JP2020034689A - Organic electronic device and charge transport film - Google Patents

Abstract

To provide an organic electronic device comprising a charge transport film with visible light absorption property.SOLUTION: There is provided the organic electronic device comprising a charge transport film, the charge transport film comprises at least one kind out of a first charge transport resin having a specific structure, a crosslinked body of a first charge transport resin, a second charge transport polyester resin having a structure expressed by the general formula (1B), and a crosslinked body of a second charge transport polyester resin. In the general formula, Ais a divalent organic group comprising a charge transport, Tis a divalent hydrocarbon group, Yis a (n3+2)-th valent non-charge transport diol residue, Yis (*-(CH)-L-Z), * is a coupling position with Y, n3 and n4 are 1 or 2, L is a divalent coupling group or a single bond, and Z is a polymerizable functional group.SELECTED DRAWING: None

Description

  The present invention relates to an organic electronic device and a charge transporting film.

In recent years, electronic devices using organic compounds, such as electrophotographic photoreceptors, organic EL devices, organic transistors, and organic solar cells, have been actively developed.
In particular, in terms of heat resistance and strength, a crosslinked structure is effective. For example, an organic EL device using a thermosetting or photocured film (for example, see Patent Document 1), containing a charge transporting group (For example, see Patent Documents 2 to 4) and an electrophotographic photosensitive member in which an acrylic polymer containing a charge transporting group and a reactive group is crosslinked after forming a film (for example, see Patent Document 5) ), And a film cured by applying a liquid containing a photocurable acrylic monomer (see, for example, Patent Document 6). In addition, a mixture of a monomer having a carbon-carbon double bond, a charge transfer material having a carbon-carbon double bond, and a binder resin may be prepared by heating the mixture of the carbon-carbon double bond of the monomer and the charge transfer material by energy of heat or light. A film formed by reacting a carbon-carbon double bond is disclosed. In particular, a monofunctional methacryl-modified charge transfer material, a methacrylic monomer having no charge transport property, and a polycarbonate resin are disclosed. One cured using an oxide is disclosed (for example, see Patent Document 7). Further, a charge transporting polyester resin having a polymerizable functional group in a polymer main chain is also disclosed (for example, see Patent Document 8).

In addition, an organic semiconductor film and an electrophotographic photoreceptor (for example, see Patent Document 9) including a cured film in which a functional group is introduced into a terminal of a charge transporting resin and cured are disclosed.
Further, a charge transporting polyester containing a polymerizable unsaturated bond in at least one of the main chain and the terminal (Patent Document 10) is disclosed.

WO 1997/033193 JP-A-5-202135 JP-A-6-256428 JP-A-9-12630 JP 2005-2291 A JP-A-5-40360 JP-A-5-216249 JP 2013-73015 A JP 2001-117252 A JP-A-2000-264961

  An object of the present invention is to provide a charge transporting film having lower visible light absorption than a case where only poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] is used as the charge transporting resin. To provide an organic electronic device having the same.

The above problem is solved by the following means. That is,
<1>
A first charge transporting resin having a structure represented by the following general formula (1A-1) and a structure represented by the following general formula (1A-2), a crosslinked product of the first charge transporting resin, Organic having a second charge-transporting polyester resin having a structure represented by the general formula (1B) and a charge-transporting film containing at least one selected from crosslinked products of the second charge-transporting polyester resin Electronic device.

In the general formulas (1A-1) and (1A-2), A ¹ and A ² each independently represent a divalent organic group having a charge transporting property, and T ¹ and T ² each independently represent A linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ¹ and Y ² each independently represent a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group; , P and q each independently represent 0 or 1.

In the general formula (1B), A ³ represents a divalent organic group having a charge transporting property, T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ³ represents a (n3 + 2) -valent uncharged transporting diol residues, n3 represents 1 or 2, ^{Y 4} is _{"* - (CH 2) n4 -L} -Z " indicates, * is ^{Y 3} And n4 represents 1 or 2, L represents a divalent linking group or a single bond composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom; Z represents a polymerizable functional group.
<2>
The polymerizable functional group includes a group represented by the following general formula (P1), a group represented by the following general formula (P2), a group represented by the following general formula (P3), and a group represented by the following general formula (P4). The organic electronic device according to <1>, which is at least one selected from a group represented by the following general formula (P5) and a group represented by the following general formula (P5).

In the general formulas (P1) to (P5), R ^{3 to} R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * indicates a bonding position.
<3>
The polymerizable functional group is at least selected from a group represented by the following formula (P1-1), a group represented by the following formula (P1-2), and a group represented by the following formula (P3-1). The organic electronic device according to <2>, which is one.

In the formulas (P1-1), (P1-2), and (P3-1), * indicates a bonding position.
<4>
^{A 1} in the general formula (1A-1), ^{A 3} in the general formula (1A-2) in ^{A 2,} and the general formula (1B) represents a divalent organic group having hole transport ability < The organic electronic device according to any one of 1> to <3>.
<5>
^{A 1} in the general formula (1A-1), ^{A 3} in ^{A 2,} and the general formula (1B) in the general formula (1A-2) is a divalent organic represented by the following general formula (2) The organic electronic device according to <4>, which represents a group.

In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent. Represents an organic group, and k and m each independently represent 0 or 1.
<6>
^{T 1} in the general formula (1A-1), ^{T 3} in the general formula (1A-2) in ^{T 2,} and the general formula (1B) is a linear or branched of 1 to 8 carbon atoms The organic electronic device according to any one of <1> to <5>, which represents a divalent hydrocarbon group.
<7>
The total number of hydroxyl groups contained in the entirety of the first charge-transporting resin and the second charge-transporting polyester resin is defined as _MH, and the total number of hydroxyl groups in the first charge-transporting resin and the second charge-transporting polyester resin is when the total number of the polymerizable functional groups contained in the entire set to M _P, organic electronic device as claimed in any one of satisfying the following formula (A1) <1> ~ <6>.
Formula (A1): 0 ≦ _MH / ( _MH + _MP ) ≦ 0.9
<8>
Wherein _{M H} and the _{M P} is an organic electronic device according to the following formula satisfies the (A2) <7>.
Formula (A2): 0 ≦ _MH / ( _MH + _MP ) ≦ 0.6

<9>
The organic electronic device according to any one of <1> to <8>, wherein the number of atoms other than hydrogen atoms among the atoms constituting Y ³ in the general formula (1B) is 2 or more and 20 or less.
<10>
The organic electron according to any one of <1> to <9>, wherein the number of atoms other than hydrogen atoms among the atoms constituting L in Y ⁴ in the general formula (1B) is 1 or more and 10 or less. device.
<11>
The number of atoms other than hydrogen atoms of the atoms constituting the ^{Y 3} in the general formula (1B), the number of the general formula wherein in ^{Y 4} in (1B) n4, ^{Y 4} in the general formula (1B) The organic electronic device according to any one of <1> to <10>, wherein the total number of atoms other than hydrogen atoms among the atoms constituting the L is 25 or less.
<12>
Any of <1> to <11>, wherein the charge transporting film contains at least one selected from a crosslinked product of the first charge transportable resin and a crosslinked product of the second charge transportable polyester resin. The organic electronic device according to one.

<13>
The organic electronic device according to any one of <1> to <12>, wherein the organic electronic device is an electrophotographic photosensitive member.
<14>
The outermost surface layer of the electrophotographic photosensitive member has a charge transporting film containing at least one selected from a crosslinked product of the first charge transportable resin and a crosslinked product of the second charge transportable polyester resin. The organic electronic device according to <13>.
<15>
The organic electronic device according to any one of <1> to <12>, wherein the organic electronic device is an organic electroluminescent element.
<16>
A first charge transporting resin having a structure represented by the following general formula (1A-1) and a structure represented by the following general formula (1A-2), a crosslinked product of the first charge transporting resin, A charge transporting film containing a second charge transporting polyester resin having a structure represented by the general formula (1B), and at least one selected from a crosslinked product of the second charge transporting polyester resin.

In the general formulas (1A-1) and (1A-2), A ¹ and A ² each independently represent a divalent organic group having a charge transporting property, and T ¹ and T ² each independently represent A linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ¹ and Y ² each independently represent a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group; , P and q each independently represent 0 or 1.

In the general formula (1B), A ³ represents a divalent organic group having a charge transporting property, T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ³ represents a (n3 + 2) -valent uncharged transporting diol residues, n3 represents 1 or 2, ^{Y 4} is _{"* - (CH 2) n4 -L} -Z " indicates, * is ^{Y 3} And n4 represents 1 or 2, L represents a divalent linking group or a single bond composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom; Z represents a polymerizable functional group.

According to the invention according to <1>, <2>, <3>, <4>, <5>, <6>, <7>, <8>, <13>, or <15>, the charge transporting property is obtained. An organic electronic device having a charge transporting film having low visible light absorption compared to a case where only poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] is used as a resin is provided.
According to the invention according to <9>, the charge transporting film having a higher charge transporting property than the case where the number of atoms other than hydrogen atoms among the atoms constituting Y ³ in the general formula (1B) is larger than 20 is provided. An organic electronic device is provided.
According to the invention according to <10>, the charge transporting property is higher than that in the case where the number of atoms other than hydrogen atoms among the atoms constituting L in Y ⁴ in General Formula (1B) is more than 10. An organic electronic device having a conductive film is provided.
According to the invention according to <11>, in the general formula (1B), the number of atoms other than the hydrogen atom among the atoms constituting Y ³ , the number of n4 in Y ⁴ in the general formula (1B), and the general formula (1B) Provided is an organic electronic device having a charge transporting film having a high charge transporting property as compared with the case where the total number of atoms other than hydrogen atoms among the atoms constituting L in Y ⁴ in (1B) is more than 25. Is done.
According to the invention according to <12>, as compared with the case where the charge transporting film does not contain any of the crosslinked product of the first charge transporting resin and the crosslinked product of the second charge transporting polyester resin, the solvent resistance is higher. An organic electronic device having a high charge transporting film is provided.
According to the invention according to <14>, the outermost surface layer of the electrophotographic photoreceptor does not include any of a crosslinked body of the first charge transportable resin and a crosslinked body of the second charge transportable polyester resin. An organic electronic device in which the outermost layer has a higher mechanical strength than a film is provided.
According to the invention according to <16>, compared with the case where only poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] is used as the charge transporting resin, the charge having a lower visible light absorption is used. A transportable membrane is provided.

FIG. 2 is a schematic partial cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member according to the exemplary embodiment. FIG. 4 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the electrophotographic photosensitive member according to the exemplary embodiment. FIG. 4 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the electrophotographic photosensitive member according to the exemplary embodiment. FIG. 2 is a schematic cross-sectional view of an image forming apparatus including the process cartridge according to the embodiment. FIG. 1 is a schematic sectional view of a tandem-type image forming apparatus according to an embodiment. (A), (B), and (C) are explanatory diagrams each showing a ghost evaluation standard. FIG. 2 is a schematic partial cross-sectional view illustrating an example of a layer configuration of the organic electroluminescent element according to the embodiment. FIG. 4 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the organic electroluminescent element according to the embodiment. FIG. 4 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the organic electroluminescent element according to the embodiment. FIG. 4 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the organic electroluminescent element according to the embodiment.

  Hereinafter, embodiments of the present invention will be described in detail. These descriptions and examples illustrate the embodiments and do not limit the scope of the invention.

[Organic electronic devices]
The organic electronic device according to this embodiment includes a first charge transporting resin having a structure represented by the following general formula (1A-1) and a structure represented by the following general formula (1A-2), , A second charge-transporting polyester resin having a structure represented by the following general formula (1B), and at least one selected from the cross-linked products of the second charge-transporting polyester resin Having a charge transporting film.
Hereinafter, at least one selected from the first charge transporting resin and the second charge transporting polyester resin may be referred to as a “specific resin”, and a crosslinked product of the specific resin may be referred to as a “specific resin crosslinked product”. There is.

In the general formulas (1A-1) and (1A-2), A ¹ and A ² each independently represent a divalent organic group having a charge transporting property, and T ¹ and T ² each independently represent A linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ¹ and Y ² each independently represent a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group; , P and q each independently represent 0 or 1.

In the general formula (1B), A ³ represents a divalent organic group having a charge transporting property, T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ³ represents a (n3 + 2) -valent uncharged transporting diol residues, n3 represents 1 or 2, ^{Y 4} is _{"* - (CH 2) n4 -L} -Z " indicates, * is ^{Y 3} And n4 represents 1 or 2, L represents a divalent linking group or a single bond composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom; Z represents a polymerizable functional group.

The charge transporting film of the organic electronic device according to the present embodiment has a high charge transporting ability because it contains at least one selected from a specific resin and a crosslinked resin. Therefore, the organic electronic device has good electric characteristics by having the charge transporting film having high charge transporting ability.
In addition, the charge transporting film of the organic electronic device contains at least one selected from a specific resin and a crosslinked specific resin, so that it hardly absorbs visible light and has high transparency of visible light. Therefore, for example, when the organic electronic device is an organic electroluminescent element, light extraction efficiency is improved by having a charge transporting film having high visible light transmittance.
In addition, the charge transporting film of the organic electronic device contains at least one selected from a specific resin and a crosslinked resin, so that the coating film has high smoothness when the charge transporting film is formed. Therefore, since the organic electronic device has the charge transporting film having high smoothness, variation in the performance of the charge transporting film in the plane direction is suppressed.

Among the organic electronic devices described above, an organic electronic device having a charge transporting film containing a crosslinked specific resin has a charge transporting film having high solvent transportability and high charge transportability. Therefore, for example, when the organic electronic device is an organic electroluminescent device, the performance of the organic electroluminescent device is improved by applying a charge transporting film containing a specific resin crosslinked body as a lower layer (that is, a layer other than the outermost layer). And productivity is improved. Specifically, since the solvent resistance of the charge transporting film containing the crosslinked specific resin is high, when forming the upper layer further, the coating method (that is, a coating solution containing a solvent is applied to form the layer) Method) ", the performance of the organic electroluminescent device is not easily reduced due to the dissolution of the charge transporting film. Therefore, by using the charge transporting film containing the crosslinked specific resin as a lower layer, productivity is improved while suppressing a decrease in performance of the organic electroluminescent device.
Further, an organic electronic device having a charge transporting film containing a crosslinked specific resin has a charge transporting film having excellent mechanical strength while obtaining high charge transporting properties. Therefore, for example, when the organic electronic device is an electrophotographic photoreceptor, by applying a charge transporting film containing a specific resin crosslinked body as the outermost surface layer, the resistance to film reduction due to rubbing with a blade or the like is high, The life of the electrophotographic photosensitive member can be extended.

  Note that the charge transporting film of the organic electronic device is formed by mixing a specific resin with a monomer having a polyfunctional polymerizable functional group to form a film, thereby further increasing the cross-linking density and increasing the mechanical strength and the resistance. Solvent properties may be further enhanced. The charge transporting film obtained by mixing and forming a film having a monomer having a polyfunctional polymerizable functional group has a state in which the polymerizable functional group contained in the specific resin is branched from the main chain (that is, free movement). It is presumed that by being present in a high degree of state), cross-linking is efficiently performed.

<First charge transporting resin>
The first charge transporting resin has a structure represented by the following general formula (1A-1) and a structure represented by the following general formula (1A-2).

In the general formulas (1A-1) and (1A-2), A ¹ and A ² each independently represent a divalent organic group having a charge transporting property, and T ¹ and T ² each independently represent A linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ¹ and Y ² each independently represent a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group; , P and q each independently represent 0 or 1.

-Explanation of each group in general formula (1A-1) and general formula (1A-2)-
A ¹ and A ² in the general formula (1A-1) and the general formula (1A-2) each independently represent a divalent organic group having a charge transporting property, and specifically, a phthalocyanine compound, From porphyrin compounds, azobenzene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, quinone compounds, fluorenone compounds, etc. Derived divalent organic groups are mentioned.
A ¹ and A ² in the general formula (1A-1) and the general formula (1A-2) are preferably an organic group having a hole transporting ability among these, and among them, triarylamine More preferably, it is an organic group having at least one selected from a skeleton, a benzidine skeleton, and a stilbene skeleton.

Preferably, A ¹ and A ² in the general formulas (1A-1) and (1A-2) are each independently a divalent organic group represented by the following general formula (2).

In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent group. And k and m each independently represent 0 or 1.

  X in the general formula (2) represents a substituted or unsubstituted divalent organic group, and may be a group having or not having an aromatic ring. X in the general formula (2) is more preferably a group having an aromatic ring, and among them, a substituted or unsubstituted divalent aromatic group or a substituted or unsubstituted aromatic ring having 2 to 10 aromatic rings. The following divalent polynuclear aromatic hydrocarbon groups, substituted or unsubstituted divalent fused aromatic hydrocarbon groups having 2 to 10 aromatic rings, or substituted or unsubstituted divalent aromatic heterocyclic groups More preferably, there is.

“Polynuclear aromatic hydrocarbon group” refers to a hydrocarbon group in which two or more aromatic rings composed of carbon and hydrogen exist, and the rings are bonded to each other by a carbon-carbon bond. Specifically, a hydrocarbon group in which carbons constituting an aromatic ring are directly bonded by a carbon-carbon bond, and aromatic rings are linked by a hydrocarbon group having 1 to 18 carbon atoms (an alkyl chain or an alkylene chain). And the like.
Specific examples of the polynuclear aromatic hydrocarbon group include divalent groups from which two hydrogen atoms have been removed, such as biphenyl, terphenyl, stilbene, and triphenylethylene.
Note that the aromatic ring constituting the polynuclear aromatic hydrocarbon group may be a condensed aromatic hydrocarbon group described later or an aromatic heterocyclic ring. Specific examples of the condensed aromatic hydrocarbon group and the aromatic heterocyclic ring constituting the polynuclear aromatic hydrocarbon group include, for example, those similar to the compounds of the specific examples of the condensed aromatic hydrocarbon group and the aromatic heterocyclic ring described below. No.

  A “condensed aromatic hydrocarbon group” is a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen exist, and these aromatic rings share a pair of carbon atoms that are adjacently bonded to each other. Represents a group. Specifically, a divalent group from which two hydrogen atoms have been removed, such as naphthalene, anthracene, phenanthrene, pyrene, perylene, and fluorene, may be mentioned.

“Aromatic heterocycle” refers to an aromatic ring that also contains elements other than carbon and hydrogen.
Examples of the number of atoms (Nr) constituting the ring skeleton of the aromatic heterocycle include Nr = 5, Nr = 6, and the like. The type and number of atoms (heteroatoms) other than carbon atoms constituting the ring skeleton are not limited. Examples of the type of the hetero atom include a sulfur atom, a nitrogen atom, and an oxygen atom. Further, the aromatic heterocyclic ring may include two or more hetero atoms in the ring skeleton, or may include two or more hetero atoms.

  In particular, examples of the heterocycle having a ring skeleton structure of Nr = 5 (that is, a 5-membered ring structure) include, for example, thiophene, thiofin, pyrrole, furan, or a heterocycle obtained by further substituting the carbon at the 3- and 4-positions with nitrogen. And the like. Examples of the heterocyclic ring having a ring skeleton structure of Nr = 6 (that is, a 6-membered ring structure) include a pyridine ring and the like.

Examples of the substituent for the aromatic ring, the polynuclear aromatic ring, and the condensed aromatic ring include an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a substituted amino group, and a halogen atom.
The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
The alkoxyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a toluyl group.
The aralkyl group preferably has 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, and an aralkyl group, and specific examples are as described above.
Examples of the substituent of the substituted aryl group and the substituted aralkyl group include a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, and a halogen atom.

  Preferred examples of X in the general formula (2) include groups selected from the following formulas (X1) to (X7).

Formula (X1) in ~ ^{(X7), R 13} is a hydrogen atom, 1 or more and 4 or less carbon atoms alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl ^{group, R} 14 to R ^{And 19} independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom. , A represents 0 or 1, and V represents at least one group selected from the following formulas (V8) to (V17).

  In the above formulas (V8) to (V17), b represents an integer of 1 or more and 10 or less, and c represents an integer of 1 or more and 3 or less.

  X in the general formula (2) is preferably a divalent organic group selected from the group (A) shown below, and more preferably a divalent organic group selected from the group (B) shown below. Particularly preferred.

R ¹ and R ² in the general formula (2) each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a substituted or unsubstituted aryl group.
The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
The alkoxyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a toluyl group.
Examples of the substituent of the substituted aryl group include an alkyl group, an alkoxy group, a substituted amino group, and a halogen atom.

Among the above R ¹ and R ² , a hydrogen atom, a methyl group, an ethyl group, and a phenyl group are particularly preferable.
The position where R ¹ and R ² are substituted is preferably a meta position or a para position with respect to the position where nitrogen (N) is bonded.

Note that the ^{A 2} in the general formula ^{A 1} and the formula in (1A-1) (1A- 2), may be different even in the same. Further, when a plurality of the structure in which the first charge transport resin is represented by the general formula (1A-1), a plurality of A ^1, all may be the same or may be a part of the same, it may be different from each other However, it is preferable that 80% or more of the whole is the same, more preferably 90% or more of the whole is the same, and it is further preferable that they are all the same. If the first charge transporting resins having a plurality of structures represented by the general formula (1A-2), a plurality of A ^2, all may be the same or may be a part of the same, may be different from each other, It is preferable that 80% or more of the whole is the same, more preferably 90% or more of the whole is the same, and it is further preferable that they are all the same.

T ¹ and T ² in the general formula (1A-1) and the general formula (1A-2) each independently represent a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. T ¹ and T ² in the general formula (1A-1) and the general formula (1A-2) are each independently a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms. Is preferred. When the divalent hydrocarbon group is linear, the number of carbon atoms is more preferably in the range of 1 or more and 6 or less, and further preferably in the range of 2 or more and 6 or less. When the divalent hydrocarbon group is branched, the number of carbon atoms is more preferably in the range of 2 or more and 10 or less, and further preferably in the range of 3 or more and 7 or less.
The following are examples of specific structure of the group represented by group and T ² is represented by T ¹ (hydrocarbon group T-. 1 to hydrocarbon radicals T-32). However, A ¹ or A ² in the general formulas (1A-1) and (1A-2) may be bonded to either side of the following hydrocarbon group. For example, when represented by T-5r, the structure T on the right side of -5, the left side of the structure T-5 if referred to as T-5l, indicating that ^{the a 1} or ^{a 2} is bonded in the formula (1A-1) and the general formula (1A-2).

In General Formula (1A-1), when p is 1, T ¹ adjacent to the carbonyl group is preferably the above-described structures T-1, T-2, and T-4. Similarly, in the general formula (1A-2), when q is 1, the ^{T 2} adjacent to the carbonyl group, the structure T-1, T-2, and T-4 is preferred.

Note that the ^{T 2} in ^{T 1} and the general formula in formula (1A-1) (1A- 2), may be different even in the same. Also, if the first charge transporting resins having a plurality of structures represented by the general formula (1A-1), a plurality of T ^1, all may be the same or may be a part of the same, may be different from each other However, it is preferable that 80% or more of the whole is the same, more preferably 90% or more of the whole is the same, and it is further preferable that they are all the same. If the first charge transporting resins having a plurality of structures represented by the general formula (1A-2), a plurality of T ² are all may be the same or may be a part of the same, may be different from each other, It is preferable that 80% or more of the whole is the same, more preferably 90% or more of the whole is the same, and it is further preferable that they are all the same.

Hereinafter, A ¹ and T ¹ in the case where A ¹ and A ^{2 in the} general formulas (1A-1) and (1A-2) each represent a divalent organic group represented by the general formula (2). (Ie, X, R ¹ , R ² , k, and m in the general formula (2), and T ¹ and p in the general formula (1A-1)) or A ² and T combination of ² and q (i.e., ^X in formula (2) ^{in, R 1, R 2, k} , and m, and the general formula (a combination of 1A-2) in the ^{T 2} and q) a specific example of Although shown, the present invention is not limited to these specific examples.
In addition, in the following table, the numbers described in the columns of “R ¹ ” and “R ² ” represent the positions of the bonds. Also, the number that is listed in the "T ¹ or T ^2" is above specifically indicated structural formulas given number of hydrocarbon group (T-1) means - a (T-32). In the column of “T ¹ or T ² ”, for example, when “T-5r” is written, an aryl is placed on the right of the structure T-5, and when “T-5l” is written, an aryl is placed on the left of the structure T-5. This indicates that an amine skeleton (that is, A ¹ or A ² in the general formulas (1A-1) and (1A-2)) is bonded. Further, in the following table, the value shown in the “bonding position” indicates that the bond is at the position of the numerical value described in the benzene ring in the general formula (2), and when k is 1, when (k) is 1, The benzene ring in parentheses indicates that it is bonded to the same position as the benzene ring in which the number is described.

