JP7323026B2 - Organic electronic device and charge transport film - Google Patents

Description

The present invention relates to organic electronic devices and charge-transporting films.

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, it is effective to have a crosslinked structure. electrophotographic photoreceptors using an acrylic polymer (see, for example, Patent Documents 2 to 4), an electrophotographic photoreceptor in which an acrylic polymer containing a charge-transporting group and a reactive group is crosslinked after film formation (see, for example, Patent Document 5) ), a film obtained by coating and curing a liquid containing a photocurable acrylic monomer (see, for example, Patent Document 6). Alternatively, 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 is heated or light energy is applied to the carbon-carbon double bond of the monomer and the charge transfer material. Disclosed is a film formed by reacting a carbon-carbon double bond, in particular a monofunctional methacrylic-modified charge transfer material, a methacrylic monomer having no charge-transporting property, a polycarbonate resin, and an organic peroxide. A product cured using an oxide is disclosed (see, for example, Patent Document 7). Also disclosed is a charge-transporting polyester resin having a polymerizable functional group in the polymer main chain (see, for example, Patent Document 8).

Further, an organic semiconductor film and an electrophotographic photoreceptor (see, for example, Patent Document 9), etc., are disclosed which are composed of a cured film obtained by introducing a functional group to the end of a charge-transporting resin.
Furthermore, a charge-transporting polyester containing a polymerizable unsaturated bond in at least one of the main chain and terminal is disclosed (Patent Document 10).

WO 1997/033193 JP-A-5-202135 JP-A-6-256428 JP-A-9-12630 Japanese Unexamined Patent Application Publication No. 2005-2291 JP-A-5-40360 JP-A-5-216249 JP 2013-73015 A JP-A-2001-117252 JP-A-2000-264961

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

The above problems are solved by the following means. Namely
<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, An organic having a charge-transporting film containing at least one selected from a second charge-transporting polyester resin having a structure represented by the general formula (1B) and a crosslinked product 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 transport property, and T ¹ and T ² each independently 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; , p and q each independently represent 0 or 1.

In the general formula (1B), A ³ represents a divalent organic group having charge transport properties, T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ³ represents a (n3+2)-valent non-charge-transporting diol residue, n3 represents 1 or 2, Y ⁴ represents "*-(CH ₂ ) _n4 -LZ", and * represents 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 carbon atoms, oxygen atoms, and hydrogen atoms, 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 groups represented by the following general formula (P5) and groups represented by the following general formula (P5).

In general formulas (P1) to (P5), R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * represents 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 the binding position.
<4>
A ¹ in the general formula (1A-1), A ² in the general formula (1A-2), and A ³ in the general formula (1B) represent a divalent organic group having a hole-transporting ability< The organic electronic device according to any one of 1> to <3>.
<5>
A ¹ in the general formula (1A-1), A ² in the general formula (1A-2), and A ³ in the general formula (1B) are divalent organic compounds represented by the following general formula (2) The organic electronic device according to <4> showing 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 is a substituted or unsubstituted divalent represents an organic group, and k and m each independently represents 0 or 1;
<6>
T ¹ in the general formula (1A-1), T ² in the general formula (1A-2), and T ³ in the general formula (1B) are linear or branched having 1 to 8 carbon atoms. The organic electronic device according to any one of <1> to <5>, which exhibits a divalent hydrocarbon group.
<7>
Let _MH be the total number of hydroxyl groups contained in the first charge-transporting resin and the second charge-transporting polyester resin, and The organic electronic device according to any one of <1> to <6>, which satisfies the following formula (A1), where _MP is the total number of the polymerizable functional groups contained in the whole.
Formula (A1): 0≦M _H /(M _H +M _P )≦0.9
<8>
The organic electronic device according to <7>, wherein the _MH and the _MP satisfy the following formula (A2).
Formula (A2): 0≦M _H /(M _H +M _P )≦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 general formula (1B) is 1 or more and 10 or less. device.
<11>
The number of atoms other than hydrogen atoms among the atoms constituting Y ³ in the general formula (1B), the number of the n4 in Y ⁴ in the general formula (1B), and 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 L in the organic electronic device is 25 or less.
<12>
Any one of <1> to <11>, wherein the charge-transporting film contains at least one selected from a crosslinked body of the first charge-transporting resin and a crosslinked body of the second charge-transporting polyester resin. 1. An 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 photoreceptor.
<14>
The electrophotographic photoreceptor has, as the outermost layer, a charge-transporting film containing at least one selected from the crosslinked first charge-transporting resin and the crosslinked second charge-transporting 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 at least one selected from a second charge-transporting polyester resin having a structure represented by general formula (1B) and 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 transport property, and T ¹ and T ² each independently 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; , p and q each independently represent 0 or 1.

In the general formula (1B), A ³ represents a divalent organic group having charge transport properties, T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ³ represents a (n3+2)-valent non-charge-transporting diol residue, n3 represents 1 or 2, Y ⁴ represents "*-(CH ₂ ) _n4 -LZ", and * represents 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 carbon atoms, oxygen atoms, and hydrogen atoms, Z represents a polymerizable functional group.

According to the inventions <1>, <2>, <3>, <4>, <5>, <6>, <7>, <8>, <13>, or <15>, the charge transport property Provided is an organic electronic device having a charge-transporting film with lower visible light absorption than when only poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] is used as the resin.
According to the invention according to <9>, the charge-transporting film has a high charge-transporting property compared to the case where the number of atoms other than hydrogen atoms among the atoms constituting Y ³ in the general formula (1B) is more than 20. An organic electronic device is provided.
According to the invention according to <10>, charge transport with high charge transport property compared to 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 thin film is provided.
According to the invention according to <11>, the number of atoms other than hydrogen atoms among the atoms constituting Y ³ in general formula (1B), the number of n4 in Y ⁴ in general formula (1B), and the general formula Provided is an organic electronic device having a charge-transporting film with a high charge-transporting property compared to the case where the total number of atoms other than hydrogen atoms among the atoms constituting L in ^Y4 in (1B) is greater than 25. be done.
According to the invention according to <12>, the solvent resistance is higher than that in the case where the charge-transporting film contains neither the crosslinked first charge-transporting resin nor the crosslinked second charge-transporting polyester resin. Organic electronic devices having high charge transport films are provided.
According to the invention according to <14>, the outermost layer of the electrophotographic photoreceptor contains neither the crosslinked first charge-transporting resin nor the crosslinked second charge-transporting polyester resin. An organic electronic device is provided in which the mechanical strength of the outermost surface layer is higher than in the case of a film.
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 visible light absorbing charge is low. A transport membrane is provided.

1 is a schematic partial cross-sectional view showing an example of the layer structure of an electrophotographic photoreceptor according to the exemplary embodiment; FIG. 4 is a schematic partial cross-sectional view showing another example of the layer structure of the electrophotographic photoreceptor according to the exemplary embodiment; FIG. 4 is a schematic partial cross-sectional view showing another example of the layer structure of the electrophotographic photoreceptor according to the exemplary embodiment; FIG. 1 is a schematic cross-sectional view of an image forming apparatus equipped with a process cartridge according to this embodiment; FIG. 1 is a schematic cross-sectional view of a tandem-type image forming apparatus according to an embodiment; FIG. (A), (B), and (C) are explanatory diagrams showing standards for ghost evaluation, respectively. 1 is a schematic partial cross-sectional view showing an example of the layer structure of an organic electroluminescence device according to this embodiment; FIG. FIG. 3 is a schematic partial cross-sectional view showing another example of the layer structure of the organic electroluminescence device according to this embodiment. FIG. 3 is a schematic partial cross-sectional view showing another example of the layer structure of the organic electroluminescence device according to this embodiment. FIG. 3 is a schematic partial cross-sectional view showing another example of the layer structure of the organic electroluminescence device according to this embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. These descriptions and examples are illustrative of embodiments and do not limit the scope of the invention.

[Organic electronic device]
The organic electronic device according to this embodiment comprises 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); at least one selected from a crosslinked charge-transporting resin, a second charge-transporting polyester resin having a structure represented by the following general formula (1B), and a crosslinked body of the second charge-transporting polyester resin has a charge-transporting film containing
Hereinafter, at least one selected from the first charge-transporting resin and the second charge-transporting polyester resin may be referred to as the "specific resin", and the crosslinked product of the specific resin may be referred to as the "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 transport property, and T ¹ and T ² each independently 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; , p and q each independently represent 0 or 1.

In the general formula (1B), A ³ represents a divalent organic group having charge transport properties, T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ³ represents a (n3+2)-valent non-charge-transporting diol residue, n3 represents 1 or 2, Y ⁴ represents "*-(CH ₂ ) _n4 -LZ", and * represents 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 carbon atoms, oxygen atoms, and hydrogen atoms, Z represents a polymerizable functional group.

The charge-transporting film of the organic electronic device according to the present embodiment contains at least one selected from the specific resin and the specific resin crosslinked product, and therefore has high charge-transporting ability. Therefore, the organic electronic device has good electrical properties by having a charge-transporting film with high charge-transporting ability.
In addition, the charge-transporting film of the organic electronic device contains at least one selected from the specific resin and the specific resin crosslinked body, so that it hardly absorbs visible light and has high visible light transmittance. Therefore, for example, when the organic electronic device is an organic electroluminescent device, the light extraction efficiency is improved by having a charge-transporting film with high visible light transmittance.
Further, since the charge-transporting film of the organic electronic device contains at least one selected from the specific resin and the specific resin crosslinked body, the smoothness of the coating film when the charge-transporting film is formed is high. Therefore, since the organic electronic device has a charge-transporting film with high smoothness, variations in performance in the planar direction of the charge-transporting film are suppressed.

Among the above organic electronic devices, in particular, an organic electronic device having a charge-transporting film containing a specific crosslinked resin has a charge-transporting film with high solvent resistance while obtaining high charge-transporting properties. Therefore, for example, when the organic electronic device is an organic electroluminescent element, the performance of the organic electroluminescent element can be 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 increase productivity. Specifically, since the charge-transporting film containing the specific crosslinked resin has high solvent resistance, when forming the upper layer, a coating method (i.e., coating a coating liquid containing a solvent to form a layer) is used. method)”, the performance of the organic electroluminescence device is less likely to deteriorate due to the dissolution of the charge-transporting film. Therefore, by using the charge-transporting film containing the specific crosslinked resin as the lower layer, the productivity of the organic electroluminescence device is improved while suppressing the deterioration of the performance of the organic electroluminescent device.
Further, an organic electronic device having a charge-transporting film containing a specific crosslinked resin has a charge-transporting film having high charge-transporting properties and excellent mechanical strength. 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, resistance to film reduction due to rubbing with a blade or the like is high, It is possible to extend the life of the electrophotographic photoreceptor.

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, thereby further increasing the cross-linking density and increasing the mechanical strength and resistance. It may be one with a higher solvent property. A charge-transporting film obtained by forming a film by mixing a monomer having a polyfunctional polymerizable functional group is in a state in which the polymerizable functional group contained in the specific resin is branched from the main chain (i.e., free to move). It is speculated that by existing in a state of high degree), efficient cross-linking occurs.

<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 transport property, and T ¹ and T ² each independently 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; , p and q each independently represent 0 or 1.

-Description of each group in general formula (1A-1) and general formula (1A-2)-
A ¹ and A ² in the general formulas (1A-1) and (1A-2) each independently represent a divalent organic group having a charge-transporting property, 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. Induced divalent organic groups are included.
Among these, A ¹ and A ² in the general formulas (1A-1) and (1A-2) are preferably organic groups having hole-transporting ability, and among these, triarylamine More preferably, it is an organic group having at least one selected from a skeleton, a benzidine skeleton, and a stilbene skeleton.

A ¹ and A ² in general formulas (1A-1) and (1A-2) are preferably 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 is a substituted or unsubstituted divalent and k and m each independently represent 0 or 1.

X in the general formula (2) represents a substituted or unsubstituted divalent organic group, which may or may not have an aromatic ring. In addition, X in the general formula (2) is more preferably a group having an aromatic ring, and among these, a substituted or unsubstituted divalent aromatic group, a substituted or unsubstituted The following divalent polynuclear aromatic hydrocarbon group, substituted or unsubstituted divalent condensed aromatic hydrocarbon group having 2 to 10 aromatic rings, or substituted or unsubstituted divalent aromatic heterocyclic group It is more preferable to have

A “polynuclear aromatic hydrocarbon group” is a hydrocarbon group in which two or more aromatic rings composed of carbon and hydrogen are present and the rings are bonded to each other by carbon-carbon bonds. Specifically, a hydrocarbon group in which the carbon atoms constituting the aromatic ring are directly bonded to each other by a carbon-carbon bond, and a hydrocarbon group (alkyl chain or alkylene chain) in which the aromatic rings have 1 to 18 carbon atoms are linked to each other. and the hydrocarbon groups described above.
Specific examples of polynuclear aromatic hydrocarbon groups include divalent groups in which two hydrogen atoms are removed, such as biphenyl, terphenyl, stilbene, and triphenylethylene.
In addition, the aromatic ring constituting the polynuclear aromatic hydrocarbon group may be a condensed aromatic hydrocarbon group described later, or may be an aromatic heterocyclic ring. Specific examples of the condensed aromatic hydrocarbon group and aromatic heterocyclic ring that constitute the polynuclear aromatic hydrocarbon group include, for example, the same compounds as specific examples of the condensed aromatic hydrocarbon group and aromatic heterocyclic ring described later. mentioned.

"Condensed aromatic hydrocarbon group" means a hydrocarbon having two or more aromatic rings composed of carbon and hydrogen and sharing a pair of carbon atoms in which these aromatic rings are adjacently bonded. represents a group. Specific examples include divalent groups in which two hydrogen atoms are removed, such as naphthalene, anthracene, phenanthrene, pyrene, perylene, and fluorene.

"Heteroaromatic ring" 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 heterocyclic ring include Nr=5 and Nr=6. In addition, the type and number of atoms other than carbon atoms (heteroatoms) constituting the ring skeleton are not limited. Types of heteroatoms include, for example, a sulfur atom, a nitrogen atom, an oxygen atom, and the like. In addition, the aromatic heterocyclic ring may contain two or more heteroatoms in the ring skeleton, and may contain two or more heteroatoms.

In particular, the heterocyclic ring having a ring skeleton structure of Nr=5 (that is, a 5-membered ring structure) includes, for example, thiophene, thiophine, pyrrole, furan, or a heterocyclic ring 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.

Substituents for the aromatic rings, polynuclear aromatic rings and condensed aromatic rings include alkyl groups, alkoxy groups, aryl groups, aralkyl groups, substituted amino groups, halogen atoms and the like.
The alkyl group preferably has 1 or more and 10 or less carbon atoms, and examples thereof include methyl, ethyl, propyl and isopropyl groups.
The alkoxyl group preferably has 1 or more and 10 or less 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 or more and 20 or less carbon atoms, such as a phenyl group and a toluyl group.
The aralkyl group preferably has 7 or more and 20 or less carbon atoms, such as a benzyl group and a phenethyl group.
Substituents for the substituted amino group include alkyl groups, aryl groups, aralkyl groups, etc. Specific examples are as described above.
Substituents for the substituted aryl group and substituted aralkyl group include a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom, and the like.

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

In formulas (X1) to (X7), R ¹³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group, and R ¹⁴ to R ¹⁹ each independently represents 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.

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

R ¹ and R ² in 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 or more and 10 or less carbon atoms, and examples thereof include methyl, ethyl, propyl and isopropyl groups.
The alkoxyl group preferably has 1 or more and 10 or less carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
The aryl group preferably has 6 or more and 20 or less carbon atoms, such as a phenyl group and a toluyl group.
Substituents for the substituted aryl group include alkyl groups, alkoxy groups, substituted amino groups, halogen atoms and the like.

Among R ¹ and R ² above, a hydrogen atom, a methyl group, an ethyl group, and a phenyl group are particularly preferred.
In addition, the positions to be substituted with R ¹ and R ² are preferably meta-positions or para-positions with respect to the position to which nitrogen (N) is bonded.

A ¹ in general formula (1A-1) and A ² in general formula (1A-2) may be the same or different. Further, when the first charge-transporting resin has a plurality of structures represented by the general formula (1A-1), the plurality of ^A1 's may be all the same, partially the same, or 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 more preferably that the whole is the same. When the first charge-transporting resin has a plurality of structures represented by general formula (1A-2), the plurality of ^A2 's may all be the same, some of them may be the same, or they may be different from each other. 80% or more of the whole is preferably the same, more preferably 90% or more of the whole is the same, and more preferably all the same.

T ¹ and T ² in general formulas (1A-1) and (1A-2) each independently represent a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. T ¹ and T ² in general formulas (1A-1) and (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 more preferably in the range of 2 or more and 6 or less. Moreover, when the divalent hydrocarbon group is branched, the number of carbon atoms is more preferably in the range of 2 to 10, more preferably in the range of 3 to 7.
Specific structural examples of the group represented by T ¹ and the group represented by T ² (hydrocarbon group T-1 to hydrocarbon group T-32) are shown below. However, A ¹ or A ² in general formula (1A-1) and general formula (1A-2) may be bonded to either side of the following hydrocarbon group. T-5l on the right side of -5 indicates that A ¹ or A ² in general formulas (1A-1) and (1A-2) is bound to the left side of structure T-5.

