JP2013073015A - Charge transport polyester resin, charge transport polyester resin solution, photoelectric conversion device, and electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charge transport polyester resin which provides a film having both an excellent electrical property and resistance to external stimulation.SOLUTION: Provided is a charge transport polyester resin represented by the general formula (1). In the general formula (1), A represents a divalent organic group having a charge transport property, T represents a linear or branched chain divalent hydrocarbon group with the carbon number 1-10, and n represents an integer from 5 to 5000.

Description

  The present invention relates to a charge transporting polyester resin, a charge transporting polyester resin solution, a photoelectric conversion device, and an electrophotographic photosensitive member.

In recent years, electronic devices using organic compounds such as electrophotographic photosensitive members, 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, for example, an organic EL device using a heat or photocured film (for example, see Patent Document 1), containing a charge transporting group An electrophotographic photoreceptor using an acrylic polymer (for example, see Patent Documents 2 to 4), and an electrophotographic photoreceptor obtained by crosslinking an acrylic polymer containing a charge transporting group and a reactive group after film formation (see, for example, Patent Document 5). ), A film obtained by applying and curing a liquid containing a photocurable acrylic monomer (see, for example, Patent Document 6), and the like. In addition, a mixture of a monomer having a carbon-carbon double bond, a charge transfer material having a carbon-carbon double bond, and a binder resin is subjected to heat or light energy to form the carbon-carbon double bond of the monomer and the charge transfer material. In particular, a film formed by reacting a carbon-carbon double bond is disclosed. In particular, a monofunctional methacryl-modified charge transfer material, a methacrylic monomer having no charge transport property, and a polycarbonate resin are combined with an organic solvent. What hardened | cured using the oxide is disclosed (for example, refer patent document 7).

  Also disclosed are organic semiconductor films, electrophotographic photoreceptors (see, for example, Patent Document 8) and the like, which are formed by introducing a functional group into the terminal of the charge transporting polyester resin and curing the film.

International Publication No. 2009/733193 Japanese Patent Laid-Open No. 5-202135 JP-A-6-256428 Japanese Patent Laid-Open No. 9-12630 Japanese Patent Laying-Open No. 2005-2291 JP-A-5-40360 JP-A-5-216249 JP 2001-117252 A

  An object of the present invention is to provide a charge transporting polyester resin having excellent electrical properties and resistance to external stimuli in a film formed using the same.

The above object is achieved by the present invention described below.
That is, the invention according to claim 1
It is a charge transporting polyester resin represented by the following general formula (1).

[In the general formula (1), A represents a divalent organic group having a charge transport property, T represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, n Represents an integer of 5 or more and 5000 or less. ]

The invention according to claim 2
2. The charge transporting polyester resin according to claim 1, wherein the A in the general formula (1) is a divalent organic group having a hole transporting property.

The invention according to claim 3
The charge transporting polyester resin according to claim 1 or 2, wherein A in the general formula (1) is a group represented by the following general formula (2).

[In the general formula (2), R ₁ and R ₂ are each independently hydrogen, an alkyl group, an alkoxy group, a halogen, a substituted or unsubstituted aryl group, and X is a substituted or unsubstituted divalent organic group. , K and m each independently represent 0 or 1. ]

The invention according to claim 4
X in the general formula (2) is a substituted or unsubstituted divalent aromatic group, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, substituted or unsubstituted. The charge transporting polyester resin according to claim 3, which represents a divalent condensed aromatic hydrocarbon group having 2 to 10 aromatic rings, or a substituted or unsubstituted divalent aromatic heterocyclic group.

The invention according to claim 5
The charge transporting polyester resin according to claim 3 or 4, wherein X in the general formula (2) is a divalent organic group selected from the group (A) shown below.

The invention according to claim 6
The charge transporting polyester resin according to any one of claims 3 to 5, wherein the X in the general formula (2) is a divalent organic group selected from the group (B) shown below. is there.

The invention according to claim 7 provides:
A charge transporting polyester resin solution in which the charge transporting polyester resin defined in claim 1 is dissolved in a solvent.

The invention according to claim 8 provides:
Photoelectric conversion provided with a film containing a polyester polymer having a structure represented by the following general formula (1) as a partial structure, or a polyester crosslinked polymer having a structure represented by the following general formula (1 ') as a partial structure It is a device.

[In the general formulas (1) and (1 ′), A represents a divalent organic group having a charge transporting property, and T represents a linear or branched divalent group having 1 to 10 carbon atoms. N represents an integer of 5 or more and 5000 or less. Further, in the general formula (1 ′), it represents that crosslinking polymerization is performed at the position of [*]. ]

The invention according to claim 9 is:
The photoelectric conversion device according to claim 8, wherein the film contains a polyester cross-linked polymer having a structure represented by the general formula (1 ′) as a partial structure.

The invention according to claim 10 is:
An electron comprising a photosensitive layer containing a polyester polymer having a structure represented by the following general formula (1) as a partial structure, or a polyester crosslinked polymer having a structure represented by the following general formula (1 ′) as a partial structure It is a photographic photoreceptor.

[In the general formulas (1) and (1 ′), A represents a divalent organic group having a charge transporting property, and T represents a linear or branched divalent group having 1 to 10 carbon atoms. N represents an integer of 5 or more and 5000 or less. Further, in the general formula (1 ′), it represents that crosslinking polymerization is performed at the position of [*]. ]

The invention according to claim 11 is:
The electrophotographic photosensitive member according to claim 10, wherein the photosensitive layer contains a polyester cross-linked polymer having a structure represented by the general formula (1 ′) as a partial structure.

  According to the invention of claim 1, compared to a material other than the charge transporting polyester resin represented by the general formula (1), a charge having excellent electrical characteristics and resistance to external stimuli in a film formed using the resin A transportable polyester resin is provided.

  According to the invention of claim 2, compared to the case where A in the general formula (1) is not a divalent organic group having hole transportability, the film formed using the same has excellent hole transportability. A charge transporting polyester resin is provided.

  According to the invention according to claim 3, the charge transporting polyester resin having excellent hole transporting property in the film formed by using the resin other than the charge transporting polyester resin represented by the general formula (2). Is provided.

  According to the invention of claim 4, X in the general formula (2) is a substituted or unsubstituted divalent aromatic group, a substituted or unsubstituted divalent polynuclear aromatic having 2 to 10 aromatic rings. Compared with the case where it is not a hydrocarbon group, a divalent condensed aromatic hydrocarbon group having 2 or more and 10 or less substituted or unsubstituted aromatic rings, or a substituted or unsubstituted divalent aromatic heterocyclic group, A charge transporting polyester resin having excellent hole transportability in the formed film is provided.

  According to the invention of claim 5, the hole transportability is excellent in the film formed using X as compared with the case where X in the general formula (2) is not a divalent organic group selected from the group (A). A charge transporting polyester resin is provided.

  According to the invention of claim 6, compared to the case where X in the general formula (2) is not a divalent organic group selected from the group (B), excellent hole transportability in a film formed using it A charge transporting polyester resin is provided.

  According to the seventh aspect of the invention, compared with the case where the charge transporting polyester resin represented by the general formula (1) is not dissolved, the film formed using the resin has excellent electrical characteristics and resistance to external stimuli. There is provided a charge transporting polyester resin solution having:

  According to the invention of claim 8, a polyester polymer having a structure represented by the general formula (1) as a partial structure or a polyester crosslinked polymer having a structure represented by the general formula (1 ′) as a partial structure. A photoelectric conversion device having excellent electrical characteristics and excellent solvent resistance is provided as compared with a case where a film to be contained is not provided.

  According to the invention of claim 9, a photoelectric conversion device having excellent solvent resistance as compared with a case where a film containing a polyester cross-linked polymer having a structure represented by the general formula (1 ′) as a partial structure is not provided. Is provided.

  According to the invention which concerns on Claim 10, the polyester polymer which has the structure represented by general structure (1 ') as a partial structure or the polyester crosslinked polymer which has a structure represented by general formula (1') as a partial structure An electrophotographic photoreceptor excellent in electrical characteristics and mechanical resistance is provided as compared with a case where the photosensitive layer is not provided.

  According to the eleventh aspect of the present invention, the electrophotographic photosensitive member is excellent in mechanical resistance as compared with the case where the photosensitive layer containing the polyester cross-linked polymer having the partial structure represented by the general formula (1 ′) is not provided. The body is provided.

FIG. 3 is a schematic partial cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member according to the present embodiment. FIG. 5 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the electrophotographic photosensitive member according to the embodiment. FIG. 5 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the electrophotographic photosensitive member according to the embodiment. 1 is a schematic cross-sectional view of an image forming apparatus including a process cartridge according to an embodiment. 1 is a schematic sectional view of a tandem type image forming apparatus according to an embodiment. (A) (B) (C) is explanatory drawing which shows the reference | standard of ghost evaluation, respectively. FIG. 3 is a schematic partial cross-sectional view illustrating an example of a layer configuration of the organic electroluminescent element of the present embodiment. The schematic fragmentary sectional view which shows another example of the layer structure of the organic electroluminescent element of this embodiment. The schematic fragmentary sectional view which shows another example of the layer structure of the organic electroluminescent element of this embodiment. The graph which shows IR spectrum of the charge transportable polyester resin synthesize | combined in the Example. The graph which shows IR spectrum of the charge transportable polyester resin synthesize | combined in the Example. The graph which shows IR spectrum of the charge transportable polyester resin synthesize | combined in the Example.

  Hereinafter, embodiments of the present invention will be described in detail.

<Charge transporting polyester resin>
The charge transporting polyester resin according to this embodiment is represented by the following general formula (1).

[In the general formula (1), A represents a divalent organic group having a charge transport property, T represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, n Represents an integer of 5 or more and 5000 or less. ]

The charge transporting polyester resin represented by the general formula (1) has a relatively small number of polar groups that impede carrier transport such as —OH and —NH— as polar groups. Presumably, the formation of traps to be captured is suppressed, and the accumulation of residual potential is suppressed.
Therefore, the thickness of the film to be formed can be further increased while obtaining excellent electrical characteristics.

  In addition, for the purpose of increasing the strength of the formed film, the charge transport material may be mixed with a polyfunctional acrylic monomer, or the charge transport material may or may not have a polymerizable functional group. When forming a film, the charge transporting polyester resin represented by the general formula (1) has an ester structure similar to that of the polyfunctional acrylic monomer, or has or has the polymerizable functional group. Therefore, it is presumed that a film having electrical characteristics and strength can be obtained by cross-linking without causing phase separation, because it has a charge transporting structure similar to that of a non-charge transporting material.

Furthermore, by forming a film using the charge transporting polyester resin represented by the general formula (1), it is possible to easily obtain a thin film in which crystallization is suppressed and thickness unevenness is suppressed. It is presumed to be excellent.
In addition, by setting it as a crosslinked structure, a film with much higher heat resistance and solvent resistance can be obtained, and stable performance can be obtained over a long period of time.

-Explanation of each group in General formula (1)-
A in the charge transporting polyester resin represented by the general formula (1) represents a divalent organic group having charge transporting properties, and specifically includes a phthalocyanine compound, a porphyrin compound, an azobenzene compound, and a triaryl. Divalent organic groups derived from amine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, quinone compounds, fluorenone compounds, etc. It is done. Among these, those having a triarylamine skeleton, a benzidine skeleton, and a stilbene skeleton are preferable.

  In particular, A in the general formula (1) is preferably a structure represented by the following general formula (2).

[In the general formula (2), R ₁ and R ₂ are each independently hydrogen, an alkyl group, an alkoxy group, a halogen, a substituted or unsubstituted aryl group, and X is a substituted or unsubstituted divalent organic group. , K and m each independently represent 0 or 1. ]

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

The “polynuclear aromatic hydrocarbon group” represents a hydrocarbon group in which two or more aromatic rings composed of carbon and hydrogen are present, and the rings are bonded by a carbon-carbon bond. Specifically, a hydrocarbon group in which carbons constituting an aromatic ring are directly bonded by a carbon-carbon bond, or aromatic rings are connected by a carbon chain having 1 to 18 carbon atoms (an alkyl chain or an alkylene chain). The hydrocarbon group etc. which are made are mentioned.
Specific examples of the polynuclear aromatic hydrocarbon group include divalent groups in which one hydrogen atom is removed, such as biphenyl, terphenyl, stilbene, and triphenylethylene.
The aromatic ring constituting the polynuclear aromatic hydrocarbon group may be a condensed aromatic hydrocarbon group described later or an aromatic heterocyclic ring. Specific examples of the condensed aromatic hydrocarbon group and the aromatic heterocyclic ring constituting the polynuclear aromatic hydrocarbon group include the same compounds as the specific examples described later.

