JP5640772B2 - Thiol group-containing charge transport material, thiol group-containing charge transport material solution, photoelectric conversion device, and electrophotographic photoreceptor - Google Patents

Description

  The present invention relates to a thiol group-containing charge transport material, a thiol group-containing charge transport material solution, a photoelectric conversion device, and an electrophotographic photoreceptor.

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).

  Further, a film made of a compound obtained by polymerizing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule (see, for example, Patent Document 8), and a hole transporting compound having a thiol group in the siloxane matrix An electrophotographic photoreceptor using a film obtained by doping and curing a film (see, for example, Patent Document 9), and an electrophotographic photoreceptor using a film obtained by doping a hole transporting compound having a thiol group into an oxetane matrix and curing the film ( For example, refer to Patent Document 10).

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 2000-206715 A JP 2000-310870 A JP-A-2006-184803

  An object of the present invention is to obtain excellent electrical characteristics in a film formed using a material other than the thiol group-containing charge transporting material represented by the general formula (1).

The above object is achieved by the present invention described below.
That is, the invention according to claim 1
It is a thiol group-containing charge transport material represented by the following general formula (1).
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.

The invention according to claim 2
2. The thiol group-containing charge transport material according to claim 1, wherein the F in the general formula (1) is an organic group having a hole transport capability.

The invention according to claim 3
The thiol group-containing charge transport material according to claim 1 or 2 represented by the following general formula (2).

(In Formula (2), D represents a linking group represented by-(G) _a -XY-SH, Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, and Ar ⁵ represents a substitution. Or an unsubstituted aryl group or a substituted or unsubstituted arylene group, G is a divalent organic group having 1 to 5 carbon atoms, X is a -CO-O- group or -O-CO- group, Represents a divalent organic group having 1 to 5 carbon atoms, and a represents 0 or 1. One to four of Ar ^{1 to} Ar ⁵ is-(G) _a -XY-SH. And has a bond that can be bonded to the bonding group represented, c1 to c5 each independently represents an integer of 0 to 2, and k represents 0 or 1.)

The invention according to claim 4
A thiol group-containing charge transport material solution in which a thiol group-containing charge transport material represented by the following general formula (1) is dissolved in a solvent.
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.

The invention according to claim 5
It is a photoelectric conversion device provided with the film | membrane formed using the solution which the thiol group containing charge transport material shown by following General formula (1) melt | dissolved.
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.

The invention according to claim 6
The photoelectric conversion device according to claim 5, wherein the film contains a polymer obtained by polymerizing the thiol group-containing charge transport material.

The invention according to claim 7 provides:
An electrophotographic photoreceptor having a layer formed on a conductive substrate using a solution in which a thiol group-containing charge transport material represented by the following general formula (1) is dissolved.
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.

  According to the first aspect of the present invention, excellent electrical characteristics can be obtained in a film formed using a material other than the thiol group-containing charge transporting material represented by the general formula (1).

  According to the second aspect of the present invention, compared with the case where F in the general formula (1) is not an organic group having a hole transporting ability, excellent hole transportability can be obtained in a film formed using the group.

  According to the invention of claim 3, excellent hole transportability can be obtained in a film formed using a material other than the thiol group-containing charge transport material represented by the general formula (2).

  According to the fourth aspect of the present invention, excellent electrical characteristics can be obtained in a film formed using the thiol group-containing charge transport material represented by the general formula (1) as compared with the case where the thiol group-containing charge transport material is not dissolved.

  According to the fifth aspect of the present invention, the photoelectric characteristics excellent in electrical characteristics can be obtained as compared with the case where the film formed using the solution in which the thiol group-containing charge transporting material represented by the general formula (1) is dissolved is not provided. A conversion device is obtained.

  According to the invention of claim 6, the photoelectric conversion device is superior in mechanical strength and heat resistance as compared with a case where the thiol group-containing charge transport material represented by the general formula (1) does not contain a polymer obtained by polymerization. Is obtained.

  According to the invention according to claim 7, an electron excellent in electrical characteristics as compared with a case where the layer formed using a solution in which the thiol group-containing charge transporting material represented by the general formula (1) is dissolved is not included. A photographic photoreceptor is obtained.

