WO2016159293A1

WO2016159293A1 - Copolymer, material for electronic element, material for organic electroluminescent element, and organic electroluminescent element

Info

Publication number: WO2016159293A1
Application number: PCT/JP2016/060784
Authority: WO
Inventors: 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: 2015-03-31
Filing date: 2016-03-31
Publication date: 2016-10-06

Abstract

Provided are: a copolymer which has positive hole transport properties and solubility and which is suitable for the formation of films by a coating method; a material for an electronic element and a material for an organic EL element which comprise the copolymer; a solution containing the copolymer; and an organic EL element. Provided are a copolymer containing a structural unit A represented by general formula (A), a structural unit B represented by general formula (B), and at least one structural unit C selected from a structural unit C1 represented by general formula (C1) and a structural unit C2 represented by general formula (C2), an organic electroluminescent element, an electronic device equipped with the organic electroluminescent element, a material for an organic electroluminescent element which comprises the copolymer, and a coating liquid.

Description

Copolymer, material for electronic device, material for organic electroluminescence device, and organic electroluminescence device

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. About.

Conventionally, in an electronic device such as an organic EL device, a film containing a material for causing the device to function is generally formed by a vapor deposition method. On the other hand, 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.

International Publication No. 2007/133632 JP 2010-196040 A JP 2005-309898 A

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.

As a result of intensive studies to achieve the above object, the present inventors have found that a copolymer containing the structural unit A, the structural unit B, and the structural unit C1 or the structural unit C2 has the above object. It has been found that this has been achieved, and the present invention has been completed.

[1] 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), and the following general formula A copolymer comprising at least one structural unit C selected from structural units C2 represented by (C2).

[Wherein, 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. ]

[In the formula, * 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;
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 .
However, the case of having an 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. ]

[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). Group, ether bond, thioether bond, ester bond, thioester bond,
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, A group represented by the general formula (B1) or a group represented by the following general formula (B2);
R ¹² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
n is an integer of 1 to 5.
However, when L ¹¹ is a group obtained by removing one hydrogen atom from the substituent represented by the general formula (A1), 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). ]

[In the formula, * 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. ]

[In the formula, * 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. ]

[In the formula, 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. A group having a methacrylate structure, a group having a methacrylamide structure, a group having a vinyl ether structure, a vinylamino group, or a group having a silanol structure;
R ⁵² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]

[Wherein, 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. Indicate
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. Substituted or unsubstituted ring-forming carbon atoms having a group having, a group having a methacrylic structure, a group having a methacrylate structure, a group having a methacrylamide structure, a group having a vinyl ether structure, a vinylamino group, or a group having a silanol structure An aromatic hydrocarbon ring group of 6 to 60, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms;
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 substituted or unsubstituted aromatic carbon atom having 6 to 60 ring carbon atoms having a group, a group having a methacrylate structure, a group having a methacrylamide structure, a group having a vinyl ether structure, a vinylamino group, or a group having a silanol structure A hydrogen ring group or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms is shown.
a is 0 or 1, b is 0 or 1, c is 0 or 1, and d is 0 or 1.
However, when b is 0, c is 1, and when c is 0, b is 1. ]
[2] The copolymer according to [1], wherein the content of the structural units C1 and C2 is 0.1 to 20% by mass based on the total of the structural units A, B, C1 and C2.
[3] The copolymer according to [1] or [2], wherein a mass ratio (A / B) between the structural unit A and the structural unit B is 90/10 to 10/90.
[4] The copolymer according to any one of [1] to [3], wherein the copolymer has a weight average molecular weight of 10,000 to 5,000,000.
[5] 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). The copolymer according to any one of [1] to [4].