  “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 adjacent to each other and bonded together. Represents a group. Specifically, a divalent group obtained by removing one hydrogen atom such as naphthalene, anthracene, phenanthrene, pyrene, perylene, fluorene, and the like can be given.

“Aromatic heterocycle” refers to an aromatic ring containing 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 or Nr = 6. Further, the type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not limited. Examples of the hetero atom include a sulfur atom, a nitrogen atom, and an oxygen atom. In addition, the aromatic heterocycle may contain two or more heteroatoms in the ring skeleton, and may contain two or more heteroatoms.

  In particular, examples of the heterocyclic ring having a ring skeleton structure of Nr = 5 (that is, a five-membered ring structure) include, for example, thiophene, thiofin, pyrrole, furan, or a heterocycle in which the 3- and 4-position carbons are further substituted with nitrogen. A ring etc. are mentioned. Examples of the heterocyclic ring having a ring skeleton structure of Nr = 6 (that is, a 6-membered ring structure) include a pyridine ring.

Examples of the substituent of the aromatic ring, polynuclear aromatic ring and condensed aromatic ring include a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a substituted amino group, and a halogen atom.
As an alkyl group, a C1-C10 thing is desirable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group etc. are mentioned.
As an alkoxyl group, a C1-C10 thing is desirable, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group etc. are mentioned.
As the aryl group, those having 6 to 20 carbon atoms are desirable, and examples thereof include a phenyl group and a toluyl group.
As the aralkyl group, those having 7 to 20 carbon atoms are desirable, and examples thereof include a benzyl group and a phenethyl group.
Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, an aralkyl group, and the like, and specific examples are as described above.
Examples of the substituent for the substituted aryl group and the substituted aralkyl group include a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, and a halogen atom.

  Examples of X in the general formula (2) include groups selected from the following formulas (1) to (7).

In formulas (1) to (7), R ⁷ 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 ^{8 to} R ¹⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom. , A means 0 or 1, and V represents at least one group selected from the following formulas (8) to (17).

  In the above formulas (8) to (17), b represents an integer of 1 to 10, and c represents an integer of 1 to 3.

  In addition, as X in General formula (2), the bivalent organic group selected from the group (A) shown below is preferable, Furthermore, the bivalent organic group selected from the group (B) shown below is further. Particularly preferred.

R ₁ and R ₂ in the general formula (2) each independently represent hydrogen, an alkyl group, an alkoxy group, a halogen, a substituted or unsubstituted aryl group.
As an alkyl group, a C1-C10 thing is desirable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group etc. are mentioned.
As an alkoxyl group, a C1-C10 thing is desirable, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group etc. are mentioned.
Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As the aryl group, those having 6 to 20 carbon atoms are desirable, and examples thereof include a phenyl group and a toluyl group.
Examples of the substituent of the substituted aryl group include a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, and a halogen atom.

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

T in the general formula (1) represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. In the case where the divalent hydrocarbon group is linear, the carbon number is preferably in the range of 1 to 6, more preferably in the range of 2 to 6, and the divalent hydrocarbon group is branched. In this case, the carbon number is preferably in the range of 2 to 10 and more preferably in the range of 3 to 7.
Examples of specific structures of the group represented by T (hydrocarbon group T-1 to hydrocarbon group T-32) are shown below. However, the arylamine skeleton (that is, A in the general formula (1)) may be bonded to either side of the following hydrocarbon group.

  N in the general formula (1) represents an integer of 5 or more and 5000 or less, more preferably 7 or more and 4500 or less, and particularly preferably 10 or more and 4000 or less.

  Hereinafter, specific examples of the charge transporting polyester resin in which A in the general formula (1) is the general formula (2) will be shown, but the invention is not limited to these specific examples.

In the table below, the numbers described in the columns “R ₁ ” and “R ₂ ” represent the position of the bond. Moreover, the value described in the column of “T” means the numbers (T-1) to (T-32) given to the structural formulas of the hydrocarbon groups specifically shown above. In the “T” column, for example, when “T-5r” is described, an arylamine skeleton (that is, on the right side of the structure T-5, and when “T-5l” is described, the left side of the structure T-5 (ie, , A) in the general formula (1) is bound. Further, in the following table, the value shown in “bonding position” indicates that the bond is at the numerical position described in the benzene ring in the general formula (2), and when k is 1, The benzene ring in the parenthesis indicates that it is bonded to the same position as the benzene ring on which the number is written.

Next, the synthesis method will be described.
The charge transporting polyester resin according to the present embodiment is synthesized with the following combinations as monomers.
(1) In the case of HO-TA-T-OH and itaconic acid The diol component monomer and itaconic acid are mixed in an equivalent amount and polymerized using an acid catalyst. As the acid catalyst, those used for usual esterification reaction such as sulfuric acid, toluenesulfonic acid, trifluoroacetic acid and the like are used, and preferably 1 / 10,000 parts by mass or more and 1/10 of 1 part by mass of the dicarboxylic acid component monomer. It is used in the range of not more than part by mass, more preferably not less than 1/1000 parts by mass and not more than 1/50 parts by mass. In order to remove water generated during the polymerization, it is preferable to use a solvent that can be azeotroped with water, and toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and are preferably used with respect to 1 part by mass of the generated polymer. Is used in the range of 1 to 100 parts by mass, more preferably 2 to 50 parts by mass. The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization.

  When the solvent is not used after completion of the reaction, it is dissolved in a solvent that can be dissolved. When a solvent is used, the reaction solution is dropped as it is into a poor solvent in which alcohols such as methanol and ethanol and polymers such as acetone are difficult to dissolve, to precipitate a charge transporting polyester resin, and charge transporting polyester After separating the resin, it is washed with water or an organic solvent and dried.

  Furthermore, you may repeat the reprecipitation process which melt | dissolves in a suitable organic solvent, is dripped in a poor solvent, and deposits a charge transportable polyester resin. The reprecipitation treatment is preferably carried out with efficient stirring using a mechanical stirrer or the like. The solvent for dissolving the charge transporting polyester resin in the reprecipitation treatment is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 2 parts by mass or more and 50 parts by mass or less with respect to 1 part by mass of the polymer to be generated. It is used in the range. Further, the poor solvent is preferably used in an amount of 1 to 1000 parts by mass, more preferably 10 to 500 parts by mass with respect to 1 part by mass of the polymer to be produced. After completion of the reaction, the reaction solution is poured into water, extracted with a solvent such as toluene, hexane, or ethyl acetate, washed with water, and if necessary, purified using an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay. You may go.

(2) In the case of HO-TA-T-OH and itaconic acid diester Itaconic acid diester is added in an amount equal to or more than 3 equivalents to HO-TA-T-OH. For example, Experimental Chemistry Course, 4th edition 28, p. As described in 217 and the like, it can be synthesized by transesterification by heating using an organometallic compound such as titanium, tin, and zinc, or an inorganic acid such as sulfuric acid and phosphoric acid as a catalyst. The catalyst is preferably used in an amount of 1 / 10,000 parts by mass or more and 1 part by mass or less, more preferably 1/1000 parts by mass or more and 1/2 part by mass or less with respect to 1 part by mass of the polymer to be produced. The reaction is preferably carried out at a reaction temperature of 100 ° C. or more and 300 ° C. or less, and in order to accelerate the polymerization, the reaction is preferably carried out under a reduced pressure of 0.01 mmHg to 100 mmHg, more preferably 0.05 mmHg to 20 mmHg. Moreover, you may make it react, removing excess itaconic acid diester using high boiling-point solvents, such as 1-chloro naphthalene.

(3) In the case of B-T-A-T-B and itaconic acid (B represents chlorine, bromine and iodine)
B-T-A-T-B and itaconic acid are mixed in an equivalent amount, and organic bases such as pyridine, piperidine, dimethylaminopyridine, trimethylamine, DBU, and triethylamine, sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide, Polymerize using an inorganic base such as potassium hydroxide. The base is preferably used in an amount of 1 equivalent to 10 equivalents, more preferably 2 equivalents to 5 equivalents, relative to itaconic acid. Solvents include methylene chloride, diethyl ether, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, Is effective, and is preferably used in the range of 1 to 100 parts by mass, more preferably 2 to 50 parts by mass with respect to 1 part by mass of the polymer to be produced. The reaction temperature can be arbitrarily set. After the polymerization, reprecipitation treatment is performed as described above, and purification is performed.

  The charge transporting polyester resin may be only one kind of -TAT-component and itaconic acid component, but a charge transporting component having a structure different from -TAT-component or a charge transporting component You may mix the monomer which does not have. As the monomer having no charge transport component, isophthalic acid, terephthalic acid, adipic acid, its acid chloride, or dimethyl ester is used as the dicarboxylic acid component, and ethylene glycol, propylene glycol, diethylene glycol are used as the diol component. Bisphenol and the like are used.

  Among these synthesis methods, the method (1) or (3) is preferable because it is easy to obtain a high molecular weight polymer. Further, the ratio of the number of units [J] having a charge transporting property and the number of units [K] having no charge transporting property in the polymer is 0.5 ≦ [J] / [J] + [K] ≦ 1. More preferably, 0.7 ≦ [J] / [J] + [K] ≦ 1, more preferably 0.8 ≦ [J] / [J] + [K] ≦ 1.

  The degree of polymerization p of the charge transporting polyester resin is used in the range of 5 or more and 5000 or less, preferably 7 or more and 3000 or less, more preferably 10 or more and 1000 or less. Furthermore, k in the general formula (2) represents an integer selected from 0 or 1, and k is preferably 1.

The charge transporting polyester resin according to this embodiment is applied to an electrophotographic photosensitive member or an organic electroluminescent element, and may contain an insulating polymer that is singly or compatible with it.
Specifically, a structure in which a layer containing the charge transporting polyester resin is provided on a support is used as the organic electronic device. A typical example of the organic electronic device includes an electrophotographic photosensitive member having a photosensitive layer, and in particular, the one containing the charge transporting polyester resin of the present embodiment in the surface layer of the electrophotographic photosensitive member. . In addition, as the charge transport material in the photosensitive layer, an electrophotographic photoreceptor containing the charge transporting polyester resin of the present embodiment and a known charge generating material, particularly an electrophotographic photoreceptor containing a phthalocyanine compound crystal is also preferable.
As the phthalocyanine crystal used in combination with the charge transporting polyester resin in the electrophotographic photosensitive member in the present embodiment, a gallium halide phthalocyanine crystal disclosed in JP-A-5-98181, Tin halide 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, The oxytitanium phthalocyanine hydrate crystals disclosed in JP-A 189873 and JP-A-5-43813 are used.

<Charge transporting polyester resin solution>
The charge transporting polyester resin solution according to this embodiment is obtained by dissolving the charge transporting polyester resin represented by the general formula (1) in a solvent.

  Solvents include aromatics such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran and dioxane, cellosolves such as ethylene glycol monomethyl ether, and the like. Solvents such as alcohols such as isopropyl alcohol and butanol are used alone or as a mixed solvent.

  In addition, as a dissolution method for dissolving the charge transporting polyester resin represented by the general formula (1) in these solvents, stirring and mixing with a solvent at 10 ° C. to 150 ° C., preferably 15 ° C. to 120 ° C., or It can be carried out by a usual method such as stirring with sonication.

  The charge transporting polyester resin solution according to the present embodiment is used, for example, for forming a film in a photoelectric conversion device (organic EL device, electrophotographic photosensitive member, etc.), forming a solar cell, an organic transistor, or the like.

<Photoelectric conversion device>
Next, the photoelectric conversion device will be described.
The charge transporting polyester resin according to the present embodiment can form a film using a solution in which the charge transporting polyester resin is dissolved. Further, this film may contain a cross-linked product obtained by polymerizing the charge transporting polyester resin.
A cured film obtained by mixing and curing the charge transporting polyester resin with a resin such as a polycarbonate resin, a polyarylate resin, or a polyester resin, or a monomer, oligomer, or polymer having a double bond is also preferably used.

Non-reactive binder resin When the above charge transporting polyester resin is compatible with the resin, known non-reactive binder resins such as polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, etc. A reactive binder resin may be mentioned.

  The total content of the non-reactive binder resin is desirably 0% by mass or more and 60% by mass or less, and more desirably 0% by mass or more and 55% by mass with respect to the total solid content of the composition used for forming the film. % Or less, more desirably 0% by mass or more and 50% by mass or less.

-Reactive compound When cured, the charge transporting polyester resin represented by the general formula (1) may further contain a reactive compound, and in particular, a monomer containing two or more double bonds in the same molecule. It is preferable to cure by mixing an oligomer or polymer.

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

  As a reactive compound, bifunctional monomers include, for example, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane. Examples include diol di (meth) acrylate, divinylbenzene, diallyl phthalate.

