, an unsubstituted or substituted carboxyl group, a cyano group, or a nitro group.
- a plurality of R x may be the same or different.
- r2 has the same meaning as described above
- the compound of the present embodiment is a compound represented by the following formula (3-3) useful for the production of the above polymer compound.
- Z 5 and Z 6 represent the same meaning as Z 7 and Z 8 .
- nc represents an integer of 0 to 3
- nd represents an integer of 0 to 12
- nB represents 0 or 1
- k represents an integer of 1 to 4.
- L c and L d each independently represent an unsubstituted or substituted alkylene group or an unsubstituted or substituted phenylene group. When a plurality of L c are present, they may be the same or different. When a plurality of L d are present, they may be the same or different.
- L B represents an oxygen atom or a sulfur atom. When a plurality of LB are present, they may be the same or different.
- Q 1 ′ represents an unsubstituted or substituted aryl group having a cyclobutene structure and an unsubstituted or substituted monovalent heterocyclic group having a cyclobutene structure.
- Q 1 When a plurality of Q 1 are present, they may be the same or different.
- R 90 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted monovalent heterocyclic ring A group or an unsubstituted or substituted heterocyclic oxy group; When a plurality of R 90 are present, they may be the same or different.
- a preferred form of the compound represented by the formula (3-3) is a compound represented by the following formula (3-4).
- nc, nd, nB, k, L c , L d , L B , R 90 , Z 5 and Z 6 represent the same meaning as described above, but nd is an integer of 1 to 12 It is preferable that
- a preferred form of the compound represented by the formula (3-4) is a compound represented by the following formula (3-5).
- nc, nd, nB, L c , L d , L B , Z 5 and Z 6 represent the same meaning as described above.
- a preferred form of the compound represented by the formula (3-5) is a compound represented by the following formula (3-6).
- the compound represented by the formula (3-6) can be synthesized by, for example, the following scheme B (Scheme B).
- an aryl anion is generated by reaction of a compound represented by the formula (3-6a) with a base such as lithium amide represented by lithium diisopropylamide in an organic solvent, and trimethylsilyl chloride is added.
- a base such as lithium amide represented by lithium diisopropylamide in an organic solvent
- trimethylsilyl chloride is added.
- the compound represented by the formula (3-6b) can be derived.
- the compound represented by the formula (3-6b) is reacted with a lithiating agent such as alkyllithium represented by butyllithium in an organic solvent to generate a lithiated compound by halogen-metal exchange reaction.
- the compound represented by the formula (3-6c) can be added to the compound represented by the formula (3-6d).
- the compound represented by the formula (3-6d) is reacted with, for example, a lithiating agent such as alkyl lithium typified by butyl lithium in an organic solvent to generate a lithiated compound by halogen-metal exchange reaction.
- a compound represented by the formula (3-6e) can be derived by adding a compound represented by the formula (3-6c).
- the compound represented by the formula (3-6e) is derived into the compound represented by the formula (3-6Br) by reacting with a brominating agent such as N-bromosuccinimide or bromine in an organic solvent. be able to.
- the group represented by Z 5 and Z 6 is selected from the substituent group (a) or the substituent group (b) excluding the bromine atom by a known method. It can be derived into a compound represented by the formula (3-6) converted into a group. In addition, the compound represented by the formula (3-6Br) can be used as it is as the compound represented by the formula (3-6).
- composition contains the polymer compound of the present invention and at least one selected from the group consisting of a hole transport material, an electron transport material and a light emitting material. This composition can be used suitably for manufacture of a light emitting element.
- hole transport materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, polyaniline and derivatives thereof, polythiophene and Examples thereof include polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, and the like.
- the content of the hole transport material is preferably 1 to 500 parts by weight, more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention in the composition.
- Electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene And derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, anthracene and derivatives thereof, and copolymers of anthracene and fluorene It is done.
- JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, and JP-A-3- Examples thereof include electron transport materials described in Japanese Patent No. 37992 and Japanese Patent Laid-Open No. 3-152184.
- the content of the electron transport material is preferably 1 to 500 parts by weight, more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention in the composition.
- the light emitting material examples include a low molecular fluorescent light emitting material and a phosphorescent light emitting material, and a phosphorescent light emitting material is preferable.
- the luminescent material examples include naphthalene derivatives, anthracene and derivatives thereof, copolymers of anthracene and fluorene, perylene and derivatives thereof, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, and the like, 8 -Metal complexes having hydroxyquinoline as a ligand, metal complexes having 8-hydroxyquinoline derivative as a ligand, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and its Derivatives, fluorescent materials of low molecular weight compounds such as stilbene, silicon-containing aromatics, oxazoles, furoxans, thiazoles, tetraary
- Examples of the phosphorescent material include the following, and from the viewpoint of luminance lifetime, Ir-2a to Ir-6a, Ir-10a to Ir-13a, Ir-17a to Ir-24a, Ir-2b to Ir-6b, Ir Compounds represented by ⁇ 10b to Ir-13b, Ir-18b to Ir-29b, Ir-1c to Ir-14c, Ir-1d to Ir-19d are preferred, and Ir-10a to Ir-13a, Ir-17a to Ir-24a, Ir-10b to Ir-13b, Ir-18b to Ir-29b, Ir-1c, Ir-5c, Ir-8c, Ir-10c to Ir-14c, Ir-1d to Ir-2d, Ir- Compounds represented by 6d to Ir-12d and Ir-15d to Ir-19d are more preferable.
- Rp described as a substituent of the dendron moiety is preferably an alkyl group or an alkoxy group, more preferably an alkyl group, ease of synthesis, and emission of the resulting phosphorescent compound. From the viewpoint of ease of dissolution in an organic solvent when used in the production of an element, a tert-butyl group, a hexyl group, and an ethylhexyl group are more preferable.
- the content of the luminescent material is preferably 1 to 500 parts by weight, more preferably 5 to 200 parts by weight, with respect to 100 parts by weight of the polymer compound of the present invention in the composition.
- the polymer compound of the present embodiment may be a composition dissolved or dispersed in a solvent, preferably an organic solvent (hereinafter, referred to as “liquid composition”.
- liquid composition examples include solutions and dispersions. .).
- Such a liquid composition is also called ink or varnish.
- the liquid composition is preferably a solution.
- the liquid composition may contain at least one selected from the group consisting of a hole transport material, an electron transport material and a light emitting material in addition to the polymer compound of the present embodiment.
- other substances may be added to the liquid composition as long as the effects of the present invention are not hindered. Examples of other substances include an antioxidant, a viscosity modifier, and a surfactant.
- the organic solvent is not particularly limited as long as the polymer compound of the present embodiment is dissolved or dispersed, and examples thereof include the following organic solvents.
- Aromatic hydrocarbon solvents toluene, xylene (each isomer or a mixture thereof), 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, mesitylene (1,3,5-trimethylbenzene), Ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, isobutylbenzene, 2-phenylbutane, tert-butylbenzene, pentylbenzene, neopentylbenzene, isoamylbenzene, hexylbenzene, cyclohexylbenzene, heptylbenzene, octylbenzene, 3-propyltoluene 4-propyltoluene, 1-methyl-4-propylbenzene, 1,4-diethylbenzene, 1,4-dipropylbenzene, 1,4-di-tert-butyl
- Aliphatic hydrocarbon solvents n-pentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, decalin, etc.
- Aromatic ether solvents anisole, ethoxybenzene, propoxybenzene, butyroxybenzene, pentyloxybenzene, cyclopentyloxybenzene, hexyloxybenzene, cyclohexyloxybenzene, heptyloxybenzene, octyloxybenzene, 2-methylanisole, 3-methyl Anisole, 4-methylanisole, 4-ethylanisole, 4-propylanisole, 4-butylanisole, 4-pentylanisole, 4-hexylanisole, diphenylether, 4-methylphenoxybenzene, 4-ethylphenoxybenzene, 4-propylphenoxy Benzene, 4-butylphenoxybenzene, 4-pentylphenoxybenzene, 4-hexylphenoxybenzene, 4-phenoxytoluene, 3- Enokishitoruen, 1,3-dimethoxybenzene, 2,6-dimethyl anisole,
- Aliphatic ether solvents tetrahydrofuran, dioxane, dioxolane and the like.
- Ketone solvents acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, etc.
- Ester solvent ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate, etc.
- Chlorinated solvent methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene and the like.
- Alcohol solvents methanol, ethanol, propanol, isopropanol, cyclohexanol, phenol, etc.
- Polyhydric alcohol and its derivatives ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexane Diol etc.
- Aprotic polar solvents dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
- organic solvents may be used alone or in combination of two or more.
- a mixed solvent it is preferable to combine two or more of the above solvent groups. However, even if a plurality of solvents from the same system illustrated above are combined, one or more from a group of solvents of different systems may be combined. May be.
- the composition ratio can be determined in consideration of the physical properties of each solvent and the solubility of a polymer compound or the like.
- Preferable examples in the case of selecting and combining a plurality of types from the same solvent group include a plurality of types from aromatic hydrocarbon solvents, a plurality of types from aromatic ether solvents, and the like.
- Preferred examples in the case of selecting and combining one or more from different solvent groups include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and aromatic ether solvents, aromatics Examples thereof include a combination of a hydrocarbon solvent and an aliphatic ether solvent, an aromatic hydrocarbon solvent and an aprotic polar solvent, an aromatic ether solvent and an aprotic polar solvent, and the like.
- water can also be added to a single solvent or a mixed solvent.
- a single solvent or a mixed solvent containing one or more organic solvents having a structure containing a benzene ring, a melting point of 0 ° C. or less, and a boiling point of 100 ° C. or more has viscosity, film-forming properties.
- a single solvent or a mixed solvent containing at least one aromatic hydrocarbon solvent or aromatic ether solvent is more preferable.
- the organic solvent may be used singly or in combination of two or more as a mixed solvent, but is preferably used as a mixed solvent from the viewpoint of controlling film formability. Moreover, you may use an organic solvent, after refine
- the organic thin film containing the high molecular compound of this embodiment can be manufactured easily.
- an organic thin film containing the polymer compound of the present embodiment can be produced by applying the liquid composition on a substrate and distilling off the organic solvent by heating, blowing, reducing pressure, or the like. it can.
- the evaporation of the organic solvent can be changed depending on the organic solvent used. For example, the step of heating at a temperature of 50 ° C. or higher and 250 ° C. or lower, or a reduced pressure atmosphere of about 10 ⁇ 3 Pa is maintained. And the like.
- a coating method such as a printing method, a flexographic printing method, an offset printing method, an ink jet printing method, or a nozzle coating method can be used.
- the suitable viscosity of the liquid composition varies depending on the printing method, but at 25 ° C., it is preferably 0.5 to 1000 mPa ⁇ s, more preferably 0.5 to 500 mPa ⁇ s. Further, when the liquid composition passes through a discharge device as in the ink jet printing method, the viscosity at 25 ° C. is preferably 0.5 to 50 mPa ⁇ s in order to prevent clogging and flight bending at the time of discharge. More preferably, it is 0.5 to 20 mPa ⁇ s.
- the concentration of the polymer compound of the present embodiment in the liquid composition is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.
- the organic thin film of this embodiment contains the polymer compound or composition.
- the organic thin film of this embodiment can be easily produced from the liquid composition.
- the second organic thin film of the present invention is an insolubilized organic thin film obtained by insolubilizing the polymer compound of the present embodiment by crosslinking, and is usually cured by crosslinking by external stimulation such as heating or light irradiation. is there. Since the insolubilized organic thin film is hardly soluble in a solvent, it is advantageous for stacking light emitting elements.
- the heating temperature for crosslinking the organic thin film is generally in the range of room temperature to 300 ° C., and the upper limit thereof is preferably 250 ° C. from the viewpoint of luminous efficiency, more preferably 200 ° C., It is especially preferable that it is 180 degreeC. Further, the lower limit is preferably 50 ° C., more preferably 70 ° C., and particularly preferably 100 ° C. from the viewpoint of easy formation of the insolubilized organic thin film.
- ultraviolet light, near ultraviolet light, and visible light are used for light irradiation for crosslinking the organic thin film, but ultraviolet light and near ultraviolet light are preferably used.
- the organic thin film and the insolubilized organic thin film of the present embodiment can be suitably used as a hole injection layer or a hole transport layer in a light emitting device to be described later. Moreover, it can be suitably used for organic semiconductor elements such as organic transistors and organic solar cells. Since the organic thin film and the insolubilized organic thin film of the present embodiment are produced using the above polymer compound or composition, the light emission of the light emitting element when used as a hole injection layer or a hole transport layer of the light emitting element. The efficiency becomes better.
- the light emitting device of this embodiment has the organic thin film or the insolubilized organic thin film.
- the light-emitting device of this embodiment has an anode, a cathode, and a layer containing the polymer compound of the present invention between the anode and the cathode.
- the layer containing the polymer compound is preferably a layer composed of the organic thin film or the insolubilized organic thin film, and the layer preferably functions as a hole injection layer or a hole transport layer.
- the layer containing the polymer compound of the present invention functions as a hole injection layer or a hole transport layer
- the layer is preferably a layer made of the insolubilized organic thin film.
- Examples of the light emitting device of the present embodiment include a light emitting device in which an electron transport layer is provided between a cathode and a light emitting layer, a light emitting device in which a hole transport layer is provided between an anode and a light emitting layer, and a cathode and a light emitting layer. And a light emitting element in which an electron transport layer is provided between the anode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.
- the light emitting device of this embodiment include the following structures a) to d). a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)
- the polymer compound of this embodiment can be used for the hole transport layer.
- hole transport materials including low molecular weight and high molecular weight compounds
- Examples of the hole transport material include those exemplified for the hole transport material that may be contained in the composition of the present invention.
- hole transport material examples include JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2. Examples thereof are those described in JP-A Nos. 209988, 3-37992, and 3-152184.
- hole transport material used for the hole transport layer polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amine compound groups in the side chain or main chain, polyaniline and derivatives thereof
- High molecular weight hole transport materials such as polythiophene and its derivatives, poly (p-phenylene vinylene) and its derivatives, poly (2,5-thienylene vinylene) and its derivatives, polyvinyl carbazole and its derivatives, polysilane and A polysiloxane derivative having an aromatic amine in its derivative, side chain or main chain is more preferred.
- examples of the low molecular weight hole transport material include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives.
- a low molecular weight hole transport material it is preferably used by being dispersed in a polymer binder.
- Polymer binder those that do not extremely inhibit charge transport are preferable, and those that do not strongly absorb visible light are suitably used.
- Polymer binders include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
- Polyvinylcarbazole and its derivatives can be obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.
- polysilanes and derivatives thereof include the compounds described in Chem. Rev. 89, 1359 (1989), and GB 2300196 published specification. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.
- polysiloxane and derivatives thereof those having the structure of the low molecular weight hole transporting material in the side chain or main chain are preferably used because the siloxane skeleton structure has almost no hole transporting property.
- those having a hole transporting aromatic amine in the side chain or main chain are exemplified.
- a method for forming the hole transport layer for a low molecular weight hole transport material, a method by film formation from a mixed solution with a polymer binder is exemplified.
- a method of film formation from a solution that is, a mixture of a hole transport material and a solvent is exemplified.
- the solvent used for film formation from a solution a solvent capable of dissolving or uniformly dispersing the hole transport material is preferable.
- the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene and the like.
- Aromatic hydrocarbon solvents such as ketone solvents, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxy ether
- ketone solvents such as ketone solvents, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate
- ethylene glycol ethylene glycol monobutyl ether
- ethylene glycol monoethyl ether ethylene glycol monomethyl ether
- dimethoxy ether Polyhydric alcohols and derivatives thereof such as ethylene, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, alcohol solvents such as methanol,
- film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.
- the thickness of the hole transport layer differs depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element may increase, which is not preferable. Accordingly, the thickness of the hole transport layer is usually 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.
- an electron transport material (there are low molecular weight and high molecular weight compounds) can be used for the electron transport layer.
- the electron transport material include those exemplified for the electron transport material that may be contained in the composition of the present invention.
- the electron transport material examples include JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-135. Examples are those described in Japanese Patent No. 209988, Japanese Patent Laid-Open No. 3-37992, and Japanese Patent Laid-Open No. 3-152184.
- oxadiazole derivatives benzoquinone and its derivatives, anthraquinone and its derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives are preferred. More preferred are-(4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline.
- Examples of the film formation method of the electron transport layer include low-molecular weight electron transport materials, vacuum deposition method from powder, and film deposition methods from solution or molten state, and high molecular weight electron transport materials include solution or melt.
- a method by film formation from the state is exemplified.
- the polymer binder may be used in combination.
- a solvent used for film formation from a solution a solvent capable of dissolving or uniformly dispersing an electron transport material and / or a polymer binder is preferable.
- a solvent used for the film-forming from the solution of a positive hole transport layer in the term of the said positive hole transport layer is mentioned. These solvents may be used alone or in combination of two or more.
- Examples of the film formation method from a solution or a molten state include those exemplified as the film formation method from the solution of the hole transport layer in the section of the hole transport layer.
- the thickness of the electron transport layer varies depending on the material used and may be selected so that the drive voltage and light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is usually 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.
- hole transport layer and electron transport layer provided adjacent to the electrode, those having the function of improving the charge injection efficiency from the electrode and having the effect of lowering the driving voltage of the element are particularly positive.
- a hole injection layer or an electron injection layer hereinafter, these generic names may be referred to as “charge injection layers”).
- the charge injection layer or the insulating layer may be provided adjacent to the electrode in order to improve adhesion with the electrode or charge injection from the electrode, and also improve adhesion at the interface or prevent mixing.
- a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.
- the order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.
- examples of the light emitting element provided with the charge injection layer include a light emitting element provided with the charge injection layer adjacent to the cathode and a light emitting element provided with the charge injection layer adjacent to the anode.
- the following structures e) to p) can be mentioned.
- the light emitting device of this embodiment includes those in which the polymer compound of this embodiment is contained in the hole transport layer and / or the electron transport layer. Further, the light emitting device of this embodiment includes those in which the polymer compound of this embodiment is contained in the hole injection layer and / or the electron injection layer.
- the polymer compound or composition of the present embodiment is used for the hole injection layer, it is preferably used simultaneously with the electron accepting compound.
- the polymer compound or composition of the present embodiment is used for an electron injection layer, it is preferably used simultaneously with an electron donating compound.
- simultaneous use there are methods such as mixing, copolymerization and introduction as a side chain.
- a specific example of the charge injection layer is a layer containing a conductive polymer, provided between the anode and the hole transport layer, and having an intermediate value between the anode material and the hole transport material contained in the hole transport layer.
- Examples include a layer including a material having an ionization potential, a layer including a material provided between the cathode and the electron transport layer, and having a material having an electron affinity intermediate between the cathode material and the electron transport material included in the electron transport layer. It is done.
- the electrical conductivity of the conductive polymer is preferably 10 ⁇ 5 S / cm or more and 10 3 S / cm or less. for the smaller is more preferably less 10 -5 S / cm or more and 10 2 S / cm, more preferably not more than 10 -5 S / cm or more and 10 1 S / cm.
- the conductive polymer is doped with an appropriate amount of ions.
- the kind of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer.
- anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and the like.
- the cation include lithium ion, sodium ion, potassium ion, tetrabutylammonium ion and the like.
- the thickness of the charge injection layer is usually 1 nm to 100 nm, preferably 2 nm to 50 nm.
- the material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer.
- the thickness of the insulating layer is usually 0.5 to 7.0 nm and has a function of facilitating charge injection.
- Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.
- Examples of the light emitting element provided with an insulating layer include a light emitting element provided with an insulating layer adjacent to the cathode and a light emitting element provided with an insulating layer adjacent to the anode. Specific examples include the following structures q) to ab).
- the light-emitting device of this embodiment is the same as that of any one of the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer in the device structures exemplified in the above a) to ab).
- the hole injection layer and / or the hole transport layer contains the polymer compound or composition of the present embodiment.
- the light emitting device of this embodiment is usually formed on a substrate.
- This substrate may be any substrate that does not change when an electrode is formed and an organic layer is formed.
- the material for the substrate include glass, plastic, polymer film, and silicon.
- the opposite electrode that is, the electrode far from the substrate
- the opposite electrode is preferably transparent or translucent.
- at least one of the anode and the cathode included in the light emitting device of the present embodiment is transparent or translucent.
- the anode side is preferably transparent or translucent.
- a conductive metal oxide film, a translucent metal thin film, or the like is used as the anode material.
- ITO indium / tin / oxide
- NESA indium / zinc / oxide
- gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable.
- a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
- organic transparent conductive films such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an anode.
- the thickness of the anode can be appropriately adjusted in consideration of light transmittance and electric conductivity, but is usually 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, more preferably 40 nm to 500 nm. .
- a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode.
- the cathode material a material having a small work function is preferable.
- metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used.
- the cathode may have a laminated structure of two or more layers.
- the thickness of the cathode can be appropriately adjusted in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, more preferably 50 nm to 500 nm.
- a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used.
- a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the organic layer, and the light emitting element is protected after the cathode is manufactured.
- a protective layer may be provided. In order to use the light emitting element stably for a long period of time, it is preferable to provide a protective layer and / or a protective cover in order to protect the element from the outside.
- the protective layer polymer compounds, metal oxides, metal fluorides, metal borides, metal nitrides, organic-inorganic hybrid materials, and the like can be used.
- a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing and sealing the cover with an element substrate with a thermosetting resin or a photocurable resin is preferably used. It is done. If a space is maintained using a spacer, it is easy to prevent the element from being damaged.
- the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element. Among these, it is preferable to take any one or more measures.
- the light emitting device of the present embodiment includes, for example, a planar light source (for example, illumination) such as a curved light source or a planar light source; a segment display device (for example, a segment type display device); a dot matrix display device (for example, a dot matrix).
- a planar light source for example, illumination
- a segment display device for example, a segment type display device
- a dot matrix display device for example, a dot matrix.
- Flat display liquid crystal display devices (for example, liquid crystal display devices, backlights of liquid crystal displays) and the like.
- the planar anode and cathode may be arranged so as to overlap each other.
- both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymeric fluorescent substances having different emission colors or a method using a color filter or a fluorescence conversion filter.
- the dot matrix element can be driven passively, or may be actively driven in combination with a TFT or the like.
- the planar light-emitting element is self-luminous and thin, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can also be used as a curved light source or display device.
- HPLC High performance liquid chromatography
- LC-20A manufactured by Shimadzu Corporation
- Column: Kaseisorb LC ODS 2000 manufactured by Tokyo Chemical Industry Co., Ltd.
- SPD-M20A manufactured by Shimadzu Corporation
- ⁇ Analysis condition 2> Measuring device: Device having performance equivalent to analysis condition 1 Column: Ascentis Express C18, or column having equivalent performance Detector: Device having performance equivalent to analysis condition 1 Detection wavelength: Target and impurities can be measured As the mobile phase of wavelength HPLC, water and tetrahydrofuran were used and flowed by a gradient analysis of water / tetrahydrofuran 100/0 to 0/100 (volume ratio) at a flow rate of 1 mL / min.
- NMR measurement was performed using a sample prepared by dissolving 5 to 20 mg of a measurement sample in about 0.5 mL of an organic solvent. Write the measurement frequency in the measurement data. 300 MHz was carried out using NMR (trade name: INOVA300, manufactured by Varian, Inc.).
- the LC-MS measurement was performed by the following method.
- the measurement sample was dissolved in an appropriate organic solvent (chloroform, tetrahydrofuran, ethyl acetate, toluene, etc.) to a concentration of 1 to 10 mg / mL, and measured and analyzed by LC-MS.
- an appropriate organic solvent chloroform, tetrahydrofuran, ethyl acetate, toluene, etc.
- LC-MS ion-exchanged water, acetonitrile, tetrahydrofuran or a mixture thereof was used, and acetic acid was added as necessary.
- TLC-MS was measured by the following method. Dissolve the measurement sample in an appropriate organic solvent (chloroform, tetrahydrofuran, ethyl acetate, toluene, etc.) to a concentration of 1 to 10 mg / mL, place the sample solution on a glass plate, measure by TLC-MS, Analyzed. Measuring device: Accu TOF TLC (manufactured by JEOL)
- CM1 was synthesized according to the synthesis method described in JP2010-189630A.
- CM2 was synthesized by the following method.
- CM3 was synthesized according to the synthesis method described in JP2010-189630A.
- CM4 was synthesized according to the synthesis method described in JP2010-189630A.
- CM5 was synthesized according to the synthesis method described in JP2011-174061A.
- CM6 was synthesized according to the synthesis method described in WO2002 / 045184.
- CM7 was synthesized according to the synthesis method described in WO2009 / 131255.
- CM8 was synthesized according to the synthesis method described in WO2002 / 045184.
- CM9 was synthesized according to the synthesis method described in WO2009 / 131255.
- CM10 was synthesized according to the synthesis method described in WO2005 / 049546.
- CM11 was synthesized according to the synthesis method described in WO2011 / 049241.
- CM12 was synthesized according to the synthesis method described in JP-A-2009-052032.
- CM13 was synthesized according to the synthesis method described in WO2009 / 110642.
- CM14 was synthesized according to the synthesis method described in WO2002 / 045184.
- CM15 was synthesized according to the synthesis method described in JP-A-2006-169265.
- CM16 was synthesized according to the synthesis method described in JP-A-2006-169265.
- CM17 was synthesized according to the synthesis method described in JP2010-189630A.
- CM18 was synthesized by the following method.
- CM19 was synthesized by the following method.
- CM20 was synthesized by the following method.
- CM21 was synthesized by the following method.
- CM22 was synthesized according to the synthesis method described in JP-A-2008-106241.
- CM23 was synthesized according to the synthesis method described in JP 2010-215886 A.
- CM24 was synthesized according to the synthesis method described in JP2010-215886A.
- CM25 was synthesized by the following method.
- CM26 was synthesized by the following method.
- CM27 was synthesized by the following method.
- CM2a 100 g, 288 mmol
- bispinacolate diboron 168 g, 660 mmol
- potassium acetate 170 g, 1724 mmol
- dehydrated dioxane 1340 mL
- PdCl 2 (dppf) 2 .CH 2 Cl 2 14.12 g, 17.28 mmol
- the filtrate was washed repeatedly with ion exchange water (1.5 L).
- the organic layer was dehydrated with Na 2 SO 4 and the solvent was distilled off under reduced pressure to obtain 185 g of a dark red tar-like product.
- This product was dissolved in toluene (2 L), 200 g of activated carbon was added, the mixture was heated and stirred at 80 ° C. for 2 hours, filtered with celite while hot, and the solvent was distilled off under reduced pressure.
- the residue was recrystallized in the order of hexane (150 mL), ethanol (800 mL) and ethanol (550 mL), and the resulting white crystals were dried under reduced pressure to obtain 80 g of the target monomer CM2 (yield 63). %).
- N-Hexane was added to the resulting mixture and stirred, and after standing, the separated aqueous layer was separated from the oil layer.
- a 10% aqueous potassium phosphate solution (5 L) was added to the obtained oil layer, stirred for 2 hours, and allowed to stand, and then the separated aqueous layer was separated from the oil layer.
- the oil layer was washed with water, anhydrous sodium sulfate was added and stirred, and the filtrate was concentrated under reduced pressure to remove the solvent and obtain an oil.
- a solution prepared by dissolving the oil in dichloromethane (610 mL) is added to stirred methanol (8.5 L) over 1 hour, and the mixture is further stirred for 3 hours. The precipitated crystals are filtered and dried under reduced pressure. As a result, 538 g of the target compound CM18d was obtained.
- the oil layer was concentrated under reduced pressure to remove the solvent to obtain an oil.
- the oil was dissolved in toluene (500 mL) to prepare a solution, and the solution was passed through a filter packed with celite and a filter packed with silica gel. The obtained filtrate was concentrated under reduced pressure to remove the solvent to obtain an oily substance. Isopropyl alcohol and dichloromethane were added to the oil and allowed to stand, and the precipitated crystals were filtered to obtain a yellow solid. The solid was recrystallized from isopropyl alcohol and toluene to obtain 94 g of the target compound CM18f.
- the oil layer was concentrated under reduced pressure to remove the solvent to obtain an oil.
- the oil was dissolved in toluene (200 mL) to prepare a solution, and the solution was passed through a filter packed with Celite and a filter packed with silica gel.
- the obtained filtrate was concentrated under reduced pressure to remove the solvent to obtain an oily substance.