[Wherein 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. Or an 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. Show.
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.
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 one. ]

[Wherein, 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] An aromatic heterocyclic group 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. 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.
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 one. ]

[Wherein 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. Show.
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.
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 one. ]

[In the formula, 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. Show
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.
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 one. ]

[ _Wherein , 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. Represents a 5-60 aromatic heterocyclic group, or a substituted or unsubstituted arylamino group;
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. ]
[6] 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.
[7] The copolymer according to any one of [1] to [6], wherein the structural unit C is the structural unit C1.
[8] An organic thin film layer composed of one layer or a plurality of layers is sandwiched between an anode and a cathode, and the organic thin film layer includes a light emitting layer, and at least one of the organic thin film layers includes [1 ] An organic electroluminescence device comprising the copolymer according to any one of [7] to [7].
[9] The organic electroluminescence device according to [8], wherein the organic thin film layer has a hole transport layer, and the hole transport layer includes the copolymer.
[10] An electronic device equipped with the organic electroluminescence element according to [9].
[11] A material for an organic electroluminescence device comprising the copolymer according to any one of [1] to [7].
[12] A coating solution comprising the copolymer according to any one of [1] to [7] and a solvent.
[13] A method for producing an organic electroluminescent element, comprising forming a thin film using the coating liquid according to [12].
[14] The method for producing an organic electroluminescent element according to [13], wherein the thin film is formed by a wet film forming method.

According to the present invention, 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). By having the said structure, the copolymer which has a hole transport characteristic and solubility and is suitable for forming a film | membrane by the apply | coating method is obtained.

In the present specification, 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.
Further, in the present specification, “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.

When the term “substituted or unsubstituted” is used, 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. More preferably 5 or 6 cycloalkyl group; 6 to 50 ring forming carbon atoms, preferably 6 to 24, more preferably 6 to 12 aryl groups; 6 to 50 ring forming carbon atoms, preferably 6 to 24 carbon atoms; More preferably, it has an aryl group of 6 to 12 and the alkyl moiety has 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; an amino group; 1 to 50 carbon atoms, preferably Mono- or dialkylamino group having an alkyl group of 1 to 10, more preferably 1 to 5; mono- or having an aryl group having 6 to 50 ring carbon atoms, preferably 6 to 24, more preferably 6 to 12 The A reelamino group; an alkoxy group having an alkyl group having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; 6 to 50 ring carbon atoms, preferably 6 to 24 carbon atoms, more preferably 6 to 12 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 mono-, di- or tri-substituted silyl group having a group selected from 12 aryl groups; 5 to 50, preferably 5 to 24, more preferably 5 to 12 ring-forming atoms and a heteroatom (nitrogen atom, oxygen atom) A heterocyclic group containing 1 to 5, preferably 1 to 3, more preferably 1 to 2 carbon atoms; 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. 1 to 8 A haloalkyl group having preferably 1 to 5, more preferably 1 to 3 halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) A group and an atom selected from the group consisting of a cyano group and a nitro group are preferred.
Among the above substituents, 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.

[Copolymer]
The structural unit A contained in the copolymer is represented by the following general formula (A).

[In the formula, * 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;
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 ^{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.
Examples of the alkyl group for R ¹ 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).

Wherein, 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. Show.
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. ]

[In the formula, 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. ]

[In the formula, 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). ]

[In the formula, 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). ]

[In the formula, 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 .) ]

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.

Wherein, 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). ]

Wherein, 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). ]

[In the formula, 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 Ar ₆ ^′ may be bonded to each other to form a ring,
Ar ₇ ^′ and Ar ₉ ^′ may be bonded to each other to form a ring,
Ar ₁₀ ^′ and Ar ₁₂ ^′ may be bonded to each other to form a ring.
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). ]

Specific examples of the 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.
Examples of the aromatic hydrocarbon ring group 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-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl Group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenyl-4-yl group Examples include a 4 ″ -t-butyl-p-terphenyl-4-yl group, a fluoren-1-yl group, a fluoren-2-yl group, a fluoren-3-yl group, and a fluoren-4-yl group. Preferably, phenyl group, naphthyl group, anthryl group, biphenyl group, p-terphenyl group, tolyl group, fluorenyl group, phenylene group, naphthylene group, anthracenylene group, biphenylene group, p-terphenylene group, tolylene group, fluorenylene group Etc.
Examples of these 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.