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

  As the reactive compound, examples of the tetrafunctional monomer include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and aliphatic tetra (meth) acrylate.

  As a reactive compound, pentafunctional or higher monomers include, for example, (pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.), polyester skeleton, urethane skeleton, phosphazene skeleton (meth) acrylate, etc. Is mentioned.

  Further, as reactive compounds, reactive polymers include, for example, JP-A-5-216249, JP-A-5-323630, JP-A-11-52603, JP-A-2000-264961, and JP-A-2005. Examples disclosed in Japanese Patent No. 2291.

  When using a reactive compound, it is used individually or in mixture of 2 or more types. The reactive compound is preferably used in an amount of 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less, based on the total solid content of the composition used for forming the film. The

-Polymerization and curing When using a solution in which the charge transporting polyester resin is dissolved to obtain a cured film by polymerizing the components in the solution, heat, light, radiation, etc. are generated during the polymerization. Used. When polymerization and curing are performed with heat and light, a polymerization initiator is not necessarily required, but a photocuring catalyst or a thermal polymerization initiator may be used. As this photocuring catalyst and thermal polymerization initiator, a known photocuring catalyst or thermal polymerization initiator is used. The radiation is preferably an electron beam.

-Electron beam curing-
When an electron beam is used, the acceleration voltage is preferably 300 KV or less, and more 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, damage caused by electron beam irradiation on the characteristics of the photoreceptor is suppressed. Further, when the dose is 1 Mrad or more, crosslinking is performed, and when the dose is 100 Mrad or less, deterioration of the photoreceptor is suppressed.

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

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

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

Examples of the photocuring catalyst include intramolecular cleavage types such as benzyl ketal, alkylphenone, aminoalkylphenone, phosphine oxide, titanocene, and oxime.
More specifically, examples of the benzyl ketal system include 2,2-dimethoxy-1,2-diphenylethane-1-one.

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

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

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

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

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

Examples of the hydrogen abstraction type include benzophenone series, thioxanthone series, benzyl series, and Michler ketone series.
More specifically, examples of the benzophenone series include 2-benzoylbenzoic acid, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, p, p′-bisdiethylaminobenzophenone, and the like. Can be mentioned.

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

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

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

-Thermosetting-
As thermal polymerization initiators, V-30, V-40, V-59, V601, V65, V-70, VF-096, VE-73, Vam-110, Vam-111 (manufactured by Wako Pure Chemical Industries), OTazo -15, OTazo-30, AIBM, AMBN, ADVN, ACVA (Otsuka Chemical) and other azo initiators; Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H, Park Mill H, Park Mill H P, Permenta H, Perocta H, Perbutyl C, Perbutyl D, Parhexyl D, Parroyl IB, Parroyl 355, Parroyl L, Parroyl SA, Nipper BW, Nipper BMT-K40 / M, Parroyl IPP, Parroyl NPP, Parroyl TCP, Parroyl OPP , Parroyl SBP, Park Mill D, 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), Kayaketal AM-C55, Trigonox 36-C75, Laurox, Parkadox L-W75, Parkadox CH-50L, Trigonox TMBH, Kayacumene H, Kayabutyl H-70, Percadox BC-FF, Kaya Hexa AD, Parka Dox 14, Kaya Butyl C, Kaya Butyl D, Kaya Hexa YD-E85, Parka Dox 12-XL25, Cadox 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, Kaya ester P-70, Kaya ester TMPO-70, Trigonox 121, Kaya ester O, Kaya ester HTP-65W, Kaya ester AN, Trigonox 42, Trigonox F-C50, Kayabutyl B, Kaya Carbon EH-C70, Kaya Carbon EH- W60, Kayacaron I-20, Kayacaron BIC-75, Trigonox 117, Kayalen 6-70 (manufactured by Kayaku Akzo), Lurpelox 610, Lupelock 188, Lupelox 844, Lupelox 259, Lupelox 10, Lupelox 701, Lupelox 11, Lupelox 26, Lupelox 80, Lupelox 7, Lupelox 270, Lupelox P, Lupelox 546, Lupelox 554, Lupelox TANPO 55 , Lupelox TAP, Lupelox TBIC, Lupelox TBEC, Lupelox JW, Lupelox TAIC, Lupelox TAEC, Lupelox DC, Lupelox 101, Lupelox F, Lupelox DI, Lupelox 130, Lupelox 220, Lupelox 230, Lupelox 233, Lupelox 233, etc.

  Among these, when an azo polymerization initiator having a molecular weight of 250 or more is used, the reaction proceeds without unevenness at a low temperature, so that formation of a high-strength film with suppressed unevenness can be achieved. More preferably, the molecular weight of the azo polymerization initiator is 250 or more, and more preferably 300 or more.

  The heating is performed under an inert gas atmosphere such as nitrogen or argon, and the oxygen concentration is preferably 1000 ppm or less, more preferably 500 ppm or less, preferably 50 ° C. or more and 170 ° C. or less, more preferably 70 ° C. or more and 150 ° C. or less. Preferably it is 10 minutes or more and 120 minutes or less, More preferably, 15 minutes or more and 100 minutes or less are heated.

  The total content of the photocuring catalyst or the 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, based on the total solid content in the solution for forming the layer. 8 mass% or less is more preferable, and the range of 0.1 mass% or more and 5 mass% or less is especially preferable.

[Electrophotographic photoconductor]
The electrophotographic photoreceptor according to this embodiment has a layer formed on a conductive substrate using a solution in which the charge transporting polyester resin represented by the general formula (1) is dissolved.

  That is, a layer containing a polyester polymer having a structure represented by the following general formula (1) as a partial structure or a polyester crosslinked polymer having a structure represented by the following general formula (1 ′) as a partial structure is provided. .

[In the general formulas (1) and (1 ′), A represents a divalent organic group having a charge transporting property, and T represents a linear or branched divalent group having 1 to 10 carbon atoms. N represents an integer of 5 or more and 5000 or less. Further, in the general formula (1 ′), it represents that crosslinking polymerization is performed at the position of [*]. ]

  In addition, it is more preferable to contain the polyester crosslinked polymer which has a structure represented by the said general formula (1 ') as a partial structure.

  Furthermore, the crosslinkable monomer itself may be a polyfunctional charge transporting monomer.

In the electrophotographic photoreceptor according to the exemplary embodiment, a polyester polymer having a structure represented by the following general formula (1) as a partial structure, or a polyester having a structure represented by the following general formula (1 ′) as a partial structure. What has a layer containing a crosslinked polymer as the outermost surface layer is preferable, and the outermost surface layer only needs to form the uppermost surface of the electrophotographic photosensitive member itself, and serves as a protective layer or a charge transport layer. It is provided as a functional layer.
In the case where the outermost surface layer is a layer that functions as a protective layer, a photosensitive layer composed of a charge transport layer and a charge generation layer or a single-layer type photosensitive layer is provided below the protective layer.

In the case where the outermost surface layer functions as a protective layer, it has a photosensitive layer and a protective layer as the outermost surface layer on the conductive substrate, and the protective layer has the charge transport property represented by the general formula (1). The form containing the composition containing the polymer formed using the polyester resin, or the layer containing the hardened | cured material is mentioned.
On the other hand, when the outermost surface layer is a layer that functions as a charge transport layer, it has a charge generation layer and a charge transport layer as the outermost surface layer on the conductive substrate, and the charge transport layer is represented by the general formula (1). Examples include a composition containing a polymer formed using the charge transporting polyester resin shown, or a layer containing a cured product thereof.
Moreover, you may mix the charge transport material which does not have reactivity, such as a thiol group and an unsaturated bond.

  Hereinafter, the electrophotographic photoreceptor according to the exemplary embodiment in the case where the outermost surface 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 description is omitted.

  FIG. 1 is a schematic cross-sectional view showing a preferred example of the electrophotographic photoreceptor according to the present exemplary embodiment. 2 to 3 are schematic sectional views showing electrophotographic photosensitive members according to other embodiments.

  An electrophotographic photoreceptor 7A shown in FIG. 1 is a so-called function-separated photoreceptor (or laminated photoreceptor), and an undercoat layer 1 is provided on a conductive substrate 4, on which a charge generation layer 2, a charge The transport layer 3 and the protective layer 5 have a structure formed in order. In the electrophotographic photoreceptor 7 </ b> A, the charge generation layer 2 and the charge transport layer 3 constitute a photosensitive layer.

An electrophotographic photoreceptor 7B shown in FIG. 2 is a function-separated type 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.
In the electrophotographic photoreceptor 7B shown in FIG. 2, 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 is what has. In the electrophotographic photoreceptor 7B, the charge transport layer 3 and the charge generation layer 2 constitute a photosensitive layer.

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

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

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

-Protective layer-
First, the protective layer 5 that is the outermost surface layer in the electrophotographic photoreceptor 7A will be described.
The protective layer 5 is the outermost surface layer in the electrophotographic photoreceptor 7A, and is preferably formed using a solution in which the charge transporting polyester resin represented by the general formula (1) is dissolved. It is preferable to contain a polymer containing the structure shown in (2) as a partial structure, and it is most preferred that the polymer is further cured, that is, contains a polymer obtained by polymerizing the charge transporting polyester resin.

  As a curing 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 film unevenness and wrinkles is suppressed, and therefore it is desirable to polymerize under conditions where radical generation occurs relatively slowly. From this point, thermal polymerization that allows easy adjustment of the polymerization rate is preferred.

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

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

  The non-reactive charge transport material is desirably used in an amount of 0% by mass to 30% by mass, and more desirably 1% by mass to 25% by mass with respect to the total solid content in the coating solution for layer formation. More preferably, it is 5 mass% or more and 25 mass% or less.

-Other additives The cured film constituting the protective layer (outermost surface layer) 5 is made of another coupling agent, particularly fluorine, for the purpose of adjusting the film formability, flexibility, lubricity, and adhesion. You may mix and use the containing coupling agent. As such a compound, various silane coupling agents and commercially available silicone hard coat agents are used. Moreover, you may use the silicon compound and fluorine-containing compound which have a radically polymerizable group.

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

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

Although the silane coupling agent is used in an arbitrary amount, the amount of the fluorine-containing compound may be 0.25 times or less by mass with respect to the compound containing no fluorine from the viewpoint of the film formability of the crosslinked film. desirable. Furthermore, you may mix the reactive fluorine compound etc. which are disclosed by Unexamined-Japanese-Patent No. 2001-166510 etc.
Examples of the silicon compound and the fluorine-containing compound having a radical polymerizable group include compounds described in JP-A No. 2007-11005.

It is preferable to add a deterioration preventing agent to the cured film constituting the protective layer (outermost surface layer) 5. As the degradation inhibitor, hindered phenols or hindered amines are desirable, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. , Etc., may be used.
The addition amount of the deterioration inhibitor is preferably 20% by mass or less, and more preferably 10% by mass or less.

Examples of the hindered phenol antioxidant include Irganox 1076, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076 (above, manufactured by Ciba Japan), 3,5- And di-t-butyl-4-hydroxybiphenyl.
Examples of hindered amine antioxidants include Sanol LS2626, Sanol LS765, Sanol LS770, Sanol LS744 (Sankyo Lifetech), Tinuvin 144, Tinuvin 622LD (above, manufactured by Ciba Japan), Mark LA57, Mark LA67, Mark LA62. , Mark LA68, Mark LA63 (manufactured by Adeka Co., Ltd.), thioethers as Sumilizer TPS and Sumiser TP-D (Sumitomo Chemical Co., Ltd.), and phosphites as Mark 2112, Mark PEP -8, mark PEP-24G, mark PEP-36, mark 329K, mark HP-10 (manufactured by Adeka) and the like.

Furthermore, conductive particles, organic or inorganic particles may be added to the cured film constituting the protective layer (outermost surface layer) 5.
An example of such particles is silicon-containing particles. Silicon-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles. The colloidal silica used as the silicon-containing particles is preferably silica having an average particle diameter of 1 nm or more and 100 nm or less, more preferably 10 nm or more and 30 nm or less in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone, or ester. It is selected from those dispersed in. As the particles, commercially available particles may be used.

  The solid content of the colloidal silica in the protective layer is not particularly limited, but is 0.1% by mass or more and 50% by mass or less, preferably 0.1% based on the total solid content of the protective layer 5. It is used in the range of mass% to 30 mass%.

The silicone particles used as the silicon-containing particles may be selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and commercially available particles may be used.
These silicone particles are spherical, and the average particle diameter is preferably 1 nm to 500 nm, more preferably 10 nm to 100 nm.
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 amount of the total solid content of the protective layer 5. is there.