- Isopropyl alcohol and methanol were added to the oily substance, and the mixture was stirred and allowed to stand to remove the separated supernatant.
- the solvent was removed from the resulting oily substance under reduced pressure to obtain 82 g of the target compound CM18g.
- the obtained solid was recrystallized using ethanol-ion exchange water, then recrystallized twice with chloroform-hexane, further added with activated carbon in a state dissolved in ethanol, heated to reflux, and then filtered through Celite. The activated carbon was filtered off. Thereafter, the filtrate was concentrated and purified by adding hexane to precipitate a solid.
- the obtained solid was collected by filtration and dried under reduced pressure to obtain the target compound CM19b (52.8 g) as a skin-colored solid. Yield 58.9%.
- the HPLC area percentage value of the obtained compound CM19b measured under analysis condition 1 was 97.6%.
- the mixture was dissolved in ethyl acetate (80 ml) with heating, hexane (320 ml) was added dropwise, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration.
- the obtained solid was dissolved again in ethyl acetate (68 ml) by heating, hexane (280 ml) was added dropwise, and the mixture was cooled to room temperature, and the precipitated solid was collected by filtration.
- the obtained solid was dried under reduced pressure to obtain the target compound CM19c (39.0 g) as a pale yellow solid. Yield 67.0%.
- the HPLC area percentage value of the obtained compound measured under analysis condition 1 was 98.5%.
- the target component was extracted with chloroform from the celite and silica gel residues used above, and purified by the same operation as above to recover Compound CM19d (8.7 g) as a white solid.
- the HPLC area percentage value of the obtained compound CM19d measured under analysis condition 1 was 99.3% (UV254 nm). Yield 22.1%. From the above, the total yield was 28.0 g, and the yield was 71.2%.
- the precipitated solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 11.1 g of a white solid. Purify by medium pressure silica gel chromatography ( ⁇ 5 ⁇ 30cm, hexane), combine fractions containing the target compound, concentrate, dissolve in hexane (232 ml), add activated clay (23 g), stir for 1 hour at room temperature. did. Thereafter, the solid was filtered off, the filtrate was concentrated, and then recrystallized from ethyl acetate, filtered and dried under reduced pressure to obtain 19 g (10.85 g) of the target compound CM as light yellow crystals. Yield 74.8%.
- celite was further washed with toluene (twice with 100 ml), and the filtrates were combined and concentrated. Next, hexane (280 ml) and activated carbon (21 g) were added, and the mixture was stirred for 1 hour under heating and refluxing, then cooled to room temperature, and passed through a filter covered with celite to remove insoluble matters. Further, celite was washed with toluene (twice with 100 ml), and the filtrates were combined and concentrated. The operation of concentration was repeated twice, ethanol (250 ml) was added, and the mixture was stirred with heating under reflux for 1 hour.
- a saturated aqueous solution of sodium dithionite was added to the resulting reaction solution to decompose excess bromine, and then the solvent was removed by concentration under reduced pressure to obtain a solid.
- Add tetrahydrofuran (1 L) to the obtained solid stir at 70 ° C. for 1 hour, cool to room temperature, add water to dissolve the precipitated inorganic salt, and then concentrate again under reduced pressure.
- the tetrahydrofuran was removed by a solid-liquid mixture.
- the precipitated solid was collected by filtration, dissolved by adding toluene, passed through a silica gel short column, and the obtained toluene solution was concentrated to obtain a solid.
- ⁇ Third step> After adding pyridine (34.70 mL) to the above compound CM20d (12.22 g, 34.70 mmol), benzyltrimethylammonium hydroxide (40% pyridine solution) (prepared according to the following, 0.87 mL) was added at room temperature. The mixture was heated in an oil bath at 40 ° C. while aeration was conducted in the reaction vessel and stirred for 16 hours. Thereafter, benzyltrimethylammonium hydroxide (40% pyridine solution) (prepared according to the following, 0.87 mL) was added again, heated in an oil bath at 60 ° C., and stirred for 8 hours to obtain a reaction solution.
- Benzyltrimethylammonium hydroxide (40% pyridine solution) After adding pyridine (50 mL) to benzyltrimethylammonium hydroxide (40% methanol solution) (commonly known as TRITON B, manufactured by Kanto Chemical Co., Inc., 50 mL), it is concentrated to 25 mL or less with an evaporator, and pyridine is added again. Prepared by diluting to 50 mL. The solution obtained by this operation is called benzyltrimethylammonium hydroxide (40% pyridine solution).
- the compound CM20e (11.87 g, 32.4 mmol) was added little by little so that the temperature of the solution was maintained at ⁇ 75 ° C. or lower, and after further stirring for 2 hours, methanol (about 20 mL) was slowly added. Then, the dry ice-methanol bath was removed and the temperature was slowly raised to room temperature. After the solvent was distilled off by concentration under reduced pressure, the resulting reaction solution was added with hexane and washed with ion-exchanged water to obtain an oil layer.
- methyl iodide (6.34 g, 44.7 mmol) was added dropwise, and the mixture was stirred at 0 to 5 ° C. for 4 hours.
- the ice bath was removed, ion-exchanged water was added, and extraction with hexane was performed to obtain an oil layer.
- the obtained oil layer was dried using anhydrous sodium sulfate, insolubles were filtered off, the solvent was distilled off, and the residue was purified by medium pressure silica gel column chromatography (hexane).
- the obtained solution was dried over anhydrous sodium sulfate, insoluble matters were filtered off, the solvent was distilled off by concentration under reduced pressure, and toluene was added to obtain a uniform solution.
- Activated carbon is added to the resulting solution, stirred for 30 minutes while heating in an oil bath at 70 ° C., cooled to room temperature, then insolubles are removed by celite filtration, and the resulting solution is concentrated and recrystallized. Purification (mixed solvent of toluene and acetonitrile) was performed. The obtained crystals were collected by filtration and dried under reduced pressure to obtain the target monomer CM20 (6.94 g) as a white solid. Yield 82%.
- the oil was dissolved in a hexane / toluene mixed solvent, passed through a filter packed with Florisil through the hexane / toluene mixed solvent, and the resulting filtrate was concentrated under reduced pressure to obtain an oil.
- the oil was dissolved in hexane, passed through a filter packed with Florisil with hexane, and the obtained filtrate was dried under reduced pressure to obtain an oil.
- Isopropanol was added to the oil, methanol was added to the resulting oil, and the solid was filtered. The solid was recrystallized from methanol / toluene and dichloromethane / methanol was added to obtain 95.79 g of the target compound CM25b.
- the HPLC area percentage value measured under analysis condition 2 of the obtained compound CM25b was 99.21%.
- the oil was dissolved in dichloromethane and passed through a filter packed with silica gel, and the obtained filtrate was dried under reduced pressure to obtain an oil.
- the solid obtained by adding isopropanol to the oil was filtered.
- the solid was recrystallized from toluene / isopropanol, toluene / butyl acetate, toluene / acetonitrile.
- the obtained solid was dissolved in dichloromethane, filtered through filter paper, and isopropanol was added to obtain a solid.
- the solid was heated to reflux with acetonitrile for 1 hour, and the solid obtained after cooling to room temperature was filtered to obtain 83.77 g of the target monomer CM25.
- CM27a 26 g, 39.6 mmol
- tetrahydrofuran 500 mL
- Potassium-tert-butoxide 17.75 g, 158.5 mmol
- Ice water 500 mL was added to the reaction solution, and the oil layer separated after standing was separated from the aqueous layer and combined with the ethyl acetate extract of the aqueous layer.
- the oil layer was concentrated under reduced pressure to remove the solvent to obtain an oil.
- the oil was separated and purified by silica gel column chromatography using hexane to obtain 14.5 g of the target compound CM27b.
- the HPLC area percentage value of the obtained compound CM27b measured under analysis condition 2 (detection wavelength: 240 nm) was 99.68%.
- reaction solution was warmed to room temperature and stirred overnight. Next, the reaction solution was cooled to 0 ° C., and 2 mol / L hydrochloric acid in diethyl ether was added dropwise until the reaction solution became transparent. The product was extracted with diethyl ether and concentrated under reduced pressure to remove the solvent and obtain a solid. Acetonitrile (150 mL) was added to the solid and stirred at room temperature for 2 hours, and the resulting solid was filtered. Acetonitrile (100 mL) was added to the solid again, and the mixture was stirred at room temperature for 2 hours and further recrystallized twice with acetonitrile to obtain 3.60 g of the target monomer CM27.
- HPLC area percentage value of the obtained monomer CM27 measured under analysis condition 2 was 99.90%.
- the acetonitrile filtrates at the time of recrystallization were combined and recrystallized twice with acetonitrile to obtain 1.4 g of CM27 (HPLC area percentage value measured under analysis condition 2 was 99.76%).
- 1 H-NMR (500 MHz, THF) ⁇ (ppm) 7.53 (s, 2H), 5.83 (m, 2H), 4.99 (d, 2H), 4.90 (d, 2H), 2.82 (t, 4H), 2.07 (m, 4H), 1.56 (m, 4H), 1.45 (m, 4H), 1.33 (s, 24H).
- CM28a (35.31 g) and methanol (1100 mL) were placed in a 2000 mL four-necked flask equipped with a stirrer, and the gas in the flask was replaced with argon.
- Dimethyl 1,3-acetone dicarboxylate (34.65 g) was slowly added thereto, and then sodium methoxide (5 mol / L methanol solution) (67.62 g) was slowly added dropwise. Thereafter, the mixture was kept at room temperature for 2 hours, then heated to the reflux temperature and stirred for 6 hours. The reaction was cooled to room temperature and 35% hydrochloric acid (37.41 g) was added.
- CM28b 60.10 g
- acetic acid 450 mL
- ion-exchanged water 60 mL
- the reaction solution was cooled to room temperature, water and toluene were added, the aqueous layer was separated, and the organic layer was washed with a saturated aqueous sodium chloride solution. Sodium sulfate was added to the obtained organic layer, filtered and concentrated to obtain a crude product.
- the crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate mixed solution) to obtain 19.5 g of CM28c as a white solid.
- LC-MS (APCI, positive): [M + H] + 457.
- Heptyltriphenylphosphonium bromide (82.29 g) was placed in a 1 L four-necked flask equipped with a stirrer, and the gas in the flask was replaced with argon.
- Toluene (520 mL) was placed in the flask and cooled to 5 ° C. or lower.
- Potassium tert-butoxide (20.92 g) was added, and the mixture was warmed to room temperature and stirred at room temperature for 3 hours.
- CM28c (18.0 g) was added to the red slurry produced in the reaction solution, and the mixture was stirred while keeping at room temperature for 6 hours and 30 minutes.
- Acetic acid (7.2 g) was added to the reaction mixture and stirred for 15 minutes, and then water and hexane were added. After stirring at room temperature, the aqueous layer was separated, and the organic layer was washed with a saturated aqueous sodium chloride solution. Sodium sulfate was added to the obtained organic layer, filtered, and concentrated to obtain a crude product.
- the crude product was purified with a silica gel column (developing solvent hexane), activated carbon was added to the obtained hexane solution, and the mixture was stirred at 50 ° C. for 1 hour while being kept warm.
- ⁇ Third step> After putting CM28d (18.6 g) in a 1 L four-necked flask equipped with a stirrer, ethyl acetate (165 mL) and ethanol (150 mL) were added, and the gas in the flask was replaced with nitrogen. After 5 wt% Pd / C (about 50 wt% water-containing product) (3.7 g) was added, the gas in the flask was replaced with hydrogen, and the mixture was stirred while being kept at 50 ° C. for 49 hours in a hydrogen atmosphere.
- CM28e (17.0 g) was placed in a 500 mL four-necked flask equipped with a stirrer, and the gas in the flask was replaced with argon. Chloroform (230 mL) and trifluoroacetic acid (22 mL) were placed in the flask and cooled to 5 ° C. or lower. The whole four-necked flask was shielded from light, and a mixture of bromine (8.9 g) and chloroform (45 mL) was dropped into the flask over 15 minutes and stirred while keeping the temperature for 3 hours.
- a 10 wt% aqueous sodium sulfite solution was added to the reaction solution, and the temperature was raised to room temperature.
- the aqueous layer was separated from the reaction solution, and the oil layer was washed with water, 5 wt% aqueous sodium hydrogen carbonate solution and water in this order.
- the obtained oil layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated to obtain a crude product.
- the crude product was purified with a silica gel column (developing solvent hexane), activated carbon was added to the obtained hexane solution, and the mixture was stirred at 50 ° C. for 1 hour while being kept warm.
- ⁇ Fifth process> Dehydrated tetrahydrofuran (210 mL) was placed in a 1000 mL four-necked flask equipped with a stirrer and cooled to ⁇ 70 ° C. or lower. n-Butyllithium (1.6M hexane solution) (70 mL) was slowly added dropwise over 30 minutes, and the mixture was stirred while being kept warm for 30 minutes. A mixture of CM28f (18.2 g) and dehydrated tetrahydrofuran (210 mL) was slowly added dropwise over 30 minutes, and the mixture was stirred while being kept warm for 1 hour.
- CM28f 18.2 g
- dehydrated tetrahydrofuran 210 mL
- reaction solution was diluted with ethyl acetate (50 mL) at room temperature, and the solution was passed through a filter packed with celite.
- the obtained filtrate was washed with water, and the aqueous layer separated after standing was removed from the oil layer.
- the oil layer was concentrated under reduced pressure to remove the solvent to obtain an oil.
- the oil was purified by silica gel column chromatography to obtain 69.5 g of the target compound MM1c.
- the HPLC area percentage value measured under analysis condition 2 (detection wavelength: 379 nm) of the obtained compound MM1c was 99.35%.
- ⁇ Third step Synthesis of monomer MM1> Under a nitrogen gas atmosphere, a solution of N-bromosuccinimide (11.3 g, 63.8 mmol) in dimethylformamide (100 mL) was added to a solution consisting of compound MM1c (29.6 g, 31.9 mmol) and chloroform (300 mL) at ⁇ 20 ° C. And added dropwise over 2 hours and 30 minutes and stirred for 3 hours. Thereafter, the mixture was stirred at room temperature for 16 hours, and the reaction solution was slowly added dropwise to ice water (500 mL).
- the oil layer was washed with water, the aqueous layer separated after standing was removed from the oil layer, the oil layer was concentrated under reduced pressure to remove the solvent, and an oily substance was obtained.
- the oil was repeatedly purified by silica gel column chromatography (7 times) to obtain 26 g of the target monomer MM1.
- the HPLC area percentage value measured under analysis condition 2 (detection wavelength: 350 nm) of the obtained monomer MM1 was 99.68%.
- Example M2 Synthesis of monomer MM2> (1) Compound MM2c was synthesized according to the following first to second steps.
- the solution was warmed to room temperature, stirred overnight, and quenched with 2 mol / L hydrochloric acid (50 mL).
- the oil layer separated after standing was separated from the aqueous layer and combined with the dichloromethane extract of the aqueous layer.
- the oil layer was concentrated under reduced pressure to remove the solvent to obtain an oil.
- the HPLC area percentage value of the obtained oily substance (MM2c-2, 84 g) measured under analysis condition 2 was 90%.
- ⁇ Third step Synthesis of MM2e>
- the reaction was carried out in the same procedure as the synthesis of compound MM2d using compound MM2d (27.5 g, 58 mmol) under a nitrogen gas atmosphere.
- acetonitrile was added at room temperature to obtain a white solid to obtain 25.2 g of the target compound MM2e.
- the HPLC area percentage value of the obtained compound MM2e measured under analysis condition 2 was 96.2%.
- reaction solution was passed through a filter packed with silica gel / Florisil / Celite and dissolved in toluene to obtain a reaction mixture (22 g, HPLC area percentage value measured under analysis condition 2 was 97.4%).
- Acetonitrile was added to the reaction mixture at room temperature and the mixture was stirred and filtered. Recrystallization was performed with acetonitrile, toluene / acetonitrile, butyl acetate / acetonitrile, and 22 g of the target monomer MM3 was obtained.
- the HPLC area percentage value of the obtained monomer MM3 measured under analysis condition 2 was 98.8%.
- Example 1 Synthesis of polymer compound 1> Under a nitrogen atmosphere, a mixture of monomer CM1 (1.7273 g), monomer CM10 (2.6683 g), monomer CM11 (0.2231 g) and toluene (73 ml) as a solvent was heated to about 80 ° C. Thereafter, palladium acetate (0.77 mg), tris (2-methoxyphenyl) phosphine (4.90 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (12.3 g) were added, and the mixture was stirred under reflux for about 4 hours.
- phenylboronic acid (85.6 mg), palladium acetate (0.72 mg), tris (2-methoxyphenyl) phosphine (4.89 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (12.3 g) were added. Further, the mixture was stirred for about 19.5 hours under reflux. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (0.98 g) in ion-exchanged water (20 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C.
- the organic layer was washed successively with 3.6 wt% hydrochloric acid twice, 2.5 wt% aqueous ammonia solution twice, and ion-exchanged water five times.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 1 (2.907 g).
- Polymer compound 1 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized Is done.
- the energy gap of polymer compound 1 was calculated by the above method and found to be 3.01 eV.
- Example 2 Synthesis of polymer compound 2> Under a nitrogen atmosphere, a mixture of monomer CM2 (1.4280 g), monomer CM10 (2.5001 g), monomer CM11 (0.2079 g) and solvent toluene (63 ml) was heated to about 80 ° C. Thereafter, palladium acetate (1.11 mg), tris (2-methoxyphenyl) phosphine (6.91 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (11.5 g) were added, and the mixture was stirred under reflux for about 5.5 hours. .
- phenylboronic acid 39.7 mg
- palladium acetate (1.16 mg)
- tris (2-methoxyphenyl) phosphine (6.94 mg)
- a 20 wt% tetraethylammonium hydroxide aqueous solution (11.5 g) were added.
- the mixture was further stirred for about 17 hours under reflux.
- a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.40 g) in ion-exchanged water (28 ml) was added, and the mixture was stirred for 2.5 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid twice and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 2 (2.601 g).
- Polymer compound 2 has the following structural units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 2 was calculated by the above method and found to be 3.01 eV.
- Example 3 Synthesis of polymer compound 3> Under nitrogen atmosphere, monomer CM1 (0.8534 g), monomer CM3 (0.7051 g), monomer CM10 (2.6361 g), monomer CM11 (0.2192 g) and toluene as a solvent (67 ml) ) was heated to about 80 ° C., then palladium acetate (1.20 mg), tris (2-methoxyphenyl) phosphine (7.21 mg) and 20 wt% aqueous tetraethylammonium hydroxide (12.1 g) were added, Stir for about 6 hours under reflux.
- phenylboronic acid (42.0 mg), palladium acetate (1.17 mg), tris (2-methoxyphenyl) phosphine (7.33 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (12.1 g) were added. Further, the mixture was stirred for about 16 hours under reflux. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.53 g) in ion-exchanged water (30 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid twice and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 3 (2.689 g).
- Polymer compound 3 has the following structural units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized: Is done.
- the energy gap of the polymer compound 3 was calculated by the above method and found to be 3.01 eV.
- Example 4 Synthesis of polymer compound 4> Under nitrogen atmosphere, monomer CM1 (1.0465 g), monomer CM4 (0.4817 g), monomer CM10 (2.7100 g), monomer CM11 (0.2253 g) and toluene as a solvent (83 ml) ) was heated to about 80 ° C., bistriphenylphosphine palladium dichloride (2.43 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (12.1 g) were added, and the mixture was stirred under reflux for about 30 hours.
- phenylboronic acid (22.5 mg), bistriphenylphosphine palladium dichloride (2.45 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (12.1 g) were added, and the mixture was further stirred under reflux for about 17.5 hours. did. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.94 g) in ion-exchanged water (39 ml) was added, and the mixture was stirred for 3 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid twice and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 4 (2.62 g).
- the polymer compound 4 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- Example 5 Synthesis of polymer compound 5>
- monomer CM1 (1.4951 g), monomer CM12 (3.4363 g), monomer CM11 (0.1931 g) and toluene (33 ml) as a solvent was heated to about 80 ° C.
- bistriphenylphosphine palladium dichloride (2.17 mg) and a 20 wt% aqueous tetraethylammonium hydroxide solution (10.4 g) were added, and the mixture was stirred under reflux for about 48 hours.
- phenylboronic acid (0.3671 g), bistriphenylphosphine palladium dichloride (2.12 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (10.4 g) were added, and the mixture was further stirred under reflux for about 23 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.83 g) dissolved in ion-exchanged water (33 ml) was added, and the mixture was stirred for 2.5 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid twice and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 5 (3.349 g).
- Polymer compound 5 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized: Is done.
- the energy gap of the polymer compound 5 was calculated by the above method and found to be 3.14 eV.
- phenylboronic acid (91.4 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (6.62 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (26.0 g) were added, and the mixture was further refluxed. For about 15 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (4.17 g) in ion-exchanged water (84 ml) was added and stirred for 2 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3.0% by weight acetic acid aqueous solution twice, and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 9 (6.34 g).
- the polymer compound 9 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 9 was calculated by the above method and found to be 3.01 eV.
- Example 7 Synthesis of polymer compound 10>
- monomer CM1 (0.9967 g), monomer CM10 (1.4574 g), monomer CM22 (0.1057 g), monomer CM23 (0.0920 g) and toluene as a solvent ( 47 ml) was heated to about 80 ° C.
- 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 g) was added, and the mixture was refluxed. Stir for about 23 hours.
- phenylboronic acid (26.6 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.76 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 g) were added, and further refluxed. For about 23 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (22 ml) was added, and the mixture was stirred for 3 hours while being heated to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3.0% by weight acetic acid aqueous solution twice, and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 10 (1.46 g).
- the polymer compound 10 has the following structural units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which the structural unit of (PA) and the structural unit selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 10 was calculated by the above method and found to be 3.01 eV.
- Example 8 Synthesis of polymer compound 11>
- a monomer CM21 (0.8564 g), monomer CM10 (1.5485 g), and a mixture of monomer CM22 (0.1585 g) and toluene (47 ml) as a solvent are heated to about 80 ° C.
- dichlorobis tris (2-methoxyphenyl) phosphine
- a 20 wt% tetraethylammonium hydroxide aqueous solution (7.8 g) were added, and the mixture was stirred under reflux for about 7.5 hours.
- phenylboronic acid (26.5 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.77 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (7.8 g) were added, and the mixture was further refluxed. For about 15 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (22 ml) was added and stirred for 1.5 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3.0% by weight acetic acid aqueous solution twice, and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 11 (1.30 g).
- the polymer compound 11 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 11 was calculated by the above method and found to be 3.00 eV.
- Example 9 Synthesis of polymer compound 12>
- monomer CM1 (0.9967 g), monomer CM13 (0.8189 g), monomer CM9 (0.2578 g), monomer CM23 (0.0920 g), and monomer CM24 ( 0.1337 g) and toluene as a solvent (44 ml) were heated to about 80 ° C., and then palladium acetate (0.3 mg), tris (2-methoxyphenyl) phosphine (3.0 mg), 20 wt% tetraethylammonium An aqueous hydroxide solution (8.8 g) was added, and the mixture was stirred under reflux for about 18 hours.
- phenylboronic acid (0.25 g), palladium acetate (0.5 mg), and tris (2-methoxyphenyl) phosphine (3.0 mg) were added, and the mixture was stirred under reflux for about 4 hours. Further, bromobenzene (0.45 g) was added, and the mixture was stirred for about 4 hours under reflux. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.1 g) in ion-exchanged water (22 ml) was added, and the mixture was stirred for 6 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3.0% by weight acetic acid aqueous solution twice, and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 12 (1.030 g).
- the polymer compound 12 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 12 was calculated by the above method and found to be 3.12 eV.
- Example 10 Synthesis of polymer compound 13>
- a monomer CM19 (1.4924 g), monomer CM10 (1.6539 g), and a mixture of monomer CM11 (0.1375 g) and toluene as a solvent (57 ml) were heated to about 80 ° C.
- tris (2-methoxyphenyl) phosphine (4.57 mg) 4.57 mg
- 20 wt% tetraethylammonium hydroxide aqueous solution (7.7 g) were added, and the mixture was stirred under reflux for about 6 hours.
- phenylboronic acid (26.3 mg), palladium acetate (0.82 mg), tris (2-methoxyphenyl) phosphine (4.58 mg), and 20 wt% tetraethylammonium hydroxide aqueous solution (7.7 g) were added.
- the mixture was further stirred for about 14.5 hours under reflux.
- a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.21 g) in ion-exchanged water (24 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C.
- the organic layer was washed sequentially with ion-exchanged water twice, 3% by weight acetic acid twice, and ion-exchanged water three times.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 13 (2.148 g).
- the polymer compound 13 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- Example 11 Synthesis of polymer compound 14>
- monomer CM20 (1.4093 g)
- monomer CM10 (1.4574 g)
- monomer CM22 (0.1057 g)
- monomer CM23 0.0920 g
- toluene as a solvent ( 58 ml)
- dichlorobis tris (2-methoxyphenyl) phosphine
- 20 wt% tetraethylammonium hydroxide aqueous solution (6.29 g) was added, and the mixture was refluxed. Stir for about 4.5 hours.
- phenylboronic acid (24.4 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.76 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (6.29 g) were added, and the mixture was further refluxed. For about 18 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (27 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3.0% by weight acetic acid aqueous solution twice, and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 14 (1.77 g).
- the polymer compound 14 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which (PA) constitutional units and (PB) constitutional units are alternately polymerized. Is done.
- the energy gap of the polymer compound 14 was calculated by the above method and found to be 2.97 eV.
- Example 12 Synthesis of polymer compound 15>
- monomer CM1 (0.9967 g), monomer CM18 (1.7588 g), monomer CM22 (0.1057 g), and monomer CM23 (0.0920 g) and toluene as a solvent ( 55 ml) was heated to about 80 ° C.
- dichlorobis tris (2-methoxyphenyl) phosphine
- 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 g) was added, and the mixture was refluxed. Stir for about 6 hours.
- phenylboronic acid (26.1 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.76 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 g) were added. For about 15 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (26 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3.0% by weight acetic acid aqueous solution twice, and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 15 (1.57 g).
- the polymer compound 15 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 15 was calculated by the above method and found to be 3.04 eV.
- Example 13 Synthesis of polymer compound 16>
- monomer CM20 (1.4093 g), monomer CM18 (1.7588 g), monomer CM22 (0.1057 g), monomer CM23 (0.0920 g) and toluene as a solvent ( 45 ml) was heated to about 80 ° C.
- 20 wt% tetraethylammonium hydroxide aqueous solution 7.3 g
- phenylboronic acid (24.6 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.74 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (7.4 g) were added, and the mixture was further refluxed. For about 13.5 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (31 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C.
- the organic layer was washed successively with ion-exchanged water twice, 3.0% by weight acetic acid aqueous solution twice, and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 16 (1.92 g).
- the polymer compound 16 has the following constituent units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constituent units of (PA) and constituent units selected from (PB) are alternately polymerized. Is done.
- the energy gap of the polymer compound 16 was calculated by the above method and found to be 2.97 eV.
- Example 14 Synthesis of polymer compound 17> Under a nitrogen atmosphere, a mixture of monomer CM1 (1.0148 g), monomer CM18 (1.7588 g), monomer CM22 (0.2114 g) and toluene (55 ml) as a solvent was heated to about 80 ° C. Later, dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (7.09 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (6.9 g) were added, and the mixture was stirred for about 9 hours under reflux.
- dichlorobis tris (2-methoxyphenyl) phosphine
- phenylboronic acid (24.5 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.76 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (6.9 g) were added, and the mixture was further refluxed. For about 12 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (26 ml) was added, and the mixture was stirred for 2 hours while heating to 80 ° C.
- the organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 17 (1.64 g).
- the polymer compound 17 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which (PA) constitutional units and (PB) constitutional units are alternately polymerized. Is done.
- the energy gap of the polymer compound 17 was calculated by the above method and found to be 3.04 eV.
- Example 15 Synthesis of polymer compound 18> In a nitrogen atmosphere, a mixture of monomer CM20 (1.0661 g), monomer CM10 (1.1614 g), monomer CM22 (0.1189 g) and toluene (50 ml) as a solvent was heated to about 80 ° C. Later, dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.33 mg) and a 20 wt% aqueous tetraethylammonium hydroxide solution (5.4 g) were added, and the mixture was stirred under reflux for about 7 hours.