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), and (C) are explanatory views showing ghost evaluation criteria, 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. It is a graph which shows IR spectrum of the thiol group containing charge transport material synthesize | combined in the Example. It is a graph which shows IR spectrum of the thiol group containing charge transport material synthesize | combined in the Example. It is a graph which shows IR spectrum of the thiol group containing charge transport material synthesize | combined in the Example.

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

The thiol group-containing charge transport material according to this embodiment is represented by the following general formula (1).
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.

The thiol group-containing charge transporting material represented by the general formula (1) has —SH as a polar group, and since there are relatively few polar groups that hinder carrier transport such as —OH and —NH—, this is used. In the film formed in this way, it is presumed that formation of traps for trapping charges is suppressed, and accumulation of residual potential is suppressed.
In addition, in a film obtained by crosslinking a polyfunctional charge transport material, the residual strain in the film increases as it is immobilized, but the thiol group-containing charge represented by the general formula (1) In the transport material, the charge transport component is cross-linked through a thioester group having a high degree of freedom of movement, so that residual strain in the film is suppressed and structural traps are hardly generated. It is assumed that it will be obtained.
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, when the polyfunctional acrylic monomer is further mixed with the charge transport material, the above-mentioned polyfunctional is used because the compatibility between the two is low in the ordinary charge transport material. There is a limit to increasing the amount of acrylic monomer added. However, since the thiol group-containing charge transporting material represented by the general formula (1) has an ester structure similar to that of a polyfunctional acrylic monomer and both are excellent in compatibility, it is compatible with the polyfunctional acrylic monomer. It is presumed that a film having both electrical properties and strength can be obtained by crosslinking without causing separation.

Furthermore, by forming a film using the thiol group-containing charge transporting material represented by the general formula (1), a thin film in which crystallization is suppressed and thickness unevenness is easily suppressed can be easily obtained. It is assumed that it is 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.

<Thiol group-containing charge transport material>
The novel thiol group-containing charge transport material of this embodiment is represented by the following general formula (1).
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.

  G is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms (including linear, branched or cyclic), a substituted or unsubstituted alkenyl group having 1 to 5 carbon atoms, An organic group in which a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms and —O— is combined, and an organic group in which a substituted or unsubstituted alkenyl group having 1 to 5 carbon atoms and —O— is combined. Group, etc. are mentioned as preferred. Among these, a linear and unsubstituted alkylene group having 1 to 5 carbon atoms, a linear and unsubstituted alkylene group having 1 to 5 carbon atoms, and a combination of —O—. Is more preferable.

  In addition, as said substituent, a halogen, an alkyl group, an alkoxy group etc. are mentioned, for example.

More specifically, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —O—C ₂ H ₄ —O—, _{-CH 2 -O-C 2 H 4} -O -, - CH = CH-CH 2 -, - O-C 2 H 2 -O -, - CH 2 -O-C 2 H 2 -O- are preferred Among them, among them, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —O—C ₂ H ₄ — O— and —CH ₂ —O—C ₂ H ₄ —O— are particularly preferred.

Y represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms (including linear, branched or cyclic), a substituted or unsubstituted alkenyl group having 1 to 5 carbon atoms, and the like. Is preferable. Examples of the substituent include —SH, halogen, an alkyl group, and an alkoxy group. Among these, an —SH group is particularly preferable.
Among these, an alkylene group which is linear or branched, is substituted with an —SH group or is unsubstituted, and has 1 to 5 carbon atoms is more preferable.

More specifically, —CH ₂ —, —C ₂ H ₄ —, —CH (CH ₃ ) —CH ₂ —, —CH (CH ₃ ) —, —CH ₂ —CH (SH) —CH ₂ —, _{-CH 2 -CH (CH 2 -SH)} - , and the like as preferred.

  F represents a structure having charge transporting properties, specifically, phthalocyanine compounds, porphyrin compounds, azobenzene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, Stilbene compounds, anthracene compounds, hydrazone compounds, quinone compounds, fluorenone compounds, and the like are used.

  Among these, those having an arylamine skeleton are preferable because of their high charge transport properties, and among the thiol group-containing charge transport materials represented by the general formula (1), those represented by the following general formula (2) are preferable. Most preferred.