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, and vinylidene fluoride. 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 —TiO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, MgO, and other semiconductive metal oxides. Furthermore, various known dispersing materials may be used to disperse the particles.

Oil such as silicone oil may be added.
Silicone oils include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane; amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, mercapto-modified poly Reactive silicone oils such as siloxane and phenol-modified polysiloxane; cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; 1,3,5- Trimethyl-1.3.5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclo Cyclic methylphenylcyclosiloxanes such as trasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane; cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane Fluorine-containing cyclosiloxanes such as 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane; Hydrosilyl group-containing cyclosiloxanes such as methylhydrosiloxane mixture, pentamethylcyclopentasiloxane, and phenylhydrocyclosiloxane And vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane.

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

(Composition)
The composition used for forming the protective layer 5 is prepared as a solution (coating liquid for forming a protective layer) in which the charge transporting polyester resin represented by the general formula (1) is dissolved in a solvent. desirable.
This coating solution for forming the protective layer may be solvent-free, and if necessary, aromatics such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, butyl acetate and the like. It is prepared using a solvent such as an ester solvent, an ether solvent such as tetrahydrofuran or dioxane, a cellosolv solvent such as ethylene glycol monomethyl ether, or an alcohol solvent such as isopropyl alcohol or butanol.

  In addition, when obtaining the coating liquid by reacting the above-mentioned components, each component may be simply mixed and dissolved, but preferably room temperature (20 ° C.) to 100 ° C., more preferably 30 ° C. to 80 ° C. Thus, the heating is preferably performed for 10 minutes to 100 hours, more preferably for 1 hour to 50 hours. It is also desirable to irradiate ultrasonic waves at this time.

(Preparation of protective layer 5)
The coating liquid for forming the protective layer is formed on the surface to be coated (the charge transport layer 3 in the embodiment shown in FIG. 1) by a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife. The coating is performed by a normal method such as a coating method, a curtain coating method, or an ink jet coating method.
Thereafter, light, electron beam or heat is applied to the obtained coating film to cause radical polymerization, thereby polymerizing and curing the coating film.

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

  In the polymerization and curing reaction, the oxygen concentration is desirably 10% or less in a vacuum or an inert gas atmosphere so that a chain reaction can be performed without deactivation of radicals generated by light, electron beam or heat. More preferably, it is performed at a low oxygen concentration of 5% or less, more preferably 2% or less, and most preferably 500 ppm or less.

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

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

  The structure of each layer in the function-separated type photosensitive layer has been described above with reference to the electrophotographic photoreceptor 7A shown in FIG. 1. However, in each layer in the function-separated type electrophotographic photoreceptor 7B shown in FIG. Configurations can be employed. Further, in the case of the single-layer type photosensitive layer 6 of the electrophotographic photosensitive member 7C shown in FIG.

  That is, the content of the charge generating material in the single-layer type photosensitive layer 6 is 5% by mass to 50% by mass with respect to the total solid content of the composition used when forming the protective layer (outermost surface layer) 5. More preferably, the content is more preferably 10% by mass or more and 40% by mass or less, and particularly preferably 15% by mass or more and 35% by mass or less.

  As a method for forming the single-layer type photosensitive layer 6, a method for forming the charge generation layer 2 or the charge transport layer 3 can be adopted. The film thickness of the single-layer type photosensitive layer 6 is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less.

  In the above-described embodiment, the embodiment in which the outermost surface layer is the protective layer 5 has been described. However, in the case of a layer configuration without the protective layer 5, the charge transport layer located on the outermost surface in the layer configuration is the outermost layer. It becomes a surface layer. When the outermost surface layer is a charge transport layer, the thickness of this layer is preferably 7 μm or more and 70 μm or less, and more preferably 10 μm or more and 60 μm or less.

-Conductive substrate-
Examples of the conductive substrate 4 include a metal plate, a metal drum, and a metal belt formed using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, and platinum. Is mentioned. Examples of the conductive substrate 4 include paper, plastic film, belt, etc. coated, vapor-deposited or laminated with a conductive polymer, a conductive compound such as indium oxide, or a metal or alloy such as aluminum, palladium, or gold.
Here, “conductive” means that the volume resistivity is less than 10 ¹³ Ωcm.

  When the electrophotographic photosensitive member 7A is used in a laser printer, the surface of the conductive substrate 4 has a center line average roughness Ra of 0.04 μm or more to prevent interference fringes generated when laser light is irradiated. It is desirable to roughen the surface to 5 μm or less. When non-interfering light is used as a light source, it is not particularly necessary to roughen the surface to prevent interference fringes.

  Surface roughening methods include wet honing by suspending an abrasive in water and spraying it on the support, or centerless grinding and anodic oxidation in which the support is brought into contact with a rotating grindstone for continuous grinding. Processing is desirable.

  As another roughening method, a conductive or semiconductive powder is dispersed in a resin without roughening the surface of the conductive substrate 4 to form a layer on the support surface. A method of roughening with particles dispersed in the layer is also desirably used.

Here, the roughening treatment by anodic oxidation is to form an oxide film on the aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the porous anodic oxide film formed by anodic oxidation is chemically active as it is. Therefore, the pores in the anodized film are sealed with pressurized water vapor or boiling water (a metal salt such as nickel may be added) by volume expansion due to a hydration reaction, and a sealing process is performed to change to a more stable hydrated oxide. It is desirable.
The thickness of the anodic oxide film is desirably 0.3 μm or more and 15 μm or less.

Further, the conductive substrate 4 may be subjected to treatment with an acidic aqueous solution or boehmite treatment. The treatment with an acidic treatment solution composed of phosphoric acid, chromic acid and hydrofluoric acid is carried out as follows.
First, an acidic treatment liquid is prepared. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10% by mass to 11% by mass, chromic acid is in the range of 3% by mass to 5% by mass, and hydrofluoric acid is 0.00%. The concentration of these acids 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 more and 48 ° C. or less. However, by keeping the treatment temperature high, a thicker film can be formed faster. The film thickness is preferably from 0.3 μm to 15 μm.

  The boehmite treatment is preferably performed by immersing in pure water of 90 ° C. or more and 100 ° C. or less for 5 minutes or more and 60 minutes or less, or by contacting with heated steam of 90 ° C. or more and 120 ° C. or less for 5 minutes or more and 60 minutes or less. The film thickness is preferably 0.1 μm or more and 5 μm or less. This may be further anodized using an electrolyte 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 1 is configured by containing inorganic particles in a binder resin, for example.
As the inorganic particles, those having a powder resistance (volume resistivity) of 10 ² Ω · cm to 10 ¹¹ Ω · cm are desirably used.

  Among these, inorganic particles such as tin oxide, titanium oxide, zinc oxide, and zirconium oxide are preferably used as the inorganic particles having the resistance value, and zinc oxide is particularly preferably used.

In addition, the inorganic particles may be subjected to a surface treatment, or may be used as a mixture of two or more types such as those having different surface treatments or particles having different particle diameters.
The specific surface area of the inorganic particles by the BET method is preferably 10 m ² / g or more.
The volume average particle size of the inorganic particles is desirably in the range of 50 nm to 2000 nm (desirably 60 nm to 1000 nm).

Furthermore, it is preferable to contain an acceptor compound together with the inorganic particles.
The acceptor compound is not limited as long as the above characteristics can be obtained, and quinone compounds such as chloranil and bromoanil, tetracyanoquinodimethane compounds, 2,4,7-trinitrofluorenone, 2,4,4 Fluorenone compounds such as 5,7-tetranitro-9-fluorenone, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole and 2,5-bis (4 -Naphthyl) -1,3,4-oxadiazole, oxadiazole compounds such as 2,5-bis (4-diethylaminophenyl) 1,3,4 oxadiazole, xanthone compounds, thiophene compounds, 3, Electron transporting substances such as diphenoquinone compounds such as 3 ′, 5,5′tetra-t-butyldiphenoquinone are desirable, especially anthraquinone structures Compounds having desirable. Furthermore, acceptor compounds having an anthraquinone structure such as hydroxyanthraquinone compounds, aminoanthraquinone compounds, aminohydroxyanthraquinone compounds, and the like are desirably used, and specific examples include anthraquinone, alizarin, quinizarin, anthralfin, and purpurin.

  The content of these acceptor compounds is not limited as long as the above characteristics are obtained, but is desirably contained in the range of 0.01% by mass to 20% by mass with respect to the inorganic particles, and further 0.05% by mass. It is desirable to add in the range of not less than 10% and not more than 10% by mass.

The acceptor compound may be simply added to the coating solution for forming the undercoat layer, or may be previously attached to the surface of the inorganic particles.
Examples of the method for imparting the acceptor compound to the surface of the inorganic particles include a dry method or a wet method.

  When surface treatment is performed by the dry method, the inorganic particles are agitated with a mixer having a large shearing force, etc., and the acceptor compound dissolved directly or in an organic solvent is dropped and sprayed with dry air or nitrogen gas. Is done. The addition or spraying is preferably performed at a temperature below the boiling point of the solvent. After addition or spraying, baking may be performed at 100 ° C. or higher. The baking temperature and time are carried out in an arbitrary range.

  Also, as a wet method, inorganic particles are dispersed in a solvent using stirring, ultrasonic waves, a sand mill, an attritor, a ball mill, etc., and an acceptor compound is added and stirred or dispersed, followed by removing the solvent. . The solvent removal method is distilled off by filtration or distillation. After removing the solvent, baking may be performed at 100 ° C. or higher. The baking is not particularly limited as long as it is a temperature and time for obtaining electrophotographic characteristics. In the wet method, the water containing inorganic particles may be removed before adding the surface treatment agent. For example, a method of removing with stirring and heating in a solvent used for the surface treatment, a method of removing by azeotropic distillation with the solvent. May be used.

  The inorganic particles may be subjected to a surface treatment before the acceptor compound is applied. The surface treatment agent is not particularly limited as long as desired characteristics can be obtained, and is selected from known materials. For example, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a surfactant, and the like can be given. In particular, silane coupling agents are desirably used because they provide good electrophotographic properties. Furthermore, a silane coupling agent having an amino group is desirably used.

  Any silane coupling agent having an amino group may be used as long as electrophotographic photoreceptor characteristics are obtained. Specific examples include γ-aminopropyltriethoxysilane and N-β- (aminoethyl). -Γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, and the like. However, it is not limited to these.

  Two or more silane coupling agents may be mixed and used. Examples of silane coupling agents that may be used in combination with the silane coupling agent having an amino group include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -Γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyl Trimethoxysilane, etc. The present invention is not limited.

  Further, the surface treatment method using these surface treatment agents may be any known method, and a dry method or a wet method is used. Moreover, you may perform the provision of an acceptor compound and surface treatment by surface treatment agents, such as a coupling agent, all at once.

  The amount of the silane coupling agent with respect to the inorganic particles in the undercoat layer 1 is not limited as long as the electrophotographic characteristics can be obtained, and is preferably 0.5% by mass or more and 10% by mass or less with respect to the inorganic particles.

The undercoat layer 1 may contain a binder resin.
As the binder resin contained in the undercoat layer 1, any known resin may be used as long as it can form a good film and can obtain desired characteristics. Acetal resin such as butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride Known polymer resin compounds such as resins, silicone resins, silicone-alkyd resins, phenol resins, phenol-formaldehyde resins, melamine resins, urethane resins, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, titanium alkanes Kishido compounds, organic titanium compounds, known materials such as a silane coupling agent is used.
Further, as the binder resin contained in the undercoat layer 1, a charge transporting resin having a charge transporting group, a conductive resin such as polyaniline, or the like may be used. Among these, resins that are insoluble in the upper-layer coating solvent are preferable, and phenol resins, phenol-formaldehyde resins, melamine resins, urethane resins, epoxy resins, and the like are particularly preferable. When these are used in combination of two or more, the mixing ratio is set as necessary.

  In the coating solution for forming the undercoat layer, the ratio of the inorganic particles (metal oxide provided with acceptor properties) to which the acceptor compound is added and the binder resin or the ratio of the inorganic particles and the binder resin is the characteristics of the electrophotographic photosensitive member. Is set within the range where.

Various additives may be used in the undercoat layer 1.
As additives, known materials such as polycyclic condensation type, azo type electron transporting pigments, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, silane coupling agents and the like are used. It is done. The silane coupling agent is used for the surface treatment of the inorganic particles as described above, but may be further added to the coating solution for forming the undercoat layer as an additive.

Specific examples of the silane coupling agent as an additive include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β Examples include-(aminoethyl) -γ-aminopropylmethyldimethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, and γ-chloropropyltrimethoxysilane.
Examples of zirconium chelate compounds include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, octanoic acid. Zirconium, zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

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

  Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) and the like.

