WO2016159293A1 - Copolymère, matériau pour élément électronique, matériau pour élément électroluminescent organique et élément électroluminescent organique - Google Patents

Copolymère, matériau pour élément électronique, matériau pour élément électroluminescent organique et élément électroluminescent organique Download PDF

Info

Publication number
WO2016159293A1
WO2016159293A1 PCT/JP2016/060784 JP2016060784W WO2016159293A1 WO 2016159293 A1 WO2016159293 A1 WO 2016159293A1 JP 2016060784 W JP2016060784 W JP 2016060784W WO 2016159293 A1 WO2016159293 A1 WO 2016159293A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
ring
substituted
carbon atoms
unsubstituted aromatic
Prior art date
Application number
PCT/JP2016/060784
Other languages
English (en)
Japanese (ja)
Inventor
松尾　茂
宏典 川上
祐一郎 河村
舟橋　正和
藤山　高広
Original Assignee
出光興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Publication of WO2016159293A1 publication Critical patent/WO2016159293A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present invention relates to a copolymer, a material for an electronic device and a material for an organic electroluminescence device (hereinafter sometimes abbreviated as an organic EL device), an organic EL device, a coating liquid, and a method for producing the organic EL device.
  • an organic EL device a material for an organic electroluminescence device
  • an organic EL device an organic electroluminescence device
  • a coating liquid a method for producing the organic EL device.
  • a film containing a material for causing the device to function is generally formed by a vapor deposition method.
  • formation of a film by a coating method is also being studied, but in reality, a material suitable for a coating solution has not been obtained, and the development of a polymer material having charge transport properties and solubility has been developed. It is being advanced.
  • Polyvinylcarbazole (hereinafter sometimes abbreviated as PVK) as an organic EL element material has been known for a long time (see Patent Document 1, page 2, upper right column), and coupled with improvements in organic EL elements, Improvements are also being made.
  • Patent Document 2 describes an organic EL device using a polymer obtained by copolymerizing a vinyl anthracene derivative and a vinyl carbazole derivative, but no high molecular weight product is obtained.
  • Patent Document 3 discloses a copolymer of a unit having a carbazole derivative and a unit having an amino group, but no high molecular weight product is obtained.
  • the present invention provides a copolymer suitable for forming a film by a coating method, a material for an electronic device and a material for an organic EL device, a solution containing the copolymer, and an organic EL device.
  • Structural unit A represented by the following general formula (A)
  • structural unit B represented by the following general formula (B)
  • structural unit C1 represented by the following general formula (C1)
  • copolymer comprising at least one structural unit C selected from structural units C2 represented by (C2).
  • a 1 is a group represented by the following general formula (A1)
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • Ar 1 , Ar 2 , and Ar 3 are each independently a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms. A cyclic group or a substituted or unsubstituted arylamino group is shown. Ar 2 and Ar 3 may combine with each other to form a ring.
  • a ′ is 0 or 1; When a ′ is 0, the binding site * is located on the nitrogen atom, When a ′ is 1, the binding site * may be substituted with any of Ar 1 , Ar 2 , and Ar 3 .
  • R 11 is an alkyl or alkenyl group having 4 to 60 carbon atoms, an alkoxy group having 4 to 60 carbon atoms, a polyalkylene glycol group having 4 to 60 carbon atoms, an aralkyl group having 4 to 60 carbon atoms in the alkyl moiety,
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • n is an integer of 1 to 5.
  • R 11 is a group represented by the following general formula (B1), or the following general formula ( It is not a group represented by B2).
  • * represents a binding site that may be substituted for any of the above
  • R a represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • z1 is an integer of 0 to 5.
  • R b and R c each independently represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • . z2 and z3 are each independently an integer of 0 to 5.
  • L 51 is a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, and one hydrogen atom removed from the substituent represented by the general formula (A1).
  • a substituted or unsubstituted aliphatic group having 1 to 60 carbon atoms, X 51 and X 52 each independently represent a single bond, an ether bond, a thioether bond, an ester bond or a thioester bond;
  • R 51 has a group having a small ring having 3 to 4 ring atoms, a vinyl group, an ethynyl group, a butenyl group, a group having an acrylic structure, a group having an acrylate structure, a group having an acrylamide structure, or a methacrylic structure.
  • R 52 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • X 51 and X 52 each independently represents a thioether bond, an ester bond, an ether bond, an alkylenediyl group or a carbonyl group;
  • Ar 51 and Ar 52 each independently represent a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • Ar 53 and Ar 54 each independently represent a group having a small ring having 3 to 4 ring atoms, a vinyl group, an ethynyl group, a butenyl group, a group having an acrylic structure, a group having an acrylate structure, or an acrylamide structure.
  • Ar 55 has a group having a small ring with 3 to 4 ring atoms, a vinyl group, an ethynyl group, a butenyl group, a group having an acrylic structure, a group having an acrylate structure, a group having an acrylamide structure, or a methacrylic structure
  • a 1 is a substituent represented by any one of the following general formula (A2a), general formula (A2b), general formula (A2c), general formula (A2d), or general formula (A2e).
  • Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms, or a substituted group.
  • Ar 2 ′ and Ar 3 ′ each independently represent a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms
  • R 2 and R 3 each independently represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • R 2 and R 3 may combine with each other to form a ring
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring.
  • a ′ is 0 or 1
  • m and n are each independently an integer of 0 to 5.
  • Ar 1 , Ar 4 , Ar 5 are each independently a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted ring atom number of 5 to 60]
  • Ar 2 ′ and Ar 3 ′ each independently represent a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms,
  • R 2 and R 3 each independently represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • Show L 1 represents a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • R 2 and R 3 may combine with each other to form a ring
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring
  • Ar 4 and Ar 5 may combine with each other to form a ring.
  • a ′ is 0 or 1
  • m is an integer from 0 to 5
  • n ′ is an integer of 0-4.
  • Ar 1 , Ar 4 , Ar 5 , Ar 6 , Ar 7 are each independently a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, a substituted or unsubstituted ring, An aromatic heterocyclic group having 5 to 60 atoms or a substituted or unsubstituted arylamino group;
  • Ar 2 ′ and Ar 3 ′ each independently represent a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, R 2 and R 3 each independently represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • L 1 and L 2 are each independently a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms.
  • a heterocyclic group is shown.