(In Formula (2), D represents a linking group represented by-(G) _a -XY-SH, Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, and Ar ⁵ represents a substitution. Or an unsubstituted aryl group or a substituted or unsubstituted arylene group, G is a divalent organic group having 1 to 5 carbon atoms, X is a -CO-O- group or -O-CO- group, Represents a divalent organic group having 1 to 5 carbon atoms, and a represents 0 or 1. One to four of Ar ^{1 to} Ar ⁵ is-(G) _a -XY-SH. And has a bond that can be bonded to the bonding group represented, c1 to c5 each independently represents an integer of 0 to 2, and k represents 0 or 1.)

In the general formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, and Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same. But it may be different or different.
Here, as a substituent in the substituted aryl group, an alkyl group having 1 to 4 carbon atoms, carbon other than -D (that is, a linking group represented by-(G) _a -XY-SH), carbon Examples thereof include an alkoxy group having 1 to 4 carbon atoms and an aryl group having 6 to 10 carbon atoms, and these alkyl groups, alkoxy groups, and aryl groups may be substituted or unsubstituted.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are preferably any of the following formulas (1) to (7). The following formulas (1) to (7) collectively indicate “— (D) _C1 ” to “— (D) _C4 ” that can be linked to each of Ar ¹ , Ar ² , Ar ^3, and Ar ^4. It is shown together with "-(D) _C ".

In the above formulas (1) to (7), R ¹ is substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents one selected from the group consisting of a phenyl group, an unsubstituted phenyl group, and an aralkyl group having 7 to 10 carbon atoms, wherein R ² , R ³ and R ⁴ are each independently a hydrogen atom, a carbon number An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, And Ar represents a substituted or unsubstituted arylene group, D represents a linking group represented by-(G) _a -X-Y-SH, and c represents Represents 0, 1 or 2 S represents 0 or 1, t represents an integer of 0 to 3, and Z ′ represents a divalent organic linking group.

  Here, as Ar in Formula (7), what is represented by following Structural formula (8) or (9) is desirable.

In the above formulas (8) and (9), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. It represents one selected from the group consisting of the following phenyl groups substituted with alkoxy groups, unsubstituted phenyl groups, aralkyl groups having 7 to 10 carbon atoms, and halogen atoms, and t ′ is 0 or more and 3 or less, respectively. Represents an integer.

  In the formula (7), Z ′ is preferably represented by any one of the following formulas (10) to (17). S represents 0 or 1, respectively.

In the above formulas (10) to (17), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. It represents one selected from the group consisting of a phenyl group substituted with the following alkoxy group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, W represents a divalent group, q and r each independently represent an integer of 1 to 10, and t ″ represents an integer of 0 to 3.

  W in the formulas (16) to (17) is preferably any one of divalent groups represented by the following (18) to (26). However, in formula (25), u represents an integer of 0 or more and 3 or less.

In general formula (2), Ar ⁵ is a substituted or unsubstituted aryl group when k is 0, and examples of the aryl group include the aryl groups exemplified in the description of Ar ^{1 to} Ar ^4. It is done. When k is 1, Ar ⁵ is a substituted or unsubstituted arylene group. The arylene group includes an arylene group obtained by removing one hydrogen atom from the aryl group exemplified in the description of Ar ^{1 to} Ar ^4. Is mentioned.

As G and Y in -D in General Formula (2) (that is, a linking group represented by-(G) _a -XY-SH), each group exemplified in the description of General Formula (1) is Can be mentioned.

  In the general formula (2), c1 to c5 each independently represents 0, 1 or 2, and the total number of D is 1 or more. From the viewpoint of increasing the strength of the resulting cured film and suppressing the deterioration of image quality after repeated use, the total number of D is preferably 2 or more, and more preferably 4 or more.

Here, although the specific example of the thiol group containing charge transport material shown by General formula (1) is illustrated below, it is not restricted to this. In the following table showing examples of the compound represented by the general formula (1), the connecting portion of F- (G) _a -and -X- is represented by "*", -X- and -Y-SH and The connection part is represented by “#”.