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

Solvents for preparing the coating solution for forming the undercoat layer include known organic solvents such as alcohols, aromatics, halogenated hydrocarbons, ketones, ketone alcohols, ethers, esters, etc. Optionally selected.
Specific examples of the solvent include methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, and acetic acid. Usual organic solvents such as n-butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene and toluene are used.

  These solvents may be used alone or in combination of two or more. When mixing, any solvent can be used as long as it can dissolve the binder resin as the mixed solvent.

As a dispersion method of the inorganic particles when preparing the coating liquid for forming the undercoat layer, known methods such as a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker are used.
Furthermore, as a coating method used when the undercoat layer 1 is provided, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Is used.

  The undercoat layer 1 is formed on the conductive substrate using the undercoat layer-forming coating solution thus obtained.

The undercoat layer 1 preferably has a Vickers hardness of 35 or more.
Further, the undercoat layer 1 may be set to any thickness as long as desired characteristics can be obtained, but the thickness is preferably 15 μm or more, and more preferably 15 μm or more and 50 μm or less. .

Further, the surface roughness (ten-point average roughness) of the undercoat layer 1 is preferably adjusted from 1 / 4n (n is the refractive index of the upper layer) to 1 / 2λ of the exposure laser wavelength λ used. .
In order to adjust the surface roughness, particles such as a resin may be added to the undercoat layer. As the resin particles, silicone resin particles, cross-linked polymethyl methacrylate resin particles and the like are used.
Further, the surface of the undercoat layer may be polished for adjusting the surface roughness. As a polishing method, buffing, sandblasting, wet honing, grinding, or the like is used. When a non-coherent light source such as an LED or an organic EL image array is used, a smooth surface may be used.

  The undercoat layer 1 can be obtained by drying the above-described undercoat layer forming coating solution applied onto the conductive substrate 4, and the normal drying is performed at a temperature at which the solvent can be evaporated to form a film.

-Charge generation layer-
The charge generation layer 2 is a layer containing a charge generation material and a binder resin. Moreover, you may form as a vapor deposition film which does not contain binder resin. In particular, it is preferable when an incoherent light source such as an LED or an organic EL image array is used.
Examples of the charge generation material include azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, perylene pigments, pyrrolopyrrole pigments, phthalocyanine pigments, zinc oxide, and trigonal selenium. Among these, it is desirable to use a metal phthalocyanine pigment and a metal-free phthalocyanine pigment as the charge generation material in order to cope with near-infrared laser exposure, and in particular, JP-A-5-263007 and JP-A-5 Hydrogallium phthalocyanine disclosed in JP-A-2799591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, dichloromethane disclosed in JP-A-5-11172, JP-A-5-11173, etc. Tin phthalocyanine, and titanyl phthalocyanine disclosed in JP-A-4-189873, JP-A-5-43813 and the like are more preferable. Further, in order to cope with near-ultraviolet laser exposure, as a charge generation material, a condensed aromatic pigment such as dibromoanthanthrone, a thioindigo pigment, a porphyrazine compound, zinc oxide, trigonal selenium, It is more desirable to use bisazo pigments and the like disclosed in JP-A-78147 and JP-A-2005-181992.

The binder resin used for the charge generation layer 2 is selected from a wide range of insulating resins, and selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. Also good. Desirable 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, polyamides. Resins, acrylic resins, polyacrylamide resins, polyvinyl pyridine resins, cellulose resins, urethane resins, epoxy resins, caseins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, and the like.
These binder resins are used alone or in combination of two or more. The blending ratio of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10 by mass ratio.
Here, “insulating” means that the volume resistivity is 10 ¹³ Ωcm or more.

  The charge generation layer 2 is formed using a charge generation layer forming coating solution in which the above-described charge generation material and binder resin are dispersed in a predetermined solvent. Moreover, you may form as a vapor deposition film which does not contain binder resin.

  Solvents used for dispersion include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. , Chloroform, chlorobenzene, toluene and the like. These may be used alone or in combination of two or more.

Further, as a method for dispersing the charge generating material and the binder resin in the solvent, usual methods such as a ball mill dispersion method, an attritor dispersion method, and a sand mill dispersion method are used.
Further, in this dispersion, the average particle size of the charge generating material is desirably 0.5 μm or less, more desirably 0.3 μm or less, and particularly desirably 0.15 μm or less.

  Further, when forming the charge generation layer 2, a usual method such as a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method or a curtain coating method is used. .

  The film thickness of the charge generation layer 2 obtained in this manner is desirably 0.1 μm or more and 5.0 μm or less, and more desirably 0.2 μm or more and 2.0 μm or less.

-Charge transport layer-
The charge transport layer 3 shown in FIG. 1 includes a charge transport material and a binder resin, or a polymer charge transport material.

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

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

(In the structural formula (a-1), R ⁹ represents a hydrogen atom, a methyl group, —C (R ¹⁰ ) ═C (R ¹¹ ) (R ¹² ), or —CH═CH—CH═C (R ¹³ ) (R ¹⁴ ), 1 represents 1 or 2. Ar ⁶ and Ar ⁷ are each independently a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ¹⁰ ) ═C (R ¹¹ ) (R ¹² ) or —C ₆ H ₄ —CH═CH—CH═C (R ¹³ ) (R ¹⁴ ), wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom. Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)

  Here, the substituent of each of the above groups is a substituent 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 3 carbon atoms. An amino group is mentioned.

(In the structural formula (a-2), R ¹⁵ and R ^{15 ′} 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 ¹⁶ , R ^{16 ′} , R ¹⁷ and R ^{17 ′} each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 2 carbon atoms. An amino group substituted with the following alkyl group, a substituted or unsubstituted aryl group, —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —CH═CH—CH═C (R ²¹ ) ( R ²² ) and each of R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and m and n are 0 or more independently for each It shows the following integer.)

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 ═C (R ¹³ ) (R ¹⁴ ) ”and a benzidine derivative having“ —CH═CH—CH═C (R ²¹ ) (R ²² ) ”have charge mobility, protective layer and It is excellent and desirable from the standpoints of adhesiveness and afterimage (hereinafter sometimes referred to as “ghost”) caused by the history of the previous image remaining.

The binder resin used for the charge transport layer 3 is polycarbonate resin, polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer. , Vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly- N-vinyl carbazole, polysilane, etc. are mentioned. Polyester type polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 may be used. Of these, polycarbonate resin or polyarylate resin is preferred.
These binder resins are used alone or in combination of two or more. The blending ratio of the charge transport material and the binder resin is desirably 10: 1 to 1: 5 by mass ratio.

In particular, when the charge transport layer 3 is provided with a protective layer (outermost surface layer) made of a cured film of a composition containing a reactive charge transport material and a polycarbonate resin, the binder resin used for the charge transport layer 3 The viscosity average molecular weight is preferably 50000 or more, more preferably 55000 or more.
The upper limit of the viscosity average molecular weight of the binder resin used for the charge transport layer 3 is preferably 100,000 or less.
Here, the viscosity average molecular weight of the binder resin in the present embodiment is a value measured by a capillary viscometer.
When the outermost surface layer is a charge transport layer, the viscosity average molecular weight of the binder resin contained in the lower layer is preferably in the above range.

  In addition, a polymer charge transport material may be used as the charge transport material. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane are used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293, JP-A-8-208820 and the like are particularly desirable. The polymer charge transport material can be formed by itself, but may be formed by mixing with the above-described binder resin.

The charge transport layer 3 is formed using a charge transport layer forming coating solution containing the above-described constituent materials.
Solvents used in the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride. Ordinary organic solvents such as aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether, or straight chain ethers may be used alone or in admixture of two or more. Moreover, a well-known method is used as a dissolution method of each said constituent material.

  The coating method for applying the charge transport layer forming coating solution onto the charge generation layer 2 includes blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, A usual method such as a curtain coating method is used.

The film thickness of the charge transport layer 3 is desirably 5 μm or more and 50 μm or less, and more desirably 10 μm or more and 30 μm or less.
The surface layer material of the present embodiment may be used as the charge transport layer.

<Process cartridge and image forming apparatus>
Next, a process cartridge and an image forming apparatus using the electrophotographic photosensitive member of this embodiment will be described.
The process cartridge of this embodiment is for an image forming apparatus that transfers a toner image obtained by developing an electrostatic latent image on the surface of a latent image holding member to a recording medium and forms an image on the recording medium. The electrophotographic photosensitive member according to the present embodiment as the latent image holding member is provided at least.

  The image forming apparatus of the present embodiment exposes the surface of the electrophotographic photosensitive member according to the above-described electrophotographic photosensitive member, a charging device that charges the electrophotographic photosensitive member, and the charged electrophotographic photosensitive member. An exposure device for forming an electrostatic latent image on the surface; a developing device for developing the electrostatic latent image with a developer to form a toner image; and a transfer device for transferring the toner image to a recording medium. It is a configuration. The image forming apparatus of the present embodiment may be a so-called tandem machine having a plurality of photoreceptors corresponding to the toners of the respective colors. In this case, all the photoreceptors are the electrophotographic photoreceptors of the embodiment. Is desirable. The toner image may be transferred by an intermediate transfer system using an intermediate transfer member.

  FIG. 4 is a schematic configuration diagram illustrating the image forming apparatus according to the present embodiment. The image forming apparatus 100 is as shown in FIG. A process cartridge 300 including the electrophotographic photosensitive member 7, an exposure device 9, a transfer device 40, and an intermediate transfer member 50 are provided. In the image forming apparatus 100, the exposure device 9 is disposed at a position where the electrophotographic photosensitive member 7 can be exposed from the opening of the process cartridge 300, and the transfer device 40 is interposed between the electrophotographic photosensitive member via the intermediate transfer member 50. 7, and a part of the intermediate transfer member 50 is disposed in contact with the electrophotographic photosensitive member 7.

  The process cartridge 300 in FIG. 4 integrally supports the electrophotographic photoreceptor 7, the charging device 8, the developing device 11, and the cleaning device 13 in a housing. The cleaning device 13 has a cleaning blade (cleaning member), and the cleaning blade 131 is disposed so as to contact the surface of the electrophotographic photosensitive member 7.

  In addition, an example is shown in which a fibrous member 132 (roll shape) that supplies the lubricant 14 to the surface of the photoreceptor 7 and a fibrous member 133 (flat brush shape) that assists in cleaning are used. However, it may not be used.

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

  Although not shown, a photosensitive member heating member for raising the temperature of the electrophotographic photosensitive member 7 and reducing the relative temperature may be provided around the electrophotographic photosensitive member 7.

  Examples of the exposure device 9 include optical system devices that expose the surface of the photoreceptor 7 with light such as semiconductor laser light, LED light, and liquid crystal shutter light in a predetermined image-like manner. The wavelength of the light source is in the spectral sensitivity region of the photoreceptor. As the wavelength of the semiconductor laser, near infrared having an oscillation wavelength near 780 nm is the mainstream. However, the present invention is not limited to this wavelength, and a laser having an oscillation wavelength of 600 nm or a laser having an oscillation wavelength of 400 nm to 450 nm as a blue laser may be used. A surface-emitting laser light source that can output a multi-beam is also effective for color image formation.

  As the developing device 11, for example, a general developing device that performs development by bringing a magnetic or non-magnetic one-component developer or two-component developer into contact or non-contact with each other may be used. The developing device 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 the one-component developer or the two-component developer to the photoreceptor 7 using a brush, a roller, or the like can be used. Among these, those using a developing roller holding the developer on the surface are desirable.

Hereinafter, the toner used in the developing device 11 will be described.
The toner used in the image forming apparatus of this embodiment has an average shape factor ((ML ² / A) × (π / 4) × 100, where ML represents the maximum length of the particles, and A represents the projected area of the particles. Is preferably from 100 to 150, more preferably from 105 to 145, and even more preferably from 110 to 140. Further, the toner preferably has a volume average particle size of 3 μm to 12 μm, and more preferably 3.5 μm to 9 μm.

  The toner is not particularly limited by the production method. For example, a kneading and pulverizing method in which a binder resin, a colorant and a release agent, and a charge control agent are further added, kneaded, pulverized, and classified; A method of changing the shape of particles obtained by the method by mechanical impact force or thermal energy; a dispersion monomer formed by emulsion polymerization of a polymerizable monomer of a binder resin, a colorant and a release agent In addition, an emulsion polymerization aggregation method for obtaining toner particles by mixing a dispersion liquid such as a charge control agent and aggregating and heat-fusing to obtain toner particles; a polymerizable monomer for obtaining a binder resin, a colorant and a release agent Suspension polymerization method in which a solution of an agent, a charge control agent, etc. is suspended in an aqueous solvent for polymerization; a binder resin, a coloring agent, a release agent, and a solution of a charge control agent, etc., in an aqueous solvent Toner produced by the suspension method, etc. It is use.