Specific examples of the 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.
Examples of the aromatic heterocyclic group 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-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, -Isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group Group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridyl group Nyl group, 1,7-phenanthroline-2-yl group, 1,7-phenanthroline-3-yl group, 1,7-phenanthroline-4-yl group, 1,7-phenanthroline-5-yl group, 1,7 -Phenanthroline-6-yl group, 1,7-phenanthroline-8-yl group, 1,7-phenanthroline-9-yl group, 1,7-phenanthroline-10-yl group, 1,8-phenanthroline-2-yl group 1,8-phenanthroline-3-yl group, 1,8-phenanthroline-4-yl group, 1,8-phenanthroline-5-yl group, 1,8-phenanthroline-6-yl group, 1,8- Phenanthroline-7-yl group, 1,8-phenanthroline-9-yl group, 1,8-phenanthroline-10-yl group, 1,9-phenanthroline-2-yl group, 1,9- Phenanthroline-3-yl group, 1,9-phenanthroline-4-yl group, 1,9-phenanthroline-5-yl group, 1,9-phenanthroline-6-yl group, 1,9-phenanthroline-7-yl group 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-yl group, 1,10-phenanthroline-2-yl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline -4-yl group, 1,10-phenanthroline-5-yl group, 2,9-phenanthroline-1-yl group, 2,9-phenanthroline-3-yl group, 2,9-phenanthroline-4-yl group, 2,9-phenanthroline-5-yl group, 2,9-phenanthroline-6-yl group, 2,9-phenanthroline-7-yl group, 2,9-phenant Rin-8-yl group, 2,9-phenanthroline-10-yl group, 2,8-phenanthroline-1-yl group, 2,8-phenanthroline-3-yl group, 2,8-phenanthroline-4-yl group 2,8-phenanthroline-5-yl group, 2,8-phenanthroline-6-yl group, 2,8-phenanthroline-7-yl group, 2,8-phenanthroline-9-yl group, 2,8-phenanthroline -10-yl group, 2,7-phenanthrolin-1-yl group, 2,7-phenanthroline-3-yl group, 2,7-phenanthroline-4-yl group, 2,7-phenanthroline-5-yl group, 2,7-phenanthroline-6-yl group, 2,7-phenanthroline-8-yl group, 2,7-phenanthroline-9-yl group, 2,7-phenanthroline-10-y Group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl Group, 2-methylpyrrol-3-yl group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl Group, 3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2 -Methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group, 4-t- Butyl-1-indolyl group, 2-t-butyl-3-indolyl group, 4-t-butyl-3-indolyl group, 2-thienyl group, 3-thienyl group, 2-benzothiophenyl group, 3-thiophenyl group 4-thiophenyl group, 5-thiophenyl group, 6-thiophenyl group, 7-thiophenyl group, 1-isothiophenyl group, 3-isothiophenyl group, 4-isothiophenyl group, 5-isothiophenyl group, 6 -Isothiophenyl group, 7-isothiophenyl group, 2-dibenzothiophenyl group, 4-dibenzothiophenyl group and the like.
Examples of the substituent 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.
Among these, preferably, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 2-dibenzothiophenyl group, 4-dibenzothiophenyl group, 2,2-bipyridin-4-yl group, 2,2-bipyridin-6-yl group, 2,2 ′: 2 ′, 2 ″ -terpyridin-4′-yl group, 2,2 ′: 6 ′, 2 ″ -terpyridin-4′-phenyl-4-yl group, benzothiazol-4-yl group, benzothiazol-5-yl group, trans-stilben-4-yl group, 2,2′-bithiophene-3- Yl group, 2,2'-bithiophen-5-yl group, 3,4-ethylenedioxythiophen-2-yl group, 7- (2-thienyl) -2,1,3-benzothiadiazole-4- (2 -Thienyl-5-yl) group and a divalent group thereof.

As the substituted or unsubstituted 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. In any case, as 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.
However, the case of having an 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.