  • R 2 and R 3 may combine with each other to form a ring
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring
  • Ar 4 and Ar 5 may combine with each other to form a ring
  • Ar 6 and Ar 7 may combine with each other to form a ring.
  • a ′ is 0 or 1
  • m ′ and n ′ are integers from 0 to 4.
  • Ar 1 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 , Ar 12 each independently represent a substituted or unsubstituted ring carbon number of 6 to 60 aromatic hydrocarbon ring group, substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms, or substituted or unsubstituted arylamino group
  • Ar 2 ′ and Ar 3 ′ each independently represent a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms
  • R 2 and R 3 each independently represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • L 1 , L 2 , L 3 and L 4 are each independently a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted ring forming atom number. 5 to 60 aromatic heterocyclic groups are shown.
  • R 2 and R 3 may combine with each other to form a ring
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring
  • Ar 4 and Ar 6 may combine with each other to form a ring
  • Ar 7 and Ar 9 may combine with each other to form a ring
  • Ar 10 and Ar 12 may be bonded to each other to form a ring.
  • a ′ is 0 or 1
  • m ′ and n ′ are integers from 0 to 4.
  • the binding site * is located on the nitrogen atom
  • the binding site * may be substituted with any one.
  • Ar 1a , Ar 2a , Ar 1b , Ar 2b are each independently a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted ring forming atom number.
  • A represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms,
  • L a and L b are each independently a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms.
  • a heterocyclic group is shown.
  • Ar 1a and Ar 2a may combine with each other to form a ring
  • Ar 1b and Ar 2b may combine with each other to form a ring
  • x is an integer of 1 or more.
  • the binding site * may be substituted for any.
  • R 11 is an alkyl or alkenyl group having 4 to 60 carbon atoms, an alkoxy group having 4 to 60 carbon atoms, a polyalkylene glycol group having a total carbon number of 4 to 60, or an aralkyl having 4 to 60 carbon atoms in the alkyl moiety.
  • the copolymer according to any one of [1] to [5], which is a group.
  • a material for an organic electroluminescence device comprising the copolymer according to any one of [1] to [7].
  • a coating solution comprising the copolymer according to any one of [1] to [7] and a solvent.
  • a method for producing an organic electroluminescent element comprising forming a thin film using the coating liquid according to [12].
  • a copolymer having hole transport properties and solubility and suitable for forming a film by a coating method, a material for an electronic device and a material for an organic EL device, and a solution containing the same, and An organic EL element can be provided.
  • the copolymer of the present invention includes a structural unit A represented by the general formula (A), a structural unit B represented by the general formula (B), a structural unit C1 represented by the general formula (C1), or a general unit. And a structural unit C2 represented by the formula (C2).
  • the “hydrogen atom” includes isotopes having different numbers of neutrons, that is, light hydrogen (protium), deuterium (triuterium), and tritium (tritium). This interpretation is similarly applied to all hydrogen atoms present in the copolymer which is an embodiment of the present invention.
  • carbon number ab in the expression “substituted or unsubstituted XX group having carbon number ab” (including expressions substantially the same as those described above) refers to XX group The number of carbon atoms of the substituent when is substituted is not included.
  • the optional substituent is an alkyl group having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; 3 to 50 ring carbon atoms, preferably 3 to 6 carbon atoms.
  • An aryloxy group having 1 to 50 carbon atoms an alkyl group having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and 6 to 50 ring carbon atoms, preferably 6 to 24 carbon atoms, more preferably 6 to 6 carbon atoms.
  • a group and an atom selected from the group consisting of a cyano group and a nitro group are preferred.
  • a halogen atom, a cyano group, a trialkylsilyl group having an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, and a ring-forming carbon Preference is given to groups and atoms selected from the group consisting of several 6 to 12 aryl groups.
  • a 1 is a group represented by the following general formula (A1), and R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • * indicates a binding site;
  • Ar 1 , Ar 2 , and Ar 3 are each independently a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • a cyclic group or a substituted or unsubstituted arylamino group is shown.
  • Ar 2 and Ar 3 may combine with each other to form a ring.
  • a ′ is 0 or 1;
  • the binding site * is located on the nitrogen atom,
  • the binding site * may be substituted with any of Ar 1 , Ar 2 , and Ar 3 .
  • R 1 in the structural unit A preferably represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and still more preferably a hydrogen atom.
  • alkyl group for R 1 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group (including isomer groups), Hexyl group (including isomer group), heptyl group (including isomer group), octyl group (including isomer group), nonyl group (including isomer group), decyl group (including isomer group), And an undecyl group (including an isomer group) and a dodecyl group (including an isomer group).
  • a 1 is preferably a substituent represented by any of the following general formula (A2a), general formula (A2b), general formula (A2c), general formula (A2d), or general formula (A2e), More preferably, it is a substituent represented by any one of General Formula (A2a), General Formula (A2b), and General Formula (A2c).
  • Ar 1 is the same as Ar 1 in formula (A1)
  • Ar 2 ′ and Ar 3 ′ each independently represent a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms
  • R 2 and R 3 each independently represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • R 2 and R 3 may combine with each other to form a ring
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring.
  • a ′ and the bonding position * are the same as those in the general formula (A1) (note that the bonding position * may be substituted for any one of R 2 , R 3 , Ar 2 ′ and Ar 3 ′ ). .), m and n are each independently an integer of 0 to 5.
  • Ar 1 , Ar 4 and Ar 5 are the same as Ar 1 in the general formula (A1); Ar 2 ', Ar 3' is similar to Ar 2 'of the general formula (A2a), R 2 and R 3 are the same as R 2 in the general formula (A2a), L 1 represents a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • R 2 and R 3 may combine with each other to form a ring
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring
  • Ar 4 and Ar 5 may combine with each other to form a ring.
  • a ′ and the bonding position * are the same as those in the general formula (A1) (the bonding position * includes R 2 , R 3 , L 1 , Ar 4 , Ar 5 , Ar 2 ′ , Ar 3 ′). Any of these may be substituted)
  • m is the same as m in the general formula (A2a);
  • n ′ is an integer of 0-4.