- dichlorobis tris (2-methoxyphenyl) phosphine
- phenylboronic acid (18.4 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.32 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (5.4 g) were added, and the mixture was further refluxed. For about 12 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (0.90 g) in ion-exchanged water (22 ml) was added, and the mixture was stirred for 2 hours while being heated to 80 ° C.
- the organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 18 (1.16 g).
- the polymer compound 18 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized. Is done.
- the energy gap of the polymer compound 18 was calculated by the above method and found to be 2.97 eV.
- Example 16 Synthesis of polymer compound 19> Under nitrogen atmosphere, monomer CM1 (1.4953 g), monomer CM25 (1.9554 g), monomer CM22 (0.1585 g), monomer CM23 (0.1381 g) and toluene as a solvent (73 ml) ) Is heated to about 80 ° C., then dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (2.60 mg) and 20 wt% aqueous tetraethylammonium hydroxide (10 g) are added and about 4 Stir for hours.
- dichlorobis tris (2-methoxyphenyl) phosphine
- phenylboronic acid (36.6 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (2.60 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (10 g) were added, and the mixture was further refluxed. Stir for 14 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.67 g) in ion-exchanged water (33 ml) was added, and the mixture was stirred for 2 hours while heating to 80 ° C.
- the organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 19 (1.74 g).
- the polymer compound 19 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 19 was calculated by the above method and found to be 3.08 eV.
- Example 17 Synthesis of polymer compound 20> Under nitrogen atmosphere, monomer CM1 (1.4801 g), monomer CM26 (1.9074 g), monomer CM22 (0.1585 g), monomer CM23 (0.1381 g) and toluene as a solvent (73 ml) ) Is heated to about 80 ° C., then dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (2.60 mg) and 20 wt% aqueous tetraethylammonium hydroxide (10 g) are added and about 4 Stir for hours.
- dichlorobis tris (2-methoxyphenyl) phosphine
- phenylboronic acid (36.6 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (2.60 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (10 g) were added, and the mixture was further refluxed. Stir for 14 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.67 g) in ion-exchanged water (33 ml) was added, and the mixture was stirred for 2 hours while heating to 80 ° C.
- the organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 20 (1.92 g).
- the polymer compound 20 has the following structural units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which the structural unit of (PA) and the structural unit selected from (PB) are alternately polymerized. Is done.
- the energy gap of the polymer compound 20 was calculated by the above method and found to be 3.13 eV.
- Example 18 Synthesis of polymer compound 21> In a nitrogen atmosphere, monomer CM1 (1.7941 g), monomer CM27 (0.2215 g), monomer MM3 (0.3036 g), monomer CM18 (4.9464 g) and toluene as a solvent (110 ml) ) Is heated to about 80 ° C., then dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (4.00 mg) and 20 wt% aqueous tetraethylammonium hydroxide (15 g) are added and about 4 Stir for hours.
- phenylboronic acid (54.9 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (4.00 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (15 g) were added, and the mixture was further refluxed. Stir for 14 hours. Thereafter, a solution obtained by dissolving sodium N, N-diethyldithiocarbamate trihydrate (2.50 g) in ion-exchanged water (50 ml) was added, and the mixture was stirred for 2 hours while being heated to 80 ° C.
- the organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 21 (3.32 g).
- the polymer compound 21 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which (PA) constitutional units and constitutional units selected from (PB) are alternately polymerized. Is done.
- the energy gap of the polymer compound 21 was calculated by the above method and found to be 3.04 eV.
- Example 19 Synthesis of polymer compound 22> Under nitrogen atmosphere, monomer CM1 (1.4951 g), monomer CM18 (2.6638 g), monomer MM1 (0.3261 g), monomer CM23 (0.1381 g) and toluene as a solvent (73 ml) ) Is heated to about 80 ° C., then dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (2.60 mg) and 20 wt% aqueous tetraethylammonium hydroxide (10 g) are added and about 4 Stir for hours.
- dichlorobis tris (2-methoxyphenyl) phosphine
- phenylboronic acid (36.6 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (2.60 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (10 g) were added, and the mixture was further refluxed. Stir for 14 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.67 g) in ion-exchanged water (33 ml) was added, and the mixture was stirred for 2 hours while heating to 80 ° C.
- the organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 22 (2.87 g).
- the polymer compound 22 has the following constitutional units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units (PA) and constitutional units selected from (PB) are alternately polymerized. Is done.
- the energy gap of the polymer compound 22 was calculated by the above method and found to be 3.03 eV.
- Example 20 Synthesis of polymer compound 23>
- monomer CM28 (1.1061 g), monomer CM18 (1.0992 g), monomer CM22 (0.0660 g), monomer CM23 (0.0575 g) and toluene as a solvent (47 ml) )
- dichlorobis tris (2-methoxyphenyl) phosphine
- a 20 wt% tetrabutylammonium hydroxide aqueous solution (7.6 g) were added, and the mixture was refluxed. For about 6 hours.
- phenylboronic acid (15.3 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.06 mg), and a 20 wt% tetrabutylammonium hydroxide aqueous solution (7.6 g) were added, and the mixture was further refluxed. Stir below for about 16 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (0.71 g) in ion-exchanged water (22 ml) was added, and the mixture was stirred for 2 hours while heating to 80 ° C.
- the organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 23 (1.58 g).
- the polymer compound 23 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 23 was calculated by the above method and found to be 3.00 eV.
- phenylboronic acid pinacol ester (0.9268 g), palladium acetate (1.4 mg) and tris (2-methoxyphenyl) phosphine (9.4 mg) were added, and the mixture was further stirred under reflux for about 4 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (2.74 g) in ion-exchanged water (27 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C. Thereafter, the organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid twice and ion-exchanged water twice.
- the organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance.
- the obtained solution was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain polymer compound 6 (4.254 g).
- Polymer compound 6 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which the structural units of (PA) and the structural units selected from (PB) are alternately polymerized: Is done.
- the energy gap of the polymer compound 6 was calculated by the above method and found to be 2.78 eV.
- phenylboronic acid pinacol ester (0.21 g) was added, and the mixture was further stirred under reflux for about 18 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.22 g) dissolved in ion-exchanged water (12 ml) was added, and the mixture was stirred for 2 hours while being heated to 85 ° C. Thereafter, the organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid twice and ion-exchanged water twice. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- Polymer compound 7 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 7 was calculated by the above method and found to be 2.76 eV.
- phenylboronic acid (0.49 g) was added, and the mixture was further stirred under reflux for about 2 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (24.3 g) in ion-exchanged water (240 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C. Thereafter, the organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid twice and ion-exchanged water twice. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- the polymer compound 8 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.
- the energy gap of the polymer compound 8 was calculated by the above method and found to be 2.79 eV.
- phenylboronic acid (40.6 mg) was added, and the mixture was further stirred under reflux for about 2 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (0.46 g) in ion-exchanged water (9 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C. Thereafter, the organic layer was washed successively with 3.6 wt% hydrochloric acid twice, 2.5 wt% aqueous ammonia solution twice, and ion-exchanged water five times. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid.
- the polymer compound L1 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which the structural unit of (PA) and the structural unit selected from (PB) are alternately polymerized Is done.
- Phenylboronic acid (0.22 g, 1.8 mmol) was then added and the resulting mixture was stirred for 14 hours. After allowing to cool, the aqueous layer was removed, an aqueous sodium diethyldithiocarbamate solution was added and stirred, the aqueous layer was removed, and the organic layer was washed with water and 3% aqueous acetic acid. The organic layer was poured into methanol to precipitate a polymer compound, and then the polymer compound collected by filtration was dissolved again in toluene and passed through silica gel and alumina columns.
- the eluted toluene solution containing the polymer compound was recovered, and the recovered toluene solution was poured into methanol to precipitate the polymer compound.
- the precipitated polymer compound was vacuum dried at 50 ° C. to obtain polymer compound L2 (12.5 g).
- the polymer compound L2 had a polystyrene equivalent weight average molecular weight of 3.1 ⁇ 10 5 and a molecular weight distribution index (Mw / Mn) of 2.9.
- Polymer compound L2 has the following structural units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which the structural unit of (PA) and the structural unit selected from (PB) are alternately polymerized Is done.
- an organic thin film of polymer compound 1 having a thickness of 20 nm was formed by spin-coating the glass substrate on which the above Plexcore OC 1200 was formed. This was heated at 180 ° C. for 60 minutes on a hot plate in a nitrogen gas atmosphere to obtain an insolubilized organic thin film.
- the composition mixed so that the polymer compound L2 / phosphorescent material 2 95 wt% / 5 wt% was dissolved in xylene to prepare a 1.7 wt% xylene solution.
- xylene solution an organic thin film having a thickness of 80 nm was formed by spin-coating on the glass substrate on which the insolubilized organic thin film of the polymer compound 1 was formed, and the film was formed at 130 ° C. for 10 minutes in a nitrogen atmosphere. Heat-dried. Then, about 4 nm of sodium fluoride and then about 80 nm of aluminum were vapor-deposited as a cathode, and the light emitting element D1 was produced. Note that metal deposition was started after the degree of vacuum reached 1 ⁇ 10 ⁇ 4 Pa or less.
- Example D2 Production and evaluation of light-emitting element D2> A light emitting device D2 was produced in the same manner as in Example D1, except that the polymer compound 2 was used instead of the polymer compound 1 in Example D1, and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D2, EL light emission having a peak at 625 nm was obtained from this device, and the maximum external quantum efficiency was 13.7%. The results are shown in Table 3.
- Example D3 Production and evaluation of light-emitting element D3> A light emitting device D3 was produced in the same manner as in Example D1, except that the polymer compound 3 was used in place of the polymer compound 1 in Example D1, and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D3, EL light emission having a peak at 625 nm was obtained from this device, and the maximum external quantum efficiency was 13.7%. The results are shown in Table 3.
- Example D4 Production and evaluation of light-emitting element D4>
- a light emitting device D4 was produced in the same manner as in Example D1, except that the polymer compound 13 was used instead of the polymer compound 1 in Example D1, and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 625 nm was obtained from this device, and the maximum external quantum efficiency was 13.6%.
- Table 3 The results are shown in Table 3.
- Example CD1 Production and Evaluation of Light-Emitting Element CD1>
- a light emitting device CD1 was produced in the same manner as in Example D1, except that the polymer compound 7 was used instead of the polymer compound 1 in Example D1, and a 0.8 wt% xylene solution was prepared.
- voltage was applied to the resulting light emitting device CD1
- EL light emission having a peak at 625 nm was obtained from this device, and the maximum external quantum efficiency was 9.0%.
- Table 3 The results are shown in Table 3.
- an organic thin film of polymer compound 1 having a thickness of 20 nm was formed by spin-coating the glass substrate on which the above Plexcore OC 1200 was formed. This was heated at 180 ° C. for 60 minutes on a hot plate in a nitrogen gas atmosphere to obtain an insolubilized organic thin film.
- the polymer compound L1 / phosphorescent material 1 the composition mixed so as to be 70% by weight / 30% by weight was dissolved in xylene to prepare a 2.0% by weight xylene solution.
- xylene solution an organic thin film having a thickness of 80 nm is formed by spin coating on the glass substrate on which the insolubilized thin film of the polymer compound 1 is formed, and heated at 130 ° C. for 10 minutes in a nitrogen atmosphere. After drying, about 4 nm of sodium fluoride and then about 80 nm of aluminum were vapor-deposited as a cathode, and the light emitting element D5 was produced. Note that metal deposition was started after the degree of vacuum reached 1 ⁇ 10 ⁇ 4 Pa or less.
- Example D6 Production and evaluation of light-emitting element D6> A light emitting device D6 was produced in the same manner as in Example D5 except that the polymer compound 2 was used in place of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D6, EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 22.8%. The results are shown in Table 4.
- Example D7 Production and Evaluation of Light-Emitting Element D7>
- a light emitting device D7 was produced in the same manner as in Example D5 except that the polymer compound 3 was used in place of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 23.6%.
- Table 4 The results are shown in Table 4.
- Example D8 Production and evaluation of light-emitting element D8>
- a light emitting device D8 was produced in the same manner as in Example D5 except that the polymer compound 4 was used in place of the polymer compound 1 in Example D5 and a 1.0 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 23.2%.
- the results are shown in Table 4.
- Example D9 Production and evaluation of light-emitting element D9>
- a light emitting device D9 was produced in the same manner as in Example D5 except that the polymer compound 5 was used in place of the polymer compound 1 in Example D5 and a 0.9 wt% xylene solution was prepared.
- EL light emission having a peak at 515 nm was obtained from this device, and the maximum external quantum efficiency was 23.4%.
- the results are shown in Table 4.
- Example D10 Production and evaluation of light-emitting element D10>
- a light emitting device D10 was produced in the same manner as in Example D5 except that the polymer compound 9 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 21.9%.
- the results are shown in Table 4.
- Example D11 Production and evaluation of light-emitting element D11> A light emitting device D11 was produced in the same manner as in Example D5 except that the polymer compound 10 was used instead of the polymer compound 1 in Example D5 and a 0.8 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D11, EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 22.2%. In addition, when the device was driven at a constant current with an initial luminance of 12,000 cd / m 2 , the time until the luminance became 60% of the initial luminance (LT60) was 129.6 hours. The results are shown in Table 4.
- Example D12 Production and evaluation of light-emitting element D12>
- a light emitting device D12 was produced in the same manner as in Example D5 except that the polymer compound 11 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 20.9%.
- the results are shown in Table 4.
- Example D13 Production and evaluation of light-emitting element D13> A light emitting device D13 was produced in the same manner as in Example D5 except that the polymer compound 12 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D13, EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 23.8%. The results are shown in Table 4.
- Example D14 Production and evaluation of light-emitting element D14>
- a light emitting device D14 was produced in the same manner as in Example D5 except that the polymer compound 13 was used in place of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 22.2%.
- the results are shown in Table 4.
- Example D15 Production and evaluation of light-emitting element D15> A light emitting device D15 was produced in the same manner as in Example D5 except that the polymer compound 14 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D15, EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 19.2%. In addition, when the device was driven at a constant current with an initial luminance of 12,000 cd / m 2 , the time until the luminance became 60% of the initial luminance (LT60) was 154.6 hours. The results are shown in Table 4.
- Example D16 Production and evaluation of light-emitting element D16>
- a light emitting device D16 was produced in the same manner as in Example D5 except that the polymer compound 15 was used in place of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 21.4%.
- the device was driven at a constant current at an initial luminance of 12,000 cd / m 2 , the time until the luminance became 60% of the initial luminance (LT60) was 218.0 hours.
- Table 4 The results are shown in Table 4.
- Example D17 Production and evaluation of light-emitting element D17>
- a light emitting device D17 was produced in the same manner as in Example D5 except that the polymer compound 16 was used in place of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 18.7%.
- the device was driven at a constant current at an initial luminance of 12,000 cd / m 2 , the time until the luminance became 60% of the initial luminance (LT60) was 192.9 hours.
- Table 4 The results are shown in Table 4.
- Example D18 Production and evaluation of light-emitting element D18>
- a light emitting device D18 was produced in the same manner as in Example D5 except that the polymer compound 17 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 21.4%.
- the device was driven at a constant current at an initial luminance of 12,000 cd / m 2 , the time until the luminance became 60% of the initial luminance (LT60) was 167.0 hours. The results are shown in Table 4.
- Example D19 Production and evaluation of light-emitting element D19>
- a light emitting device D19 was produced in the same manner as in Example D5 except that the polymer compound 18 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 18.7%.
- the device was driven at a constant current at an initial luminance of 12,000 cd / m 2 , the time until the luminance became 60% of the initial luminance (LT60) was 112.0 hours. The results are shown in Table 4.
- Example D20 Production and evaluation of light-emitting element D20>
- a light emitting device D20 was produced in the same manner as in Example D5 except that the polymer compound 19 was used in place of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 22.3%.
- Table 4 The results are shown in Table 4.
- Example D21 Production and evaluation of light-emitting element D21>
- a light emitting device D21 was produced in the same manner as in Example D5 except that the polymer compound 20 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 23.4%.
- the results are shown in Table 4.
- Example D22 Production and evaluation of light-emitting element D22> A light emitting device D22 was produced in the same manner as in Example D5 except that the polymer compound 21 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D22, EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 19.9%. The results are shown in Table 4.
- Example D23 Production and evaluation of light-emitting element D23> A light emitting device D23 was produced in the same manner as in Example D5 except that the polymer compound 22 was used in place of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D23, EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 19.6%. The results are shown in Table 4.
- Example D24 Production and evaluation of light-emitting element D24>
- a light emitting device D24 was produced in the same manner as in Example D5 except that the polymer compound 23 was used in place of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 20.2%.
- the results are shown in Table 4.
- Example CD2 Production and Evaluation of Light-Emitting Element CD2>
- a light emitting device CD2 was produced in the same manner as in Example D5 except that the polymer compound 6 was used instead of the polymer compound 1 in Example D5 and 0.8 wt% xylene was prepared.
- voltage was applied to the resultant light emitting device CD2
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 13.1%.
- Table 4 The results are shown in Table 4.
- Example CD3 Production and Evaluation of Light-Emitting Element CD3>
- a light emitting device CD3 was produced in the same manner as in Example D5 except that the polymer compound 7 was used instead of the polymer compound 1 in Example D5 and a 0.8 wt% xylene solution was prepared.
- voltage was applied to the resultant light emitting device CD3
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 9.3%.
- Table 4 The results are shown in Table 4.
- Example CD4 Production and Evaluation of Light-Emitting Element CD4>
- a light emitting device CD4 was produced in the same manner as in Example D5 except that the polymer compound 8 was used instead of the polymer compound 1 in Example D5 and a 0.7 wt% xylene solution was prepared.
- voltage was applied to the resultant light emitting device CD4
- EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 11.0%.
- Table 4 The results are shown in Table 4.
- an organic thin film of polymer compound 1 having a thickness of 20 nm was formed by spin-coating the glass substrate on which the above Plexcore OC 1200 was formed. This was heated at 180 ° C. for 60 minutes on a hot plate in a nitrogen gas atmosphere to obtain an insolubilized organic thin film.
- the polymer compound L2 was dissolved in xylene to prepare a 1.3% by weight xylene solution.
- xylene solution an organic thin film having a thickness of 60 nm is formed by spin-coating on a glass substrate on which the insolubilized thin film of the above-described polymer compound 1 is formed, and dried by heating at 130 ° C. for 10 minutes in a nitrogen atmosphere. Then, about 4 nm of sodium fluoride and then about 80 nm of aluminum were vapor-deposited as a cathode, and the light emitting element D25 was produced. Note that metal deposition was started after the degree of vacuum reached 1 ⁇ 10 ⁇ 4 Pa or less.
- Example D26 Production and evaluation of light-emitting element D26> A light emitting device D26 was produced in the same manner as in Example D25 except that the polymer compound 2 was used in place of the polymer compound 1 in Example D25, and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D26, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.6%. The results are shown in Table 5.
- Example D27 Production and evaluation of light-emitting element D27> A light emitting device D27 was produced in the same manner as in Example D25 except that the polymer compound 3 was used instead of the polymer compound 1 in Example D25, and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D27, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.6%. The results are shown in Table 5.
- Example D28 Production and evaluation of light-emitting element D28>
- a light emitting device D28 was produced in the same manner as in Example D25 except that the polymer compound 4 was used in place of the polymer compound 1 in Example D25 and a 1.0 wt% xylene solution was prepared.
- EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.8%.
- Table 5 The results are shown in Table 5.
- Example D29 Production and evaluation of light-emitting element D29>
- a light emitting device D29 was produced in the same manner as in Example D25 except that the polymer compound 9 was used in place of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.0%.
- Table 5 The results are shown in Table 5.
- Example D30 Production and Evaluation of Light-Emitting Element D30>
- a light emitting device D30 was produced in the same manner as in Example D25 except that the polymer compound 10 was used instead of the polymer compound 1 in Example D25 and a 0.8 wt% xylene solution was prepared.
- EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.0%.
- the device was driven at a constant current at an initial luminance of 4,000 cd / m 2 , the time until the luminance became 50% of the initial luminance (LT50) was 78.0 hours. The results are shown in Table 5.
- Example D31 Production and evaluation of light-emitting element D31> A light emitting device D31 was produced in the same manner as in Example D25 except that the polymer compound 11 was used instead of the polymer compound 1 in Example D25, and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D31, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.0%. The results are shown in Table 5.
- Example D32 Production and Evaluation of Light-Emitting Element D32>
- a light emitting device D32 was produced in the same manner as in Example D25 except that the polymer compound 12 was used instead of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.0%.
- Table 5 The results are shown in Table 5.
- Example D33 Production and evaluation of light-emitting element D33> A light emitting device D33 was produced in the same manner as in Example D25 except that the polymer compound 13 was used in place of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D33, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.8%. The results are shown in Table 5.
- Example D34 Production and evaluation of light-emitting element D34> A light emitting device D34 was produced in the same manner as in Example D25 except that the polymer compound 14 was used instead of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D34, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.8%. In addition, when the device was driven at a constant current at an initial luminance of 4,000 cd / m 2 , the time until the luminance became 50% of the initial luminance (LT50) was 82.5 hours. The results are shown in Table 5.
- Example D35 Production and evaluation of light-emitting element D35>
- a light emitting device D35 was produced in the same manner as in Example D25 except that the polymer compound 15 was used in place of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.9%.
- the device was driven at a constant current at an initial luminance of 4,000 cd / m 2 , the time until the luminance became 50% of the initial luminance (LT50) was 80.5 hours. The results are shown in Table 5.
- Example D36 Production and evaluation of light-emitting element D36> A light emitting device D36 was produced in the same manner as in Example D25 except that the polymer compound 16 was used instead of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D36, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 5.7%. In addition, when the device was driven at a constant current at an initial luminance of 4,000 cd / m 2 , the time until the luminance became 50% of the initial luminance (LT50) was 104.1 hours. The results are shown in Table 5.
- Example D37 Production and evaluation of light-emitting element D37> A light emitting device D37 was produced in the same manner as in Example D25 except that the polymer compound 17 was used in place of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D37, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.8%. In addition, when the device was driven at a constant current at an initial luminance of 4,000 cd / m 2 , the time until the luminance became 50% of the initial luminance (LT50) was 53.9 hours. The results are shown in Table 5.
- Example D38 Production and evaluation of light-emitting element D38> A light emitting device D38 was produced in the same manner as in Example D25 except that the polymer compound 18 was used instead of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D38, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.5%. In addition, when the device was driven at a constant current at an initial luminance of 4,000 cd / m 2 , the time until the luminance became 50% of the initial luminance (LT50) was 56.0 hours. The results are shown in Table 5.
- Example D39 Production and evaluation of light-emitting element D39> A light emitting device D39 was produced in the same manner as in Example D25 except that the polymer compound 19 was used instead of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D39, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.9%. The results are shown in Table 5.
- Example D40 Production and Evaluation of Light-Emitting Element D40>
- a light emitting device D40 was produced in the same manner as in Example D25 except that the polymer compound 20 was used in place of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 7.1%.
- Table 5 The results are shown in Table 5.
- Example D41 Production and evaluation of light-emitting element D41> A light emitting device D41 was produced in the same manner as in Example D25 except that the polymer compound 21 was used instead of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D41, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.1%. The results are shown in Table 5.
- Example D42 Production and evaluation of light-emitting element D42> A light emitting device D42 was produced in the same manner as in Example D25 except that the polymer compound 22 was used in place of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared. When voltage was applied to the resultant light emitting device D42, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 5.9%. The results are shown in Table 5.
- Example D43 Production and Evaluation of Light-Emitting Element D43>
- a light emitting device D43 was produced in the same manner as in Example D25 except that the polymer compound 23 was used in place of the polymer compound 1 in Example D25, and a 0.7 wt% xylene solution was prepared.
- EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 6.4%.
- Table 5 The results are shown in Table 5.
- Example CD5 Production and Evaluation of Light-Emitting Element CD5>
- a light emitting device CD5 was produced in the same manner as in Example D25 except that the polymer compound 6 was used instead of the polymer compound 1 in Example D25 and a 0.8 wt% xylene solution was prepared.
- voltage was applied to the resultant light emitting device CD5
- EL light emission having a peak at 470 nm was obtained from this device, and the maximum external quantum efficiency was 5.3%.
- Table 5 The results are shown in Table 5.
- Example CD6 Production and Evaluation of Light-Emitting Element CD6>
- a light emitting device CD6 was produced in the same manner as in Example D25 except that the polymer compound 7 was used in place of the polymer compound 1 in Example D25 and a 0.8 wt% xylene solution was prepared.
- voltage was applied to the resultant light emitting device CD6, EL light emission having a peak at 460 nm was obtained from this device, and the maximum external quantum efficiency was 5.2%.
- Table 5 The results are shown in Table 5.
- Example CD7 Production and Evaluation of Light-Emitting Element CD7>
- a light emitting device CD7 was produced in the same manner as in Example D25 except that the polymer compound 8 was used in place of the polymer compound 1 in Example D25 and a 0.7 wt% xylene solution was prepared.
- voltage was applied to the resultant light emitting device CD7, EL light emission having a peak at 475 nm was obtained from this device, and the maximum external quantum efficiency was 5.2%.
- Table 5 The results are shown in Table 5.
- an organic thin film having a thickness of 80 nm was formed by spin coating the glass substrate on which the above Plexcore OC 1200 was formed. This was heated at 180 ° C. for 60 minutes on a hot plate in a nitrogen gas atmosphere to obtain an insolubilized organic thin film. Then, about 4 nm of sodium fluoride and then about 80 nm of aluminum were vapor-deposited as a cathode, and the light emitting element D42 was produced. Note that metal deposition was started after the degree of vacuum reached 1 ⁇ 10 ⁇ 4 Pa or less.
- Example CD8 Production and Evaluation of Light-Emitting Element CD8>
- a light emitting device CD8 was produced in the same manner as in Example D42, except that it was prepared. When voltage was applied to the resulting light emitting device CD8, EL light emission having a peak at 520 nm was obtained from this device, and the maximum external quantum efficiency was 0.1 cd / A.