Next, the synthesis method will be described.
The thiol group-containing charge transport material represented by the general formula (1) is synthesized by a normal esterification reaction.
For example, a method of transesterifying an arylamine compound containing an ester group described in JP-A-9-31039 with an thiol-containing alcohol, or free hydrolysis of an arylamine compound containing an ester group by hydrolysis. The acid is synthesized by a method of esterifying with a thiol-containing alcohol or a thiol-containing hydrocarbon chlorinated, brominated or iodinated, etc. In addition, an arylamine compound containing an ester group is synthesized by reducing it to the corresponding alcohol with lithium aluminum hydride, sodium borohydride or the like and then reacting with the corresponding thiol-containing carboxylic acid compound.

  Further, an alcohol represented by the following general formula (3), a carboxylic acid represented by the following general formula (4), a carboxylic acid represented by the following general formula (5), and an alcohol represented by the following general formula (6) Is synthesized by esterification using an acid catalyst such as sulfuric acid or p-toluenesulfonic acid. Moreover, you may use the corresponding carboxylic acid chloride instead of carboxylic acid.

F-[(G) _a -OH] _b General formula (3)
HOOC-Y-SH General formula (4)
F-[(G) _a -COOH] _b General formula (5)
HO-Y-SH General formula (6)
(In the formula, F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and Y represents a divalent organic group having 1 to 5 carbon atoms. A represents 0 or 1, and b represents an integer of 1 to 6.

  Transesterification is described in, for example, Experimental Chemistry Course, 4th edition, volume 28, p. As described in 217 and the like, it is carried out by heating using an excess amount of a thiol-containing alcohol and an organometallic compound such as titanium, tin, or zinc.

The thiol-containing alcohol is preferably added in an amount of 1 equivalent or more, preferably 1.2 equivalents or more, more preferably 1.5 equivalents or more with respect to the ester group of the arylamine compound.
An inorganic acid such as sulfuric acid or phosphoric acid, an acetate or carbonate such as titanium alkoxide, calcium or cobalt, or an oxide of zinc or lead may be added as a catalyst. The catalyst is preferably used in an amount of 1/10000 parts by mass or more and 1 part by mass or less, and 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 arylamine compound.

  The reaction is preferably performed at a reaction temperature of 100 ° C. or higher and 300 ° C. or lower, more preferably at a boiling point or higher of the alcohol to be eliminated.

The ester group of the arylamine compound is preferably an ester with a low-boiling alcohol such as methanol or ethanol in order to promote the transesterification reaction.
The reaction is preferably performed in an inert gas such as nitrogen or argon, and may be performed using a high boiling point solvent such as p-cymene or 1-chloronaphthalene.

The arylamine compound carboxylic acid is prepared by reacting an ester group of an arylamine compound with, for example, Experimental Chemistry Course, 4th Edition, Volume 20, P.I. As described in No. 51 and the like, it is carried out by hydrolysis using a basic catalyst such as NaOH and K ₂ CO ₃ or an acidic catalyst such as phosphoric acid and sulfuric acid. In this case, various solvents are used, but it is preferable to use an alcohol such as methanol, ethanol, ethylene glycol, or a mixture of water. Further, when the solubility is low, methylene chloride, chloroform, toluene, dimethyl sulfoxide, ether, tetrahydrofuran or the like may be added.
Although there is no restriction | limiting in particular in the amount of solvents, It is preferable to use 1 to 100 mass parts with respect to 1 mass part of arylamine compounds containing an ester group, Preferably it is 2 to 50 mass parts.
The reaction temperature is set from room temperature (20 ° C.) to the boiling point of the solvent, and is preferably 50 ° C. or higher in view of the reaction rate.
Although there is no restriction | limiting in particular about the quantity of a catalyst, 0.001 mass part or more and 1 mass part or less with respect to 1 mass part of arylamine compounds containing an ester group, Preferably it is 0.01 mass part or more and 0.5 mass part or less. It is preferable to use in.
When hydrolysis is performed with a basic catalyst after the hydrolysis reaction, the resulting salt is neutralized with an acid such as hydrochloric acid and released. Furthermore, after washing thoroughly with water, use it after drying, or if necessary, recrystallize it with an appropriate solvent such as methanol, ethanol, toluene, ethyl acetate, acetone, etc., and use it after drying. Also good.