Hereinafter, specific examples of the substituents of A ^1, is not limited to the following examples. In the specific formula, the bonding site may be substituted with any hydrogen.

Preferred examples of the structural unit A are as follows.

The structural unit B is represented by the general formula (B).

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.
Examples of the aromatic hydrocarbon ring group 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-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl Group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenyl-4-yl group Examples include a 4 ″ -t-butyl-p-terphenyl-4-yl group, a fluoren-1-yl group, a fluoren-2-yl group, a fluoren-3-yl group, and a fluoren-4-yl group. Preferably, phenyl group, naphthyl group, anthryl group, biphenyl group, p-terphenyl group, tolyl group, fluorenyl group, phenylene group, naphthylene group, anthracenylene group, biphenylene group, p-terphenylene group, tolylene group, fluorenylene group Etc.
Examples of these 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.
Examples of the alkyl group or alkenyl group having 4 to 60 carbon atoms of R ¹¹ 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), decyl group (including isomer groups), undecyl group (Including isomeric groups) and dodecyl groups (including isomeric groups) N-butyl group, sec-butyl group, t-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, or iso-octyl group is more preferable. preferable.

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. Examples of Y include an alkylene group having 2 to 4 carbon atoms. Examples of 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. Examples of Z include the above aryls. Examples of groups are given. 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.

[In the formula, * 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. In addition, R ^a may be substituted with any phenyl group, and the binding site * may be substituted with any, including R ^a . ]

[In the formula, * 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. Incidentally, 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.

Specific examples of the structural unit B are shown below, but are not limited to the following examples.

Among the examples of the structural unit B, more preferable examples are as follows.

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).

[Wherein, 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. Indicate
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. Substituted or unsubstituted ring-forming carbon atoms having a group having, a group having a methacrylic structure, a group having a methacrylate structure, a group having a methacrylamide structure, a group having a vinyl ether structure, a vinylamino group, or a group having a silanol structure An aromatic hydrocarbon ring group of 6 to 60, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms;
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 substituted or unsubstituted aromatic carbon atom having 6 to 60 ring carbon atoms having a group, a group having a methacrylate structure, a group having a methacrylamide structure, a group having a vinyl ether structure, a vinylamino group, or a group having a silanol structure A hydrogen ring group or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms is shown.
a is 0 or 1, b is 0 or 1, c is 0 or 1, and d is 0 or 1.
However, when b is 0, c is 1, and when c is 0, b is 1. ]

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.

In the general formula (C2), 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.

Specific examples of the structural unit C are shown below, but are not limited to the following examples.

Among the examples of the structural unit C, more preferable examples are as follows.

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.

For polymerization of the copolymer, 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.

In the polymerization of the copolymer, a chain transfer agent may be used as necessary to adjust the molecular weight.
Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, β-mercaptopropionic acid and methyl mercaptoacetate, α-methylstyrene dimer, and the like. When a chain transfer agent is used, 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.

When a solvent is used in the polymerization, 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 combination of two or more.

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 temperature and polymerization concentration (polymerization concentration (mass%) = [total mass of monomer components / (total mass of monomer components + solvent mass)] × 100) are the types and ratios of the monomers used, The polymerization concentration is, for example, 50 to 100% by mass although it varies depending on the molecular weight of the target copolymer.

When bulk polymerization is performed, 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. Moreover, the manufacturing method of the organic EL element of this invention is a method of forming an organic thin film layer by the apply | coating method using the coating liquid containing the polymer of this invention mentioned above.
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.
In the present invention, the polymer is more preferably contained as a main component of at least one of a hole transport layer and a hole injection layer. Specifically, in the hole transport layer or hole injection layer, the content of the polymer of the present invention is preferably 51 to 100% by mass.