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Abstract
Description
下記式(2)で表される構成単位と、
下記式(3)で表される構成単位および/または下記式(4’)で表される構成単位と、
を含む高分子化合物。
[式中、
Ar1およびAr3は、それぞれ独立に、非置換若しくは置換のアリーレン基または非置換若しくは置換の2価の複素環基を表す。
Ar2およびAr4は、それぞれ独立に、非置換若しくは置換のアリーレン基、非置換若しくは置換の2価の複素環基、または、アリーレン基および2価の複素環基から選ばれる同一若しくは異なる2以上の基が連結した2価の基(該基は、置換基を有していてもよい。)を表す。
Ar5、Ar6およびAr7は、それぞれ独立に、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を表す。
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6およびAr7はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接結合されていてもよく、-O-、-S-、-C(=O)-、-C(=O)-O-、-N(Ra)-、-C(=O)-N(Ra)-または-C(Ra)2-を介して結合されていてもよい。Raは、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、ハロゲン原子または非置換若しくは置換の1価の複素環基を表す。Raが2個存在する場合、それらは同一であっても異なっていてもよい。
xおよびyは、それぞれ独立に、0または1を表し、x+y=1である。]
[式中、
Ar8は、(2+p)価の芳香族炭化水素基、または(2+p)価の複素環基を表す。
R1は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、オキシカルボニル基、1価の複素環基、複素環オキシ基、複素環チオ基、イミン残基、アミド化合物残基、酸イミド残基、カルボキシル基、ヒドロキシル基、ニトロ基またはシアノ基を表す。R1が複数個存在する場合、それらは同一であっても異なっていてもよい。なお、少なくとも1つのR1は、芳香族炭化水素基または複素環基における他の構成単位と結合を形成する炭素原子の隣の炭素原子に直接結合する水素原子を置換する。
pは1以上の整数を表す。]
[式中、
naは0~3の整数を示し、nbは0~12の整数を示し、nAは0または1を示し、nは1~4の整数を示す。
Ar10は非置換若しくは置換の(2+n)価の芳香族炭化水素基または非置換若しくは置換の(2+n)価の複素環基を示す。
LaおよびLbは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Laが複数存在する場合、それらは同一でも異なっていてもよい。Lbが複数存在する場合、それらは同一でも異なっていてもよい。
LAは、酸素原子または硫黄原子を示す。LAが複数存在する場合、それらは同一でも異なっていてもよい。
Q1は1価の架橋性基を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
なお、式(3)で示される構成単位は、式(2)で示される構成単位とは異なる。]
[式中、
cは0または1を示し、dは0~4の整数を示し、
Ar20およびAr40は、それぞれ独立に、非置換若しくは置換のアリーレン基または非置換若しくは置換の2価の複素環基を示し、Ar30’は、非置換若しくは置換の(2+d)価の芳香族炭化水素基、非置換若しくは置換の(2+d)価の複素環基、または、2価の芳香族炭化水素基および2価の複素環基から選ばれる同一若しくは異なる2以上の基が連結した(2+d)価の基(当該(2+d)価の基は置換基を有していてもよい)を示す。
Q2’、Q3’およびQ4’は、1価の架橋性基、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を示すが、Q2’、Q3’およびQ4’の少なくとも一つは1価の架橋性基である。Q4’が複数存在する場合、それらは同一でも異なっていてもよい。
naは0~3の整数を示し、nbは0~12の整数を示し、nAは0または1を示す。
LaおよびLbは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Laが複数存在する場合、それらは同一でも異なっていてもよい。Lbが複数存在する場合、それらは同一でも異なっていてもよい。
LAは、酸素原子または硫黄原子を示す。LAが複数存在する場合、それらは同一でも異なっていてもよい。
ngは0~3の整数を示し、nhは0~12の整数を示し、nDは0または1を示す。
LgおよびLhは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lgが複数存在する場合、それらは同一でも異なっていてもよい。Lhが複数存在する場合、それらは同一でも異なっていてもよい。
LDは、酸素原子または硫黄原子を示す。LDが複数存在する場合、それらは同一でも異なっていてもよい。
なお、式(4’)で示される構成単位は、式(1)で示される構成単位とは異なる。]
[2] [1]に記載の高分子化合物と、正孔輸送材料、電子輸送材料および発光材料からなる群から選ばれる少なくとも1種の材料と、を含有する、組成物。
[3] [1]に記載の高分子化合物を含む、有機薄膜。
[4] [3]に記載の有機薄膜を、加熱することで溶媒に対して不溶化させた、不溶化有機薄膜。
[5] [3]に記載の有機薄膜または[4]に記載の不溶化有機薄膜を有する、発光素子。
アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、イソアミル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基、ノニル基、デシル基、3,7-ジメチルオクチル基、ドデシル基が挙げられる。
アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、シクロヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、2-エチルヘキシルオキシ基、ノニルオキシ基、デシルオキシ基、3,7-ジメチルオクチルオキシ基、ドデシルオキシ基が挙げられる。
アルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、プロピルチオ基、イソプロピルチオ基、ブチルチオ基、イソブチルチオ基、sec-ブチルチオ基、tert-ブチルチオ基、ペンチルチオ基、ヘキシルチオ基、シクロヘキシルチオ基、ヘプチルチオ基、オクチルチオ基、2-エチルヘキシルチオ基、ノニルチオ基、デシルチオ基、3,7-ジメチルオクチルチオ基、ドデシルチオ基が挙げられる。
アリール基としては、例えば、フェニル基、1-ナフチル基、2-ナフチル基、1-アントラセニル基、2-アントラセニル基、9-アントラセニル基、2-フルオレニル基が挙げられる。
アリールオキシ基としては、例えば、フェノキシ基、1-ナフチルオキシ基、2-ナフチルオキシ基、1-アントラセニルオキシ基、2-アントラセニルオキシ基、9-アントラセニルオキシ基、2-フルオレニルオキシ基が挙げられる。
アリールチオ基としては、例えば、フェニルチオ基、1-ナフチルチオ基、2-ナフチルチオ基、1-アントラセニルチオ基、2-アントラセニルチオ基、9-アントラセニルチオ基、2-フルオレニルチオ基が挙げられる。
アルケニル基としては、例えば、ビニル基、1-プロペニル基、2-プロペニル基、1-ブテニル基、2-ブテニル基、1-ペンテニル基、2-ペンテニル基、1-ヘキセニル基、2-ヘキセニル基、1-オクテニル基が挙げられる。
アルキニル基としては、例えば、エチニル基、1-プロピニル基、2-プロピニル基、1-ブチニル基、2-ブチニル基、1-ペンチニル基、2-ペンチニル基、1-ヘキシニル基、2-ヘキシニル基、1-オクチニル基が挙げられる。
アシル基としては、例えば、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、ピバロイル基、ベンゾイル基が挙げられる。また、置換基を有するアシル基としては、置換基としてハロゲン原子を有するアシル基(例えば、トリフルオロアセチル基、ペンタフルオロベンゾイル基)等が挙げられる。
アシルオキシ基としては、例えば、アセトキシ基、プロピオニルオキシ基、ブチリルオキシ基、イソブチリルオキシ基、ピバロイルオキシ基、ベンゾイルオキシ基が挙げられる。また、置換基を有するアシルオキシ基としては、置換基としてハロゲン原子を有するアシルオキシ基(例えば、トリフルオロアセチルオキシ基、ペンタフルオロベンゾイルオキシ基)等が挙げられる。
複素環オキシ基としては、例えば、ピリジルオキシ基、ピリダジニルオキシ基、ピリミジニルオキシ基、ピラジニルオキシ基、トリアジニルオキシ基が挙げられる。
複素環チオ基としては、例えば、ピリジルチオ基、ピリダジニルチオ基、ピリミジニルチオ基、ピラジニルチオ基、トリアジニルチオ基が挙げられる。
イミン残基としては、例えば、以下の構造式で示される基が挙げられる。
アミド化合物残基としては、例えば、ホルムアミド残基、アセトアミド残基、プロピオアミド残基、ブチロアミド残基、ベンズアミド残基、トリフルオロアセトアミド残基、ペンタフルオロベンズアミド残基、ジホルムアミド残基、ジアセトアミド残基、ジプロピオアミド残基、ジブチロアミド残基、ジベンズアミド残基、ジトリフルオロアセトアミド残基、ジペンタフルオロベンズアミド残基が挙げられる。
酸イミド残基としては、例えば以下の構造式で示される基が挙げられる。
アリーレン基としては、例えば、1,4-フェニレン基、1,3-フェニレン基、1,2-フェニレン基等のフェニレン基;1,4-ナフタレンジイル基、1,5-ナフタレンジイル基、2,6-ナフタレンジイル、2,7-ナフタレンジイル基等のナフタレンジイル基;1,4-アントラセンジイル基、1,5-アントラセンジイル基、2,6-アントラセンジイル基、9,10-アントラセンジイル基等のアントラセンジイル基;2,7-フェナントレンジイル基等のフェナントレンジイル基;9,10-ジヒドロフェナントレン-2,7-ジイル基等のジヒドロフェナントレンジイル基;1,7-ナフタセンジイル基、2,8-ナフタセンジイル基、5,12-ナフタセンジイル基等のナフタセンジイル基;2,7-フルオレンジイル基、3,6-フルオレンジイル基等のフルオレンジイル基;1,6-ピレンジイル基、1,8-ピレンジイル基、2,7-ピレンジイル基、4,9-ピレンジイル基等のピレンジイル基;3,8-ペリレンジイル基、3,9-ペリレンジイル基、3,10-ペリレンジイル基等のペリレンジイル基;9,9’-スピロフルオレン-2,7-ジイル基、9,9’-スピロフルオレン-3,6-ジイル基、9,9’-スピロフルオレン-2,2’-ジイル基等のスピロフルオレンジイル基が挙げられる。
本実施形態に係る高分子化合物は、下記式(1)で表される構成単位と、下記式(2)で表される構成単位と、下記式(3)で表される構成単位および/または下記式(4’)で表される構成単位と、を含む。該高分子化合物は、これらの構成単位を有することにより、発光効率に優れる発光素子の製造に有用なものとなる。
本発明の高分子化合物に含まれる第一構成単位は、下記式(1)で表される構成単位である。
Ar1およびAr3は、それぞれ独立に、非置換若しくは置換のアリーレン基または非置換若しくは置換の2価の複素環基を表す。
Ar2およびAr4は、それぞれ独立に、非置換若しくは置換のアリーレン基、非置換若しくは置換の2価の複素環基、または、アリーレン基および2価の複素環基から選ばれる同一若しくは異なる2以上の基が連結した2価の基(該基は、置換基を有していてもよい。)を表す。
Ar5、Ar6およびAr7は、それぞれ独立に、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を表す。
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6およびAr7はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接結合されていてもよく、-O-、-S-、-C(=O)-、-C(=O)-O-、-N(Ra)-、-C(=O)-N(Ra)-または-C(Ra)2-を介して結合されていてもよい。Raは、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、ハロゲン原子または非置換若しくは置換の1価の複素環基を表す。Raが2個存在する場合、それらは同一であっても異なっていてもよい。
xおよびyは、それぞれ独立に、0または1を表し、x+y=1であることが好ましい。
h、iおよびjは、それぞれ独立に、0~5の整数を表す。h、iおよびjは、好ましくは、0~3の整数であり、より好ましくは、1~3の整数である。
アリーレン基としては、例えば、フェニレン基(例えば、1,2-フェニレン基、1,3-フェニレン基、1,4-フェニレン基)、ナフタレンジイル基(例えば、1,4-ナフタレンジイル基、2,6-ナフタレンジイル基、2,7-ナフタレンジイル基)、アントラセンジイル基(例えば、2,6-アントラセンジイル基、9,10-アントラセンジイル基)、フェナントレンジイル基(例えば、2,7-フェナントレンジイル基)、ジヒドロフェナントレンジイル基(例えば、9,10-ジヒドロフェナントレン-2,7-ジイル基)、ナフタセンジイル基(例えば、5,12-ナフタセンジイル基)、フルオレンジイル基(例えば、2,7-フルオレンジイル基、3,6-フルオレンジイル基)、スピロフルオレンジイル基(例えば、9,9’-スピロフルオレン-2,7-ジイル基、9,9’-スピロフルオレン-3,6-ジイル基、9,9’-スピロフルオレン-2,2’-ジイル基)、および、ペリレンジイル基(例えば、3,8-ペリレンジイル基)が挙げられ、これらの基は上記の置換基を有していてもよい。
前記Ar2またはAr4は、好ましくは、非置換若しくは置換のアリーレン基、または、アリーレン基および2価の複素環基から選ばれる同一若しくは異なる2以上の基が連結した2価の基(該基は、置換基を有していてもよい。)であり、より好ましくは、非置換若しくは置換のフェニレン基、非置換若しくは置換のビフェニリレン基、非置換若しくは置換のスピロフルオレンジイル基、非置換若しくは置換のフェナントレンジイル基、非置換若しくは置換のジヒドロフェナントレンジイル基または非置換若しくは置換のフルオレンジイル基であり、さらに好ましくは非置換若しくは置換のフルオレンジイル基であり、本実施形態の高分子化合物を用いて製造される発光素子の寿命特性が優れるので、特に好ましくは、非置換若しくは置換の2,7-フルオレンジイル基である。
前記Raで表される非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、ハロゲン原子、非置換若しくは置換の1価の複素環基の定義や例は、上記置換基として記載のアルキル基、アルコキシ基、アリール基、ハロゲン原子、1価の複素環基の定義や例と同じである。
本発明の高分子化合物に含まれる第二構成単位は、下記式(2)で表される構成単位である。
Ar8は、(2+p)価の芳香族炭化水素基、または(2+p)価の複素環基を表す。
R1は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、オキシカルボニル基、1価の複素環基、複素環オキシ基、複素環チオ基、イミン残基、アミド化合物残基、酸イミド残基、カルボキシル基、ヒドロキシル基、ニトロ基またはシアノ基を表す。R1が複数個存在する場合、それらは同一であっても異なっていてもよい。なお、少なくとも1つのR1は、芳香族炭化水素基または複素環基における他の構成単位と結合を形成する炭素原子の隣の炭素原子に直接結合する水素原子を置換する。
pは1以上の整数を表す。
本発明の高分子化合物に含まれる第三構成単位は、下記式(3)で表される構成単位および下記式(4’)で表される構成単位から選択される構成単位である。
Ar10は非置換若しくは置換の(2+n)価の芳香族炭化水素基または非置換若しくは置換の(2+n)価の複素環基を示す。
LaおよびLbは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Laが複数存在する場合、それらは同一でも異なっていてもよい。Lbが複数存在する場合、それらは同一でも異なっていてもよい。
LAは酸素原子または硫黄原子を示す。
Q1は1価の架橋性基を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
なお、式(3)で示される構成単位は、式(2)で示される構成単位とは異なる。
上記芳香族炭化水素としては、ベンゼン、ナフタレン、アントラセン、1-テトラセン、ピレン、ペリレン、フルオレン、ベンゾフルオレン、フェナントレン、ジヒドロフェナントレン、クリセン、コロネン等が挙げられ、本実施形態の高分子化合物の安定性がより優れ、かつ、当該高分子化合物を用いて製造される発光素子の正孔輸送性が優れるので、ベンゼン、ナフタレン、アントラセン、ピレン、フルオレン、ベンゾフルオレン、フェナントレン、ジヒドロフェナントレンが好ましく、ベンゼン、ナフタレン、フルオレンがより好ましい。
上記複素環式化合物としては、例えば、ピリジン、ピリミジン、トリアジン、キノリン、イソキノリン、キノキサリン、ジベンゾフラン、ジベンゾチオフェン、カルバゾール、フェノキサジン、フェノチアジン、ベンゾチアジアゾール、ジベンゾシロールなどが挙げられる。
アルキレン基としては、メチレン基、1,2-エチレン基、1,3-プロピレン基、1,3-ブチレン基、1,3-ペンチレン基、1,4-ペンチレン基、1,5-ペンチレン基、1,4-ヘキシレン基、1,6-ヘキシレン基、1,7-ヘプチレン基、1,6-オクチレン基、1,8-オクチレン基等が挙げられる。
Q1としては、例えば、非置換若しくは置換のアジリジニル基、非置換若しくは置換のアゼチジニル基、アジド基、非置換若しくは置換のエポキシ基、非置換若しくは置換のオキセタニル基、非置換若しくは置換のアルケニル基、非置換若しくは置換のアルキニル基、シクロブテン構造を有する基などが挙げられ、原料となるモノマー合成が容易となるため、非置換若しくは置換のアジリジニル基、アジド基、非置換若しくは置換のエポキシ基、非置換若しくは置換のオキセタニル基、非置換若しくは置換のアルケニル基、非置換若しくは置換のアルキニル基、シクロブテン構造を有する非置換若しくは置換のアリール基、シクロブテン構造を有する非置換若しくは置換の1価の複素環基が好ましく、非置換若しくは置換のアルケニル基、シクロブテン構造を有する非置換若しくは置換のアリール基、シクロブテン構造を有する非置換若しくは置換の1価の複素環基がより好ましく、非置換若しくは置換のアルケニル基、シクロブテン構造を有する非置換若しくは置換のアリール基がさらに好ましい。
LX1は酸素原子、硫黄原子、カルボニル基または-O-CO-で表される基を示す。
R21、R22、R23、R24およびR25は、それぞれ独立に、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアルキルチオ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換のアリールチオ基、非置換若しくは置換の1価の複素環基、非置換若しくは置換のアミノ基、非置換若しくは置換のシリル基、非置換若しくは置換のアシル基、非置換若しくは置換のアシルオキシ基、ハロゲン原子、シアノ基またはニトロ基を示す。
RXは水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアルキルチオ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換のアリールチオ基、非置換若しくは置換のアミノ基、非置換若しくは置換のシリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、カルバモイル基、酸イミド基、非置換若しくは置換の1価の複素環基、非置換若しくは置換のカルボキシル基、シアノ基またはニトロ基を表す。複数存在するRXは、同一であっても異なっていてもよい。
RNは、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアシル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を表す。
RXとしては、原料となるモノマー合成が容易となるため、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換の1価の複素環基が好ましく、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基がより好ましい。
RNとしては、原料となるモノマー合成が容易になるため、アリール基で置換されたアルキル基、非置換若しくは置換のアシル基、非置換若しくは置換の1価の複素環基が好ましい。
なお、式(Q-01)~(Q-19)中、「*」は結合手を示す。
RYは水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアルキルチオ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換のアリールチオ基、非置換若しくは置換のアミノ基、非置換若しくは置換のシリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、カルバモイル基、酸イミド基、非置換若しくは置換の1価の複素環基、非置換若しくは置換のカルボキシル基、シアノ基またはニトロ基を表す。複数あるRYは、同一であっても異なっていてもよい。
RYとしては、原料となるモノマー合成が容易となるため、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基または非置換若しくは置換の1価の複素環基であることが好ましく、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基または非置換若しくは置換のアリール基であることより好ましく、水素原子または非置換若しくは置換のアルキル基であることがさらに好ましい。なお、式(Q-1-1)および(Q-1-2)中、「*」は結合手を示す。
LcおよびLdは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lcが複数存在する場合、それらは同一でも異なっていてもよい。Ldが複数存在する場合、それらは同一でも異なっていてもよい。
LBは酸素原子または硫黄原子を示す。LBが複数存在する場合、それらは同一でも異なっていてもよい。
Q1は前記と同じ意味を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
R80は、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換の1価の複素環基または非置換若しくは置換の複素環オキシ基を示す。
Ldは前記Lbと同じ意味を示し、前記Lbにおける例示および好ましい範囲と同一である。
LBは前記LAと同じ意味を示し、前記LAにおける例示および好ましい範囲と同一である。
Q1は前記式(3)におけるQ1と同じ意味を表し、式(3)における例示および好ましい範囲と同一である。
LcおよびLdは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lcが複数存在する場合、それらは同一でも異なっていてもよい。Ldが複数存在する場合、それらは同一でも異なっていてもよい。
LBは酸素原子または硫黄原子を示す。LBが複数存在する場合、それらは同一でも異なっていてもよい。
Q1は前記と同じ意味を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
R90は、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換の1価の複素環基または非置換若しくは置換の複素環オキシ基を示す。R90が複数存在する場合、それらは同一でも異なっていてもよい。]
Ar20およびAr40は、それぞれ独立に、非置換若しくは置換のアリーレン基または非置換若しくは置換の2価の複素環基を示し、Ar30’は、非置換若しくは置換の(2+d)価の芳香族炭化水素基、非置換若しくは置換の(2+d)価の複素環基、または、芳香環および複素環から選ばれる同一若しくは異なる2以上の環が連結した構造を有する(2+d)価の基(当該(2+d)価の基は置換基を有していてもよい)を示す。
Q2’、Q3’およびQ4’は、それぞれ独立に、1価の架橋性基、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を示すが、Q2’、Q3’およびQ4’の少なくとも一つは1価の架橋性基である。Q4’が複数存在する場合、それらは同一でも異なっていてもよい。
naは0~3の整数を示し、nbは0~12の整数を示し、nAは0または1を示す。
LaおよびLbは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Laが複数存在する場合、それらは同一でも異なっていてもよい。Lbが複数存在する場合、それらは同一でも異なっていてもよい。
LAは、酸素原子または硫黄原子を示す。LAが複数存在する場合、それらは同一でも異なっていてもよい。
ngは0~3の整数を示し、nhは0~12の整数を示し、nDは0または1を示す。
LgおよびLhは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lgが複数存在する場合、それらは同一でも異なっていてもよい。Lhが複数存在する場合、それらは同一でも異なっていてもよい。
LDは、酸素原子または硫黄原子を示す。LDが複数存在する場合、それらは同一でも異なっていてもよい。
なお、式(4’)で示される構成単位は、式(1)で示される構成単位とは異なる。
式(4’)において、Ar20およびAr40におけるアリーレン基としては、例えば、1,2-フェニレン基、1,3-フェニレン基、1,4-フェニレン基、1,4-ナフタレンジイル基、2,6-ナフタレンジイル基、2,7-ナフタレンジイル基、2,6-アントラセンジイル基、9,10-アントラセンジイル基、2,7-フェナントレンジイル基、5,12-ナフタセンジイル基、2,7-フルオレンジイル基、3,6-フルオレンジイル基、1,6-ピレンジイル基、2,7-ピレンジイル基および3,8-ペリレンジイル基が挙げられ、1,4-フェニレン基、2,7-フルオレンジイル基、2,6-アントラセンジイル基、9,10-アントラセンジイル基、2,7-フェナントレンジイル基または1,6-ピレンジイル基が好ましく、1,4-フェニレン基がさらに好ましい。なお、これらの基は上記置換基を有していてもよい。
芳香族炭化水素としては、例えば、ベンゼン、ナフタレン、アントラセン、1-テトラセン、ピレン、ペリレン、フルオレン、ベンゾフルオレン、フェナントレン、ジヒドロフェナントレン、クリセン、コロネンが挙げられ、本実施形態の高分子化合物の安定性がより優れ、かつ、本実施形態の高分子化合物を用いて製造される発光素子の正孔輸送性が優れるので、ベンゼン、ナフタレン、アントラセン、ピレン、フルオレン、ベンゾフルオレン、フェナントレンまたはジヒドロフェナントレンが好ましく、ベンゼン、ナフタレンまたはフルオレンがより好ましい。
複素環式化合物としては、例えば、ピリジン、ピリミジン、トリアジン、キノリン、イソキノリン、キノキサリン、ジベンゾフラン、ジベンゾチオフェン、カルバゾール、フェノキサジン、フェノチアジン、ベンゾチアジアゾール、ジベンゾシロールが挙げられる。
アルキレン基としては、メチレン基、1,2-エチレン基、1,3-プロピレン基、1,3-ブチレン基、1,3-ペンチレン基、1,4-ペンチレン基、1,5-ペンチレン基、1,4-ヘキシレン基、1,6-ヘキシレン基、1,7-ヘプチレン基、1,6-オクチレン基、1,8-オクチレン基等が挙げられる。
式(4’)において、Q2’、Q3’およびQ4’が示す1価の架橋性基としては、例えば、非置換若しくは置換のアジリジニル基、非置換若しくは置換のアゼチジニル基、アジド基、非置換若しくは置換のエポキシ基、非置換若しくは置換のオキセタニル基、非置換若しくは置換のアルケニル基、非置換若しくは置換のアルキニル基、シクロブテン構造を有する基が挙げられ、原料となるモノマー合成が容易となるため、非置換若しくは置換のアジリジニル基、アジド基、非置換若しくは置換のエポキシ基、非置換若しくは置換のオキセタニル基、非置換若しくは置換のアルケニル基、非置換若しくは置換のアルキニル基、シクロブテン構造を有する非置換若しくは置換のアリール基は、シクロブテン構造を有する非置換若しくは置換の1価の複素環基が好ましく、非置換若しくは置換のアルケニル基、シクロブテン構造を有する非置換若しくは置換のアリール基、シクロブテン構造を有する非置換若しくは置換の1価の複素環基がより好ましく、非置換若しくは置換のアルケニル基、シクロブテン構造を有する非置換若しくは置換のアリール基がさらに好ましい。
d1は1~4の整数を示し、
Ar50およびAr60は、それぞれ独立に、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を示す。
Q4は、1価の架橋性基を示す。
式(4)中、c、Ar20およびAr40は、前記と同じ意味を表す。
Ar30は、非置換若しくは置換のアリーレン基、非置換若しくは置換の2価の複素環基、または、アリーレン基および2価の複素環基から選ばれる同一若しくは異なる2以上の基が連結した2価の基(当該基は置換基を有していてもよい)を示す。
Q2は1価の架橋性基を示し、Q3は1価の架橋性基、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を示す。
前記式(1)で表される構成単位と、前記式(2)で表される構成単位と、前記式(3)で表される構成単位および前記式(4’)で表される構成単位からなる群から選ばれる少なくとも2種類の構成単位と、を含む高分子化合物であることが好ましく、
前記式(1)で表される構成単位と、前記式(2)で表される構成単位と、少なくとも2種類の前記式(3)で表される構成単位と、を含む高分子化合物であることがより好ましく、
本実施形態の高分子化合物を用いて製造される発光素子の耐久性が優れるので、前記式(1)で表される構成単位と、前記式(2)で表される構成単位と、2種類の前記式(3)で表される構成単位と、を含む高分子化合物であることがさらに好ましく、
前記式(1)で表される構成単位と、前記式(2)で表される構成単位と、前記式(3-103)で表される構成単位、前記式(3-105)で表される構成単位、前記式(3-132)で表される構成単位、前記式(3-137)で表される構成単位および前記式(3-140)で表される構成単位から選ばれる2種類の構成単位と、を含む高分子化合物であることが特に好ましく、
前記式(1)で表される構成単位と、前記式(2)で表される構成単位と、前記式(3-132)で表される構成単位と、前記式(3-140)で表される構成単位と、を含む高分子化合物であることがとりわけ好ましい。
本発明の高分子化合物は、上記の第一構成単位、第二構成単位および第三構成単位以外の構成単位を含んでいてもよい。
[式中、
Rは、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、オキシカルボニル基、1価の複素環基、複素環オキシ基、複素環チオ基、イミン残基、アミド化合物残基、酸イミド残基、カルボキシル基、ヒドロキシル基、ニトロ基またはシアノ基を表す。
Arは、ヘテロ原子を含んでいてもよい炭素原子数6~60の芳香族炭化水素基を表す。]
本実施形態の高分子化合物は、例えば、下記式(1M)で表される化合物(以下、場合により「化合物1M」という。)と、下記式(2M)で表される化合物(以下、場合により「化合物2M」という。)と、下記式(3M)で表される化合物(以下、場合により「化合物3M」という。)および/または下記式(4’M)で表される化合物(以下、場合により「化合物4’M」という。)を縮合重合させることにより製造することができる。