  Further, a known method such as a production method in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to give a core-shell structure is used. The toner production method is preferably a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method in which an aqueous solvent is used from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly desirable.

  The toner base particles desirably contain a binder resin, a colorant, and a release agent, and may further contain silica or a charge control agent.

  Binder resins used for toner base particles include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Α-methylene aliphatics such as vinyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers and copolymers of monocarboxylic acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone , Polyester resins by copolymerization of dicarboxylic acids and diols.

  Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. A polymer, polyethylene, a polypropylene, a polyester resin etc. are mentioned. Further, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can be mentioned.

  In addition, as colorants, magnetic powders such as magnetite and ferrite, carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, Lamp Black, Rose Bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 is exemplified as a representative example.

  Typical examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer tropical wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  As the charge control agent, known ones are used, and azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups are used. When toner is manufactured by a wet manufacturing method, it is desirable to use a material that is difficult to dissolve in water. The toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  The toner used in the developing device 11 is manufactured by mixing the toner base particles and the external additive with a Henschel mixer or a V blender. Further, when the toner base particles are produced by a wet method, they may be externally added by a wet method.

  Lubricating particles may be added to the toner used in the developing device 11. Lubricating particles include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids and fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, silicones having a softening point upon heating, oleic amides , Erucic acid amide, ricinoleic acid amide, stearic acid amide and other aliphatic amides, carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil and other plant waxes, beeswax animal wax, montan wax, ozokerite , Ceresin, paraffin wax, microcrystalline wax, minerals such as Fischer-Tropsch wax, petroleum wax, and modified products thereof. These are used individually by 1 type or in combination of 2 or more types. However, the average particle size is preferably in the range of 0.1 μm or more and 10 μm or less, and those having the above chemical structure may be pulverized to make the particle sizes uniform. The amount added to the toner is desirably in the range of 0.05% by mass to 2.0% by mass, and more desirably in the range of 0.1% by mass to 1.5% by mass.

  To the toner used in the developing device 11, inorganic particles, organic particles, composite particles obtained by attaching inorganic particles to the organic particles, or the like may be added.

  Inorganic particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used.

  In addition, the inorganic particles may be mixed with titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, γ- (2- Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxy Silane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane The treatment may be performed with a silane coupling agent such as run, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. In addition, those hydrophobized with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate, calcium stearate and the like are also desirably used.

  Examples of the organic particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  The particle diameter is preferably 5 nm to 1000 nm, more preferably 5 nm to 800 nm, and even more preferably 5 nm to 700 nm in terms of number average particle diameter. Moreover, it is desirable that the sum of the addition amounts of the above-described particles and the lubricating particles is 0.6% by mass or more.

  As the other inorganic oxide added to the toner, it is desirable to use a small-diameter inorganic oxide having a primary particle size of 40 nm or less, and further add an inorganic oxide having a larger diameter. Known inorganic oxide particles are used, but it is desirable to use silica and titanium oxide in combination.

  Moreover, you may surface-treat about a small diameter inorganic particle. Furthermore, it is also desirable to add carbonates such as calcium carbonate and magnesium carbonate and inorganic minerals such as hydrotalcite.

  In addition, the color toner for electrophotography is used by mixing with a carrier. As the carrier, iron powder, glass beads, ferrite powder, nickel powder, or those coated with a resin are used. The mixing ratio with the carrier is set as necessary.

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

  As the intermediate transfer member 50, a belt-like member (intermediate transfer belt) made of polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber or the like having semiconductivity is used. Further, as the form of the intermediate transfer member 50, a drum-like one is used in addition to the belt shape.

  In addition to the above-described devices, the image forming apparatus 100 may include, for example, a light neutralizing device that performs light neutralization on the photoconductor 7.

  FIG. 5 is a schematic cross-sectional view showing an image forming apparatus according to another embodiment. As shown in FIG. 5, the image forming apparatus 120 is a tandem multicolor image forming apparatus equipped with four process cartridges 300. In the image forming apparatus 120, four process cartridges 300 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member is used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

  In the image forming apparatus (process cartridge) according to the present embodiment, the developing device is a developing roller that is a developer holder that moves (rotates) in the opposite direction to the moving direction (rotating direction) of the electrophotographic photosensitive member. You may have. Here, the developing roller has a cylindrical developing sleeve that holds developer on the surface, and the developing device has a configuration that includes a regulating member that regulates the amount of developer supplied to the developing sleeve. Can be mentioned. By moving (rotating) the developing roller of the developing device in a direction opposite to the rotation direction of the electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is rubbed with toner remaining between the developing roller and the electrophotographic photosensitive member. The

  In the image forming apparatus according to the present exemplary embodiment, the distance between the developing sleeve and the photosensitive member is desirably 200 μm or more and 600 μm or less, and more desirably 300 μm or more and 500 μm or less. In addition, the distance between the developing sleeve and the regulating blade, which is a regulating member that regulates the developer amount, is desirably 300 μm or more and 1000 μm or less, and more desirably 400 μm or more and 750 μm or less.

  Further, it is desirable that the absolute value of the moving speed of the developing roll surface is 1.5 times or more and 2.5 times or less of the absolute value (process speed) of the moving speed of the photosensitive member surface. It is more desirable to make it 0 times or less.

  Further, in the image forming apparatus (process cartridge) according to the present embodiment, the developing device (developing unit) includes a developer holding body having a magnetic material, and is a two-component developer containing a magnetic carrier and toner. It is desirable to develop an image.

[Organic EL device]
Next, the organic EL device will be described.
The organic EL device according to this embodiment has a film formed by using a solution in which the charge transporting polyester resin represented by the general formula (1) is dissolved.

  That is, a film containing a polyester polymer having a structure represented by the following general formula (1) as a partial structure or a polyester crosslinked polymer having a structure represented by the following general formula (1 ′) as a partial structure is provided. .

[In the general formulas (1) and (1 ′), A represents a divalent organic group having a charge transporting property, and T represents a linear or branched divalent group having 1 to 10 carbon atoms. N represents an integer of 5 or more and 5000 or less. Further, in the general formula (1 ′), it represents that crosslinking polymerization is performed at the position of [*]. ]

  In addition, it is more preferable to contain the polyester crosslinked polymer which has a structure represented by the said general formula (1 ') as a partial structure.

  When used as an organic EL device or a solar battery, it may be in a single layer or laminated form, and may be used in any layer.

As an example of the organic EL device, an organic electroluminescent element will be described in detail with reference to the drawings.
7 to 9 are schematic cross-sectional views showing an embodiment of the organic electroluminescence device of the present embodiment, in which 21 is a substrate, 22 is an anode, 23 is a hole injection layer, and 24 is a hole transport layer. , 25 represents a light emitting layer, 26 represents an electron transport layer, and 27 represents a cathode, but the device structure is not limited thereto.

The substrate 21 serves as a support for the organic electroluminescence device, and a quartz or glass plate, a metal plate or a metal foil, a plastic film, a sheet, or the like is used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable.
When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. For this reason, a method of providing a dense silicon oxide film or the like on one or both sides of the synthetic resin substrate is also a preferable method.

An anode 22 is provided on the substrate 21. The anode 22 plays a role of hole injection into the hole injection layer 23. The anode 22 is usually composed of a metal such as aluminum, gold, silver, nickel, palladium, or platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, carbon black, or the like. Is done. In general, the anode 22 is often formed by a sputtering method, a vacuum deposition method, or the like. Further, the anode 22 is formed by dispersing metal particles such as silver, particles such as copper iodide, carbon black, conductive metal oxide particles and the like in an appropriate binder resin solution and coating the substrate 21. Also good. The anode 22 may be formed by stacking different materials.
Although the thickness of the anode 22 varies depending on the required transparency, it is generally preferable that the transparency is higher. Therefore, the visible light transmittance is usually 60% or more, preferably 80% or more. Is usually 10 nm to 1000 nm, preferably 20 nm to 500 nm.

  For the purpose of laser oscillation from the end face and for the purpose of reflecting between the two electrodes, the anode 22 may be the one used for the substrate 21 when it may be opaque, such as when a metal vapor deposition film is provided. Further, different conductive materials may be laminated on the anode 22.

  In the element structure of FIGS. 7 to 9 given as a representative example of this embodiment, a hole injection layer 23 is provided on the anode 22.

In the present embodiment, the layer formed using the charge transporting polyester resin represented by the general formula (1) is formed by vapor deposition or a coating method, and the coating method is preferable when it is cured. For example, the case where it forms as a hole injection layer is demonstrated to an example.
If necessary, a binder resin that does not trap holes, a coating property improver, a chain polymerizable monomer, an oligomer, or the like may be added to the predetermined amount of the charge transporting polyester resin represented by the general formula (1). . It is also preferable to use a charge transport material having an alkoxysilyl group at the terminal, and other silane coupling agents, aluminum coupling agents, titanate coupling agents and the like may be added for various purposes. A coating solution in which these are dissolved is prepared to a desired concentration, applied on the anode 22 by a method such as spin coating or dip coating, and dried to form the hole injection layer 23.
The film thickness of the hole injection layer 23 thus formed is usually 5 nm to 3000 nm, preferably 10 nm to 2000 nm.

  A light emitting layer 25 is provided on the hole injection layer 23. The light emitting layer 25 is made of a material that efficiently recombines electrons injected from the cathode 27 and holes transported from the hole injection layer 23 between electrodes to which an electric field is applied, and efficiently emits light by recombination. It is formed. Examples of materials that satisfy this condition include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline (Japanese Patent Laid-Open No. 6-322362). Bisstyrylbenzene derivatives (JP-A-1-245087 and JP-A-2-222484), bisstyrylarylene derivatives (JP-A-2-247278), metal complexes of (2-hydroxyphenyl) benzothiazole 8-315983), silole derivatives and the like.

  These light emitting layer materials are usually laminated on the hole injection layer 23 by vacuum deposition or coating. In the case of using the coating method, it is preferable to use a solvent that does not substantially dissolve the hole injection layer 23. However, in this embodiment, when the lower layer is three-dimensionally cross-linked, the resistance to the solvent is high, and the solvent Can be selected from a wide range.

For the purpose of improving the luminous efficiency of the device and changing the emission color, for example, doping a fluorescent dye for lasers such as coumarin with an aluminum complex of 8-hydroxyquinoline as a host material (J. Appl. Phys., Volume 65). 3610 (1989)). For example, using a metal complex such as an aluminum complex of 8-hydroxyquinoline as a host material, a naphthacene derivative represented by rubrene (JP-A-4-335087), a quinacridone derivative (JP-A-5-70773), perylene, etc. A condensed polycyclic aromatic ring (Japanese Patent Laid-Open No. 5-198377) is doped in an amount of 0.1% by mass to 10% by mass with respect to the host material. As a method of doping the host material of the light emitting layer with a fluorescent dye such as the naphthacene derivative, quinacridone derivative, or perylene, there are a method by co-evaporation and a method in which an evaporation source is mixed at a predetermined concentration.
Examples of the polymer light emitting layer material include poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene], poly (3-alkyl) mentioned above. Examples thereof include a polymer material such as thiophene) and a system in which a light emitting material and an electron transfer material are mixed with a polymer such as polyvinyl carbazole.

These materials are formed on the hole injection layer 23 by a method such as spin coating or dip coating as in the case of the hole injection layer to form a thin film. When using the coating method, the hole injection layer 23 is not substantially dissolved. Although it is preferable to use a solvent, in this embodiment, when the lower layer is three-dimensionally cross-linked, resistance to the solvent is high, and the solvent can be selected from a wide range.
The film thickness of the light emitting layer 25 thus formed is usually 10 nm to 200 nm, preferably 30 nm to 100 nm.