In formulas (1A-1) and (1A-2), Y ¹ and Y ² each independently represent a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group.
Examples of the polymerizable functional group include a group containing at least one selected from a carbon-carbon double bond, an epoxy group, and an oxetane group. Specific examples of the polymerizable functional group include, for example, a vinyl group, a vinyl ether group, a group represented by the following general formula (P1), a group represented by the following general formula (P2), and a group represented by the following general formula (P3). A group represented by the following general formula (P4), a group represented by the following general formula (P5), and the like.
Among these, the polymerizable functional group includes a group represented by the following general formula (P1), a group represented by the following general formula (P2), a group represented by the following general formula (P3), and a group represented by the following general formula (P3). It is preferably at least one selected from the group represented by P4) and the group represented by the following general formula (P5).

In the general formulas (P1) to (P5), R ^{3 to} R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * indicates a bonding position.
The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkyl group preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and particularly preferably has 1 to 2 carbon atoms.
The alkoxyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. The alkoxy group preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and particularly preferably has 1 to 2 carbon atoms.
The substitution position of the group represented by the general formula (P3) may be any of the ortho position, the meta position, and the para position, and among them, at least one selected from the meta position and the para position is preferable, and the para position is preferable. Is more preferred. In the case where the first charge transporting resin has a plurality of groups represented by the general formula (P3), at least two kinds of substitution positions selected from the ortho, meta, and para positions are mixed. It may be.

When Y ¹ and Y ² in the general formulas (1A-1) and (1A-2) represent a group having a polymerizable functional group, for example, the polymerizable functional group further having a substituent may be an oxygen atom And the case where the substituted or unsubstituted polymerizable functional group is bonded to an oxygen atom via a linking group.

Examples of the substituent further included in the polymerizable functional group include a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a substituted amino group, and a halogen atom.
The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkyl group preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and particularly preferably has 1 to 2 carbon atoms.
The alkoxyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. The alkoxy group preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and particularly preferably has 1 to 2 carbon atoms.
The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a toluyl group.
The aralkyl group preferably has 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, and an aralkyl group, and specific examples are as described above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.

  Examples of the linking group linking the polymerizable functional group and the oxygen atom include, for example, a divalent linking group composed of at least one atom selected from a carbon atom and an oxygen atom (hereinafter, also referred to as L1). ). Examples of L1 include a group formed by arbitrarily combining alkylene, -O-, and -C (= O)-. The total number of atoms other than hydrogen atoms constituting L1 is, for example, 1 or more and 15 or less, preferably 1 or more, and more preferably 1 or more and 6 or less. When the total number of atoms other than the hydrogen atoms constituting L1 is in the above range, the ratio of the charge transporting skeleton is higher than in the case where the number is more than the above range, and the electric characteristics are improved.

The following, among the groups represented by group and Y ² is expressed by Y ^1, examples of the specific structure of the group having a polymerizable functional group or a polymerizable functional group (group Y-. 1 to group Y-22 ). However, in the following formula, Me means a methyl group and Et means an ethyl group.

Note that Y ¹ in the general formula (1A-1) and Y ² in the general formula (1A-2) may be the same or different. Further, the plurality of Y ¹ in the first charge transporting resin may be all the same, partly the same, or different from each other. Similarly, the plurality of Y ² in the first charge transporting resin may be all the same, partly the same, or different from each other.
That is, in the molecule of the first charge transporting resin, a hydrogen atom, a polymerizable functional group, and a polymerizable functional group are represented as Y ¹ and Y ² in the general formulas (1A-1) and (1A-2). At least one kind of group selected from the groups may be present. Further, all of the plurality of Y ¹ and the plurality of Y ² may be hydrogen atoms, and all of the plurality of Y ¹ and the plurality of Y ² are selected from a polymerizable functional group and a group having a polymerizable functional group. At least one type may be used.

The number of structures represented by the general formula (1A-1) included in the first charge transporting resin is, for example, 5 or more and 5000 or less, preferably 5 or more and 2000 or less, and more preferably 10 or more and 1000 or less. It is as follows. Note that a plurality of structures represented by the general formula (1A-1) may not be adjacent to each other.
The number of structures represented by the general formula (1A-2) in the first charge transporting resin is, for example, 5 or more and 5000 or less, preferably 5 or more and 2000 or less, and more preferably 10 or less. It is 1000 or more. Similarly, a plurality of structures represented by the general formula (1A-2) may not be adjacent to each other.
Note that the first charge transporting resin has 5 or more of the structure represented by the general formula (1A-1) and the structure represented by the general formula (1A-2), respectively, and has a weight average molecular weight of 20. It is preferably not more than 10,000.

  The first charge transporting resin has, for example, a region in which the structure represented by the general formula (1A-1) and the structure represented by the general formula (1A-2) are alternately adjacently bonded. It may be. That is, the first charge transporting resin may be a resin having a structure represented by the following general formula (1A-3). The number of structures represented by the following general formula (1A-3) contained in the first charge transporting resin is, for example, 5 or more and 5000 or less, preferably 5 or more and 2000 or less, more preferably 10 or more and 1000 or less. preferable. Further, the proportion of the structure represented by the following general formula (1A-3) with respect to the entire first charge transporting resin is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. .

In the general formula (1A-3), A ¹ and A ² each independently represent a divalent organic group having a charge transporting property, and T ¹ and T ² each independently represent a straight chain having 1 to 10 carbon atoms. Jo or shows a branched divalent hydrocarbon group, Y ¹ and Y ² each independently represent a hydrogen atom, polymerizable functional group, or a group having a polymerizable functional group, p and q are each independently 0 Or 1 is shown.
That is, in the general formula (1A-3), A ¹ , A ² , T ¹ , T ² , Y ¹ , Y ² , p, and q represent the general formula (1A-1) and the general formula (1A), respectively. The same as A ¹ , A ² , T ¹ , T ² , Y ¹ , Y ² , p and q in -2).

-Description of the first charge transporting resin-
The first charge transporting resin only needs to have at least a structure represented by the general formula (1A-1) and a structure represented by the general formula (1A-2) in a molecule, and the first charge transporting resin has the general formula (1A) In addition to the structure represented by -1) and the structure represented by the general formula (1A-2), another structure may be included in the molecule. For example, a form in which a monovalent substituent or another monovalent structural unit is bonded to the terminal of the structure represented by the general formula (1A-1), or the terminal of the structure represented by the general formula (1A-2) Examples include a form in which a monovalent substituent or another monovalent structural unit is bonded. Examples of the form having a structure represented by the general formula (1A-1) and a structure other than the structure represented by the general formula (1A-2) in the main chain of the first charge transporting resin include: For example, a form in which the unit of the structure represented by the general formula (1A-1) and the unit of the structure represented by the general formula (1A-2) are bonded via another structure is exemplified.
When the first charge transporting resin has another structure in the molecule, the structure represented by the general formula (1A-1) and the general formula (1A-2) based on the entire first charge transporting resin. The ratio of the total structure is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
Note that the total ratio of the structure represented by the general formula (1A-1) and the structure represented by the general formula (1A-2) is calculated from an area ratio of each peak in an NMR spectrum or an infrared absorption spectrum. Is done. Alternatively, it may be calculated by quantifying the amount of a monomer remaining without polymerization (for example, a compound represented by the following general formula (3A) and a compound represented by the general formula (4A)).

The total number of hydroxyl groups contained in the entire first charge transport resin and M _H, when the total number of polymerizable functional groups contained in the entire first charge transporting resin was M _P, satisfies the following formula (A1) It is more preferable that the following formula (A2) is satisfied, and it is more preferable that the following formula (A3) is satisfied.
Formula (A1): 0 ≦ _MH / ( _MH + _MP ) ≦ 0.9
Formula (A2): 0 ≦ _MH / ( _MH + _MP ) ≦ 0.6
Formula (A3): 0 ≦ _MH / ( _MH + _MP ) ≦ 0.3
The value of M _H / (M _H + M _P ) is calculated from the area ratio of each peak in the NMR spectrum or infrared absorption spectrum.

The weight average molecular weight of the first charge transporting resin is, for example, 2,000 to 500,000, preferably 3,000 to 200,000, more preferably 4,000 to 100,000.
The weight-average molecular weight is measured by preparing a 0.1% by mass THF (tetrahydrofuran) solution of a compound to be measured and using a differential refractive index detector (RI) to perform gel permeation chromatography (GPC) on a standard sample. Using a styrene polymer.

Hereinafter, specific examples of the first charge transporting resin in which A ¹ in the general formula (1A-1) and A ² in the general formula (1A-2) are the above general formula (2) are shown. It is not limited to the examples.
In the following table, the numbers described in the columns of “A ¹ , T ¹ , p” and “A ² , T ² , q” correspond to A ¹ , T ^1, and p in the general formula (1A-1). Or the numbers (2-1) to (2-102) given to specific examples of the combination of A ² , T ² and q in the general formula (1A-2). In addition, among the numbers described in the column of “Y ¹ or Y ² ”, H means a hydrogen atom, and the other numbers indicate specific structures of the polymerizable functional group or the group having a polymerizable functional group. The numbers (Y-1) to (Y-22) attached to the examples are meant. In the following table, “n1” means the number of structures represented by the general formula (1A-1) possessed by the first charge transporting resin, and “n2” possessed by the first charge transporting resin It means the number of structures represented by the general formula (A1-2).

-Synthesis method (first charge transporting resin production method)-
Next, a method for synthesizing the first charge transporting resin will be described.
Among the first charge transporting resins, a charge transporting resin in which all of a plurality of Y ¹ and a plurality of Y ² are hydrogen atoms (hereinafter also referred to as “specific charge transporting resin (AI)”) is, for example, It is obtained by polymerization of a compound represented by the general formula (3A) and a compound represented by the following general formula (4A) (polymerization step).
Specifically, for example, the synthesis is carried out using an equivalent amount of a compound represented by the following general formula (3A) and a compound represented by the following general formula (4A) and using a catalyst in a solvent.

In the general formulas (3A) and (4A), A ¹ and A ² each independently represent a divalent organic group having a charge transporting property, and T ¹ and T ² each independently represent a C ^{1 to} C 10 having no more than 10 carbon atoms. It represents a linear or branched divalent hydrocarbon group, and p and q each independently represent 0 or 1.
Note that A ¹ and A ² , T ¹ and T ² , and p and q in the general formulas (3A) and (4A) are the same as those in the general formulas (1A-1) and (1A-2). Same as A ¹ and A ² , T ¹ and T ² , and p and q.

The specific charge transporting resin (AI) is synthesized, for example, by using an equivalent amount of the compound represented by the general formula (3A) and the compound represented by the general formula (4A) and using a catalyst in a solvent.
Examples of the solvent include toluene, xylene, tetrahydrofuran, monochlorobenzene and the like. These may be used alone or in combination of two or more.
Examples of the solvent include toluene, xylene, tetrahydrofuran, monochlorobenzene and the like. These may be used alone or in combination of two or more.
Examples of the catalyst include quaternary ammonium salts, tertiary amines, tertiary phosphines, quaternary phosphonium salts, lithium halides, trifluoroboron complex salts and the like. These may be used alone or in combination of two or more.

  As the quaternary ammonium salt, for example, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydroxide, methyltributylammonium chloride, tetramethylammonium chloride Propyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, tetrabutyl ammonium hydroxide, tetrabutyl ammonium hydrogen sulfate, methyl trioctyl ammonium chloride, methyl trioctyl ammonium bromide, ethyl trioct Ammonium chloride, ethyltrioctylammonium bromide, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, stearyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyl Triethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium hydroxide and the like.

Examples of the tertiary amine include triethylamine, tributylamine, dimethylethanolamine, tris (N, N-dimethylaminomethyl) phenol, tris (N, N-diethylaminomethyl) phenol, N, N-dimethylaminomethylphenol, N , N-dimethylbenzylamine and the like.
As the tertiary phosphine, for example, triphenylphosphine and the like can be mentioned.
As the quaternary phosphonium salt, for example, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, methyltributylphosphonium iodide, methyltrioctylphosphonium chloride, methyltrioctyl Examples thereof include phosphonium bromide, ethyltrioctylphosphonium chloride, ethyltrioctylphosphonium bromide, decyltributylphosphonium chloride, hexadecyltributylphosphonium chloride, and ethyltrioctylphosphonium chloride.
Examples of the lithium halide include lithium chloride and lithium bromide.
Examples of the trifluoroboron complex salt include boron trifluoride diethyl ether complex.

The amount of the catalyst to be added is, for example, 1 part by mass of the total mass of the monomers (that is, the sum of the mass of the compound represented by the general formula (3A) and the mass of the compound represented by the general formula (4A)). , 1 / 10,000 to 1/10 parts by mass, preferably 1/1000 to 1/50 parts by mass.
The addition amount of the solvent is, for example, 1 part by mass or more and 100 parts by mass or less, preferably 2 parts by mass or more and 50 parts by mass or less with respect to 1 part by mass of the generated charge transporting resin.
The reaction temperature (that is, the polymerization temperature of the compound represented by the general formula (3A) and the compound represented by the general formula (4A)) is not particularly limited, and may be, for example, in the range of 30 ° C to 100 ° C. No.

After the polymerization reaction between the compound represented by the general formula (3A) and the compound represented by the general formula (4A) is completed, for example, a poor solvent (for example, methanol) in which the obtained charge transporting resin is difficult to dissolve. , An alcohol such as ethanol, acetone, etc.) to precipitate the charge transporting resin, separate it, wash it with water, an organic solvent or the like, and dry it.
Further, if necessary, the re-precipitation treatment of dissolving in an organic solvent, dropping it into a poor solvent, and depositing a charge transporting resin may be repeated. The reprecipitation treatment is preferably performed while stirring with a mechanical stirrer or the like. The amount of the solvent for dissolving the charge transporting resin during the reprecipitation treatment is, for example, in the range of 1 part by weight or more and 100 parts by weight or less based on 3 parts by weight of the charge transporting compound, preferably 2 parts by weight. It is not less than 50 parts by mass and not more than 50 parts by mass. The amount of the poor solvent is, for example, 1 part by mass or more and 1000 parts by mass or less, preferably 10 parts by mass or more and 500 parts by mass or less based on 1 part by mass of the charge transporting resin.
After the polymerization reaction between the compound represented by the general formula (3A) and the compound represented by the general formula (4A) is completed, for example, the reaction solution is poured into water and a solvent such as toluene, hexane, or ethyl acetate is added. , And may be further washed with an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay if necessary.
Thus, by polymerizing the compound represented by the general formula (3A) and the compound represented by the general formula (4A), the structure represented by the general formula (1A-1) and the general formula (1A) Among the first charge transporting resins having the structure represented by -2), the first charge transporting resin having the structure represented by the general formula (1-3) is obtained.

Charge transport having at least one selected from a polymerizable functional group and a group having a polymerizable functional group as at least a part of the plurality of Y ¹ and the plurality of Y ² in the first charge transport resin. The reactive resin (hereinafter also referred to as “specific charge transporting resin (AII)”) is obtained by, for example, polymerizing a compound represented by the general formula (3A) and a compound represented by the general formula (4A) ( That is, after the polymerization step), the obtained polymer is reacted with a compound having a polymerizable functional group to introduce a polymerizable functional group into the polymer.
In this manner, the compound represented by the general formula (1A-1) is obtained by polymerizing the compound represented by the general formula (3A) and the compound represented by the general formula (4A) and then reacting with the compound having a polymerizable functional group. Among the first charge transporting resins having the structure represented by the general formula (1A-2) and the structure represented by the general formula (1A-2), the first charge transporting resin having the structure represented by the general formula (1-3) A resin is obtained.
The step of polymerizing the compound represented by the general formula (3A) and the compound represented by the following general formula (4A) (polymerization step) is described in the method for synthesizing the specific charge transport resin (AI). As you did.
In the step of introducing a polymerizable functional group into the obtained polymer (that is, the introduction step), specifically, for example, the obtained polymer and a compound having a polymerizable functional group are added to a solvent, and The reaction is carried out using a catalyst according to.

  Examples of the compound having a polymerizable functional group include, for example, leaving groups (for example, an OH group, a halogen atom, or a leaving group) at Y-1 to Y-4, Y-13 to Y-14, and Y-16 to Y-18. A carboxylic acid derivative substituted with another carboxylic acid or the like, or a leaving group (for example, a halogen atom, a trifluoromethanesulfonyloxy group, or a trifluoromethanesulfonyloxy group) on Y-5 to Y-12, Y-15, and Y-19 to Y-22; or (p-toluenesulfonyloxy group, etc.). A polymerizable functional group is introduced by adding a known catalyst or a condensing agent or the like as necessary to the reaction.

Examples of the solvent used in the step of introducing a polymerizable functional group into the obtained polymer include methylene chloride, diethyl ether, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene, acetone, methyl ethyl ketone, N, N- Examples include dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and the like.
The amount of the solvent to be added is, for example, 1 part by mass or more and 100 parts by mass or less, preferably 2 parts by mass or more and 50 parts by mass or less based on 1 part by mass of the obtained charge transporting resin.

When a compound having a carboxy group is used as the compound having a polymerizable functional group, for example, sulfuric acid, p-toluenesulfonic acid, or the like may be used as a catalyst.
When at least one of a carboxylic anhydride and a halide is used as the compound having a polymerizable functional group, for example, pyridine, piperidine, dimethylaminopyridine, trimethylamine, 1,8-diazabicyclo [5.4. 0] -7-undecene (DBU), triethylamine and the like; inorganic bases such as sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide and potassium hydroxide; and the like.
The addition amount of the catalyst is, for example, 1 equivalent to 10 equivalents, preferably 2 equivalents to 5 equivalents, based on the compound having a polymerizable functional group.
The reaction temperature (that is, the reaction temperature between the polymer and the compound having a polymerizable functional group) is not particularly limited, and may be, for example, in a range of 30 ° C or more and 100 ° C or less.

  After the reaction between the polymer and the compound having a polymerizable functional group is completed, as in the case where the compound represented by the general formula (3A) and the compound represented by the general formula (4A) are polymerized, Reprecipitation treatment and purification may be performed.

<Second charge transporting polyester resin>
The second charge transporting polyester resin has a structure represented by the following general formula (1B).

In the general formula (1B), A ³ represents a divalent organic group having a charge transporting property, T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ³ represents a (n3 + 2) -valent uncharged transporting diol residues, n3 represents 1 or 2, ^{Y 4} is _{"* - (CH 2) n4 -L} -Z " indicates, * is ^{Y 3} And n4 represents 1 or 2, L represents a divalent linking group or a single bond composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom; Z represents a polymerizable functional group.

-Description of each group in general formula (1B)-
A ³ in the general formula (1B) represents a divalent organic group having a charge transporting property, and specifically, a phthalocyanine compound, a porphyrin compound, an azobenzene compound, a triarylamine compound, a benzidine compound. And divalent organic groups derived from arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, quinone compounds, fluorenone compounds, and the like.
A ³ in the general formula (1B) is preferably an organic group having a hole transporting ability among these, and among them, at least one selected from a triarylamine skeleton, a benzidine skeleton, and a stilbene skeleton is preferable. It is more preferable that the organic group has an organic group.

A ³ in the general formula (1B) is preferably a divalent organic group represented by the following general formula (2).

In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent group. And k and m each independently represent 0 or 1.
The details of each group in the general formula (2) are as described above.

If the second charge-transporting polyester resin having a plurality of structures represented by the general formula (1B), a plurality of A ^3, all may be the same or may be a part of the same, may be different from each other, overall Is preferably the same, and more preferably 90% or more of the whole is the same, and all the same is more preferable.

T ³ in the general formula (1B) represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. T ³ in the general formula (1B) is preferably a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms. When the divalent hydrocarbon group is linear, the number of carbon atoms is more preferably in the range of 1 or more and 6 or less, and further preferably in the range of 2 or more and 6 or less. When the divalent hydrocarbon group is branched, the number of carbon atoms is more preferably in the range of 2 or more and 10 or less, and further preferably in the range of 3 or more and 7 or less.
In addition, as an example of the specific structure of the group represented by T ³ , for example, “carbonized” exemplified as the specific structure of the group represented by T ¹ and the group represented by T ² described above. Hydrogen group T-1 to hydrocarbon group T-32 ".

When the second charge-transporting polyester resin having a plurality of structures represented by the general formula (1B), a plurality of T ³ are all may be the same or may be a part of the same, may be different from each other , 80% or more of the whole is preferably the same, 90% or more of the whole is more preferably the same, and all the same is more preferable.

Hereinafter, when A ^{3 in the} general formula (1B) represents a divalent organic group represented by the general formula (2), a combination of A ³ and T ³ (that is, a combination of A ³ and T ³ in the general formula (2)) Specific examples of X, R ¹ , R ² , k, and m, and T ^{3 in} the general formula (1B) are shown below, but the present invention is not limited to these specific examples.
In addition, in the following table, the numbers described in the columns of “R ¹ ” and “R ² ” represent the positions of the bonds. Further, the numbers described in the column of “T ³ ” mean the numbers (T-1) to (T-32) given to the structural formulas of the hydrocarbon groups specifically shown above. Incidentally, in the column of "T ^3", for example, the right-hand structure T-5 if referred to as "T-5r", "T-5l" and arylamine skeleton on the left side of the structure T-5 if referred ( That is, it indicates that A ³ ) in the general formula (1B) is bonded. Further, in the following table, the value shown in the “bonding position” indicates that the bond is at the position of the numerical value described in the benzene ring in the general formula (2), and when k is 1, when (k) is 1, The benzene ring in parentheses indicates that it is bonded to the same position as the benzene ring in which the number is described.

Y ³ in the general formula (1B) represents a (n3 + 2) -valent non-charge-transporting diol residue. The diol residue is a linking group connecting an oxygen atom to an oxygen atom, and is preferably a linking group composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom.
The linking group represented by Y ³ is preferably a hydrocarbon group or a linking group combining a hydrocarbon group and an oxygen atom, and is a hydrocarbon group or a linking group combining a hydrocarbon group and an ether bond. More preferably, there is. The hydrocarbon group may be any of a saturated hydrocarbon group, an unsaturated hydrocarbon group, and an aromatic hydrocarbon group, and may be a group obtained by combining two or more of these hydrocarbon groups. The two or more hydrocarbon groups may be the same hydrocarbon group or different hydrocarbon groups.

The saturated hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Examples of the saturated hydrocarbon group include a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 2 to 10 carbon atoms, a cyclic alkylene group having 5 to 8 carbon atoms, and a combination thereof. And the like.
The unsaturated hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Examples of the unsaturated hydrocarbon group include a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, and a cyclic alkenyl group having 5 to 8 carbon atoms, or a combination thereof. And the like.
The aromatic hydrocarbon group is a cyclic linking group containing at least an aromatic ring, and examples thereof include a divalent group excluding a hydrogen atom such as benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, and fluorene.
Examples of the group in which two or more hydrocarbon groups are combined include, in addition to a group in which two or more aromatic hydrocarbon groups are combined, an aromatic hydrocarbon group, a saturated hydrocarbon group and an unsaturated hydrocarbon group. A group to which at least one kind of group is bonded is exemplified.

Among these, the linking group represented by Y ³ is a hydrocarbon group obtained by combining two or more of at least one group selected from a saturated hydrocarbon group, an aromatic hydrocarbon group, a saturated hydrocarbon group and an aromatic hydrocarbon group. And a group obtained by combining these hydrocarbon groups with an oxygen atom is preferable, and at least one group selected from a saturated hydrocarbon group, an aromatic hydrocarbon group, a saturated hydrocarbon group and an aromatic hydrocarbon group is two or more. Hydrocarbon groups in combination, and groups in which these hydrocarbon groups and ether bonds are combined are more preferable, and saturated hydrocarbon groups and groups in which saturated hydrocarbon groups and ether bonds are combined are even more preferable.