本明細書において、化合物1M、化合物2M、化合物3Mおよび化合物4’Mを総称して、「モノマー」ということがある。
塩素原子、臭素原子、ヨウ素原子、-O-S(=O)2R31(R31は、アルキル基、または、アルキル基、アルコキシ基、ニトロ基、フッ素原子若しくはシアノ基で置換されていてもよいアリール基を表す。)で表される基。
-B(OR32)2(R32は、水素原子またはアルキル基を表し、複数存在するR32は互いに同一でも異なっていてもよく、互いに結合してそれぞれが結合する酸素原子とともに環構造を形成していてもよい。)で表される基、-BF3Q10(Q10は、Li+、Na+、K+、Rb+およびCs+からなる群より選ばれる1価の陽イオンを表す。)で表される基、-MgY1(Y1は、塩素原子、臭素原子またはヨウ素原子を表す。)で表される基、-ZnY2(Y2は、塩素原子、臭素原子またはヨウ素原子を表す。)で表される基、および、-Sn(R33)3(R33は水素原子またはアルキル基を表し、複数存在するR33は互いに同一でも異なっていてもよく、互いに結合してそれぞれが結合するスズ原子とともに環構造を形成していてもよい。)で表される基。
ZT-ArT (1T)
本実施形態の化合物は、上記の高分子化合物の製造に有用な下記式(4-1)で表される化合物である。
式(4-3b)で表される化合物は、有機溶媒中、ナトリウム-tert-ブトキシド等の塩基、[トリス(ジベンジリデンアセトン)]ジパラジウムに代表されるパラジウム化合物、および、式(4-3b’)で表される化合物によるブッフバルト反応により、式(4-3c)で表される化合物に誘導することができる。
式(4-3c)で表される化合物は、有機溶媒中、N-ブロモスクシンイミド等の臭素化剤と反応させることで、式(4-3Br)で表される化合物に誘導することができる。
式(4-3Br)で表される化合物は、公知の方法により、Z7およびZ8で表される基を、臭素原子を除く置換基(a)群または置換基(b)群から選ばれる基に変換した式(4-3)で表される化合物に誘導することができる。また、式(4-3Br)で表される化合物をそのまま式(4-3)で表される化合物として用いることもできる。
ncは0~3の整数を示し、ndは0~12の整数を示し、nBは0または1を示し、kは1~4の整数を示す。
LcおよびLdは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lcが複数存在する場合、それらは同一でも異なっていてもよい。Ldが複数存在する場合、それらは同一でも異なっていてもよい。
LBは酸素原子または硫黄原子を示す。LBが複数存在する場合、それらは同一でも異なっていてもよい。
Q1’はシクロブテン構造を有する非置換若しくは置換のアリール基、シクロブテン構造を有する非置換若しくは置換の1価の複素環基を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
R90は、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換の1価の複素環基または非置換若しくは置換の複素環オキシ基を示す。R90が複数存在する場合、それらは同一でも異なっていてもよい。
式(3-6b)で表される化合物は、例えば、有機溶媒中、ブチルリチウムに代表されるアルキルリチウム等のリチオ化剤と反応させ、ハロゲン-金属交換反応によりリチオ化体を発生させ、次に式(3-6c)で表される化合物を加えることにより、式(3-6d)で表される化合物に誘導することができる。
式(3-6d)で表される化合物は、例えば、有機溶媒中、ブチルリチウムに代表されるアルキルリチウム等のリチオ化剤と反応させ、ハロゲン-金属交換反応によりリチオ化体を発生させ、次に、式(3-6c)で表される化合物を加えることにより、式(3-6e)で表される化合物に誘導することができる。
式(3-6e)で表される化合物は、例えば、有機溶媒中、N-ブロモスクシンイミドや臭素等のブロモ化剤と反応させることで、式(3-6Br)で表される化合物に誘導することができる。
式(3-6Br)で表される化合物は、公知の方法により、Z5およびZ6で表される基を、臭素原子を除く置換基(a)群または置換基(b)群から選ばれる基に変換した式(3-6)で表される化合物に誘導することができる。また、式(3-6Br)で表される化合物をそのまま式(3-6)で表される化合物として用いることもできる。
本発明の組成物は、本発明の高分子化合物と、正孔輸送材料、電子輸送材料および発光材料からなる群より選ばれる少なくとも一種と、を含有する。この組成物は、発光素子の製造に好適に使用できる。
本実施形態の高分子化合物は、溶媒、好ましくは有機溶媒に溶解または分散させた組成物(以下、「液状組成物」ということがある。液状組成物としては、溶液および分散液の形態がある。)としてもよい。このような液状組成物は、インク、ワニスとも呼ばれる。
発光素子に使用する有機薄膜を形成するためにこの液状組成物を用いる場合、液状組成物は、溶液であることが好ましい。
また、単独溶媒または混合溶媒に水を添加することもできる。
本実施形態の有機薄膜は、上記高分子化合物または組成物を含有する。本実施形態の有機薄膜は、上記液状組成物から容易に製造することができる。また、本発明の第二の有機薄膜は、本実施形態の高分子化合物を架橋により不溶化させた、不溶化有機薄膜であり、通常、加熱または光照射等の外部刺激により架橋させ、硬化したものである。不溶化有機薄膜は、溶媒に難溶のため、発光素子の積層化等に有利である。
本実施形態の発光素子は、上記の有機薄膜または不溶化有機薄膜を有する。
a)陽極/発光層/陰極
b)陽極/正孔輸送層/発光層/陰極
c)陽極/発光層/電子輸送層/陰極
d)陽極/正孔輸送層/発光層/電子輸送層/陰極
(ここで、/は各層が隣接して積層されていることを示す。以下同じ。)
e)陽極/正孔注入層/発光層/陰極
f)陽極/発光層/電子注入層/陰極
g)陽極/正孔注入層/発光層/電子注入層/陰極
h)陽極/正孔注入層/正孔輸送層/発光層/陰極
i)陽極/正孔輸送層/発光層/電子注入層/陰極
j)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
k)陽極/正孔注入層/発光層/電子輸送層/陰極
l)陽極/発光層/電子輸送層/電子注入層/陰極
m)陽極/正孔注入層/発光層/電子輸送層/電子注入層/陰極
n)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/陰極
o)陽極/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
p)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
q)陽極/絶縁層/発光層/陰極
r)陽極/発光層/絶縁層/陰極
s)陽極/絶縁層/発光層/絶縁層/陰極
t)陽極/絶縁層/正孔輸送層/発光層/陰極
u)陽極/正孔輸送層/発光層/絶縁層/陰極
v)陽極/絶縁層/正孔輸送層/発光層/絶縁層/陰極
w)陽極/絶縁層/発光層/電子輸送層/陰極
x)陽極/発光層/電子輸送層/絶縁層/陰極
y)陽極/絶縁層/発光層/電子輸送層/絶縁層/陰極
z)陽極/絶縁層/正孔輸送層/発光層/電子輸送層/陰極
aa)陽極/正孔輸送層/発光層/電子輸送層/絶縁層/陰極
ab)陽極/絶縁層/正孔輸送層/発光層/電子輸送層/絶縁層/陰極
以下の合成例、実施例では、数平均分子量および重量平均分子量の測定、高速液体クロマトグラフィー(HPLC)、NMR、LC-MS、TLC-MS、高分子化合物のエネルギーギャップの測定を、以下のようにして実施した。
数平均分子量(Mn)および重量平均分子量(Mw)については、ゲル浸透クロマトグラフィー(GPC)により分析し、その分析結果からポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)を算出した。
<分析条件>
測定装置:HLC-8320GPC(東ソー株式会社製)
カラム:PLgel MIXED-B(ポリマーラボラトリーズ社製)
カラム温度:40℃
移動層:テトラヒドロフラン
流量:2.0mL/min
検出波長:228nm
化合物の純度の指標として、HPLC面積百分率の値を用いた。測定する化合物は、0.01~0.2重量%の濃度になるようにテトラヒドロフランまたはクロロホルムに溶解させ、HPLCに、濃度に応じて1~10μL注入した。
<分析条件1>
測定装置:LC-20A(島津製作所製)
カラム:Kaseisorb LC ODS 2000(東京化成工業製)、または同等の性能を有するカラム
検出器:SPD-M20A(島津製作所製)
検出波長:254nm
HPLCの移動相には、アセトニトリルおよびテトラヒドロフランを用い、1mL/分の流速で、アセトニトリル/テトラヒドロフラン=100/0~0/100(容積比)のグラジエント分析で流した。
<分析条件2>
測定装置:分析条件1と同等の性能を有する装置
カラム:Ascentis Express C18、または同等の性能を有するカラム
検出器:分析条件1と同等の性能を有する装置
検出波長:目的物および不純物が測定可能な波長
HPLCの移動相には、水およびテトラヒドロフランを用い、1mL/分の流速で、水/テトラヒドロフラン=100/0~0/100(容積比)のグラジエント分析で流した。
<分析条件1>
測定装置:1100LCMSD(アジレント・テクノロジー製)
カラム:L-column 2 ODS(3μm)(化学物質評価研究機構製、内径:4.6mm、長さ:250mm、粒子径3μm)
<分析条件2>
測定装置:分析条件1と同等の性能を有する装置
カラム:Zorbax Extend C18(内径:4.6mm、長さ:50mm、粒子径5μm)
測定装置:Accu TOF TLC(日本電子製)
高分子化合物の0.8重量%キシレン溶液を、石英板上にスピンコートすることで高分子化合物からなる有機薄膜を作製した。該有機薄膜を測定試料として、高分子化合物の吸収スペクトルを紫外・可視分光光度計(Varian社製、商品名:Cary5E)により測定した。
得られた吸収端波長と、下記計算式(E)を用いて、高分子化合物のエネルギーギャップを算出した。
計算式(E):エネルギーギャップ(eV)=1239/吸収端波長(nm)
CM1は特開2010-189630号公報記載の合成法に従い合成した。
CM2は下記の方法により合成した。
CM3は特開2010-189630号公報記載の合成法に従い合成した。
CM4は特開2010-189630号公報記載の合成法に従い合成した。
CM5は特開2011-174061号公報記載の合成法に従い合成した。
CM6はWO2002/045184記載の合成法に従い合成した。
CM7はWO2009/131255記載の合成法に従い合成した。
CM8はWO2002/045184記載の合成法に従い合成した。
CM9はWO2009/131255記載の合成法に従い合成した。
CM10はWO2005/049546記載の合成法に従い合成した。
CM11はWO2011/049241記載の合成法に従い合成した。
CM12は特開2009-052032号公報記載の合成法に従い合成した。
CM13は、WO2009/110642記載の合成法に従い合成した。
CM14はWO2002/045184号公報記載の合成法に従い合成した。
CM15は特開2006-169265号公報記載の合成法に従い合成した。
CM16は特開2006-169265号公報記載の合成法に従い合成した。
CM17は特開2010-189630号公報記載の合成法に従い合成した。
CM18は下記の方法により合成した。
CM19は下記の方法により合成した。
CM20は下記の方法により合成した。
CM21は下記の方法により合成した。
CM22は特開2008-106241号公報記載の合成法に従い合成した。
CM23は特開2010-215886号公報記載の合成法に従い合成した。
CM24は特開2010-215886号公報記載の合成法に従い合成した。
CM25は下記の方法により合成した。
CM26は下記の方法により合成した。
CM27は下記の方法により合成した。
CM28は下記の方法により合成した。
滴下ロートを備えた四つ口フラスコを遮光し、フラスコ内をアルゴンガスで置換した後に、1,4-ジブチルベンゼン(100g、0.53mol)、鉄粉(2.9g、0.053mol)、CHCl3(140mL)およびトリフルオロ酢酸(以下、「TFA」ということがある。)(4mL)を加えた。その後、フラスコを氷浴にて冷却しながら、臭素(185g、1.16mol)をCHCl3(330mL)に溶かした溶液を、前記滴下ロートより滴下した。滴下終了後、遮光、氷浴の条件下にて4時間撹拌した。その後、反応溶液を2Mの水酸化カリウム水溶液(250mL)で洗浄し、イオン交換水(250mL)で水層が無色透明になるまで繰り返し洗浄した。有機層をNa2SO4で乾燥させた後、溶媒を減圧留去するとオレンジ色の液体が得られた。この液体をヘキサン(500mL)に溶解させ、活性炭(15g)を加え撹拌した後に、珪藻土濾過を行い、溶媒を減圧留去した。得られた残渣をエタノール(100mL)にて3回再結晶を行うことで、極僅かに黄味を帯びた白色粉末CM2aを120g得た(収率94%)。
1HNMR(300MHz,CDCl3):δ(ppm)=7.35(s,2H),2.64(t,J=8.0Hz,4H),1.61-1.51(m,4H),1.42-1.35(m,4H),0.94(t,J=7.4Hz,6H).
13CNMR(75.5MHz,CDCl3):δ(ppm)=141.56,134.05,123.35,35.52,32.24,22.73,14.21.
分析条件1で測定したLC-MS(APPI,positive):m/z+=346([M]+).
1HNMR(300MHz,CDCl3):δ(ppm)=7.53(s,2H),2.82(t,J=7.9Hz,4H),1.59-1.33(mult,32H(4H+4H+24H)),0.92(t,J=7.2Hz,6H).
13CNMR(75.5MHz,CDCl3):δ(ppm)=146.09,136.47,83.26,35.97,35.19,24.83,23.00,14.02.
TLC-MS(DART,positive):m/z+=440([M]+),441([M+H]+).
窒素ガス雰囲気下、1-ブロモ-3,5-ジ-n-ヘキシルベンゼン(化合物CM18a、650g)およびテトラヒドロフラン(6.5L)からなる溶液に、-75~-70℃にてn-ブチルリチウム(1.6Mヘキサン溶液、1237mL)を1時間かけて滴下し、同温度でさらに4時間攪拌した。次いで、2,7-ジブロモフルオレノン(化合物CM18b、613g)を-75~-70℃にて1時間かけて加え、攪拌しながら反応混合物の温度を室温まで上げた。次いで、2M塩酸(982mL)を加え、反応混合物のpHを7に調整した。減圧下、テトラヒドロフランを除去し、残った混合物にn-ヘキサンを加え攪拌し、分液して得られた油層を水洗した。該油層に無水硫酸ナトリウムを加え攪拌し、濾過したのち、濾液を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をn-ヘキサンによって再結晶することにより、目的とする化合物CM18c(674g)を得た。
窒素ガス雰囲気下、化合物CM18c(674g)にn-ヘキサン(1215mL)を加え、10℃にて攪拌しながらトリフルオロ酢酸(877mL)を加え、次いで、トリエチルシラン(147g)およびn-ヘキサン(300mL)からなる溶液を10-15℃にて滴下した。次いで、反応混合物を室温にて一晩攪拌した。次いで、得られた反応混合物に、10℃にて水(1200mL)をゆっくり加え、減圧濃縮により溶媒を除去した。得られた混合物に、n-ヘキサンを加えて攪拌し、静置後分液した水層を油層から分離した。得られた油層に、10%リン酸カリウム水溶液(5L)を加え、2時間攪拌し、静置後分液した水層を油層から分離した。該油層を水洗した後、無水硫酸ナトリウムを加え攪拌し、濾過した濾液を減圧濃縮することによって溶媒を除去し、油状物を得た。該油状物をジクロロメタン(610mL)に溶解して調製した溶液を、攪拌したメタノール(8.5L)に1時間かけて加え、さらに3時間攪拌し、析出した結晶を濾過し、減圧下乾燥することにより、目的とする化合物CM18dを538g得た。
窒素ガス雰囲気下、化合物CM18d(25g)、1-ブロモオクタン(12.9g)、テトラエチルアンモニウムクロライド(Aldrich製:商標Aliquat336)からなる混合物に、攪拌しながら85℃にて26.7重量%水酸化カリウム水溶液をゆっくり加え、同温度にて20時間攪拌した。得られた反応混合物に、室温にて、水(120mL)およびジクロロメタン(250mL)を加え攪拌し、静置後分液して得られた水層を油層から除去した。該油層に無水硫酸ナトリウムを加えて攪拌し、濾過して得られた濾液を減圧濃縮し、溶媒を除去し、油状物を得た。該油状物にジクロロメタンとメタノールを加え、再結晶することにより、白色固体を得た。該固体をイソプロピルアルコールから再結晶することにより、目的とする、化合物CM18eを22g得た。
窒素ガス雰囲気下、化合物CM18e(125g)、2,4,6-トリメチルアニリン(54.63g)、トルエン(1.7L)、[トリス(ジベンジリデンアセトン)]ジパラジウム(0.84g)、トリ-tert-ブチルホスフィンテトラフルオロボレート(t-Bu3P・BF4H、0.400g)、ナトリウムtert-ブトキシド(53g)を還流下、16時間攪拌した。次いで、室温にて、水(400mL)を加え攪拌し、静置後分液した水層を油層から除去した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をトルエン(500mL)に溶解して溶液を調製し、セライトを敷き詰めた濾過器、シリカゲルを敷き詰めた濾過器の順に該溶液を通した。得られた濾液を減圧濃縮して溶媒を除去し、油状物を得た。該油状物にイソプロピルアルコールおよびジクロロメタンを加え、静置して析出した結晶を濾過し、黄色固体を得た。該固体をイソプロピルアルコールおよびトルエンにて再結晶することにより、目的とする化合物CM18fを94g得た。
窒素ガス雰囲気下、化合物CM18f(94.2g)、ブロモベンゼン(32mLg)、トルエン(1.4L)、[トリス(ジベンジリデンアセトン)]ジパラジウム(1.09g)、トリ-tert-ブチルホスフィンテトラフルオロボレート(t-Bu3P・BF4H、0.69g)、ナトリウムtert-ブトキシド(34.4g)を還流下、一晩攪拌した。次いで、室温にて、水(300mL)を加え攪拌し、静置後分液した水層を油層から除去した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をトルエン(200mL)に溶解して溶液を調製し、セライトを敷き詰めた濾過器、シリカゲルを敷き詰めた濾過器の順に該溶液を通した。得られた濾液を減圧濃縮して溶媒を除去し、油状物を得た。該油状物にイソプロピルアルコールおよびメタノールを加え攪拌し、静置して分液した上澄みを除去し、得られた油状物から減圧下溶媒を除去することにより、目的とする化合物CM18gを82g得た。
化合物CM18g(55.8g)およびクロロホルム(550mL)からなる溶液に、攪拌しながら-15℃にてN-ブロモスクシンイミド(NBS、21.2g)およびN,N-ジメチルホルムアミド(550mL)からなる溶液を滴下し、同温度で3時間攪拌した。次いで、室温にてメタノール(400mL)を加え攪拌し、水(400mL)を加え攪拌し、減圧下濃縮して溶媒を除去した。得られた混合物を静置した後、上澄みを除去して褐色固体を得た。該固体にジクロロメタン(500mL)を加え溶解させ、水を加えて攪拌し、静置後分液した水層を油層から除去した。次いで、10%炭酸ナトリウム水溶液を加えて攪拌し、静置後分液した水層を油層から除去した。次いで、水を加えて攪拌し、静置後分液した水層を油層から除去した。得られた油層を減圧下で溶媒を除去し、褐色の油状物を得た。該褐色の油状物を、セライトとシリカゲルを使用したカラムクロマトグラフィーを行い、溶媒を除去することにより、透明な油状物を得た。該透明な油状物にイソプロピルアルコールとトルエンを加えて攪拌し、静置した後、上澄みを除去して粘性の高い固体を得た。次いで、該固体にメタノールを加えて激しく攪拌し、得られた固体を濾過した。次いで、メタノールおよび酢酸n-ブチルを使用して再結晶することにより、目的とする単量体CM18を40.6g得た。
単量体CM19は以下の第一工程~第七工程に従い合成した。
反応容器に、アセトアミド(59.1g、1.00mol)、トリス(ジベンジリデンアセトン)ジパラジウム(0)(3.66g、4mmol)、4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン(通称Xantphos、6.94g、12mmol)、炭酸セシウム(391g、1.20mol)、1,4-ジオキサン(800ml)およびイオン交換水(7.2ml)を加え、更にアルゴンガスをバブリングすることにより反応容器内をアルゴンガス雰囲気に置換した。100℃まで加熱した後に、9,9-ジヘキシル-2,7-ジブロモフルオレン(上記化合物CM19a、98.5g、200mmol)を1,4-ジオキサン(300ml)に溶解した溶液を約0.5時間かけてゆっくりと加えた後に、同温度で4時間攪拌した。得られた反応混合物をシリカゲルパッドに通液し、得られたろ液を濃縮してからイオン交換水中に、ゆっくりと加え、攪拌することにより析出した固体をろ取し、イオン交換水で洗浄し、減圧乾燥することにより、94.5gの固体を得た。得られた固体を、エタノール-イオン交換水を用いて再結晶した後に、更に、クロロホルム-ヘキサンで2回再結晶し、更に、エタノールに溶解した状態で活性炭を加えて加熱還流した後にセライトろ過により活性炭をろ別した。その後、ろ液を濃縮し、ヘキサンを加え固体を析出させる操作を行うことにより精製した。得られた固体を、ろ取、減圧乾燥することにより、目的物である化合物CM19b(52.8g)を肌色固体として得た。収率58.9%。得られた化合物CM19bの分析条件1で測定したHPLC面積百分率値は97.6%を示した。
1H-NMR(300MHz,THF-d8)δ(ppm)=9.05(s,2H),7.69(s,2H),7.51(t,4H),2.06(s,6H),1.95(m,4H),1.10(m,12H),0.78(t,6H),0.66(m,4H).
13C-NMR(75MHz,THF-d8)δ(ppm)=169.1,152.9,140.8,138.3,120.9,119.6,115.3,56.9,42.7,33.7,31.9,25.8,25.3,24.6,15.5.
上記化合物CM19b(43.1g、96mmol)、炭酸カルシウム(11.5g、115mmol)、クロロホルム(384ml)、メタノール(384ml)を混合し、窒素ガスをバブリングすることにより系内を窒素ガス雰囲気に置換した。遮光下で、上記混合物を攪拌しながら、ベンジルトリメチルアンモニウムトリブロミド(89.84g、230mmol)を1時間かけて少しずつゆっくりと加えた。その後、室温で17時間攪拌し、ついで、50℃に加熱しながら、2時間攪拌し、再び室温で23時間攪拌し、50℃で9時間攪拌した。室温まで冷却した後に、不溶物をろ過により除去した後に、10重量%亜硫酸ナトリウム水溶液(384ml)を加え、1時間攪拌した後、水層を分液により除き、得られた油層を5重量%炭酸水素ナトリウム水溶液(384ml)、イオン交換水(384ml)、15重量%食塩水(384ml)で順次洗浄し、減圧濃縮することにより、約80gの固体を得た。得られた固体を酢酸エチル(400ml)に室温にて溶解させた後に、シリカゲル(40g)を加え、30分攪拌してから、シリカゲルをろ過により除去し、得られたろ液を濃縮した。酢酸エチル(80ml)に加熱溶解させ、ヘキサン(320ml)を滴下し、室温まで冷却してから、析出した固体をろ取した。得られた固体を、再度酢酸エチル(68ml)に加熱溶解させ、ヘキサン(280ml)を滴下し、室温まで冷却してから、析出した固体をろ取した。得られた固体を、減圧乾燥することにより、目的物である化合物CM19c(39.0g)を薄黄色固体として得た。収率67.0%。得られた化合物の分析条件1で測定したHPLC面積百分率値は98.5%を示した。なお、再結晶のろ液を合一して濃縮した後に、同様の条件で再結晶精製し、得られた結晶をろ取、減圧乾燥することにより、化合物CM19c(7.56g)を回収した。収率13.0%。得られた化合物CM19cの分析条件1で測定したHPLC面積百分率値は96.6%を示した。以上より総収率は80.0%であった。
1H-NMR(300MHz,THF-d8)δ(ppm)=8.36(s,2H),8.26(s,2H),7.96(s,2H),2.16(s,6H),1.98(m,4H),1.11(m,12H),0.79(t,6H),0.68(m,4H).
13C-NMR(75MHz,THF-d8)δ(ppm)=169.5,152.8,139.1,137.8,125.5,120.0,114.8,57.3,41.9,33.5,31.7,25.8,25.2,24.6,15.5.
上記化合物CM19c(42.5g、70mmol)、ブチルボロン酸(28.5g、280mmol)、酢酸パラジウム(157mg、0.70mmol)、トリ-tert-ブチルホスフィンテトラフルオロボレート塩(204mg、0.70mmol)、無水炭酸カリウム(58.1g、420mmol)、市販脱水トルエン(700ml)を混合し、アルゴンガスをバブリングすることにより、系中を不活性ガスで置換した。オイルバスで加熱し、還流下で19時間攪拌した。HPLCにより反応進行を確認した後に、トルエン(350ml)および酢酸エチル(350ml)で希釈し、室温まで冷却した後に、セライトろ過およびシリカゲルパッドへの通液を行うことで不溶物および極性の高い不純物を除去した。得られた溶液を濃縮した後に、酢酸エチルを用いて再結晶精製し、得られた結晶をろ取、減圧乾燥することにより、目的物である化合物CM19d(19.3g)を白色固体として得た。得られた化合物のHPLC面積百分率値は99.2%(UV254nm)を示した。収率49.1%。なお、上記で用いたセライト、シリカゲルの残渣から目的成分をクロロホルムで抽出し、上記と同様の操作で精製することにより、化合物CM19d(8.7g)を白色固体として回収した。得られた化合物CM19dの分析条件1で測定したHPLC面積百分率値は99.3%(UV254nm)を示した。収率22.1%。以上より総得量で28.0g、収率71.2%。
1H-NMR(300MHz,THF-d8)δ(ppm)=8.30(s,2H),7.66(s,2H),7.49(s,2H),2.66(t,4H),2.07(s,6H),1.93(m,4H),1.67(m,4H),1.44(m,4H),1.15(m,12H),0.99(t,6H),0.79(t,6H),0.73(m,4H).
13C-NMR(75MHz,THF-d8)δ(ppm)=169.1,150.7,139.9,137.3,135.6,121.5,121.3,56.5,42.3,34.3,33.6,33.2,31.9,26.7,25.9,24.8,24.6,15.6,15.5.
上記化合物CM19d(28.0g、50mmol)を2-プロパノール(500ml)に室温にて溶解させた後に、48重量%濃度のHBr水溶液(569ml)、イオン交換水(50ml)を加え、加熱還流下で33時間攪拌した。この時、フラスコ内は白色のスラリー状であった。反応終了後、室温まで冷却し、析出した固体をろ取、イオン交換水(250ml)で2回洗浄した。その後、室温で5時間減圧乾燥した後に、50℃で一晩減圧乾燥することにより、目的物である化合物CM19e(26.3g)を白色固体として得た。収率82.2%。得られた化合物CM19eの分析条件1で測定したHPLC面積百分率値は92.7%を示した。
1H-NMR(300MHz,Methanol-d4)δ(ppm)=7.93(s,2H),7.44(s,2H),4.91(s,6H),2.85(t,4H),2.09(m,4H),1.80(m,4H),1.56(m,4H),1.07(m,18H),0.77(t,6H),0.59(m,4H).
13C-NMR(75MHz,Methanol-d4)δ(ppm)=152.4,143.0,137.8,130.6,124.1,119.9,57.3,42.0,34.2,33.5,32.2,31.4,25.83,24.7,24.3,15.2,15.1.
上記化合物CM19e(12.8g、20mmol)、市販脱水テトラヒドロフラン(1000ml)、市販脱水エタノール(200ml)、48重量%濃度のHBr水溶液(60ml)を順次加えた。この時、溶液は薄黄色透明を呈していた。氷浴により内温を1℃まで冷却してから、亜硝酸-tert-ブチル(tert-BuONO、含量90%、4.82g、42mmol)を市販脱水テトラヒドロフラン(252ml)に希釈した溶液を30分間かけて滴下することにより加えた。氷浴のまま、更に30分間攪拌した後に、50重量%ジ亜燐酸水溶液(H3PO2、200ml)を1時間かけて滴下することにより加えた。滴下終了後、氷浴のまま、5時間攪拌した後に、室温にて一晩静置した。得られた反応溶液にイオン交換水を加え、酢酸エチルで3回抽出し、得られた有機層を合一してから、5重量%炭酸水素ナトリウム水溶液、イオン交換水、15重量%食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、不溶物をろ別し、ろ液を濃縮することにより、10.8gの黒色アメ状物を得た。
上記と同様の操作により、化合物CM19e(9.58g)から得た7.98gの黒色アメ状物と合一した後に、中圧シリカゲルクロマトグラフィー(φ6x30cm、ヘキサン)で精製し、目的物が含まれるフラクションを合一し、活性白土(31g)を加え、1時間室温にて攪拌した後に、固体をろ別し、ろ液を濃縮することにより、目的物である化合物CM19f(10.72g)を黄色油状物として得た。収率68.6%。得られた化合物CM19fの分析条件1で測定したHPLC面積百分率値は95.1%を示した。
1H-NMR(300MHz,CDCl3)δ(ppm)=7.49(s,2H),7.20(d,2H),7.08(d,2H),2.68(t,4H),1.89(m,4H),1.67(m,4H),1.40(m,4H),1.04(m,12H),0.95(t,6H),0.76(t,6H),0.66(m,4H).
13C-NMR(75MHz,CDCl3)δ(ppm)=148.8,141.56,141.52,127.4,122.9,119.7,54.6,40.7,36.2,34.3,31.9,30.2,24.2,23.0,22.9,14.40,14.36.
上記化合物CM19f(10.1g、23mmol)、クロロホルム(345ml)を加え、アルゴンガスをバブリングした後に、遮光下、室温にて、N-ブロモスクシンイミド(12.31g、69mmol)を加え、室温にて、10分間攪拌した。氷浴にて、0℃に冷却した後に、トリフルオロ酢酸(85ml)を30分間かけて滴下することにより加えた。滴下終了後、氷浴を外し、室温にて1.5時間攪拌した。別の容器に移した後、メタノール(1700ml)を加え、室温にて1時間攪拌した。析出した固体をろ取、メタノールで洗浄、減圧乾燥することにより、11.1gの白色固体を得た。中圧シリカゲルクロマトグラフィー(φ5x30cm、ヘキサン)で精製し、目的物が含まれるフラクションを合一し、濃縮後、ヘキサン(232ml)で溶解させ、活性白土(23g)を加え、1時間室温にて攪拌した。その後、固体をろ別し、ろ液を濃縮し、その後酢酸エチルから再結晶、ろ取、減圧乾燥することにより、目的物である化合物CM19g(10.85g)を薄黄色結晶として得た。収率74.8%。得られた化合物CM19gの分析条件1で測定したHPLC面積百分率値は99.52%を示した。
1H-NMR(300MHz,CDCl3)δ(ppm)=7.49(s,2H),7.43(s,2H),2.79(t,4H),1.86(m,4H),1.67(m,4H),1.45(m,4H),1.05(m,12H),0.99(t,6H),0.78(t,6H),0.63(m,4H).
13C-NMR(75MHz,CDCl3)δ(ppm)=149.1,148.2,130.5,120.9,83.5,54.8,40.3,36.3,36.2,31.8,31.0,25.3,24.0,23.3,22.9,14.5,14.4.
TLC-MS:[M]+=602.