It is preferable to add 1 equivalent or more, preferably 1.2 equivalent or more, more preferably 1.5 equivalent or more of the thiol-containing alcohol to the arylamine compound carboxylic acid.
It is synthesized by dehydration and esterification using an inorganic acid such as sulfuric acid and phosphoric acid and an organic acid such as p-toluenesulfonic acid as a catalyst. The catalyst is preferably used in an amount of 1/10000 parts by mass or more and 1 part by mass or less, and 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 arylamine compound.

In the reaction, in order to remove water generated during the polymerization, it is preferable to use a solvent that can be azeotroped with water. Toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and used in the range of 1 part by mass to 100 parts by mass, preferably 2 parts by mass to 50 parts by mass with respect to 1 part by mass of the arylamine compound carboxylic acid. Is preferred.
The reaction temperature is freely 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. 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 further purified using an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay if necessary. Also good.

In addition, the thiol-containing hydrocarbon having a halogen group such as Cl, Br, or I is 1 equivalent or more and 5 equivalents or less, preferably 1.1 equivalent or more and 3 equivalents or less with respect to the acid group of the arylamine compound carboxylic acid. And bases such as pyridine, piperidine, triethylamine, dimethylaminopyridine, trimethylamine, DBU, sodium hydride, sodium hydroxide, potassium hydroxide, etc., and non-bases such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, etc. It is synthesized by reacting in an organic solvent such as a protic polar solvent, a ketone solvent such as acetone or methyl ethyl ketone, or an ether solvent such as diethyl ether or tetrahydrofuran.
The base is preferably used in an amount of 1 to 3 equivalents, preferably 1 to 2 equivalents, relative to the carboxylic acid. The aprotic organic solvent to be used is used in an amount of 1 to 50 parts by mass, preferably 1.5 to 30 parts by mass, based on the carboxylic acid derivative.
The reaction temperature is freely set between 0 ° C. and the boiling point of the solvent, but preferably 0 ° C. or more and 150 ° C. or less. 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 further purified using an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay if necessary. Also good.

  In addition, the ester group of the arylamine compound is described in, for example, Experimental Chemistry Course, 4th Edition, Volume 20, P.I. 10 or the like, it may be synthesized by reducing to the corresponding alcohol using lithium aluminum hydride, sodium borohydride or the like, and esterifying with a thiol-containing carboxylic acid.

<Thiol group-containing charge transport material solution>
The thiol group-containing charge transport material solution according to this embodiment is obtained by dissolving the thiol group-containing charge transport material 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 thiol group-containing charge transport material represented by the general formula (1) in these solvents, 10 to 150 ° C., preferably 15 to 120 ° C., and stirring and mixing with the solvent, or It can be carried out by a usual method such as stirring with ultrasonic irradiation.

  The thiol group-containing charge transport material solution according to the present embodiment is used, for example, for forming a film in a photoelectric conversion device (organic EL device, electrophotographic photoreceptor, etc.), forming a solar cell, an organic transistor, or the like.

<Photoelectric conversion device>
Next, the photoelectric conversion device will be described.
The thiol group-containing charge transport material according to this embodiment may form a film as a vapor deposition film alone, but may also form a film using a solution in which the thiol group-containing charge transport material is dissolved. Further, this film may contain a polymer obtained by polymerizing the thiol group-containing charge transport material.
A film in which the thiol group-containing charge transport material is molecularly dispersed in a resin such as a polycarbonate resin, a polyarylate resin, or a polyester resin has excellent practicality and is mixed with a monomer, oligomer, or polymer having a double bond. The cured film is most preferably used.

-Non-reactive binder resin When the above thiol group-containing charge transport material is compatible with the resin, polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, etc. Non-reactive binder resin is 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 In the case of curing, the thiol group-containing charge transporting material represented by the general formula (1) may further contain a reactive compound, particularly including two or more double bonds in the same molecule. It is preferable to improve the strength by mixing monomers, oligomers or polymers and curing.

  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 thiol group-containing charge transport material is dissolved and obtaining a cured film by polymerizing the components in the solution, heat, light, radiation, etc. Is 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 optimally 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 sufficiently 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 photosensitive member according to this embodiment has a layer formed on a conductive substrate using a solution in which the thiol group-containing charge transport material represented by the general formula (1) is dissolved.