As typical element configurations of the organic EL element of the present invention, the following structures (1) to (13) can be mentioned.
(1) Anode / light emitting layer / cathode (2) Anode / hole injection layer / light emitting layer / cathode (3) Anode / light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / light emitting layer / electron Injection layer / cathode (5) Anode / organic semiconductor layer / light emitting layer / cathode (6) Anode / organic semiconductor layer / electron barrier layer / light emitting layer / cathode (7) Anode / organic semiconductor layer / light emitting layer / adhesion improving layer / Cathode (8) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode (9) Anode / insulating layer / light emitting layer / insulating layer / cathode (10) Anode / inorganic semiconductor layer / insulating layer / Light emitting layer / insulating layer / cathode (11) Anode / organic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode (12) Anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / insulating layer / Cathode (13) Anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode Among these, the structure of the usual (8) Is preferably used, but is not limited thereto.

Each layer of the organic EL element can be formed by a conventionally known vacuum deposition method, spin coating method, or the like. For example, by 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.

The thickness of 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 μm. It is preferably 5 nm to 10 μm, more preferably 5 nm to 1 μm, and still more preferably 5 nm to 0.2 μm.

The layer containing the compound of the present invention (light emitting layer, hole transporting layer, electron transporting layer) 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.

As the coating method, 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. In particular, when fine patterning is required, 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. In addition, after the polymer is formed on the transfer precursor substrate by the wet film forming method, 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, toluene, ethyltoluene, methoxytoluene, dimethoxytoluene, trimethoxy Toluene, isopropyltoluene, xylene, butylxylene, isopropylxylene, anisole, ethylanisole, dimethylanisole, trimethylanisole, propylanisole, isopropylanisole, butylanisole, methylethylanisole, anetholeanisyl alcohol, methylbenzoate, ethylbenzoate, Propyl benzoate, butyl benzoate, diphenyl ether, Aromatic hydrocarbon solvents such as tilphenyl ether, benzyl methyl ether, benzyl ethyl ether, methylene dioxybenzene, methyl naphthalene, tetrahydronaphthalene, aniline, methyl aniline, ethyl aniline, butyl aniline, biphenyl, methyl biphenyl, isopropyl biphenyl, Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, tetradecane, decalin, isopropylcyclohexane, acetone , Ketone solvents such as methyl ethyl ketone, cyclohexanone, acetophenone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, phenyl acetate, ethylene glycol Polyhydric alcohols such as ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and the like Examples include derivatives, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. . These organic solvents can be used alone or in combination.

Of the above solvents, at least toluene, xylene, ethylbenzene, amylbenzene, anisole, 4-methoxytoluene, 2-methoxytoluene, 1,2-dimethoxybenzene from the viewpoints of solubility, film formation uniformity, viscosity characteristics, etc. , Mesitylene, tetrahydronaphthalene, cyclohexylbenzene, 2,3-dihydrobenzofuran, cyclohexanone, and methylcyclohexanone are preferably included.

Among the above-mentioned solvents, it is more preferable to use the above-described compound and a solvent represented by the following general formula (S1) having a boiling point of 110 ° C. or higher and a solubility in water at 20 ° C. of 1% by mass or less. .

(In the general formula (S1), each independently, R is a substituent having 1 to 20 carbon atoms, and n represents an integer of 0 to 6)

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. Preferably there is. In addition, 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. For 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.

In 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. For example, 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. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but more preferably in the range of 5 nm to 0.2 μm.
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.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[NMR measurement apparatus]
The nuclear magnetic resonance spectrum of the compound was measured with GSX-400 (trade name, resolution 400 MHz) manufactured by JEOL Ltd. Deuterated chloroform was used as the solvent.

[GPC measuring device]
Size exclusion chromatography (SEC) was used for molecular weight measurement. The measurement was performed by injecting 100 μl of a solution prepared by dissolving 10 mg of a sample in 10 ml of THF (tetrahydrofuran). The flow rate was 1 ml / min and the column temperature was set to 40 ° C. As the SEC apparatus, HLC-8220 manufactured by Tosoh Corporation was used. As the detector, a differential refraction (RI) detector or an ultraviolet-visible (UV) detector was used. As the column, two TSKgel GMH-XL and one TSKgel G2000-XL manufactured by Tosoh Corporation were used, and TSK standard polystyrene manufactured by Tosoh Corporation was used as the standard sample polystyrene.