上記化合物CM19g(10.6g、17.5mmol)に、ビスピナコラートジボロン(13.3g、52.5mmol)、市販脱水1,4-ジオキサン(140ml)を加え、45℃に加熱し溶解させた後に、アルゴンガスで30分間バブリングした。酢酸カリウム(10.3g、105mmol)を加え、再度アルゴンガスでバブリングした後に、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]パラジウム(II)ジクロリド ジクロロメタン付加物(PdCl2(dppf)・CH2Cl2、400mg、0.49mmol)、1,1’-ビス(ジフェニルホスフィノ)フェロセン(dppf、290mg、0.53mmol)を加え、オイルバスにより加熱しながら、還流下で20時間攪拌した。トルエン(100ml)で希釈し、室温まで冷却した。その後、セライトを敷いたろ過器に通液することにより、不溶物を除去し、更にセライトをトルエン(100mlで2回)洗浄し、ろ液を合一した後に、濃縮した。次に、ヘキサン(280ml)、活性炭(21g)を加え、加熱還流下で1時間攪拌した後に、室温まで冷却し、セライトを敷いたろ過器に通液することにより、不溶物を除去した。更にセライトをトルエン(100mlで2回)洗浄し、ろ液を合一した後に、濃縮するという操作を二回繰り返した後に、エタノール(250ml)を加え、加熱還流下で1時間攪拌した。その後、室温まで冷却し、固体をろ取、エタノール(30mlで2回)洗浄し、減圧乾燥することにより、11.3gの白色固体を得た。ヘキサン(45ml)に加熱完溶させ、エタノール(270g)を滴下することにより加え、室温まで冷却した後に、析出した固体をろ取、少量のメタノールで洗浄し、減圧乾燥するという操作を2回繰り返すことにより、目的物である単量体CM19(9.88g)を白色結晶として得た。収率69.8%。得られた単量体CM19の分析条件1で測定したHPLC面積百分率値は99.96%を示した。
1H-NMR(300MHz,CDCl3)δ(ppm)=7.66(s,2H),7.49(s,2H),2.95(t,4H),1.93(m,4H),1.59(m,4H),1.41(m,28H),1.08(m,12H),0.95(t,6H),0.76(t,6H),0.64(m,4H).
13C-NMR(75MHz,CDCl3)δ(ppm)=149.1,148.2,130.5,120.9,83.5,54.8,40.3,36.3,36.2,31.8,31.0,25.3,24.0,23.3,22.9,14.5,14.4.
TLC-MS:[M]+=698.
単量体CM20は以下の第一工程~第七工程に従い合成した。
アルゴンガス雰囲気下、還流冷却装置を取り付けた反応容器内で、3-ブロモ-4-クロロトルエン(上記化合物CM20a、30.82g、150mmol)、2,5-ジメチルフェニルボロン酸(上記化合物CM20b、24.75g、165mmol)、無水炭酸カリウム(124.39g、900mmol)、酢酸パラジウム(II)(0.67g、6mmol)、トリシクロヘキシルホスフィン(1.68g、12mmol)、ジメチルアセトアミド(市販脱水品、600ml)、ピバル酸(15.32g、150mmol)の混合物を150℃に設定した油浴で加熱しながら10時間攪拌した。トルエン(500ml)で希釈した後に、イオン交換水を用いて3回洗浄分液を行った。続いて、得られた油層に活性白土和光純薬工業株式会社製、60g)を加えて2時間攪拌した後に、不溶物をセライトおよびシリカゲルパッドに通液することにより除去する操作2度繰り返した。得られた溶液から溶媒を減圧濃縮により除去した後に、再結晶精製(クロロホルムおよびエタノールの混合溶媒)を行い、析出した結晶をろ取、減圧乾燥することにより、目的物であるCM20c(35.5g)を薄黄色~白色を呈する固体として得た。収率51%。得られた化合物CM20cの分析条件1で測定したHPLC面積百分率値は99.3%(UV254nm)を示した。
アルゴンガス雰囲気下、上記化合物CM20c(14.58g、75mmol)に、トリフルオロ酢酸(11.15mL、150mmol)、クロロホルム(市販脱水品、400mL)を加え、均一とした混合物を、氷浴を用いて5℃以下に冷却した。そこへ、混合物の温度が5℃を超えることが無いように注意しながら、臭素(8.46mL、165mmol)をゆっくりと加えた後、氷浴を外し、室温にて4時間攪拌し反応溶液を得た。得られた反応溶液に、亜ジチオン酸ナトリウムの飽和水溶液を加え、余剰の臭素を分解した後に、減圧下で濃縮することにより溶媒を除去し、固体を得た。得られた固体にテトラヒドロフラン(1L)を加え、70℃にて1時間攪拌した後に、室温まで冷却し、水を加え、析出している無機塩を溶解させた後に、再度減圧下で濃縮することによりテトラヒドロフランを除去したところ、固液混合物を得た。析出している固体をろ取し、トルエンを加え溶解させた後に、シリカゲルショートカラムに通液し、得られたトルエン溶液を濃縮することにより固体を得た。得られた固体をトルエンおよびイソプロパノールの混合溶媒を用いて再結晶精製する操作を繰り返すことにより、目的物である化合物CM20d(22.3g)を得た(収率84%)。得られた化合物CM20dは、分析条件1で測定したHPLC面積百分率値(UV254nm)で>99.9%を示した。
1H-NMR(300MHz,CDCl3):δ(ppm)=7.67(s,2H),7.58(s,2H),3.79(s,2H),2.48(s,6H).
上記化合物CM20d(12.22g、34.70mmol)にピリジン(34.70mL)を加えた後に、室温にて、ベンジルトリメチルアンモニウムヒドロキシド(40%ピリジン溶液)(下記に従い調製、0.87mL)を加え、反応容器内に大気を通気させながら、40℃のオイルバスで加熱し、16時間攪拌した。その後、再度、ベンジルトリメチルアンモニウムヒドロキシド(40%ピリジン溶液)(下記に従い調製、0.87mL)を加え、60℃のオイルバスで加熱し、8時間攪拌することにより、反応溶液を得た。
得られた反応溶液にイオン交換水と酢酸を加え、酸性条件とした後に、室温にて1時間攪拌し、析出した黄色固体をろ取し、水でよく洗浄した。得られた固体は、乾燥した後に、テトラヒドロフランおよびメタノールの混合溶媒(テトラヒドロフラン/メタノール=4/30(v/v))に分散させ、80℃のオイルバスで加熱しながら1.5時間攪拌し、室温まで冷却した後に析出している固体をろ取、減圧乾燥することにより、目的物である化合物CM20e(11.87g)を黄色固体として得た。収率93.5%。得られた化合物CM20eは分析条件1で測定したHPLC面積百分率値(UV254nm)で96.7%を示した。
1H-NMR(300MHz,CDCl3):δ(ppm)=7.77(s,2H),7.36(s,2H),2.47(s,6H).
分析条件1で測定したLC-MS(APPI(posi)):364[M]+.
ベンジルトリメチルアンモニウムヒドロキシド(40%メタノール溶液)(通称TRITON B、関東化学株式会社製、50mL)に対してピリジン(50mL)を加えた後にエバポレーターにて25mL以下まで濃縮し、再度、ピリジンを加えて50mLになるように希釈することにより調製した。この操作により得られた溶液を、ベンジルトリメチルアンモニウムヒドロキシド(40%ピリジン溶液)と呼ぶ。
アルゴンガス雰囲気下、3,5-ジ-n-ヘキシル-1-ブロモベンゼン(上記化合物CM20f,13.82g、42.5mmol)をテトラヒドロフラン(市販脱水品、324mL)に溶解させた溶液を攪拌しながら、-78℃のドライアイス-メタノールバスを用いて冷却した。その後、上記溶液の温度が-75℃以下を保持するように、n-ブチルリチウムのヘキサン溶液(1.63mol/L、25.7mL)をゆっくりと滴下することにより加え、更に1時間攪拌した。次いで、上記化合物CM20e(11.87g、32.4mmol)を、上記溶液の温度が-75℃以下を保持するように、少量ずつ加え、更に、2時間攪拌した後に、メタノール(約20mL)をゆっくりと滴下により加えてから、ドライアイス-メタノールバスを外し、室温までゆっくりと昇温した。得られた反応溶液は、溶媒を減圧濃縮により留去した後に、ヘキサンを加え、イオン交換水で洗浄することにより、油層を得た。得られた油層を無水硫酸ナトリウムで乾燥し、不溶分をろ別した後に、減圧濃縮により溶媒を留去し、更に、再結晶精製(ヘキサン)を行い、ろ取、減圧乾燥することにより、目的物である化合物CM20g(9.12g)を白色固体として得た。収率45%。得られた化合物CM20gは分析条件1で測定したHPLC面積百分率値(UV254nm)で97.9%を示した。
分析条件1で測定したLC-MS(ESI(posi)):610[M]+.
アルゴンガス雰囲気下、上記化合物CM20g(9.12g、14.89mmol)、トリエチルシラン(4.53mL、59.6mmol)、ヘキサン(39mL)を混合し、70℃のオイルバスで加熱を開始した後に、トリフルオロ酢酸(4.5mL、59.6mmol)を滴下により加え、更に3時間加熱下で攪拌することにより反応溶液を得た。
得られた反応溶液を室温まで冷却した後に、10重量%濃度のリン酸カリウム水溶液を加え、更に、有機層を飽和食塩水により洗浄し、無水硫酸ナトリウムにより乾燥し、不溶物をろ別した後に、減圧濃縮および減圧乾燥により溶媒を留去し、化合物CM20hを含む油状物(8.9g)を得た。得られた油状物は、これ以上の精製は行わずに次工程に用いた。
分析条件1で測定したLC-MS(ESI(posi)):594[M]+.
アルゴンガス雰囲気下、上記化合物CM20hを含む油状物(8.9g)にN,N-ジメチルホルムアミド(74mL)を加え均一な溶液を得た。アルゴンガスバブリングを15分間行い、次いで、氷浴を用いて5℃以下に冷却した後に、水酸化カリウム(2.76g、49.1mmol)をイオン交換水(2.4mL)に溶解させた後にアルゴンガスをバブリングすることによりアルゴンガス雰囲気に置換した水酸化カリウム水溶液を加えた。続いて、ヨウ化メチル(6.34g、44.7mmol)を滴下により加え、0~5℃にて4時間攪拌した。氷浴を外し、イオン交換水を加え、更にヘキサンにより抽出することにより、油層を得た。得られた油層を無水硫酸ナトリウムを用いて乾燥し、不溶物をろ別、溶媒を留去した後に、中圧シリカゲルカラムクロマトグラフィー(ヘキサン)により精製した。目的物CM20iを含むフラクションを統合し、濃縮した後に、再結晶精製(ヘキサンおよびイソプロパノールの混合溶媒)を行い、得られた結晶をろ取、減圧乾燥することにより、目的物である化合物CM20i(7.10g)を白色固体として得た。収率77%。得られた化合物CM20iは分析条件1で測定したHPLC面積百分率値(UV254nm)で>99.9%を示した。
1H-NMR(300MHz,CDCl3):δ(ppm)=7.57(s,2H),7.35(s,2H),6.83(s,1H),6.71(s,2H),2.50-2.44(m,10H),1.79(s,3H),1.54-1.45(m,4H),1.34-1.17(m,12H),0.84(t,6H).
分析条件1で測定したLC-MS(ESI(posi)):608[M]+.
アルゴンガス雰囲気下、ビスピナコールジボロン(9.10g、35.9mmol)、酢酸カリウム(7.04g、71.7mmol)、1,4-ジオキサン(36mL)、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウム(II)のジクロロメタン錯体(1:1)(Pd(dppf)Cl2・CH2Cl2、CAS番号95464-05-4、Sigma-Aldrich Co. LLC製、0.293g、0.36mmol)の混合物を115℃のオイルバスで加熱しながら攪拌した中へ、別途調製した上記化合物CM20i(7.13g、11.9mmol)を1,4-ジオキサン(36mL)に溶解した溶液を2時間かけて滴下することにより加えた後に、同温度で約18時間攪拌することにより、反応溶液を得た。得られた反応溶液を室温まで冷却した後に、トルエンを加えて希釈し、続いて、セライトおよびシリカゲルパッドに通液することにより不溶物と極性成分を除去した。得られた溶液を無水硫酸ナトリウムで乾燥し、不溶物をろ別した後に、減圧濃縮により溶媒を留去してから、トルエンを加え均一な溶液を得た。得られた溶液に活性炭を加え、70℃のオイルバスで加熱しながら30分間攪拌し、室温まで冷却した後に不溶物をセライトろ過により除去する操作を行い、得られた溶液を濃縮した後に再結晶精製(トルエンおよびアセトニトリルの混合溶媒)を行った。得られた結晶をろ取、減圧乾燥することにより、目的物である単量体CM20(6.94g)を白色固体として得た。収率82%。得られた単量体CM20は分析条件1で測定したHPLC面積百分率値(UV254nm)で>99.9%を示した。
1H-NMR(300MHz,CDCl3):δ(ppm)=7.64(s,2H),7.55(s,2H),6.81(s,2H),6.77(s,1H),2.62(s,6H),2.48-2.42(m,4H),1.85(s,3H),1.55-1.45(m,4H),1.31(s,24H),1.31-1.17(m,12H),0.83(t,6H).
分析条件1で測定したLC-MS(ESI(posi)):704[M]+.
単量体CM21は以下の第一工程~第三工程に従い合成した。
窒素ガス雰囲気下、テトラヒドロフラン(市販脱水品、600mL)、マグネシウム(168.2g、6.92mol)、ヨウ素(0.7g、2.7mmol)の混合物を45℃に加熱した後に、n-ヘキシルブロミド(224g、1.36mol)を滴下により加え、テトラヒドロフラン(市販脱水品、880mL)を加え、更に、n-ヘキシルブロミド(895g、5.42mol)をテトラヒドロフラン(市販脱水品、1.82L)で希釈した溶液を3時間かけて滴下により加え、続いて50℃で2時間撹拌した。[1,3-ビス(ジフェニルホスフィノ)プロパン]ニッケル(II)ジクロリド(NiCl2(dppp),29.4g、54.2mmol)を加え、次いで、4-クロロトルエン(上記化合物CM21a,343.5g、2.71mol)を45℃で滴下により加えた。続いて加熱により65℃まで昇温し、同温度で5時間撹拌することにより反応溶液を得た。得られた反応溶液にテトラヒドロフラン(市販脱水品、5.5L)を加えた。続いて室温まで冷却した後に、該溶液を、7℃まで冷却した2mol/L濃度の塩酸(3.4L)へ滴下により加えた。続いてトルエンを用いて有機層を抽出し、得られた有機層を水で洗浄した後に、減圧下で溶媒を留去することにより、目的物である化合物CM21b(425g)を微黄色油状物として得た。収率82%。化合物CM21bはこれ以上の精製をせずに次工程に用いた。
分析条件1で測定したLC-MS(APPI、positive):[M+]176.
窒素ガス雰囲気下、上記化合物CM21b(424.4g、純分393.3g、2.23mmol)、ジクロロメタン(1.7L)、ヨウ素(56.6g、223mmol)を仕込み、3℃まで冷却して臭素(908.7g、5.69mol)を2時間かけて滴下により加えた。5℃で1時間撹拌したのち、10重量%濃度の水酸化ナトリウム水溶液を滴下した。イオン交換水およびジクロロメタンを流入して抽出し、得られた有機層を減圧濃縮した。トルエン、活性炭を加え、室温で1時間撹拌したのち濾過した。得られた有機層を減圧下で濃縮することにより、目的物である化合物CM21c(745.7g)を黄色油状物として得た。収率87%。化合物CM21cはこれ以上の精製をせずに次工程に用いた。
LC-MS(APPI、positive):[M+]332.
アルゴンガス雰囲気下、化合物CM21c(744.5g、純分644.9g、1.93mol)、1,2-ジメトキシエタン(6.2L)、酢酸カリウム(1136g、11.6mol)、ビス(ピナコラート)ジボロン(別名4,4,4’,4’,5,5,5’,5’-オクタメチル-2,2’-ビ-1,3,2-ジオキサボロラン、1.12kg、4.44mol)を仕込み、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]パラジウム(II)ジクロリド ジクロロメタン付加物(PdCl2(dppf)・CH2Cl2、47.3g、57.9mmol)を加えて加熱し、85℃で24時間撹拌した。室温でトルエンと水を加えて抽出し、得られた有機層を減圧下で溶媒留去した。得られた濃縮残渣にトルエンと活性炭を加え、室温で1時間撹拌したのち濾過した。得られた有機層を塩化ナトリウム水溶液および水で洗浄した後、減圧濃縮し、メタノールを加え、析出した固体をろ取し、乾燥させた。得られた固体にイソプロパノールを加え、加熱溶解したのちに冷却し、析出した固体をろ取し、乾燥させることにより、単量体CM21(709g)を白色粉末固体として得た。収率86%。得られた単量体CM21の分析条件1で測定したHPLC面積百分率値は>99.5%を示した。
1H-NMR(300MHz,CDCl3)δ(ppm)=7.53(s,2H),2.81(t,2H),2.48(s,3H),1.55-1.29(m,32H),0.88(t,3H).
LC-MS(APPI、positive):[M+]428.
単量体CM25は以下の第一工程~第二工程に従い合成した。
窒素ガス雰囲気下、N,N’-ジフェニルベンジジン(CM25a,65.16g,194mmol)、1-ブロモ-4-n-ブチル-2,5-ジメチルベンゼン(140.13g,582mmol)、トルエン(750mL)に[トリス(ジベンジリデンアセトン)]ジパラジウム(6.99g,4.3mmol)、トリ-tert-ブチルホスフィンテトラフルオロボレート(t-Bu3P・BF4H、2.53g,8.7mmol)、ナトリウム-tert-ブトキシド(74.44g, 775mmol)を加えて、130℃で24時間反応させた。次いで、0℃で水(500mL)を加えて、静置後、分液した油層を水層から分離し、水層のトルエン抽出分と合一した。該油層に硫酸マグネシウムを加えてろ過し、ろ液を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をトルエンに溶解させ、シリカゲルを敷き詰めた濾過器にヘキサン/トルエン混合溶媒で通して、得られたろ液を減圧濃縮し、油状物を得た。該油状物をヘキサン/トルエン混合溶媒に溶解させ、フロリジールを敷き詰めた濾過器にヘキサン/トルエン混合溶媒で通して、得られたろ液を減圧濃縮し、油状物を得た。該油状物をヘキサンに溶解させ、フロリジールを敷き詰めた濾過器にヘキサンで通して、得られたろ液を減圧乾燥し、油状物を得た。該油状物にイソプロパノールを加え、得られた油状物にメタノールを加えて、固体を濾過した。該固体をメタノール/トルエンで再結晶し、ジクロロメタン/メタノールを加えて、目的とする化合物CM25bを95.79g得た。得られた化合物CM25bの分析条件2で測定したHPLC面積百分率値は99.21%を示した。
窒素ガス雰囲気下、化合物CM25b(95.79g,146mmol)をジクロロメタン(1420mL)に溶解させた溶液に、0℃で、N-ブロモスクシンイミド(52.16g,293mmol)を加えて、室温まで昇温させて一晩攪拌した。
反応溶液をジクロロメタン(650mL)で希釈し、10wt%炭酸ナトリウム水溶液および水で分液し、油層に硫酸マグネシウムを加えてろ過し、ろ液を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をジクロロメタンに溶解させ、シリカゲルを敷き詰めた濾過器に通して、得られたろ液を減圧乾燥し、油状物を得た。該油状物にイソプロパノールを加えて得られた固体を濾過した。該固体をトルエン/イソプロパノール、トルエン/酢酸ブチル、トルエン/アセトニトリルで再結晶した。得られた固体をジクロロメタンに溶解させ、ろ紙で濾過し、イソプロパノールを加えて固体を得た。
該固体をアセトニトリルで1時間加熱還流し、室温まで冷却後に得られた固体を濾過し、目的とする単量体CM25を83.77g得た。得られた単量体CM25の分析条件2で測定したHPLC面積百分率値は99.69%を示した。
1H-NMR(600MHz,CDCl3)δ(ppm)=7.39(d,J=8.4Hz,4H),7.27(d,J=8.8Hz,4H),6.99(d,J=8.1Hz,4H),6.93(s,4H),6.86(d,J=8.7Hz,4H),2.58(t,J=7.74Hz,4H),2.00(s,12H),1.62(m,4H),1.39(m,4H),0.96(t,J=7.38Hz,6H).
単量体CM26は以下の第一工程~第二工程に従い合成した。
窒素ガス雰囲気下、N,N’-ジフェニルベンジジン(CM26a,59.51g,228.6mmol)、2,6-ジメチル-4-ヘキシルブロモベンゼン(129.24g,480mmol)、トルエン(1500mL)に[トリス(ジベンジリデンアセトン)]ジパラジウム、トリ-tert-ブチルホスフィンテトラフルオロボレート(t-Bu3P・BF4H)、ナトリウム-tert-ブトキシドを加えて、16時間加熱還流させた。次いで、0℃で1時間攪拌後、静置し、分液した油層を水層から分離し、水層のトルエン抽出分と合一し、該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をトルエンに溶解させ、フロリジール/シリカゲル/アルミナを敷き詰めた濾過器にヘキサン/トルエン混合溶媒で通して、得られたろ液を減圧濃縮し、油状物を得た。該油状物にヘキサンを加えて攪拌し、固体を濾過し、目的とする化合物CM26bを得た。得られた化合物CM26bの分析条件2で測定したHPLC面積百分率値は99.3%を示した。
窒素ガス雰囲気下、化合物CM26b(50g, 78.5mmol)をジクロロメタン(1000mL)に溶解させた溶液に、-30℃で、N-ブロモスクシンイミド(28.65g,161.0mmol)を加えて、室温まで昇温させて一晩攪拌した。
反応溶液を水洗し、油層に硫酸マグネシウムを加えてろ過し、ろ液を減圧濃縮して溶媒を除去し、固体を得た。該固体をヘキサンで洗浄し、加熱したトルエン/イソプロパノールで6回再結晶し、白色固体として、目的とする単量体CM26を得た。得られた単量体CM26の分析条件2で測定したHPLC面積百分率値は99.62%を示した。
1H-NMR(400MHz,CDCl3)δ(ppm)=7.22(d,J=9Hz,4H),6.90(s,4H),6.84(s,4H),6.75(d,J=9Hz,4H),2.54(m,4H),1.99(s,12H),1.33(m,12H),0.99(t,6H).
単量体CM27は以下の第一工程~第二工程に従い合成した。
窒素ガス雰囲気下、CM27a(26g,39.6mmol)をテトラヒドロフラン(500mL)に溶解させ、0℃~5℃に冷却した。カリウム-tert-ブトキシド (17.75g,158.5mmol)を0℃~5℃の範囲でゆっくりと加えて、反応溶液を室温まで昇温させ、24時間攪拌した。反応溶液に氷水(500mL)を加え、静置後分液した油層を水層から分離し、水層の酢酸エチル抽出分と合一した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をヘキサンを用いてシリカゲルカラムクロマトグラフィーで分離精製し、目的とする化合物CM27bを14.5g得た。得られた化合物CM27bの分析条件2(検出波長240nm)で測定したHPLC面積百分率値は99.68%を示した。
1H-NMR(400MHz,CDCl3)δ(ppm)=7.37(s,2H),5.81-5.87(m,2H),4.96-5.07(m,4H),2.67(t,J=7.64Hz,4H),2.09-2.15(m,4H),1.57-1.64(m,4H),1.47-1.53(m,4H).
13C-NMR(100MHz,CDCl3)δ(ppm)=141.19,138.67,133.79,123.08,114.60,35.36,33.54,29.28,28.56.
窒素ガス雰囲気下、化合物CM27b(11.66g,29.1mmol)をテトラヒドロフラン(220mL)に溶解させ、-75℃に冷却し、sec-ブチルリチウム(94mL,131.1mmol)を内温-65℃以下で2時間かけて滴下し、内温-65℃以下で5.5時間攪拌した。この反応溶液にビス(ピナコレート)ジボロン(30mL,145.7mmol)を-70℃で30分かけて滴下した。反応溶液を室温に昇温し、一晩攪拌した。次に反応溶液を0℃に冷却し、2mol/L塩酸のジエチルエーテル溶液を反応溶液が透明になるまで滴下した。生成物はジエチルエーテルで抽出し、減圧濃縮して溶媒を除去し固体を得た。該固体にアセトニトリル(150mL)を加えて室温で2時間攪拌し、得られた固体をろ過した。該固体に再度、アセトニトリル(100mL)を加えて室温で2時間攪拌し、さらにアセトニトリルで2回再結晶し、目的とする単量体CM27を3.60g得た。得られた単量体CM27の分析条件2で測定したHPLC面積百分率値は99.90%を示した。
再結晶時のアセトニトリルのろ液を合一し、アセトニトリルで2回再結晶し、CM27を1.4g(分析条件2で測定したHPLC面積百分率値は99.76%)を得た。
1H-NMR(500MHz,THF)δ(ppm)=7.53(s,2H),5.83(m,2H),4.99(d,2H),4.90(d,2H),2.82(t,4H),2.07(m,4H),1.56(m,4H),1.45(m,4H),1.33(s,24H).
単量体CM28は、以下の第一工程~第五工程に従い合成した。
撹拌器を備えた2000mLの四つ口フラスコに、CM28a(35.31g)とメタノール(1100mL)を入れ、フラスコ内の気体をアルゴンで置換した。そこに、1,3-アセトンジカルボン酸ジメチル(34.65g)をゆっくり加えた後、ナトリウムメトキシド(5mol/L メタノール溶液)(67.62g)をゆっくり滴下した。その後、室温で2時間保温させた後、還流温度まで昇温し、6時間保温しながら撹拌した。反応液を室温まで冷却し、35%塩酸(37.41g)を加えた。水およびトルエンを入れ、室温で撹拌後、水層を分離し、有機層を飽和塩化ナトリウム水溶液で洗浄した。得られた有機層に硫酸ナトリウムを入れ、ろ過後、濃縮し、CM28bを60.1g得た。
その後、撹拌器を備えた1000mLの四つ口フラスコに、CM28b(60.10g)、酢酸(450mL)、イオン交換水(60mL)を入れ、フラスコ内の気体をアルゴンで置換した。その後、還流温度まで昇温し、5時間保温しながら撹拌した。反応液を室温まで冷却し、水およびトルエンを入れ、水層を分離し、有機層を飽和塩化ナトリウム水溶液で洗浄した。得られた有機層に硫酸ナトリウムを入れ、ろ過後、濃縮し、粗生成物を得た。粗生成物をシリカゲルカラム(展開溶媒 ヘキサン/酢酸エチル混合液)を用いて精製し、白色固体としてCM28cを19.5g得た。
LC-MS(APCI、positive):[M+H]+457.
撹拌器を備えた1Lの四つ口フラスコにヘプチルトリフェニルホスホニウムブロミド(82.29g)入れ、フラスコ内の気体をアルゴンで置換した。このフラスコ内に、トルエン(520mL)を入れ、5℃以下に冷却した。カリウムtert-ブトキシド(20.92g)を入れ、室温まで昇温した後、室温で3時間保温撹拌した。反応液中に生じた赤色スラリーに、CM28c(18.0g)を入れ、室温で6時間30分保温撹拌した。反応液に酢酸(7.2g)を入れて15分撹拌した後、水およびヘキサンを入れ、室温で撹拌後、水層を分離し、有機層を飽和塩化ナトリウム水溶液で洗浄した。得られた有機層に硫酸ナトリウムを入れ、ろ過後、濃縮することで粗生成物が得られた。この粗生成物をシリカゲルカラム(展開溶媒 ヘキサン)にて精製し、得られたヘキサン溶液に活性炭を加え、50℃で1時間、保温しながら撹拌した。室温まで冷却し、セライトをプレコートした濾過器により濾過し、残渣をヘキサンで複数回洗浄し、複数回分のろ液を合わせて濃縮し、無色透明液体としてCM28dを18.8g得た。
LC-MS(APCI、positive):[M+H]+621.