  As shown in FIG. 8, a hole transport layer 24 is provided between the hole injection layer 23 and the light emitting layer 25, and further, as shown in FIG. 9, an electron transport layer 26 is provided between the light emitting layer 25 and the cathode 27. For example, the function separation type is provided. 8 and 9, the material of the hole transport layer 24 is a material that has a high hole injection efficiency from the hole injection layer 23 and can efficiently transport the injected holes. It is desirable that As this hole transport material, for example, an aromatic diamine compound in which a tertiary aromatic amine unit such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane is linked (Japanese Patent Laid-Open No. 59-194393). Gazette), 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl represented by two or more tertiary amines and two or more condensed aromatic rings substituted with nitrogen atoms Aromatic amine (Japanese Patent Laid-Open No. 5-234681), an aromatic triamine having a starburst structure with a derivative of triphenylbenzene (US Pat. No. 4,923,774), N, N′-diphenyl-N, N Aromatic diamines (US Pat. No. 4,764,625) such as' -bis (3-methylphenyl) biphenyl-4,4'-diamine, Phenylamine derivatives (JP-A-4-129271), compounds in which a plurality of aromatic diamino groups are substituted on pyrenyl groups (JP-A-4-175395), aromatics in which tertiary aromatic amine units are linked by ethylene groups Diamine (JP-A-4-264189), aromatic diamine having a styryl structure (JP-A-4-290851), and aromatic tertiary amine unit linked by thiophene group (JP-A-4-304466) A starburst type aromatic triamine (Japanese Patent Laid-Open No. 4-308688), a benzylphenyl compound (Japanese Patent Laid-Open No. 4-364153), a tertiary amine linked by a fluorene group (Japanese Patent Laid-Open No. 5-25473), Triamine compounds (JP-A-5-239455), bisdipyridylaminobiphenyl (JP-A-5-239455) No. 5-320634), N, N, N-triphenylamine derivatives (JP-A-6-1972), aromatic diamines having a phenoxazine structure (JP-A-7-138562), diaminophenylphenanthridine Derivatives (JP-A-7-252474), silazane compounds (US Pat. No. 4,950,950), silanamin derivatives (JP-A-6-49079), phosphamine derivatives (JP-A-6-25659), etc. Is mentioned. These compounds may be used alone or as a mixture of two or more as necessary. In addition to the above compounds, materials for the hole transport layer 24 include polyvinyl carbazole, polysilane, polyphosphazene (JP-A-5-310949), polyamide (JP-A-5-310949), polyvinyltriphenylamine ( JP-A-7-53953), a polymer having a triphenylamine skeleton (JP-A-4-133055), and a polymer material such as polymethacrylate containing an aromatic amine.

  The hole transport layer 24 is formed by laminating the above hole transport material on the hole injection layer 23 by a coating method or a vacuum deposition method. In the case of the coating method, an additive such as a binder resin or a coating property improving agent that does not trap holes is added to one or more of the hole transport materials, if necessary, and dissolved to prepare a coating solution. Then, it is applied on the hole injection layer 23 by a method such as spin coating, and dried to form the hole transport layer 24. When the coating method is used, it is preferable to use a solvent that does not substantially dissolve the hole injection layer 23. However, when the lower layer is three-dimensionally cross-linked in this embodiment, the resistance to the solvent is high, and the solvent is widely used. You can choose from a wide range.

  Here, examples of the binder resin include polycarbonate, polyarylate, and polyester. The addition amount of the binder resin is usually preferably 50% by mass or less.

In the case of the vacuum deposition method, the hole transport material is put in a crucible installed in a vacuum vessel, and after evacuating the inside of the vacuum vessel to about 10 ⁻⁴ Pa with a suitable vacuum pump, the crucible is heated, The hole transport material is evaporated, and the hole transport layer 24 is formed on the substrate 21 on which the anode 22 and the hole injection layer 23 are formed, facing the crucible.
The film thickness of the hole transport layer 24 thus formed is usually from 10 nm to 300 nm, preferably from 30 nm to 100 nm.
In general, the above vacuum deposition method is often used.

Further, the compound used for the electron transport layer 26 is required to easily inject electrons from the cathode 27 and to have a larger electron transport capability. Examples of the electron transport material include 8-hydroxyquinoline aluminum complexes and oxadiazole derivatives (Appl. Phys. Lett., 55, 1489, 1989) already mentioned in the light-emitting layer materials and polymethyl methacrylate. (PMMA) or other resin-dispersed system, phenanthroline derivative (Japanese Patent Laid-Open No. 5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthraquinonediimine, n-type hydrogenated amorphous Examples thereof include silicon carbide, n-type zinc sulfide, and n-type zinc selenide.
The film thickness of the electron transport layer 26 is usually 5 nm to 200 nm, preferably 10 nm to 100 nm.

The cathode 27 serves to inject electrons into the light emitting layer 25. As the material used for the cathode 27, the material used for the anode 22 is used. However, for efficient electron injection, a metal having a low work function is preferable, such as tin, magnesium, indium, calcium, aluminum, silver, and the like. Suitable metals or their alloys are used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.
The film thickness of the cathode 27 usually includes the range described in the description of the anode 22.

In order to protect the cathode 27 made of a low work function metal, it is also effective to stack a metal layer having a high work function and stable to the atmosphere. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, platinum are used. Furthermore, it is also an effective method to insert a very thin insulating film (0.1 nm or more and 5 nm or less) such as LiF, MgF ₂ , or Li ₂ O at the interface between the cathode 27 and the light emitting layer 25 or the electron transport layer 26 (Appl Phys. Lett., 70, 152, 1997; JP-A-10-74586; IEEE Trans. Devices, 44, 1245, 1997).

  7 to 9 are examples of the element structure employed in the present embodiment, and the present embodiment is not limited to the illustrated one. For example, the cathode 27, the light emitting layer 25, the hole injection layer 23, and the anode 22 may be laminated in this order on the substrate 21, that is, at least one of which is transparent as described above. The organic electroluminescent element of this embodiment may be provided between two high substrates. 8 and 9 may be laminated in the reverse structure. Further, it is effective to form a sealing layer that is sealed with a material such as resin or metal to protect it from the air or water, or to have a structure in which the element itself is operated in a vacuum system.

  EXAMPLES Examples and comparative examples will be described below, but the present invention is not limited to the following examples. In the following, “part” is based on mass unless otherwise specified.

[Example 1: Synthesis of compound (II-7)]
A 500 ml flask is charged with 20 g of the compound (D) represented by the following structural formula, 5.94 g of itaconic acid, 0.5 g of 4-nitro-benzenesulfonic acid hydrate, and 200 ml of toluene. While removing with a Dean-Stark trap, the mixture was heated to reflux for 10 hours. After the reaction, it was washed with an aqueous potassium carbonate solution, then washed with distilled water, and then dropped into 2000 ml of methanol to precipitate a polymer. After washing with methanol, it was dried to obtain 15.4 g of compound (II-7). When the molecular weight was measured by GPC, it was 15000 in terms of polystyrene.
FIG. 10 shows the IR spectrum of the obtained compound (II-7).

[Example 2: Synthesis of compound (II-29)]
A 500 ml flask is charged with 20 g of the compound (E) represented by the following structural formula, 3.78 g of itaconic acid, 0.5 g of paratoluenesulfonic acid, 0.1 g of nitrobenzene, and 200 ml of toluene. The mixture was heated to reflux for 10 hours while being removed with a Stark trap. After the reaction, it was washed with an aqueous potassium carbonate solution, then washed with distilled water, and then dropped into 2000 ml of methanol to precipitate a polymer. After washing with methanol and drying, 16.9 g of compound (II-29) was obtained. When the molecular weight was measured by GPC, it was 22,000 in terms of polystyrene.
An IR spectrum of the obtained compound (II-29) is shown in FIG.

[Example 3: Synthesis of compound (II-20)]
In a 500 ml flask, 20 g of compound (F) represented by the following structural formula, 3.90 g of itaconic acid, 0.1 g of 4-nitro-benzenesulfonic acid hydrate, 4.14 g of potassium carbonate, 200 ml of N, N-dimethylformamide After replacing with nitrogen and heating at 80 ° C. for 10 hours. After the reaction, 200 ml of toluene was added, washed with dilute hydrochloric acid and then with water, and then dropped into 2000 ml of methanol to precipitate a polymer. After washing with methanol, it was dried to obtain 15.9 g of compound (II-20). When the molecular weight was measured by GPC, it was 25000 in terms of polystyrene.
FIG. 12 shows the IR spectrum of the obtained compound (II-20).

[Example 4]
<Production of photoconductor>
(Preparation of undercoat layer)
100 parts of zinc oxide (average particle size 70 nm: manufactured by Teika: specific surface area value 15 m ² / g) is stirred and mixed with 500 parts of tetrahydrofuran, and 1.3 parts of a silane coupling agent (KBM503: manufactured by Shin-Etsu Chemical Co., Ltd.) is added. And stirred for 2 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 3 hours to obtain a surface-treated zinc oxide having a silane coupling agent.
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, zinc oxide to which alizarin was imparted by filtration under reduced pressure was filtered off, and further dried at 60 ° C. under reduced pressure to obtain alizarin-given zinc oxide.
60 parts of this alizarin-provided zinc oxide, 13.5 parts of a curing agent (blocked isocyanate, Sumidur 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) and 15 parts of butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.) 85 parts of methyl ethyl ketone 38 parts of the solution dissolved in 25 parts of methyl ethyl ketone was mixed and dispersed in a sand mill for 2 hours using 1 mmφ glass beads to obtain a dispersion.
To the obtained dispersion, 0.005 part of dioctyltin dilaurate and 45 parts of silicone resin particles (Tospearl 145, manufactured by GE Toshiba Silicone) were added as a catalyst to obtain a coating liquid for undercoat layer. This coating solution was applied by dip coating onto an aluminum substrate having a diameter of 30 mm, a length of 340 mm, and a thickness of 1 mm, followed by drying and curing at 170 ° C. for 40 minutes to obtain an undercoat layer having a thickness of 18 μm.

(Preparation of charge generation layer)
Bragg angles (2θ ± 0.2 °) of X-ray diffraction spectrum using Cukα characteristic X-ray as a charge generating material are at least 7.3 °, 16.0 °, 24.9 °, 28.0 ° A mixture of 15 parts of hydroxygallium phthalocyanine having a diffraction peak, 10 parts of vinyl chloride / vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar) as a binder resin, and 200 parts of n-butyl acetate was used. The glass beads were used for dispersion for 4 hours in a sand mill. To the obtained dispersion, 175 parts of n-butyl acetate and 180 parts of methyl ethyl ketone were added and stirred to obtain a charge generation layer coating solution. 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 compound (II-7) and 0.2 part of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight 354.4) were added to 40 parts of chlorobenzene and dissolved to obtain a charge transport layer coating solution. This coating solution is applied onto the charge generation layer by push-up coating, air-dried at room temperature (20 ° C.) for 30 minutes, and then at a rate of 10 ° C./minute from room temperature (20 ° C.) under nitrogen with an oxygen concentration of 200 ppm. The electrophotographic photosensitive member of Example 4 was manufactured by heating to 150 ° C. and curing by heating at 150 ° C. for 1 hour to form a charge transport layer having a thickness of 18 μm.

<Evaluation of image quality>
The electrophotographic photosensitive member produced as described above was mounted on Apeos Port-IV C4470 manufactured by Fuji Xerox Co., Ltd. Was continuously evaluated.

  First, 10,000 sheets of image formation tests were performed in a low-temperature and low-humidity (8 ° C., 20% RH) environment, and image quality evaluation (ghost, fogging, streaks, image flow described below) was performed for the 10,000th sheet. Next, image quality evaluation was performed on the first image quality after being left for 24 hours in a low temperature and low humidity (8 ° C., 20% RH) environment.

Following the image quality evaluation under this low temperature and low humidity environment, an image formation test of 10,000 sheets was performed in an environment of high temperature and high humidity (30 ° C., 85% RH), and the image quality evaluation of the 10,000th sheet was performed. Next, image quality evaluation was performed on the image quality of the first sheet after being left for 24 hours in an environment of high temperature and high humidity (30 ° C., 85% RH).
The results are shown in Tables 2 and 3.

(Ghost evaluation)
For the ghost, a chart of a pattern having a gray region with G and an image density of 50% shown in FIG.
A: Good or slight as shown in FIG.
B: Slightly noticeable as shown in FIG.
C: It is clearly confirmed as shown in FIG.

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

(Streak evaluation)
The streak evaluation was judged visually using the same sample as the ghost evaluation described above.
A: Good.
B: Streaks are partially generated.
C: Streaks that cause image quality problems.

(Image flow evaluation)
The image flow was judged visually using the same sample as the ghost evaluation described above.
A: Good.
B: No problem during continuous print test, but occurs after standing for 1 day (24 hours).
C: Occurs during continuous print test.

<Evaluation of increase in residual potential>
The residual potential was measured by the following method, and the increase in the residual potential before and after the print test was evaluated. A potential sensor was attached to a modified Apeos Port-IV C4470 manufactured by Fuji Xerox Co., Ltd., and the residual potential was measured before the print test under low temperature and low humidity (8 ° C., 20% RH). Next, immediately after the print test of 10,000 sheets under low temperature and low humidity (8 ° C., 20% RH), the residual potential on the surface of the electrophotographic photosensitive member is measured similarly under low temperature and low humidity (8 ° C., 20% RH). Went. The difference between the initial potential and the residual potential after the 10,000-sheet print test (residual potential after the 10,000-sheet print test-initial residual potential) was defined as the increment.