In general formula (1A-1), when p is 1, structures T-1, T-2 and T-4 above are preferred as T ¹ adjacent to the carbonyl group. Similarly, in general formula (1A-2), when q is 1, structures T-1, T-2 and T-4 above are preferred as T ² adjacent to the carbonyl group.

Note that T ¹ in general formula (1A-1) and T ² in general formula (1A-2) may be the same or different. Further, when the first charge-transporting resin has a plurality of structures represented by general formula (1A-1), the plurality of T ¹ may be all the same, partly the same, or 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 more preferably that the whole is the same. When the first charge-transporting resin has a plurality of structures represented by general formula (1A-2), the plurality of T ² may be all the same, partially the same, or different from each other, 80% or more of the whole is preferably the same, more preferably 90% or more of the whole is the same, and more preferably 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) represent a divalent organic group represented by the general formula (2) and p (that is, the combination of X, R ¹ , R ² , k, and m in general formula (2) and T ¹ and p in general formula (1A-1)) or A ² and T Specific examples of the combination of ² and q (that is, the combination of X, R ¹ , R ² , k, and m in general formula (2) and T ² and q in general formula (1A-2)) are shown, but not limited to these specific examples.
In addition, the numbers described in the columns of “R ¹ ” and “R ² ” in the table below represent the binding positions. Further, the numbers described in the "T ¹ or T ² " column mean the numbers (T-1) to (T-32) attached to the structural formulas of the hydrocarbon groups specifically shown above. In the column of “T ¹ or T ² ”, for example, when “T-5r” is written, the aryl group is on the right side of structure T-5, and when “T-5l” is written, the aryl It indicates that the amine skeleton (that is, A ¹ or A 2 in general formulas (1A-1) and (1A- ² )) is bonded. Further, in the table below, the value shown in "bonding position" indicates that it is bonded to the numerical value described in the benzene ring in the general formula (2), and when k is 1, ( ) indicates that the benzene ring within is also bonded to the same position as the benzene ring where the number is described.

Y ¹ and Y ² in general formulas (1A-1) and (1A-2) each independently represent a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group.
Polymerizable functional groups include, for example, groups containing at least one selected from carbon-carbon double bonds, epoxy groups, and oxetane groups. 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 is 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 ( It is preferably at least one selected from a group represented by P4) and a group represented by the following general formula (P5).

In general formulas (P1) to (P5), R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * represents a bonding position.
The alkyl group preferably has 1 or more and 10 or less carbon atoms, and examples thereof include methyl, ethyl, propyl and isopropyl groups. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
The alkoxyl group preferably has 1 or more and 10 or less 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 1 to 3 carbon atoms, and particularly preferably 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 more preferred. When the first charge-transporting resin has a plurality of groups represented by general formula (P3), at least two or more selected from ortho-position, meta-position, and para-position are mixed in the substitution positions thereof. You may have

When Y ¹ and Y 2 in general formula (1A-1) and general formula (1A- ² ) represent a group having a polymerizable functional group, for example, the polymerizable functional group further having a substituent is an oxygen atom In addition to the case where the substituted or unsubstituted polymerizable functional group is bound to an oxygen atom via a linking group, the case is mentioned.

Examples of substituents further possessed by the polymerizable functional group include hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aralkyl groups, substituted amino groups, and halogen atoms.
The alkyl group preferably has 1 or more and 10 or less carbon atoms, and examples thereof include methyl, ethyl, propyl and isopropyl groups. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
The alkoxyl group preferably has 1 or more and 10 or less 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 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
The aryl group preferably has 6 or more and 20 or less carbon atoms, such as a phenyl group and a toluyl group.
The aralkyl group preferably has 7 or more and 20 or less carbon atoms, such as a benzyl group and a phenethyl group.
Substituents for the substituted amino group include alkyl groups, aryl groups, aralkyl groups, etc. Specific examples are as described above.
Halogen atoms include, for example, fluorine, chlorine, and bromine atoms.

The linking group that connects the polymerizable functional group and the oxygen atom includes, for example, a divalent linking group composed of at least one atom selected from carbon atoms and oxygen atoms (hereinafter also referred to as L1 ) is shown. L1 includes, for example, groups formed by any combination of 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 10 or less, and most preferably 1 or more and 6 or less. When the total number of atoms other than hydrogen atoms constituting L1 is within the above range, the ratio of the charge-transporting skeleton is higher and the electrical properties are better than when the total number is more than the above range.

Specific structural examples of the group represented by Y ¹ and the group represented by Y ² , the polymerizable functional group or the group having a polymerizable functional group (group Y-1 to group Y-22 ). However, in the following formulas, Me means a methyl group and Et means an ethyl group.

Y ¹ in general formula (1A-1) and Y ² in general formula (1A-2) may be the same or different. Also, the plurality of ^Y1 's in the first charge-transporting resin may be all the same, partially the same, or different from each other. Similarly, a plurality of ^Y2 's in the first charge-transporting resin may be all the same, partially 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 added as Y ¹ and Y ² in general formulas (1A-1) and (1A-2). may be mixed with at least one group selected from the groups having 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 may be used.

The number of structures represented by general formula (1A-1) 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. It is below. The structures represented by the general formula (1A-1) do not have to be adjacent to each other.
The number of structures represented by 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. It is more than 1000 or less. Similarly, multiple structures represented by general formula (1A-2) may not be adjacent to each other.
The first charge-transporting resin has 5 or more structures represented by general formula (1A-1) and 5 or more structures represented by general formula (1A-2), and has a weight-average molecular weight of 20. It is preferably 10,000 or less.

The first charge-transporting resin has regions in which, for example, the structure represented by the general formula (1A-1) and the structure represented by the general formula (1A-2) are alternately adjacent to each other and bonded. You may have That is, the first charge-transporting resin may be a resin having a structure represented by general formula (1A-3) below. 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, and more preferably 10 or more and 1000 or less. preferable. The ratio of the structure represented by the following general formula (1A-3) to the first charge-transporting resin as a whole 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 transport property, and T ¹ and T ² each independently represent a linear chain having 1 to 10 carbon atoms. represents a divalent hydrocarbon group having a straight or branched shape, Y ¹ and Y ² each independently represents a hydrogen atom, a polymerizable functional group, or a group having a polymerizable functional group, p and q each independently represent 0 or 1.
That is, in general formula (1A-3), A ¹ , A ² , T ¹ , T ² , Y ¹ , Y ² , p, and q are respectively general formula (1A-1) and general formula (1A -2) are the same as A ¹ , A ² , T ¹ , T ² , Y ¹ , Y ² , p, and q.

-Description of the first charge-transporting resin-
The first charge-transporting resin may have at least the structure represented by the general formula (1A-1) and the structure represented by the general formula (1A-2) in the molecule, and the general formula (1A -1) and the structure represented by the general formula (1A-2) may have other structures in the molecule. For example, a form in which a monovalent substituent or other monovalent structural unit is bound to the end of the structure represented by general formula (1A-1), at the end of the structure represented by general formula (1A-2) Examples include a form in which a monovalent substituent or other monovalent structural unit is bonded. Further, as a form having a structure other than the structure represented by general formula (1A-1) and the structure represented by general formula (1A-2) in the main chain of the first charge-transporting resin, For example, a structural unit represented by general formula (1A-1) and a structural unit represented by general formula (1A-2) are combined via another structure.
When the first charge-transporting resin has another structure in the molecule, the structure represented by the general formula (1A-1) for the entire first charge-transporting resin and the structure represented by the general formula (1A-2) The ratio of the total structure of the structure is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
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 the area ratio of each peak in the NMR spectrum or infrared absorption spectrum. be done. Alternatively, it may be calculated by quantifying the amount of a monomer remaining without polymerization (for example, a compound represented by general formula (3A) and a compound represented by general formula (4A) described later).

When the total number of hydroxyl groups contained in the entire first charge-transporting resin is _MH , and the total number of polymerizable functional groups contained in the entire first charge-transporting resin is _MP , the following formula (A1) is satisfied. More preferably, it satisfies the following formula (A2), and even more preferably satisfies the following formula (A3).
Formula (A1): 0≦M _H /(M _H +M _P )≦0.9
Formula (A2): 0≦M _H /(M _H +M _P )≦0.6
Formula (A3): 0≦M _H /(M _H +M _P )≦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 or more and 500,000 or less, preferably 3,000 or more and 200,000 or less, and more preferably 4,000 or more and 100,000 or less.
Measurement of the weight average molecular weight is performed by preparing a 0.1% by mass THF (tetrahydrofuran) solution of the compound to be measured, and using a differential refractive index detector (RI) by gel permeation chromatography (GPC). A styrene polymer is used as the

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 represented by the general formula (2) are shown below. Examples are not limiting.
In the table below, 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 of general formula (1A-1). or the numbers (2-1) to (2-102) assigned to specific examples of combinations of A ² , T ² and q in general formula (1A-2). Further, among the numbers described in the column of “Y ¹ or Y ² ”, H means a hydrogen atom, and other numbers represent specific structures of the polymerizable functional group or groups having a polymerizable functional group. It means the numbers (Y-1) to (Y-22) attached to the examples. In the table below, "n1" means the number of structures represented by 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 general formula (A1-2).

-Synthesis method (method for producing the first charge-transporting resin)-
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 Y1 ^'s and a plurality of ^Y2 's are all hydrogen atoms (hereinafter also referred to as "specific charge-transporting resin (AI)") is, for example, It is obtained by polymerizing a compound represented by the general formula (3A) and a compound represented by the following general formula (4A) (polymerization step).
Specifically, for example, equivalent amounts of a compound represented by the following general formula (3A) and a compound represented by the following general formula (4A) are used, and synthesis is performed in a solvent using a catalyst.

In the general formulas (3A) and (4A), A ¹ and A ² each independently represent a divalent organic group having charge transport properties, and T ¹ and T ² each independently have 1 to 10 carbon atoms. represents a linear or branched divalent hydrocarbon group, and p and q each independently represent 0 or 1;
A ¹ and A ² , T ¹ and T ² , and p and q in general formulas (3A) and (4A) are 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 equivalent amounts 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 solvents include toluene, xylene, tetrahydrofuran, monochlorobenzene and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of solvents include toluene, xylene, tetrahydrofuran, monochlorobenzene and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of catalysts include quaternary ammonium salts, tertiary amines, tertiary phosphines, quaternary phosphonium salts, lithium halides, and trifluoroboron complex salts. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydroxide, methyltributylammonium chloride, tetra Propyl ammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogen sulfate, methyltrioctylammonium chloride, methyltrioctylammonium bromide, ethyltrioctylammonium chloride , ethyltrioctylammonium bromide, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, stearyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltriethylammonium chloride , benzyltriethylammonium bromide, benzyltriethylammonium hydroxide and the like.

Examples of tertiary amines include triethylamine, tributylamine, dimethylethanolamine, tris(N,N-dimethylaminomethyl)phenol, tris(N,N-diethylaminomethyl)phenol, N,N-dimethylaminomethylphenol, N , N-dimethylbenzylamine and the like.
Examples of tertiary phosphines include triphenylphosphine and the like.
Examples of quaternary phosphonium salts include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, methyltributylphosphonium iodide, methyltrioctylphosphonium chloride, and methyltrioctyl. Phosphonium bromide, ethyltrioctylphosphonium chloride, ethyltrioctylphosphonium bromide, decyltributylphosphonium chloride, hexadecyltributylphosphonium chloride, ethyltrioctylphosphonium chloride and the like.
Examples of lithium halides include lithium chloride and lithium bromide.
Examples of trifluoroboron complex salts include boron trifluoride diethyl ether complex and the like.

The amount of the catalyst added is, for example, the total mass of the monomer (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)) per 1 part by mass. , 1/10000 parts by mass or more and 1/10 parts by mass or less, preferably 1/1000 parts by mass or more and 1/50 parts by mass or less.
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, relative to 1 part by mass of the charge-transporting resin to be produced.
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. mentioned.

After the polymerization reaction between the compound represented by the general formula (3A) and the compound represented by the general formula (4A) is completed, a poor solvent (e.g., methanol , alcohols such as ethanol, acetone, etc.) to precipitate the charge-transporting resin. After separation, the resin is washed with water, an organic solvent, or the like, and dried.
Further, if necessary, reprecipitation may be repeated by dissolving in an organic solvent and adding dropwise to a poor solvent to precipitate the charge-transporting resin. 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 in the reprecipitation process is, for example, 1 part by mass or more and 100 parts by mass or less, preferably 2 parts by mass, with respect to 3 parts by mass of the charge-transporting compound. It is at least 50 parts by mass and no 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, relative to 1 part by mass of the charge-transporting resin.
Further, 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 washed with water, and if necessary, purification may be performed using an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay.
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) -2), the first charge-transporting resin having the structure represented by the general formula (1-3) is obtained.

In the first charge-transporting resin, as at least part of the plurality of Y1 ^'s and the plurality of ^Y2's , at least one selected from a polymerizable functional group and a group having a polymerizable functional group is a charge transporter. The flexible resin (hereinafter also referred to as “specific charge-transporting resin (AII)”) is obtained, for example, after polymerizing the compound represented by the general formula (3A) and the 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 the polymerizable functional group into the polymer.
Thus, by reacting with a compound having a polymerizable functional group after polymerizing the compound represented by the general formula (3A) and the compound represented by the general formula (4A), the general formula (1A-1 ) and the first charge-transporting resin having 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 flexible 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-transporting resin (AI). As I said.
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 necessary The reaction is carried out using a catalyst depending on the

Compounds having a polymerizable functional group include, for example, leaving groups (e.g., OH groups, halogen atoms, or Other carboxylic acids, etc.) substituted carboxylic acid derivatives, Y-5 to Y-12, Y-15, and Y-19 to Y-22 have leaving groups (e.g., halogen atoms, trifluoromethanesulfonyloxy groups, or (p-toluenesulfonyloxy group, etc.) is substituted to form an electrophile. A polymerizable functional group is introduced by adding a known catalyst or a condensing agent to these, if necessary, and performing a reaction.

Solvents used in the step of introducing a polymerizable functional group into the resulting polymer include, for example, methylene chloride, diethyl ether, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene, acetone, methyl ethyl ketone, N,N- 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, relative to 1 part by mass of the charge-transporting resin to be obtained.

When a compound having a carboxyl group is used as the compound having a polymerizable functional group, a catalyst such as sulfuric acid, p-toluenesulfonic acid, or the like may be used.
Further, when at least one of carboxylic acid anhydrides and halides is used as the compound having a polymerizable functional group, the catalyst may be, for example, pyridine, piperidine, dimethylaminopyridine, trimethylamine, 1,8-diazabicyclo [5.4. 0]-7-undecene (DBU), organic bases such as triethylamine; inorganic bases such as sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide; and the like may be used.
The amount of the catalyst to be added is, for example, 1 equivalent or more and 10 equivalents or less, preferably 2 equivalents or more and 5 equivalents or less, relative to 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 is, for example, in the range of 30°C or higher and 100°C or lower.

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

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

In the general formula (1B), A ³ represents a divalent organic group having charge transport properties, T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, Y ³ represents a (n3+2)-valent non-charge-transporting diol residue, n3 represents 1 or 2, Y ⁴ represents "*-(CH ₂ ) _n4 -LZ", and * represents 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 carbon atoms, oxygen atoms, and hydrogen atoms, Z represents a polymerizable functional group.

-Description of each group in general formula (1B)-
^A3 in the general formula (1B) represents a divalent organic group having a charge-transporting property, and specifically includes a phthalocyanine-based compound, a porphyrin-based compound, an azobenzene-based compound, a triarylamine-based compound, and a benzidine-based compound. , arylalkane-based compounds, aryl-substituted ethylene-based compounds, stilbene-based compounds, anthracene-based compounds, hydrazone-based compounds, quinone-based compounds, fluorenone-based compounds, and the like.
Among these, A ³ in the general formula (1B) is preferably an organic group having a hole-transporting ability. more preferably an organic group having

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

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 is a substituted or unsubstituted divalent and k and m each independently represent 0 or 1.
The details of each group in formula (2) are as described above.

When the second charge-transporting polyester resin has a plurality of structures represented by general formula (1B), the plurality of ^A3 may be all the same, partly the same, or different from each other. preferably 80% or more of the same, more preferably 90% or more of the whole, and even more preferably all the same.

T ³ in general formula (1B) represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. T ³ in 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 more preferably in the range of 2 or more and 6 or less. Moreover, when the divalent hydrocarbon group is branched, the number of carbon atoms is more preferably in the range of 2 to 10, more preferably in the range of 3 to 7.
Examples of specific structures ^of the group represented by ^T3 include ^the above-mentioned "carbonized hydrogen group T-1 to hydrocarbon group T-32”.

When the second charge-transporting polyester resin has a plurality of structures represented by general formula (1B), the plurality of ^T3s may be all the same, partially the same, or different from each other. , preferably 80% or more of the same, more preferably 90% or more of the whole, still more preferably all the same.