Also, if the linking group represented by Y ³ is an oxygen atom, the linking group represented by Y ³ may be a through an oxygen atom plurality of hydrocarbon radicals linked group. The plurality of hydrocarbon groups may be the same kind of hydrocarbon group or different kinds of hydrocarbon groups.
However, the main chain terminal of the atoms of the linking group represented by Y ³ (i.e., among the atoms constituting the linking group represented by Y ^3, directly attached to atoms to the oxygen atom in the general formula (1B)), the Both are preferably carbon atoms.
Of the atoms constituting the linking group represented by Y ³ , the atom directly bonded to the group represented by Y ⁴ is preferably a carbon atom, and among them, the main chain of the linking group represented by Y ³ is More preferably, it is a constituent carbon atom.

The number of atoms other than hydrogen atoms among the atoms constituting the linking group represented by Y ³ is, for example, 2 or more and 32 or less, preferably 2 or more and 22 or less, more preferably 2 or more and 20 or less, and more preferably 2 or more and 15 or less. The following are more preferred. When the number of atoms other than the hydrogen atoms constituting the linking group represented by Y ³ is in the above range, the ratio of the charge transporting skeleton to the second charge transporting polyester resin is smaller than that in the case where the number is larger than the above range. In many cases, the charge characteristics of the second charge transporting polyester resin are improved. Further, when the number of atoms other than hydrogen atoms constituting the linking group represented by Y ³ is within the above range, the molecular weight can be adjusted during the synthesis of the second charge transporting polyester resin as compared with the case where the number is smaller than the above range. Easier to do.
The number of atoms other than hydrogen atoms among the atoms constituting the linking group represented by Y ³ is not only the atom directly involved in the link, but also the atom not directly involved in the link (for example, a branched chain, aromatic Ring). For example, the number of atoms other than hydrogen atoms of the atoms constituting the following specific examples Y ³ -12 is 31.

Hereinafter, a specific example of a structure including the linking group and the oxygen atom of its ends represented by Y ³ (i.e., O-Y 3 ^-O). However, "*" in the following structure shows the binding position of the group represented by Y ^4.

When the second charge-transporting polyester resin has a plurality of structures represented by the general formula (1B), the plurality of Y ³ may be all the same, may be partially the same, or may be different from each other. , 80% or more of the whole is preferably the same, 90% or more of the whole is more preferably the same, and all the same is more preferable.

Y ⁴ in the general formula (1B) represents a group represented by “*-(CH ₂ ) _n4 -LZ”, n4 represents 1 or 2, and L represents a carbon atom, an oxygen atom, and a hydrogen atom. A divalent linking group or a single bond composed of at least one atom selected from the group consisting of: and Z represents a polymerizable functional group.

First, _{"* - (CH 2) n4 -L} -Z " for linking groups described for L in the group represented by.
The linking group represented by L is a divalent linking group composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom. Examples of the linking group represented by L include an alkylene group, an ether bond (that is, “—O—”), a carbonyl group (that is, “—C (＝ O) —”), and a group obtained by combining these. .
Examples of a group obtained by combining the above (that is, a group obtained by combining at least two or more selected from an alkylene group, an ether bond, and a carbonyl group) include, for example, a combination of an ether bond and an alkylene group, and a combination of an ether bond and a carbonyl group. (Eg, an ester bond), a combination of an ether bond, a carbonyl group, and an alkylene group (eg, a combination of an ester bond and an alkylene group), and the like.
The linking group represented by L preferably contains at least an ether bond.

The number of atoms other than hydrogen atoms among the atoms constituting the group represented by L (the linking group represented by L or the single bond represented by L) is, for example, 0 or more and 16 or less, and 1 or more and 11 or less. It is preferably 1 or more and 10 or less, more preferably 1 or more and 7 or less. When the number of atoms other than hydrogen atoms constituting the group represented by L is within the above range, the ratio of the charge transporting skeleton to the second charge transporting polyester resin is larger than in the case where the number is larger than the above range, The charge characteristics of the second charge transporting polyester resin are improved. Further, when the number of atoms other than hydrogen atoms constituting the group represented by L is in the above range, the crosslinking reaction of the second charge transporting polyester resin is more likely to occur than in the case where the number is less than the above range, A film having excellent solvent properties and mechanical strength can be easily obtained.
In addition, the number of atoms other than the hydrogen atom among the atoms constituting the group represented by L is not only the atom directly involved in the connection but also the atom not directly involved in the connection (for example, the oxygen atom of the carbonyl group, etc.). ). For example, among the atoms constituting the following specific example L-9, the number of atoms other than hydrogen atoms is 11.

Hereinafter, specific examples of the linking group represented by L are shown. In addition, among the two “*” in the following structure, “*” shown on the left side indicates a bonding position with “− (CH ₂ ) _n4 −”, and “*” shown on the right side is Z. The bonding position with the indicated polymerizable functional group is shown.

Then, _{"* - (CH 2) n4 -L} -Z " in a group represented about polymerizable functional group represented by Z will be described.
Examples of the polymerizable functional group include a group containing at least one selected from a carbon-carbon double bond, an epoxy group, and an oxetane group. Specific examples of the polymerizable functional group include, for example, a vinyl group, a vinyl ether group, a group represented by the following general formula (P1), a group represented by the following general formula (P2), and a group represented by the following general formula (P3). A group represented by the following general formula (P4), a group represented by the following general formula (P5), and the like.
Among these, the polymerizable functional group includes a group represented by the following general formula (P1), a group represented by the following general formula (P2), a group represented by the following general formula (P3), and a group represented by the following general formula (P3). It is preferably at least one selected from the group represented by P4) and the group represented by the following general formula (P5).

In the general formulas (P1) to (P5), R ^{3 to} R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * indicates a bonding position.
The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkyl group preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and particularly preferably has 1 to 2 carbon atoms.
The alkoxyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. The alkoxy group preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and particularly preferably has 1 to 2 carbon atoms.
The substitution position of the group represented by the general formula (P3) may be any of the ortho position, the meta position, and the para position, and among them, at least one selected from the meta position and the para position is preferable, and the para position is preferable. Is more preferred. In the case where the second charge-transporting polyester resin has a plurality of groups represented by the general formula (P3), at least two kinds of substitution positions thereof are selected from an ortho position, a meta position, and a para position. They may be mixed.

Hereinafter, examples of the specific structure of the polymerizable functional group represented by Z are shown. In the following structures, * indicates the bonding position with the group represented by L.
Among the specific examples below, the polymerizable functional group represented by Z is a group represented by the following formula (P1-1), a group represented by the following formula (P1-2), and a group represented by the following formula (P3-1). ) Is preferred.
When the polymerizable functional group represented by Z is a group represented by the following formula (P1-1) or a group represented by the following formula (P1-2), the group represented by L is a linking group. And among the atoms constituting the linking group represented by L, the atom directly bonded to the polymerizable functional group represented by Z is an oxygen atom (that is, having an acrylate or methacrylate structure) Is preferred.

In the case n4 in Y ⁴ in the general formula (1B) is 2, the two Y ⁴ may be the same, may be different, preferably the same.
When the second charge transporting polyester resin has a plurality of structures represented by the general formula (1B), the plurality of Y ⁴ may be all the same, may be partially the same, or may be different from each other. , 80% or more of the whole is preferably the same, 90% or more of the whole is more preferably the same, and all the same is more preferable.

Among the atoms constituting the linking group represented by Y ³ in the general formula (1B), the number of atoms other than hydrogen atoms, the number of n4 in Y ⁴ in the general formula (1B), and the number of Y in the general formula (1B) The total of the number of atoms other than hydrogen atoms among the atoms constituting the group represented by L in ⁴ is, for example, 30 or less, preferably 25 or less, more preferably 15 or less. When the total is in the range, the ratio of the charge-transporting skeleton to the second charge-transporting polyester resin is larger than in the case where the total is larger than the range, and the charge characteristics of the second charge-transporting polyester resin are good. Becomes Further, when the total is within the above range, the crosslinking reaction of the second charge transporting polyester resin is more likely to occur than in the case where the total is less than the above range, and a film having excellent solvent resistance and mechanical strength is obtained. It will be easier.

Hereinafter, specific examples of the combination of O—Y ³ —O, n3, and Y ⁴ (that is, the combination of O—Y ³ —O, n3, n4, L, and Z) are shown, but are not limited to these specific examples. Not necessarily.
In the table below, “*” in the column of “O—Y ³ —O” indicates a bonding position with the group represented by Y ⁴ . Also, the numbers described indicate the positions of the bonds. In addition, of the two “*” in the “L” column, “*” shown on the left side indicates a bonding position with “— (CH ₂ ) _n4 —” in the group represented by Y ⁴ , “*” Shown on the right side indicates the bonding position with the polymerizable functional group represented by Z. Further, “*” in the column of “Z” indicates a bonding position with the group represented by L. In the following specific examples, for example n3 is 2, two Y ⁴ is an example of the same.

-Explanation of the second charge transporting polyester resin-
The second charge transporting polyester resin only needs to have at least the structure represented by the general formula (1B) in the molecule, and has another structure in addition to the structure represented by the general formula (1B). You may have inside. When the second charge transporting polyester resin has another structure in the molecule, the ratio of the structure represented by the general formula (1B) to the entire second charge transporting polyester resin is preferably 80% by mass or more. , 90% by mass or more, more preferably 95% by mass or more.
The number of structures represented by the general formula (1B) in the second charge transporting polyester resin is, for example, 5 or more and 5000 or less, preferably 5 or more and 2000 or less, and more preferably 10 or more. 1000 or less.

The weight average molecular weight of the second charge transporting polyester resin is preferably from 2,000 to 500,000, more preferably from 3,000 to 200,000, even more preferably from 4,000 to 100,000.
The weight-average molecular weight is measured by preparing a 0.1% by mass THF (tetrahydrofuran) solution of a compound to be measured and using a differential refractive index detector (RI) to perform gel permeation chromatography (GPC) on a standard sample. Using a styrene polymer.

Hereinafter, specific examples of the second charge-transporting polyester resin in the case where A ³ in the general formula (1B) represents a divalent organic group represented by the general formula (2) will be described. It is not limited.
In the following table, number that is listed in the "combined AT" and "combination Y", respectively, ^{A 3} and ^{T 3} and No. AT-1~AT-102 and O which was subjected to a specific example of a combination of means -Y ³ -O and n3 and ^{Y 4} and No. Y-1 to Y-63 which was subjected to the specific examples of the combination. The number described in the column of “number of structures” means the number of structures represented by the general formula (1B) possessed by the second charge transporting polyester resin.

-Synthesis method (second charge transporting polyester resin production method)-
Next, the synthesis method will be described.
The second charge transporting resin is, for example, a compound represented by the following general formula (3B) (hereinafter, also referred to as a “charge transporting monomer”) and a compound represented by the following general formula (4B) (hereinafter, “ (Also referred to as "non-charge transporting monomer").

^{A 3,} T ³ in the general formula (3B) and ^{(4B), Y 3, n3} , and ^{Y 4, A 3,} T 3 in the general formula ^{(1B), Y 3, n3} , and ^{Y 4} Is the same as
That is, in the general formulas (3B) and (4B), A ³ represents a divalent organic group having a charge transporting property, and T ³ represents a linear or branched divalent organic group having 1 to 10 carbon atoms. a hydrocarbon group, ^{Y 3} represents a (n3 + 2) -valent uncharged transporting diol residues, n3 represents 1 or 2, ^{Y 4} is _{"* - (CH 2) n4 -L} -Z " the * Indicates a bonding position to Y ³ , n4 indicates 1 or 2, L is a divalent linking group composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom Or Z represents a single bond, and Z represents a polymerizable functional group.

In the general formulas (3B) and (4B), Z ¹ and Z ² each represent a group capable of performing a polycondensation reaction with each other.
Specifically, when the group represented by Z ¹ is a hydroxyl group, the group represented by Z ^2, for example, a hydroxyl group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), methanesulfonic An acid ester group, a trifluoromethanesulfonic acid ester group, a p-toluenesulfonic acid ester group and the like can be mentioned.
When the group represented by Z ² is a hydroxyl group, examples of the group represented by Z ¹ include an alkoxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and other organic acids. And the residue of a mixed anhydride. In addition, as said other organic acid, acetic acid, trifluoroacetic acid, isobutyl formate, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc. are mentioned, for example.

  In the polycondensation reaction between the charge-transporting monomer and the non-charge-transporting monomer, known additives, catalysts, and the like (specifically, for example, an acid catalyst, a condensing agent, A capturing agent for capturing generated water, alcohol, acid, etc.) may be used.

As described above, the non-charge transporting monomer contains a polymerizable functional group. Therefore, during the polycondensation reaction between the charge-transporting monomer and the non-charge-transporting monomer, the polymerizable functional group of the non-charge-transporting monomer (ie, “*-(CH ₂ ) _n4 -L- represented by Y ⁴ ) Polycondensation reaction conditions may be selected so that the group represented by Z in “Z” does not react. Specifically, for example, if necessary, a known polymerization inhibitor may be added to carry out the polycondensation reaction.

Further, in place of the non-charge-transporting monomer, a monomer having no polymerizable functional group represented by Z is used, and a polyester is obtained by performing a polycondensation reaction with the charge-transporting monomer. May introduce a polymerizable functional group represented by Z into the polyester (that is, a polyester having no polymerizable functional group).
When carrying out a polycondensation reaction between a monomer having no polymerizable functional group represented by Z and a charge transporting monomer, a functional group for introducing the polymerizable functional group represented by Z later undergoes polycondensation. The polycondensation may be performed by appropriately protecting the functional group so as not to react with the compound.
Examples of a method for introducing a polymerizable functional group represented by Z later include a method of reacting a polyester having no polymerizable functional group with a compound having a polymerizable functional group.

  Examples of the compound having a polymerizable functional group include, for example, a carboxylic acid derivative in which a leaving group (for example, a hydroxyl group, a halogen atom, or another carboxylic acid, etc.) is substituted for the polymerizable functional group to be introduced; Examples include compounds in which a leaving group (for example, a halogen atom, a trifluoromethanesulfonyloxy group, a p-toluenesulfonyloxy group, or the like) is substituted to become an electrophile.

The charge transporting monomer and the non-charge transporting monomer can be obtained by synthesizing each by a known method. Further, as the non-charge transporting monomer having a polymerizable functional group represented by Z, a commercially available product may be used. As a non-charge transporting monomer, the group represented by Z ² as a reaction site of polycondensation may be used as the diol monomer is a hydroxyl group, by the polycondensation reaction conditions, the hydroxyl group of the diol monomers, known It may be converted to a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a methanesulfonic acid ester group, a trifluoromethanesulfonic acid ester group, a p-toluenesulfonic acid ester group, or the like by a method. .

Of the non-charge transporting monomer having a polymerizable functional group represented by Z, as a method of the group represented by Z ² to synthesize diol monomer is a hydroxyl group may, for example, a commercially available polymer having an epoxy group or an oxetane group Examples of the method include a method in which water is added to a compound having an acidic functional group (for example, a (meth) acrylate ester, a styrene derivative, or the like) to open a ring of an epoxy group or an oxetane group.
Further, as a method for synthesizing the diol monomer, a carboxy group or a hydroxyl group-containing polymerizable functional group-containing compound (for example, (meth) Acrylic acid, hydroxy-substituted styrene, hydroxymethyl-substituted styrene, vinylbenzoic acid, etc.) may be added, and the epoxy group or oxetane group may be ring-opened.
In addition, as a method for synthesizing the diol monomer, a polymerizable functional group-containing compound having a carboxy group or a hydroxyl group with respect to a halogen-containing diol represented by 3-chloro-1,2-propanediol (for example, (meth) Acrylic acid, hydroxy-substituted styrene, hydroxymethyl-substituted styrene, vinylbenzoic acid, etc.) may be reacted and substituted.
In addition, “(meth) acryl” means at least one selected from “acryl” and “methacryl”. Further, “(meth) acrylate” means at least one selected from “acrylate” and “methacrylate”.

Regarding the non-charge-transporting diol monomer having two polymerizable functional groups in one molecule, a polymerizable functional group-containing compound having two polymerizable functional groups represented by a commercially available bifunctional epoxy (meth) acrylate May be used as is.
As a method of synthesizing a non-charge-transporting diol monomer having two polymerizable functional groups in one molecule, for example, a polymerizable compound having a carboxy group or a hydroxyl group with respect to a bifunctional epoxide or a bifunctional oxetane compound is used. A method in which a functional group-containing compound (for example, (meth) acrylic acid, hydroxy-substituted styrene, hydroxymethyl-substituted styrene, vinylbenzoic acid, or the like) is added and an epoxy group or an oxetane group is ring-opened to obtain a method.

The synthesis of the second charge-transporting polyester resin using the charge-transporting monomer and the non-charge-transporting monomer includes, for example, using an equivalent amount of the charge-transporting monomer and the non-charge-transporting monomer, and adding a known additive in a solvent. This is performed by using an agent or a catalyst (for example, an acid catalyst, a condensing agent, a trapping agent for trapping water, alcohol, acid, and the like by-produced in condensation) and the like.
Examples of the solvent include toluene, xylene, tetrahydrofuran, monochlorobenzene and the like. These may be used alone or in combination of two or more.

Example of Synthesis (Polycondensation) of Second Charge-Transporting Polyester Resin The polymerization method of the above-mentioned charge-transporting monomer and non-charge-transporting monomer is described in, for example, Vol. Various methods may be adopted. For example, the following method can be used.

(1) Polymerization of dihydric alcohol and divalent carboxylic acid using a catalyst In the polymerization of dihydric alcohol and a divalent carboxylic acid using a catalyst, a dihydric alcohol and a divalent carboxylic acid are obtained by Approximately equivalent amounts are mixed and polymerized using an acid catalyst.
As the acid catalyst, those used in a usual esterification reaction such as sulfuric acid, toluenesulfonic acid, and trifluoroacetic acid are used, and 1/10000 to 1/10 parts by mass, preferably 1/100 parts by mass with respect to 1 part by mass of the monomer. It is used in the range of 1000 to 1/50 parts by mass. In order to remove water generated during the polymerization, it is preferable to use a solvent capable of azeotropic distillation with water, and toluene, chlorobenzene and the like are effective, and 1 to 100 parts by mass, preferably 1 to 100 parts by mass, preferably 1 part by mass of the monomer It is used in the range of 2 to 50 parts by mass. The reaction temperature is arbitrarily set, but the reaction is preferably performed at the boiling point of the solvent in order to remove water generated during the polymerization. After completion of the reaction, if no solvent is used, the solvent is dissolved in a soluble solvent. When a solvent is used, the reaction solution is directly dropped into a poor solvent in which alcohols such as methanol and ethanol and polymers such as acetone are difficult to dissolve, and a charge-transporting polyester resin is precipitated. , And then sufficiently washed with water, an organic solvent or the like, and dried. Further, if necessary, the re-precipitation treatment of dissolving in a suitable organic solvent, dropping it into a poor solvent, and precipitating the charge transporting polyester resin may be repeated. In the case of the reprecipitation treatment, it is preferable to carry out the stirring while efficiently stirring with a mechanical stirrer or the like. The solvent for dissolving the charge transporting polyester resin in the reprecipitation treatment is used in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 1 part by weight of the charge transporting polyester resin. The poor solvent is used in an amount of 1 to 1000 parts by weight, preferably 10 to 500 parts by weight, based on 1 part by weight of the charge transporting resin.

  When a dihydric alcohol having a high acidity is used as a monomer, an interfacial polymerization method may be used. That is, polymerization is carried out by adding a dihydric alcohol to water, adding an equivalent of a base and dissolving the same, and then adding a solution of the dihydric alcohol and an equivalent of a charge-transporting monomer with vigorous stirring. At this time, water is used in an amount of 1 to 1000 parts by mass, preferably 2 to 500 parts by mass, based on 1 part by mass of the dihydric alcohol. As a solvent for dissolving the other monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene and the like are effective. The reaction temperature is arbitrarily set, and it is effective to use a phase transfer catalyst such as an ammonium salt or a sulfonium salt to promote the reaction. The phase transfer catalyst is used in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, based on 1 part by mass of the monomer.

(2) Polymerization of dihydric alcohol and divalent carboxylic acid using condensing agent In the polymerization of dihydric alcohol and divalent carboxylic acid using the condensing agent, the dihydric alcohol and the divalent carboxylic acid are used. Are mixed in approximately equivalent amounts and polymerized using a condensing agent. Known condensing agents are used, and specific examples thereof include carbodiimide-based, imidazole-based, triazine-based, phosphonium-based, uronium-based, halouronium-based, and Mitsunobu reagents (diethyl azodicarboxylate and triphenylphosphine). Can be
When the divalent alcohol and the divalent carboxylic acid are used in an equivalent amount, the condensing agent is added in an amount of 1 to 5 molar equivalents, preferably 1.05 to 3 molar equivalents, most preferably 1 to 5 molar equivalents with respect to the dihydric alcohol. 0.1 to 2 molar equivalents.
If necessary, a base may be added. As the base, an organic base is preferred. Specific examples include pyridine, triethylamine, 4-dimethylaminopyridine, imidazole and the like. These are used in an amount of 0.05 to 2 molar equivalents, preferably 0.1 to 1.5 molar equivalents, and most preferably 0.15 to 1.3 molar equivalents, based on the condensing agent.

(3) Polymerization of dihydric alcohol and divalent carboxylic acid ester In the polymerization of dihydric alcohol and divalent carboxylic acid ester, dihydric alcohol is added to divalent carboxylic acid ester, and sulfuric acid, phosphoric acid, etc. It is synthesized by transesterification by heating using an inorganic acid, an acetate or carbonate such as titanium alkoxide, calcium and cobalt, or an oxide of zinc or lead as a catalyst.
In particular, when a charge transporting monomer having a high boiling point is used as the divalent carboxylic acid ester, it is preferable to use a divalent alcohol having a relatively low boiling point in excess of the carboxylic acid ester. The dihydric alcohol is used in an amount of 2 to 100 equivalents, preferably 3 to 50 equivalents, per equivalent of the charge transporting monomer. The catalyst is used in an amount of 1/1000 to 1 part by mass, preferably 1/1000 to 1/2 part by mass, per 1 part by mass of the charge transporting monomer. The reaction is carried out at a reaction temperature of 200 to 300 ° C. After the transesterification, the reaction is preferably carried out under reduced pressure in order to promote the polymerization by elimination of the dihydric alcohol. Alternatively, the reaction may be carried out using a high-boiling solvent such as 1-chloronaphthalene which azeotropes with the dihydric alcohol while removing the dihydric alcohol azeotropically under normal pressure.

(4) Polymerization of dihydric alcohol derivative and divalent carboxylic acid In the polymerization of dihydric alcohol derivative and divalent carboxylic acid, a divalent halogen compound is preferably used as the dihydric alcohol derivative. In this case, the divalent halogen compound and the divalent carboxylic acid may be mixed so as to be substantially equivalent, and polymerized using a basic catalyst. Examples of the basic catalyst include common organic bases such as triethylamine, diethylamine, diazabicycloundecene, 1,4-diazabicyclo [2.2.2] octane, pyridine and piperidine, K ₂ CO ₃ , Na ₂ CO _{3 and the} like. Is used in an amount of 1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the monomer. The solvent used for the reaction is not particularly limited, but when an inorganic base is used as the base, an aprotic polar solvent such as N, N-dimethylformamide, dimethylsulfoxide and the like is particularly preferable. The reaction temperature is not particularly limited and may be freely set, but is desirably set to a value between 0 degrees and the boiling point of the reaction solvent.

The amount of the catalyst added is, for example, 1 / 10,000 parts by mass or more and 1/10 part by mass with respect to 1 part by mass of the total monomer mass (that is, the sum of the mass of the charge transporting monomer and the mass of the non-charge transporting monomer). Or less, preferably from 1/1000 part by mass to 1/50 part by mass.
The amount of the solvent to be added is, for example, 1 part by mass or more and 100 parts by mass or less, preferably 2 parts by mass or more and 50 parts by mass or less with respect to 1 part by mass of the second charge transporting polyester resin to be produced. is there.
The reaction temperature (that is, the polymerization temperature of the charge-transporting monomer and the non-charge-transporting monomer) is not particularly limited, and may be, for example, in a range from 30 ° C to 100 ° C.