  Furthermore, strength may be imparted without reducing the concentration of the charge transport component by making the crosslinkable monomer itself a polyfunctional charge transport monomer.

In the electrophotographic photoreceptor according to the exemplary embodiment, it is preferable that the outermost surface layer includes a layer containing the thiol group-containing charge transporting material represented by the general formula (1), and the outermost surface layer is formed of the electrophotographic photoreceptor itself. The uppermost surface may be formed and provided as a layer functioning as a protective layer or a layer functioning as a charge transport 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.

When 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 contains a thiol group represented by the general formula (1) Examples include a composition containing a polymer formed using a charge transport material, or a layer containing a cured product thereof.
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 general formula (1) Examples include a composition containing a polymer formed using the thiol group-containing charge transporting material 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 thiol group-containing charge transport material represented by the general formula (1) is dissolved. It is preferable to contain a polymer containing the structure shown in 1) as a partial structure, and it is most preferable that the polymer is further cured, that is, contains a polymer obtained by polymerizing the thiol group-containing charge transport material.

  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, and 3,5-di-t-butyl-4- And hydroxybiphenyl.
Examples of the hindered amine antioxidant include Sanol LS2626, Sanol LS765, Sanol LS770, Sanol LS744, Tinuvin 144, Tinuvin 622LD, Mark LA57, Mark LA67, Mark LA62, Mark LA68, and Mark LA63. The phosphite system includes mark 2112, mark PEP-8, mark PEP-24G, mark PEP-36, mark 329K, mark HP-10, 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 Examples thereof include semiconductive metal oxides such as —TiO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. 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 solution for forming a protective layer) in which the thiol group-containing charge transporting material represented by the general formula (1) is dissolved in a solvent. Is 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 reactions as described above, the oxygen concentration is preferably set in a vacuum or an inert gas atmosphere so that the radical generated by light, electron beam or heat can be chain-reacted without being deactivated. It is performed at a low oxygen concentration of 10% or less, more desirably 5% or less, even more desirably 2% or less, and most desirably 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, anthracine, 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, ethyl 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 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 generating 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, titanyl phthalocyanine disclosed in JP-A-4-189873, JP-A-5-43823 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 through 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 an oscillation wavelength laser in the 600 nm range or a laser having an oscillation wavelength in the vicinity 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 heated and 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, caryl 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 using a solution in which the thiol group-containing charge transport material represented by the general formula (1) is dissolved.

  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 thiol group-containing charge transporting material represented by the general formula (1) is formed by vapor deposition or a coating method, and the coating method is preferable when cured. For example, the case where it forms as a positive hole injection layer is demonstrated to an example.
If necessary, a binder resin, a coating property improving agent, a chain polymerizable monomer, an oligomer, or the like that does not trap holes may be added to a predetermined amount of the thiol group-containing charge transporting material 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 onto 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. Materials satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (JP 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline (JP 6-322362 A). Gazette), bisstyrylbenzene derivatives (JP-A-1-245087, JP-A-2-222484), bisstyrylarylene derivatives (JP-A-2-247278), metal complexes of (2-hydroxyphenyl) benzothiazole ( JP-A-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 such a 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. 59-86). No. 194393), including two or more tertiary amines represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, and two or more condensed aromatic rings are nitrogen atoms Aromatic amines substituted with the above (Japanese Patent Laid-Open No. 5-234681), triphenylbenzene derivatives and aromatic triamines having a starburst structure (US Pat. No. 4,923,774), N, N′-diphenyl-N , N′-bis (3-methylphenyl) biphenyl-4,4′-diamine, etc. (US Pat. No. 4,764,625), sterically unpaired as a whole molecule Triphenylamine derivatives (JP-A-4-129271), compounds in which a pyrenyl group is substituted with a plurality of aromatic diamino groups (JP-A-4-175395), and tertiary aromatic amine units linked by an ethylene group Aromatic diamines (JP-A-4-264189), aromatic diamines having a styryl structure (JP-A-4-290851), and aromatic tertiary amine units linked by thiophene groups (JP-A-4-304466) Gazette), starburst type aromatic triamine (JP-A-4-308688), benzylphenyl compound (JP-A-4-364153), and a tertiary amine linked by a fluorene group (JP-A-5-25473) ), A triamine compound (JP-A-5-239455), bisdipyridylaminobiphenyl JP-A-5-320634), N, N, N-triphenylamine derivatives (JP-A-6-1972), aromatic diamines having a phenoxazine structure (JP-A-7-138562), diaminophenylphenol Nantridine derivative (JP-A-7-252474), silazane compound (US Pat. No. 4,950,950), silanamine derivative (JP-A-6-49079), phosphamine derivative (JP-A-6-25659) ) And the like. 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 such an 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 polymethacrylic acid. A system dispersed in a resin such as methyl acid (PMMA), a phenanthroline derivative (Japanese Patent Laid-Open No. 5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthraquinonediimine, non-hydrogenated n-type Examples thereof include crystalline 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 (13)]
A 500 ml flask is charged with 20 g of the compound represented by the following structural formula (A), 15 g of 3-mercaptopropionic acid, 0.5 g of paratoluenesulfonic acid, and 200 ml of toluene. After replacing with nitrogen, the generated water is removed 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 purified by silica gel column chromatography to obtain 23 g of compound (13) as an oil.
FIG. 10 shows the IR spectrum of the obtained compound (13).