撹拌器を備えた1Lの四つ口フラスコにCM28d(18.6g)を入れた後、酢酸エチル(165mL)とエタノール(150mL)を入れ、フラスコ内の気体を窒素で置換した。5重量%Pd/C(約50重量%含水品)(3.7g)を入れた後、フラスコ内の気体を水素で置換し、水素雰囲気下、50℃で49時間保温しながら撹拌した。室温まで冷却し、セライトをプレコートした濾過器により濾過し、残渣を酢酸エチルで複数回洗浄し、複数回分のろ液を合わせて濃縮することにより、粗生成物を得た。この粗生成物をシリカゲルカラム(展開溶媒 ヘキサン)にて精製し、得られたヘキサン溶液に活性炭を加え、50℃で1時間、保温しながら撹拌した。室温まで冷却し、セライトをプレコートした濾過器により濾過し、残渣をヘキサンで複数回洗浄し、複数回分のろ液を合わせて濃縮し、無色透明液体としてCM28eを17.6g得た。
LC-MS(APCI、positive):[M+H]+625.
撹拌器を備えた500mLの四つ口フラスコにCM28e(17.0g)を入れ、フラスコ内の気体をアルゴンで置換した。このフラスコ内に、クロロホルム(230mL)、トリフルオロ酢酸(22mL)を入れ、5℃以下に冷却した。四つ口フラスコ全体を遮光し、臭素(8.9g)とクロロホルム(45mL)の混合物を、15分かけてフラスコ内に滴下し、3時間保温しながら撹拌した。反応液に10重量%亜硫酸ナトリウム水溶液入れ、室温まで昇温した。反応液から水層を分離し、油層を水、5重量%炭酸水素ナトリウム水溶液、水の順に洗浄した。得られた油層を硫酸マグネシウムで乾燥させ、濾過し、ろ液を濃縮することにより、粗生成物を得た。この粗生成物をシリカゲルカラム(展開溶媒 ヘキサン)にて精製し、得られたヘキサン溶液に活性炭を加え、50℃で1時間、保温しながら撹拌した。室温まで冷却し、セライトをプレコートした濾過器により濾過し、残渣をヘキサンで複数回洗浄し、複数回分のろ液を合わせて濃縮した。この操作を2回繰り返すことにより、無色透明液体としてCM28fを19.3g得た。
LC-MS(APCI、positive):[M+H]+781.
1H-NMR(CDCl3、300MHz)δ(ppm):0.91(12H、m)、1.18~1.43(36H、m)、1.56~1.77(8H、m)、2.15~2.33(4H、m)、2.70~2.75(4H、m)、7.39~7.53(2H、m)、7.61~7.66(2H、m).
撹拌器を備えた1000mLの四つ口フラスコに脱水テトラヒドロフラン(210mL)を入れ、-70℃以下に冷却した。n-ブチルリチウム(1.6M ヘキサン溶液)(70mL)を30分以上かけてゆっくり滴下し、30分保温しながら撹拌した。そこにCM28f(18.2g)と脱水テトラヒドロフラン(210mL)の混合物を30分以上かけてゆっくり滴下し、1時間保温しながら撹拌した。2-イソプロポキシ-4、4、5、5-テトラメチル-1、3、2-ジオキサボロラン(32mL)を10分以上かけて滴下し、室温まで昇温した後、室温で4時間保温撹拌した。トルエンを入れ、反応液を希釈後、水を加え、室温で撹拌後、水層を分離し、有機層を飽和塩化ナトリウム水溶液で洗浄した。得られた有機層に硫酸ナトリウムを入れ、ろ過後、濃縮し、粗生成物を得た。粗生成物をシリカゲルカラム(展開溶媒 ヘキサン/酢酸エチル混合液)で処理した後、トルエンとアセトニトリルの混合液で、再結晶を行うことにより、白色固体として単量体CM28を14.6g得た。
LC-MS(APCI、positive):[M+H]+877.
1H-NMR(CD2Cl2、300MHz)δ(ppm):0.94(12H、m)、1.27~1.44(60H、m)、1.64~1.74(8H、m)、2.25~2.45(4H、m)、2.94(4H、m)、7.67~7.82(4H、m).
燐光発光材料1は、WO2002/066552に記載の合成法に従い合成した。
燐光発光材料2は、WO2006/062226に記載の合成法に従い合成した。
単量体MM1は以下の第一工程~第三工程に従い合成した。
窒素ガス雰囲気下、化合物MM1a(100g, 370mmol)、トルエン(2L)からなる溶液にナトリウム-tert-ブトキシド (92g, 960mmol)を加えて、窒素ガスをバブリングした後、[トリス(ジベンジリデンアセトン)]ジパラジウム(10g,11mmol)、トリ-tert-ブチルホスフィンテトラフルオロボレート(t-Bu3P・BF4H、6.4g,22mmol)を加えて窒素ガスをバブリングした。そこにアニリン(38g,410mmolを加えて、還流下、110℃で16時間攪拌した。次いで、室温にて、酢酸エチル(200mL)で反応溶液を希釈してセライトを敷き詰めた濾過器に該溶液を通した。得られた濾液を水洗し、静置後分液した水層を油層から除去した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をシリカゲルカラムクロマトグラフィーにより精製し、目的とする化合物MM1bを90g得た。得られた化合物MM1bの分析条件2(検出波長272nm)で測定したHPLC面積百分率値は99.27%を示した。
1H-NMR(400MHz,DMSO-d6)δ(ppm)=7.16(s,1H),7.01-7.05(m,2H),6.91(s,2H),6.52-6.55(m,1H),6.35(d,J=7.7Hz,2H),2.48-2.50(m,2H),2.08(s,6H),1.52-1.59(m,2H),1.23-1.31(m,6H),0.85(t,J=6.7Hz,3H).
13C-NMR(100MHz,DMSO-d6)δ(ppm)=147.32,139.33,136.10,135.56,128.96,128.16,116.28,112.25,34.81,31.18,31.06,28.51,22.11,18.10,13.99.
分析条件2で測定したLC-MS:[M]+=281.
窒素ガス雰囲気下、化合物CM22(84.5g,160mmol)、トルエン(1.7L)からなる溶液に、化合物MM1b(94.5g,336mmol)、ナトリウム-tert-ブトキシド(76.8g,800mmol)を加えて、窒素ガスでバブリングした後、2-(2’-ジ-tert-ブチルホスフィン)-ビフェニルパラジウム(II)酢酸(2.22g,4.8mmol)を加えて、還流下、120℃で16時間攪拌した。次いで、室温にて、酢酸エチル(50mL)で反応溶液を希釈してセライトを敷き詰めた濾過器に該溶液を通した。得られた濾液を水洗し、静置後分液した水層を油層から除去した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をシリカゲルカラムクロマトグラフィーにより精製し、目的とする化合物MM1cを69.5g得た。得られた化合物MM1cの分析条件2(検出波長379nm)で測定したHPLC面積百分率値は99.35%を示した。
1H-NMR(300MHz,CDCl3)δ(ppm)=7.45-7.68(m,2H),7.05-7.19(m,6H),6.87-6.97(m,7H),6.80-6.85(m,7H),6.45-6.66(m,4H),3.06-3.14(m,8H),2.52-2.70(m,4H),1.97(s,12H),1.59-1.66(m,4H),1.30-1.43(m,12H),0.85-0.94(m,6H).
分析条件2で測定したLC-MS:[M]+=928.
窒素ガス雰囲気下、化合物MM1c(29.6g,31.9mmol)、クロロホルム(300mL)からなる溶液に、N―ブロモスクシンイミド(11.3g,63.8mmol)のジメチルホルムアミド(100mL)溶液を-20℃で2時間30分かけて滴下し、3時間攪拌した。その後、室温で16時間攪拌し、該反応溶液を氷水(500mL)にゆっくりと滴下した。該油層を水洗し、静置後分液した水層を油層から除去し、該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をシリカゲルカラムクロマトグラフィーにより繰り返し精製し(7回)、目的とする単量体MM1を26g得た。得られた単量体MM1の分析条件2(検出波長350nm)で測定したHPLC面積百分率値は99.68%を示した。
1H-NMR(400MHz,DMSO-d6)δ(ppm)=7.57(d,J=8.2Hz,2H),7.27-7.30(m,4H),6.97(s,4H),6.81-6.85(m,6H),6.65-6.69(m,6H),6.51(s,2H),3.03-3.05(m,4H),2.96-2.99(m,4H),2.51-2.53(m,4H),1.85(s,12H),1.52-1.63(m,4H),1.18-1.30(m,12H),0.82(t,J=7.0Hz,6H).
分析条件2で測定したLC-MS:[M]+=1084.
(1)化合物MM2cの合成は、下記の第一工程~第二工程に従い合成した。
窒素ガス雰囲気下、化合物MM2c-1(40g, 219mmol)をテトラヒドロフラン(400mL)に溶解させた溶液に、sec-ブチルリチウム(1.4mol/L,187mL,262mmol)を-75℃で滴下した。得られた溶液を2時間攪拌し、1-ブロモ5-クロロペンテン(36.9g, 198.7mmol)をテトラヒドロフラン(300mL)に溶解させた溶液に-75℃で滴下した。溶液を室温まで昇温させ、一晩攪拌し、2mol/L塩酸(50mL)でクエンチした。静置後分液した油層を水層から分離し、水層のジクロロメタン抽出分と合一した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。得られた油状物(MM2c-2,84g)の分析条件2で測定したHPLC面積百分率値は90%を示した。
窒素ガス雰囲気下、化合物MM2c-2(77g, 370mmol)をアセトン(300mL)に溶解させた溶液に、ヨウ化ナトリウム(166g,1100mmol)をアセトン(800mL)に溶解させた溶液を室温で滴下した。得られた溶液を一晩加熱還流した。反応溶液を減圧濃縮して溶媒を除去し、得られた固形分をジクロロメタンに溶解させ、水洗し、分液後の油層を減圧濃縮して溶媒を除去し、茶色の油状物(105g)を得た。油状物の70gをヘキサン:ジクロロメタン=4:1のカラムクロマトグラフィーで精製し、黄色オイル(MM2c,67g,分析条件2で測定したHPLC面積百分率値は84%)を得た。
1H-NMR(600MHz,CDCl3)δ(ppm)=7.01(d,1H),6.97(d,1H),6.89(s,1H),3.19(t,2H),3.15(m,4H),2.59(t,2H),1.87(q,2H),1.63(q,2H),1.45(q,2H).
窒素ガス雰囲気下、リチウムジイソプロピルアミド(2mol/LのTHF溶液,117mL,233mmol)を、1,4-ジブロモベンゼン(MM2a,25g,106mmol)、テトラヒドロフラン(250mL)、トリメチルシリルクロライド(25.3g,233mmol)からなる溶液に-75℃で滴下した。得られたオレンジ色溶液を室温まで昇温させ、一晩攪拌した。その後、反応溶液を-10℃に冷却し、15%硫酸水溶液(50mL)を加えた。静置後、分液した油層を水層から分離し、水層のエーテル抽出分と合一した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物を冷却したメタノール(500mLを3回)で洗浄し、濾過して得られた固体を乾燥させた。目的とする化合物MM2bを16.5g得た。得られた化合物MM2bの分析条件2で測定したHPLC面積百分率値は100%を示した。
1H-NMR(600MHz,CDCl3)δ(ppm)=7.51(s,2H),0.38(s,18H).
窒素ガス雰囲気下、化合物MM2b(31.5g, 83mmol)をテトラヒドロフラン(320mL)に溶解させた溶液に、sec-ブチルリチウム(1.4mol/L,71mL,99.4mmol)を-75℃で滴下した。溶液は-75℃で2時間攪拌し、化合物MM2c(26.1g,87mmol)をTHF(400mL)に溶解させた溶液を-75℃で滴下した。反応溶液を室温まで昇温させ、一晩攪拌した。反応溶液の内温を-5℃に保って、塩酸(2mol/L,50mL)を加えた。静置後分液した油層を水層から分離し、水層のジクロロメタン抽出分と合一した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物をフラッシュクロマトグラフィー(ヘキサン100%)により精製し、目的とする化合物MM2dを27.5g得た。得られた化合物MM2dの分析条件2で合成したHPLC面積百分率値は92.2%を示した。
1H-NMR(600MHz,CDCl3)δ(ppm)=7.58(s,1H),7.25(s,1H),7.03(d,1H),6.98(d,1H),6.92(s,1H),3.17(s,4H),2.64(m,4H),1.68(m,2H),1.62(m,2H),1.49(m,2H),0.41(s,9H),0.34(s,9H).
窒素ガス雰囲気下、化合物MM2d(27.5g, 58mmol)を用いて、化合物MM2dの合成と同様の手順で反応を実施した。反応混合物は、室温でアセトニトリルを加えて白色固体として、目的とする化合物MM2eを25.2g得た。得られた化合物MM2eの分析条件2で測定したHPLC面積百分率値は96.2%を示した。
1H-NMR(600MHz,CDCl3)δ(ppm)=7.25(s,2H),7.02(d,2H),6.96(d,2H),6.90(s,2H),3.14(s,8H),2.65(m,4H),2.60(t,4H),1.64(m,8H),1.47(m,4H),0.31(s,18H).
窒素ガス雰囲気下、N-ブロモスクシンイミド(15.6g, 87.6mmol)をジメチルホルムアミド(50mL)に溶解させ、窒素ガスでバブリングした溶液を、化合物MM2e(24.2g,42.7mmol)を酢酸、クロロホルム、ジメチルホルムアミドの混合溶媒[1.8:10:4](v/wt)に溶解させた溶液に室温で滴下した。一晩、室温で攪拌し、水(250mL)を加えた。静置後分液した油層を水層から分離し、水層のジクロロメタン抽出分と合一した。該油層を減圧濃縮して溶媒を除去し、油状物を得た。該油状物は、室温でアセトニトリルを加えて白色固体として、目的とする単量体MM2を22g得た。得られた単量体MM2の分析条件2で測定したHPLC面積百分率値は98.8%を示した。
1H-NMR(600MHz,CDCl3)δ(ppm)=7.33(s,2H),7.03(d,2H),6.95(d,2H),6.87(s,2H),3.14(s,8H),2.64(m,4H),2.59(t,4H),1.63(m,8H),1.42(m,4H).
単量体MM3の合成は、下記に従い合成した。
窒素ガス雰囲気下、単量体MM2(17.1g,29.4mmol)、ビス(ピナコレート)ジボロン(16.4g,64.6mmol)をトルエン(170mL)に溶解させ、窒素ガスでバブリングした溶液に、ジクロロメタン1,1’-ビス(ジペニルフォスフィノ)フェロセン]ジクロロパラジウム(II)(Pd(dppf)Cl2、0.36g,0.44mmol)、1,1’-ビス(ジフェニルホスフィノ)フェロセン(dppf,0.25g,0.44mmol)を加え、反応溶液を窒素ガスでバブリングした。酢酸カリウム(17.3g,176.2mmol)を加え、110℃で一晩反応させた。反応溶液は、シリカゲル/フロリジール/セライトを敷き詰めた濾過器に通し、トルエンに溶解させ、反応混合物を得た(22g,分析条件2で測定したHPLC面積百分率値は97.4%)。反応混合物を室温でアセトニトリルを加えて攪拌濾過し、再結晶は、アセトニトリル、トルエン/アセトニトリル、酢酸ブチル/アセトニトリルで実施し、目的とする単量体MM3を22g得た。得られた単量体MM3の分析条件2で測定したHPLC面積百分率値は98.8%を示した。
1H-NMR(600MHz,CDCl3)δ(ppm)=7.54(s,2H),7.01(d,2H),6.95(d,2H),6.89(s,2H),3.14(s,8H),2.83(m,4H),2.57(t,4H),1.63(m,4H),1.57(m,4H),1.42(m,4H),1.33(s,24H).
窒素雰囲気下、単量体CM1(1.7273g)、単量体CM10(2.6836g)、単量体CM11(0.2231g)および溶媒となるトルエン(73ml)の混合物を約80℃に加熱した後に、酢酸パラジウム(0.77mg)、トリス(2-メトキシフェニル)ホスフィン(4.90mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(12.3g)を加え、還流下で約4時間攪拌した。次に、フェニルボロン酸(85.6mg)、酢酸パラジウム(0.72mg)、トリス(2-メトキシフェニル)ホスフィン(4.89mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(12.3g)を加え、更に還流下で約19.5時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(0.98g)をイオン交換水(20ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。その後、有機層を3.6重量%塩酸で2回、2.5重量%アンモニア水溶液で2回、イオン交換水で5回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物1(2.907g)を得た。高分子化合物1のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=1.9×104、Mw=9.9×104であった。
窒素雰囲気下、単量体CM2(1.4280g)、単量体CM10(2.5001g)、単量体CM11(0.2079g)および溶媒となるトルエン(63ml)の混合物を約80℃に加熱した後に、酢酸パラジウム(1.11mg)、トリス(2-メトキシフェニル)ホスフィン(6.91mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(11.5g)を加え、還流下で約5.5時間攪拌した。次に、フェニルボロン酸(39.7mg)、酢酸パラジウム(1.16mg)、トリス(2-メトキシフェニル)ホスフィン(6.94mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(11.5g)を加え、更に還流下で約17時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.40g)をイオン交換水(28ml)に溶解した溶液を加え、85℃に加熱しながら2.5時間攪拌した。その後、有機層をイオン交換水で2回、3重量%酢酸で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物2(2.601g)を得た。高分子化合物2のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=2.7×104、Mw=2.7×105であった。
窒素雰囲気下、単量体CM1(0.8534g)、単量体CM3(0.7051g)、単量体CM10(2.6361g)、単量体CM11(0.2192g)および溶媒となるトルエン(67ml)の混合物を約80℃に加熱した後に、酢酸パラジウム(1.20mg)、トリス(2-メトキシフェニル)ホスフィン(7.21mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(12.1g)を加え、還流下で約6時間攪拌した。次に、フェニルボロン酸(42.0mg)、酢酸パラジウム(1.17mg)、トリス(2-メトキシフェニル)ホスフィン(7.33mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(12.1g)を加え、更に還流下で約16時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.53g)をイオン交換水(30ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3重量%酢酸で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物3(2.689g)を得た。高分子化合物3のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=2.3×104、Mw=2.0×105であった。
窒素雰囲気下、単量体CM1(1.0465g)、単量体CM4(0.4817g)、単量体CM10(2.7100g)、単量体CM11(0.2253g)および溶媒となるトルエン(83ml)の混合物を約80℃に加熱した後に、ビストリフェニルホスフィンパラジウムジクロリド(2.43mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(12.1g)を加え、還流下で約30時間攪拌した。次に、フェニルボロン酸(42.5mg)、ビストリフェニルホスフィンパラジウムジクロリド(2.45mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(12.1g)を加え、更に還流下で約17.5時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.94g)をイオン交換水(39ml)に溶解した溶液を加え、85℃に加熱しながら3時間攪拌した。その後、有機層をイオン交換水で2回、3重量%酢酸で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物4(2.62g)を得た。高分子化合物4のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=1.3×104、Mw=5.2×104であった。
窒素雰囲気下、単量体CM1(1.4951g)、単量体CM12(3.4363g)、単量体CM11(0.1931g)および溶媒となるトルエン(33ml)の混合物を約80℃に加熱した後に、ビストリフェニルホスフィンパラジウムジクロリド(2.17mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(10.4g)を加え、還流下で約48時間攪拌した。次に、フェニルボロン酸(0.3671g)、ビストリフェニルホスフィンパラジウムジクロリド(2.12mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(10.4g)を加え、更に還流下で約23時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.83g)をイオン交換水(33ml)に溶解した溶液を加え、85℃に加熱しながら2.5時間攪拌した。その後、有機層をイオン交換水で2回、3重量%酢酸で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物5(3.349g)を得た。高分子化合物5のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=2.6×104、Mw=4.4×104であった。
窒素雰囲気下、単量体CM1(3.7376g)、単量体CM10(5.8070g)、および単量体CM22(0.5943g)と溶媒となるトルエン(182ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(6.62mg)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(26.0g)を加え、還流下で約7.5時間攪拌した。次に、フェニルボロン酸(91.4mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(6.62mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(26.0g)を加え、更に還流下で約15時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(4.17g)をイオン交換水(84ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物9(6.34g)を得た。高分子化合物9のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=5.5×104、Mw=1.4×105であった。
窒素雰囲気下、単量体CM1(0.9967g)、単量体CM10(1.4574g)、単量体CM22(0.1057g)、および単量体CM23(0.0920g)と溶媒となるトルエン(47ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.76mg)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.5g)を加え、還流下で約23時間攪拌した。次に、フェニルボロン酸(26.6mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.76mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.5g)を加え、更に還流下で約23時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.11g)をイオン交換水(22ml)に溶解した溶液を加え、85℃に加熱しながら3時間攪拌した。有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物10(1.46g)を得た。高分子化合物10のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=1.7×104、Mw=1.0×105であった。
窒素雰囲気下、単量体CM21(0.8564g)、単量体CM10(1.5485g)、および単量体CM22(0.1585g)と溶媒となるトルエン(47ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.78mg)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.8g)を加え、還流下で約7.5時間攪拌した。次に、フェニルボロン酸(26.5mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.77mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.8g)を加え、更に還流下で約15時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.11g)をイオン交換水(22ml)に溶解した溶液を加え、85℃に加熱しながら1.5時間攪拌した。有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物11(1.30g)を得た。高分子化合物11のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=8.4×104、Mw=1.6×104であった。
窒素雰囲気下、単量体CM1(0.9967g)、単量体CM13(0.8189g)、単量体CM9(0.2578g)、単量体CM23(0.0920g)、および単量体CM24(0.1337g)と溶媒となるトルエン(44ml)の混合物を約80℃に加熱した後に、酢酸パラジウム(0.3mg)、トリス(2-メトキシフェニル)ホスフィン(3.0mg)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(8.8g)を加え、還流下で約18時間攪拌した。次に、フェニルボロン酸(0.25g)、酢酸パラジウム(0.5mg)、およびトリス(2-メトキシフェニル)ホスフィン(3.0mg)、を加え、還流下で約4時間攪拌した。更に、ブロモベンゼン(0.45g)を加え、還流下で約4時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.1g)をイオン交換水(22ml)に溶解した溶液を加え、85℃に加熱しながら6時間攪拌した。有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物12(1.030g)を得た。高分子化合物12のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=8.8×104、Mw=3.0×105であった。
窒素雰囲気下、単量体CM19(1.4924g)、単量体CM10(1.6539g)、および単量体CM11(0.1375g)と溶媒となるトルエン(57ml)の混合物を約80℃に加熱した後に、酢酸パラジウム(0.80mg)、トリス(2-メトキシフェニル)ホスフィン(4.57mg)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.7g)を加え、還流下で約6時間攪拌した。次に、フェニルボロン酸(26.3mg)、酢酸パラジウム(0.82mg)、トリス(2-メトキシフェニル)ホスフィン(4.58mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.7g)を加え、更に還流下で約14.5時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.21g)をイオン交換水(24ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。有機層をイオン交換水で2回、3重量%酢酸で2回、イオン交換水で3回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物13(2.148g)を得た。高分子化合物13のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=4.2×104、Mw=2.9×105であった。
窒素雰囲気下、単量体CM20(1.4093g)、単量体CM10(1.4574g)、単量体CM22(0.1057g)、および単量体CM23(0.0920g)と溶媒となるトルエン(58ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(3.53mg)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(6.29g)を加え、還流下で約4.5時間攪拌した。次に、フェニルボロン酸(24.4mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.76mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(6.29g)を加え、更に還流下で約18時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.11g)をイオン交換水(27ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。
有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物14(1.77g)を得た。高分子化合物14のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=4.7×104、Mw=2.8×105であった。
窒素雰囲気下、単量体CM1(0.9967g)、単量体CM18(1.7587g)、単量体CM22(0.1057g)、および単量体CM23(0.0920g)と溶媒となるトルエン(55ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.77mg)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.5g)を加え、還流下で約6時間攪拌した。
次に、フェニルボロン酸(26.1mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.76mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.5g)を加え、更に還流下で約15時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.11g)をイオン交換水(26ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物15(1.57g)を得た。高分子化合物15のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=3.5×104、Mw=2.8×105であった。
窒素雰囲気下、単量体CM20(1.4093g)、単量体CM18(1.7587g)、単量体CM22(0.1057g)、および単量体CM23(0.0920g)と溶媒となるトルエン(45ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.81mg)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.3g)を加え、還流下で約9時間攪拌した。次に、フェニルボロン酸(24.6mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.74mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(7.4g)を加え、更に還流下で約13.5時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.11g)をイオン交換水(31ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物16(1.92g)を得た。高分子化合物16のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=6.4×104、Mw=2.9×105であった。
窒素雰囲気下、単量体CM1(1.0148g)、単量体CM18(1.7588g)、単量体CM22(0.2114g)および溶媒となるトルエン(55ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(7.09mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(6.9g)を加え、還流下で約9時間攪拌した。次に、フェニルボロン酸(24.5mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.76mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(6.9g)を加え、更に還流下で約12時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.11g)をイオン交換水(26ml)に溶解した溶液を加え、80℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物17(1.64g)を得た。高分子化合物17のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=4.0×104、Mw=2.5×105であった。
窒素雰囲気下、単量体CM20(1.0661g)、単量体CM10(1.1614g)、単量体CM22(0.1189g)および溶媒となるトルエン(50ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.33mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(5.4g)を加え、還流下で約7時間攪拌した。次に、フェニルボロン酸(18.4mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.32mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(5.4g)を加え、更に還流下で約12時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(0.90g)をイオン交換水(22ml)に溶解した溶液を加え、80℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物18(1.16g)を得た。高分子化合物18のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=4.4×104、Mw=3.2×105であった。
窒素雰囲気下、単量体CM1(1.4953g)、単量体CM25(1.9554g)、単量体CM22(0.1585g)、単量体CM23(0.1381g)および溶媒となるトルエン(73ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(2.60mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(10g)を加え、還流下で約4時間攪拌した。次に、フェニルボロン酸(36.6mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(2.60mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(10g)を加え、更に還流下で約14時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.67g)をイオン交換水(33ml)に溶解した溶液を加え、80℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物19(1.74g)を得た。高分子化合物19のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=5.0×104、Mw=2.3×105であった。
窒素雰囲気下、単量体CM1(1.4801g)、単量体CM26(1.9074g)、単量体CM22(0.1585g)、単量体CM23(0.1381g)および溶媒となるトルエン(73ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(2.60mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(10g)を加え、還流下で約4時間攪拌した。次に、フェニルボロン酸(36.6mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(2.60mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(10g)を加え、更に還流下で約14時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.67g)をイオン交換水(33ml)に溶解した溶液を加え、80℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物20(1.92g)を得た。高分子化合物20のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=4.9×104、Mw=7.4×105であった。
窒素雰囲気下、単量体CM1(1.7941g)、単量体CM27(0.2215g)、単量体MM3(0.3036g)、単量体CM18(4.9464g)および溶媒となるトルエン(110ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(4.00mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(15g)を加え、還流下で約4時間攪拌した。次に、フェニルボロン酸(54.9mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(4.00mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(15g)を加え、更に還流下で約14時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(2.50g)をイオン交換水(50ml)に溶解した溶液を加え、80℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物21(3.32g)を得た。高分子化合物21のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=3.3×104、Mw=2.6×105であった。
窒素雰囲気下、単量体CM1(1.4951g)、単量体CM18(2.6381g)、単量体MM1(0.3261g)、単量体CM23(0.1381g)および溶媒となるトルエン(73ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(2.60mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(10g)を加え、還流下で約4時間攪拌した。次に、フェニルボロン酸(36.6mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(2.60mg)、および20重量%テトラエチルアンモニウムヒドロキシド水溶液(10g)を加え、更に還流下で約14時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.67g)をイオン交換水(33ml)に溶解した溶液を加え、80℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物22(2.87g)を得た。高分子化合物22のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=3.8×104、Mw=3.5×105であった。
窒素雰囲気下、単量体CM28(1.1061g)、単量体CM18(1.0992g)、単量体CM22(0.0660g)、単量体CM23(0.0575g)および溶媒となるトルエン(47ml)の混合物を約80℃に加熱した後に、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.15mg)、および20重量%テトラブチルアンモニウムヒドロキシド水溶液(7.6g)を加え、還流下で約6時間攪拌した。次に、フェニルボロン酸(15.3mg)、ジクロロビス(トリス(2-メトキシフェニル)ホスフィン)パラジウム(1.06mg)、および20重量%テトラブチルアンモニウムヒドロキシド水溶液(7.6g)を加え、更に還流下で約16時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(0.71g)をイオン交換水(22ml)に溶解した溶液を加え、80℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3.0重量%酢酸水溶液で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物23(1.58g)を得た。高分子化合物23のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=4.8×104、Mw=2.9×105であった。
窒素雰囲気下、単量体CM5(3.3249g)、単量体CM10(3.4842g)、単量体CM11(0.2897g)および溶媒となるトルエン(100ml)の混合物を約80℃に加熱した後に、酢酸パラジウム(1.5mg)、トリス(2-メトキシフェニル)ホスフィン(9.5mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(15.2g)を加え、還流下で約22時間攪拌した。次に、フェニルボロン酸ピナコールエステル(0.9268g)、酢酸パラジウム(1.4mg)およびトリス(2-メトキシフェニル)ホスフィン(9.4mg)を加え、更に還流下で約4時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(2.74g)をイオン交換水(27ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3重量%酢酸で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物6(4.254g)を得た。高分子化合物6のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=4.3×104、Mw=1.3×105であった。