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 (i.e., Specific examples of combinations of X, R ¹ , R ² , k, and m, and T ³ in general formula (1B)) are shown below, but are not limited to these specific examples.
In addition, the numbers described in the columns of “R ¹ ” and “R ² ” in the table below represent the binding positions. Further, the numbers described in the "T ³ " column mean the numbers (T-1) to (T-32) attached to the structural formulas of the hydrocarbon groups specifically shown above. In the column of “T ³ ”, for example, when “T-5r” is written, the arylamine skeleton ( That is, it indicates that A ³ ) in general formula (1B) is bonded. Further, in the table below, the value shown in "bonding position" indicates that it is bonded to the numerical value described in the benzene ring in the general formula (2), and when k is 1, ( ) indicates that the benzene ring within is also bonded to the same position as the benzene ring where the number is described.

Y ³ in general formula (1B) represents a (n3+2)-valent non-charge-transporting diol residue. A diol residue is a linking group that links oxygen atoms, 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 in which a hydrocarbon group and an oxygen atom are combined, and is a linking group in which a hydrocarbon group or a hydrocarbon group and an ether bond are combined. It is more preferable to have The hydrocarbon group may be a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a combination of two or more of these hydrocarbon groups. The two or more hydrocarbon groups may be the same type of hydrocarbon group or different types of hydrocarbon groups.

The saturated hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Examples of saturated hydrocarbon groups include linear alkylene groups having 1 to 10 carbon atoms, branched alkylene groups having 2 to 10 carbon atoms, cyclic alkylene groups having 5 to 8 carbon atoms, and combinations thereof. etc.
The unsaturated hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Examples of the unsaturated hydrocarbon group include linear alkenyl groups having 2 to 10 carbon atoms, branched alkenyl groups having 3 to 10 carbon atoms, cyclic alkenyl groups having 5 to 8 carbon atoms, and combinations thereof. and the like.
The aromatic hydrocarbon group is a cyclic linking group containing at least an aromatic ring, and examples thereof include divalent groups excluding hydrogen atoms such as benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, and fluorene.
Examples of groups in which two or more hydrocarbon groups are combined include, for example, groups in which two or more aromatic hydrocarbon groups are combined, and the aromatic hydrocarbon group is selected from saturated hydrocarbon groups and unsaturated hydrocarbon groups. Groups to which at least one group is attached are included.

Among these, the linking group represented by ^Y3 is a hydrocarbon group in which 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 are combined. , and groups in which these hydrocarbon groups and oxygen atoms are combined are preferable, and two or more of at least one group selected from saturated hydrocarbon groups, aromatic hydrocarbon groups, saturated hydrocarbon groups and aromatic hydrocarbon groups More preferred are combined hydrocarbon groups and groups in which these hydrocarbon groups and ether bonds are combined, and more preferred are saturated hydrocarbon groups and groups in which saturated hydrocarbon groups and ether bonds are combined.

Moreover, when the linking group represented by ^Y3 contains an oxygen atom, the linking group represented by ^Y3 may be a group in which a plurality of hydrocarbon groups are linked via an oxygen atom. The plurality of hydrocarbon groups may be the same type of hydrocarbon groups or different types of hydrocarbon groups.
However, the terminal atom of the main chain of the linking group represented by ^Y3 (that is, among the atoms constituting the linking group represented by ^Y3 , the atom directly bonded to the oxygen atom in the general formula (1B)) is Both are preferably carbon atoms.
Further, among the atoms constituting the linking group represented by Y ³ , the atoms directly bonded to the group represented by Y ⁴ are preferably carbon atoms ^. It is more preferably a constituent carbon atom.

Among the atoms constituting the linking group represented by Y ³ , the number of atoms other than hydrogen atoms 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 2 or more and 15. More preferred are: When the number of atoms other than hydrogen atoms constituting the linking group represented by ^Y3 is within the above range, the ratio of the charge-transporting skeleton to the second charge-transporting polyester resin is higher than when the number is larger than the above range. In many cases, the charge properties of the second charge-transporting polyester resin are improved. In addition, when the number of atoms other than hydrogen atoms constituting the linking group represented by ^Y3 is within the above range, the molecular weight can be adjusted during the synthesis of the second charge-transporting polyester resin compared to when the number is less than the above range. easier to clean.
In addition, the number of atoms other than hydrogen atoms among the atoms constituting the linking group represented by Y ³ is not only the atoms directly involved in the linking, but also the atoms not directly involved in the linking (e.g., branched chain, aromatic ring, etc.). For example, among the atoms constituting Specific Example Y ³ -12 below, the number of atoms other than hydrogen atoms is 31.

Specific examples of structures including the linking group represented by Y ³ and oxygen atoms at both ends thereof (ie, O—Y ³ —O) are shown below. However, "*" in the structure below indicates the bonding position with the group represented by ^Y4 .

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

Y ⁴ in 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. represents a divalent linking group or single bond composed of at least one atom selected from and Z represents a polymerizable functional group.

First, the linking group represented by L in the group represented by "*-(CH ₂ ) _n4 -LZ" will be explained.
The linking group represented by L is a divalent linking group composed of at least one atom selected from carbon atoms, oxygen atoms and hydrogen atoms. The linking group represented by L includes, for example, an alkylene group, an ether bond (ie, "-O-"), a carbonyl group (ie, "-C(=O)-"), and groups in which these are combined. .
Further, a group combining these (that is, a group combining at least two or more selected from an alkylene group, an ether bond, and a carbonyl group) includes, for example, a combination of an ether bond and an alkylene group, an ether bond and a carbonyl group (for example, an ester bond), a combination of an ether bond, a carbonyl group, and an alkylene group (for example, a combination of an ester bond and an alkylene group).
The linking group represented by L preferably contains at least an ether bond.

Among the atoms constituting the group represented by L (the linking group represented by L or the single bond represented by L), the number of atoms other than hydrogen atoms includes, for example, 0 to 16, and 1 to 11. It is preferably 1 or more and 10 or less, and even 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 higher than when the number is larger than the above range, The charge property of the second charge-transporting polyester resin is improved. Further, when the number of atoms other than hydrogen atoms constituting the group represented by L is within the above range, the cross-linking reaction of the second charge-transporting polyester resin is more likely to occur than when the number is less than the above range. It becomes easier to obtain a film with excellent solvent resistance and mechanical strength.
In addition, the number of atoms other than hydrogen atoms among the atoms constituting the group represented by L is not only the atoms directly involved in the connection, but also the atoms not directly involved in the connection (for example, the oxygen atom of the carbonyl group, etc. ). For example, among the atoms constituting Specific Example L-9 below, the number of atoms other than hydrogen atoms is 11.

Specific examples of the linking group represented by L are shown below. Of the two "*" in the structure below, the "*" shown on the left indicates the bonding position with "-(CH ₂ ) _n4 -", and the "*" shown on the right is Z. The bonding positions with the indicated polymerizable functional groups are shown.

Next, the polymerizable functional group represented by Z in the group represented by "*-(CH ₂ ) _n4 -LZ" will be explained.
Polymerizable functional groups include, for example, groups containing at least one selected from carbon-carbon double bonds, epoxy groups, and oxetane groups. 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 is 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 ( It is preferably at least one selected from a group represented by P4) and a group represented by the following general formula (P5).

In general formulas (P1) to (P5), R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * represents a bonding position.
The alkyl group preferably has 1 or more and 10 or less carbon atoms, and examples thereof include methyl, ethyl, propyl and isopropyl groups. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
The alkoxyl group preferably has 1 or more and 10 or less 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 1 to 3 carbon atoms, and particularly preferably 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 more preferred. When the second charge-transporting polyester resin has a plurality of groups represented by the general formula (P3), the substitution positions thereof are at least two selected from ortho-position, meta-position and para-position. May be mixed.

Examples of specific structures of the polymerizable functional group represented by Z are shown below. In the structure below, * indicates the bonding position with the group represented by L.
The polymerizable functional group represented by Z is, among the specific examples below, particularly 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.
Further, 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 acrylic ester structure or a methacrylic ester structure ) is preferred.

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

The number of atoms other than hydrogen atoms among the atoms constituting the linking group represented by Y ³ in general formula (1B), the number of n4 in Y ⁴ in general formula (1B), and Y in general formula (1B) The total 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, and more preferably 15 or less. When the total is within the range, the ratio of the charge-transporting skeleton to the second charge-transporting polyester resin is higher than when the total is above the range, and the second charge-transporting polyester resin has good charge characteristics. becomes. Further, when the total is within the above range, the cross-linking reaction of the second charge-transporting polyester resin occurs more easily than when the total is less than the above range, and a film having excellent solvent resistance and mechanical strength can be obtained. easier.

Specific examples of combinations of O—Y ³ —O, n3, and Y ⁴ (that is, combinations of O—Y ³ —O, n3, n4, L, and Z) are shown below, but are not limited to these specific examples. does not mean
In the table below, “*” in the “O—Y ³ —O” column indicates the bonding position with the group represented by Y ⁴ . Also, the numbers described represent the positions of bonding. Further, of the two "*" in the "L" column, the "*" shown on the left indicates the 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. In addition, "*" in the "Z" column indicates the bonding position with the group represented by L. Further, in the following specific examples, examples in which n3 is 2 are examples in which two ^Y4 are the same.

-Description of the second charge-transporting polyester resin-
The second charge-transporting polyester resin may have at least the structure represented by general formula (1B) in the molecule, and in addition to the structure represented by general formula (1B), other structures may be added to the molecule. may have it in When the second charge-transporting polyester resin has another structure in the molecule, the ratio of the structure represented by general formula (1B) to the entire second charge-transporting polyester resin is preferably 80% by mass or more. , more preferably 90% by mass or more, and even 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 2,000 to 500,000, more preferably 3,000 to 200,000, and even more preferably 4,000 to 100,000.
Measurement of the weight average molecular weight is performed by preparing a 0.1% by mass THF (tetrahydrofuran) solution of the compound to be measured, and using a differential refractive index detector (RI) by gel permeation chromatography (GPC). A styrene polymer is used as the

Specific examples of the second charge-transporting polyester resin in the case where ^A3 in the general formula (1B) represents a divalent organic group represented by the general formula (2) are shown below. It is not limited.
In the table below, the numbers described in the columns of "Combination AT" and "Combination Y" are numbers AT ^{- 1} to AT-102 and O —Y ³ —O, n3 and Y ⁴ and numbers Y-1 to Y-63 attached to specific examples of combinations. Also, 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, a synthesis method will be explained.
The second charge-transporting resin includes, for example, a compound represented by the following general formula (3B) (hereinafter also referred to as "charge-transporting monomer") and a compound represented by the following general formula (4B) (hereinafter referred to as " It is obtained by polycondensation with a non-charge-transporting monomer.

A ³ , T ³ , Y ³ , n3, and Y ⁴ in general formulas (3B) and (4B) correspond to A ³ , T ³ , Y ³ , n3, and Y ⁴ in general formula (1B). 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. represents a hydrocarbon group, Y ³ represents a (n3+2)-valent non-charge-transporting diol residue, n3 represents 1 or 2, and Y ⁴ represents "*-(CH ₂ ) _n4 -LZ"; * indicates the bonding position with Y ³ , n4 indicates 1 or 2, L is a divalent linking group composed of at least one atom selected from carbon atoms, oxygen atoms, and hydrogen atoms or represents a single bond, and Z represents a polymerizable functional group.

Moreover, in the general formulas (3B) and (4B), Z ¹ and Z ² represent groups that form a combination capable of undergoing a polycondensation reaction with each other.
Specifically, when the group represented by Z ¹ is a hydroxyl group, examples of the group represented by Z ² include a hydroxyl group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), methanesulfone acid ester group, trifluoromethanesulfonate group, p-toluenesulfonate group and the like.
Further, 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 (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), other organic acid and mixed anhydride residues. Examples of the other organic acids include acetic acid, trifluoroacetic acid, isobutyl formate, methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid.

In the polycondensation reaction between the charge-transporting monomer and the non-charge-transporting monomer, known additives, catalysts, etc. Scavengers, etc. that capture generated water, alcohol, acid, etc.) may also be used.

As noted above, the non-charge-transporting monomer contains polymerizable functional groups. Therefore, during the polycondensation reaction between the charge-transporting monomer and the non-charge-transporting monomer, the polymerizable functional group possessed by the non-charge-transporting monomer (that is, "* ^- (CH ₂ ) _n4 -L- The polycondensation reaction conditions may be selected such 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, instead of the non-charge-transporting monomer, a monomer having no polymerizable functional group represented by Z is used to carry out a polycondensation reaction with the charge-transporting monomer to obtain a polyester. A polymerizable functional group represented by Z may be introduced into the polyester (that is, a polyester having no polymerizable functional group) by the reaction of.
When carrying out the polycondensation reaction between the monomer having no polymerizable functional group represented by Z and the charge-transporting monomer, the functional group for introducing the polymerizable functional group represented by Z is added during polycondensation. The polycondensation may be carried out by appropriately protecting the functional group so as not to react with .
As a method for subsequently introducing the polymerizable functional group represented by Z, there is a method of reacting a polyester having no polymerizable functional group with a compound having a polymerizable functional group.

Examples of compounds having a polymerizable functional group include carboxylic acid derivatives in which the polymerizable functional group to be introduced is substituted with a leaving group (e.g., hydroxyl group, halogen atom, other carboxylic acid, etc.), and the polymerizable functional group to be introduced. Compounds that have become electrophiles by substitution with a leaving group (eg, a halogen atom, a trifluoromethanesulfonyloxy group, a p-toluenesulfonyloxy group, etc.) can be mentioned.

The charge-transporting monomer and the non-charge-transporting monomer are each obtained by synthesizing by a known method. Also, as the non-charge-transporting monomer having a polymerizable functional group represented by Z, a commercial product may be used. As the non-charge-transporting monomer, a diol monomer in which the group represented by ^Z2 , which is the reaction site for polycondensation, is a hydroxyl group may be used as it is. It may be converted to a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), methanesulfonate group, trifluoromethanesulfonate group, p-toluenesulfonate group, etc. by a method. .

Among the non-charge-transporting monomers having a polymerizable functional group represented by Z, a method for synthesizing a diol monomer in which the group represented by ^Z2 is a hydroxyl group includes, for example, a commercially available polymerization method containing an epoxy group or an oxetane group. A method of adding water to a functional group-containing compound (eg, (meth)acrylic acid ester, styrene derivative, etc.) to open an epoxy group or an oxetane group.
Further, as a method for synthesizing the diol monomer, a polymerizable functional group-containing compound having a carboxy group or a hydroxyl group (for example, (meth) acrylic acid, hydroxy-substituted styrene, hydroxymethyl-substituted styrene, vinyl benzoic acid, etc.) to open the epoxy group or oxetane group.
In addition, as a method for synthesizing the diol monomer, a polymerizable functional group-containing compound having a carboxy group or a hydroxyl group (for example, (meth) acrylic acid, hydroxy-substituted styrene, hydroxymethyl-substituted styrene, vinyl benzoic acid, etc.), followed by a substitution reaction.
In addition, "(meth)acryl" means at least one selected from "acryl" and "methacryl". Moreover, "(meth)acrylate" means at least one selected from "acrylate" and "methacrylate".

For non-charge-transporting diol monomers having two polymerizable functional groups in one molecule, polymerizable functional group-containing compounds having two polymerizable functional groups, typified by commercially available bifunctional epoxy (meth)acrylates can be used as is.
As a method for synthesizing a non-charge-transporting diol monomer having two polymerizable functional groups in one molecule, for example, a polymerizable A method of adding a functional group-containing compound (eg, (meth)acrylic acid, hydroxy-substituted styrene, hydroxymethyl-substituted styrene, vinyl benzoic acid, etc.) to open an epoxy group or an oxetane group.

Synthesis of the second charge-transporting polyester resin using the charge-transporting monomer and the non-charge-transporting monomer is carried out, for example, by using the same amount of the charge-transporting monomer and the non-charge-transporting monomer in a solvent, adding It is carried out by using an agent or catalyst (for example, an acid catalyst, a condensing agent, a trapping agent for trapping water, alcohol, acid, etc., which are by-products of condensation, etc.).
Examples of solvents include toluene, xylene, tetrahydrofuran, monochlorobenzene and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

- Example of synthesis (polycondensation) of the second charge-transporting polyester resin The method of polymerizing the charge-transporting monomer and the non-charge-transporting monomer is described in Jikken Kagaku Koza, Vol. 28, 4th edition. Various methods may be employed. For example, the following methods are mentioned.

(1) Polymerization of dihydric alcohol and dicarboxylic acid using a catalyst In polymerization of a dihydric alcohol and a dihydric carboxylic acid using a catalyst, a dihydric alcohol and a dihydric carboxylic acid are Mix approximately equivalent amounts and polymerize using an acid catalyst.
As the acid catalyst, those used in ordinary esterification reactions such as sulfuric acid, toluenesulfonic acid and trifluoroacetic acid are used. It is used in the range of 1000 to 1/50 parts by mass. In order to remove water generated during polymerization, it is preferable to use a solvent that can be azeotroped with water. Toluene, chlorobenzene, etc. are effective. It is used in the range of 2 to 50 parts by mass. Although the reaction temperature can be set arbitrarily, it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water produced during polymerization. After completion of the reaction, when no solvent is used, the material is dissolved in a soluble solvent. When a solvent is used, the reaction solution is dropped as it is into an alcohol such as methanol or ethanol, or a poor solvent such as acetone in which the polymer is difficult to dissolve, to precipitate the charge-transporting polyester resin. is separated, thoroughly washed with water, an organic solvent, etc., and dried. Further, if necessary, reprecipitation may be repeated by dissolving in a suitable organic solvent, adding dropwise to a poor solvent, and precipitating the charge-transporting polyester resin. The reprecipitation treatment is preferably carried out 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 mass, preferably 2 to 50 parts by mass, per 1 part by mass of the charge-transporting polyester resin. The poor solvent is used in an amount of 1 to 1,000 parts by mass, preferably 10 to 500 parts by mass, per 1 part by mass of the charge-transporting resin.