[Example 2: Synthesis of compound (29)]
A 500 ml flask is charged with 20 g of the compound represented by the following structural formula (B), 15 g of 3-mercaptopropionic acid, 0.5 g of paratoluenesulfonic acid, and 200 ml of toluene. After replacing with nitrogen, the generated water is removed 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 purified by silica gel column chromatography to obtain 20 g of compound (29) as an oil.
FIG. 11 shows the IR spectrum of the obtained compound (29).

[Example 3: Synthesis of compound (14)]
A 500 ml flask is charged with 20 g of the compound represented by the structural formula (A), 15 g of 2-mercaptopropionic acid, 0.5 g of paratoluenesulfonic acid, and 200 ml of toluene. After nitrogen substitution, the generated water is removed 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 purified by silica gel column chromatography to obtain 26 g of compound (14) as an oil.
FIG. 12 shows the IR spectrum of the obtained compound (14).

[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)
40 parts of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine (TPD), N, N-bis (3,4 10 parts of dimethylphenyl) biphenyl-4-amine and 55 parts of bisphenol Z polycarbonate resin (PC (Z): viscosity average molecular weight: 60,000) are added to 800 parts of chlorobenzene and dissolved to obtain a coating solution for a charge transport layer. It was. This coating solution was applied onto the charge generation layer 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 (13), 10 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.2 part of OTazo-15 (manufactured by Otsuka Chemical Co., Ltd., molecular weight 354.4) are mixed with cyclopentanol. It melt | dissolved in 30 parts and it apply | coated on the said charge transport layer with a push-up coat. 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 10 μm-thick protective layer was formed to produce an electrophotographic photoreceptor of Example 4.

<Evaluation of image quality>
The electrophotographic photosensitive member produced as described above is mounted on Apeos Port-III C4400 manufactured by Fuji Xerox Co., Ltd., and at low temperature and low humidity (8 ° C., 20% RH) and high temperature and high humidity (30 ° C., 85% RH), Was continuously evaluated.

First, an image formation test of 10000 sheets of plain paper (Fuji Xerox Co., Ltd., P paper (A4 size, short feed)) is performed in a low temperature and low humidity (8 ° C., 20% RH) environment, and the image quality evaluation of the 10000th sheet (below) (Ghost, fog, streak, image flow). 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.
The results are shown in Table 2.

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 Table 3.

(Ghost evaluation)
For the ghost, a chart of a pattern having a gray area with G and an image density of 50% shown in FIG. 6A was printed, and the appearance of the letter G was visually evaluated on the 50% gray area.
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 Apeos Port-III C4400 manufactured by Fuji Xerox Co., Ltd., and the residual potential on the surface of the electrophotographic photoreceptor before the print test was measured under low temperature and low humidity (8 ° C., 20% RH). Next, immediately after a 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 was measured under low temperature and low humidity (8 ° C., 20% RH). . 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 adhesiveness of protective layer>
The adhesiveness of the protective layer was evaluated by the remaining number when a 2M square 5 × 5 piece was cut with a cutter knife on the photoconductor after the image formation test and a 3M mending tape was applied and peeled off.
The results are shown in Table 2.
A: 21 or more remained.
B: 11 to 20 remaining.
C: 10 or less remained.