  • Ar 1 , Ar 4 , Ar 5 , Ar 6 , Ar 7 are the same as Ar 1 in the general formula (A1); Ar 2 ', Ar 3' is similar to Ar 2 'of the general formula (A2a), R 2 and R 3 are the same as R 2 in the general formula (A2a), L 1, L 2 is the same as L 1 in formula (A2b), R 2 and R 3 may combine with each other to form a ring, Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring, Ar 4 and Ar 5 may combine with each other to form a ring, Ar 6 and Ar 7 may combine with each other to form a ring.
  • a ′ and the bonding position * are the same as those in the general formula (A1) (the bonding position * is R 2 , R 3 , L 1 , L 2 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar). 2 ′ and Ar 3 ′ may be substituted for any)), m ′ and n ′ are the same as n ′ in the general formula (A2b).
  • Ar 1 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 , Ar 12 are the same as Ar 1 in the general formula (A1];
  • Ar 2 ', Ar 3' is similar to Ar 2 'of the general formula (A2a),
  • R 2 and R 3 are the same as R 2 in the general formula (A2a),
  • L 1 , L 2 , L 3 and L 4 are the same as L 1 in the general formula (A2b),
  • R 2 and R 3 may combine with each other to form a ring,
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring,
  • Ar 4 and Ar 6 may combine with each other to form a ring,
  • Ar 7 and Ar 9 may combine with each other to form a ring,
  • Ar 10 and Ar 12 may be bonded to each other to form a ring.
  • a ′ and the bonding position * are the same as those in the general formula (A1) (the bonding position * is R 2 , R 3 , L 1 , L 2 , L 3 , L 4 , Ar 1 , Ar 4 , Ar). 5 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 , Ar 12 , Ar 2 ′ , Ar 3 ′ may be substituted for any).
  • m ′ and n ′ are the same as n ′ in the general formula (A2b).
  • Ar 1a , Ar 2a , Ar 1b and Ar 2b are the same as Ar 1 in the general formula (A1);
  • A represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms,
  • L a and L b are the same as L 1 in the general formula (A2b)
  • Ar 1a and Ar 2a may combine with each other to form a ring, Ar 1b and Ar 2b may combine with each other to form a ring.
  • x is an integer of 1 or more.
  • Binding site * is optionally substituted on one (i.e., bonding positions * is, L a, L b, Ar 1a, Ar 2a, Ar 1b, including Ar 2b, may be substituted on any .)
  • Binding site * is optionally substituted on one (i.e., bonding positions * is, L a
  • the substituent is preferably a substituent represented by any one of the following general formulas (A3a), (A3b), and (A3c), and more preferably represented by the following general formula (A3a) or (A3b). It is a substituent.
  • Ar 1 is the same as Ar 1 in formula (A1)
  • Ar 2 ′ , Ar 3 ′ , Ar 4 ′ and Ar 5 ′ are the same as Ar 2 ′ in the general formula (A2a)
  • R 2 , R 3 , R 4 and R 5 are the same as R 2 in the general formula (A2a)
  • L 1 is the same as L 1 in formula (A2b)
  • R 2 , R 3 , R 4 and R 5 may combine with each other to form a ring
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring
  • Ar 4 ′ and Ar 5 ′ may be bonded to each other to form a ring.
  • a ′ and the bonding position * are the same as those in the general formula (A1) (the bonding position * is R 2 , R 3 , R 4 , R 5 , L 1 , Ar 1 , Ar 2 ′ , Ar 3 ′). , Ar 4 ′ , Ar 5 ′ , and any one of them may be substituted.
  • m, p and q are the same as m in the general formula (A2a)
  • n ′ is the same as n ′ in the general formula (A2b).
  • Ar 1 is the same as Ar 1 in formula (A1)
  • Ar 2 ′ , Ar 3 ′ , Ar 4 ′ , Ar 5 ′ , Ar 6 ′ , Ar 7 ′ are the same as Ar 2 ′ in the general formula (A2a)
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same as R 2 in the general formula (A2a)
  • L 1 L 2 is the same as L 1 in formula (A2b)
  • R 2 , R 3 , R 4 and R 5 may combine with each other to form a ring
  • Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring
  • Ar 4 ′ and Ar 5 ′ may be bonded to each other to form a ring
  • Ar 6 ′ and Ar 7 ′ may be bonded to each other to form a ring.
  • a ′ and the bonding position * are the same as those in the general formula (A1) (the bonding position * is R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , L 1 , L 2 , Ar). 1 , Ar 2 ′ , Ar 3 ′ , Ar 4 ′ , Ar 5 ′ , Ar 6 ′ , Ar 7 ′ may be substituted for any one of them).
  • p, q, p ′ and q ′ are the same as m in the general formula (A2a)
  • m ′ and n ′ are the same as n ′ in the general formula (A2b).
  • Ar 1 , Ar 5 , Ar 8 and Ar 11 are the same as Ar 1 in the general formula (A1); Ar 2 ′ , Ar 3 ′ , Ar 4 ′ , Ar 6 ′ , Ar 7 ′ , Ar 9 ′ , Ar 10 ′ , Ar 12 ′ are the same as Ar 2 ′ in the general formula (A2a), R 2 , R 3 , R 5 , R 7 , R 9 , RL 1 , RL 2 , RL 3 are the same as R 2 in the general formula (A2a), L 1 ′, L 2 ′, L 3 ′, and L 4 ′ are the same as L 1 in the general formula (A2b), R 2 , R 3 , R 5 , R 7 , R 9 , RL 1 , RL 2 , RL 3 may be bonded to each other to form a ring, Ar 2 ′ and Ar 3 ′ may be bonded to each other to form a ring, Ar 4 ′ and
  • a ′ and the bond position * are the same as those in the general formula (A1) (note that the bond position * is R 2 , R 3 , R 5 , R 7 , R 9 , RL 1 , RL 2 , RL 3 , L 1 ', L 2', L 3 ', L 4', Ar 1, Ar 5, Ar 8, Ar 11, Ar 2 ', Ar 3', Ar 4 ', Ar 6', Ar 7 ', Ar 9' , Ar 10 ′ , Ar 12 ′ may be substituted for any of them)), m ′, n ′, s, t, u, v, r, and w are the same as n ′ in the general formula (A2b). ]
  • substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms of Ar 1 , R 2 , and L 1 include the aromatic hydrocarbon ring groups listed below and those 2 Examples of the valence group can be given.
  • the number of carbon atoms forming the aromatic hydrocarbon ring group is preferably 6 to 60, more preferably 6 to 30, and still more preferably 6 to 15.