After the polymerization reaction between the charge transporting monomer and the non-charge transporting monomer is completed, for example, the resulting charge transporting resin is dissolved in a poor solvent (eg, alcohols such as methanol and ethanol, acetone, etc.). By dropping the reaction solution, the charge transporting resin is precipitated, separated, washed with water, an organic solvent or the like, and dried.
Further, if necessary, the re-precipitation treatment of dissolving in an organic solvent, dropping it into a poor solvent, and depositing a charge transporting resin may be repeated. The reprecipitation treatment is preferably performed while stirring with a mechanical stirrer or the like. The amount of the solvent for dissolving the charge transporting resin during the reprecipitation treatment is, for example, in the range of 1 part by weight or more and 100 parts by weight or less based on 3 parts by weight of the charge transporting compound, preferably 2 parts by weight. It is not less than 50 parts by mass and not more than 50 parts by mass. The amount of the poor solvent is, for example, 1 part by mass or more and 1000 parts by mass or less, preferably 10 parts by mass or more and 500 parts by mass or less based on 1 part by mass of the charge transporting resin.
After the polymerization reaction between the charge transporting monomer and the non-charge transporting monomer is completed, for example, the reaction solution is poured into water, extracted with a solvent such as toluene, hexane, or ethyl acetate, washed with water, and further, if necessary. Purification may be performed using an adsorbent such as activated carbon, silica gel, porous alumina, and activated clay.

<Charge transporting film>
Next, the charge transporting film will be described.
The charge transporting film is at least one selected from a first charge transporting resin, a crosslinked product of the first charge transporting resin, a second charge transporting polyester resin, and a crosslinked product of the second charge transporting polyester resin. It contains one type (that is, at least one type selected from a specific resin and a specific resin crosslinked product).
The charge transporting film is formed, for example, by forming a film using a specific resin solution in which a specific resin is dissolved in a solvent.

-Specific resin solution-
Examples of the solvent used for the specific resin solution include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; tetrahydrofuran and dioxane. And a solvent such as a cellosolve solvent such as ethylene glycol monomethyl ether and an alcohol solvent such as isopropyl alcohol and butanol. These may be used alone or as a mixed solvent.

  As a dissolving method for dissolving the specific resin in these solvents, for example, stirring and mixing with the solvent at a temperature of 10 ° C. to 150 ° C., preferably 15 ° C. to 120 ° C. (for example, stirring and mixing while irradiating ultrasonic waves) The usual method is mentioned.

-Crosslinking of specific resin-
Among the charge transporting films, in particular, as a method for obtaining a charge transporting film containing a crosslinked specific resin, for example, a specific resin solution containing a specific resin having a polymerizable functional group is used, and heat, light, And a method of further crosslinking the specific resin by applying radiation or the like. By the crosslinking, a charge transporting film having improved strength and solvent resistance can be obtained.
When crosslinking is performed by at least one of heat and light, a polymerization initiator is not necessarily required, but at least one of a photocuring catalyst and a thermal polymerization initiator may be used. Known photocuring catalysts and thermal polymerization initiators are used as the photocuring catalyst and the thermal polymerization initiator. The radiation is preferably an electron beam.

(Electron beam crosslinking)
When an electron beam is used for crosslinking the specific resin, the acceleration voltage is preferably 300 KV or less, and most preferably 150 KV or less. The dose is preferably in the range of 1 Mrad to 100 Mrad, more preferably in the range of 3 Mrad to 50 Mrad. When the accelerating voltage is 300 KV or less, the damage of the electron beam irradiation on the characteristics of the photoconductor is suppressed. When the dose is 1 Mrad or more, crosslinking is sufficiently performed, and when the dose is 100 Mrad or less, deterioration of the photoconductor is suppressed.

  Irradiation is performed in an atmosphere of an inert gas such as nitrogen or argon at an oxygen concentration of 1000 ppm, preferably 500 ppm or less, and may be heated to 50 ° C. or more and 150 ° C. or less during or after the irradiation.

(Photocrosslinking)
As the light source, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or the like is used, and a suitable wavelength may be selected using a filter such as a band-pass filter. Irradiation time, the light intensity is selected freely, for example, the illuminance (365 nm) is 300 mW / cm ² or more, preferably 1000 mW / cm ² or less, for example, the case of irradiation with UV light of 600 mW / cm ^2, 5 seconds or more 360 Irradiation may be performed for less than a second.

  Irradiation is performed in an atmosphere of an inert gas such as nitrogen or argon at an oxygen concentration of preferably 1000 ppm or less, more preferably 500 ppm or less, and may be heated to 50 ° C. or more and 150 ° C. or less during or after the irradiation.

As the photocuring catalyst, examples of the intramolecular cleavage type include benzyl ketal type, alkylphenone type, aminoalkylphenone type, phosphine oxide type, titanocene type, oxime type and the like.
More specifically, as the benzyl ketal, 2,2-dimethoxy-1,2-diphenylethan-1-one is exemplified.

  Examples of alkylphenones include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl]. -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl- Examples include propan-1-one, acetophenone, and 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone.

  Examples of aminoalkylphenones include p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-one. Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morphonyl) phenyl] -1 -Butanone and the like.

  Examples of the phosphinoxide system include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

  Examples of the titanocene-based compound include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.

  Oxime-based compounds include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)-. 9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

Examples of the hydrogen abstraction type include benzophenone type, thioxanthone type, benzyl type and Michler's ketone type.
More specifically, benzophenones include 2-benzoylbenzoic acid, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, p, p′-bisdiethylaminobenzophenone, and the like. No.

  Examples of the thioxanthone type include 2,4-diethylthioxanthen-9-one, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

  Examples of the benzyl group include benzyl, (±) -camphorquinone, p-anisyl and the like.

  These photopolymerization initiators are used alone or in combination of two or more.

(Thermal crosslinking)
Examples of the thermal polymerization initiator include V-30, V-40, V-59, V601, V65, V-70, VF-096, VE-073, Vam-110, and Vam-111 (Fujifilm Wako Pure Chemical Industries, Ltd. Azo) initiators such as OTazo-15, OTazo-30, AIBN, AMBN, ADVN, ACVA (Otsuka Chemical); Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H Parkmill H, Parkmill P, Permentor H, Perocta H, Perbutyl C, Perbutyl D, Perhexyl D, Parloyl IB, Parloyl 355, Parloyl L, Parloyl SA, Niper BW, Niper BMT-K40 / M, Parloyl IPP, Parloyl NPP, Parloyl TCP, Parloyl OPP, Parroy SBP, Parkmill ND, Peroctal ND, Perhexyl ND, Perbutyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perhexa 250, Perocta O, Perhexyl O, Perbutyl O, Perbutyl L, Perbutyl 355, Perhexyl I, Perbutyl I, Perbutyl E, Perhexa 25Z, Perbutyl A, Perhexyl Z, Perbutyl ZT, Perbutyl Z (manufactured by NOF Chemicals), Kayaketal AM-C55, Trigonox 36-C75, Laurox, Parkadox L-W75, Parkadox CH-50L, Trigonox TMBH, Kayakumen H, Kayabutyl H-70, Perkadox BC-FF, Kayahexa AD, Parkadox 14, Kayabutyl C, Kayabutyl D, Kayahexa YD-E85, Parkadoc 12-XL25, Parkadox 12-EB20, Trigonox 22-N70, Trigonox 22-70E, Trigonox DT50, Trigonox 423-C70, Kayaester CND-C70, Kayaester CND-W50, Trigonox 23-C70, Trigonox 23- W50N, Trigonox 257-C70, Kayaester P-70, Kayaester TMPO-70, Trigonox 121, Kayaester O, Kayaester HTP-65W, Kayaester AN, Trigonox 42, Trigonox FC50, Kayabutyl B, Kayacarbon EH- C70, Kayacarbon EH-W60, Kayacarbon I-20, Kayacarbon BIC-75, Trigonox 117, Kayaren 6-70 (manufactured by Kayaku Akzo), Luperox 610, Luperox 188, Luperrox 844, Luperrox 259, Luperrox 10, Luperrox 701, Luperrox 11, Luperrox 26, Luperrox 80, Luperrox 7, Luperrox 270, Luperrox P, Luperrox 546, Luperrox 554, Luperrox TA 55, Luperrox 575 Luperrox 570, Luperrox TAP, Luperrox TBIC, Luperrox TBEC, Luperrox JW, Luperrox TAIC, Luperrox TAEC, Luperrox DC, Luperrox 101, Luperrox F, Luperrox DI, Luperrox 130, Luperrox 220, Luperlox 53, Luperrox 33, Luperloques 33, Luperrox 2 Company) .

  Among these, when an azo-based polymerization initiator having a molecular weight of 250 or more is used, the reaction proceeds evenly at a low temperature, so that a high-strength film in which unevenness is suppressed is formed. More preferably, the molecular weight of the azo-based polymerization initiator is 250 or more, and even more preferably 300 or more.

  Heating is performed under an atmosphere of an inert gas such as nitrogen or argon, with an oxygen concentration of preferably 1000 ppm or less, more preferably 500 ppm or less, preferably 50 ° C or more and 170 ° C or less, more preferably 70 ° C or more and 150 ° C or less. Heating is preferably performed for 10 minutes to 120 minutes, more preferably 15 minutes to 100 minutes.

  The total content of the photocuring catalyst or the thermal polymerization initiator is preferably from 0.1% by mass to 10% by mass, and more preferably from 0.1% by mass to 10% by mass based on the total solid content in the solution for forming a layer. 8 mass% or less is more preferable, and the range of 0.1 mass% or more and 5 mass% or less is particularly preferable.

-Other components-
The charge transporting film may be a film in which a specific resin is compatible with a binder resin other than the specific resin, and may include a monomer, oligomer, or polymer having a double bond (hereinafter, also referred to as a “reactive compound”). It may be a cured film mixed and cured.
The charge transporting film may contain at least one selected from a luminescent material, a dye compound, a hole transporting material, a hole injecting material, an electron transporting material, and an electron injecting material. Specific examples of these materials will be described later.

(Binder resin)
Examples of the binder resin include known non-reactive binder resins such as polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, and polystyrene resin.

  The total content of the binder resin is preferably from 0% by mass to 60% by mass, more preferably from 0% by mass to 55% by mass, based on the total solid content of the composition used for forming the charge transporting film. The content is more preferably 0% by mass or more and 50% by mass or less.

(Reactive compound)
Examples of the reactive compound include a monofunctional compound (that is, a compound having one double bond in a molecule) and a bifunctional or more compound (that is, a compound having two or more double bonds in the same molecule). Compounds), and among these, a bifunctional or higher functional compound is preferable from the viewpoint of improving the strength of the charge transporting film. The reactive compound may have a charge transporting structure in the molecule.

  As the reactive compound, monofunctional monomers include, for example, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate , 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate , Phenoxy polyethylene glyco Le acrylate, phenoxy polyethylene glycol methacrylate, hydroxyethyl o- phenylphenol acrylate, o- phenylphenol glycidyl ether acrylate and styrene.

  As the reactive compound, bifunctional monomers include, for example, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, divinylbenzene, diallyl phthalate and the like can be mentioned.

  Examples of the trifunctional monomer as the reactive compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, aliphatic tri (meth) acrylate, and trivinylcyclohexane.

  Examples of the reactive compound include tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and aliphatic tetra (meth) acrylate.

  As the reactive compound, monomers having five or more functional groups include, for example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a (meth) acrylate having a polyester skeleton, a urethane skeleton, and a phosphazene skeleton. Is mentioned.

  Further, as the reactive compound, reactive polymers include, for example, JP-A-5-216249, JP-A-5-323630, JP-A-11-52603, JP-A-2000-264961, and JP-A-2005-2005. -2291.

  When a reactive compound is used, it is used alone or as a mixture of two or more. The reactive compound is used in an amount of preferably not more than 60% by mass, more preferably not more than 55% by mass, more preferably not more than 50% by mass, based on the total solids of the solid used in forming the film. Used in:

<Types of organic electronic devices>
Examples of the organic electronic device include, for example, a device in which the above-described charge transporting film is provided on a support. Can be
When the organic electronic device is an electrophotographic photosensitive member having a photosensitive layer, the outermost surface layer may be the charge transporting film, and the photosensitive layer may be the charge transporting film. When the photosensitive layer is the charge transporting film, the charge transporting film as the photosensitive layer contains at least one selected from a specific resin and a specific resin crosslinked product as a charge transporting material, and a charge generating material. Is also good.
Examples of the charge generation material contained in the charge transporting film include phthalocyanine compounds. More specifically, for example, halogenated gallium phthalocyanine crystals disclosed in JP-A-5-98181, Halogenated tin phthalocyanine crystals disclosed in JP-A-140472 and JP-A-5-140473, hydroxygallium phthalocyanine crystals disclosed in JP-A-5-263007 and JP-A-5-279951, Oxytitanium phthalocyanine hydrate crystals and the like disclosed in JP-A-4-189873 and JP-A-5-43813. By using these phthalocyanine compounds, an electrophotographic photosensitive member having high sensitivity and excellent repetition stability can be obtained.
Hereinafter, an electrophotographic photosensitive member and an organic electroluminescent element will be described as examples of the organic electronic device.

-Electrophotographic photoreceptor-
Examples of the electrophotographic photoreceptor include those having the above-described charge transporting film provided on a conductive substrate. Among them, a layer in which the outermost surface layer among the layers provided on the conductive substrate is the above-described charge transporting film is preferable.
Note that the outermost surface layer only needs to form the uppermost surface of the electrophotographic photoreceptor itself, and may be a layer functioning as a protective layer or a layer functioning as a charge transport layer.
When the outermost layer is a layer that functions as a protective layer, for example, a photosensitive layer including a charge transport layer and a charge generation layer, or a single-layer type photosensitive layer is provided below the protective layer. That is, when the outermost surface layer is a layer that functions as a protective layer, for example, on a conductive substrate, a photosensitive layer, and a protective layer as an outermost surface layer, and the protective layer is the charge transporting film. Form.
On the other hand, when the outermost layer is a layer that functions as a charge transport layer, for example, a charge generation layer and a charge transport layer as the outermost layer are provided on a conductive substrate, and the charge transport layer is the charge transport layer. And a film that is a conductive film. The charge transport layer may further contain a charge transport material having no reactive group such as a thiol group or an unsaturated bond.

  Hereinafter, as an example of the electrophotographic photosensitive member, an electrophotographic photosensitive member in which the outermost layer functions as a protective layer will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts will be denoted by the same reference characters, without redundant description.

  FIG. 1 is a schematic sectional view showing a preferred example of an electrophotographic photoconductor. FIGS. 2 and 3 are schematic cross-sectional views showing another preferred example of the electrophotographic photosensitive member.

  The electrophotographic photoreceptor 7A shown in FIG. 1 is a so-called function-separated type photoreceptor (or a stacked type photoreceptor), in which an undercoat layer 1 is provided on a conductive substrate 4, on which a charge generation layer 2 and a charge It has a structure in which the transport layer 3 and the protective layer 5 are sequentially formed. In the electrophotographic photoreceptor 7A, a photosensitive layer is constituted by the charge generation layer 2 and the charge transport layer 3.

The electrophotographic photoreceptor 7B shown in FIG. 2 is a function-separated type photoreceptor in which the functions are separated into a charge generation layer 2 and a charge transport layer 3, like the electrophotographic photoreceptor 7A shown in FIG.
The electrophotographic photoreceptor 7B shown in FIG. 2 has a structure in which an undercoat layer 1 is provided on a conductive substrate 4, and a charge transport layer 3, a charge generation layer 2, and a protective layer 5 are sequentially formed thereon. It has. In the electrophotographic photoreceptor 7B, the charge transport layer 3 and the charge generation layer 2 constitute a photosensitive layer.

  The electrophotographic photoreceptor 7C shown in FIG. 3 contains a charge generation material and a charge transport material in the same layer (single-layer type photosensitive layer 6). The electrophotographic photoreceptor 7C shown in FIG. 3 has a structure in which an undercoat layer 1 is provided on a conductive substrate 4, and a single-layer type photosensitive layer 6 and a protective layer 5 are sequentially formed thereon. .

In addition, in the electrophotographic photosensitive members 7A, 7B, and 7C shown in FIGS. 1, 2, and 3, the protective layer 5 is the outermost surface layer disposed on the farthest side from the conductive substrate 4, The outermost surface layer has the above configuration.
In the electrophotographic photoreceptors shown in FIGS. 1, 2 and 3, the undercoat layer 1 may or may not be provided.

  Hereinafter, each element will be described based on the electrophotographic photosensitive member 7A shown in FIG. 1 as a representative example. The description will be omitted with reference numerals omitted.

(Conductive substrate)
Examples of the conductive substrate include a metal plate, a metal drum, and a metal belt containing a metal (aluminum, copper, zinc, chromium, nickel, molybdenum, vanadium, indium, gold, platinum, etc.) or an alloy (stainless steel, etc.). Is mentioned. Examples of the conductive substrate include paper, resin films, belts, and the like, on which a conductive compound (for example, a conductive polymer, indium oxide, or the like), a metal (for example, aluminum, palladium, gold, or the like) or an alloy is applied, deposited, or laminated. Are also mentioned. Here, “conductive” means that the volume resistivity is less than 10 ¹³ Ωcm.

  When the electrophotographic photosensitive member is used in a laser printer, the surface of the conductive substrate has a center line average roughness Ra of 0.04 μm or more and 0.5 μm or less for the purpose of suppressing interference fringes generated when irradiating laser light. The surface is preferably roughened below. In the case where non-interfering light is used as a light source, roughening for preventing interference fringes is not particularly necessary. However, since generation of defects due to irregularities on the surface of the conductive substrate is suppressed, it is suitable for longer life.

  As a method of surface roughening, for example, wet honing performed by suspending an abrasive in water and spraying the support, a centerless grinding method in which a conductive substrate is pressed against a rotating grindstone and grinding is performed continuously, Anodizing treatment and the like can be mentioned.

  As a method of surface roughening, without roughening the surface of the conductive substrate, a conductive or semiconductive powder is dispersed in a resin to form a layer on the surface of the conductive substrate, A method of roughening the surface with particles dispersed in the layer may also be used.

  The surface roughening treatment by anodic oxidation is to form an oxide film on the surface of the conductive substrate by performing anodic oxidation in an electrolyte solution using a conductive substrate made of metal (for example, aluminum) as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the porous anodic oxide film formed by anodic oxidation is chemically active as it is, is easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores of the oxide film are blocked by the volume expansion due to the hydration reaction with pressurized steam or boiling water (or a metal salt such as nickel may be added) with respect to the porous anodic oxide film. It is preferable to perform a sealing treatment for changing the material.

  The thickness of the anodic oxide film is preferably, for example, 0.3 μm or more and 15 μm or less. When the film thickness is within the above range, a barrier property against injection tends to be exhibited, and an increase in residual potential due to repeated use tends to be suppressed.

The conductive substrate may be subjected to a treatment with an acidic treatment liquid or a boehmite treatment.
The treatment with the acidic treatment liquid is performed, for example, as follows. First, an acidic treatment solution containing phosphoric acid, chromic acid and hydrofluoric acid is prepared. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is, for example, in the range of 10% by mass or more and 11% by mass or less of phosphoric acid, 3% by mass or more and 5% by mass or less of chromic acid, The concentration is 0.5% by mass or more and 2% by mass or less, and the concentration of these acids as a whole is preferably 13.5% by mass or more and 18% by mass or less. The processing temperature is preferably, for example, 42 ° C. or more and 48 ° C. or less. The thickness of the coating is preferably 0.3 μm or more and 15 μm or less.

  The boehmite treatment is performed, for example, by immersing in pure water at 90 ° C. or more and 100 ° C. or less for 5 minutes to 60 minutes, or by contacting with heated steam at 90 ° C. or more and 120 ° C. or less for 5 minutes to 60 minutes. The thickness of the coating is preferably 0.1 μm or more and 5 μm or less. This is further anodized using an electrolyte solution having low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate, etc. Good.

(Undercoat layer)
The undercoat layer is, for example, a layer containing inorganic particles and a binder resin.

Examples of the inorganic particles include inorganic particles having a powder resistance (volume resistivity) of 10 ² Ωcm to 10 ¹¹ Ωcm.
Among these, as the inorganic particles having the above resistance value, for example, metal oxide particles such as tin oxide particles, titanium oxide particles, zinc oxide particles, and zirconium oxide particles are preferable, and zinc oxide particles are particularly preferable.

The specific surface area of the inorganic particles determined by the BET method is preferably, for example, 10 m ² / g or more.
The volume average particle diameter of the inorganic particles is, for example, preferably from 50 nm to 2000 nm (preferably from 60 nm to 1000 nm).

  The content of the inorganic particles is, for example, preferably from 10% by mass to 80% by mass, more preferably from 40% by mass to 80% by mass, based on the binder resin.

  The inorganic particles may have been subjected to a surface treatment. Inorganic particles having different surface treatments or particles having different particle diameters may be used as a mixture of two or more kinds.

  Examples of the surface treatment agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and a surfactant. Particularly, a silane coupling agent is preferable, and a silane coupling agent having an amino group is more preferable.

  Examples of the silane coupling agent having an amino group include 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl) -3-amino Examples include, but are not limited to, propylmethyldimethoxysilane, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, and the like.

  Two or more silane coupling agents may be used as a mixture. For example, a silane coupling agent having an amino group and another silane coupling agent may be used in combination. Other silane coupling agents include, for example, vinyltrimethoxysilane, 3-methacryloxypropyl-tris (2-methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycol Sidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyldimethoxysilane, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, and the like, but are not limited thereto. Not something.

  The surface treatment method using the surface treatment agent may be any known method, and may be either a dry method or a wet method.

  The treatment amount of the surface treatment agent is preferably, for example, 0.5% by mass or more and 10% by mass or less based on the inorganic particles.

  Here, the undercoat layer preferably contains an electron-accepting compound (acceptor compound) together with the inorganic particles, from the viewpoint of increasing the long-term stability of electric characteristics and the carrier blocking property.

Examples of the electron-accepting compound include quinone compounds such as chloranil and bromoanil; tetracyanoquinodimethane compounds; 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone, and the like. 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (4-naphthyl) -1,3,4- Oxadiazole compounds such as oxadiazole and 2,5-bis (4-diethylaminophenyl) -1,3,4oxadiazole; xanthone compounds; thiophene compounds; 3,3 ', 5,5'tetra- electron transporting substances such as diphenoquinone compounds such as t-butyl diphenoquinone;
In particular, a compound having an anthraquinone structure is preferable as the electron accepting compound. As the compound having an anthraquinone structure, for example, a hydroxyanthraquinone compound, an aminoanthraquinone compound, an aminohydroxyanthraquinone compound and the like are preferable, and specifically, for example, anthraquinone, alizarin, quinizarin, anthralphine, purpurin and the like are preferable.

  The electron-accepting compound may be contained in the undercoat layer in a state of being dispersed together with the inorganic particles, or may be contained in a state of being attached to the surface of the inorganic particles.

  Examples of a method for attaching the electron accepting compound to the surface of the inorganic particles include a dry method and a wet method.

  In the dry method, for example, while stirring the inorganic particles with a mixer having a large shearing force, the electron-accepting compound dissolved directly or in an organic solvent is dropped, sprayed with dry air or nitrogen gas, and the electron-accepting compound is sprayed. This is a method of attaching to the surface of inorganic particles. When the electron-accepting compound is dropped or sprayed, the temperature is preferably lower than the boiling point of the solvent. After dropping or spraying the electron-accepting compound, baking may be performed at 100 ° C. or more. The printing is not particularly limited as long as the temperature and the time at which the electrophotographic characteristics can be obtained.

  The wet method includes, for example, stirring, ultrasonic waves, a sand mill, an attritor, a ball mill, etc., while dispersing the inorganic particles in a solvent, adding an electron-accepting compound, stirring or dispersing, removing the solvent, In this method, a receptive compound is attached to the surface of inorganic particles. The solvent is removed by filtration or distillation, for example. After removing the solvent, baking may be performed at 100 ° C. or more. The printing is not particularly limited as long as the temperature and the time at which the electrophotographic characteristics can be obtained. In the wet method, the water content of the inorganic particles may be removed before the addition of the electron-accepting compound, and examples thereof include a method of removing while stirring and heating in a solvent, and a method of removing by azeotropic distillation with the solvent. No.

  The attachment of the electron-accepting compound may be performed before or after the surface treatment with the surface-treating agent is performed on the inorganic particles, or may be performed simultaneously with the attachment of the electron-accepting compound and the surface treatment with the surface-treating agent.

  The content of the electron-accepting compound is, for example, preferably from 0.01% by mass to 20% by mass, and more preferably from 0.01% by mass to 10% by mass, based on the inorganic particles.