Moreover, when using dihydric alcohols with high acidity as a monomer, an interfacial polymerization method may be used. Specifically, a dihydric alcohol is added to water, an equivalent amount of a base is added and dissolved, and then a solution of a charge-transporting monomer equivalent to the dihydric alcohol is added with vigorous stirring to polymerize. At this time, water is used in an amount of 1 to 1000 parts by weight, preferably 2 to 500 parts by weight, per 1 part by weight of the dihydric alcohol. As a solvent for dissolving the other monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene, etc. 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 weight, preferably 0.2 to 5 parts by weight, per 1 part by weight of the monomer.

(2) Polymerization of dihydric alcohol and dicarboxylic acid using a condensing agent In the polymerization of dihydric alcohol and dicarboxylic acid using a condensing agent, are mixed in approximately equivalent amounts and polymerized using a condensing agent. A known condensing agent is used, and specific examples include carbodiimide-based, imidazole-based, triazine-based, phosphonium-based, uronium-based, haluronium-based, Mitsunobu reaction reagents (diethyl azodicarboxylate and triphenylphosphine), and the like. be done.
The amount of the condensing agent to be added is 1 to 5 molar equivalents, preferably 1.05 to 3 molar equivalents, most preferably 1 to the dihydric alcohol when equivalents of the dihydric alcohol and the divalent carboxylic acid are used. .1 to 2 molar equivalents.
A base may be added, if desired. Organic bases are preferred as the base. Specific examples include pyridine, triethylamine, 4-dimethylaminopyridine and imidazole. These are used in an amount of 0.05 to 2 molar equivalents, preferably 0.1 to 1.5 molar equivalents, most preferably 0.15 to 1.3 molar equivalents, relative to the condensing agent.

(3) Polymerization of a dihydric alcohol and a divalent carboxylic acid ester In the polymerization of a dihydric alcohol and a divalent carboxylic acid ester, the dihydric alcohol is added to the divalent carboxylic acid ester, followed by sulfuric acid, phosphoric acid, etc. inorganic acids, titanium alkoxides, acetates or carbonates such as calcium and cobalt, oxides of zinc or lead are used as catalysts and heated to synthesize by transesterification.
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 an excess amount of dihydric alcohol having a relatively low boiling point relative to 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 preferably carried out at a temperature of 200 to 300° C., and after the transesterification is completed, the reaction is preferably carried out under reduced pressure in order to promote polymerization by elimination of the dihydric alcohol. Alternatively, a high boiling point solvent such as 1-chloronaphthalene which is azeotropic with the dihydric alcohol may be used to perform the reaction under normal pressure while removing the dihydric alcohol azeotropically.

(4) Polymerization of Divalent Alcohol Derivative and Divalent Carboxylic Acid In the polymerization of the divalent alcohol derivative and divalent carboxylic acid, a divalent halogen compound is preferably used as the divalent alcohol derivative. In this case, a divalent halogen compound and a divalent carboxylic acid may be mixed in approximately equal amounts and polymerized using a basic catalyst. Basic catalysts include general 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. of the inorganic base is used in the range 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, aprotic polar solvents such as N,N-dimethylformamide and dimethylsulfoxide are particularly preferred. Although the reaction temperature is not particularly limited and can be set freely, it is desirable to set it between 0° C. and the boiling point of the reaction solvent.

The amount of the catalyst to be added is, for example, 1/10000 parts by mass or more and 1/10 parts by mass with respect to 1 part by mass of the total mass of the monomer (that is, the sum of the mass of the charge-transporting monomer and the non-charge-transporting monomer). parts or less, preferably 1/1000 parts by mass or more and 1/50 parts by mass or less.
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, relative to 1 part by mass of the second charge-transporting polyester resin to be produced. be.
The reaction temperature (that is, the temperature for polymerizing the charge-transporting monomer and the non-charge-transporting monomer) is not particularly limited, and is, for example, in the range of 30°C or higher and 100°C or lower.

After the polymerization reaction between the charge-transporting monomer and the non-charge-transporting monomer is completed, the resulting charge-transporting monomer is treated with a poor solvent (e.g., alcohols such as methanol and ethanol, acetone, etc.) in which the resulting charge-transporting resin is difficult to dissolve. By dropping the reaction solution, the charge-transporting resin is deposited, separated, washed with water, an organic solvent, or the like, and dried.
Further, if necessary, reprecipitation may be repeated by dissolving in an organic solvent and adding dropwise to a poor solvent to precipitate the charge-transporting resin. 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 in the reprecipitation process is, for example, 1 part by mass or more and 100 parts by mass or less, preferably 2 parts by mass, with respect to 3 parts by mass of the charge-transporting compound. It is at least 50 parts by mass and no 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, relative to 1 part by mass of the charge-transporting resin.
After completion of the polymerization reaction between the charge-transporting monomer and the non-charge-transporting monomer, for example, the reaction solution is poured into water, extracted with a solvent such as toluene, hexane, or ethyl acetate, washed with water, and if necessary, Purification may be performed using adsorbents such as activated carbon, silica gel, porous alumina, and activated clay.

<Charge-transporting film>
Next, the charge-transporting film will be explained.
The charge-transporting film is at least selected from a first charge-transporting resin, a crosslinked first charge-transporting resin, a second charge-transporting polyester resin, and a crosslinked 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 body).
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, dioxane, and the like. , cellosolve solvents such as ethylene glycol monomethyl ether, and alcohol solvents such as isopropyl alcohol and butanol, and these may be used alone or as a mixed solvent.

As a dissolution 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). Usual methods can be mentioned.

-Crosslinking of specific resin-
Among charge-transporting films, in particular, as a method for obtaining a charge-transporting film containing a specific resin crosslinked product, for example, a specific resin solution containing a specific resin having a polymerizable functional group is used, and heat and light are applied to the solution. , a method of further crosslinking the specific resin by applying radiation or the like. A charge-transporting film having improved strength and solvent resistance can be obtained by the above crosslinking.
When cross-linking 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. As the photo-curing catalyst and thermal polymerization initiator, known photo-curing catalysts and thermal polymerization initiators are used. Electron beams are preferred as the radiation.

(Electron beam cross-linking)
When electron beams are used for cross-linking 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 acceleration voltage is 300 KV or less, the damage of electron beam irradiation to the photoreceptor characteristics is suppressed. Further, when the dose is 1 Mrad or more, crosslinking is sufficiently performed, and when the dose is 100 Mrad or less, deterioration of the photoreceptor is suppressed.

Irradiation is performed in an atmosphere of an inert gas such as nitrogen or argon with an oxygen concentration of 1000 ppm, preferably 500 ppm or less.

(Photocrosslinking)
As a 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 bandpass filter. The irradiation time and light intensity can be freely selected, but for ^example , the illuminance (365 nm) is preferably 300 mW/cm ² or more and 1000 mW/cm ² or less. It is sufficient to irradiate for seconds or less.

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 higher and 150° C. or lower during or after irradiation.

Intramolecular cleavage type photocuring catalysts include benzyl ketal, alkylphenone, aminoalkylphenone, phosphine oxide, titanocene, and oxime catalysts.
More specifically, benzyl ketals include 2,2-dimethoxy-1,2-diphenylethan-1-one.

As alkylphenones, 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- Propane-1-one, acetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone.

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

Phosphine oxides include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

The titanocenes include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.

Oximes 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-based, thioxanthone-based, benzyl-based, Michler's ketone-based, and the like.
More specifically, benzophenones include 2-benzoylbenzoic acid, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, p,p′-bisdiethylaminobenzophenone, and the like. mentioned.

Thioxanthones include 2,4-diethylthioxanthen-9-one, 2-chlorothioxanthone, 2-isopropylthioxanthone, and the like.

Benzyl-based groups include benzyl, (±)-camphorquinone, p-anisyl, and the like.

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

(thermal cross-linking)
Thermal polymerization initiators include V-30, V-40, V-59, V601, V65, V-70, VF-096, VE-073, Vam-110, Vam-111 (Fujifilm Wako Pure Chemical Industries, Ltd. ), OTazo-15, OTazo-30, AIBN, AMBN, ADVN, ACVA (Otsuka Chemical) and other azo initiators; Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H , Permoyl H, Permoyl P, Permenta H, Perocta H, Perbutyl C, Perbutyl D, Perhexyl D, Perroyl IB, Perroyl 355, Perroyl L, Perroyl SA, Nyper BW, Nyper BMT-K40/M, Perroyl IPP, Perroyl NPP, Perroyl TCP, Perroyl OPP, Perroyl SBP, Permil ND, Perocta 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 Chemical Co., Ltd.), Kayaketal AM-C55, Trigonox 36-C75, Laurox, Percadox L-W75, Percadox CH -50L, Trigonox TMBH, Kayacumene H, Kayabutyl H-70, Percadox BC-FF, Kayahexa AD, Percadox 14, Kayabutyl C, Kayabutyl D, Kayahexa YD-E85, Percadox 12-XL25, Percadox 12-EB20, Trigonox 22-N70, Trigonox 22-70E, Trigonox D-T50, 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 F-C50, Kayabutyl B, Kayakone EH-C70, Kayakone EH-W60, Kayakone I-20 , Kayacarvone BIC-75, Trigonox 117, Kayalen 6-70 (manufactured by Kayaku Akzo Co., Ltd.), Luperox 610, Luperox 188, Luperox 844, Luperox 259, Luperox 10, Luperox 701, Luperox 11, Luperox 26, Luperox 80, Luperox 7 , Luperox 270, Luperox P, Luperox 546, Luperox 554, Luperox 575, Luperox TANPO, Luperox 555, Luperox 570, Luperox TAP, Luperox TBIC, Luperox TBEC, Luperox JW, Luperox TAIC, Luperox TAEC, Luperox DC, Luperox 101, Luperox F, Luperox DI, Luperox 130, Luperox 220, Luperox 230, Luperox 233, Luperox 531 (manufactured by Arkema Yoshitomi) and the like.

Among these, when an azo 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 with suppressed unevenness is formed. More preferably, the molecular weight of the azo polymerization initiator is 250 or more, more preferably 300 or more.

Heating is carried out in an inert gas atmosphere such as nitrogen or argon at an oxygen concentration of preferably 1000 ppm or less, more preferably 500 ppm or less, preferably 50 ° C. or higher and 170 ° C. or lower, more preferably 70 ° C. or higher and 150 ° C. or lower, It is preferably heated for 10 minutes or more and 120 minutes or less, more preferably 15 minutes or more and 100 minutes or less.

The total content of the photocuring catalyst or thermal polymerization initiator is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more, relative to the total solid content in the solution for layer formation. 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 ingredients-
The charge-transporting film may be a film in which a specific resin is dissolved in a binder resin other than the specific resin, and a monomer, oligomer, or polymer having a double bond (hereinafter also referred to as a “reactive compound”) may be used. It may be a cured film obtained by mixing and curing.
Also, the charge-transporting film may contain at least one selected from a light-emitting 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 binder resins include known non-reactive binder resins such as polyester resins, polyarylate resins, methacrylic resins, acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, and polystyrene resins.

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

(reactive compound)
Examples of reactive compounds include monofunctional compounds (i.e., compounds having one double bond in the molecule), and bifunctional or higher compounds (i.e., two or more double bonds in the same molecule). compounds), and among these, bifunctional or higher functional compounds are preferred from the viewpoint of improving the strength of the charge-transporting film. The reactive compound may have a charge-transporting structure in its molecule.

Examples of reactive compounds include monofunctional monomers such as 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, ethylcarbitol acrylate, phenoxyethyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate , phenoxypolyethylene glycol acrylate, phenoxypolyethylene glycol methacrylate, hydroxyethyl o-phenylphenol acrylate, o-phenylphenol glycidyl ether acrylate, styrene, and the like.

As a reactive compound, bifunctional monomers such as 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.

Examples of reactive compounds include trifunctional monomers such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, aliphatic tri(meth)acrylate, and trivinylcyclohexane.

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

As reactive compounds, pentafunctional or higher monomers include, for example, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like, as well as (meth)acrylates having a polyester skeleton, urethane skeleton, and phosphazene skeleton. is mentioned.

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

When a reactive compound is used, it is used singly or as a mixture of two or more. The reactive compound is preferably used in an amount of 60% by mass or less, more preferably 55% by mass or less, more preferably 50% by mass, based on the total solid content of the composition used for forming the film. Used below.

<Types of organic electronic devices>
Organic electronic devices include, for example, those provided with the charge-transporting film on a support, and specific examples thereof include electrophotographic photoreceptors, organic electroluminescent devices, solar cells, transistors, and the like. be done.
When the organic electronic device is an electrophotographic photoreceptor having a photosensitive layer, the outermost 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, which is 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. good too.
Examples of the charge-generating material contained in the charge-transporting film include phthalocyanine compounds. 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-5-279591; and oxytitanium phthalocyanine hydrate crystals disclosed in JP-A-4-189873 and JP-A-5-43813. By using these phthalocyanine compounds, an electrophotographic photoreceptor having high sensitivity and excellent stability over repeated use can be obtained.
An electrophotographic photoreceptor and an organic electroluminescent element will be described below as examples of organic electronic devices.

- Electrophotographic photoreceptor -
The electrophotographic photoreceptor includes, for example, a conductive substrate provided with the above-described charge-transporting film. Among the layers provided on the conductive substrate, the outermost layer is preferably the aforementioned charge-transporting film.
The outermost layer may be a layer that forms the top surface of the electrophotographic photosensitive member itself, and may be a layer that functions as a protective layer or a layer that functions as a charge transport layer.
When the outermost layer is a layer that functions as a protective layer, for example, a photosensitive layer comprising a charge-transporting layer and a charge-generating layer or a single-layer type photosensitive layer is provided below the protective layer. That is, when the outermost layer is a layer that functions as a protective layer, for example, a photosensitive layer and a protective layer as the outermost layer are provided on a conductive substrate, and the protective layer is the charge-transporting film. morphology.
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 serves as the charge transport layer. A form that is a sex membrane can be mentioned. The charge-transporting layer may further contain a charge-transporting material that does not have a reactive group such as a thiol group or an unsaturated bond.

Hereinafter, as an example of an electrophotographic photoreceptor, an electrophotographic photoreceptor whose 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 are denoted by the same reference numerals, and redundant explanations are omitted.

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

The electrophotographic photoreceptor 7A shown in FIG. 1 is a so-called function-separated photoreceptor (or laminated photoreceptor). It has a structure in which a transport layer 3 and a protective layer 5 are sequentially formed. In the electrophotographic photoreceptor 7A, the charge generation layer 2 and the charge transport layer 3 constitute a photosensitive layer.

The electrophotographic photoreceptor 7B shown in FIG. 2 is a function-separated photoreceptor in which the functions are separated into the charge generation layer 2 and the 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.

An electrophotographic photoreceptor 7C shown in FIG. 3 contains a charge generating material and a charge transporting material in the same layer (single-layer 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 monolayer type photosensitive layer 6 and a protective layer 5 are sequentially formed thereon. .

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

Each element will be described below based on the electrophotographic photoreceptor 7A shown in FIG. 1 as a representative example. In addition, the code|symbol is abbreviate|omitted and demonstrated.

(Conductive substrate)
Examples of conductive substrates include metal plates, metal drums, and metal belts containing metals (aluminum, copper, zinc, chromium, nickel, molybdenum, vanadium, indium, gold, platinum, etc.) or alloys (stainless steel, etc.). is mentioned. Examples of conductive substrates include paper, resin films, belts, etc., coated, vapor-deposited, or laminated with conductive compounds (e.g., conductive polymers, indium oxide, etc.), metals (e.g., aluminum, palladium, gold, etc.) or alloys. is also mentioned. Here, "conductivity" means that the volume resistivity is less than 10 ¹³ Ωcm.

When the electrophotographic photoreceptor 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 for the purpose of suppressing interference fringes generated when laser light is irradiated. It is preferable that the surface is roughened to the following. When non-interfering light is used as the light source, roughening is not particularly necessary to prevent interference fringes, but it is suitable for longer life because it suppresses the occurrence of defects due to irregularities on the surface of the conductive substrate.

Surface roughening methods include, for example, wet honing in which an abrasive is suspended in water and sprayed onto the support, centerless grinding in which a conductive substrate is pressed against a rotating grindstone and continuously ground. Examples include anodizing treatment and the like.