<Evaluation of protective layer wear>
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).

[Example 5]
Up to the charge transport layer was prepared by the method described in Example 4.
(Preparation of surface layer)
10 parts of the compound (13), 10 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) 5 parts were dissolved in 30 parts of cyclopentanol 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 thickness of 5 μm to produce a photoreceptor of Example 5, and evaluation was performed by the method described in Example 4.

[Example 6]
Up to the charge transport layer was prepared by the method described in Example 4.
(Preparation of surface layer)
10 parts of the compound (13) and 10 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) were dissolved in 30 parts of cyclopentanol, and applied on the charge transport layer by push-up coating. 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 having a film thickness of 5 μm was formed to produce the photoreceptor of Example 6. Evaluation was carried out by the method described in Example 4.

[Examples 7 to 18]
A photoconductor was prepared and evaluated by the method described in Example 4 except that the compound (13) in Example 4 was changed to that shown in Table 1.

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

[Comparative Example 2]
A photoreceptor was prepared and evaluated by the method described in Example 4 except that the compound (13) in Example 4 was changed to the compound (C) having the following structural formula.

  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 19]
<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).
10 parts of the compound (13), 5 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.2 part of OTazo-15 (Otsuka Chemical, molecular weight 354.4) are dissolved in 50 parts of dichloromethane. The solution was spin-coated at a rotation speed of 300 rpm, heated at 160 ° C. for 1 hour under nitrogen with an oxygen concentration of 150 ppm, and then cured to inject holes having a thickness of 600 nm (measured with a stylus thickness meter). A layer was formed.

  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 the 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 are measured, and after driving for 1000 hours at an applied voltage of 7V. Luminance was measured.

[Examples 20 to 28]
An organic EL device was prepared and evaluated by the method described in Example 19 except that the compound (13) in Example 19 was changed to the compound shown in Table 4. The results are shown in Table 4.

[Comparative Example 3]
Instead of the hole injection layer formed using the compound (13) in Example 19, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4 , 4′-diamine (TPD) was prepared and evaluated by the method described in Example 19 except that a hole injection layer vacuum-deposited with a film thickness of 600 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 (7)

A thiol group-containing charge transport material represented by the following general formula (1).
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.   The thiol group-containing charge transport material according to claim 1, wherein the F in the general formula (1) is an organic group having a hole transport capability. The thiol group-containing charge transport material according to claim 1 or 2 represented by the following general formula (2).


(In Formula (2), D represents a linking group represented by-(G) _a -XY-SH, Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, and Ar ⁵ represents a substitution. Or an unsubstituted aryl group or a substituted or unsubstituted arylene group, G is a divalent organic group having 1 to 5 carbon atoms, X is a -CO-O- group or -O-CO- group, Represents a divalent organic group having 1 to 5 carbon atoms, and a represents 0 or 1. One to four of Ar ^{1 to} Ar ⁵ is-(G) _a -XY-SH. And has a bond that can be bonded to the bonding group represented, c1 to c5 each independently represents an integer of 0 to 2, and k represents 0 or 1.) A thiol group-containing charge transport material solution in which a thiol group-containing charge transport material represented by the following general formula (1) is dissolved in a solvent.
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6. A photoelectric conversion device provided with the film | membrane formed using the solution which the thiol group containing charge transport material shown by following General formula (1) melt | dissolved.
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.   The photoelectric conversion device according to claim 5, wherein the film contains a polymer obtained by polymerizing the thiol group-containing charge transport material. An electrophotographic photoreceptor having a layer formed on a conductive substrate using a solution in which a thiol group-containing charge transport material represented by the following general formula (1) is dissolved.
F-[(G) _a -XY-SH] _b General formula (1)
(In the formula (1), F represents an organic group derived from a charge transporting compound, G represents a divalent organic group having 1 to 5 carbon atoms, and X represents a —CO—O— group or —O—CO. -Y represents a divalent organic group having 1 to 5 carbon atoms, a represents 0 or 1, and b represents an integer of 1 to 6.