Examples of the binder resin used for the undercoat layer include an acetal resin (for example, polyvinyl butyral), a polyvinyl alcohol resin, a polyvinyl acetal resin, a casein resin, a polyamide resin, a cellulose resin, a gelatin, a polyurethane resin, a polyester resin, and an unsaturated polyester. Resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, urea resin, phenol resin, phenol-formaldehyde resin, melamine resin, Known polymer compounds such as urethane resin, alkyd resin, epoxy resin, etc .; zirconium chelate compound; titanium chelate compound; aluminum chelate compound; titanium alkoxide compound ; Organic titanium compounds; known materials silane coupling agent, and the like.
Examples of the binder resin used for the undercoat layer include a charge transporting resin having a charge transporting group and a conductive resin (for example, polyaniline).

Among these, as the binder resin used for the undercoat layer, a resin that is insoluble in the coating solvent of the upper layer is preferable. Resin, alkyd resin, thermosetting resin such as epoxy resin; at least one resin selected from the group consisting of polyamide resin, polyester resin, polyether resin, methacrylic resin, acrylic resin, polyvinyl alcohol resin and polyvinyl acetal resin; Resins obtained by reaction with a curing agent are preferred.
When two or more of these binder resins are used in combination, the mixing ratio is set as necessary.

The undercoat layer may contain various additives for improving electrical properties, environmental stability, and image quality.
Examples of the additive include known materials such as a polycyclic fused system, an electron transporting pigment such as an azo system, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound, a titanium alkoxide compound, an organic titanium compound, and a silane coupling agent. Can be The silane coupling agent is used for the surface treatment of the inorganic particles as described above, but may be further added to the undercoat layer as an additive.

  Examples of the silane coupling agent as an additive include vinyltrimethoxysilane, 3-methacryloxypropyl-tris (2-methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, and the like.

  As the zirconium chelate compound, for example, zirconium butoxide, ethyl zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium butoxide acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, Examples include zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, zirconium butoxide methacrylate, zirconium butoxide stearate, zirconium butoxide isostearate, and the like.

  Examples of the titanium chelate compound include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, and titanium lactate ammonium salt , Titanium lactate, titanium lactate ethyl ester, titanium triethanol aminate, polyhydroxytitanium stearate and the like.

  Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethylacetoacetate).

  These additives may be used alone or as a mixture or a polycondensate of a plurality of compounds.

The undercoat layer preferably has a Vickers hardness of 35 or more.
The surface roughness (ten-point average roughness) of the undercoat layer ranges from 1 / (4n) (n is the refractive index of the upper layer) to 1/2 of the exposure laser wavelength λ used to suppress moire images. It is good to be adjusted to.
Resin particles or the like may be added to the undercoat layer for adjusting the surface roughness. Examples of the resin particles include silicone resin particles and cross-linked polymethyl methacrylate resin particles. Further, the surface of the undercoat layer may be polished for adjusting the surface roughness. Examples of the polishing method include buffing, sand blasting, wet honing, and grinding.

  The formation of the undercoat layer is not particularly limited, and a well-known formation method is used. Then, heating is performed as necessary.

As a solvent for preparing the coating liquid for forming the undercoat layer, known organic solvents, for example, alcohol solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents, ketone alcohol solvents, ether solvents Solvents, ester solvents and the like.
Specific examples of these solvents include, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, Usable organic solvents such as n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene.

  Examples of the method of dispersing the inorganic particles when preparing the coating liquid for forming the undercoat layer include known methods such as a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker.

  Examples of the method of applying the coating liquid for forming an undercoat layer on a conductive substrate include a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method. And the like.

  The thickness of the undercoat layer is set, for example, preferably in a range of 15 μm or more, more preferably in a range of 20 μm or more and 50 μm or less.

(Intermediate layer)
Although not shown, an intermediate layer may be further provided between the undercoat layer and the photosensitive layer.
The intermediate layer is, for example, a layer containing a resin. Examples of the resin used for the intermediate layer include an acetal resin (for example, polyvinyl butyral), a polyvinyl alcohol resin, a polyvinyl acetal resin, a casein resin, a polyamide resin, a cellulose resin, a gelatin, a polyurethane resin, a polyester resin, a methacryl resin, an acrylic resin, Polymer compounds such as a polyvinyl chloride resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate-maleic anhydride resin, a silicone resin, a silicone-alkyd resin, a phenol-formaldehyde resin, and a melamine resin.
The intermediate layer may be a layer containing an organometallic compound. Examples of the organometallic compound used for the intermediate layer include organometallic compounds containing metal atoms such as zirconium, titanium, aluminum, manganese, and silicon.
The compounds used for these intermediate layers may be used alone or as a mixture or a polycondensate of a plurality of compounds.

  Among them, the intermediate layer is preferably a layer containing an organometallic compound containing a zirconium atom or a silicon atom.

The formation of the intermediate layer is not particularly limited, and a well-known forming method is used.For example, a coating film of the coating solution for forming an intermediate layer in which the above components are added to a solvent is formed, and the coating film is dried and dried. It is performed by heating according to.
As a coating method for forming the intermediate layer, a usual method such as a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, a knife coating method, and a curtain coating method is used.

  The thickness of the intermediate layer is, for example, preferably set in a range of 0.1 μm or more and 3 μm or less. In addition, you may use an intermediate | middle layer as an undercoat layer.

(Charge generation layer)
The charge generation layer is, for example, a layer containing a charge generation material and a binder resin. Further, the charge generation layer may be a vapor deposition layer of a charge generation material. The vapor-deposited layer of the charge generating material is suitable when using a non-coherent light source such as an LED (Light Emitting Diode) and an organic EL (Electro-Luminescence) image array.

  Examples of the charge generation material include azo pigments such as bisazo and trisazo; condensed aromatic pigments such as dibromoanthanthrone; perylene pigments; pyrrolopyrrole pigments; phthalocyanine pigments; zinc oxide; and trigonal selenium.

  Among these, in order to cope with laser exposure in the near infrared region, it is preferable to use a metal phthalocyanine pigment or a metal-free phthalocyanine pigment as the charge generation material. Specifically, for example, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279951; chlorogallium phthalocyanine disclosed in JP-A-5-98181; Dichlorotin phthalocyanine disclosed in JP-A-140472 and JP-A-5-140473; and titanyl phthalocyanine disclosed in JP-A-4-189873 and the like are more preferred.

  On the other hand, in order to cope with laser exposure in the near ultraviolet region, as a charge generating material, condensed aromatic pigments such as dibromoanthanthrone; thioindigo pigments; porphyrazine compounds; zinc oxide; trigonal selenium; Bisazo pigments disclosed in JP-A-2004-78147 and JP-A-2005-181992 are preferred.

  When using a non-coherent light source such as an LED or an organic EL image array having a light emission center wavelength of 450 nm or more and 780 nm or less, the above-mentioned charge generation material may be used. When a thin film is used, the electric field strength in the photosensitive layer is increased, and the charge is reduced due to the injection of charge from the substrate, and an image defect called a so-called black spot is easily generated. This is remarkable when a p-type semiconductor such as a trigonal selenium or a phthalocyanine pigment is used, which is a charge generating material that easily generates a dark current.

On the other hand, when an n-type semiconductor such as a condensed aromatic pigment, a perylene pigment, or an azo pigment is used as the charge generation material, a dark current hardly occurs, and an image defect called a black spot can be suppressed even in a thin film. . Examples of the n-type charge generating material include compounds (CG-1) to (CG-27) described in paragraphs [0288] to [0291] of JP-A-2012-155282. It is not limited.
The n-type is determined by the polarity of the flowing photocurrent using a commonly used time-of-flight method, and the one that allows electrons to flow more easily as carriers than holes is regarded as n-type.

The binder resin used for the charge generation layer is selected from a wide range of insulating resins, and the binder resin is selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. You may choose.
Examples of the binder resin include a polyvinyl butyral resin, a polyarylate resin (eg, a polycondensate of a bisphenol and an aromatic divalent carboxylic acid), a polycarbonate resin, a polyester resin, a phenoxy resin, a vinyl chloride-vinyl acetate copolymer, Examples include polyamide resin, acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin and the like. Here, “insulating” means that the volume resistivity is 10 ¹³ Ωcm or more.
These binder resins may be used alone or as a mixture of two or more.

  The compounding ratio of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10 by mass.

  The charge generation layer may contain other well-known additives.

  The formation of the charge generation layer is not particularly limited, and a known formation method is used.For example, a coating film of a coating solution for forming a charge generation layer in which the above components are added to a solvent is formed, and the coating film is dried. Then, heating is performed as necessary. Note that the charge generation layer may be formed by vapor deposition of a charge generation material. The formation of the charge generation layer by vapor deposition is particularly suitable when a condensed aromatic pigment or perylene pigment is used as the charge generation material.

  Examples of the solvent for preparing the coating solution for forming the charge generation layer include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methylcellosolve, ethylcellosolve, acetone, methylethylketone, cyclohexanone, methyl acetate, and methyl acetate n. -Butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene and the like. These solvents may be used alone or as a mixture of two or more.

Examples of a method for dispersing particles (for example, a charge generating material) in the coating liquid for forming a charge generating layer include, for example, a media dispersing machine such as a ball mill, a vibration ball mill, an attritor, a sand mill, a horizontal sand mill, stirring, an ultrasonic dispersing machine, A medialess disperser such as a roll mill or a high-pressure homogenizer is used. Examples of the high-pressure homogenizer include a collision method in which the dispersion liquid is subjected to liquid-liquid collision or liquid-wall collision in a high pressure state to disperse the dispersion liquid, and a penetration method in which the dispersion liquid is penetrated and dispersed in a fine flow path in a high pressure state.
At the time of this dispersion, it is effective to make the average particle diameter of the charge generation material in the coating liquid for forming a charge generation layer 0.5 μm or less, preferably 0.3 μm or less, and more preferably 0.15 μm or less. .

  Examples of a method for applying the coating solution for forming the charge generation layer on the undercoat layer (or on the intermediate layer) include a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, and an air knife coating. And a usual method such as a curtain coating method.

  The thickness of the charge generation layer is set, for example, preferably in the range of 0.1 μm or more and 5.0 μm or less, and more preferably in the range of 0.2 μm or more and 2.0 μm or less.

(Charge transport layer)
The charge transport layer is, for example, a layer containing a charge transport material and a binder resin. The charge transport layer may be a layer containing a polymer charge transport material.

  Examples of the charge transport material include quinone compounds such as p-benzoquinone, chloranil, bromanyl and anthraquinone; tetracyanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone; xanthones; benzophenone compounds A cyanovinyl compound; and an electron-transporting compound such as an ethylene compound. Examples of the charge transport material include hole transport compounds such as triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, and hydrazone compounds. These charge transport materials may be used alone or in combination of two or more, but are not limited thereto.

  As the charge transport material, a triarylamine derivative represented by the following structural formula (a-1) and a benzidine derivative represented by the following structural formula (a-2) are preferable from the viewpoint of charge mobility.

In the structural formula (a-1), Ar ^T1 , Ar ^T2 , and Ar ^T3 are each independently a substituted or unsubstituted aryl group, —C ₆ H ₄ —C ( ^{RT 4} ) = C ( ^{RT 5} ) (R ^T6), or _{-C 6 H 4 -CH = CH-} CH = C (R T7) shows the ^{(R T8).} R ^T4 , R ^T5 , R ^T6 , R ^T7 , and R ^T8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
Examples of the substituent of each group include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. In addition, examples of the substituent of each of the above groups include a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms.

In the structural formula (a-2), R ^T91 and R ^T92 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ^T101 , R ^T102 , R ^T111 and R ^T112 are each independently ^substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkyl group having 1 to 2 carbon atoms. A substituted amino group, a substituted or unsubstituted aryl group, -C ( ^RT12 ) = C ( ^RT13 ) ( ^RT14 ), or -CH = CH-CH = C ( ^RT15 ) ( ^RT16 ). R ^T12 , R ^T13 , R ^T14 , R ^T15 and R ^T16 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Tm1, Tm2, Tn1, and Tn2 each independently represent an integer of 0 or more and 2 or less.
Examples of the substituent of each group include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. In addition, examples of the substituent of each of the above groups include a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms.

Here, among the triarylamine derivative represented by the structural formula (a-1) and the benzidine derivative represented by the structural formula (a-2), particularly, “—C ₆ H ₄ —CH ＝ CH—CHＣＨ C ^(R T7) triarylamine derivative having ^{(R T8)} ", and benzidine derivatives having" ^{-CH = CH-CH = C (} R T15) (R T16) ", preferable from the viewpoint of charge mobility.

  As the polymer charge transporting material, a known charge transporting material such as poly-N-vinylcarbazole and polysilane is used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 are particularly preferable. The polymer charge transport material may be used alone, or may be used in combination with a binder resin.

Binder resin used for the charge transport layer, polycarbonate resin, polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, Vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N -Vinyl carbazole, polysilane and the like. Among these, a polycarbonate resin or a polyarylate resin is preferable as the binder resin. These binder resins may be used alone or in combination of two or more.
The mixing ratio of the charge transport material to the binder resin is preferably from 10: 1 to 1: 5 by mass.

  The charge transport layer may contain other well-known additives.

  The formation of the charge transport layer is not particularly limited, and a well-known formation method is used.For example, a coating film of a charge transport layer forming coating solution obtained by adding the above components to a solvent is formed, and the coating film is dried. It is carried out by heating if necessary.

  Examples of the solvent for preparing the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; ketones such as acetone and 2-butanone; methylene chloride, chloroform and ethylene chloride. Halogenated aliphatic hydrocarbons; ordinary organic solvents such as cyclic or linear ethers such as tetrahydrofuran and ethyl ether; These solvents are used alone or in combination of two or more.

  The coating method for coating the charge transport layer forming coating liquid on the charge generating layer includes a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain. A usual method such as a coating method may be used.

  The thickness of the charge transport layer is set, for example, preferably in the range of 5 μm or more and 50 μm or less, and more preferably in the range of 10 μm or more and 30 μm or less.

(Protective layer)
The protective layer which is the outermost layer in the electrophotographic photosensitive member 7A will be described.
The protective layer is the outermost surface layer of the electrophotographic photoreceptor 7A, and is preferably formed using, for example, the above-described specific resin solution, preferably includes the above-described charge transporting film, and more preferably Most preferably, it contains a crosslinked resin.

  As a crosslinking method, radical polymerization by heat, light, radiation, or the like is performed. If the reaction is adjusted so as not to proceed too fast, the unevenness and wrinkles of the film are suppressed, and therefore it is desirable to crosslink under conditions where radical generation occurs relatively slowly. From this point, thermal crosslinking is preferable because the crosslinking speed can be easily adjusted.

-Non-reactive charge transporting material The non-reactive charge transporting material may be used together with the film constituting the protective layer (outermost surface layer) 5. Since the non-reactive charge transporting material does not have a reactive group that is not responsible for charge transport, when the non-reactive charge transporting material is used for the protective layer (outermost surface layer) 5, the charge transporting material is substantially charged. This is effective for increasing the concentration of the component and further improving the electrical characteristics. Alternatively, a non-reactive charge transport material may be added to reduce the crosslink density and adjust the strength.

As the non-reactive charge transporting material, known charge transporting materials may be used. Specifically, triarylamine-based compounds, benzidine-based compounds, arylalkane-based compounds, aryl-substituted ethylene-based compounds, stilbene-based compounds , Anthracene-based compounds, hydrazone-based compounds, and the like.
Above all, those having a triphenylamine skeleton are desirable from the viewpoint of mobility, compatibility and the like.

  The non-reactive charge transporting material is preferably used in an amount of 0% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less, based on the total solid content in the coating solution for forming a layer. And more desirably 5% by mass or more and 25% by mass or less.

-Other additives The protective layer (outermost layer) 5 is used for the purpose of further adjusting the film-forming property, flexibility, lubricity, adhesiveness, etc., and other coupling agents, especially fluorine-containing coupling agents. May be used. As such compounds, various silane coupling agents and commercially available silicone-based hard coat agents are used. Further, a silicon compound having a radical polymerizable group or a fluorine-containing compound may be used.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, Dimethyldimethoxysilane, and the like.
Commercially available hard coat agents include KP-85, X-40-9740, X-8239 (all manufactured by Shin-Etsu Chemical Co., Ltd.), AY42-440, AY42-441, AY49-208 (all manufactured by Toray Dow Corning) ) And the like.

  In order to impart water repellency and the like, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (hepta Fluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyl A fluorine-containing compound such as triethoxysilane may be added.

The silane coupling agent is used in an arbitrary amount, but the amount of the fluorine-containing compound is preferably not more than 0.25 times the mass of the fluorine-free compound from the viewpoint of the film-forming property of the crosslinked film. desirable. Further, a reactive fluorine compound or the like disclosed in JP-A-2001-166510 or the like may be mixed.
Examples of the silicon compound and the fluorine-containing compound having a radical polymerizable group include compounds described in JP-A-2007-11005.

The protective layer (outermost layer) 5 may contain a deterioration inhibitor. Hindered phenol-based and hindered amine-based antioxidants are desirable, and organic sulfur-based antioxidants, phosphite-based antioxidants, dithiocarbamate-based antioxidants, thiourea-based antioxidants, and benzimidazole-based antioxidants are preferable. And other known antioxidants.
The addition amount of the deterioration inhibitor is preferably 20% by mass or less, more preferably 10% by mass or less.

Examples of the hindered phenolic antioxidants include Irganox 1076, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076, 3,5-di-t-butyl-4-. Hydroxybiphenyl and the like.
Examples of the hindered amine antioxidants include SANOL LS2626, SANOL LS765, SANOL LS770, SANOL LS744, Tinuvin 144, Tinuvin 622LD, Mark LA57, Mark LA67, Mark LA62, Mark LA68, and Mark LA63. , And Sumilizer TP-D, and examples of the phosphite system include Mark 2112, Mark PEP-8, Mark PEP-24G, Mark PEP-36, Mark 329K, and Mark HP-10.

Further, the protective layer (outermost layer) 5 may contain conductive particles, organic or inorganic particles.
One example of the particles is silicon-containing particles. The silicon-containing particles are particles containing silicon as a constituent element, and specific examples thereof include colloidal silica and silicone particles. Colloidal silica used as the silicon-containing particles is preferably a silica having an average particle size of 1 nm or more and 100 nm or less, more preferably 10 nm or more and 30 nm or less, in an acidic or alkaline aqueous dispersion, or in an organic solvent such as alcohol, ketone, or ester. Selected from those dispersed in Generally, commercially available particles may be used as the particles.

  The solid content of the colloidal silica in the protective layer is not particularly limited, but is 0.1% by mass or more and 50% by mass or less, preferably 0.1% by mass, based on the total solid content of the protective layer. % To 30% by mass or less.

The silicone particles used as the silicon-containing particles are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and generally commercially available particles may be used.
These silicone particles are spherical and have an average particle size of preferably 1 nm or more and 500 nm or less, more preferably 10 nm or more and 100 nm or less.
The content of the silicone particles in the surface layer is preferably from 0.1% by mass to 30% by mass, more preferably from 0.5% by mass to 10% by mass, based on the total solid content of the protective layer. .

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, and vinylidene fluoride. is as shown, fluororesin and hydroxyl particles composed of a resin obtained by copolymerizing a monomer having _{a, ZnO-Al 2 O 3,} SnO 2 -Sb 2 O 3, in 2 O 3 -SnO 2, ZnO 2 - Semiconductive metal oxides such as TiO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO can be given. Further, various known dispersants may be used to disperse the particles.

Further, oil such as silicone oil may be added.
Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane; amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto-modified polysiloxane. Reactive silicone oils such as siloxane and phenol-modified polysiloxane; cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; 1,3,5- Trimethyl-1.3.5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclo Cyclic methylphenylcyclosiloxanes such as trasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane; cyclic phenylcyclosiloxane such as hexaphenylcyclotrisiloxane Fluorine-containing cyclosiloxanes such as 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane; hydrosilyl group-containing cyclosiloxanes such as methylhydrosiloxane mixtures, pentamethylcyclopentasiloxane and phenylhydrocyclosiloxane Vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane.

Further, a metal, a metal oxide, carbon black, or the like may be added. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, stainless steel, and the like, and those obtained by vapor-depositing these metals on the surfaces of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony or tantalum-doped tin oxide, and antimony-doped zirconium oxide. .
These may be used alone or in combination of two or more. When two or more kinds are used in combination, they may be simply mixed or mixed by solid solution or fusion. The average particle size of the conductive particles is preferably 0.3 μm or less, particularly preferably 0.1 μm or less.

Examples of the composition used for forming the protective layer include the above-mentioned specific resin solution.
When the above-mentioned components are reacted with a solvent in order to obtain a specific resin solution, the components may be simply mixed and dissolved, but preferably from room temperature (20 ° C.) to 100 ° C., more preferably. Is heated at a temperature of 30 ° C. to 80 ° C., preferably 10 minutes to 100 hours, more preferably 1 hour to 50 hours. At this time, it is also desirable to irradiate ultrasonic waves.

The coating liquid for forming the protective layer is applied on the surface to be coated (the charge transport layer 3 in the embodiment shown in FIG. 1) by a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife. Coating is performed by a normal method such as a coating method, a curtain coating method, and an inkjet coating method.
Thereafter, light, an electron beam, or heat is applied to the obtained coating film to cause radical polymerization, whereby the coating film is cross-linked and cured.

  When the coating film is crosslinked and cured by heat, the heating condition is desirably 50 ° C. or higher. In particular, the heating temperature is desirably from 100 ° C to 180 ° C.

  When the coating film is crosslinked and cured by light, it is irradiated with a known method such as a mercury lamp or metal halide to obtain a cured film.

  As described above, at the time of the crosslinking and curing reaction, the oxygen concentration is preferably under a vacuum or an inert gas atmosphere so that the chain reaction can be performed without deactivating the radicals generated by light, electron beam, or heat. Is performed at a low oxygen concentration of 10% or less, more preferably 5% or less, even more preferably 2% or less, and most preferably 500 ppm or less.

  In the present embodiment, a heat curing method in which radical generation occurs relatively slowly is particularly preferable.

  The thickness of the protective layer is preferably from 3 μm to 40 μm, more preferably from 5 μm to 35 μm.

In the above, the configuration of each layer in the function-separated type photosensitive layer has been described with reference to the electrophotographic photosensitive member 7A shown in FIG. 1. A configuration may be employed.
Hereinafter, the single-layer type photosensitive layer 6 of the electrophotographic photosensitive member 7C shown in FIG. 3 will be described.

(Single-layer type photosensitive layer)
The single-layer type photosensitive layer (charge generation / charge transport layer) is, for example, a layer containing a charge generation material, a charge transport material, and, if necessary, a binder resin and other known additives. These materials are the same as those described for the charge generation layer and the charge transport layer.
The content of the charge generating material in the single-layer type photosensitive layer is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.8% by mass or more and 5% by mass or less based on the total solid content. . The content of the charge transporting material in the single-layer type photosensitive layer is preferably 5% by mass or more and 50% by mass or less based on the total solid content.
The method for forming the single-layer type photosensitive layer is the same as the method for forming the charge generation layer and the charge transport layer.
The thickness of the single-layer type photosensitive layer is, for example, preferably from 5 μm to 50 μm, and more preferably from 10 μm to 40 μm.

  In the above-described embodiment, the mode in which the outermost layer is a protective layer has been described. However, in the case of a layer configuration without a protective layer, the charge transport layer located on the outermost surface in the layer configuration is the outermost layer. Becomes When the outermost surface layer is a charge transport layer, the thickness of this layer is preferably from 7 μm to 70 μm, and more preferably from 10 μm to 60 μm.

-Image forming apparatus and process cartridge-
Next, an image forming apparatus and a process cartridge using the electrophotographic photosensitive member will be described.
The image forming apparatus includes, for example, an electrophotographic photosensitive member, a charging unit that charges a surface of the electrophotographic photosensitive member, an electrostatic latent image forming unit that forms an electrostatic latent image on the surface of the charged electrophotographic photosensitive member, The image forming apparatus includes a developing unit that develops an electrostatic latent image formed on the surface of the electrophotographic photosensitive member with a developer containing a toner to form a toner image, and a transfer unit that transfers the toner image to the surface of a recording medium. Then, the above-described electrophotographic photosensitive member is applied as the electrophotographic photosensitive member.