  • aromatic hydrocarbon ring group examples include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3 -Phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, biphenyl-2-yl group Biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl- 4-yl group, m-terphenyl-3-yl group, m-terphenyl-
  • substituents include alkyl groups having 1 to 10 carbon atoms, halogen atoms, heteroaryl groups such as carbazolyl groups, dibenzofuranyl groups and dibenzothiophenyl groups, and 9,9-dioctylfluorenyl groups.
  • Examples include an aryl group, a diarylamino group such as a diphenylamino group, and a cyano group.
  • substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms of Ar 1 , R 2 and L 1 include the aromatic heterocyclic groups listed below and divalent Can be mentioned.
  • the ring-forming carbon number of the aromatic heterocyclic group is preferably 5 to 60, more preferably 5 to 30, and still more preferably 5 to 15.
  • aromatic heterocyclic group examples include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2- Indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5- Isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7- Benzofuranyl group, 1-isobenzo
  • substituents examples include aryl groups such as phenyl group, 9,9-dimethylfluorenyl group, and 9,9-dioctylfluorenyl group, heteroaryl groups such as pyridyl group, pyrimidyl group, and dibenzofuranyl group, and the number of carbon atoms. Examples thereof include 1 to 10 alkyl groups, halogen atoms, cyano groups, and combinations thereof.
  • arylamino group of Ar 1 when bonded to the main chain and the side chain via an aryl group bonded to a nitrogen atom, when bonded to the nitrogen atom via an aryl group bonded thereto, And a diarylamino group may be bonded to a side chain nitrogen atom.
  • the aryl group the above-mentioned aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms can be mentioned as a suitable group.
  • the ring forming carbon number of the aromatic hydrocarbon ring group of Ar 2 ′ is preferably 6 to 60, more preferably 6 to 30, and still more preferably 6 to 15.
  • Examples of the substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms of Ar 2 ′ include the same substituents as the aromatic hydrocarbon ring group of Ar 1 .
  • Ar 2 ′ is preferably a phenyl group.
  • the substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms and the substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms of A are the same substituents as Ar 1 above. Can be illustrated.
  • X in the general formula (A2e) is preferably an integer of 1 to 3, more preferably 1 or 2.
  • X in the general formula (A2e) is preferably an integer of 1 to 3, more preferably 1 or 2.
  • alkyl group or alkenyl group having 4 to 60 carbon atoms a polyalkylene glycol group having 4 to 60 carbon atoms in total, or an aralkyl group having 4 to 60 carbon atoms in the alkyl moiety is excluded.
  • Preferred examples of the structural unit A are as follows.
  • the structural unit B is represented by the general formula (B). [Wherein L 11 is a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, and one hydrogen atom removed from the substituent represented by the general formula (A1).
  • R 11 is an alkyl or alkenyl group having 4 to 60 carbon atoms, an alkoxy group having 4 to 60 carbon atoms, a polyalkylene glycol group having 4 to 60 carbon atoms, an aralkyl group having 4 to 60 carbon atoms in the alkyl moiety,
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • n is an integer of 1 to 5.
  • R 11 is a group represented by the following general formula (B1), or the following general formula ( It is not a group represented by B2).
  • n is preferably an integer of 1 to 3, more preferably 1 or 2, from the viewpoint of further improving the hole transport property while enhancing the solubility of the copolymer.
  • L 11 is preferably a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms.
  • the ring-forming carbon number of the aromatic hydrocarbon ring group is preferably 6-30, more preferably 6-15.
  • aromatic hydrocarbon ring group examples include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3 -Phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, biphenyl-2-yl group Biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl- 4-yl group, m-terphenyl-3-yl group, m-terphenyl-
  • substituents include alkyl groups having 1 to 10 carbon atoms, halogen atoms, heteroaryl groups such as carbazolyl groups, dibenzofuranyl groups and dibenzothiophenyl groups, and 9,9-dioctylfluorenyl groups.
  • Examples include an aryl group, a diarylamino group such as a diphenylamino group, and a cyano group.
  • R 11 is preferably an alkyl or alkenyl group having 4 to 60 carbon atoms, an alkoxy group having 4 to 60 carbon atoms, a polyalkylene glycol group having a total carbon number of 4 to 60, or an aralkyl having 4 to 60 carbon atoms in the alkyl moiety. More preferably an alkyl or alkenyl group having 4 to 60 carbon atoms or an alkoxy group having 4 to 60 carbon atoms.
  • the alkyl group of R 11 is preferably a linear or branched alkyl group having 4 to 60 carbon atoms, more preferably 4 to 50 carbon atoms, still more preferably 4 to 30 carbon atoms, and still more preferably 4 to 10 carbon atoms.
  • alkyl group or alkenyl group having 4 to 60 carbon atoms of R 11 examples include n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group (including isomer group), hexyl group (isomer) Group), heptyl group (including isomer group), octyl group (including isomer group), nonyl group (including isomer group), decyl group (including isomer group), undecyl group (isomer) Group), dodecyl group (including isomer group), and the like, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group (including isomer group), hexyl group (Including isomer groups), heptyl group (including isomer groups), octyl group (including isomer groups), nonyl group (including isomer groups), de
  • the alkoxy group of R 11 is preferably a linear or branched alkoxy group having 4 to 60 carbon atoms, more preferably 4 to 50 carbon atoms, still more preferably 4 to 30 carbon atoms, and still more preferably 4 to 10 carbon atoms.
  • the alkoxy group of R 11 is represented, for example, as —OY, and examples of Y include the above alkyl groups.
  • the polyalkylene glycol group having 4 to 60 carbon atoms is represented by, for example, — (OY) n —OZ.
  • Y include an alkylene group having 2 to 4 carbon atoms.
  • Z include 1 carbon atom. -15 alkyl groups, and the average added mole number n is 1-20.
  • An aralkyl group having 4 to 60 carbon atoms in the alkyl moiety for example, -YZ, and examples of Y include alkylene groups corresponding to the above examples of alkyl groups.
  • the aryl part of the aralkyl group preferably has 6 to 30 ring-forming carbon atoms, more preferably 6 to 15 carbon atoms.
  • the alkyl moiety preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. For example, benzyl group, phenylethyl group, 2-phenylpropan-2-yl group.