[Synthesis Example 1: Synthesis of 3- (9-phenylcarbazol-3-yl) -9- (4-vinylphenyl) carbazole (Compound A-1)]

3- (9H-carbazol-3-yl) -9-phenyl-carbazole 12.24 g (0.03 mol), 4-fluorobenzaldehyde 7.44 g (0.06 mol), cesium carbonate 9.77 g (0.03 mol) Mol) and 50 mL of N-methylpyrrolidone were placed in a 200 mL flask and heated and stirred at 180 ° C. for 4 hours under an argon atmosphere. After cooling the reaction solution, the reaction solution was poured into 500 mL of water, and the resulting solid was washed twice with water. The obtained 4- [3- (9-phenylcarbazol-3-yl) carbazol-9-yl] benzaldehyde (2) was vacuum dried and used in the next step.
In a 200 mL three-necked flask, 13.93 g (0.039 mol) of triphenyl-methyl-phosphonium bromide and 50 mL of tetrahydrofuran (THF) were placed and cooled with ice water. To this, 4.38 g of potassium tert-butoxide was added and stirred at room temperature for 15 minutes. The mixture was cooled again with ice water, and 10.0 g (0.0915 mol) of 4- [3- (9-phenylcarbazol-3-yl) carbazol-9-yl] benzaldehyde was dissolved in 30 mL of THF and added dropwise. After completion of the dropwise addition, stirring was continued at room temperature for 3 hours. The reaction product was put into 400 mL of water, and the precipitated solid was separated and purified with a silica gel column (developing solvent: toluene / hexane = 9/1 (volume ratio)) to give 3- (9-phenylcarbazol-3-yl) -9. -(4-Vinylphenyl) carbazole (A-1) was obtained. The yield was 6.9 g (71% yield).

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) Into a 50 mL Schlenk tube, 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. After cooling, a solution prepared by dissolving 14.2 g (0.08 mmol) of N-bromosuccinimide in 100 mL of DMF was slowly added dropwise. After completion of the dropwise addition, the ice-water bath was removed, the temperature was returned to room temperature, and the mixture was stirred for 8 hours.
The reaction solution was dropped into water to precipitate a solid, and a precipitate was obtained by filtration. The obtained crude product was purified by silica gel chromatography (toluene), and the obtained solid was dried under reduced pressure to obtain 14.55 g (yield 56%).

In a 100 mL flask, 10.0 g (0.0149 mol) of 4- [3-bromo-6- (6-bromo-9-phenyl-carbazol-3-yl) carbazol-9-yl] benzaldehyde, phenylboronic acid, 4. 0 g (0.028 mol), 181 mg of tri (o-tolyl) phosphine, 67 mg of palladium acetate, 14.56 g of cesium carbonate, 20 mL of dioxane, 20 mL of toluene, and 15 mL of water were added, and deaeration-argon substitution was performed 5 times. After repeating several times, the mixture was heated and stirred at 90 ° C. for 25 hours. The solid in the reaction mixture was filtered off, and the solution was poured into methanol to precipitate a solid. This solid was purified with a silica gel column (developing solvent toluene / hexane = 8/2 (volume ratio)) to give 4- [3- (6,9-diphenyl-carbazol-3-yl) -6-phenyl-carbazole-9. -Yl] benzaldehyde 4.8 g (49% yield) was obtained.

A 200 mL three-necked flask was charged with 10.75 g (0.031 mol) of triphenyl-methyl-phosphonium bromide and 50 mL of THF and cooled with ice water. To this was added 3.45 g of potassium tert-butoxide, and the mixture was stirred at room temperature for 15 minutes. Cool again with ice water and dissolve 10.19 g (0.015 mol) of 4- [3- (6,9-diphenyl-carbazol-3-yl) -6-phenyl-carbazol-9-yl] benzaldehyde in 30 mL of THF. And then dropped. After completion of the dropwise addition, stirring was continued at room temperature for 3 hours. The reaction product was put into 400 mL of water, and the precipitated solid was separated and purified with a silica gel column (developing solvent: toluene / hexane = 9/1 (volume ratio)) to give 3,9-diphenyl-6- [6-phenyl-9. -(4-Vinylphenyl) carbazol-3-yl] carbazole (Compound A-33) was obtained. 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) Into a 50 mL Schlenk tube, 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.