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

In the surface roughening treatment by anodization, an oxide film is formed on the surface of a conductive substrate by anodizing a metal (eg, aluminum) conductive substrate as an anode in an electrolytic solution. Examples of electrolyte solutions include sulfuric acid solutions and oxalic acid solutions. However, the porous anodized film formed by anodizing is chemically active as it is, is easily contaminated, and has large resistance fluctuations depending on the environment. Therefore, the micropores of the porous anodized film are filled with pressurized steam or boiling water (a metal salt such as nickel may be added) by volume expansion due to the hydration reaction, thereby achieving more stable hydration and oxidation. It is preferable to perform a pore-sealing treatment that transforms into a product.

The film thickness of the anodized film is preferably 0.3 μm or more and 15 μm or less, for example. When this film thickness is within the above range, there is a tendency for the film to exhibit barrier properties against injection, and the increase in residual potential due to repeated use tends to be suppressed.

The conductive substrate may be treated with an acidic treatment liquid or treated with boehmite.
The treatment with an acidic treatment liquid is performed, for example, as follows. First, an acidic treatment liquid 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, phosphoric acid in the range of 10% by mass to 11% by mass, chromic acid in the range of 3% by mass to 5% by mass, and hydrofluoric acid in the range of 3% by mass to 5% by mass. The range is 0.5% by mass or more and 2% by mass or less, and the concentration of these acids as a whole is preferably in the range of 13.5% by mass or more and 18% by mass or less. The treatment temperature is preferably 42° C. or higher and 48° C. or lower, for example. The film 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 the substrate in pure water at a temperature of 90° C. or higher and 100° C. or lower for 5 to 60 minutes, or by contacting the substrate with heated steam at a temperature of 90° C. or higher and 120° C. or lower for 5 to 60 minutes. The film thickness of the coating is preferably 0.1 μm or more and 5 μm or less. This may be further anodized using an electrolytic solution with 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 inorganic particles include inorganic particles having a powder resistance (volume resistivity) of 10 ² Ωcm or more and 10 ¹¹ Ωcm or less.
Among these, metal oxide particles such as tin oxide particles, titanium oxide particles, zinc oxide particles, and zirconium oxide particles are preferable as the inorganic particles having the above resistance value, and zinc oxide particles are particularly preferable.

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

The content of the inorganic particles is, for example, preferably 10% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 80% by mass or less, relative to the binder resin.

The inorganic particles may be surface-treated. Two or more kinds of inorganic particles having different surface treatments or different particle diameters may be mixed and used.

Examples of surface treatment agents include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and surfactants. In particular, a silane coupling agent is preferred, and a silane coupling agent having an amino group is more preferred.

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

You may use a silane coupling agent in mixture of 2 or more types. 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, etc., but are not limited thereto. not a thing

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 0.5% by mass or more and 10% by mass or less with respect to the inorganic particles, for example.

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

Examples of electron-accepting compounds include quinone compounds such as chloranil and bromoanil; tetracyanoquinodimethane compounds; 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone, and the like. fluorenone compounds; 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)-1,3,4 oxadiazole; xanthone compounds; thiophene compounds; 3,3′,5,5′ tetra- electron-transporting substances such as diphenoquinone compounds such as t-butyldiphenoquinone;
A compound having an anthraquinone structure is particularly preferable as the electron-accepting compound. As the compound having an anthraquinone structure, for example, hydroxyanthraquinone compounds, aminoanthraquinone compounds, aminohydroxyanthraquinone compounds, etc. are preferable, and specifically, for example, anthraquinone, alizarin, quinizarin, anthrafin, purpurin, etc. are preferable.

The electron-accepting compound may be dispersed in the undercoat layer together with the inorganic particles, or may be attached to the surfaces of the inorganic particles.

Examples of the method of adhering 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, an electron-accepting compound dissolved in an organic solvent is added dropwise while stirring inorganic particles with a mixer having a large shearing force, or the electron-accepting compound is sprayed with dry air or nitrogen gas. It is a method of adhering to the surface of inorganic particles. Dropping or spraying of the electron-accepting compound is preferably carried out at a temperature not higher than the boiling point of the solvent. After dropping or spraying the electron-accepting compound, baking may be further performed at 100° C. or higher. Baking is not particularly limited as long as the temperature and time are such that electrophotographic properties can be obtained.

In the wet method, for example, by stirring, ultrasonic waves, sand mill, attritor, ball mill, etc., while inorganic particles are dispersed in a solvent, an electron-accepting compound is added, stirred or dispersed, and then the solvent is removed to obtain electrons. This is a method of adhering a receptive compound to the surface of inorganic particles. Solvent removal methods include distilling off by filtration or distillation. After removing the solvent, baking may be further performed at 100° C. or higher. Baking is not particularly limited as long as the temperature and time are such that electrophotographic properties can be obtained. In the wet method, the water contained in the inorganic particles may be removed before adding the electron-accepting compound, examples of which include a method of removing while stirring and heating in a solvent, and a method of removing by azeotroping with a solvent. mentioned.

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

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

Examples of binder resins used in the undercoat layer include acetal resins (for example, polyvinyl butyral), polyvinyl alcohol resins, polyvinyl acetal resins, casein resins, polyamide resins, cellulose resins, gelatin, polyurethane resins, polyester resins, and unsaturated polyesters. Resins, methacrylic resins, acrylic resins, polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate-maleic anhydride resins, silicone resins, silicone-alkyd resins, urea resins, phenolic resins, phenol-formaldehyde resins, melamine resins, Urethane resins, alkyd resins, known polymer compounds such as epoxy resins; zirconium chelate compounds; titanium chelate compounds; aluminum chelate compounds; titanium alkoxide compounds;
Examples of the binder resin used in the undercoat layer include charge-transporting resins having a charge-transporting group, conductive resins (eg, polyaniline, etc.), and the like.

Among these, resins that are insoluble in the coating solvent of the upper layer are suitable as the binder resin used in the undercoat layer. Thermosetting resins such as resins, alkyd resins and epoxy resins; at least one resin selected from the group consisting of polyamide resins, polyester resins, polyether resins, methacrylic resins, acrylic resins, polyvinyl alcohol resins and polyvinyl acetal resins; 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 according to need.

The undercoat layer may contain various additives for improving electrical properties, improving environmental stability, and improving image quality.
Examples of the additive include known materials such as electron-transporting pigments such as polycyclic condensed and azo-based pigments, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, and silane coupling agents. be done. The silane coupling agent is used for the surface treatment of the inorganic particles as described above, and may be added to the undercoat layer as an additive.

Silane coupling agents as additives include, for example, vinyltrimethoxysilane, 3-methacryloxypropyl-tris(2-methoxyethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- 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.

Examples of zirconium chelate compounds include zirconium butoxide, ethyl zirconium acetoacetate, zirconium triethanolamine, zirconium acetylacetonate butoxide, ethyl zirconium butoxide acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octanoate, Zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, zirconium methacrylate butoxide, zirconium stearate butoxide, zirconium isostearate butoxide and the like.

Examples of titanium chelate compounds include tetraisopropyl titanate, tetra-normal 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 triethanolamine, polyhydroxytitanium stearate, and the like.

Examples of aluminum chelate compounds include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethylacetoacetate aluminum diisopropylate, and aluminum tris(ethylacetoacetate).

These additives may be used alone or as mixtures or polycondensates of multiple compounds.

The undercoat layer preferably has a Vickers hardness of 35 or higher.
The surface roughness (ten-point average roughness) of the undercoat layer is 1/(4n) (n is the refractive index of the upper layer) to 1/2 of the exposure laser wavelength λ used to suppress moiré images. should be adjusted to
Resin particles or the like may be added to the undercoat layer to adjust the surface roughness. Examples of resin particles include silicone resin particles and crosslinked polymethyl methacrylate resin particles. Further, the surface of the undercoat layer may be polished to adjust the surface roughness. Polishing methods include buffing, sandblasting, wet honing, and grinding.

Formation of the undercoat layer is not particularly limited, and a well-known formation method is used. and, if necessary, by heating.

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

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

Examples of methods for applying the undercoat layer-forming coating liquid onto the conductive substrate include blade coating, wire bar coating, spray coating, dip coating, bead coating, air knife coating, and curtain coating. Ordinary methods such as

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

(middle 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 resin. Resins used for the intermediate layer include, for example, acetal resins (for example, polyvinyl butyral, etc.), polyvinyl alcohol resins, polyvinyl acetal resins, casein resins, polyamide resins, cellulose resins, gelatin, polyurethane resins, polyester resins, methacrylic resins, acrylic resins, Polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate-maleic anhydride resins, silicone resins, silicone-alkyd resins, phenol-formaldehyde resins, melamine resins and other high-molecular compounds can be mentioned.
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.
These compounds used for the intermediate layer may be used singly or as a mixture or polycondensate of a plurality of compounds.

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

Formation of the intermediate layer is not particularly limited, and a well-known forming method is used. It is done by heating according to.
As a coating method for forming the intermediate layer, a usual method such as a dip coating method, a thrust coating method, a wire bar coating method, a spray coating method, a blade coating method, a knife coating method and a curtain coating method can be used.

The film thickness of the intermediate layer is preferably set in the range of 0.1 μm or more and 3 μm or less, for example. Note that the intermediate layer may be used as an undercoat layer.

(Charge generating layer)
The charge generation layer is, for example, a layer containing a charge generation material and a binder resin. Also, the charge generation layer may be a deposited layer of a charge generation material. The deposited layer of the charge generating material is suitable for use with non-coherent light sources such as LEDs (Light Emitting Diodes) and organic EL (Electro-Luminescence) image arrays.

Examples of charge-generating materials include azo pigments such as bisazo and trisazo; condensed aromatic pigments such as dibromoanthanthrone; perylene pigments; pyrrolopyrrole pigments;

Among these, it is preferable to use a metal phthalocyanine pigment or a metal-free phthalocyanine pigment as the charge generation material in order to cope with laser exposure in the near-infrared region. Specifically, for example, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591; chlorogallium phthalocyanine disclosed in JP-A-5-98181; -140472, JP-A-5-140473, etc., and titanyl phthalocyanine disclosed in JP-A-4-189873, etc. are more preferable.

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

In the case of using an incoherent light source such as an LED or an organic EL image array having a central emission wavelength of 450 nm or more and 780 nm or less, the above charge generation material may be used. When a thin film is used, the electric field strength in the photosensitive layer becomes high, and charge deterioration due to charge injection from the substrate tends to cause image defects called black spots. This becomes remarkable when a charge-generating material such as trigonal selenium, phthalocyanine pigment, or the like, which is a p-type semiconductor and tends to generate dark current, is used.

On the other hand, when n-type semiconductors such as condensed aromatic pigments, perylene pigments, and azo pigments are used as the charge generation material, dark current is less likely to occur, and image defects called black spots can be suppressed even if the film is formed into a thin film. . Examples of the n-type charge generation 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 the time-of-flight method that is commonly used, and the n-type is defined as a material in which electrons are more likely to flow as carriers than holes.

The binder resin used in 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 binder resins include polyvinyl butyral resins, polyarylate resins (polycondensates of bisphenols and aromatic divalent carboxylic acids, etc.), polycarbonate resins, polyester resins, phenoxy resins, vinyl chloride-vinyl acetate copolymers, Polyamide resin, acrylic resin, polyacrylamide resin, polyvinylpyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinylpyrrolidone resin and the like can be mentioned. Here, “insulating” means having a volume resistivity of 10 ¹³ Ωcm or more.
These binder resins may be used singly or in combination of two or more.

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

The charge generation layer may contain other known additives.

Formation of the charge-generating layer is not particularly limited, and a well-known formation method is used. and, if necessary, by heating. The charge generation layer may be formed by vapor deposition of a charge generation material. Formation of the charge-generating layer by vapor deposition is particularly suitable when a condensed ring aromatic pigment or perylene pigment is used as the charge-generating material.

Solvents for preparing the charge-generating layer-forming coating solution include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, and n-acetic acid. -butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene and the like. These solvents are used singly or in combination of two or more.

Examples of methods for dispersing particles (for example, a charge-generating material) in the coating liquid for forming the charge-generating layer include media dispersing machines such as ball mills, vibrating ball mills, attritors, sand mills, and horizontal sand mills, stirring, ultrasonic dispersing machines, and the like. Medialess dispersers such as roll mills and high-pressure homogenizers are used. The high-pressure homogenizer includes, for example, a collision system in which a dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high pressure state, and a penetration system in which a fine flow path is penetrated and dispersed in a high pressure state.
In this dispersion, it is effective to set the average particle diameter of the charge generating material in the coating liquid for forming the charge generating layer to 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. .

Examples of the method for applying the charge generation layer forming coating liquid onto the undercoat layer (or onto the intermediate layer) include blade coating, wire bar coating, spray coating, dip coating, bead coating, and air knife coating. conventional methods such as coating method, curtain coating method, and the like.

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

(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 comprising a polymeric charge transport material.

Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl and anthraquinone; tetracyanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone; xanthone compounds; cyanovinyl-based compounds; and electron-transporting compounds such as ethylene-based compounds. Charge transport materials also include hole-transporting compounds such as triarylamine-based compounds, benzidine-based compounds, arylalkane-based compounds, aryl-substituted ethylene-based compounds, stilbene-based compounds, anthracene-based compounds, and hydrazone-based compounds. These charge transport materials may be used singly or in combination of two or more, but are not limited to these.

From the viewpoint of charge mobility, the charge transport material is preferably a triarylamine derivative represented by the following structural formula (a-1) and a benzidine derivative represented by the following structural formula (a-2).

In structural formula (a-1), Ar ^T1 , Ar ^T2 and Ar ^T3 each independently represent a substituted or unsubstituted aryl group, —C ₆ H ₄ —C(R ^T4 )=C(R ^T5 )(R ^T6 ), or -C ₆ H ₄ -CH=CH-CH=C(R ^T7 )(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 substituents for the above groups include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Moreover, the substituted amino group substituted by the C1-C3 or less alkyl group is also mentioned as a substituent of each said group.

In structural formula (a-2), R ^{1 T91} and R ^{2 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, or an alkyl group having 1 to 2 carbon atoms. a substituted or unsubstituted aryl group, —C(R ^T12 )=C(R ^T13 )(R ^T14 ), or —CH=CH—CH=C(R ^T15 )(R ^T16 ); 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 substituents for the above groups include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Moreover, the substituted amino group substituted by the C1-C3 or less alkyl group is also mentioned as a substituent of each said group.

Here, among the triarylamine derivative represented by the structural formula (a-1) and the benzidine derivative represented by the structural formula (a-2), in particular, “—C ₆ H ₄ —CH=CH—CH= A triarylamine derivative having “C(R ^T7 )(R ^T8 )” and a benzidine derivative having “—CH═CH—CH═C(R ^T15 )(R ^T16 )” are preferred from the viewpoint of charge mobility.

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

Binder resins used in the charge transport layer include polycarbonate resins, polyester resins, polyarylate resins, methacrylic resins, acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl acetate resins, styrene-butadiene copolymers, 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 - includes vinylcarbazole, polysilane, and the like. Among these, polycarbonate resins and polyarylate resins are suitable as the binder resin. These binder resins are used singly or in combination of two or more.
The mixing ratio of the charge transport material and the binder resin is preferably from 10:1 to 1:5 in mass ratio.

The charge transport layer may contain other known additives.

Formation of the charge transport layer is not particularly limited, and a well-known formation method is used. , by heating if necessary.

Solvents for preparing the coating liquid 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.

Coating methods for coating the charge transport layer forming coating liquid on the charge generation layer include blade coating, wire bar coating, spray coating, dip coating, bead coating, air knife coating, and curtain. Ordinary methods such as a coating method can be used.

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

(protective layer)
The protective layer, which is the outermost layer of the electrophotographic photoreceptor 7A, will be described.
The protective layer is the outermost layer of the electrophotographic photoreceptor 7A, and is preferably formed, for example, using the above-described specific resin solution. Most preferably, it contains a crosslinked resin.

As a cross-linking method, radical polymerization by heat, light, radiation, or the like is performed. If the reaction is adjusted so that it does not proceed too quickly, the occurrence of unevenness and wrinkles in the film is suppressed. From this point of view, thermal cross-linking is suitable because the speed of cross-linking can be easily adjusted.

• Non-reactive charge-transporting material A non-reactive charge-transporting material may be used in combination 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 does not carry out charge-transporting, when the non-reactive charge-transporting material is used for the protective layer (outermost layer) 5, the charge-transporting material is substantially The concentration of the component is increased, which is effective in further improving the electrical properties. A non-reactive charge transport material may also be added to reduce crosslink density and adjust 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, and stilbene-based compounds. , anthracene-based compounds, hydrazone-based compounds, and the like are used.
Among them, 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 liquid for layer formation. and more desirably from 5% by mass to 25% by mass.

・Other additives The protective layer (outermost surface layer) 5 may contain other coupling agents, particularly fluorine-containing coupling agents, for the purpose of further adjusting film-forming properties, flexibility, lubricity, and adhesiveness. may be used. As such compounds, various silane coupling agents and commercially available silicone hard coating agents are used. A silicon compound having a radically polymerizable group and a fluorine-containing compound may also be used.

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

In addition, for imparting water repellency, etc., (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.