  As the image forming apparatus, an apparatus having a fixing unit for fixing the toner image transferred to the surface of the recording medium; an apparatus of a direct transfer system for directly transferring the toner image formed on the surface of the electrophotographic photosensitive member to the recording medium; An intermediate transfer type apparatus for primary-transferring the toner image formed on the surface of the electrophotographic photosensitive member onto the surface of the intermediate transfer member and secondary-transferring the toner image transferred on the surface of the intermediate transfer member onto the surface of the recording medium; An apparatus having cleaning means for cleaning the surface of the electrophotographic photosensitive member after transfer of the toner image and before charging; static elimination by irradiating static elimination light to the surface of the electrophotographic photosensitive member after transfer of the toner image and before charging Apparatus provided with means; a known image forming apparatus such as an apparatus provided with an electrophotographic photosensitive member heating member for raising the temperature of the electrophotographic photosensitive member and reducing the relative temperature is applied.

  In the case of an intermediate transfer type device, the transfer unit includes, for example, an intermediate transfer member on which a toner image is transferred on the surface, and a primary unit for primarily transferring the toner image formed on the surface of the electrophotographic photosensitive member to the surface of the intermediate transfer member. A configuration including a transfer unit and a secondary transfer unit that secondary-transfers the toner image transferred on the surface of the intermediate transfer body to the surface of the recording medium is applied.

  The image forming apparatus may be either a dry developing type image forming apparatus or a wet developing type (developing type using a liquid developer) image forming apparatus.

  In the image forming apparatus, for example, the portion including the electrophotographic photoreceptor may be a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge provided with the electrophotographic photosensitive member is suitably used. The process cartridge may include, for example, at least one selected from the group consisting of a charging unit, an electrostatic latent image forming unit, a developing unit, and a transfer unit, in addition to the electrophotographic photosensitive member.

  Hereinafter, an example of the image forming apparatus will be described, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

FIG. 4 is a schematic configuration diagram illustrating an example of the image forming apparatus according to the present embodiment.
As shown in FIG. 4, the image forming apparatus 100 according to the present embodiment includes a process cartridge 300 including an electrophotographic photosensitive member 7, an exposure device 9 (an example of an electrostatic latent image forming unit), and a transfer device 40 (primary image forming device). Transfer device) and an intermediate transfer member 50. In the image forming apparatus 100, the exposure device 9 is disposed at a position where the electrophotographic photosensitive member 7 can be exposed through the opening of the process cartridge 300, and the transfer device 40 is connected to the electrophotographic photosensitive member via the intermediate transfer member 50. 7, and the intermediate transfer body 50 is arranged such that a part thereof is in contact with the electrophotographic photosensitive member 7. Although not shown, it also has a secondary transfer device for transferring the toner image transferred to the intermediate transfer body 50 to a recording medium (for example, paper). The intermediate transfer body 50, the transfer device 40 (primary transfer device), and the secondary transfer device (not shown) correspond to an example of a transfer unit.

  In the process cartridge 300 in FIG. 4, the electrophotographic photoreceptor 7, the charging device 8 (an example of a charging device), the developing device 11 (an example of a developing device), and the cleaning device 13 (an example of a cleaning device) are integrated in a housing. I support it. The cleaning device 13 has a cleaning blade (an example of a cleaning member) 131, and the cleaning blade 131 is arranged so as to contact the surface of the electrophotographic photosensitive member 7. The cleaning member is not limited to the cleaning blade 131, but may be a conductive or insulating fibrous member. The cleaning member may be used alone or in combination with the cleaning blade 131.

  In FIG. 4, as an image forming apparatus, a fibrous member 132 (roll-like) for supplying the lubricant 14 to the surface of the electrophotographic photosensitive member 7 and a fibrous member 133 (flat brush-like) for assisting cleaning are provided. Are shown, but these are arranged as needed.

  Hereinafter, each configuration of the image forming apparatus according to the present embodiment will be described.

(Charging device)
As the charging device 8, for example, a contact type charger using a conductive or semiconductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube, or the like is used. In addition, a known charger such as a non-contact type roller charger, a scorotron charger using corona discharge, or a corotron charger may be used.

(Exposure equipment)
Examples of the exposure device 9 include an optical device that exposes the surface of the electrophotographic photoreceptor 7 with light such as a semiconductor laser light, an LED light, and a liquid crystal shutter light in a predetermined image. The wavelength of the light source is within the spectral sensitivity range of the electrophotographic photosensitive member. As a wavelength of a semiconductor laser, near-infrared light having an oscillation wavelength near 780 nm is mainly used. However, the wavelength is not limited to this, and an oscillation wavelength laser of the order of 600 nm or a laser having an oscillation wavelength of 400 nm or more and 450 nm or less as a blue laser may be used. For forming a color image, a surface emitting laser light source capable of outputting multiple beams is also effective.

(Developer)
The developing device 11 includes, for example, a general developing device that performs development by contacting or non-contacting a developer. The developing device 11 is not particularly limited as long as it has the above-described functions, and is selected according to the purpose. For example, a known developing device having a function of attaching a one-component developer or a two-component developer to the electrophotographic photoreceptor 7 using a brush, a roller, or the like may be used. Among them, those using a developing roller holding a developer on the surface are preferable.

  The developer used in the developing device 11 may be a one-component developer containing only the toner or a two-component developer containing the toner and the carrier. Further, the developer may be magnetic or non-magnetic. Known developers are applied to these developers.

(Cleaning device)
As the cleaning device 13, a cleaning blade type device including a cleaning blade 131 is used.
In addition to the cleaning blade system, a fur brush cleaning system and a simultaneous development cleaning system may be employed.

(Transfer device)
As the transfer device 40, for example, a belt, a roller, a film, a contact-type transfer charger using a rubber blade or the like, a transfer charger known per se such as a scorotron transfer charger using a corona discharge or a corotron transfer charger is used. No.

(Intermediate transfer member)
As the intermediate transfer member 50, a belt-like one (intermediate transfer belt) containing semiconductive polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber, or the like is used. Further, as a form of the intermediate transfer member, a drum-shaped one may be used instead of the belt-shaped one.

FIG. 5 is a schematic configuration diagram illustrating another example of the image forming apparatus.
The image forming apparatus 120 shown in FIG. 5 is a tandem type multicolor image forming apparatus having four process cartridges 300 mounted thereon. In the image forming apparatus 120, four process cartridges 300 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member is used for one color. Note that the image forming apparatus 120 has the same configuration as the image forming apparatus 100 except that the image forming apparatus 120 is of a tandem type.

-Organic electroluminescent device-
The organic electroluminescent element is a device including a pair of electrodes, at least one of which is transparent, and one or a plurality of organic compound layers including a light emitting layer sandwiched between the pair of electrodes.
In the organic electroluminescent device according to this embodiment, at least one of the organic compound layers is the above-described charge transporting film.

  In the organic electroluminescent device according to the present embodiment, when the organic compound layer is a single layer, the organic compound layer is a light emitting layer having a hole transporting performance, and the light emitting layer having the hole transporting performance is the present embodiment. In the above-described charge transporting film.

  In the organic electroluminescent device, when the organic compound layer has a plurality of layers (that is, in the case of a function separation type in which each layer has a different function), at least one of the layers is a light emitting layer. ) To (3). In the layer configurations (1) to (3), in the organic electroluminescent device according to the present embodiment, at least one layer is the charge transporting film described above.

Layer configuration (1): A function-separated layer configuration having a hole transport layer and a light emitting layer. In this configuration, at least one of the hole transporting layer and the light emitting layer may be a charge transporting film, and the hole transporting layer is preferably the above-described charge transporting film.

Layer configuration (2): a function-separated layer configuration including a hole transport layer, a light-emitting layer, and an electron transport layer. In this configuration, at least one of the hole transport layer, the light emitting layer, and the electron transport layer may be the above-described charge transport film, and the hole transport layer is preferably the above-described charge transport film.

Layer configuration (3): a function-separated type layer configuration including a light emitting layer and an electron transport layer. In this configuration, at least one of the light emitting layer and the electron transport layer may be the charge transport film described above, and the light emitting layer is preferably the charge transport film described above.

Hereinafter, the organic electroluminescent device according to the present embodiment will be described with reference to the drawings, but the present embodiment is not limited thereto.

  FIGS. 7 to 10 are schematic cross-sectional views illustrating the layer configuration of the organic electroluminescent device according to the present embodiment. FIGS. 7, 8, and 9 show the case where the organic compound layer is composed of a plurality of layers. FIG. 10 shows an example in which the organic compound layer is a single layer. 7 to 10, layers having similar functions are denoted by the same reference numerals and described.

FIG. 7 shows the layer configuration (1).
The organic electroluminescent device shown in FIG. 7 is a device in which a transparent electrode 22, a hole transport layer 23, a light emitting layer 24, and a back electrode 27 are laminated in this order on a transparent insulator substrate 21. A hole injection layer may be arranged between the transparent electrode 22 and the hole transport layer 23. In the embodiment shown in FIG. 7, it is preferable that the hole transport layer 23 is the charge transporting film described in the present embodiment, and further, if a hole injection layer is provided, May be the charge transporting film in the present embodiment.

FIG. 8 shows the layer configuration (2).
The organic electroluminescent device shown in FIG. 8 is a device in which a transparent electrode 22, a hole transport layer 23, a light emitting layer 24, an electron transport layer 25, and a back electrode 27 are laminated in this order on a transparent insulator substrate 21. . A hole injection layer may be arranged between the transparent electrode 22 and the hole transport layer 23. An electron injection layer may be provided between the electron transport layer 25 and the back electrode 27. In the embodiment shown in FIG. 8, it is preferable that the hole transport layer 23 is the charge transport film described above in the present embodiment, and further, if a hole injection layer is provided, the hole injection layer May be used as the above-described charge transporting film in the present embodiment.

FIG. 9 shows the above-mentioned layer configuration (3).
The organic electroluminescent device shown in FIG. 9 is a device in which a transparent electrode 22, a light emitting layer 26, an electron transport layer 25, and a back electrode 27 are laminated in this order on a transparent insulator substrate 21. An electron injection layer may be provided between the electron transport layer 25 and the back electrode 27. In the embodiment shown in FIG. 9, the light emitting layer 26 is preferably the charge transporting film in the present embodiment. In this case, the above-described charge transporting film in the present embodiment contains at least one light emitting material.

  FIG. 10 shows a single-layer structure. The organic electroluminescent device shown in FIG. 10 is a device in which a transparent electrode 22, a light emitting layer 26 having a hole transporting property, and a back electrode 27 are laminated in this order on a transparent insulator substrate 21. In the embodiment shown in FIG. 10, the light emitting layer 26 is the above-described charge transporting film in the present embodiment. In this case, the above-described charge transporting film in the present embodiment contains at least one light emitting material.

  In each of the organic electroluminescent devices shown in FIGS. 7 to 10, a protective layer may be provided on the back electrode 27 for the purpose of preventing the organic electroluminescent device from being deteriorated by moisture or oxygen.

  In the case of a top emission structure or when both electrodes are transparent electrodes, a structure in which a plurality of layer configurations shown in FIGS. 7 to 10 are stacked may be employed.

  Hereinafter, each layer in FIGS. 7 to 10 will be described in more detail.

Transparent with respect to the transparent insulator substrate 21 means that the transmittance of light in the visible region is 10% or more, and the transmittance is preferably 75% or more.
As the transparent insulator substrate 21, for example, a glass plate, a quartz plate, a metal foil, or a resin film is used. Examples of the material of the resin film include methacrylic resins such as polymethyl methacrylate (PMMA), polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and polycarbonate resins.
The transparent insulator substrate 21 may be subjected to a surface treatment or a laminated structure for the purpose of suppressing water permeability and gas permeability.

  Like the transparent insulator substrate 21, the transparent electrode 22 is preferably an electrode that is transparent for extracting light emission and has a large work function for injecting holes, and an electrode having a work function of 4 eV or more.

Transparent with respect to the transparent electrode 22 means that the transmittance of light in the visible region is 10% or more, and the transmittance is preferably 75% or more.
Examples of the material of the transparent electrode 22 include metal oxides such as indium tin oxide (ITO), tin oxide, indium oxide, zinc oxide, and indium zinc oxide; metals such as aluminum, nickel, gold, silver, platinum, and palladium; Metal halides such as copper; and conductive polymers such as carbon black, poly (3-methylthiophene), polypyrrole, and polyaniline.
The sheet resistance of the transparent electrode 22 is preferably as low as possible, preferably several hundred Ω / □ or less, more preferably 100 Ω / □ or less.

The organic compound layers (layers denoted by reference numerals 23 to 26 in FIGS. 7 to 10) are formed from a hole-transporting material, a hole-injecting material, an electron-transporting material, an electron-injecting material, and a light-emitting material depending on their functions. Including selected materials.
When the organic compound layer is the above-described charge transporting film in the present embodiment, a composition in which a hole transporting compound having a crosslinkable group and an electron transporting compound having a crosslinkable group are mixed with these materials is used. A layer may be formed.

  Examples of the hole transport material include a tetraphenylenediamine derivative, a triphenylamine derivative, a carbazole derivative, a stilbene derivative, an arylhydrazone derivative, and a porphyrin-based compound, and include a tetraphenylenediamine derivative, a spirofluorene derivative, and a triphenylamine derivative. .

  Examples of the hole injection material include phenylenediamine derivatives, phthalocyanine derivatives, indanthrene derivatives, polyalkylenedioxythiophene derivatives, and the like. These include organic acids such as Lewis acids and sulfonic acids, and inorganic acids such as iron chloride. May be mixed.

  Electron transport materials include oxadiazole derivatives, nitro-substituted fluorenone derivatives, diphenoquinone derivatives, thiopyrandioxide derivatives, silole derivatives, chelating organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, triazole derivatives, fluorenylidene Methane derivatives and the like can be mentioned.

  Examples of the electron injecting material include metals such as Li, Ca, and Sr, metal fluorides such as LiF and MgF, and metal oxides such as MgO, Al2O3, and LiO.

As the light emitting material, a compound exhibiting high light emission quantum efficiency in a solid state is desirable. The light emitting material may be either a low molecular compound or a high molecular compound.
Examples of the organic low molecular weight compound include a chelate type organometallic complex, a polynuclear or condensed aromatic ring compound, a perylene derivative, a coumarin derivative, a styryl arylene derivative, a silole derivative, an oxazole derivative, an oxathiazole derivative, and an oxadiazole derivative.
Examples of the organic polymer compound include a polyparaphenylene derivative, a polyparaphenylenevinylene derivative, a polythiophene derivative, and a polyacetylene derivative.

Specific examples of the light emitting material include the following exemplified compounds (VI-1) to (VI-17).
In addition, the following exemplified compounds (VI-1) to (VI-17) may be used as an electron transport material.

In the exemplified compounds (VI-13) to (VI-17), n and g are each independently an integer of 1 or more, and V is a divalent linking group. Examples of V include the following divalent groups.
In the following divalent groups, g represents an integer of 1 or more, and h represents an integer of 0 or more and 5 or less.

For the purpose of improving the durability or luminous efficiency of the organic electroluminescent element, a dye compound different from the luminescent material may be doped into the luminescent material as a guest material.
The doping amount of the dye compound is preferably from 0.001 to 40 parts by mass, more preferably from 0.01 to 10 parts by mass, based on 100 parts by mass of the host.

Examples of dye compounds for doping include coumarin derivatives, DCM derivatives, quinacridone derivatives, perimidone derivatives, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, rubrene derivatives, porphyrin derivatives; ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium. , Platinum, and metal complex compounds such as gold; and the like.
Specific examples of the dye compound for doping include exemplified compounds (VII-1) to (VII-6).

Each organic compound layer may contain a binder resin.
As the binder resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinyldene chloride-acrylonitrile Conductive resins such as copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, silicone resins, poly-N-vinyl carbazole resins, polysilane resins, polythiophenes, and polypyrroles.
Each organic compound layer may contain a known antioxidant, ultraviolet absorber, plasticizer, and the like, if necessary.

The material of the back electrode 27 is preferably a material that can be vacuum-deposited and has a small work function for performing electron injection, and is preferably a metal, a metal oxide, or a metal fluoride.
Examples of the metal include magnesium, aluminum, gold, silver, indium, lithium, calcium, and alloys thereof.
Examples of the metal oxide include lithium oxide, magnesium oxide, aluminum oxide, indium tin oxide, tin oxide, indium oxide, zinc oxide, and indium zinc oxide.
Examples of the metal fluoride include lithium fluoride, magnesium fluoride, strontium fluoride, calcium fluoride, and aluminum fluoride.

A protective layer may be provided on the back electrode 27.
Examples of the material of the protective layer include metals such as indium, tin, lead, gold, silver, copper, and aluminum; metal oxides such as magnesium oxide, silicon dioxide, and titanium oxide; resins such as polyethylene resin, polyurea resin, and polyimide resin; Is mentioned.

  The thickness of the transparent electrode 22, each organic compound layer, the back electrode 27, and the protective layer is generally 0.001 μm or more and 10 μm or less, and preferably 0.001 μm or more and 5 μm or less.

The organic electroluminescent device shown in FIGS. 7 to 10 is manufactured by sequentially forming a transparent electrode 22, each organic compound layer, and a back electrode 27 on a transparent insulator substrate 21.
The transparent electrode 22, each organic compound layer, and the back electrode 27 are formed by, for example, a vacuum deposition method, a sputtering method, a coating method, or the like.
The coating method is a film forming method in which a coating solution in which materials are dissolved or dispersed in an appropriate solvent is applied on the transparent electrode 22, and the coating film is dried.
Examples of the method for applying the coating liquid include a spin coating method, a die coating method, an ink jet method, a casting method, and a dipping method.

The content state of each material in the organic compound layer may be a state in which molecules are dispersed (molecular dispersion state) or a state in which particles are formed and dispersed (particle dispersion state).
In order to form a molecular dispersion state in a film forming method using a coating solution, a solvent of the coating solution is selected in consideration of dispersibility and solubility of each material.
In order to make the particles dispersed in a film forming method using a coating solution, a coating solution is prepared using any of a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer, and ultrasonic waves.

The image display medium is configured by arranging the organic electroluminescent elements according to the present embodiment in a matrix or a segment.
When the organic electroluminescent elements are arranged in a matrix, a mode in which only the electrodes are arranged in a matrix may be employed, or a mode in which the electrodes and the organic compound layer are arranged in a matrix.
When the organic electroluminescent element is arranged in a segment, the electrode may be arranged in a segment only, or the electrode and the organic compound layer may be arranged in a segment.
The matrix or segment organic compound layer may be formed by an inkjet method.

  Japanese Patent Application Laid-Open Nos. 2-148687, 6-301355, 5-29080, and 7 describe a driving device and a driving method for a matrix organic electroluminescent device and a segment organic electroluminescent device. The driving apparatus and the driving method described in JP-A-134558, JP-A-8-234885, JP-A-8-241047, Japanese Patent No. 2778415, U.S. Pat. No. 5,828,429, U.S. Pat. Applicable.

  Hereinafter, Examples and Comparative Examples will be described, but the present invention is not limited to the following Examples. In the following, “parts” are based on mass unless otherwise specified.

<Synthesis example A1>
As compounds 3-5, wherein is represented by the general formula (3A), and the combination of ^{A 1} and ^{T 1} and p has prepared compound is a preceding example number (2-5).
A 500 ml flask was charged with 80 g of the compound 3-5, 230 g of epichlorohydrin, 26.8 g of sodium hydroxide, and 3 g of triethylamine. After the atmosphere was replaced with nitrogen, the mixture was stirred at room temperature (25 ° C.) for 24 hours. After the reaction, the resultant was washed with a dilute hydrochloric acid aqueous solution and then with water. After concentration, the residue was purified by silica gel chromatography to obtain 64 g of compound 4-5.
The compound 4-5, wherein is represented by the general formula (4A), and the combination of ^{A 2} and ^{T 2} and q is a preceding example number (2-5).

As compounds 3-29, wherein is represented by the general formula (3A), and the combination of ^{A 1} and ^{T 1} and p has prepared compound is a preceding example number (2-29).
In a 2000 ml flask, 79.8 g of compound 3-29, 700 ml of tetrahydrofuran, and 1.8 g of boron trifluoride diethyl ether complex were placed, and the mixture was purged with nitrogen and heated to 50 ° C. A solution in which 50.0 g of the compound 4-5 was dissolved in 200 ml of tetrahydrofuran was dropped into this solution over 30 minutes. After completion of the dropping, the mixture was reacted for 2 hours, and then dropped into 10 L of methanol to precipitate a polymer. The obtained polymer was sufficiently washed with methanol and dried to obtain 107.0 g of a resin (A-1) which is a resin of the number (A-1) shown as a specific example of the first charge transporting resin. Was.
The molecular weight measured by GPC was 60000 in terms of polystyrene. The value of _MH / ( _MH + _MP ) was 1.0.

<Synthesis example A2>
10 g of the resin (A-1) obtained in Synthesis Example A1 was placed in a 300 ml flask, 18 g of 4-iodomethylstyrene and 0.1 g of nitrobenzene were placed in the flask, and 100 ml of tetrahydrofuran was added and dissolved. To this was added 5.8 g of sodium t-butoxy at room temperature (25 ° C.) over 2 hours, and the mixture was reacted at 50 ° C. for 3 hours. After completion of the reaction, 100 ml of toluene was added, washed with dilute hydrochloric acid and then with water, and dropped into 500 ml of methanol to precipitate a polymer. The obtained polymer was sufficiently washed with methanol and dried to obtain 10.1 g of a resin (A-2) which is a resin of the number (A-2) shown as a specific example of the first charge transporting resin. Was.
The molecular weight measured by GPC was 61,000 in terms of polystyrene. The value of _MH / ( _MH + _MP ) was 0.

<Synthesis example A3>
Except that the addition amount of 4-iodomethylstyrene was 1.0 g and the addition amount of sodium t-butoxy was 0.3 g, it was shown as a specific example of the first charge transporting resin in the same manner as in Synthesis Example A2. 9.9 g of resin (A-3), which is the resin of number (A-3), was obtained.
The molecular weight measured by GPC was 60000 in terms of polystyrene. The value of the _{M H / (M H + M} P) was 0.95.

<Synthesis example A4>
Except that the addition amount of 4-iodomethylstyrene was 1.8 g and the addition amount of sodium t-butoxy was 0.5 g, it was shown as a specific example of the first charge transporting resin in the same manner as in Synthesis Example A2. 9.9 g of resin (A-4), which is the resin of number (A-4), was obtained.
The molecular weight measured by GPC was 60000 in terms of polystyrene. The value of the _{M H / (M H + M} P) was 0.85.

<Synthesis example A5>
Except that the added amount of 4-iodomethylstyrene was 9.0 g and the added amount of sodium t-butoxy was 2.9 g, it was shown as a specific example of the first charge transporting resin in the same manner as in Synthesis Example A2. 9.9 g of resin (A-5), which is the resin of number (A-5), was obtained.
The molecular weight measured by GPC was 60000 in terms of polystyrene. The value of the _{M H / (M H + M} P) was 0.45.

<Synthesis example A6>
As compounds 3-17, wherein is represented by the general formula (3A), and the combination of ^{A 1} and ^{T 1} and p has prepared compound is a preceding example number (2-17).
A 500 ml flask was charged with 60 g of compound 3-17, 200 g of epichlorohydrin, 17.6 g of sodium hydroxide, and 2 g of triethylamine, and the mixture was purged with nitrogen, followed by stirring at room temperature (25 ° C.) for 24 hours. After the reaction, the resultant was washed with a dilute hydrochloric acid aqueous solution and then with water. After concentration, the residue was purified by silica gel chromatography to obtain 74.5 g of compound 4-17.
The compound 4-17, wherein is represented by the general formula (4A), and the combination of ^{A 2} and ^{T 2} and q is a preceding example number (2-17).

In a 1000 ml flask, 39.4 g of compound 3-17, 700 ml of tetrahydrofuran, and 1.0 g of boron trifluoride diethyl ether complex were placed, and the mixture was purged with nitrogen and heated to 50 ° C. To this solution, a solution of 45.2 g of compound 4-17 dissolved in 200 ml of tetrahydrofuran was added dropwise over 30 minutes. After completion of the dropping, the mixture was reacted for 2 hours, and then dropped into 10 L of methanol to precipitate a polymer. The obtained polymer was sufficiently washed with methanol and dried to obtain 75.0 g of a resin (A-6) which is a resin of the number (A-6) shown as a specific example of the first charge transporting resin. Was.
The molecular weight measured by GPC was 40,000 in terms of polystyrene. The value of _MH / ( _MH + _MP ) was 1.0.