[solution]
(Solubility test)
A ratio of 0.1, 0.5, 1.0, 2.0, 5.0, 10.0, 15.0% by mass is applied to a glass sample tube (SV-10 manufactured by Nidec Rika Glass Co., Ltd.). Assuming that the polymers of Comparative Examples 1 and 2 below, the polymers of Examples 1 and 2 and toluene (Electronic Industrial Grade manufactured by Kanto Chemical Co., Inc.) were weighed. Next, a stirrer (Azwan Laboran stirrer 10 mm × 4φ) was added, stirred at 90 ° C. for 30 minutes, and then cooled at room temperature for 1 hour. Visually check the state after cooling, and if it is transparent without any undissolved matter, it is judged that it has dissolved (○). If the liquid is cloudy or is transparent, there is a gel-like undissolved residue. In such a case, it was judged that it was not dissolved (x). The results are summarized in Table E-1.

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, and 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, and the molecular weight distribution Mw / Mn was 15.2.

(Insolubility test)
The compound of Comparative Example 2, Example 1 and Example 2 and toluene (Electronic Industrial Grade, manufactured by Kanto Chemical Co., Ltd.) are added to a glass sample tube (SV-10, manufactured by Nidec Rika Glass Co., Ltd.) at 0.8 wt%. Weighed out. Next, a stirrer (Azwan Laboran stirrer 10 mm × 4φ) was added, stirred at 90 ° C. for 30 minutes, and then cooled at room temperature for 1 hour to obtain a coating solution. 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. Using the coating solution and the glass substrate, 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 shape of the interface part immersed in the solution was measured using New View 6300 manufactured by zygo, and the insolubilization with toluene was calculated using the following formula: (residual film ratio = film thickness of the immersed part ÷ film thickness of the non-immersed part) Checked the situation. The results are shown in Table E-2.

[Organic EL device fabrication]
(Washing the substrate)
A 25 mm × 25 mm × 1.1 mm thick glass substrate with an ITO transparent electrode (manufactured by Geomatek Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 5 minutes.
(Formation of underlayer)
CLEVIUS AI4083 (trade name) manufactured by HERAEUS Co. as a material for the underlayer was formed on the ITO substrate with a thickness of 30 nm by spin coating. After the film formation, unnecessary portions were removed with acetone, and then baked in the air on a hot plate at 200 ° C. for 10 minutes to prepare a base substrate. All these operations were performed in the atmosphere.

(Formation of hole transport layer)
The compound of Comparative Example 2, Example 1 and Example 2 and toluene (Electronic Industrial Grade, manufactured by Kanto Chemical Co., Ltd.) are added to a glass sample tube (SV-10, manufactured by Nidec Rika Glass Co., Ltd.) at 0.8 wt%. Weighed out. Next, a stirrer (Azwan Laboran stirrer 10 mm × 4φ) was added, stirred at 90 ° C. for 30 minutes, and then cooled at room temperature for 1 hour to obtain a coating solution. Using this coating solution and the base substrate, a hole transport layer was formed on the AI4083 layer by spin coating. Unnecessary portions were removed from each spin-coated substrate with toluene, and then fired on a hot plate at 230 ° C. for 30 minutes to obtain a hole transport layer laminated substrate. From the preparation of the solution, all operations up to here were performed in a glove box in a nitrogen atmosphere.