Although the silane coupling agent is used in any amount, the amount of the fluorine-containing compound may be 0.25 times or less by mass that of the fluorine-free compound from the viewpoint of forming a crosslinked film. desirable. Furthermore, a reactive fluorine compound or the like disclosed in JP-A-2001-166510 may be mixed.
Silicon compounds having a radically polymerizable group and fluorine-containing compounds include compounds described in JP-A-2007-11005.

The protective layer (outermost layer) 5 may contain a deterioration inhibitor. Preferred anti-degradation agents are hindered phenols and hindered amines, including organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, and benzimidazole antioxidants. , You may use well-known antioxidants, such as.
The amount of the anti-degradation agent to be added is desirably 20% by mass or less, more desirably 10% by mass or less.

Hindered phenol 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 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. , Sumilizer TP-D, and phosphite-based products include Mark 2112, Mark PEP-8, Mark PEP-24G, Mark PEP-36, Mark 329K, Mark HP-10, and the like.

Further, the protective layer (outermost surface layer) 5 may contain conductive particles, organic or inorganic particles.
Examples of such particles include silicon-containing particles. 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 silicon-containing particles preferably has 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. are selected from those distributed over As the particles, commercially available ones may be used.

The solid content of 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. % or more and 30 mass % or less.

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

As for other particles, fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, and vinylidene fluoride are described in "8th Polymer Material Forum Lecture Preprints, p.89". Particles composed of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group, 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 mentioned. Furthermore, various known dispersing agents may be used to disperse the particles.

Moreover, you may add oil, such as a silicone oil.
Examples of silicone oils include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane; 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-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl -cyclic methylphenylcyclosiloxanes such as 1,3,5,7,9-pentaphenylcyclopentasiloxane; cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane; 3-(3,3,3-trifluoropropyl ) fluorine-containing cyclosiloxanes such as methylcyclotrisiloxane; hydrosilyl group-containing cyclosiloxanes such as methylhydrosiloxane mixtures, pentamethylcyclopentasiloxane and phenylhydrocyclosiloxane; vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane Examples include siloxanes and the like.

Also, metals, metal oxides, carbon black, and the like may be added. Examples of metals 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 metal oxides 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 are used alone or in combination of two or more. When two or more of them are used in combination, they may be simply mixed or mixed in solid solution or fusion bonding. The average particle size of the conductive particles is preferably 0.3 μm or less, particularly 0.1 μm or less.

Examples of the composition used for forming the protective layer include the aforementioned specific resin solution.
When reacting the above components with a solvent to obtain a specific resin solution, the components may be simply mixed and dissolved. is 30° C. or more and 80° C. or less, preferably 10 minutes or more and 100 hours or less, more preferably 1 hour or more and 50 hours or less. It is also desirable to irradiate ultrasonic waves at this time.

The protective layer-forming coating solution is applied onto 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, or an air knife. It is applied by an ordinary method such as a coating method, a curtain coating method, an inkjet coating method, or the like.
Thereafter, light, electron beams, or heat is applied to the obtained coating film to cause radical polymerization, thereby cross-linking and curing the coating film.

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 preferably 100° C. or higher and 180° C. or lower.

When the coating film is crosslinked and cured with light, a cured film is obtained by irradiation by a known method such as a mercury lamp or metal halide.

In the cross-linking and curing reactions as described above, the oxygen concentration is desirable in a vacuum or inert gas atmosphere so that the radicals generated by light, electron beams, or heat can be chain-reacted without deactivation. 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 this embodiment, thermal curing methods are particularly preferred in which radical generation occurs relatively slowly.

The film thickness of the protective layer is preferably 3 μm or more and 40 μm or less, more preferably 5 μm or more and 35 μm or less.

The structure of each layer in the function-separated photosensitive layer has been described above with reference to the electrophotographic photoreceptor 7A shown in FIG. configuration can be employed.
The single-layer photosensitive layer 6 of the electrophotographic photoreceptor 7C shown in FIG. 3 will be described below.

(Single layer type photosensitive layer)
The single-layer type photosensitive layer (charge-generating/charge-transporting layer) is a layer containing, for example, a charge-generating material, a charge-transporting material, and, if necessary, a binder resin and other well-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, preferably 0.8% by mass or more and 5% by mass or less, based on the total solid content. . Also, the content of the charge transport material in the single-layer type photosensitive layer is preferably 5% by mass or more and 50% by mass or less with respect to 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 film thickness of the monolayer type photosensitive layer is, for example, 5 μm or more and 50 μm or less, preferably 10 μm or more and 40 μm or less.

In the above-described embodiment, the outermost layer is the protective layer. becomes. When the outermost surface layer is the charge transport layer, the thickness of this layer is desirably 7 μm or more and 70 μm or less, more desirably 10 μm or more and 60 μm or less.

-Image forming apparatus and process cartridge-
Next, an image forming apparatus and a process cartridge using the above electrophotographic photosensitive member will be described.
The image forming apparatus includes, for example, an electrophotographic photosensitive member, charging means for charging the surface of the electrophotographic photosensitive member, electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member, Developing means for developing an electrostatic latent image formed on the surface of an electrophotographic photosensitive member with a developer containing toner to form a toner image, and transferring means for transferring the toner image to the surface of a recording medium. As an electrophotographic photoreceptor, the above electrophotographic photoreceptor is applied.

Examples of the image forming apparatus include an apparatus having fixing means for fixing a toner image transferred to the surface of a recording medium; a direct transfer type apparatus for directly transferring a toner image formed on the surface of an electrophotographic photosensitive member to a recording medium; An intermediate transfer device that primarily transfers a toner image formed on the surface of an electrophotographic photosensitive member to the surface of an intermediate transfer member, and secondarily transfers the toner image that has been transferred on the surface of the intermediate transfer member to the surface of a recording medium; A device equipped with a cleaning means for cleaning the surface of an electrophotographic photosensitive member after transferring a toner image but before charging; A known image forming apparatus such as a device having means; a device having an electrophotographic photoreceptor heating member for increasing the temperature of the electrophotographic photoreceptor and reducing the relative temperature is applied.

In the case of an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body on which a toner image is transferred, and a primary transfer means for primarily transferring a toner image formed on the surface of an electrophotographic photosensitive member to the surface of the intermediate transfer body. A configuration having transfer means and secondary transfer means for secondarily transferring the toner image transferred on the surface of the intermediate transfer member 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 image forming apparatus (a developing type using a liquid developer).

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

An example of the image forming apparatus will be shown below, but the present invention is not limited to this. Note that the main parts shown in the drawings will be explained, and the explanation of the others will be omitted.

FIG. 4 is a schematic configuration diagram showing an example of an image forming apparatus according to this 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 electrostatic latent image forming means), and a transfer device 40 (primary a transfer device) and an intermediate transfer member 50 . In the image forming apparatus 100 , the exposure device 9 is arranged 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 transfers the image to the electrophotographic photosensitive member 7 via the intermediate transfer member 50 . 7 , and the intermediate transfer member 50 is arranged so that a part of the intermediate transfer member 50 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 member 50 onto a recording medium (for example, paper). Note that the intermediate transfer member 50, the transfer device 40 (primary transfer device), and the secondary transfer device (not shown) correspond to an example of transfer means.

The process cartridge 300 in FIG. 4 integrates an electrophotographic photosensitive member 7, a charging device 8 (an example of charging means), a developing device 11 (an example of developing means), and a cleaning device 13 (an example of cleaning means) in a housing. supported by 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 may be a conductive or insulating fibrous member instead of the cleaning blade 131 , and may be used alone or in combination with the cleaning blade 131 .

FIG. 4 shows, as an image forming apparatus, a fibrous member 132 (roll-like) that supplies the lubricant 14 to the surface of the electrophotographic photosensitive member 7, and a fibrous member 133 (flat brush-like) that assists cleaning. are shown, but these are placed as needed.

Each configuration of the image forming apparatus according to the present embodiment will be described below.

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

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

(developing device)
As the developing device 11, for example, a general developing device that develops by contacting or non-contacting a developer can be used. The developing device 11 is not particularly limited as long as it has the functions described above, and is selected according to the purpose. For example, a known developing device having a function of adhering a one-component developer or a two-component developer to the electrophotographic photosensitive member 7 using a brush, a roller, or the like can be used. Among them, it is preferable to use a developing roller holding a developer on its surface.

The developer used in the developing device 11 may be a one-component developer containing only toner, or may be a two-component developer containing toner and carrier. Also, the developer may be magnetic or non-magnetic. As these developers, well-known ones are applied.

(cleaning device)
A cleaning blade type device having a cleaning blade 131 is used as the cleaning device 13 .
In addition to the cleaning blade method, a fur brush cleaning method and a simultaneous development cleaning method may be employed.

(transfer device)
As the transfer device 40, for example, a known transfer charger such as a contact type transfer charger using a belt, roller, film, rubber blade, etc., a scorotron transfer charger using corona discharge, or a corotron transfer charger. mentioned.

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

FIG. 5 is a schematic configuration diagram showing another example of the image forming apparatus.
The image forming apparatus 120 shown in FIG. 5 is a tandem type multi-color image forming apparatus in which four process cartridges 300 are mounted. 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 each color. Note that the image forming apparatus 120 has the same configuration as the image forming apparatus 100 except that it is a tandem system.

-Organic Electroluminescent Device-
An organic electroluminescent element is a device composed of a pair of electrodes, at least one of which is transparent, and one or more 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 aforementioned charge-transporting film.

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

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

Layer structure (1): A function-separated layer structure having a hole-transporting 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 aforementioned charge-transporting film.

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

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

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

7 to 10 are schematic cross-sectional views for explaining the layer structure of the organic electroluminescent device according to this embodiment, and FIGS. FIG. 10 is an example of a case where the organic compound layer is a single layer. In FIGS. 7 to 10, layers having similar functions are denoted by the same reference numerals.

FIG. 7 shows the layer configuration (1) described above.
The organic electroluminescence 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. FIG. 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, the hole transport layer 23 is preferably the charge-transporting film described above in the present embodiment. may be used as the aforementioned charge-transporting film in this embodiment.

FIG. 8 shows the layer configuration (2) described above.
The organic electroluminescence 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 disposed between the electron transport layer 25 and the back electrode 27 . In the embodiment shown in FIG. 8, the hole transport layer 23 is preferably the charge transport film described above in the present embodiment. may be used as the aforementioned charge-transporting film in this embodiment.

FIG. 9 shows the layer configuration (3) described above.
The organic electroluminescence 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 insulating substrate 21. FIG. An electron injection layer may be disposed 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 described above in this embodiment. In this case, the aforementioned charge-transporting film in this embodiment contains at least one light-emitting material.

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

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

When a top emission structure is used, or when both electrodes are transparent electrodes, a structure in which the layer structures shown in FIGS. 7 to 10 are stacked in multiple stages may be used.

Each layer in FIGS. 7 to 10 will be described in more detail below.

Regarding the transparent insulator substrate 21, being transparent 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. Materials for 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 surface-treated or may have a laminated structure for the purpose of suppressing water permeability and gas permeability.

As with the transparent insulator substrate 21, the transparent electrode 22 is preferably transparent in order to extract emitted light and has a large work function in order to inject holes, preferably an electrode having a work function of 4 eV or more.

Regarding the transparent electrode 22, being transparent means that the transmittance of light in the visible region is 10% or more, and the transmittance is preferably 75% or more.
Materials for 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; 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 composed of a hole transport material, a hole injection material, an electron transport material, an electron injection material, and a light emitting material, depending on their functions. Including selected materials.
When the organic compound layer is the aforementioned charge-transporting film in the present embodiment, a composition obtained by mixing a hole-transporting compound having a crosslinkable group and an electron-transporting compound having a crosslinkable group together with these materials is used. It may be layered.

Examples of hole-transporting materials include tetraphenylenediamine derivatives, triphenylamine derivatives, carbazole derivatives, stilbene derivatives, arylhydrazone derivatives, and porphyrin compounds, including tetraphenylenediamine derivatives, spirofluorene derivatives, and triphenylamine derivatives. .

Examples of hole injection materials include phenylenediamine derivatives, phthalocyanine derivatives, indanthrene derivatives, polyalkylenedioxythiophene derivatives, and the like. may be mixed.

Examples of electron transport materials include oxadiazole derivatives, nitro-substituted fluorenone derivatives, diphenoquinone derivatives, thiopyran dioxide derivatives, silole derivatives, chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, triazole derivatives, and fluorenylidene. methane derivatives and the like.

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

Compounds that exhibit high emission quantum efficiency in a solid state are desirable as light-emitting materials. The luminescent material may be either a low-molecular-weight compound or a high-molecular-weight compound.
Organic low-molecular-weight compounds include chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, coumarin derivatives, styrylarylene derivatives, silole derivatives, oxazole derivatives, oxathiazole derivatives, and oxadiazole derivatives.
Examples of organic polymer compounds include polyparaphenylene derivatives, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyacetylene derivatives.

Specific examples of the luminescent material include the following exemplary compounds (VI-1) to (VI-17).
The following exemplary compounds (VI-1) to (VI-17) may be used as electron transport materials.

In 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 improving the luminous efficiency of the organic electroluminescence device, the luminescent material may be doped with a dye compound different from the luminescent material as a guest material.
The doping amount of the dye compound is preferably 0.001 to 40 parts by mass, more preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the host.

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, osnium, iridium. , platinum, and metal complex compounds such as gold; and the like.
Specific examples of dye compounds for doping include Exemplary Compounds (VII-1) to (VII-6).

Each organic compound layer may contain a binder resin.
Binder resins include polycarbonate resins, polyester resins, methacrylic resins, acrylic resins, polyvinyl chloride resins, cellulose resins, urethane resins, epoxy resins, polystyrene resins, polyvinyl acetate resins, styrene-butadiene copolymers, and vinylidene chloride-acrylonitrile. Conductive resins such as copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, silicon resins, poly-N-vinylcarbazole resins, polysilane resins, polythiophenes, and polypyrroles can be mentioned.
Each organic compound layer may contain known antioxidants, ultraviolet absorbers, plasticizers and the like, if necessary.

As the material of the back electrode 27, a material that can be vacuum-deposited and has a small work function for electron injection is preferable, and a metal, a metal oxide, and a metal fluoride are preferable.
Metals include magnesium, aluminum, gold, silver, indium, lithium, calcium and alloys thereof.
Metal oxides include lithium oxide, magnesium oxide, aluminum oxide, indium tin oxide, tin oxide, indium oxide, zinc oxide, and indium zinc oxide.
Metal fluorides include lithium fluoride, magnesium fluoride, strontium fluoride, calcium fluoride, and aluminum fluoride.

A protective layer may be provided on the back electrode 27 .
Materials for 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; are 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, preferably 0.001 μm or more and 5 μm or less.

The organic electroluminescence device shown in FIGS. 7 to 10 is produced by sequentially forming a transparent electrode 22 , each organic compound layer, and a back electrode 27 on a transparent insulating 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 liquid obtained by dissolving or dispersing a material in an appropriate solvent is coated on the transparent electrode 22 and the coating film is dried.
Examples of the coating method of the coating liquid include a spin coating method, a die coating method, an inkjet method, a casting method, and a dipping method.

The state in which each material is contained in the organic compound layer may be a state in which molecules are dispersed (molecularly dispersed state) or a state in which particles are formed and dispersed (particle dispersed state).
In order to obtain a molecularly dispersed state in the film forming method using the coating liquid, the solvent of the coating liquid is selected in consideration of the dispersibility and solubility of each material.
In the film forming method using a coating liquid, a ball mill, sand mill, paint shaker, attritor, homogenizer, or ultrasonic wave is used to prepare the coating liquid in order to make the particles dispersed.

An image display medium is constructed by arranging the organic electroluminescent devices according to the present embodiment in a matrix or in a segment.
When the organic electroluminescent elements are arranged in a matrix, only the electrodes may be arranged in a matrix, or the electrodes and the organic compound layer may be arranged in a matrix.
When the organic electroluminescence elements are arranged in a segment, only the electrodes may be arranged in a segment, or the electrodes and the organic compound layer may be arranged in a segment.
The matrix-like or segment-like organic compound layer may be formed by an inkjet method.

Driving devices and driving methods for matrix-shaped organic electroluminescent elements and segment-shaped organic electroluminescent elements are disclosed in Japanese Patent Application Laid-Open Nos. 2-148687, 6-301355, 5-29080, and 7. -134558, JP-A-8-234685, JP-A-8-241047, Japanese Patent No. 2784615, US Pat. No. 5,828,429, US Pat. No. 6,023,308, etc. applicable.

Examples and comparative examples will be described below, 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 the compound 3-5, a compound represented by the general formula (3A) and having the combination of A ¹ , T ¹ and p as the specific example number (2-5) was prepared.
A 500 ml flask was charged with 80 g of compound 3-5, 230 g of epichlorohydrin, 26.8 g of sodium hydroxide and 3 g of triethylamine, and after nitrogen substitution, the mixture was stirred at room temperature (25° C.) for 24 hours. After the reaction, it was washed with a dilute hydrochloric acid aqueous solution and then with water. After concentration, purification was performed by silica gel chromatography to obtain 64 g of compound 4-5.
The compound 4-5 is represented by the above general formula (4A), and the combination of A ² , T ² and q is the above specific example number (2-5).