窒素雰囲気下、単量体CM5(1.4773g)、単量体CM12(2.2909g)、単量体CM11(0.1287g)、メチルトリオクチルアンモニウムクロライド(商品名:Aliquat(登録商標)336、アルドリッチ社製)(0.277g)および溶媒となるトルエン(40ml)の混合物を約80℃に加熱した後に、酢酸パラジウム(0.9mg)、トリス(2-メトキシフェニル)ホスフィン(3.5mg)および17.5重量%炭酸ナトリウム水溶液(10.9g)を加え、還流下で約29時間攪拌した。次に、フェニルボロン酸ピナコールエステル(0.21g)を加え、更に還流下で約18時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(1.22g)をイオン交換水(12ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3重量%酢酸で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物7(2.32g)を得た。高分子化合物7のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=4.5×104、Mw=1.1×105であった。
窒素雰囲気下、単量体CM6(21.218g)、単量体CM8(5.487g)、単量体CM13(16.377g)、単量体CM11(2.575g)、メチルトリオクチルアンモニウムクロライド(商品名:Aliquat(登録商標)336、アルドリッチ社製)(5.17g)および溶媒となるトルエン(400ml)の混合物を約80℃に加熱した後に、ビストリフェニルホスフィンパラジウムジクロリド(56.2mg)および17.5重量%炭酸ナトリウム水溶液(109g)を加え、還流下で約6時間攪拌した。
次に、フェニルボロン酸(0.49g)を加え、更に還流下で約2時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(24.3g)をイオン交換水(240ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。その後、有機層をイオン交換水で2回、3重量%酢酸で2回、イオン交換水で2回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物8(26.23g)を得た。高分子化合物8のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=6.4×104、Mw=1.9×105であった。
窒素雰囲気下、単量体CM1(0.8222g)、単量体CM9(0.8507g)、単量体CM17(0.2097g)および溶媒となるトルエン(37ml)の混合物を約80℃に加熱した後に、酢酸パラジウム(0.41mg)、トリス(2-メトキシフェニル)ホスフィン(2.30mg)および20重量%テトラエチルアンモニウムヒドロキシド水溶液(5.8g)を加え、還流下で約4時間攪拌した。次に、フェニルボロン酸(40.6mg)を加え、更に還流下で約2時間攪拌した。その後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物(0.46g)をイオン交換水(9ml)に溶解した溶液を加え、85℃に加熱しながら2時間攪拌した。その後、有機層を3.6重量%塩酸で2回、2.5重量%アンモニア水溶液で2回、イオン交換水で5回、順次洗浄した。有機層をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、予めトルエンを通液したシリカゲルカラムおよびアルミナカラムに通液した。得られた溶液をメタノールに滴下し高分子化合物を沈殿させ、ろ取、乾燥させることにより、高分子化合物L1(1.110g)を得た。高分子化合物L1のポリスチレン換算の数平均分子量(Mn)および重量平均分子量(Mw)は、Mn=8.7×104、Mw=2.3×105であった。
不活性ガス雰囲気下、単量体CM8(9.0g、16.4mmol)、単量体CM15(1.3g、1.8mmol)、単量体CM7(13.4g、18.0mmol)、テトラエチルアンモニウムヒドロキシド(43.0g、58.3mmol)、酢酸パラジウム(8mg、0.04mmol)、トリ(2-メトキシフェニル)ホスフィン(0.05g、0.1mmol)およびトルエン(200mL)を混合し、90℃で8時間加熱攪拌した。次いで、フェニルボロン酸(0.22g、1.8mmol)を添加し、得られた混合物を14時間撹拌した。放冷後、水層を除去し、ジエチルジチオカルバミン酸ナトリウム水溶液を添加し撹拌した後、水層を除去し、有機層を水、3%酢酸水で洗浄した。有機層をメタノールに注いで高分子化合物を沈殿させた後、濾取した高分子化合物を再度トルエンに溶解させ、シリカゲルおよびアルミナのカラムに通液した。高分子化合物を含む溶出トルエン溶液を回収し、回収した前記トルエン溶液をメタノールに注いで高分子化合物を沈殿させた。沈殿した高分子化合物を50℃で真空乾燥し、高分子化合物L2(12.5g)を得た。高分子化合物L2のポリスチレン換算の重量平均分子量は3.1×105であり、分子量分布指数(Mw/Mn)は2.9であった。
スパッタ法により45nmの厚みでITO膜を付けたガラス基板に、ポリチオフェンスルホン酸のエチレングリコールモノブチルエーテル/水=3/2(体積比)の混合溶液(シグマアルドリッチ社、商品名:Plexcore OC 1200)を用いてスピンコートにより65nmの厚さで成膜し、ホットプレート上で170℃で15分間乾燥させた。次に、高分子化合物1をキシレンに溶解させ0.8重量%のキシレン溶液を調製した。
このキシレン溶液を用いて、上記のPlexcore OC 1200が成膜されたガラス基板にスピンコートすることにより、厚さ20nmの高分子化合物1の有機薄膜を成膜した。これを窒素ガス雰囲気中において、ホットプレート上で180℃、60分間加熱することで、不溶化有機薄膜とした。
実施例D1における高分子化合物1に代えて高分子化合物2を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D1と同様にして発光素子D2を作製した。得られた発光素子D2に電圧を印加したところ、この素子から625nmにピークを有するEL発光が得られ、最大の外部量子効率は13.7%であった。結果を表3に示す。
実施例D1における高分子化合物1に代えて高分子化合物3を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D1と同様にして発光素子D3を作製した。得られた発光素子D3に電圧を印加したところ、この素子から625nmにピークを有するEL発光が得られ、最大の外部量子効率は13.7%であった。結果を表3に示す。
実施例D1における高分子化合物1に代えて高分子化合物13を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D1と同様にして発光素子D4を作製した。得られた発光素子D4に電圧を印加したところ、この素子から625nmにピークを有するEL発光が得られ、最大の外部量子効率は13.6%であった。結果を表3に示す。
実施例D1における高分子化合物1に代えて高分子化合物7を用い、0.8重量%のキシレン溶液を調製したこと以外は、実施例D1と同様にして発光素子CD1を作製した。得られた発光素子CD1に電圧を印加したところ、この素子から625nmにピークを有するEL発光が得られ、最大の外部量子効率は9.0%であった。結果を表3に示す。
スパッタ法により45nmの厚みでITO膜を付けたガラス基板に、ポリチオフェンスルホン酸のエチレングリコールモノブチルエーテル/水=3/2(体積比)の混合溶液(シグマアルドリッチ社、商品名:Plexcore OC 1200)を用いてスピンコートにより65nmの厚さで成膜し、ホットプレート上で170℃で15分間乾燥させた。次に、高分子化合物1をキシレンに溶解させ0.8重量%のキシレン溶液を調製した。
このキシレン溶液を用いて、上記のPlexcore OC 1200が成膜されたガラス基板にスピンコートすることにより、厚さ20nmの高分子化合物1の有機薄膜を成膜した。これを窒素ガス雰囲気中において、ホットプレート上で180℃、60分間加熱することで、不溶化有機薄膜とした。
実施例D5における高分子化合物1に代えて高分子化合物2を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D6を作製した。得られた発光素子D6に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は22.8%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物3を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D7を作製した。得られた発光素子D7に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は23.6%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物4を用い、1.0重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D8を作製した。得られた発光素子D8に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は23.2%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物5を用い、0.9重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D9を作製した。得られた発光素子D9に電圧を印加したところ、この素子から515nmにピークを有するEL発光が得られ、最大の外部量子効率は23.4%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物9を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D10を作製した。得られた発光素子D10に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は21.9%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物10を用い、0.8重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D11を作製した。得られた発光素子D11に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は22.2%であった。また、初期輝度12,000cd/m2で定電流駆動した際に、輝度が初期輝度の60%となるまでの時間(LT60)は、129.6時間であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物11を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D12を作製した。得られた発光素子D12に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は20.9%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物12を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D13を作製した。得られた発光素子D13に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は23.8%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物13を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D14を作製した。得られた発光素子D14に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は22.2%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物14を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D15を作製した。得られた発光素子D15に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は19.2%であった。また、初期輝度12,000cd/m2で定電流駆動した際に、輝度が初期輝度の60%となるまでの時間(LT60)は、154.6時間であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物15を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D16を作製した。得られた発光素子D16に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は21.4%であった。また、初期輝度12,000cd/m2で定電流駆動した際に、輝度が初期輝度の60%となるまでの時間(LT60)は、218.0時間であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物16を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D17を作製した。得られた発光素子D17に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は18.7%であった。また、初期輝度12,000cd/m2で定電流駆動した際に、輝度が初期輝度の60%となるまでの時間(LT60)は、192.9時間であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物17を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D18を作製した。得られた発光素子D18に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は21.4%であった。また、初期輝度12,000cd/m2で定電流駆動した際に、輝度が初期輝度の60%となるまでの時間(LT60)は、167.0時間であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物18を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D19を作製した。得られた発光素子D19に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は18.7%であった。また、初期輝度12,000cd/m2で定電流駆動した際に、輝度が初期輝度の60%となるまでの時間(LT60)は、112.0時間であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物19を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D20を作製した。得られた発光素子D20に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は22.3%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物20を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D21を作製した。得られた発光素子D21に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は23.4%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物21を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D22を作製した。得られた発光素子D22に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は19.9%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物22を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D23を作製した。得られた発光素子D23に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は19.6%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物23を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子D24を作製した。得られた発光素子D24に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は20.2%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物6を用い、0.8重量%のキシレンを調製したこと以外は、実施例D5と同様にして発光素子CD2を作製した。得られた発光素子CD2に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は13.1%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物7を用い、0.8重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子CD3を作製した。得られた発光素子CD3に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は9.3%であった。結果を表4に示す。
実施例D5における高分子化合物1に代えて高分子化合物8を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D5と同様にして発光素子CD4を作製した。得られた発光素子CD4に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は11.0%であった。結果を表4に示す。
スパッタ法により45nmの厚みでITO膜を付けたガラス基板に、ポリチオフェンスルホン酸のエチレングリコールモノブチルエーテル/水=3/2(体積比)の混合溶液(シグマアルドリッチ社、商品名:Plexcore OC 1200)を用いてスピンコートにより65nmの厚さで成膜し、ホットプレート上で170℃で15分間乾燥させた。次に、高分子化合物1をキシレンに溶解させ0.8重量%のキシレン溶液を調製した。
このキシレン溶液を用いて、上記のPlexcore OC 1200が成膜されたガラス基板にスピンコートすることにより、厚さ20nmの高分子化合物1の有機薄膜を成膜した。これを窒素ガス雰囲気中において、ホットプレート上で180℃、60分間加熱することで、不溶化有機薄膜とした。
実施例D25における高分子化合物1に代えて高分子化合物2を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D26を作製した。得られた発光素子D26に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.6%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物3を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D27を作製した。得られた発光素子D27に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.6%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物4を用い、1.0重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D28を作製した。得られた発光素子D28に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.8%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物9を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D29を作製した。得られた発光素子D29に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.0%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物10を用い、0.8重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D30を作製した。得られた発光素子D30に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.0%であった。また、初期輝度4,000cd/m2で定電流駆動した際に、輝度が初期輝度の50%となるまでの時間(LT50)は、78.0時間であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物11を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D31を作製した。得られた発光素子D31に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.0%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物12を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D32を作製した。得られた発光素子D32に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.0%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物13を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D33を作製した。得られた発光素子D33に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.8%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物14を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D34を作製した。得られた発光素子D34に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.8%であった。また、初期輝度4,000cd/m2で定電流駆動した際に、輝度が初期輝度の50%となるまでの時間(LT50)は、82.5時間であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物15を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D35を作製した。得られた発光素子D35に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.9%であった。また、初期輝度4,000cd/m2で定電流駆動した際に、輝度が初期輝度の50%となるまでの時間(LT50)は、80.5時間であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物16を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D36を作製した。得られた発光素子D36に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は5.7%であった。また、初期輝度4,000cd/m2で定電流駆動した際に、輝度が初期輝度の50%となるまでの時間(LT50)は、104.1時間であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物17を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D37を作製した。得られた発光素子D37に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.8%であった。また、初期輝度4,000cd/m2で定電流駆動した際に、輝度が初期輝度の50%となるまでの時間(LT50)は、53.9時間であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物18を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D38を作製した。得られた発光素子D38に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.5%であった。また、初期輝度4,000cd/m2で定電流駆動した際に、輝度が初期輝度の50%となるまでの時間(LT50)は、56.0時間であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物19を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D39を作製した。得られた発光素子D39に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.9%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物20を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D40を作製した。得られた発光素子D40に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は7.1%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物21を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D41を作製した。得られた発光素子D41に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.1%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物22を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D42を作製した。得られた発光素子D42に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は5.9%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物23を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子D43を作製した。得られた発光素子D43に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は6.4%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物6を用い、0.8重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子CD5を作製した。得られた発光素子CD5に電圧を印加したところ、この素子から470nmにピークを有するEL発光が得られ、最大の外部量子効率は5.3%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物7を用い、0.8重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子CD6を作製した。得られた発光素子CD6に電圧を印加したところ、この素子から460nmにピークを有するEL発光が得られ、最大の外部量子効率は5.2%であった。結果を表5に示す。
実施例D25における高分子化合物1に代えて高分子化合物8を用い、0.7重量%のキシレン溶液を調製したこと以外は、実施例D25と同様にして発光素子CD7を作製した。得られた発光素子CD7に電圧を印加したところ、この素子から475nmにピークを有するEL発光が得られ、最大の外部量子効率は5.2%であった。結果を表5に示す。
スパッタ法により45nmの厚みでITO膜を付けたガラス基板に、ポリチオフェンスルホン酸のエチレングリコールモノブチルエーテル/水=3/2(体積比)の混合溶液(シグマアルドリッチ社、商品名:Plexcore OC 1200)を用いてスピンコートにより65nmの厚さで成膜し、ホットプレート上で170℃で15分間乾燥させた。高分子化合物14/燐光発光材料1=70重量%/30重量%となるように混合した組成物をキシレンに溶解させ、2.0重量%のキシレン溶液を調製した。このキシレン溶液を用いて、上記のPlexcore OC 1200が成膜されたガラス基板にスピンコートすることにより、厚さ80nmの有機薄膜を成膜した。これを窒素ガス雰囲気中において、ホットプレート上で180℃、60分間加熱することで、不溶化有機薄膜とした。 その後、陰極として、フッ化ナトリウムを約4nm、次いでアルミニウムを約80nm蒸着して、発光素子D42を作製した。なお、真空度が、1×10-4Pa以下に到達した後に金属の蒸着を開始した。
実施例D42における高分子化合物14に代えて高分子化合物6を用い、高分子化合物6/燐光発光材料1=70重量%/30重量%となるように混合した2.0重量%のキシレン溶液を調製したこと以外は、実施例D42と同様にして発光素子CD8を作製した。得られた発光素子CD8に電圧を印加したところ、この素子から520nmにピークを有するEL発光が得られ、最大の外部量子効率は0.1cd/Aであった。
Claims (23)
- 下記式(1)で表される構成単位と、
下記式(2)で表される構成単位と、
下記式(3)で表される構成単位および/または下記式(4’)で表される構成単位と、
を含む高分子化合物。
[式中、
Ar1およびAr3は、それぞれ独立に、非置換若しくは置換のアリーレン基または非置換若しくは置換の2価の複素環基を表す。
Ar2およびAr4は、それぞれ独立に、非置換若しくは置換のアリーレン基、非置換若しくは置換の2価の複素環基、または、アリーレン基および2価の複素環基から選ばれる同一若しくは異なる2以上の基が連結した2価の基(該基は、置換基を有していてもよい。)を表す。
Ar5、Ar6およびAr7は、それぞれ独立に、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を表す。
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6およびAr7はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接結合されていてもよく、-O-、-S-、-C(=O)-、-C(=O)-O-、-N(Ra)-、-C(=O)-N(Ra)-または-C(Ra)2-を介して結合されていてもよい。Raは、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、ハロゲン原子または非置換若しくは置換の1価の複素環基を表す。Raが2個存在する場合、それらは同一であっても異なっていてもよい。
xおよびyは、それぞれ独立に、0または1を表し、x+y=1である。]
[式中、
Ar8は、(2+p)価の芳香族炭化水素基、または(2+p)価の複素環基を表す。
R1は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、オキシカルボニル基、1価の複素環基、複素環オキシ基、複素環チオ基、イミン残基、アミド化合物残基、酸イミド残基、カルボキシル基、ヒドロキシル基、ニトロ基またはシアノ基を表す。R1が複数個存在する場合、それらは同一であっても異なっていてもよい。なお、少なくとも1つのR1は、前記芳香族炭化水素基または前記複素環基における他の構成単位と結合を形成する炭素原子の隣の炭素原子に直接結合する水素原子を置換する。
pは1以上の整数を表す。]
[式中、
naは0~3の整数を示し、nbは0~12の整数を示し、nAは0または1を示し、nは1~4の整数を示す。
Ar10は非置換若しくは置換の(2+n)価の芳香族炭化水素基または非置換若しくは置換の(2+n)価の複素環基を示す。
LaおよびLbは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Laが複数存在する場合、それらは同一でも異なっていてもよい。Lbが複数存在する場合、それらは同一でも異なっていてもよい。
LAは、酸素原子または硫黄原子を示す。LAが複数存在する場合、それらは同一でも異なっていてもよい。
Q1は1価の架橋性基を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
なお、式(3)で示される構成単位は、式(2)で示される構成単位とは異なる。]
[式中、
cは0または1を示し、dは0~4の整数を示し、
Ar20およびAr40は、それぞれ独立に、非置換若しくは置換のアリーレン基または非置換若しくは置換の2価の複素環基を示し、Ar30’は、非置換若しくは置換の(2+d)価の芳香族炭化水素基、非置換若しくは置換の(2+d)価の複素環基、または、芳香環および複素環から選ばれる同一若しくは異なる2以上の環が連結した構造を有する(2+d)価の基(当該(2+d)価の基は置換基を有していてもよい)を示す。
Q2’、Q3’およびQ4’は、1価の架橋性基、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を示すが、Q2’、Q3’およびQ4’の少なくとも一つは1価の架橋性基である。Q4’が複数存在する場合、それらは同一でも異なっていてもよい。
naは0~3の整数を示し、nbは0~12の整数を示し、nAは0または1を示す。
LaおよびLbは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Laが複数存在する場合、それらは同一でも異なっていてもよい。Lbが複数存在する場合、それらは同一でも異なっていてもよい。
LAは、酸素原子または硫黄原子を示す。LAが複数存在する場合、それらは同一でも異なっていてもよい。
ngは0~3の整数を示し、nhは0~12の整数を示し、nDは0または1を示す。
LgおよびLhは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lgが複数存在する場合、それらは同一でも異なっていてもよい。Lhが複数存在する場合、それらは同一でも異なっていてもよい。
LDは、酸素原子または硫黄原子を示す。LDが複数存在する場合、それらは同一でも異なっていてもよい。
なお、式(4’)で示される構成単位は、式(1)で示される構成単位とは異なる。] - 前記式(4’)で表される構成単位が、下記式(4)で表される構成単位である、請求項1に記載の高分子化合物。
[式中、
cは0または1を示し、
Ar20およびAr40は、それぞれ独立に、非置換若しくは置換のアリーレン基または非置換若しくは置換の2価の複素環基を示し、Ar30は、非置換若しくは置換のアリーレン基、非置換若しくは置換の2価の複素環基、または、アリーレン基および2価の複素環基から選ばれる同一若しくは異なる2以上の基が連結した2価の基(当該2価の基は置換基を有していてもよい)を示す。
Q2は1価の架橋性基を示し、Q3は1価の架橋性基、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を示す。] - 前記式(1)で表される構成単位が、下記式(1A)で表される構成単位である、請求項1または2に記載の高分子化合物。
[式中、
R5、R6およびR7は、それぞれ独立に、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、オキシカルボニル基、1価の複素環基、複素環オキシ基、複素環チオ基、イミン残基、アミド化合物残基、酸イミド残基、カルボキシル基、ヒドロキシ基、ニトロ基またはシアノ基を表す。R5が複数個存在する場合、それらは同一であっても異なっていてもよく、R6が複数個存在する場合、それらは同一であっても異なっていてもよく、R7が複数個存在する場合、それらは同一であっても異なっていてもよい。
h、iおよびjは、それぞれ独立に、0~5の整数を表す。] - 前記Ar1およびAr3が、非置換若しくは置換のフェニレン基であり、
前記Ar2またはAr4が、非置換若しくは置換のフェニレン基、非置換若しくは置換のビフェニリレン基および非置換若しくは置換のフルオレンジイル基からなる群から選ばれる1種の基である、請求項1~3のいずれか一項に記載の高分子化合物。 - 前記Ar1およびAr3が、非置換若しくは置換の1,4-フェニレン基である、請求項4に記載の高分子化合物。
- 前記Ar2またはAr4が、非置換若しくは置換の2,7-フルオレンジイル基である、請求項4または5に記載の高分子化合物。
- 前記xが1であり、前記yが0である、請求項1~6のいずれか一項に記載の高分子化合物。
- 前記Ar8が、フェニレン基である、請求項1~7のいずれか一項に記載の高分子化合物。
- 前記Ar8が、フルオレンジイル基である、請求項1~7のいずれか一項に記載の高分子化合物。
- 前記式(3)で表される構成単位が、下記式(3-1)で表される構成単位である、請求項1~9のいずれか一項に記載の高分子化合物。
[式中、
ncは0~3の整数を示し、ndは0~12の整数を示し、nBは0または1を示し、mは1または2を示す。
LcおよびLdは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lcが複数存在する場合、それらは同一でも異なっていてもよい。Ldが複数存在する場合、それらは同一でも異なっていてもよい。
LBは酸素原子または硫黄原子を示す。LBが複数存在する場合、それらは同一でも異なっていてもよい。
Q1は前記と同じ意味を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
R80は、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換の1価の複素環基または非置換若しくは置換の複素環オキシ基を示す。] - 前記式(3)で表される構成単位が、下記式(3-2)で表される構成単位である、請求項1~10のいずれか一項に記載の高分子化合物。
[式中、
ncは0~3の整数を示し、ndは0~12の整数を示し、nBは0または1を示し、kは1~4の整数を示す。
LcおよびLdは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lcが複数存在する場合、それらは同一でも異なっていてもよい。Ldが複数存在する場合、それらは同一でも異なっていてもよい。
LBは酸素原子または硫黄原子を示す。LBが複数存在する場合、それらは同一でも異なっていてもよい。
Q1は前記と同じ意味を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
R90は、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換の1価の複素環基または非置換若しくは置換の複素環オキシ基を示す。R90が複数存在する場合、それらは同一でも異なっていてもよい。] - 前記式(1)で表される構成単位と、
前記式(2)で表される構成単位と、
少なくとも2種類の前記式(3)で表される構成単位と、
を含む請求項1~12のいずれか一項に記載の高分子化合物。 - 請求項1~13のいずれか一項に記載の高分子化合物と、
正孔輸送材料、電子輸送材料および発光材料からなる群から選ばれる少なくとも1種の材料と、を含有する、組成物。 - 請求項1~13のいずれか一項に記載の高分子化合物と、溶媒と、を含有する組成物。
- さらに溶媒を含有する、請求項14または15に記載の組成物。
- 請求項1~13のいずれか一項に記載の高分子化合物を含む、有機薄膜。
- 請求項17に記載の有機薄膜を、加熱することで溶媒に対して不溶化させた、不溶化有機薄膜。
- 請求項17に記載の有機薄膜または請求項18に記載の不溶化有機薄膜を有する、発光素子。
- 請求項17に記載の有機薄膜または請求項18に記載の不溶化有機薄膜が、正孔輸送層である、請求項19に記載の発光素子。
- 下記式(4-1)で表される化合物。
[式中、
Z7およびZ8は、それぞれ独立に、塩素原子、臭素原子、ヨウ素原子、-O-S(=O)2R31で表される基、-B(OR32)2で表される基、-BF3Q10で表される基、-MgY1で表される基、-ZnY2で表される基、または-Sn(R33)3で表される基である。
R31は、アルキル基、または、アルキル基、アルコキシ基、ニトロ基、フッ素原子若しくはシアノ基で置換されていてもよいアリール基を表す。
R32は、水素原子またはアルキル基を表し、複数存在するR32は互いに同一でも異なっていてもよく、互いに結合してそれぞれが結合する酸素原子とともに環構造を形成していてもよい。
Q10は、Li+、Na+、K+、Rb+およびCs+からなる群より選ばれる1価の陽イオンを表す。
Y1およびY2は、それぞれ、塩素原子、臭素原子またはヨウ素原子を表す。
R33は水素原子またはアルキル基を表し、複数存在するR33は互いに同一でも異なっていてもよく、互いに結合してそれぞれが結合するスズ原子とともに環構造を形成していてもよい。
d1は1~4の整数を示し、
Ar20およびAr40は、それぞれ独立に、非置換若しくは置換のアリーレン基または非置換若しくは置換の2価の複素環基を示し、Ar30’は、非置換若しくは置換の(2+d1)価の芳香族炭化水素基、非置換若しくは置換の(2+d1)価の複素環基、または、芳香環および複素環から選ばれる同一若しくは異なる2以上の環が連結した構造を有する(2+d1)価の基(当該(2+d1)価の基は置換基を有していてもよい)を示す。
Ar50およびAr60は、それぞれ独立に、非置換若しくは置換のアリール基または非置換若しくは置換の1価の複素環基を示す。
Q4は、1価の架橋性基を示す。Q4が複数個存在する場合は、それらは同一でも異なっていてもよい。
naは0~3の整数を示し、nbは0~12の整数を示し、nAは0または1を示す。
LaおよびLbは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Laが複数存在する場合、それらは同一でも異なっていてもよい。Lbが複数存在する場合、それらは同一でも異なっていてもよい。
LAは、酸素原子または硫黄原子を示す。LAが複数存在する場合、それらは同一でも異なっていてもよい。] - 下記式(3-3)で表される化合物。
[式中、
Z5およびZ6は、請求項21に記載のZ7、Z8と同じ意味を表す。
ncは0~3の整数を示し、ndは0~12の整数を示し、nBは0または1を示し、kは1~4の整数を示す。
LcおよびLdは、それぞれ独立に、非置換若しくは置換のアルキレン基または非置換若しくは置換のフェニレン基を示す。Lcが複数存在する場合、それらは同一でも異なっていてもよい。Ldが複数存在する場合、それらは同一でも異なっていてもよい。
LBは酸素原子または硫黄原子を示す。LBが複数存在する場合、それらは同一でも異なっていてもよい。
Q1’はシクロブテン構造を有する非置換若しくは置換のアリール基またはシクロブテン構造を有する非置換若しくは置換の1価の複素環基を示す。Q1が複数存在する場合、それらは同一でも異なっていてもよい。
R90は、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、非置換若しくは置換の1価の複素環基または非置換若しくは置換の複素環オキシ基を示す。R90が複数存在する場合、それらは同一でも異なっていてもよい。]
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Publication number | Publication date |
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KR101993496B1 (ko) | 2019-06-26 |
KR20140148424A (ko) | 2014-12-31 |
TWI580706B (zh) | 2017-05-01 |
JP5955946B2 (ja) | 2016-07-20 |
EP2832761A4 (en) | 2015-11-04 |
CN104321362B (zh) | 2017-02-22 |
EP2832761A1 (en) | 2015-02-04 |
JPWO2013146806A1 (ja) | 2015-12-14 |
CN104321362A (zh) | 2015-01-28 |
EP2832761B1 (en) | 2020-11-18 |
US9929347B2 (en) | 2018-03-27 |
TW201345947A (zh) | 2013-11-16 |
US20150115204A1 (en) | 2015-04-30 |
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