(Formation of light emitting layer)
Compound H-1 as a host material and the following compound D-1 as a dopant material were used, and 1.6% by weight of toluene in a mixing ratio such that Compound H-1: Compound D-1 was 95: 5 by weight. A solution was prepared. Using this toluene solution, it was applied and laminated on the hole transport layer laminated substrate by spin coating so as to have a film thickness of 50 nm. After the coating film formation, unnecessary portions were removed with toluene, and dried by heating on a hot plate at 100 ° C. to prepare a coated laminated substrate on which a light emitting layer was formed. Note that all operations for forming the light emitting layer were performed in a glove box in a nitrogen atmosphere.

(Vapor deposition, sealing)
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.

Claims

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), and General formula (C2) A copolymer comprising at least one structural unit C selected from structural units C2 represented by

[Wherein, 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. ]

[In the formula, * 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;
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 .
However, the case of having an 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. ]

[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). Group, ether bond, thioether bond, ester bond, thioester bond,
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, A group represented by the general formula (B1) or a group represented by the following general formula (B2);
R 12 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
n is an integer of 1 to 5.
However, when L 11 is a group obtained by removing one hydrogen atom from the substituent represented by the general formula (A1), 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). ]

[In the formula, * 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. ]

[In the formula, * 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. ]

[In the formula, 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. A group having a methacrylate structure, a group having a methacrylamide structure, a group having a vinyl ether structure, a vinylamino group, or a group having a silanol structure;
R 52 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]

[Wherein, 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. Indicate
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. Substituted or unsubstituted ring-forming carbon atoms having a group having, a group having a methacrylic structure, a group having a methacrylate structure, a group having a methacrylamide structure, a group having a vinyl ether structure, a vinylamino group, or a group having a silanol structure An aromatic hydrocarbon ring group of 6 to 60, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms;
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 substituted or unsubstituted aromatic carbon atom having 6 to 60 ring carbon atoms having a group, a group having a methacrylate structure, a group having a methacrylamide structure, a group having a vinyl ether structure, a vinylamino group, or a group having a silanol structure A hydrogen ring group or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms is shown.
a is 0 or 1, b is 0 or 1, c is 0 or 1, and d is 0 or 1.
However, when b is 0, c is 1, and when c is 0, b is 1. ]
The copolymer according to claim 1, wherein the content of the structural units C1 and C2 is 0.1 to 20% by mass with respect to the total of the structural units A, B, C1 and C2.
The copolymer according to claim 1 or 2, wherein a mass ratio (A / B) between the structural unit A and the structural unit B is 90/10 to 10/90.
The copolymer according to any one of claims 1 to 3, wherein the copolymer has a weight average molecular weight of 10,000 to 5,000,000.
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). 5. The copolymer according to any one of 1 to 4.

[Wherein 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. Or an 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. Show.
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.
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 one. ]

[Wherein, 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] An aromatic heterocyclic group 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. 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.
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 one. ]

[Wherein 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. Show.
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.
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 one. ]

[In the formula, 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. Show
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.
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 one. ]

[ Wherein , 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. Represents a 5-60 aromatic heterocyclic group, or a substituted or unsubstituted arylamino group;
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 4 to 60 carbon atoms in total, or an aralkyl group having 4 to 60 carbon atoms in the alkyl moiety. The copolymer according to any one of claims 1 to 5.
The copolymer according to any one of claims 1 to 6, wherein the structural unit C is the structural unit C1.
An organic electroluminescent device comprising an organic thin film layer comprising a single layer or a plurality of layers sandwiched between an anode and a cathode, wherein the organic thin film layer includes a light emitting layer, wherein at least one layer of the organic thin film layer is provided. Organic electroluminescent element containing the copolymer of any one of these.
The organic electroluminescence device according to claim 8, wherein the organic thin film layer has a hole transport layer, and the hole transport layer contains the copolymer.
An electronic device equipped with the organic electroluminescence element according to claim 9.
An organic electroluminescent element material comprising the copolymer according to any one of claims 1 to 7.
A coating solution comprising the copolymer according to any one of claims 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 claim 12.
The method for producing an organic electroluminescent element according to claim 13, wherein the thin film is formed by a wet film forming method.