As the compound 3-29, a compound represented by the general formula (3A) and having the combination of A ¹ , T ¹ and p represented by the above specific example number (2-29) was prepared.
A 2000 ml flask was charged with 79.8 g of compound 3-29, 700 ml of tetrahydrofuran, and 1.8 g of boron trifluoride diethyl ether complex, and the atmosphere was purged with nitrogen and heated to 50°C. A solution of 50.0 g of compound 4-5 dissolved in 200 ml of tetrahydrofuran was added dropwise to this solution over 30 minutes. After completion of the dropwise addition, the mixture was allowed to react for 2 hours, and then added dropwise to 10 L of methanol to precipitate a polymer. The obtained polymer was thoroughly washed with methanol and dried to obtain 107.0 g of resin (A-1), which is resin number (A-1) shown as a specific example of the first charge-transporting resin. rice field.
When the molecular weight was measured by GPC, it was 60000 in terms of polystyrene. Moreover, the value of said M _H /(M _H +M _P ) was 1.0.

<Synthesis Example A2>
10 g of Resin (A-1) obtained in Synthesis Example A1 was put into a 300 ml flask, 18 g of 4-iodomethylstyrene and 0.1 g of nitrobenzene were put into the flask, and 100 ml of tetrahydrofuran was added to dissolve them. To this, 5.8 g of t-butoxysodium was added at room temperature (25°C) over 2 hours, and then 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 then added dropwise to 500 ml of methanol to precipitate a polymer. The resulting polymer was thoroughly washed with methanol and dried to obtain 10.1 g of resin (A-2), which is the resin number (A-2) shown as a specific example of the first charge-transporting resin. rice field.
When the molecular weight was measured by GPC, it was 61000 in terms of polystyrene. In addition, the value of M _H /(M _H +M _P ) was zero.

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

<Synthesis Example A4>
A specific example of the first charge-transporting resin was shown in the same manner as in Synthesis Example A2, except that the amount of 4-iodomethylstyrene added was 1.8 g and the amount of t-butoxysodium added was 0.5 g. 9.9 g of resin (A-4), which is resin number (A-4), was obtained.
When the molecular weight was measured by GPC, it was 60000 in terms of polystyrene. Moreover, the value of said M _H /(M _H +M _P ) was 0.85.

<Synthesis Example A5>
A specific example of the first charge-transporting resin was shown in the same manner as in Synthesis Example A2, except that the amount of 4-iodomethylstyrene added was 9.0 g and the amount of t-butoxysodium added was 2.9 g. 9.9 g of resin (A-5), which is the resin of number (A-5), was obtained.
When the molecular weight was measured by GPC, it was 60000 in terms of polystyrene. In addition, the value of M _H /(M _H +M _P ) was 0.45.

<Synthesis Example A6>
As the compound 3-17, a compound represented by the general formula (3A) and having the combination of A ¹ , T ¹ and p represented by the specific example number (2-17) was prepared.
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 after nitrogen substitution, the mixture was stirred at room temperature (25° C.) for 24 hours. After the reaction, it was washed with a dilute hydrochloric acid aqueous solution and then with water. After concentration, purification was performed by silica gel chromatography to obtain 74.5 g of compound 4-17.
Compound 4-17 is represented by general formula (4A) above, and the combination of A ² , T ² and q is specific example number (2-17) above.

A 1000 ml flask was charged with 39.4 g of compound 3-17, 700 ml of tetrahydrofuran, and 1.0 g of boron trifluoride diethyl ether complex, and the atmosphere was purged with nitrogen and heated to 50°C. A solution prepared by dissolving 45.2 g of compound 4-17 in 200 ml of tetrahydrofuran was added dropwise to this solution over 30 minutes. After completion of the dropwise addition, the mixture was allowed to react for 2 hours, and then added dropwise to 10 L of methanol to precipitate a polymer. The obtained polymer was thoroughly washed with methanol and dried to obtain 75.0 g of resin (A-6), which is resin number (A-6) shown as a specific example of the first charge-transporting resin. rice field.
When the molecular weight was measured by GPC, it was 40,000 in terms of polystyrene. Moreover, the value of said M _H /(M _H +M _P ) was 1.0.

<Synthesis Example A7>
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 g of triethylamine are placed in a 200 ml flask and reacted at room temperature (25° C.) for 24 hours. bottom. After completion of the reaction, the mixture was added dropwise to 1 L of methanol to precipitate a polymer. The resulting polymer was thoroughly washed with methanol and dried to obtain 7.1 g of resin (A-7), which is the resin number (A-7) shown as a specific example of the first charge-transporting resin. rice field.
When the molecular weight was measured by GPC, it was 41000 in terms of polystyrene. In addition, the value of M _H /(M _H +M _P ) was zero.

<Synthesis Example A8>
Into a 500 ml flask, 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 ml of triethylamine are added, and reacted at room temperature (25° C.) for 24 hours. bottom. After completion of the reaction, the mixture was added dropwise to 1 L of methanol to precipitate a polymer. The resulting polymer was sufficiently washed with methanol and dried to obtain 7.4 g of resin (A-8), which is resin number (A-8) shown as a specific example of the first charge-transporting resin. rice field.
When the molecular weight was measured by GPC, it was 40,000 in terms of polystyrene. In addition, the value of 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 numbered (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. ).

<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. Stir at 40° C. for 48 hours. After completion of the reaction, the mixture was added dropwise to 1 L of methanol to precipitate a polymer. The obtained polymer was thoroughly washed with methanol and dried to obtain 7.8 g of resin (A-32), which is the resin number (A-32) shown as a specific example of the first charge-transporting resin. rice field.
When the molecular weight was measured by GPC, it was 31000 in terms of polystyrene. In addition, the value of M _H /(M _H +M _P ) was 0.45.

<Synthesis Example A33>
The number (A- 7.9 g of resin (A-33), which is the resin of 33), was obtained.
When the molecular weight was measured by GPC, it was 31000 in terms of polystyrene. In addition, the value of M _H /(M _H +M _P ) was zero.

<Synthesis Example A34>
Resin No. (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 resin (A-34) was obtained.
When the molecular weight was measured by GPC, it was 31000 in terms of polystyrene. In addition, the value of M _H /(M _H +M _P ) was zero.

<Synthesis Example B1>
Compound A-4 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-4, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (that is, a dicarboxylic acid monomer corresponding to Specific Example AT-4) was prepared.
Further, the compound B-2 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-2, and Z ² A non-charge-transporting diol monomer (product name: Blenmer 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), 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. under a stream of nitrogen while stirring. 6.83 g (0.044 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 4 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-1 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 28,000.

<Synthesis Example B2>
Compound A-4 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-4, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (that is, a dicarboxylic acid monomer corresponding to Specific Example AT-4) was prepared.
Further, the compound B-43 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example 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.
In a flask, 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), 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. under a stream of nitrogen while stirring. 6.83 g (0.044 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 4 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with stirring in 200 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 11.17 g of Resin B-2 (Resin B-2 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of Resin B-2 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 27,000.

<Synthesis Example B3>
The compound A-6 is represented by the general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-6, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (that is, a dicarboxylic acid monomer corresponding to Specific Example AT-6) was prepared.
Further, the compound B-2 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-2, and Z ² A non-charge-transporting diol monomer (product name: Blenmer GLM, manufactured by NOF Corporation) in which the group represented by is a hydroxyl group was prepared.
Into a flask, compound A-6 (molecular weight 465.54) 5.00 g (0.0107 mol), compound B-2 (molecular weight 160.17) 1.89 g (0.0118 mol), 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. under a stream of nitrogen while stirring. 3.67 g (0.024 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight: 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 4 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-3 was measured by GPC, the polystyrene-equivalent weight average molecular weight 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 stirred at 80° C. for 1 hour. After that, once the temperature was 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 reacted at 80°C for 5 hours. rice field. After the reaction, toluene was added, washed with water, concentrated, and purified by silica gel chromatography to obtain 147.61 g of compound B-3 (molecular weight: 194.23).
The compound B-3 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of Specific Example Y-3, and Z ² is A non-charge-transporting diol monomer in which the groups shown are hydroxyl groups.

The compound A-6 is represented by the general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-6, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (that is, a dicarboxylic acid monomer corresponding to Specific Example AT-6) was prepared.
In a flask, compound A-6 (molecular weight 465.54) 5.00 g (0.0107 mol), compound B-3 (molecular weight 194.23) 2.29 g (0.0118 mol), 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. under a stream of nitrogen while stirring. 3.67 g (0.024 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight: 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 4 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-4 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 26,000.

<Synthesis Example B5>
Compound A-18 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-18, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-18) was prepared.
Further, the compound B-2 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-2, and Z ² A non-charge-transporting diol monomer (product name: Blenmer GLM, manufactured by NOF Corporation) in which the group represented by is a hydroxyl group was prepared.
In a flask, compound A-18 (molecular weight 784.94) 6.65 g (0.0085 mol), compound B-2 (molecular weight 160.17) 1.43 g (0.0089 mol), 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 cooled to 0° C. while stirring under a nitrogen stream. 2.89 g (0.0186 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 7 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-11 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 12,000.

<Synthesis Example B6>
Glycidol (molecular weight 74.08) 74.08 g (1.0 mol), 4-vinylbenzoic acid (molecular weight 148.16) 148.16 g (1.0 mol), tetrabutylammonium chloride (molecular weight 277.92) were placed in a 2 L flask. 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 under reflux for 7 hours under a nitrogen stream. After the reaction, the product was washed with water, concentrated, and purified by silica gel chromatography to obtain 184.46 g of compound B-5 (molecular weight: 222.24).
The compound B-5 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of Specific Example Y-5, and Z ² is A non-charge-transporting diol monomer in which the groups shown are hydroxyl groups.

Compound A-18 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-18, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-18) was prepared.
In a flask, compound A-18 (molecular weight 784.94) 6.65g (0.0085mol), compound B-5 (molecular weight 222.24) 1.98g (0.0089mol), 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 cooled to 0° C. while stirring under a nitrogen stream. 2.89 g (0.0186 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 7 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-13 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 16,000.

<Synthesis Example B7>
Compound A-43 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-43, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-43) was prepared.
Further, the compound B-2 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-2, and Z ² A non-charge-transporting diol monomer (product name: Blenmer GLM, manufactured by NOF Corporation) in which the group represented by is a hydroxyl group was prepared.
In a flask, compound A-43 (molecular weight 861.03) 7.75g (0.009mol), compound B-2 (molecular weight 160.17) 1.59g (0.0099mol), 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 cooled to 0° C. while stirring under nitrogen flow. 3.07 g (0.0198 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 7 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-20 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 14,000.

<Synthesis Example B8>
A 2 L flask was charged with 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: 277.92) 27.79 g (0.1 mol), nitrobenzene (molecular weight 123.06) 1.23 g (0.01 mol), and methyl ethyl ketone 700 ml were added, and the mixture was heated under reflux for 7 hours under a nitrogen stream. After the reaction, the product was washed with water, concentrated, and purified by silica gel chromatography to obtain 143.55 g of compound B-23 (molecular weight: 214.26).
The compound B-23 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-23, and Z ² A non-charge-transporting diol monomer in which the groups shown are hydroxyl groups.

Compound A-43 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-43, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-43) was prepared.
In a flask, compound A-43 (molecular weight 861.03) 7.75g (0.009mol), compound B-23 (molecular weight 214.26) 2.12g (0.0099mol), 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 cooled to 0° C. while stirring under nitrogen flow. 3.07 g (0.0198 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 7 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with stirring in 100 ml of methanol. The solid collected by filtration was vacuum-dried 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 Resin B-21 was measured by GPC, the polystyrene-equivalent weight average molecular weight 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 under reflux for 7 hours under a nitrogen stream. After the reaction, the product was washed with water, concentrated, and purified by silica gel chromatography to obtain 198.05 g of compound B-30 (molecular weight: 314.37).
The compound B-30 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-30, and Z ² A non-charge-transporting diol monomer in which the groups shown are hydroxyl groups.

Compound A-43 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-43, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-43) was prepared.
In a flask, compound A-43 (molecular weight 861.03) 7.75 g (0.009 mol), compound B-30 obtained in the above synthesis example (molecular weight 314.37) 3.11 g (0.0099 mol), 4- 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. 3.07 g (0.0198 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 7 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-24 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 14,000.

<Synthesis Example B10>
Compound A-47 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-47, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-47) was prepared.
Further, the compound B-41 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example 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, compound A-47 (molecular weight 764.95) 6.88 g (0.009 mol), compound B-41 (molecular weight 360.40) 3.57 g (0.0099 mol), 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 cooled to 0° C. while stirring under nitrogen flow. 3.07 g (0.0198 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 10 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with stirring in 200 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 8.65 g of Resin B-26 (Resin B-26 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of Resin B-26 was measured by GPC, the polystyrene-equivalent weight average molecular weight 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 under reflux for 7 hours under nitrogen stream. After the reaction, the product was washed with water, concentrated, and purified by silica gel chromatography to obtain 361.59 g of compound B-39 (molecular weight: 430.45).
The compound B-39 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-39, and Z ² A non-charge-transporting diol monomer in which the groups shown are hydroxyl groups.

Compound A-64 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-64, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-64) was prepared.
A flask was charged with 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), 4-dimethylaminopyridine (molecular weight 122.99 mol). 17) 2.25 g (0.0184 mol), 50 ml of tetrahydrofuran, and 15 ml of N-methylpyrrolidone were added and cooled to 0° C. while stirring under nitrogen flow. 3.07 g (0.0198 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 14 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-28 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 29,000.

<Synthesis Example B12>
In a 2 L flask, 9,9-bis(4-glycidyloxyphenyl)fluorene (molecular weight 462.55) 231.28 g (0.5 mol), methacrylic acid (molecular weight 86.06) 86.06 g (1.0 mol), tetra 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 under reflux for 7 hours under a nitrogen stream. . After the reaction, the reaction mixture was washed with water, concentrated, and purified by silica gel chromatography to obtain 246.63 g of compound B-60 (molecular weight: 758.85).
The compound B-60 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-60, and Z ² is A non-charge-transporting diol monomer in which the groups shown are hydroxyl groups.

Compound A-64 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-64, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-64) was prepared.
A flask was charged with 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), 4-dimethylaminopyridine (molecular weight 122.99 mol). 17) 2.25 g (0.0184 mol), 50 ml of tetrahydrofuran, and 15 ml of N-methylpyrrolidone were added and cooled to 0° C. while stirring under nitrogen flow. 3.07 g (0.0198 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 14 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with stirring in 200 ml of methanol. The solid collected by filtration was vacuum-dried to obtain 11.34 g of Resin B-29 (Resin B-29 shown as a specific example of the second charge-transporting polyester resin). When the molecular weight of Resin B-29 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 32,000.

<Synthesis Example B13>
Compound A-67 is represented by general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-67, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (ie, a dicarboxylic acid monomer corresponding to Specific Example AT-67) was prepared.
Further, the compound B-54 is represented by the general formula (4B), the combination Y (that is, the combination of O—Y ³ —O, n3, and Y ⁴ ) is the combination of specific example Y-54, and 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, compound A-67 (molecular weight 716.91) 6.45 g (0.009 mol), compound B-54 (molecular weight 512.59) 5.07 g (0.0099 mol), 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 cooled to 0° C. while stirring under nitrogen flow. 3.07 g (0.0198 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 14 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-30 was measured by GPC, the polystyrene-equivalent weight average molecular weight 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 - 700 ml of methylpyrrolidone was added and stirred at room temperature for 1 hour. After that, 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, washed with water, concentrated, and purified by silica gel chromatography to obtain 150.25 g of compound B-61 (molecular weight: 190.19).
The compound B-61 is represented by the general formula (4B), the combination Y (that is, the combination of O-Y3-O, n3, and Y4) is a combination of specific examples Y-61, and the group represented by Z2 is a non-charge-transporting diol monomer in which is a hydroxyl group.

The compound A-6 is represented by the general formula (3B), and the combination AT (that is, the combination of A ³ and T ³ ) is the combination of specific example AT-6, and the group represented by Z ¹ is a hydroxyl group. A charge-transporting monomer (that is, a dicarboxylic acid monomer corresponding to Specific Example AT-6) was prepared.

In a flask, compound A-6 (molecular weight 465.54) 5.00 g (0.0107 mol), compound B-61 (molecular weight 190.19) 2.24 g (0.0118 mol), 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. under a stream of nitrogen while stirring. 3.67 g (0.024 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight: 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 4 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-31 was measured by GPC, the polystyrene-equivalent weight average molecular weight 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 stirred at room temperature for 1 hour. After that, 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, washed with water, concentrated, and purified by silica gel chromatography to obtain 110.26 g of compound B-62 (molecular weight: 162.14).
The compound B-62 is represented by the general formula (4B), the combination Y (that is, the combination of O-Y3-O, n3, and Y4) is a combination of specific examples Y-62, and the group represented by Z2 is a non-charge-transporting diol monomer in which is a hydroxyl group.

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

In a flask, compound A-18 (molecular weight 784.94) 6.65g (0.0085mol), compound B-62 (molecular weight 162.14) 1.44g (0.0089mol), 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 cooled to 0° C. while stirring under a nitrogen stream. 2.89 g (0.0186 mol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (molecular weight 155.24) was added thereto, and the reaction temperature was gradually returned to room temperature (25°C). Stirred for 7 hours. Thereafter, the reaction solution was added dropwise to water for reprecipitation, and diluted hydrochloric acid was added for neutralization. The solid collected by filtration was washed with 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 Resin B-32 was measured by GPC, the polystyrene-equivalent weight average molecular weight was 15,000.