<Synthesis example A7>
A 200 ml flask was charged with 8.0 g of the resin (A-6) obtained in Synthesis Example A6, 100 ml of tetrahydrofuran, 52.0 g of methacrylic acid chloride, and 50.0 of triethylamine, and reacted at room temperature (25 ° C.) for 24 hours. did. After completion of the reaction, the polymer was dropped into 1 L of methanol to precipitate the polymer. The obtained polymer was sufficiently washed with methanol and dried to obtain 7.1 g of a resin (A-7) which is a resin of the number (A-7) shown as a specific example of the first charge transporting resin. Was.
The molecular weight measured by GPC was 41,000 in terms of polystyrene. The value of _MH / ( _MH + _MP ) was 0.

<Synthesis example A8>
A 500 ml flask was charged with 8.0 g of the resin (A-6) obtained in Synthesis Example A6, 100 ml of tetrahydrofuran, 1.0 g of methacrylic acid chloride, and 1.0 of triethylamine, and reacted at room temperature (25 ° C.) for 24 hours. did. After completion of the reaction, the polymer was dropped into 1 L of methanol to precipitate the polymer. The obtained polymer was sufficiently washed with methanol and dried to obtain 7.4 g of a resin (A-8) which is a resin of the number (A-8) shown as a specific example of the first charge transporting resin. Was.
The molecular weight measured by GPC was 40,000 in terms of polystyrene. The value of the _{M H / (M H + M} P) was 0.95.

<Synthesis Example A9 to Synthesis Example A31>
Resins (A-9) to (A-31), which are resins of numbers (A-9) to (A-31) shown as specific examples of the first charge transporting resin, in the same manner as in Synthesis Examples A1 to A8. ) Got.

<Synthesis example A32>
A 200 ml flask was charged with 8.0 g of the resin (A-9) obtained in Synthesis Example A9, 100 ml of tetrahydrofuran, 50 g of epichlorohydrin, 4.4 g of sodium hydroxide, and 2.5 g of triethylamine. Stirred at 40 ° C. for 48 hours. After completion of the reaction, the polymer was dropped into 1 L of methanol to precipitate the polymer. The obtained polymer was sufficiently washed with methanol and dried to obtain 7.8 g of a resin (A-32) which is a resin of the number (A-32) shown as a specific example of the first charge transporting resin. Was.
The molecular weight measured by GPC was 31,000 in terms of polystyrene. The value of the _{M H / (M H + M} P) was 0.45.

<Synthesis example A33>
The same number as the synthesis example A32 (A- 7.9 g of resin (A-33) which is the resin of 33) was obtained.
The molecular weight measured by GPC was 31,000 in terms of polystyrene. The value of _MH / ( _MH + _MP ) was 0.

<Synthesis example A34>
A resin of the number (A-34) shown as a specific example of the first charge transporting resin in the same manner as in Synthesis Example A33 except that epichlorohydrin was changed to 3- (chloromethyl) -3-methyloxetane (A-34) was obtained.
The molecular weight measured by GPC was 31,000 in terms of polystyrene. The value of _MH / ( _MH + _MP ) was 0.

<Synthesis example B1>
As Compound A-4, is represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-4, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-4).
Further, as the compound B-2, is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , and combinations ^{Y 4)} is a combination of specific example Y-2, ^{Z 2} A non-charge-transporting diol monomer (product name: Blemmer GLM, manufactured by NOF Corporation) in which the group represented by is a hydroxyl group was prepared.
In a flask, 8.35 g (0.02 mol) of compound A-4 (molecular weight 417.5), 3.20 g (0.02 mol) of compound B-2 (molecular weight 160.17), and 4-dimethylaminopyridine (molecular weight 122. 17) 2.44 g (0.02 mol) and 50 ml of tetrahydrofuran were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. To this, 6.83 g (0.044 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 4 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum dried to obtain 7.85 g of Resin B-1 (Resin B-1 shown as a specific example of the second charge transporting polyester resin). When the molecular weight of the resin B-1 was measured by GPC, the weight average molecular weight in terms of polystyrene was 28,000.

<Synthesis example B2>
As Compound A-4, is represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-4, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-4).
The compound B-43 is represented by the general formula (4B), and the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is a combination of the specific examples Y-43, and Z ² A non-charge-transporting diol monomer (product name: epoxy ester 40EM, manufactured by Kyoeisha Chemical Co., Ltd.) in which the group represented by is a hydroxyl group was prepared.
8.35 g (0.02 mol) of compound A-4 (molecular weight 417.5), 7.77 g (0.02 mol) of compound B-43 (molecular weight 388.45) and 4-dimethylaminopyridine (molecular weight 122. 17) 2.44 g (0.02 mol) and 50 ml of tetrahydrofuran were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. To this, 6.83 g (0.044 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 4 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 200 ml of methanol. The solid collected by filtration was vacuum dried to obtain 11.17 g of a resin B-2 (resin B-2 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-2 was measured by GPC, the weight average molecular weight in terms of polystyrene was 27000.

<Synthesis example B3>
As Compound A-6, is represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-6, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-6).
Further, as the compound B-2, is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , and combinations ^{Y 4)} is a combination of specific example Y-2, ^{Z 2} A non-charge-transporting diol monomer (product name: Blemmer GLM, manufactured by NOF Corporation) in which the group represented by is a hydroxyl group was prepared.
In a flask, 5.00 g (0.0107 mol) of compound A-6 (molecular weight 465.54), 1.89 g (0.0118 mol) of compound B-2 (molecular weight 160.17), and 4-dimethylaminopyridine (molecular weight 122.54). 17) 2.69 g (0.0220 mol) and 25 ml of tetrahydrofuran were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. Thereto, 3.67 g (0.024 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 4 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 5.85 g of Resin B-3 (Resin B-3 shown as a specific example of the second charge transporting polyester resin). When the molecular weight of the resin B-3 was measured by GPC, the weight average molecular weight in terms of polystyrene was 22,000.

<Synthesis example B4>
In a 2 L flask, 120.15 g (1.0 mol) of 4-hydroxystyrene (molecular weight 120.15), 93.88 g (1.03 mol) of tetramethylammonium hydroxide (molecular weight 91.15), nitrobenzene (molecular weight 123.06) 1.23 g (0.01 mol) and 700 ml of N-methylpyrrolidone were added, and the mixture was stirred at 80 ° C for 1 hour. After the temperature was once returned to room temperature (25 ° C.), 110.54 g (1.0 mol) of 3-chloro-1,2-propanediol (molecular weight 110.54) was added, and the mixture was reacted at 80 ° C. for 5 hours. Was. After the reaction, toluene was added and the mixture was washed with water, concentrated, and purified by silica gel chromatography to obtain 147.61 g of a compound B-3 (molecular weight: 194.23).
The above compound B-3 is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , a combination of and ^{Y 4)} is a combination of embodiment Y-3, with ^{Z 2} A non-charge-transporting diol monomer in which the group shown is a hydroxyl group.

As Compound A-6, is represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-6, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-6).
In a flask, 5.00 g (0.0107 mol) of compound A-6 (molecular weight 465.54), 2.29 g (0.0118 mol) of compound B-3 (molecular weight 194.23), and 4-dimethylaminopyridine (molecular weight 122.54) were added. 17) 2.69 g (0.0220 mol) and 25 ml of tetrahydrofuran were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. Thereto, 3.67 g (0.024 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 4 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 6.31 g of resin B-4 (resin B-4 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-4 was measured by GPC, the weight average molecular weight in terms of polystyrene was 26,000.

<Synthesis example B5>
As Compound A-18, represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-18, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-18).
Further, as the compound B-2, is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , and combinations ^{Y 4)} is a combination of specific example Y-2, ^{Z 2} A non-charge-transporting diol monomer (product name: Blemmer GLM, manufactured by NOF Corporation) in which the group represented by is a hydroxyl group was prepared.
In a flask, 6.65 g (0.0085 mol) of compound A-18 (molecular weight 784.94), 1.43 g (0.0089 mol) of compound B-2 (molecular weight 160.17), 4-dimethylaminopyridine (molecular weight 122. 17) 2.12 g (0.0174 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C while stirring under a nitrogen stream. Thereto, 2.89 g (0.0186 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C.). Stir for 7 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 5.37 g of Resin B-11 (Resin B-11 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-11 was measured by GPC, the weight average molecular weight in terms of polystyrene was 12,000.

<Synthesis Example B6>
In a 2 L flask, 74.08 g (1.0 mol) of glycidol (molecular weight 74.08), 148.16 g (1.0 mol) of 4-vinylbenzoic acid (molecular weight 148.16), tetrabutylammonium chloride (molecular weight 277.92) 27.79 g (0.1 mol), 1.23 g (0.01 mol) of nitrobenzene (molecular weight 123.06) and 700 ml of methyl ethyl ketone were added, and the mixture was heated and refluxed for 7 hours under a nitrogen stream. After the reaction, the mixture was washed with water, concentrated and purified by silica gel chromatography to obtain 184.46 g of a compound B-5 (molecular weight: 222.24).
The compound B-5 is represented by the general formula (4B), wherein the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is a combination of the specific examples Y-5, and Z ² is A non-charge-transporting diol monomer in which the group shown is a hydroxyl group.

As Compound A-18, represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-18, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-18).
In a flask, 6.65 g (0.0085 mol) of compound A-18 (molecular weight 784.94), 1.98 g (0.0089 mol) of compound B-5 (molecular weight 222.24), and 4-dimethylaminopyridine (molecular weight 122.94). 17) 2.12 g (0.0174 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C while stirring under a nitrogen stream. Thereto, 2.89 g (0.0186 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C.). Stir for 7 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 6.39 g of Resin B-13 (Resin B-13 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-13 was measured by GPC, the weight average molecular weight in terms of polystyrene was 16,000.

<Synthesis example B7>
As Compound A-43, represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-43, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-43).
Further, as the compound B-2, is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , and combinations ^{Y 4)} is a combination of specific example Y-2, ^{Z 2} A non-charge-transporting diol monomer (product name: Blemmer GLM, manufactured by NOF Corporation) in which the group represented by is a hydroxyl group was prepared.
In a flask, 7.75 g (0.009 mol) of compound A-43 (molecular weight 861.03), 1.59 g (0.0099 mol) of compound B-2 (molecular weight 160.17), and 4-dimethylaminopyridine (molecular weight 122. 17) 2.25 g (0.0184 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C while stirring under a nitrogen stream. Thereto, 3.07 g (0.0198 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 7 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 7.23 g of resin B-20 (resin B-20 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-20 was measured by GPC, the weight average molecular weight in terms of polystyrene was 14,000.

<Synthesis example B8>
In a 2 L flask, 116.16 g (1.0 mol) of 3-ethyl-3-oxetanemethanol (molecular weight 116.16), 86.06 g (1.0 mol) of methacrylic acid (molecular weight 86.06), tetrabutylammonium chloride (molecular weight) 27.92 g (0.1 mol), 1.23 g (0.01 mol) of nitrobenzene (molecular weight 123.06), and 700 ml of methyl ethyl ketone were added, and the mixture was heated and refluxed for 7 hours under a nitrogen stream. After the reaction, the mixture was washed with water, concentrated, and purified by silica gel chromatography to obtain 143.55 g of a compound B-23 (molecular weight: 214.26).
The compound B-23 is represented by the general formula (4B), and the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is a combination of the specific examples Y-23, and Z ² is A non-charge-transporting diol monomer in which the group shown is a hydroxyl group.

As Compound A-43, represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-43, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-43).
7.75 g (0.009 mol) of compound A-43 (molecular weight 861.03), 2.12 g (0.0099 mol) of compound B-23 (molecular weight 214.26), and 4-dimethylaminopyridine (molecular weight 122. 17) 2.25 g (0.0184 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. Thereto, 3.07 g (0.0198 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 7 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was dried under vacuum to obtain 7.02 g of resin B-21 (resin B-21 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-21 was measured by GPC, the weight average molecular weight in terms of polystyrene was 16,000.

<Synthesis example B9>
In a 2 L flask, 114.14 g (1.0 mol) of 1,5-hexadiene diepoxide (molecular weight 114.14), 172.12 g (2.0 mol) of methacrylic acid (molecular weight 86.06), tetrabutylammonium chloride (molecular weight 277) .92), 27.79 g (0.1 mol), 1.23 g (0.01 mol) of nitrobenzene (molecular weight 123.06) and 700 ml of methyl ethyl ketone were added, and the mixture was heated and refluxed for 7 hours under a nitrogen stream. After the reaction, the mixture was washed with water, concentrated, and purified by silica gel chromatography to obtain 198.05 g of a compound B-30 (molecular weight: 314.37).
The compound B-30 is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , a combination of and ^{Y 4)} is a combination of specific example Y-30, with ^{Z 2} A non-charge-transporting diol monomer in which the group shown is a hydroxyl group.

As Compound A-43, represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-43, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-43).
7.75 g (0.009 mol) of compound A-43 (molecular weight 861.03), 3.11 g (0.0099 mol) of compound B-30 (molecular weight 314.37) obtained in the above Synthesis Example, 2.25 g (0.0184 mol) of dimethylaminopyridine (molecular weight 122.17), 50 ml of tetrahydrofuran, and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C while stirring under a nitrogen stream. Thereto, 3.07 g (0.0198 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 7 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 7.46 g of resin B-24 (resin B-24 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-24 was measured by GPC, the weight average molecular weight in terms of polystyrene was 14,000.

<Synthesis example B10>
As Compound A-47, represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-47, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-47).
The compound B-41 is represented by the general formula (4B), and the combination Y (that is, the combination of OY ³ —O, n3, and Y ⁴ ) is a combination of the specific examples Y-41, and Z ² A non-charge-transporting diol monomer (product name: epoxy ester 70PA, manufactured by Kyoeisha Chemical Co., Ltd.) in which the group represented by is a hydroxyl group was prepared.
In a flask, 6.88 g (0.009 mol) of compound A-47 (molecular weight 764.95), 3.57 g (0.0099 mol) of compound B-41 (molecular weight 360.40), and 4-dimethylaminopyridine (molecular weight 122. 17) 2.25 g (0.0184 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C while stirring under a nitrogen stream. Thereto, 3.07 g (0.0198 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stirred for 10 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 200 ml of methanol. The solid collected by filtration was vacuum dried to obtain 8.65 g of a resin B-26 (resin B-26 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-26 was measured by GPC, the weight average molecular weight in terms of polystyrene was 14,000.

<Synthesis example B11>
In a 2 L flask, 142.20 g (1.0 mol) of 1,7-octadiene diepoxide (molecular weight 142.20), 288.26 g (2.0 mol) of β-carboxyethyl acrylate (molecular weight 144.13), tetrabutylammonium 27.79 g (0.1 mol) of chloride (molecular weight 277.92), 1.23 g (0.01 mol) of nitrobenzene (molecular weight 123.06), and 700 ml of methyl ethyl ketone were added, and the mixture was heated and refluxed for 7 hours under a nitrogen stream. After the reaction, the mixture was washed with water, concentrated, and purified by silica gel chromatography to obtain 361.59 g of a compound B-39 (molecular weight: 430.45).
The compound B-39 is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , and combinations ^{Y 4)} is a combination of specific example Y-39, with ^{Z 2} A non-charge-transporting diol monomer in which the group shown is a hydroxyl group.

The compound A-64 is represented by the general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is a combination of the specific examples AT-64, and the group represented by Z ¹ is a hydroxyl group (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-64).
In a flask, 7.32 g (0.009 mol) of compound A-64 (molecular weight 812.99), 4.26 g (0.0099 mol) of compound B-39 (molecular weight 430.45), and 4-dimethylaminopyridine (molecular weight 122. 17) 2.25 g (0.0184 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. Thereto, 3.07 g (0.0198 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 14 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 200 ml of methanol. The solid collected by filtration was vacuum dried to obtain 8.65 g of Resin B-28 (Resin B-28 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-28 was measured by GPC, the weight average molecular weight in terms of polystyrene was 29000.

<Synthesis example B12>
In a 2 L flask, 23,28 g (0.5 mol) of 9,9-bis (4-glycidyloxyphenyl) fluorene (molecular weight 462.55), 86.06 g (1.0 mol) of methacrylic acid (molecular weight 86.06), 13.90 g (0.05 mol) of butylammonium chloride (molecular weight 277.92), 0.62 g (0.005 mol) of nitrobenzene (molecular weight 123.06), and 700 ml of methyl ethyl ketone were added, and the mixture was heated and refluxed for 7 hours under a nitrogen stream. . After the reaction, the reaction solution was washed with water, concentrated, and purified by silica gel chromatography to obtain 246.63 g of a compound B-60 (molecular weight: 758.85).
The compound B-60 is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , and combinations ^{Y 4)} is a combination of specific example Y-60, with ^{Z 2} A non-charge-transporting diol monomer in which the group shown is a hydroxyl group.

The compound A-64 is represented by the general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is a combination of the specific examples AT-64, and the group represented by Z ¹ is a hydroxyl group (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-64).
In a flask, 7.32 g (0.009 mol) of compound A-64 (molecular weight 812.99), 7.51 g (0.0099 mol) of compound B-60 (molecular weight 758.85), and 4-dimethylaminopyridine (molecular weight 122.99). 17) 2.25 g (0.0184 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. Thereto, 3.07 g (0.0198 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 14 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 200 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 11.34 g of a resin B-29 (resin B-29 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-29 was measured by GPC, the weight average molecular weight in terms of polystyrene was 32,000.

<Synthesis example B13>
As Compound A-67, represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-67, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-67).
Further, as the compound B-54, is represented by the general formula (4B), the combination Y ^{(i.e., O-Y 3 -O, n3} , and combinations ^{Y 4)} a combination of specific example Y-54, ^{Z 2} A non-charge-transporting diol monomer (product name: epoxy ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.) in which the group represented by is a hydroxyl group was prepared.
In a flask, 6.45 g (0.009 mol) of compound A-67 (molecular weight 716.91), 5.07 g (0.0099 mol) of compound B-54 (molecular weight 512.59), 4-dimethylaminopyridine (molecular weight 122. 17) 2.25 g (0.0184 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. Thereto, 3.07 g (0.0198 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 14 hours. Thereafter, the reaction solution was dropped into water to cause re-precipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 200 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 8.50 g of Resin B-30 (Resin B-30 shown as a specific example of the second charge transporting polyester resin). When the molecular weight of the resin B-30 was measured by GPC, the weight average molecular weight in terms of polystyrene was 26,000.

<Synthesis example B14>
In a 2 L flask, 116.12 g (1.0 mol) of 3-methyl-3-oxetanecarboxylic acid (molecular weight 116.12), 93.88 g (1.03 mol) of tetramethylammonium hydroxide (molecular weight 91.15), and N -Methylpyrrolidone (700 ml) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, 110.54 g (1.0 mol) of 3-chloro-1,2-propanediol (molecular weight 110.54) was added and reacted at 80 ° C. for 5 hours. After the reaction, toluene was added, the mixture was washed with water, concentrated, and purified by silica gel chromatography to obtain 150.25 g of a compound B-61 (molecular weight: 190.19).
The compound B-61 is represented by the general formula (4B), and the combination Y (that is, the combination of O—Y3—O, n3, and Y4) is a combination of the specific examples Y-61, and the group represented by Z2 Is a non-charge transporting diol monomer having a hydroxyl group.

As Compound A-6, is represented by the general formula (3B), and the combination AT (i.e., the combination of ^{A 3} and ^{T 3)} is a combination of specific example AT-6, hydroxyl groups represented by ^{Z 1} (I.e., a dicarboxylic acid monomer corresponding to the specific example AT-6).

  In a flask, 5.00 g (0.0107 mol) of compound A-6 (molecular weight 465.54), 2.24 g (0.0118 mol) of compound B-61 (molecular weight 190.19), and 4-dimethylaminopyridine (molecular weight 122. 17) 2.69 g (0.0220 mol) and 25 ml of tetrahydrofuran were added, and the mixture was cooled to 0 ° C. while stirring under a nitrogen stream. Thereto, 3.67 g (0.024 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C). Stir for 4 hours. Thereafter, the reaction solution was dropped into water to cause reprecipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 6.28 g of Resin B-31 (Resin B-31 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of the resin B-31 was measured by GPC, the weight average molecular weight in terms of polystyrene was 25,000.

<Synthesis example B15>
In a 2 L flask, 88.06 g (1.0 mol) of oxirane-2-carboxylic acid (molecular weight 88.06), 93.88 g (1.03 mol) of tetramethylammonium hydroxide (molecular weight 91.15), and N-methylpyrrolidone 700 ml was added and the mixture was stirred at room temperature for 1 hour. Thereafter, 110.54 g (1.0 mol) of 3-chloro-1,2-propanediol (molecular weight 110.54) was added and reacted at 80 ° C. for 5 hours. After the reaction, toluene was added, the mixture was washed with water, concentrated, and purified by silica gel chromatography to obtain 110.26 g of a compound B-62 (molecular weight: 162.14).
The compound B-62 is represented by a general formula (4B), wherein the combination Y (that is, the combination of O—Y3—O, n3, and Y4) is a combination of the specific examples Y-62, and the group represented by Z2 Is a non-charge transporting diol monomer having a hydroxyl group.

  The compound A-18 is represented by the general formula (3B), the combination AT (that is, the combination of A3 and T3) is a combination of the specific examples AT-18, and the group represented by Z1 is a hydroxyl group. A transportable monomer (that is, a dicarboxylic acid monomer corresponding to the specific example AT-18) was prepared.

  In a flask, 6.65 g (0.0085 mol) of compound A-18 (molecular weight 784.94), 1.44 g (0.0089 mol) of compound B-62 (molecular weight 162.14), and 4-dimethylaminopyridine (molecular weight 122.14). 17) 2.12 g (0.0174 mol), 50 ml of tetrahydrofuran and 15 ml of N-methylpyrrolidone were added, and the mixture was cooled to 0 ° C while stirring under a nitrogen stream. Thereto, 2.89 g (0.0186 mol) of 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (molecular weight 155.24) was added, and the reaction temperature was gradually returned to room temperature (25 ° C.). Stir for 7 hours. Thereafter, the reaction solution was dropped into water to cause reprecipitation, and neutralized by further adding dilute hydrochloric acid. The solid collected by filtration was washed by stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 6.63 g of Resin B-32 (Resin B-32 shown as a specific example of the second charge transporting polyester resin). When the molecular weight of the resin B-32 was measured by GPC, the weight average molecular weight in terms of polystyrene was 15,000.

<Example A1-1>
-Preparation of undercoat layer-
100 parts of zinc oxide (average particle diameter: 70 nm, manufactured by Teica: specific surface area: 15 m ² / g) is stirred and mixed with 500 parts of tetrahydrofuran, and 1.3 parts of a silane coupling agent (KBM503: manufactured by Shin-Etsu Chemical Co., Ltd.) is added. And stirred for 2 hours. Thereafter, the toluene was distilled off under reduced pressure and baked at 120 ° C. for 3 hours to obtain a silane coupling agent surface-treated zinc oxide.
110 parts of the surface-treated zinc oxide was mixed with 500 parts of tetrahydrofuran with stirring, a solution of 1.0 part of alizarin dissolved in 50 parts of tetrahydrofuran was added, and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the zinc oxide to which alizarin had been applied was filtered off under reduced pressure, and further dried at 60 ° C. under reduced pressure to obtain alizarin-added zinc oxide.

85 parts of methyl ethyl ketone was obtained by mixing 60 parts of this alizarin-added zinc oxide, 13.5 parts of a curing agent (blocked isocyanate, Sumidur 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) and 15 parts of a butyral resin (Eslec BM-1, manufactured by Sekisui Chemical Co., Ltd.). Was mixed with 25 parts of methyl ethyl ketone and dispersed in a sand mill using 1 mmφ glass beads for 2 hours to obtain a dispersion.
0.005 parts of dioctyltin dilaurate as a catalyst and 45 parts of silicone resin particles (Tospearl 145, manufactured by Momentive Performance Materials) were added to the resulting dispersion to obtain a coating liquid for an undercoat layer. This coating solution was applied on an aluminum substrate having a diameter of 30 mm, a length of 340 mm and a thickness of 1 mm by a dip coating method, and dried and cured at 170 ° C. for 40 minutes to obtain an undercoat layer having a thickness of 18 μm.