  • R 11 is preferably a group represented by the following general formula (B1) or a group represented by the following general formula (B2) from the viewpoint of forming a three-dimensional twisted structure and increasing the solubility of the copolymer. It is.
  • * represents a binding site that may be substituted for any of the above
  • R a represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • z1 is an integer of 0 to 5.
  • R a may be substituted with any phenyl group
  • the binding site * may be substituted with any, including R a .
  • * represents a binding site that may be substituted for any of the above
  • R b and R c each independently represents a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • . z2 and z3 are each independently an integer of 0 to 5.
  • the binding site * is, R b, including R c, it may be replaced by any.
  • the substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms and the substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms of R a , R b and R c are: it is similar to the example shown in L 11 described above.
  • z1 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
  • z2 and z3 are each independently preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
  • the structural unit C is a structural unit C1 represented by the following general formula (C1) or a structural unit C2 represented by the following general formula (C2).
  • the structural unit C is preferably a structural unit C1 represented by the following general formula (C1).
  • L 51 is a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, and one hydrogen atom removed from the substituent represented by the general formula (A1).
  • a substituted or unsubstituted aliphatic group having 1 to 60 carbon atoms, X 51 and X 52 each independently represent a single bond, an ether bond, a thioether bond, an ester bond or a thioester bond;
  • R 51 has a group having a small ring having 3 to 4 ring atoms, a vinyl group, an ethynyl group, a butenyl group, a group having an acrylic structure, a group having an acrylate structure, a group having an acrylamide structure, or a methacrylic structure.
  • R 52 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • X 51 and X 52 each independently represents a thioether bond, an ester bond, an ether bond, an alkylenediyl group or a carbonyl group;
  • Ar 51 and Ar 52 each independently represent a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms.
  • Ar 53 and Ar 54 each independently represent a group having a small ring having 3 to 4 ring atoms, a vinyl group, an ethynyl group, a butenyl group, a group having an acrylic structure, a group having an acrylate structure, or an acrylamide structure.
  • Ar 55 has a group having a small ring with 3 to 4 ring atoms, a vinyl group, an ethynyl group, a butenyl group, a group having an acrylic structure, a group having an acrylate structure, a group having an acrylamide structure, or a methacrylic structure
  • L 51 is preferably a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms.
  • the substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms of L 51 is the same as the above-described example of L 11 .
  • Examples of the substituted or unsubstituted alkyl group or alkenyl group having 1 to 60 carbon atoms of L 51 are the same as the above-described examples of methyl group, ethyl group, n-propyl group, isopropyl group and L 11 described above.
  • R 51 is preferably a group having a small ring having 3 to 4 ring atoms.
  • Examples of the small ring having 3 to 4 ring atoms of R 51 include a cyclopropyl group, a cyclobutyl group, an epoxy group, an oxetanyl group, a diketenyl group, and an epithio group.
  • Examples of the group having a small ring having 3 to 4 ring atoms include a group having a structure in which an unsubstituted aromatic hydrocarbon ring group having 6 to 60 carbon atoms and a cyclobutane ring are condensed.
  • Examples of the group having a structure in which an unsubstituted aromatic hydrocarbon ring group having 6 to 60 carbon atoms and a cyclobutane ring are condensed include a residue obtained by removing at least one hydrogen atom from benzocyclobutane (BCB).
  • Examples of R 51 include the following specific examples.
  • R 52 is preferably a hydrogen atom.
  • X 51 and X 52 are each independently preferably a thioether bond, an ester bond, an alkylenediyl group, or a carbonyl group, and more preferably a thioether bond.
  • Examples of the substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 60 ring carbon atoms and the substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms of Ar 51 and Ar 52 include the above-mentioned examples.
  • L 11 is similar to the example shown in.
  • Ar 55 is the same as the example shown for R 51 described above.
  • the copolymer structure of the polymer compound of the present invention is not limited, and examples thereof include an alternating copolymer structure and a random copolymer structure.
  • Examples of the repeating unit of the alternating copolymer structure include the following structures.
  • the mass ratio (A / B) between the structural unit A and the structural unit B is preferably 99/1 to 1/99, more preferably 90/10 to 10/90, still more preferably 90/10 to 30/70, More preferably, it is 85/15 to 50/50, and still more preferably 80/20 to 55/45.
  • the content of the structural units C1 and C2 is preferably 0.1 to 20% by mass, more preferably 1 to 18% by mass, and still more preferably 3 to 15% with respect to the total of the structural units A, B, C1 and C2. % By mass.
  • the copolymer may have a repeating unit having a structure other than the structural units A, B, C1, and C2 as long as it does not contradict its purpose.
  • the weight average molecular weight Mw of the copolymer is preferably 10,000 to 5,000,000, more preferably 30,000 to 1,000,000, still more preferably 50,000 to 500,000.
  • the number average molecular weight Mn of the copolymer is preferably 1,000 to 5,000,000, more preferably 3,000 to 500,000, and still more preferably 5,000 to 100,000.
  • the molecular weight distribution (Mw / Mn) is preferably 1.0 to 20, more preferably 1.2 to 18, and still more preferably 1.5 to 15.
  • the number average molecular weight and the weight average molecular weight can be determined by gel permeation chromatography (GPC), and more specifically, by the method described in Examples.
  • the production method of the copolymer of the present invention is not particularly limited, and various conventionally known polymerization methods can be adopted, and examples thereof include a bulk polymerization method and a solution polymerization method. Moreover, radical polymerization and thermal polymerization are preferable.
  • a polymerization initiator may be used as necessary.
  • As polymerization initiators cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethyl Organic peroxides such as hexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2, And azo compounds such as 2′-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2′-azobis (2-methylpropionate).
  • These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be appropriately set according to the combination of monomers used, the reaction conditions, the molecular weight of the target copolymer, etc., and is not particularly limited, but the weight average molecular weight is 100,000 to 3,000,000. From the viewpoint that a copolymer can be obtained, the content is preferably from 1 to 0.005 mol%, more preferably from 0.5 to 0.01 mol%, based on all monomer components.
  • a chain transfer agent may be used as necessary to adjust the molecular weight.
  • the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, ⁇ -mercaptopropionic acid and methyl mercaptoacetate, ⁇ -methylstyrene dimer, and the like.
  • the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target copolymer, and the like.
  • examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, and propylene glycol Esters such as monomethyl ether acetate and 3-methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene Chlorine-containing hydrocarbon compounds such as chloroform and methylene chloride; dimethylformamide, dimethyl Sulfoxides and the like. These solvents may be used alone or in
  • the reaction pressure at the time of polymerization is an absolute pressure, preferably 0.01 to 10 MPa, more preferably normal pressure to 1 MPa.
  • the polymerization concentration is, for example, 50 to 100% by mass although it varies depending on the molecular weight of the target copolymer.
  • the polymerization temperature is preferably equal to or higher than the melting point of the monomer as the main component of the copolymer and close to the melting point. In this case, the possibility that the polymer precipitates during the polymerization is reduced, and a high molecular weight polymer is easily obtained. That is, the polymerization is preferably performed at a temperature equal to or higher than the melting point of the monomer used to form the structural unit A and the structural unit B and in the vicinity thereof (for example, the melting point to the melting point + 10 ° C.). When solution polymerization is performed using a solvent, the polymerization may be performed at a lower temperature, for example, about 0 ° C. to room temperature (25 ° C.). The polymerization temperature is preferably 0 to 150 ° C., more preferably 0 to 100 ° C. is there.
  • the polymer of the present invention is useful as a material for electronic devices and a material for organic electroluminescence devices.
  • Examples of electronic elements other than organic electroluminescence elements include organic thin film solar cells and organic thin film transistors.
  • the polymer of the present invention is particularly suitable as a material for an organic electroluminescence element, particularly a material (hole transport layer, hole injection layer, etc.) used in a light emitting layer or a hole transport region.
  • the organic EL device of the present invention is an organic electroluminescence device having an anode, a cathode, and an organic thin film layer, and includes the polymer of the present invention in at least one layer of the organic thin film layer.
  • the manufacturing method of the organic EL element of this invention is a method of forming an organic thin film layer by the apply
  • the organic thin film layer containing the polymer of the present invention is preferably a hole transport region. Examples of the layer formed in the hole transport region include a hole transport layer and a hole injection layer. Furthermore, it is preferable that the hole transport layer or the hole injection layer is in contact with the light emitting layer.
  • the polymer is more preferably contained as a main component of at least one of a hole transport layer and a hole injection layer.
  • the content of the polymer of the present invention is preferably 51 to 100% by mass.
  • Each layer of the organic EL element can be formed by a conventionally known vacuum deposition method, spin coating method, or the like.
  • vacuum deposition molecular beam deposition (MBE), or coating methods such as dipping, spin coating, casting, bar coating, roll coating, etc., using a solution of a compound that forms a layer. It can be formed by a known method.
  • MBE molecular beam deposition
  • each organic layer is not particularly limited, but in general, if the film thickness is too thin, defects such as pinholes are likely to occur. Conversely, if it is too thick, a high driving voltage is required and the efficiency is lowered, so normally 1 nm to 15 ⁇ m. It is preferably 5 nm to 10 ⁇ m, more preferably 5 nm to 1 ⁇ m, and still more preferably 5 nm to 0.2 ⁇ m.
  • the layer containing the compound of the present invention is preferably formed by the above coating method using a solution (ink composition) containing a solvent and the compound.
  • the ink composition may contain other materials such as a dopant as necessary.
  • a wet film-forming method is preferably used, and a relief printing method, an intaglio printing method, a lithographic printing method, a stencil printing method, and a printing method combining these and an offset printing method, an inkjet printing method, a dispenser coating method.
  • Methods such as spin coating, bar coating, dip coating, spray coating, slit coating, roll coating, cap coating, gravure roll coating, and meniscus coating are applicable.
  • a relief printing method, an intaglio printing method, a lithographic printing method, a stencil printing method, a printing method combining these and an offset printing method, an inkjet printing method, a dispenser coating, and the like are preferable.
  • a method of transferring the polymer onto a wiring substrate having a target electrode by laser light, heat pressing, or the like can be used. Film formation by these methods can be performed under conditions well known to those skilled in the art, and details thereof are omitted.
  • the coating liquid (ink composition) used in the coating method only needs to contain at least one copolymer of the present invention, and may be dissolved or dispersed in a solvent.
  • the content of the copolymer of the present invention in the coating solution (ink composition) is preferably from 0.1 to 15% by mass, more preferably from 0.5 to 10% by mass, based on the entire film-forming solution.
  • the solvent is preferably an organic solvent, and examples of the organic solvent include chloroform, chlorobenzene, chlorotoluene, chloroxylene, chloroanisole, dichloromethane, dichlorobenzene, dichlorotoluene, dichloroethane, trichloroethane, trichlorobenzene, trichloromethylbenzene, and bromobenzene.
  • Chlorine solvents such as dibromobenzene and bromoanisole, ether solvents such as tetrahydrofuran, dioxane, dioxolane, oxazole, methylbenzoxazole, benzoisoxazole, furan, furazane, benzofuran, dihydrobenzofuran, ethylbenzene, diethylbenzene, triethylbenzene, trimethyl Benzene, trimethoxybenzene, propylbenzene, isopropylbenzene, diisopropyl Benzene, dibutylbenzene, amylbenzene, dihexylbenzene, cyclohexylbenzene, tetramethylbenzene, dodecylbenzene, benzonitrile, acetophenone, methylacetophenone, methoxyacetophenone, toluic acid ethyl ester, tol
  • a coating liquid for film formation (ink composition) containing the compound and a solvent described in the above general formula (S1) having a boiling point of 110 ° C. or more and a water solubility at 20 ° C. of 1% by mass or less.
  • a viscosity adjusting agent, a surface tension adjusting agent, a crosslinking reaction initiator, and a crosslinking reaction catalyst may be added to the coating liquid (ink composition) for film formation, as necessary.
  • the viscosity modifier, surface tension modifier, crosslinking reaction initiator, and crosslinking reaction catalyst select one that does not affect the device characteristics even if it remains in the film, or in the film formation process. What can be removed from inside is desirable.
  • the organic EL device of the present invention known members can be used for the constituent members other than the organic thin film layer containing the polymer of the present invention.
  • the light emitting layer can illustrate an embodiment containing a styrylamine compound, an arylamine compound or a fluoranthene compound.
  • Formation other than the organic thin film layer containing the polymer of the present invention can be performed by dry deposition methods such as vacuum deposition, sputtering, plasma, and ion plating, coating methods such as spin coating, dipping, and flow coating, and wet methods such as printing methods.