<Example A1-1>
-Preparation of undercoat layer-
100 parts of zinc oxide (average particle diameter: 70 nm: Tayca: specific surface area value: 15 m ² /g) was 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.) was added. and stirred for 2 hours. After that, toluene was distilled off under reduced pressure, and baking was carried out at 120° C. for 3 hours to obtain silane coupling agent surface-treated zinc oxide.
110 parts of the surface-treated zinc oxide was stirred and mixed with 500 parts of tetrahydrofuran, 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 alizarin-imparted zinc oxide was separated by filtration under reduced pressure, and dried under reduced pressure at 60° C. to obtain alizarin-imparted zinc oxide.

60 parts of this alizarin-imparted zinc oxide, 13.5 parts of a curing agent (blocked isocyanate, Sumidur 3175, manufactured by Sumitomo Bayern Urethane) and 15 parts of butyral resin (S-Lec BM-1, manufactured by Sekisui Chemical Co., Ltd.) were added to 85 parts of methyl ethyl ketone. and 25 parts of methyl ethyl ketone were mixed and dispersed in a sand mill for 2 hours using glass beads of 1 mmφ to obtain a dispersion liquid.
To the resulting dispersion were added 0.005 parts of dioctyltin dilaurate as a catalyst and 45 parts of silicone resin particles (Tospearl 145, manufactured by Momentive Performance Materials) to obtain an undercoat layer coating liquid. This coating liquid was applied to an aluminum substrate having a diameter of 30 mm, a length of 340 mm and a thickness of 1 mm by dip coating, 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°, and 28.0° A mixture of 15 parts of hydroxygallium phthalocyanine having a diffraction peak at 1 mmφ, 10 parts of vinyl chloride/vinyl acetate copolymer resin (VMCH, manufactured by NUC Co., Ltd.) as a binder resin, and 200 parts of n-butyl acetate It was dispersed for 4 hours in a sand mill using glass beads. 175 parts of n-butyl acetate and 180 parts of methyl ethyl ketone were added to the resulting dispersion, and the mixture was stirred to obtain a charge generation layer coating liquid. This charge generation layer coating solution was dip-coated on the undercoat layer and dried at room 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 parts of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight: 354.4) were added to 40 parts of chlorobenzene and dissolved to prepare a charge transport layer coating solution. got This coating solution was applied onto the charge generating layer by push-up coating, air-dried at room temperature (20° C.) for 30 minutes, and then dried under nitrogen with an oxygen concentration of 200 ppm from room temperature (20° C.) at a rate of 10° C./min to 150°C. C. and cured by heat treatment at 150.degree.

-Evaluation of image quality-
The electrophotographic photoreceptor prepared as described above was mounted on ApeosPort-IV C4470 manufactured by Fuji Xerox Co., Ltd., and under low temperature and low humidity (8° C., 20% RH) and high temperature and high humidity (30° C., 85% RH). , the following evaluations were performed consecutively.

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

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

(ghost evaluation)
As for the ghost, a pattern chart having G and a gray area with an image density of 50% was printed as shown in FIG.
A: Good or slight as shown in FIG. 6(A).
B: Slightly conspicuous as shown in FIG. 6(B).
C: Clearly confirmed as shown in FIG. 6(C).

(Fog evaluation)
The evaluation of fog was made by visually observing the degree of toner adhering to the white background using the same sample as the evaluation of the ghost described above.
A: Good.
B: Slight fogging is observed.
C: Fog that poses a problem in terms of image quality is observed.

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

(Image deletion evaluation)
Image smearing was judged visually using the same sample as the ghost evaluation described above.
A: Good.
B: No problem during continuous print test, but occurred after leaving for 1 day (24 hours).
C: Occurs even during continuous print test.

-Evaluation of Residual Potential Rise-
The residual potential was measured by the following method, and the increase in 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., Ltd., 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 The residual potential after 10,000 sheets) was measured. The difference between the initial potential and the residual potential after 10,000 sheets (residual potential after 10,000 sheets−initial potential) was defined as the “increase in residual potential”. Table 2 shows the results.

-Evaluation of Abrasion Amount of Charge Transport Layer-
The initial film thickness of the photoreceptor (that is, the total film thickness of the undercoat layer, charge generation layer, and charge transport layer) before performing the image formation test, The film thickness of the photoreceptor was measured by an eddy current measuring device (Fisherscope MMS) after the image forming test was completed under a high-temperature and high-humidity (30° C., 85% RH) environment, and the amount of wear was evaluated. Table 2 shows the results.

<Examples A1-2 to A1-7>
The method described in Example A1-1 was followed up to the preparation of the charge generating layer.
Then, an electrophotographic photoreceptor was prepared in the same manner as in Example A1-1, except that the first charge-transporting resin shown in Table 1 was used in place of the resin (A-2) in the preparation of the charge-transporting layer. made and evaluated. 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., Ltd., molecular weight: 354.4) was not added in the preparation of the charge transport layer. An electrophotographic photoreceptor was produced and evaluated in the same manner as in -1. Evaluation results are shown in Tables 2 and 3.

<Examples A1-9 to A1-10>
The method described in Example A1-1 was followed up to the preparation of the charge generation layer.
Then, in the preparation of the charge transport layer, the first charge transport resin shown in Table 1 was used instead 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 part of boron trifluoride diethyl ether complex was used instead of . Evaluation results are shown in Tables 2 and 3.

<Example A1-11>
The method described in Example A1-1 was followed until the preparation of the charge generation layer.
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, (manufactured by BASF) was dissolved in 40 parts of monochlorobenzene, and the resulting solution was applied onto 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 an oxygen concentration of 200 ppm under the following conditions: 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, it was dried at 130° C. for 20 minutes to form a surface layer having a thickness of 17 μm to prepare an electrophotographic photosensitive member, which was evaluated by the method described in Example A1-1. Evaluation results are shown in Tables 2 and 3.

<Example A1-12>
The method described in Example A1-1 was followed up to the preparation of the charge generating layer.
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) It was dissolved in 40 parts of monochlorobenzene, and the resulting solution was applied onto 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 treatment was performed at 150°C for 1 hour to cure. , an electrophotographic photoreceptor was prepared by forming a charge transport layer having a thickness of 18 μm, and was evaluated by the method described in Example A1-1. Evaluation results are shown in Tables 2 and 3.

<Example A1-13>
The method described in Example A1-1 was followed up to the preparation of the charge generating layer.
Then, 10 parts of the resin (A-2) obtained in Synthesis Example A2 and 0.8 parts of polytetrafluoroethylene fine particles (Lubron L-2, manufactured by Daikin Industries, Ltd.) were dissolved in 40 parts of monochlorobenzene, and a nanomizer (NM2 -L200AR-D08, manufactured by Nanomizer), 0.2 parts of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight 354.4) are added and dissolved, and the resulting solution is charged with a push-up coat. Coated on the 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 with an oxygen concentration of 200 ppm, and heat treatment was performed at 150°C for 1 hour to cure. , an electrophotographic photoreceptor was prepared by forming a charge transport layer having a thickness of 18 μm, and was evaluated by the method described in Example A1-1. Evaluation results are shown in Tables 2 and 3.

<Example A1-14>
The method described in Example A1-1 was followed up to the preparation of the charge generating layer.
On this charge generation layer, 40 parts by weight of N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1']biphenyl-4,4'-diamine (TPD), N, 10 parts by weight of N-bis(3,4-dimethylphenyl)biphenyl-4-amine and 55 parts by weight of bisphenol Z polycarbonate resin (PC(Z): viscosity average molecular weight: 60,000) were added to 800 parts by weight of chlorobenzene and dissolved. The resulting 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, 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 resulting solution was applied onto the charge transport layer by push-up coating. After air-drying at room temperature (20° C.) for 30 minutes, the photoreceptor was rotated at a speed of 300 rpm under nitrogen with an oxygen concentration of 20 ppm. The photoreceptor was irradiated with an electron beam under the condition that the irradiation time was 1.0 second. Immediately after the irradiation, the mixture was heated to 150° C. under nitrogen with an oxygen concentration of 20 ppm and held for 10 minutes to complete the curing reaction, forming a protective layer having a thickness of 4 μm to prepare an electrophotographic photoreceptor. Evaluation was performed by the method described in -1. Evaluation results are shown in Tables 2 and 3.

<Examples B1-1 to B1-15>
The method described in Example A1-1 was followed up to the preparation of the charge generating layer.
Then, an electrophotographic photoreceptor was prepared in the same manner as in Example A1-1, except that the second charge-transporting polyester resin shown in Table 1 was used instead of the resin (A-2) in the preparation of the charge-transporting layer. was produced and evaluated. Evaluation results are shown in Tables 2 and 3.

<Comparative Example 1-1>
The method described in Example A1-1 was followed up to the preparation of the charge generation layer.
Then, in the preparation of the charge transport layer, Example A1 was prepared except that Comparative Resin 1 (poly(9-vinylcarbazole), manufactured by Sigma-Aldrich, number average molecular weight: 25000) was used instead of Resin (A-2). An electrophotographic photoreceptor was produced and evaluated in the same manner as in -1. Evaluation results are shown in Tables 2 and 3.

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

<Comparative Example 1-3>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example A1-14, except that the thickness of the charge generating layer was 25 μm and no protective layer was formed. Evaluation results are shown in Tables 2 and 3.

From the results shown in Tables 2 and 3, it can be seen that the electrophotographic photoreceptors of Examples are capable of suppressing deterioration in image quality after repeated use over a long period of time.

<Example A2-1>
-Production of organic EL element-
A glass substrate provided with an ITO film having a thickness of 150 nm was cleaned with oxygen plasma for 30 seconds using a plasma cleaner (BP1, manufactured by Samco International). Furthermore, after washing by immersing in each liquid in the order of neutral detergent, water, acetone (for electronic industry, manufactured by Kanto Chemical) and isopropanol (for electronic industry, manufactured by Kanto Chemical) and applying ultrasonic waves for 5 minutes each, Dried with a spin coater.
A solution obtained by dissolving 3 parts by mass of the resin (A-2) and 0.06 parts by mass of OTazo-15 (Otsuka Chemical Co., Ltd., molecular weight 354.4) in 97 parts by mass of dichloromethane was added to a PTFE filter having a pore size of 0.1 μm. to obtain a coating liquid. The coating liquid was spin-coated onto the glass substrate. The number of revolutions was adjusted so as to obtain a film thickness (400 nm), which will be described later. By heating at 160° C. for 1 hour in an inert gas atmosphere with an oxygen concentration of 150 ppm, a hole transport layer having a thickness of 400 nm (measured with a stylus thickness gauge) was formed.

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

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

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

The smoothness of the coating film during the formation of the charge-transporting film was evaluated as follows. Specifically, after the charge-transporting film (hole-transporting layer) of the present invention was produced, the film was cut out with a cutter or the like, and the surface roughness Ra was measured using a surface profiler DEKTAK6M (manufactured by ULVAC). , was evaluated according to the following criteria.
The measurement conditions were based on JIS B0601 (1994) with a measurement length of 4 mm, a measurement speed of 0.3 mm/sec, a cutoff wavelength of 0.8 mm, and a cutoff type of 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

(Solvent resistance evaluation of charge-transporting film)
After forming the hole transport layer and before vapor-depositing the light-emitting layer, the charge-transporting film provided as the hole transport layer was evaluated for solvent resistance. Specifically, an ultraviolet-visible absorption measurement was performed on a 2.5 cm square film to be measured, and the absorbance (absorbance before standing in toluene) at the wavelength (λmax) showing the maximum value on the long wavelength side was determined. After that, the charge-transporting film was placed on the pedestal of a spin coater, and 2 ml of toluene was placed on the film and allowed to stand still for 30 seconds. An absorption measurement was performed to determine the absorbance at λmax (absorbance after removal of toluene).
The residual film ratio was calculated from the following formula, and the solvent resistance of the film was evaluated according to the following criteria. Table 5 shows the results.
Formula: Remaining film ratio = (absorbance after toluene removal/absorbance before toluene standing) x 100 (%)
A: Remaining film rate is 95% or more B: Remaining film rate is 90% or more and less than 95% C: Remaining film rate is less than 90%

<Example A2-2>
Example A2-1 was repeated except that resin (A-2) was replaced with 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. An organic EL device was produced and evaluated by the described method. Also, 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>
An organic EL device was produced and evaluated 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. Also, 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>
An organic EL device was produced and evaluated 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. Also, 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>
Resin (A-1) in Example A2-2 to Comparative Resin 2 (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], manufactured by Sigma-Aldrich, number average molecular weight: 7000) An organic EL device was produced and evaluated by the method described in Example A2-2, except that it was changed. Also, 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 fabricated and evaluated by the method described in Example A2-1, except that a hole transport layer formed by vacuum deposition of biphenyl-4,4'-diamine (TPD) to a film thickness of 400 nm was used. 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 devices of Examples can provide stable light emission characteristics over a long period of time.
Further, from the results of the solvent resistance of the charge-transporting film, it can be seen that when a layer is formed by coating on the charge-transporting film of the present invention in the future, mixing at the interface between both layers is suppressed. . Therefore, it can be expected that the organic electroluminescence device of the applied lamination type will also exhibit good luminescence characteristics.

REFERENCE SIGNS LIST 1 undercoat layer 2 charge generation layer 3 charge transport layer 4 conductive substrate 5 protective layer 6 single layer 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, 50 intermediate transfer member 100 image forming apparatus 120 image forming apparatus 131 cleaning blade 132 fibrous member (roll shape) 133 fibrous member (flat brush shape) 300 process cartridge

Claims (13)

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


(In the general formula (1B), A ³ represents a divalent organic group having charge transport properties, and T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. , Y ³ represents a (n3+2)-valent non-charge-transporting diol residue, n3 represents 1 or 2, Y ⁴ represents "*-(CH ₂ ) _n4 -LZ", * represents Y ³ , n4 is 1 or 2, L is a divalent linking group or a single bond composed of at least one atom selected from carbon atoms, oxygen atoms, and hydrogen atoms. , Z represents a polymerizable functional group, and the polymerizable functional group is a group represented by the following general formula (P1), a group represented by the following general formula (P2), or a group represented by the following general formula (P3). is at least one selected from a group represented by the following general formula (P4), and a group represented by the following general formula (P5).)


(In general formulas (P1) to (P5), R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * represents 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) The organic electronic device of claim 1 , wherein there is one.


(In the above formulas (P1-1), (P1-2), and (P3-1), * indicates the binding position.) 3. The organic electronic device according to claim 1 , wherein ^A3 in the general formula (1B) represents a divalent organic group capable of transporting holes. The organic electronic device according to claim ³ , wherein A3 in the general formula (1B) represents 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 is a substituted or unsubstituted divalent and k and m each independently represent 0 or 1.) The organic electron according to any one of claims 1 to 4 , wherein T ³ in the general formula (1B) represents a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms. device. The organic electronic device according to any one of claims 1 to 5 , 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. The organic electron according to any one of claims 1 to 6 , wherein the number of atoms other than hydrogen atoms among the atoms constituting said L in Y ⁴ in said general formula (1B) is 1 or more and 10 or less. device. The number of atoms other than hydrogen atoms among the atoms constituting Y ³ in the general formula (1B), the number of the n4 in Y ⁴ in the general formula (1B), and Y ⁴ in the general formula (1B) The organic electronic device according to any one of claims 1 to 7 , wherein the total number of atoms other than hydrogen atoms among the atoms constituting said L in the organic electronic device is 25 or less. 9. The organic electronic device according to claim 1, wherein the charge-transporting film contains a crosslinked product of the second charge-transporting polyester resin. 10. The organic electronic device according to any one of claims 1 to 9 , wherein the organic electronic device is an electrophotographic photoreceptor. 11. The organic electronic device according to claim 10 , comprising a charge-transporting film containing a crosslinked body of the second charge-transporting polyester resin as the outermost layer of the electrophotographic photosensitive member. The organic electronic device according to any one of claims 1 to 9 , wherein the organic electronic device is an organic electroluminescence element. A charge-transporting film containing at least one selected from a second charge-transporting polyester resin having a structure represented by the following general formula (1B) and a crosslinked product of the second charge-transporting polyester resin.


(In the general formula (1B), A ³ represents a divalent organic group having charge transport properties, and T ³ represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. , Y ³ represents a (n3+2)-valent non-charge-transporting diol residue, n3 represents 1 or 2, Y ⁴ represents "*-(CH ₂ ) _n4 -LZ", * represents Y ³ , n4 is 1 or 2, L is a divalent linking group or a single bond composed of at least one atom selected from carbon atoms, oxygen atoms, and hydrogen atoms. , Z represents a polymerizable functional group, and the polymerizable functional group is a group represented by the following general formula (P1), a group represented by the following general formula (P2), or a group represented by the following general formula (P3). is at least one selected from a group represented by the following general formula (P4), and a group represented by the following general formula (P5).)


(In general formulas (P1) to (P5), R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and * represents a bonding position.)

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