-Preparation of charge generation layer-
Positions where the Bragg angles (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα characteristic X-rays as the charge generating substance are at least 7.3 °, 16.0 °, 24.9 °, 28.0 ° A mixture of 15 parts of hydroxygallium phthalocyanine having a diffraction peak, 10 parts of a vinyl chloride / vinyl acetate copolymer resin (VMCH, manufactured by NUC Co., Ltd.) as a binder resin, and 200 parts of n-butyl acetate was used. The mixture was dispersed in a sand mill using glass beads for 4 hours. 175 parts of n-butyl acetate and 180 parts of methyl ethyl ketone were added to the obtained dispersion and stirred to obtain a charge generating layer coating liquid. This coating solution for a charge generation layer was applied onto the undercoat layer by dip coating, and dried at normal temperature (20 ° C.) to form a charge generation layer having a thickness of 0.2 μm.

-Preparation of charge transport layer-
10 parts of the resin (A-2) obtained in Synthesis Example A2 and 0.2 part of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight 354.4) were added to 40 parts of chlorobenzene and dissolved, and the coating solution for the charge transport layer was dissolved. I got This coating solution was applied on the charge generation layer by push-up coating, air-dried at room temperature (20 ° C.) for 30 minutes, and then heated from room temperature (20 ° C.) at a rate of 10 ° C./min. The mixture was heated to 150 ° C., cured by heating at 150 ° C. for 1 hour, and a charge transport layer having a thickness of 18 μm was formed to produce an electrophotographic photosensitive member of Example A1-1.

-Evaluation of image quality-
The electrophotographic photoreceptor produced as described above was mounted on ApeosPort-IV C4470 manufactured by Fuji Xerox Co., Ltd., and was subjected to low temperature and low humidity (8 ° C., 20% RH) and high temperature and high humidity (30 ° C., 85% RH), respectively. The following evaluation was continuously performed.

First, an image formation test was performed on 10,000 sheets in a low-temperature and low-humidity (8 ° C., 20% RH) environment, and the image quality evaluation of the 10,000th sheet (that is, ghost, fog, streak, and image deletion described below) was performed. Next, the image quality of the first sheet after left for 24 hours in a low temperature and low humidity (8 ° C., 20% RH) environment was further evaluated.
Table 2 shows the results.

Subsequent to the image quality evaluation under the low-temperature and low-humidity environment, an image forming test was performed on 10,000 sheets in an environment of high temperature and high humidity (30 ° C., 85% RH), and the image quality of the 10,000th sheet was evaluated. Next, the image quality of the first image after left for 24 hours in a high temperature and high humidity (30 ° C., 85% RH) environment was further evaluated.
Table 3 shows the results.

(Ghost evaluation)
The ghost printed a chart of G and a pattern having a gray area with an image density of 50% shown in FIG. 6A, and visually evaluated the appearance of the letter G in the 50% gray area.
A: Good or slight as shown in FIG.
B: Somewhat noticeable as shown in FIG.
C: It is clearly confirmed as shown in FIG.

(Fog evaluation)
The fog evaluation was performed by visually observing the degree of adhesion of the toner on the white background using the same sample as the above-mentioned ghost evaluation.
A: Good.
B: There is slight fog.
C: There is fog which is a problem in image quality.

(Streak evaluation)
The streak evaluation was visually determined using the same sample as the ghost evaluation described above.
A: Good.
B: Streaks are partially generated.
C: Streak which causes a problem in image quality.

(Image deletion evaluation)
The image deletion was visually determined using the same sample as the ghost evaluation described above.
A: Good.
B: No problem during continuous print test, but occurred after standing for one day (24 hours).
C: Also occurs during a continuous print test.

−Evaluation of rise in residual potential−
The residual potential was measured by the following method, and the increase in the residual potential before and after the image forming test was evaluated. Specifically, a potential sensor was attached to a modified ApeosPort-IV C4470 manufactured by Fuji Xerox Co., and the potential (initial potential) before the image formation test was measured under low temperature and low humidity (8 ° C., 20% RH). . Then, after performing a print test of 10,000 sheets under low temperature and low humidity (8 ° C., 20% RH), the residual potential (1) on the surface of the electrophotographic photoreceptor was similarly similarly low temperature and low humidity (8 ° C., 20% RH). (Residual potential after 10,000 sheets) was measured. The difference between the initial potential and the residual potential after 10,000 copies (the residual potential after 10,000 copies minus the initial potential) was defined as “the rise in the residual potential”. Table 2 shows the results.

-Evaluation of the amount of wear of the charge transport layer-
The initial photoreceptor film thickness before performing the image forming test (that is, the total film thickness of the undercoat layer, the charge generation layer, and the charge transport layer) and the low temperature and low humidity (8 ° C., 20% RH) environment and The photoreceptor film thickness after completion of the image formation test in a high temperature and high humidity (30 ° C., 85% RH) environment was measured with an eddy current measuring device (Fisher scope MMS) to evaluate the amount of abrasion. Table 2 shows the results.

<Examples A1-2 to A1-7>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
Then, in the preparation of the charge transport layer, an electrophotographic photoreceptor was prepared in the same manner as in Example A1-1, except that the first charge transport resin shown in Table 1 was used instead of the resin (A-2). Fabricated and evaluated. The evaluation results are shown in Tables 2 and 3.

<Example A1-8>
Example A1 except that the resin (A-2) was replaced with the resin (A-1) and 0.2 parts of OTazo-15 (manufactured by Otsuka Chemical Co., molecular weight 354.4) was not added in the preparation of the charge transport layer. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example-1. The evaluation results are shown in Tables 2 and 3.

<Examples A1-9 to A1-10>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
Then, in the preparation of the charge transport layer, the first charge transport resin shown in Table 1 was used in place of the resin (A-2), and 0.2 parts of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight 354.4) was used. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example A1-1, except that 0.05 parts of boron trifluoride diethyl ether complex was used in place of the above. The evaluation results are shown in Tables 2 and 3.

<Example A1-11>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
Then, 10 parts of the resin (A-4) obtained in Synthesis Example A4, 2 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, 0.2 part (manufactured by BASF) was dissolved in 40 parts of monochlorobenzene, and the obtained solution was applied on the charge transport layer by push-up coating. After air-drying at room temperature (20 ° C.) for 30 minutes, light irradiation was performed under nitrogen with a 200 ppm oxygen concentration under the conditions of a metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , irradiation time: 60 seconds. Then, the coating film was cured. Further, drying was performed at 130 ° C. for 20 minutes to form a surface layer having a film thickness of 17 μm to produce an electrophotographic photosensitive member, which was evaluated by the method described in Example A1-1. The evaluation results are shown in Tables 2 and 3.

<Example A1-12>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
Then, 10 parts of the resin (A-7) obtained in Synthesis Example A7, 2 parts of the compound represented by the following structural formula (G), and 0.2 parts of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight 354.4) were added. The solution was dissolved in 40 parts of monochlorobenzene, and the obtained solution was applied on the charge transport layer by push-up coating. After air-drying at room temperature (20 ° C.) for 30 minutes, the temperature was raised from room temperature (20 ° C.) to 150 ° C. at a rate of 10 ° C./min under nitrogen with an oxygen concentration of 200 ppm, and heat-treated at 150 ° C. for 1 hour to cure. A charge transport layer having a thickness of 18 μm was formed to produce an electrophotographic photoreceptor, which was evaluated by the method described in Example A1-1. The evaluation results are shown in Tables 2 and 3.

<Example A1-13>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
Next, 10 parts of the resin (A-2) obtained in Synthesis Example A2 and 0.8 parts of polytetrafluoroethylene fine particles (Rublon L-2, manufactured by Daikin Industries, Ltd.) were dissolved in 40 parts of monochlorobenzene, and the mixture was treated with a Nanomizer (NM2). -L200AR-D08, manufactured by Nanomizer Co., Ltd., and dissolved by adding 0.2 parts of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight: 354.4). Coated on transport layer. After air-drying at room temperature (20 ° C.) for 30 minutes, the temperature was raised from room temperature (20 ° C.) to 150 ° C. at a rate of 10 ° C./min under nitrogen having an oxygen concentration of 200 ppm, and heat-treated at 150 ° C. for 1 hour to cure. A charge transport layer having a thickness of 18 μm was formed to produce an electrophotographic photoreceptor, which was evaluated by the method described in Example A1-1. The evaluation results are shown in Tables 2 and 3.

<Example A1-14>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
On this charge generation layer, 40 parts by mass of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine (TPD), 10 parts by mass of N-bis (3,4-dimethylphenyl) biphenyl-4-amine and 55 parts by mass of bisphenol Z polycarbonate resin (PC (Z): viscosity average molecular weight: 60,000) are added to 800 parts by mass of chlorobenzene and dissolved. The applied coating solution was applied and dried at 130 ° C. for 45 minutes to form a charge transport layer having a thickness of 15 μm.

-Preparation of protective layer-
10 parts of the resin (A-10) obtained in Synthesis Example A10 and 3 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) were dissolved in 20 parts of monochlorobenzene and 40 parts of toluene. The dissolved solution was applied on the charge transport layer by a push-up coat. After air-drying at room temperature (20 ° C.) for 30 minutes, the irradiation distance is 30 mm, the electron beam acceleration voltage is 90 kV, the electron beam current is 2 mA, and the electron beam is rotated while rotating the photoconductor at a speed of 300 rpm under nitrogen having an oxygen concentration of 20 ppm. The photosensitive member was irradiated with an electron beam under the condition that the irradiation time was 1.0 second. Immediately after the irradiation, the film was heated to 150 ° C. under nitrogen having an oxygen concentration of 20 ppm and maintained for 10 minutes to complete the curing reaction, and a 4 μm-thick protective layer was formed to produce an electrophotographic photoreceptor. The evaluation was performed by the method described in -1. The evaluation results are shown in Tables 2 and 3.

<Examples B1-1 to B1-15>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
Then, in the preparation of the charge transport layer, an electrophotographic photoreceptor was prepared in the same manner as in Example A1-1, except that the second charge transport polyester resin shown in Table 1 was used instead of the resin (A-2). Was prepared and evaluated. The evaluation results are shown in Tables 2 and 3.

<Comparative Example 1-1>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
Then, in the preparation of the charge transporting layer, Example A1 was used except that Comparative resin 1 (poly (9-vinylcarbazole), manufactured by Sigma-Aldrich, number average molecular weight: 25,000) was used instead of resin (A-2). In the same manner as in Example 1, an electrophotographic photosensitive member was prepared and evaluated. The evaluation results are shown in Tables 2 and 3.

<Comparative Example 1-2>
Preparation of the charge generation layer was performed by the method described in Example A1-1.
Next, an electrophotographic photoreceptor was prepared in the same manner as in Example A1-1, except that the compound (H) having the following structural formula was used instead of the resin (A-2) in the preparation of the charge transport layer. evaluated. The evaluation results are shown in Tables 2 and 3.

<Comparative Example 1-3>
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example A1-14, except that the thickness of the charge generation layer was 25 μm and the protective layer was not formed in Example A1-14. The evaluation results are shown in Tables 2 and 3.

  From the results shown in Tables 2 and 3, it can be seen that in the electrophotographic photoreceptors of the examples, deterioration in image quality after repeated use over a long period was suppressed.

<Example A2-1>
-Preparation of organic EL device-
The glass substrate provided with the 150-nm-thick ITO film was cleaned with oxygen plasma for 30 seconds using a plasma cleaning machine (BP1 manufactured by Samco International). Further, after washing with a neutral detergent, water, acetone (for electronic industry, manufactured by Kanto Chemical) and isopropanol (for electronic industry, manufactured by Kanto Chemical) in this order, ultrasonic waves were applied for 5 minutes each, and then washed. It was dried with a spin coater.
A solution prepared by dissolving 3 parts by mass of the resin (A-2) and 0.06 parts by mass of OTazo-15 (Otsuka Chemical Co., molecular weight 354.4) in 97 parts by mass of dichloromethane was used as a PTFE filter having a pore size of 0.1 μm. To obtain a coating solution. The coating solution was spin-coated on the glass substrate. The number of rotations was adjusted so as to be a film thickness (400 nm) described later. By heating at 160 ° C. for 1 hour in an inert gas atmosphere having an oxygen concentration of 150 ppm, a hole transport layer having a thickness of 400 nm (measured with a stylus thickness meter) was formed.

  Next, on the hole transport layer, as a material for the light emitting layer, exemplary compound (VI-1): tris (8-hydroxyquinoline) aluminum (Alq) is vacuum-deposited to a thickness of 50 nm, and then magnesium / silver. An alloy cathode was evaporated to a thickness of 200 nm to produce an organic EL device.

-Performance evaluation of organic EL element-
Using an ITO electrode of the organic EL element as an anode and a magnesium / silver alloy electrode as a cathode, a current of 7 V was applied, and the current density was determined by the following method, and the luminance was measured by the following method. Further, the luminance after operation for 1000 hours was measured by the following method. Table 4 shows the results.
The current density, voltage, and luminance were measured using an organic EL luminous efficiency measuring device (manufactured by Tokyo Instruments) as a measuring device, and adjusting the measurement conditions to 25 ° C. In addition, when the organic EL element is used for a display or a laser, a high current injection is required. Therefore, the current density and the luminance were measured at an applied voltage of 7 V.

-Evaluation of visible light transmittance of charge transporting film-
After forming the hole transport layer and before depositing the light emitting layer, the visible light transmittance of the charge transporting film provided as the hole transport layer was evaluated. Specifically, the average transmittance (%) in the visible light region (380 nm to 780 nm) of the charge transporting film provided as the hole transporting layer was measured using a spectrophotometer (U-4100, Hitachi, Ltd.). Was evaluated according to the following criteria. Table 5 shows the results.
A: Average transmittance is 97% or more B: Average transmittance is 90% or more and less than 97% C: Average transmittance is less than 90%

The smoothness of the coating film during the formation of the charge transporting film was evaluated as follows. Specifically, after preparing the charge transporting film (hole transporting layer) of the present invention, the film is cut out with a cutter or the like, and the surface roughness Ra is measured using a surface shape measuring device DEKTAK6M (manufactured by ULVAC). Was evaluated according to the following criteria.
The measurement conditions were based on JIS B0601 (1994), and the measurement length was 4 mm, the measurement speed was 0.3 mm / sec, the cutoff wavelength was 0.8 mm, and the cutoff type was Gaussian. Table 5 shows the results.
A: Ra is less than 25 B: Ra is 25 or more and less than 45 C: Ra is 45 or more

(Evaluation of solvent resistance of charge transporting film)
After forming the hole transport layer and before depositing the light emitting layer, the charge transporting film provided as the hole transport layer was evaluated for solvent resistance. Specifically, ultraviolet-visible absorption measurement was performed on a 2.5 cm square film to be measured, and the absorbance (absorbance before standing still in toluene) at a wavelength (λmax) showing a maximum value on the long wavelength side was determined. Thereafter, the charge transporting film is placed on a pedestal of a spin coater, and 2 ml of toluene is placed on the film and allowed to stand for 30 seconds. Then, the film is spun at 200 rpm for 10 seconds and at 2,000 rpm for 20 seconds to remove the toluene, and the ultraviolet-visible light is again emitted. Absorption measurement was performed to determine the absorbance at λmax (absorbance after removing toluene).
The residual film ratio was calculated from the following equation, and the solvent resistance of the film was evaluated according to the following criteria. Table 5 shows the results.
Formula: Percentage of remaining film = (absorbance after removing toluene / absorbance before standing still in toluene) × 100 (%)
A: Remaining film ratio is 95% or more B: Remaining film ratio is 90% or more and less than 95% C: Remaining film ratio is less than 90%

<Example A2-2>
Example A2-1 was carried out in the same manner as in Example A2-1, except that the resin (A-2) was replaced with the resin (A-1), and OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight: 354.4) was not added in the preparation of the hole transport layer. Production and evaluation of the organic EL device were performed by the methods described. Further, the charge transporting film was evaluated by the method described in Example A2-1. The results are shown in Tables 4 and 5.

<Examples A2-3 to A2-10>
Preparation and evaluation of an organic EL device were performed by the method described in Example A2-1, except that the resin (A-2) in Example A2-1 was changed to the resin shown in Table 4. Further, the charge transporting film was evaluated by the method described in Example A2-1. The results are shown in Tables 4 and 5.

<Examples B2-1 to B2-10>
Preparation and evaluation of an organic EL device were performed by the method described in Example A2-1, except that the resin (A-2) in Example A2-1 was changed to the resin shown in Table 4. Further, the charge transporting film was evaluated by the method described in Example A2-1. The results are shown in Tables 4 and 5.

<Comparative Example 2-1>
The resin (A-1) in Example A2-2 was used as a comparative resin 2 (poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], manufactured by Sigma-Aldrich, number average molecular weight: 7000). Except for changing, the production and evaluation of the organic EL device were performed by the method described in Example A2-2. Further, the charge transporting film was evaluated by the method described in Example A2-2. The results are shown in Tables 4 and 5.

<Comparative Example 2-2>
Instead of the hole transport layer formed using the resin (A-2) in Example A2-1, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′ An organic EL device was prepared and evaluated by the method described in Example A2-1, except that a hole transport layer obtained by vacuum-depositing biphenyl-4,4'-diamine (TPD) with a thickness of 400 nm was applied. The results are shown in Tables 4 and 5.

From the results shown in Tables 4 and 5, it can be seen that the organic EL elements of the examples can obtain stable light-emitting characteristics over a long period of time.
Further, from the result of the solvent resistance of the charge transporting film, it can be seen that, in the case where a layer is formed in a coating form on the charge transporting film of the present invention in the future, it has an effect of suppressing mixing at the interface between both layers. . Therefore, it can be expected that the organic electroluminescent device of the coating and lamination type also shows good light emitting characteristics.

REFERENCE SIGNS LIST 1 undercoat layer, 2 charge generation layer, 3 charge transport layer, 4 conductive substrate, 5 protective layer, 6 single-layer type photosensitive layer, 7, 7A, 7B, 7C electrophotographic photoreceptor, 8 charging device, 9 exposure device , 11 developing device, 13 cleaning device, 14 lubricant, 21 transparent insulator substrate, 22 transparent electrode, 23 hole transport layer, 24 light emitting layer, 25 electron transport layer, 26 light emitting layer, 27 back electrode, 40 transfer device, Reference Signs List 50 intermediate transfer member, 100 image forming apparatus, 120 image forming apparatus, 131 cleaning blade, 132 fibrous member (roll), 133 fibrous member (flat brush), 300 process cartridge

Claims (16)

A first charge transporting resin having a structure represented by the following general formula (1A-1) and a structure represented by the following general formula (1A-2), a crosslinked product of the first charge transporting resin, Organic having a second charge-transporting polyester resin having a structure represented by the general formula (1B) and a charge-transporting film containing at least one selected from crosslinked products of the second charge-transporting polyester resin Electronic device.

(In the general formula (1A-1) and the general formula (1A-2), A ¹ and A ² each independently represent a divalent organic group having a charge transporting property, and T ¹ and T ² each independently represent Represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, and Y ¹ and Y ² each independently represent a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group. And p and q each independently represent 0 or 1.)

(In the general formula (1B), A ³ represents a divalent organic group having a charge transporting property, and T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. , ^{Y 3} represents a (n3 + 2) -valent uncharged transporting diol residues, n3 represents 1 or 2, ^{Y 4} is _{"* - (CH 2) n4 -L} -Z " indicates, * is Y ³ represents a bonding position, n4 represents 1 or 2, L represents a divalent linking group or a single bond composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom. , Z represents a polymerizable functional group.) The polymerizable functional group includes a group represented by the following general formula (P1), a group represented by the following general formula (P2), a group represented by the following general formula (P3), and a group represented by the following general formula (P4). The organic electronic device according to claim 1, wherein the organic electronic device is at least one selected from a group represented by a group represented by the following general formula (P5) and a group represented by the following general formula (P5).

(In the general formulas (P1) to (P5), R ^{3 to} R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * indicates a bonding position.) The polymerizable functional group is at least selected from a group represented by the following formula (P1-1), a group represented by the following formula (P1-2), and a group represented by the following formula (P3-1). 3. The organic electronic device according to claim 2, wherein the number is one.

(In the formulas (P1-1), (P1-2), and (P3-1), * indicates a bonding position.) ^{A 3} in the general formula ^{(1A-1) A} 1 in the general formula (1A-2) in ^{A 2,} and the general formula (1B), a request indicating a divalent organic group having hole transportability The organic electronic device according to any one of claims 1 to 3. ^{A 1} in the general formula (1A-1), ^{A 3} in ^{A 2,} and the general formula (1B) in the general formula (1A-2) is a divalent organic represented by the following general formula (2) 5. The organic electronic device of claim 4, wherein the organic electronic device represents a group.

(In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent. Wherein k and m each independently represent 0 or 1.) ^{T 1} in the general formula (1A-1), ^{T 3} in the general formula (1A-2) in ^{T 2,} and the general formula (1B) is a linear or branched of 1 to 8 carbon atoms The organic electronic device according to any one of claims 1 to 5, which shows a divalent hydrocarbon group. The total number of hydroxyl groups contained in the entirety of the first charge-transporting resin and the second charge-transporting polyester resin is defined as _MH, and the total number of hydroxyl groups in the first charge-transporting resin and the second charge-transporting polyester resin is when the total number of the polymerizable functional groups contained in the entire set to M _P, organic electronic device according to any one of claims 1 to 6 which satisfies the following formula (A1).
Formula (A1): 0 ≦ _MH / ( _MH + _MP ) ≦ 0.9 Wherein _{M H} and the _{M P} is an organic electronic device of claim 7, satisfying the following formula (A2).
Formula (A2): 0 ≦ _MH / ( _MH + _MP ) ≦ 0.6 The organic electronic device according to any one of the general formula wherein the number of atoms other than hydrogen atoms of the atoms constituting the Y ³ in (1B) is 2 to 20 claim 1 to claim 8. The organic electron according to any one of claims 1 to 9, wherein the number of atoms other than hydrogen atoms among the atoms constituting L in Y ⁴ in the general formula (1B) is 1 or more and 10 or less. device. The number of atoms other than hydrogen atoms of the atoms constituting the ^{Y 3} in the general formula (1B), the number of the general formula wherein in ^{Y 4} in (1B) n4, ^{Y 4} in the general formula (1B) The organic electronic device according to any one of claims 1 to 10, wherein the total of the number of atoms other than hydrogen atoms among the atoms constituting the L is 25 or less.   The charge transporting film according to any one of claims 1 to 11, wherein the charge transporting film contains at least one selected from a crosslinked product of the first charge transportable resin and a crosslinked product of the second charge transportable polyester resin. 2. The organic electronic device according to claim 1.   The organic electronic device according to claim 1, wherein the organic electronic device is an electrophotographic photoreceptor.   The outermost surface layer of the electrophotographic photosensitive member has a charge transporting film containing at least one selected from a crosslinked product of the first charge transportable resin and a crosslinked product of the second charge transportable polyester resin. An organic electronic device according to claim 13.   The organic electronic device according to any one of claims 1 to 12, wherein the organic electronic device is an organic electroluminescent element. A first charge transporting resin having a structure represented by the following general formula (1A-1) and a structure represented by the following general formula (1A-2), a crosslinked product of the first charge transporting resin, A charge transporting film containing a second charge transporting polyester resin having a structure represented by the general formula (1B), and at least one selected from a crosslinked product of the second charge transporting polyester resin.

(In the general formula (1A-1) and the general formula (1A-2), A ¹ and A ² each independently represent a divalent organic group having a charge transporting property, and T ¹ and T ² each independently represent Represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, and Y ¹ and Y ² each independently represent a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group. And p and q each independently represent 0 or 1.)

(In the general formula (1B), A ³ represents a divalent organic group having a charge transporting property, and T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. , ^{Y 3} represents a (n3 + 2) -valent uncharged transporting diol residues, n3 represents 1 or 2, ^{Y 4} is _{"* - (CH 2) n4 -L} -Z " indicates, * is Y ³ represents a bonding position, n4 represents 1 or 2, L represents a divalent linking group or a single bond composed of at least one atom selected from a carbon atom, an oxygen atom, and a hydrogen atom. , Z represents a polymerizable functional group.)