  • a known method such as a film forming method can be applied.
  • the thickness of each layer is not particularly limited, but must be set to an appropriate thickness.
  • An organic EL device is produced by forming an anode, a light emitting layer, a hole injection / transport layer as required, and an electron injection / transport layer as necessary, and further forming a cathode by various materials and layer forming methods. be able to. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.
  • SEC Size exclusion chromatography
  • Example 1 3- (9-phenylcarbazol-3-yl) -9- (4-vinylphenyl) carbazole (Compound A-1), 4-n-octylstyrene (Compound B-1), and vinyl benzo Copolymer with cyclobutene (compound C-1)
  • 1060 mg of 3- (9-phenylcarbazol-3-yl) -9- (4-vinylphenyl) carbazole (compound A-1) , 4-n-octylstyrene (740 mg), vinylbenzocyclobutene (200 mg), and AIBN (21 mg) (2 mol% based on the total monomers) were added to obtain a homogeneous solution.
  • Degassing-argon substitution was repeated 5 times and heated in an oil bath at 65 ° C. for 16 hours. During heating, stirring was performed as much as possible with a stirring bar. After heating, 30 mL of toluene was added to form a solution, which was poured into methanol to precipitate a solid. The solid was washed twice more with methanol and dried. The yield was 1.53g.
  • the number average molecular weight Mn was 43,700, the weight average molecular weight Mw was 326,000, and the molecular weight distribution (Mw / Mn) was 7.46.
  • Synthesis Example 2 Synthesis of 3,9-diphenyl-6- [6-phenyl-9- (4-vinylphenyl) carbazol-3-yl] carbazole (Compound A-3) Under a nitrogen atmosphere, 19.8 g (0.039 mol) of 4- [3- (9-phenylcarbazol-3-yl) carbazol-9-yl] benzaldehyde was added to dimethylformamide (DMF) in a 500 mL three-necked flask with a condenser. ) 100 mL was added and cooled to 0 ° C. in an ice water bath.
  • DMF dimethylformamide
  • the yield was 7.5 g (74% yield).
  • Example 2 3,9-diphenyl-6- [6-phenyl-9- (4-vinylphenyl) carbazol-3-yl] carbazole (Compound A-33) and 4-n-octylstyrene (Compound B- Copolymer of 1) and vinyl benzocyclobutene (compound C-1)
  • 3,9-diphenyl-6- [6-phenyl-9- (4-vinylphenyl) carbazole- 3-Iyl] carbazole Compound A-3) 1060 mg, 4-n-octylstyrene 740 mg, vinylbenzocyclobutene 200 mg, and AIBN 21 mg (2 mol% based on the total monomers) were added to obtain a homogeneous solution.
  • Degassing-argon substitution was repeated 5 times and heated in an oil bath at 65 ° C. for 16 hours. During heating, stirring was performed as much as possible with a stirring bar. After heating, 30 mL of toluene was added to form a solution, which was poured into methanol to precipitate a solid. The solid was washed twice more with methanol and dried. The yield was 1.62 g, the number average molecular weight Mn was 30,100, the weight average molecular weight Mw was 56,400, and the molecular weight distribution (Mw / Mn) was 1.86.
  • the polymer of Comparative Example 1 has the following repeating units A-1 (66 parts by mass), BC-1 (30 parts by mass), and C-1 (4 parts by mass).
  • the number average molecular weight Mn was 7,900
  • the weight average molecular weight Mw was 99,000
  • the molecular weight distribution (Mw / Mn) was 12.
  • the polymer of Comparative Example 2 has the following repeating units.
  • the number average molecular weight Mn was 26,800
  • the weight average molecular weight Mw was 408,300
  • the molecular weight distribution Mw / Mn was 15.2.
  • a white glass plate (Asahi Glass Co., Ltd.) was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and then UV ozone cleaning for 5 minutes to obtain a glass substrate for coating.
  • a hole transport layer was formed by spin coating to obtain a hole transport layer-coated glass substrate.
  • Each spin-coated substrate was heated and dried at 230 ° C. for 30 minutes using a hot plate. All operations from preparation of the solution to heat drying were performed in a glove box in a nitrogen atmosphere. After drying by heating and cooling to room temperature, a part of the film was scraped off, and half of the scraped part was immersed in toluene for 30 seconds.
  • the coated laminated substrate was conveyed into a vapor deposition chamber, and the following compound ET-1 was deposited as an electron transport layer by 50 nm. Furthermore, 1 nm of lithium fluoride and 80 nm of aluminum were deposited and laminated. After all the vapor deposition steps were completed, sealing with counterbore glass was performed in a glove box under a nitrogen atmosphere, and an organic EL device was produced.
  • Organic EL device evaluation The obtained organic EL element was made to emit light by direct current drive, and the external quantum yield (EQE) at a current density of 10 mA / cm 2 was measured. The measurement results are shown in Table E-3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un copolymère présentant des propriétés de transport de trous positifs et une solubilité et qui est approprié pour la formation d'un film par un procédé de revêtement, un matériau pour un élément électronique et un matériau pour un élément EL organique qui comprennent le copolymère, une solution contenant le copolymère, et un élément EL organique. L'invention concerne un copolymère contenant un motif structural A représenté par la formule générale (A), un motif structural B représenté par la formule générale (B), et au moins un motif structural C choisi à partir d'un motif structural C1 représenté par la formule générale (C1) et d'un motif structural en C2 représenté par la formule générale (C2), un élément électroluminescent organique, un dispositif électronique équipé de l'élément électroluminescent organique, un matériau pour un élément électroluminescent organique qui comprend le copolymère, et un liquide de revêtement.