<Evaluation of wear amount of charge transport layer>
The initial film thickness of the photoconductor is vortexed after completion of the image formation test in the low temperature and low humidity (8 ° C., 20% RH) environment and the high temperature and high humidity (30 ° C., 85% RH) environment. The amount of wear was evaluated by measuring with a current measuring device (Fisherscope MMS).

[Examples 5 to 10]
The charge generation layer was produced by the method described in Example 4. Subsequently, the charge transport layer was prepared and evaluated in the same manner as in Example 4 except that the charge transport layer material was changed as shown in Table 1. The materials used are summarized in Table 1.

[Example 11]
The charge generation layer was produced by the method described in Example 4. Next, 10 parts of compound (II-7), 2 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) 0.2 part was dissolved in 40 parts of monochlorobenzene and applied on the charge transport layer by push-up coating. After air drying at room temperature (20 ° C.) for 30 minutes, light irradiation was performed under nitrogen with an oxygen concentration of 200 ppm under the conditions of a metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , irradiation time: 60 seconds. Then, the coating film was cured. Further, drying was performed at 130 ° C. for 20 minutes to form a surface layer having a film thickness of 17 μm to produce a photoreceptor of Example 11, and evaluation was performed by the method described in Example 4.

[Example 12]
The charge generation layer was produced by the method described in Example 4. Next, 10 parts of compound (II-7), 2 parts of compound (G) represented by the following structural formula, 0.2 part of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight 354.4) were dissolved in 40 parts of monochlorobenzene. Then, it was applied on the charge transport layer by a push-up coating. After air drying at room temperature (20 ° C.) for 30 minutes, the temperature is raised from room temperature (20 ° C.) to 150 ° C. at a rate of 10 ° C./minute under nitrogen with an oxygen concentration of 200 ppm, and cured by heating at 150 ° C. for 1 hour. Then, a 18 μm-thick charge transport layer was formed to produce an electrophotographic photosensitive member of Example 12, and evaluation was performed by the method described in Example 4.

[Example 13]
The charge generation layer was produced by the method described in Example 4. Next, 10 parts of compound (II-7) and 0.8 parts of polytetrafluoroethylene particles (Lublon L-2, manufactured by Daikin Industries) were dissolved in 40 parts of monochlorobenzene, and nanomizer (NM2-L200AR-D08, Nanomizer) Then, 0.2 part of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight 354.4) was added and dissolved, and applied on the charge transport layer by push-up coating. After air drying at room temperature (20 ° C.) for 30 minutes, the temperature is raised from room temperature (20 ° C.) to 150 ° C. at a rate of 10 ° C./minute under nitrogen with an oxygen concentration of 200 ppm, and cured by heating at 150 ° C. for 1 hour. Then, an electrophotographic photosensitive member of Example 13 was produced by forming a charge transport layer having a thickness of 18 μm and evaluated by the method described in Example 4.

[Example 14]
The charge generation layer was produced by the method described in Example 4. On this charge generation layer, 40 parts by mass of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine (TPD), N, 10 parts by mass of N-bis (3,4-dimethylphenyl) biphenyl-4-amine and 55 parts by mass of bisphenol Z polycarbonate resin (PC (Z): viscosity average molecular weight: 60,000) were added to 800 parts by mass of chlorobenzene. The dissolved 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 surface layer)
10 parts of the compound (II-20) and 3 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) are dissolved in 20 parts of monochlorobenzene and 40 parts of toluene. It was applied to. After air drying at room temperature (20 ° C.) for 30 minutes, while rotating the photoconductor at a speed of 300 rpm under nitrogen with an oxygen concentration of 20 ppm, the irradiation distance is 30 mm, the electron beam acceleration voltage is 90 kV, the electron beam beam current is 2 mA, the electron beam The photosensitive member was irradiated with an electron beam under an irradiation time of 1.0 second. Immediately after irradiation, the film was heated to 150 ° C. under nitrogen with an oxygen concentration of 20 ppm, held for 10 minutes to complete the curing reaction, and a surface layer with a film thickness of 4 μm was formed to produce the photoreceptor of Example 14. Evaluation was carried out by the method described in Example 4.

[Examples 15 to 18]
A photoconductor was prepared and evaluated by the method described in Example 14 except that the compound (II-20) in Example 14 was changed to that shown in Table 1.

[Example 19]
The charge generation layer was produced by the method described in Example 4.
Subsequently, 10 parts of compound (II-7) was added to 40 parts of chlorobenzene and dissolved to obtain a coating solution for charge transport layer. This coating solution was applied onto the charge generation layer by push-up coating, air-dried at room temperature (20 ° C.) for 30 minutes, and then heated from room temperature (20 ° C.) to 150 ° C. at a rate of 10 ° C./min. The electrophotographic photosensitive member of Example 19 was prepared by heating and drying at 0 ° C. for 1 hour to form a charge transport layer having a thickness of 25 μm, and evaluation was performed by the method described in Example 4.

[Comparative Example 1]
Evaluation was carried out by the method described in Example 4 with the charge transport layer of Example 14 having a thickness of 25 μm and the surface layer not formed as a photoreceptor of Comparative Example 1.

[Comparative Example 2]
A photoconductor was prepared and evaluated by the method described in Example 4 except that the compound (II-7) in Example 4 was changed to the compound (H) having the following structural formula.

[Comparative Example 3]
100 parts by mass of the compound (I) having the following structural formula, 100 parts by mass of glycidyl methacrylate, 2 parts by mass of azobisisobutyronitrile, and 460 parts by mass of toluene were charged into a three-necked flask and purged with nitrogen at room temperature for 30 minutes. After heating to 75 ° C. and reacting for 7 hours, the reaction was terminated by diluting with 200 parts by mass of toluene. After adding 28 parts by mass of acrylic acid, 0.4 parts by mass of hydroquinone monomethyl ether and 1 part by mass of triphenylphosphine to this reaction solution, the mixture was reacted at 90 ° C. for 7 hours, diluted with 2000 parts by mass of toluene, and injected into 15000 parts by mass of methanol. And precipitated. The polymer was filtered, washed with methanol, and then vacuum dried to obtain 205 parts by mass of a reactive charge transporting polymer described in Example 1 of JP-A-2005-2291 (P-1). The polystyrene equivalent molecular weight Mw by GPC was 18000. A photoconductor of Comparative Example 3 was produced in the same manner as in Example 14 except that this reactive charge transporting polymer was used instead of the compound (II-20) of Example 14.

  As shown in Tables 2 and 3, the electrophotographic photosensitive member of the example has suppressed deterioration in image quality after repeated use over a long period of time.

[Example 20]
<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 cleaning machine (manufactured by Samco International, BP1).
A solution prepared by dissolving 10 parts of the compound (II-7) and 0.2 parts of OTazo-15 (Otsuka Chemical, molecular weight 354.4) in 50 parts of dichloromethane was spin-coated at a rotation speed of 300 rpm, and then an oxygen concentration of 150 ppm. By heating and curing at 160 ° C. for 1 hour under nitrogen, a hole injection layer having a thickness of 400 nm (measured with a stylus thickness meter) was formed.
The obtained cured film (hole injection layer) did not dissolve even when immersed in toluene at room temperature and 50 ° C. for 10 minutes, and was stable with respect to the solvent and heat.

  Next, on this hole injection layer, tris (8-hydroxyquinoline) aluminum (Alq) as a material for the light emitting layer is vacuum-deposited to a thickness of 50 nm, and then a magnesium / silver alloy cathode is deposited to a thickness of 200 nm. Then, an organic EL element was produced.

<Evaluation>
Using the ITO electrode of this organic EL element as the anode, the magnesium / silver alloy electrode as the cathode, a direct current of 7 V was applied, the current density was determined by the following method, and the luminance was measured by the following method. Further, the luminance after 1000 hours of operation was measured by the following method, and the results are shown in Table 4.

The current density, voltage, and luminance were measured by using an organic EL luminous efficiency measuring device (manufactured by Tokyo Instruments Co., Ltd.) as a measuring device and adjusting the measuring conditions to 25 ° C.

  In addition, when an organic EL element is used for a display or a laser, high current injection is required. Therefore, the current density and luminance at an applied voltage of 7V were measured. The results are shown in Table 4. Further, luminance after driving for 1000 hours at an applied voltage of 7 V was measured and shown in Table 4.

[Examples 21-29]
An organic EL device was prepared and evaluated by the method described in Example 20 except that the compound (II-7) in Example 20 was changed to the compound shown in Table 4. The results are shown in Table 4.
In addition, the cured films (hole injection layers) in these examples did not dissolve even when immersed in toluene at room temperature and 50 ° C. for 10 minutes, and were stable to solvents and heat.

[Comparative Example 4]
Instead of the hole injection layer formed using the compound (II-7) in Example 20, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl An organic EL device was prepared and evaluated by the method described in Example 20 except that a hole injection layer obtained by vacuum-depositing -4,4'-diamine (TPD) at a film thickness of 400 nm was applied. The results are shown in Table 4.

  As shown in Table 4 above, the organic EL elements of the examples can obtain stable emission characteristics over a long period of time.

DESCRIPTION OF SYMBOLS 1 ... Undercoat layer, 2 ... Charge generation layer, 3 ... Charge transport layer, 4 ... Conductive substrate, 5 ... Protective layer, 6 ... Single layer type photosensitive layer, 7A, 7B, 7C, 7 ... Electrophotographic photoreceptor, DESCRIPTION OF SYMBOLS 8 ... Charging device, 9 ... Exposure device, 11 ... Developing device, 13 ... Cleaning device, 14 ... Lubricant, 21 ... Substrate, 22 ... Anode, 23 ... Hole injection layer, 24 ... Hole transport layer, 25 ... Light emission Layer, 26 ... electron transport layer, 27 ... cathode, 40 ... transfer device, 50 ... intermediate transfer member, 100 ... image forming device, 120 ... image forming device, 300 ... process cartridge

Claims (11)

A charge transporting polyester resin represented by the following general formula (1).


[In the general formula (1), A represents a divalent organic group having a charge transport property, T represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, n Represents an integer of 5 or more and 5000 or less. ]   The charge transporting polyester resin according to claim 1, wherein the A in the general formula (1) is a divalent organic group having a hole transporting property. The charge transporting polyester resin according to claim 1 or 2, wherein the A in the general formula (1) is a group represented by the following general formula (2).


[In the general formula (2), R ₁ and R ₂ are each independently hydrogen, an alkyl group, an alkoxy group, a halogen, a substituted or unsubstituted aryl group, and X is a substituted or unsubstituted divalent organic group. , K and m each independently represent 0 or 1. ]   X in the general formula (2) is a substituted or unsubstituted divalent aromatic group, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, substituted or unsubstituted. The charge transporting polyester resin according to claim 3, which represents a divalent condensed aromatic hydrocarbon group having 2 or more and 10 or less aromatic rings, or a substituted or unsubstituted divalent aromatic heterocyclic group. The charge transporting polyester resin according to claim 3 or 4, wherein the X in the general formula (2) is a divalent organic group selected from the group (A) shown below.

The charge transporting polyester resin according to any one of claims 3 to 5, wherein X in the general formula (2) is a divalent organic group selected from the following group (B).

  A charge transporting polyester resin solution in which the charge transporting polyester resin defined in claim 1 is dissolved in a solvent. Photoelectric conversion provided with a film containing a polyester polymer having a structure represented by the following general formula (1) as a partial structure, or a polyester crosslinked polymer having a structure represented by the following general formula (1 ') as a partial structure device.


[In the general formulas (1) and (1 ′), A represents a divalent organic group having a charge transporting property, and T represents a linear or branched divalent group having 1 to 10 carbon atoms. N represents an integer of 5 or more and 5000 or less. Moreover, in general formula (1 '), it represents that it has bridge | crosslinked polymerization at the position of [*]. ]   The photoelectric conversion device according to claim 8, wherein the film contains a polyester cross-linked polymer having a structure represented by the general formula (1 ′) as a partial structure. An electron comprising a photosensitive layer containing a polyester polymer having a structure represented by the following general formula (1) as a partial structure, or a polyester crosslinked polymer having a structure represented by the following general formula (1 ′) as a partial structure Photoconductor.


[In the general formulas (1) and (1 ′), A represents a divalent organic group having a charge transporting property, and T represents a linear or branched divalent group having 1 to 10 carbon atoms. N represents an integer of 5 or more and 5000 or less. Moreover, in general formula (1 '), it represents that it has bridge | crosslinked polymerization at the position of [*]. ]   The electrophotographic photosensitive member according to claim 10, wherein the photosensitive layer contains a polyester cross-linked polymer having a structure represented by the general formula (1 ′) as a partial structure.