PCT/JP2016/060784 2015-03-31 2016-03-31 Copolymère, matériau pour élément électronique, matériau pour élément électroluminescent organique et élément électroluminescent organique WO2016159293A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015074544 2015-03-31
JP2015-074544 2015-03-31

Publications (1)

Publication Number Publication Date
WO2016159293A1 true WO2016159293A1 (fr) 2016-10-06

Family

ID=57006045

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/060784 WO2016159293A1 (fr) 2015-03-31 2016-03-31 Copolymère, matériau pour élément électronique, matériau pour élément électroluminescent organique et élément électroluminescent organique

Country Status (1)

Country Link
WO (1) WO2016159293A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020008957A1 (fr) * 2018-07-06 2020-01-09 富士フイルム株式会社 Composition, film, lentille, élément d'imagerie à l'état solide, et composé
US11498987B2 (en) 2018-02-28 2022-11-15 Lg Chem, Ltd. Polymer, coating composition comprising same, and organic light emitting element using same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001277731A (ja) * 2000-03-29 2001-10-10 Fuji Photo Film Co Ltd 画像形成材料
WO2013096918A1 (fr) * 2011-12-22 2013-06-27 Georgia Tech Research Corporation Polymères transporteurs de trous à base de triscarbazole réticulables
JP2013533603A (ja) * 2010-05-05 2013-08-22 コモンウェルス サイエンティフィック アンドインダストリアル リサーチ オーガナイゼーション ポリマー系有機エレクトロルミネセント素子
WO2014057852A1 (fr) * 2012-10-09 2014-04-17 出光興産株式会社 Copolymère, matériau pour élément électronique organique, matériau pour élément électroluminescent organique et élément électroluminescent organique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001277731A (ja) * 2000-03-29 2001-10-10 Fuji Photo Film Co Ltd 画像形成材料
JP2013533603A (ja) * 2010-05-05 2013-08-22 コモンウェルス サイエンティフィック アンドインダストリアル リサーチ オーガナイゼーション ポリマー系有機エレクトロルミネセント素子
WO2013096918A1 (fr) * 2011-12-22 2013-06-27 Georgia Tech Research Corporation Polymères transporteurs de trous à base de triscarbazole réticulables
WO2014057852A1 (fr) * 2012-10-09 2014-04-17 出光興産株式会社 Copolymère, matériau pour élément électronique organique, matériau pour élément électroluminescent organique et élément électroluminescent organique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BIWU MA: "New Thermally Cross-Linkable Polymer and Its Application as a Hole-Transporting Layer for Solution Processed Multilayer Organic Light Emitting Diodes", CHEM.MATER., vol. 19, 25 August 2007 (2007-08-25), pages 4827 - 4832, XP055067971 *
YING-HUNG SO ET AL.: "Styrene 4-Vinylbezocyclobutene Copolymer for Microelectronic Applications", JOURNAL OF POLYMER SCIENCE :PART A:POLYMER CHEMISTRY, vol. 46, 2008, pages 2799 - 2806, XP055316148 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11498987B2 (en) 2018-02-28 2022-11-15 Lg Chem, Ltd. Polymer, coating composition comprising same, and organic light emitting element using same
WO2020008957A1 (fr) * 2018-07-06 2020-01-09 富士フイルム株式会社 Composition, film, lentille, élément d'imagerie à l'état solide, et composé
KR20210005669A (ko) * 2018-07-06 2021-01-14 후지필름 가부시키가이샤 조성물, 막, 렌즈, 고체 촬상 소자, 화합물
JPWO2020008957A1 (ja) * 2018-07-06 2021-04-30 富士フイルム株式会社 組成物、膜、レンズ、固体撮像素子、化合物
KR102477393B1 (ko) * 2018-07-06 2022-12-14 후지필름 가부시키가이샤 조성물, 막, 렌즈, 고체 촬상 소자, 화합물
JP7296960B2 (ja) 2018-07-06 2023-06-23 富士フイルム株式会社 組成物、膜、レンズ、固体撮像素子、化合物
TWI830746B (zh) * 2018-07-06 2024-02-01 日商富士軟片股份有限公司 組成物、膜、透鏡、固體攝像元件、化合物

Similar Documents

Publication Publication Date Title
US9425402B2 (en) Polymerizable monomer, and material for organic device, hole injection/transport material, material for organic electroluminescence element and organic electroluminescent element each comprising polymer (polymeric compound) of the polymerizable monomer
JP6106680B2 (ja) 高分子化合物、電子素子用材料、有機エレクトロルミネッセンス素子用材料及び有機エレクトロルミネッセンス素子
JP2012111719A (ja) 重合性単量体、その重合体を含む有機デバイス用材料、正孔注入輸送材料及び有機エレクトロルミネッセンス素子用材料、並びに有機エレクトロルミネッセンス素子
JP6307565B2 (ja) カルバゾール系重合体とそれを用いた有機エレクトロルミネッセンス素子
JP5802651B2 (ja) 芳香族アミン誘導体、及びそれを含む有機デバイス用材料、正孔注入輸送材料、有機エレクトロルミネッセンス素子用材料、並びに有機エレクトロルミネッセンス素子。
WO2014141725A1 (fr) Dérivé d'anthracène et élément électroluminescent organique l'utilisant
KR101933241B1 (ko) 가교형 중합체 및 그것을 이용한 유기 전계 발광 소자
US9837616B2 (en) Aromatic amine derivative, and organic electroluminescent element containing same
WO2014132636A1 (fr) Monomère polymérisable, matériau pour dispositif organique comprenant ledit polymère, matériau d'injection/de transport de trou, matériau pour élément électroluminescent organique et élément électroluminescent organique
JP2012062450A (ja) 新規重合性単量体と高分子化合物、それを用いた有機デバイス用材料、有機エレクトロルミネッセンス用材料、有機デバイス及び有機エレクトロルミネッセンス素子
US20120018710A1 (en) Novel polymerizable monomer and polymer of the polymerizable monomer, and material for organic device, hole injection/transport material and organic electroluminescent element each comprising the polymer
JPWO2009075223A1 (ja) 高分子化合物及びそれを用いた有機エレクトロルミネッセンス素子
JP2017066416A (ja) 共重合体、有機電子素子用材料、有機エレクトロルミネッセンス素子用材料及び有機エレクトロルミネッセンス素子
JP6737264B2 (ja) 交差共役系重合体、電子素子用材料、有機エレクトロルミネッセンス素子用材料及び有機エレクトロルミネッセンス素子
WO2016159293A1 (fr) Copolymère, matériau pour élément électronique, matériau pour élément électroluminescent organique et élément électroluminescent organique
JP2013087217A (ja) 架橋型重合体及びそれを用いた有機エレクトロルミネッセンス素子
JP2010034316A (ja) インク及びそれを用いて作成した有機エレクトロルミネッセンス素子
JP2013087216A (ja) 架橋型重合体及びそれを用いた有機エレクトロルミネッセンス素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16773173

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16773173

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP