JP2008165248A - Electrophotographic photosensitive member, process cartridge and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photosensitive member which is excellent in deposition, wear and scratch resistances and very good in electrophotographic characteristics such as sensitivity and residual potential, and exhibits stable performances even in repeated use, a process cartridge and an electrophotographic apparatus. <P>SOLUTION: The electrophotographic photosensitive member has a photosensitive layer on an electroconductive support, wherein the photosensitive layer comprises a polymerizate of a hole-transporting compound having two or more chain polymerization function groups in its molecule represented by formula (1) wherein A denotes a hole-transporting group, and P<SP>1</SP>and P<SP>2</SP>independently denote a chain polymerization function group of formula (9) or (10). A hole-transporting compound prepared by substituting linking sites of A with P<SP>1</SP>and Z by hydrogen atoms is represented by a formula (2) or (3). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrophotographic photosensitive member, a process cartridge having an electrophotographic photosensitive member, and an electrophotographic apparatus, and more specifically, an electrophotographic photosensitive member having a surface layer containing a specific resin, a process cartridge having the electrophotographic photosensitive member, and The present invention relates to an electrophotographic apparatus.

  Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been known as photoconductive materials used for electrophotographic photoreceptors. On the other hand, polyvinylcarbazole, phthalocyanine, and azo pigments, which are organic materials, are attracting attention for advantages such as high productivity and non-pollution, and tend to be inferior in terms of photoconductive properties and durability compared to inorganic materials. It has come to be widely used.

  These electrophotographic photoreceptors are often used as function-separated electrophotographic photoreceptors in which a charge generation layer and a charge transport layer are laminated in order to satisfy both electrical and mechanical characteristics. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, optical characteristics, and durability characteristics according to the applied electrophotographic process.

  In particular, in an electrophotographic photosensitive member that is repeatedly used, an electric and mechanical external force such as charging, image exposure, toner development, transfer to paper, and cleaning processing is directly applied to the surface of the photosensitive member. Durability is required. Specifically, durability against surface wear and scratches caused by rubbing is required, and durability against surface deterioration due to charging is also required.

  In general, the surface of the electrophotographic photosensitive member is a thin resin layer, and the characteristics of the resin are very important. In recent years, acrylic resins and polycarbonate resins have been put to practical use as resins that satisfy the above-mentioned conditions to some extent, but not all of the above-mentioned characteristics are satisfied with these resins, and in particular, electrophotographic photoreceptors. It is difficult to say that the coating film hardness of the resin is sufficiently high in order to achieve high durability. Even when these resins are used as the resin for forming the surface layer, there is a problem that the surface layer is worn during repeated use, and further scratches are generated.

  Furthermore, due to the recent demand for higher sensitivity of organic electrophotographic photoreceptors, low molecular weight compounds such as charge transport materials are often added in a relatively large amount. In this case, due to the plasticizer action of these low molecular weight materials. The film strength is remarkably lowered, and there is a problem that the surface layer is worn or scratched during repeated use. Further, when the electrophotographic photosensitive member is stored for a long period of time, the above-mentioned low molecular weight component is precipitated, resulting in a problem of layer separation.

  As means for solving these problems, an attempt to use a curable resin as a resin for a charge transport layer is disclosed in, for example, Japanese Patent Application Laid-Open No. 2-127852. Thus, the mechanical strength is increased by curing and crosslinking the charge transport layer using a curable resin as the charge transport layer resin, and the abrasion resistance and scratch resistance during repeated use are greatly improved. However, even if a curable resin is used, the low molecular weight component acts as a plasticizer in the binder resin to the last, so the problems of precipitation and layer separation as described above are not fundamental solutions.

  In addition, in charge transport layers composed of organic charge transport materials and binder resins, the charge transport ability is highly dependent on the resin. For example, curable resins with sufficiently high hardness do not have sufficient charge transport ability and are used repeatedly. At the same time, the residual potential has been increased, and both have not been satisfied. In JP-A-5-216249, JP-A-7-72640 and the like, a monomer having a carbon-carbon double bond is contained in the charge transport layer, and the carbon-carbon double bond and heat of the charge transport material are included. Alternatively, an electrophotographic photosensitive member in which a charge transport layer cured film is formed by reaction with light energy is disclosed, but the charge transport material is only fixed in a pendant form to the polymer main skeleton, and the above-mentioned plastic The mechanical strength is not sufficient because the mechanical action cannot be sufficiently eliminated. In addition, if the concentration of the charge transport material is increased to improve the charge transport capability, the crosslink density is lowered and sufficient mechanical strength cannot be ensured.

As another solution, for example, JP-A-8-248649 discloses an electrophotographic photoreceptor in which a charge transport layer is formed by introducing a group having a charge transport ability into a thermoplastic polymer main chain. However, compared with conventional molecular dispersion type charge transport layer, it is effective for precipitation and layer separation, and mechanical strength is improved, but it is a thermoplastic resin to the last. There is a limit, and it is difficult to say that handling and productivity including resin solubility are sufficient. As described above, the conventional systems have not achieved both high mechanical strength and charge transport ability.
JP-A-2-127852 JP-A-5-216249 Japanese Patent Laid-Open No. 7-72640 JP-A-8-248649

  The object of the present invention is to solve the problems of conventional electrophotographic photoreceptors using a resin as a surface layer, to improve the wear resistance and scratch resistance by increasing the film strength, and An object of the present invention is to provide an electrophotographic photosensitive member having good precipitation properties.

  Another object of the present invention is to provide an electrophotographic photosensitive member that exhibits very little change or deterioration in electrophotographic photosensitive member characteristics such as an increase in residual potential during repeated use, and that can exhibit stable performance even during repeated use. It is to provide.

  Still another object of the present invention is to improve the wear resistance and scratch resistance of the surface layer of an electrophotographic photosensitive member, and to provide a long-life and high-quality electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and electrophotography. To provide an apparatus.

  According to the present invention, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, the photosensitive layer has a positive chain having two or more chain polymerizable functional groups in the same molecule as represented by the following general formula (1). An electrophotographic photoreceptor containing a compound obtained by polymerizing a hole transporting compound, a process cartridge having the electrophotographic photoreceptor and an electrophotographic apparatus are provided.

In the formula, A represents a hole transporting group. P ¹ and ^{P 2} represents a chain polymerizable functional group. P ¹ and P ² may be the same or different. Z represents an organic residue which may have a substituent. a, b, and d represent 0 or an integer of 1 or more, and a + b × d represents an integer of 2 or more. When a is 2 or more, P ¹ may be the same or different. When d is 2 or more, P ² may be the same or different. When b is 2 or more, Z and P ² are the same or different. May be.

  The electrophotographic photosensitive member of the present invention has an effect excellent in precipitation resistance, abrasion resistance and scratch resistance. Furthermore, electrophotographic characteristics such as sensitivity and residual potential are very good, and stable performance can be exhibited even during repeated use. Further, the effect of the electrophotographic photosensitive member is naturally exerted also in the process cartridge and the electrophotographic apparatus having the electrophotographic photosensitive member, and high image quality is maintained for a long time.

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

  First, the chain polymerizable functional group in the present invention will be described. The chain polymerization in the present invention refers to the former polymerization reaction mode when the polymer formation reaction is largely divided into chain polymerization and sequential polymerization. For details, see, for example, “Basic Chemistry Resin Chemistry” by Tadahiro Miwa. (New Edition) ”July 25, 1995 (1 edition, 8 prints) As described in FIG. 24, it means unsaturated polymerization, ring-opening polymerization, isomerization polymerization, etc. in which the reaction proceeds mainly via intermediates such as radicals or ions.

The chain-polymerizable functional groups P ¹ and P ² in the general formula (1) mean functional groups capable of the above-described reaction form, but here occupy most of them and have a wide range of applications such as unsaturated polymerization or ring-opening. Specific examples of the polymerizable functional group are shown.

  Unsaturated polymerization is a reaction in which unsaturated groups such as C═C, C≡C, C═O, C═N, and C≡N are polymerized by radicals, ions, etc., but mainly C═C. It is. Specific examples of the unsaturated polymerizable functional group are shown in Table 1, but are not limited thereto.

  In the table, R has an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. An aryl group such as a phenyl group, a naphthyl group and an anthryl group, or a hydrogen atom may be used.

  Ring-opening polymerization means that unstable cyclic structures with distortions such as carbocycles, oxo rings, and nitrogen heterocycles are activated by the action of a catalyst, and at the same time, the polymerization is repeated to produce a chain polymer. In this case, most of the reactions basically have ions acting as active species. Specific examples of the ring-opening polymerizable functional group are shown in Table 2, but are not limited thereto.

  In the table, R has an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. An aryl group such as a phenyl group, a naphthyl group and an anthryl group, or a hydrogen atom may be used.

  Among the chain polymerizable functional groups according to the present invention as described above, those represented by the following general formulas (6) to (8) are preferable.

In the formula, E may have a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, an optionally substituted alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, or a substituent. Aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, optionally substituted phenyl group, naphthyl group, anthryl group, pyrenyl group, thiophenyl group and furyl group, aryl groups such as An alkoxy group such as a CN group, a nitro group, a methoxy group, an ethoxy group and a propoxy group, -COOR ¹⁶ or -CONR ¹⁷ R ¹⁸ are shown.

W is a divalent phenylene group which may have a substituent, an arylene group such as a naphthylene group and an anthracenylene group, a methylene group which may have a substituent, a divalent alkylene group such as an ethylene group and a butylene group, -COO -, - O -, - OO -, - represented by S- or -CONR ^19.

Here, R ^{16 to} R ¹⁹ may have a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, and a substituent. An aralkyl group such as a benzyl group and a phenethyl group, or an aryl group such as a phenyl group, a naphthyl group and an anthryl group which may have a substituent, R ¹⁷ and R ¹⁸ may be the same or different from each other. F represents 0 or 1.

  Substituents that may be present in E and W include halogen atoms such as fluorine, chlorine, bromine and iodine; or nitro groups or cyano groups or hydroxyl groups; or methyl groups, ethyl groups, propyl groups and butyl groups. An alkyl group; or an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group; or an aryloxy group such as a phenoxy group and a naphthoxy group; or an aralkyl group such as a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and a thienyl group; Or aryl groups, such as a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group, etc. are mentioned.

In the formula, R ²⁰ and R ²¹ are a hydrogen atom, an optionally substituted alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an optionally substituted benzyl group and a phenethyl group, and the like. An aryl group such as a phenyl group and a naphthyl group which may have an aralkyl group or a substituent, and n represents an integer of 1 to 10.

In the formula, R ²² and R ²³ are a hydrogen atom, an alkyl group such as an optionally substituted methyl group, an ethyl group, a propyl group and a butyl group, an optionally substituted benzyl group and a phenethyl group, and the like. An aryl group such as a phenyl group and a naphthyl group which may have an aralkyl group or a substituent, and n represents 0 or an integer of 1 to 10.

As the R ²⁰ to R ²³ are substituents which may have the general formula (7) and the general formula (8), fluorine, chlorine, bromine and halogen atom such as iodine; or a methyl group, an ethyl group, Alkyl groups such as propyl group and butyl group; or alkoxy groups such as methoxy group, ethoxy group and propoxy group; or aryloxy groups such as phenoxy group and naphthoxy group; or benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and And aralkyl groups such as thienyl group; or aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group.

  Among the general formulas (6) to (8), more particularly preferable chain polymerizable functional groups include those represented by the following general formulas (9) to (15).

  Furthermore, among the general formulas (9) to (15), the acryloyloxy group of the general formula (9) or the methacryloyloxy group of the general formula (10) is particularly preferable from the viewpoint of polymerization characteristics.

  In the present invention, the “hole transportable compound having a chain polymerizable functional group” means that the chain polymerizable group described above is chemically bonded to the hole transportable compound described above as a functional group in two or more. Compounds are shown. In this case, the chain polymerizable functional groups may be the same or different. The hole transporting compound having two or more of those chain polymerizable functional groups is represented by the general formula (1).

In the general formula (1), “when a is 2 or more, P ¹ may be the same or different” means that n types of different chain polymerizable functional groups are P ¹¹ , P ¹² , P ¹³ , P ¹⁴ , When P ¹⁵ ... P ¹ⁿ is indicated, for example, when a = 3, three chain polymerizable functional groups P ¹ directly bonded to the hole transporting compound A may be the same or two. Means that they may be different (eg, P ¹¹ , P ¹¹ and P ¹² ), or may be different from each other (eg, P ¹² , P ¹⁵ and P ¹⁷ ) (“d This means that when P is 2 or more, P ² may be the same or different, and “when b is 2 or more, Z and P ² may be the same or different”. ).

A represents a hole transporting group, and a hydrogenation compound (hole transport compound) in which the bonding site between A, P ¹ and Z is replaced with a hydrogen atom is represented by the following general formula (2) and general formula (3 ).

In the formula, m represents 0 or 1, preferably m = 1, and R ^{1 to} R ⁴ each have 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group which may have a substituent. The following alkyl groups, optionally substituted benzyl groups, phenethyl groups, naphthylmethyl groups, furfuryl groups and thienyl groups such as phenyl groups, naphthyl groups, anthryl groups, which may have substituents, Indicates aryl groups such as phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoquinolyl, carbazolyl, phenothiazinyl, benzofuryl, benzothiophenyl, dibenzofuryl, and dibenzothiophenyl , R ^{1 to} R ⁴ may be the same or different.

Ar ¹ is an arylene group which may have a substituent (two from benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. Ar ² is a group from which hydrogen is removed, and when m = 0, Ar ² may have a phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group , Quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group, dibenzofuryl group, dibenzothiophenyl group and the like, and when m = 1, arylene similar to Ar ¹ above Indicates a group. In addition, when m = 1, Ar ¹ and Ar ² may be the same or different.

Further, preferably R ¹ and R ² is an aryl group which may have a substituent in formula (2) Among them, all have substituent the at R ¹ to R ⁴ are four Particularly preferred is a good aryl group. In the general formula (2), R ¹ and R ^2, R ³ and R ^4, or Ar ¹ and Ar ² may be bonded directly or via a bonding group, and the bonding group is methylene. Group, alkylene group such as ethylene group and propylene group, hetero atom such as oxygen and sulfur atom, CH═CH group and the like. Among these, an alkylene group is preferable.

In the formula, R ⁵ , R ⁶ , R ⁹ and R ¹⁰ have an alkyl group having 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, which may have a substituent, and a substituent. Aralkyl groups such as benzyl, phenethyl, naphthylmethyl, furfuryl and thienyl groups or phenyl groups optionally having substituents, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl , Pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group, dibenzofuryl group, dibenzothiophenyl group and the like, and aryl groups such as R ⁵ , R ⁶ , R ⁹ and R Each of ¹⁰ may be the same or different. R ⁷ and R ⁸ are an methylene group which may have a substituent, an alkylene group having 10 or less carbon atoms such as an ethylene group and a propylene group, or an arylene group which may have a substituent (benzene, naphthalene, anthracene, Phenanthrene, pyrene, thiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc.), wherein R ⁷ and R ⁸ are the same May be different. Q represents an organic residue which may have a substituent.

Furthermore, among them, two or more of R ⁵ , R ⁶ , R ⁹ and R ^{10 in} the general formula (3) are aryl groups which may have a substituent, and R ⁷ and R ⁸ are substituted. The arylene group which may have a group is preferable, and the case where all of R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are all aryl groups which may have a substituent is particularly preferable. In addition, any two of R ^5, R ⁶ or R ^{7 in} the general formula (3) or any two of R ^8, R ⁹ or R ¹⁰ are bonded directly or via a bonding group, respectively. As the bonding group, an alkylene group such as a methylene group, an ethylene group and a propylene group, a hetero atom such as an oxygen and sulfur atom, a CH═CH group, and the like can be given.

Similarly, the general formula (1) Z or the general formula in in (3) Q is an optionally substituted alkylene group, an arylene group which may have a substituent group, CR 11 ⁼ CR ¹² (R ¹¹ and R ¹² represent an alkyl group, an aryl group or a hydrogen atom, and R ¹¹ and R ¹² may be the same or different), C═O, S═O, SO ₂ , oxygen atom or sulfur atom. One or any combination of organic residues. Among them, those represented by the following general formula (4) are preferable, and those represented by the following general formula (5) are particularly preferable.

In the general formula (4), X ^{1 to} X ³ are a methylene group which may have a substituent, an alkylene group having 20 or less carbon atoms such as an ethylene group and a propylene group, (CR ¹³ = CR ¹⁴ ) m ¹ , C═O, S═O, SO ₂ , an oxygen atom or a sulfur atom, Ar ³ and Ar ⁴ are arylene groups (benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, pyridine, which may have a substituent) A group obtained by removing two hydrogen atoms from quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, and the like. R ¹³ and R ¹⁴ are optionally substituted alkyl groups such as methyl, ethyl and propyl groups, optionally substituted phenyl groups, naphthyl groups and thiophenyl groups such as aryl groups or hydrogen atoms. R ¹³ and R ¹⁴ may be the same or different. m ¹ represents an integer of ¹ to 5, and pt represents 0 or an integer of 1 to 10 (provided that pt is not simultaneously 0).

In the general formula (5), X ⁴ and X ⁵ represent (CH ₂ ) _g , (CH═CR ¹⁵ ) _h , C═O, or an oxygen atom, and Ar ⁵ represents an arylene which may have a substituent. Group (a group in which two hydrogen atoms have been removed from benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, and the like). R ¹⁵ represents an alkyl group such as a methyl group, an ethyl group or a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group or a thiophenyl group which may have a substituent, or a hydrogen atom. g is an integer of 1 to 10, h is an integer of 1 to 5, u to w are 0 or an integer of 1 to 10 (particularly preferred is an integer of 0 or an integer of 1 to 5. However, u to w are simultaneously Never zero).

In addition, as substituents that R ^{1 to} R ¹⁵ , Ar ^{1 to} Ar ⁵ , X ^{1 to} X ⁵ , Z, and Q in the above general formulas (1) to (5) may have, fluorine, chlorine Halogen atoms such as bromine and iodine; or nitro groups or cyano groups or hydroxyl groups; or alkyl groups such as methyl, ethyl, propyl and butyl groups; or alkoxy groups such as methoxy, ethoxy and propoxy groups; or Aryloxy groups such as phenoxy group and naphthoxy group; or aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group; or aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group; or Substituents such as dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group and di (p-tolyl) amino group Amino group; or an aryl vinyl group such as a styryl group and Nafuchirubiniru group.

  In addition, the hole transporting compound having two or more chain polymerizable functional groups in the same molecule in the present invention preferably has an oxidation potential of 1.2 (V) or less, 0.4 to 1.2 (V) is more preferable. That is, when the oxidation potential exceeds 1.2 (V), injection of charges (holes) from the charge generating material is difficult to occur, resulting in problems such as increase in residual potential, deterioration in sensitivity, and increase in potential fluctuation during repeated use. If it is less than 0.4 (V), in addition to problems such as a decrease in charging ability, the compound itself is easily oxidized and easily deteriorates, resulting in deterioration in sensitivity, image blurring, and potential during repeated use. This is because problems such as large fluctuations are likely to occur.

  The oxidation potential described here is measured by the following method.

(Measurement method of oxidation potential)
Saturated calomel electrode as a reference electrode, 0.1 N in an electrolytic solution ^{_{(n-Bu) 4 N +}} ClO 4 - with acetonitrile solution, sweeping the potential applied to the working electrode (platinum) by the potential sweeper, resulting current The potential when the potential curve showed a peak was taken as the oxidation potential. Specifically, the sample ^{_{0.1N (n-Bu) 4 N}} + ClO 4 - are dissolved so as to become a concentration of about 5～10Mmol% acetonitrile solution. Then, a voltage is applied to the sample solution with the working electrode, and a current change when the voltage is linearly changed from a low potential (0 V) to a high potential (+1.5 V) is measured to obtain a current-potential curve. In this current-potential curve, the potential at the peak top position when the current value showed a peak (or the first peak when there are a plurality of peaks) was defined as the oxidation potential.

Further, the hole transporting compound having the chain polymerizable functional group preferably has a drift mobility of 1 × 10 ⁻⁷ (cm ² /V.sec) or more as a hole transporting ability (however, Applied electric field: 5 × 10 ⁴ V / cm). If it is less than 1 × 10 ⁻⁷ (cm ² /V.sec), holes cannot move sufficiently until development after exposure as an electrophotographic photosensitive member, so that the sensitivity is apparently reduced and the residual potential is also increased. May occur.

  Although the typical example of the hole transportable compound which has a chain polymerizable functional group concerning this invention below is given, it is not limited to these.

  In the present invention, a typical synthesis method of a hole transporting compound having a chain polymerizable functional group is shown below.

(Synthesis Example 1: Synthesis of Compound No. 1-24)
Synthesized according to the following route.

  1 (50 g: 0.123 mol), 2 (62.4 g: 0.369 mol), anhydrous potassium carbonate (25.5 g) and copper powder (32 g) with 200 g of 1,2-dichlorobenzene heated and stirred at 180 to 190 ° C. For 18 hours. After the reaction solution was filtered, the solvent was removed under reduced pressure, and the residue was recrystallized twice with a toluene / methanol mixed solvent to obtain 60.2 g of 3.

  After cooling 242 g of N, N-dimethylformamide (DMF) to 0 to 5 ° C., phosphorus oxychloride (84.8 g: 553.2 mmol) was slowly added dropwise so as not to exceed 10 ° C. After stirring for 15 minutes after completion of the dropwise addition, a 3 (45.0 g: 92.2 mmol) / 135 g DMF solution was slowly added dropwise. After completion of dropping, the mixture was stirred as it was for 30 minutes, then returned to room temperature, stirred for 2 hours, further heated to 80 to 85 ° C. and stirred for 8 hours. The reaction solution was poured into 2.5 kg of about 15% sodium acetate aqueous solution and stirred for 12 hours. After neutralization, extraction was performed using toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 40.5 g of 4.

  To a place where 0.89 g of lithium aluminum hydride was added to 100 ml of dry tetrahydrofuran (THF) and the mixture was stirred at room temperature, a solution of 4 (37 g: 68 mmol) / 600 ml of dry THF was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours, and 500 ml of 5% hydrochloric acid aqueous solution was slowly added dropwise. After completion of dropping, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 26.3 g of 5.

  5 (20 g: 36 mmol) and triethylamine (12.8 g: 126 mol) were added to 130 ml of dry THF and cooled to 0-5 ° C., and then acryloyl chloride (9.8 g: 108 mmol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 6 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified using a silica gel column to obtain 11.2 g of 6 (Compound No. 1-24) (oxidation potential: 0.80 V).

(Synthesis Example 2: Synthesis of Compound No. 1-78)
Synthesized according to the following route.

  7 (50 g: 0.172 mol), 8 (14.4 g: 0.069 mol), anhydrous potassium carbonate (36 g) and copper powder (33 g) together with 120 g of 1,2-dichlorobenzene and stirring with heating at 180-190 ° C. 15 Went for hours. After the reaction solution was filtered, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to obtain 28.5 g of 9.

  9 (25 g: 47 mmol) was added to 250 g of methyl cellosolve, and sodium methylate (25 g) was slowly added with stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour and then further heated and stirred at 70 to 80 ° C. for 12 hours. The reaction solution was poured into water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 17.8 g of 10.

  10 (15 g: 40 mmol) and triethylamine (14 g: 139 mmol) were added to 100 ml of dry THF and cooled to 0-5 ° C., and then acryloyl chloride (10.9 g: 120 mmol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified using a silica gel column to obtain 11.9 g of 11 (Compound No. 1-78) (oxidation potential: 0.78 V).

(Synthesis Example 3: Synthesis of Compound No. 2-33)
Synthesized according to the following route.

  1 (70 g: 0.35 mol), 2 (98 g: 0.42 mol), anhydrous potassium carbonate (73 g) and copper powder (111 g) were heated and stirred at 180-190 ° C. for 10 hours with 600 g of 1,2-dichlorobenzene. It was. After the reaction solution was filtered, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to obtain 86.2 g of 3.

  3 (80 g: 0.26 mol) was added to 300 g of N, N-dimethylformamide, and ethanethiol sodium salt (about 90%: 62 g) was slowly added with stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and further heated and stirred under reflux for 3 hours. After cooling, the reaction solution is poured into water and made weakly acidic with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer is further extracted with 1.2N aqueous sodium hydroxide solution, the aqueous layer is made acidic with dilute hydrochloric acid, and extracted with ethyl acetate. After drying with sodium sulfate, the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 64 g of 4.

  4 (60 g: 0.21 mol) was added to 300 g of N, N-dimethylformamide, and caustic soda (8.3 g) was slowly added while stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 30 minutes, and 1,2-diiodoethane (31.7 g: 0.1 mol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 30 minutes, and further heated and stirred at 70 ° C. for 5 hours. The reaction solution was poured into water and extracted with toluene. The organic layer was further washed with water and dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 49.1 g of 5.

  After cooling 182 g of DMF to 0 to 5 ° C., 63.6 g of phosphorus oxychloride was slowly added dropwise so as not to exceed 10 ° C. After completion of the dropping, the mixture was stirred for 15 minutes, and then a 5 (42.2 g: 0.07 mol) / DMF 102 g solution was slowly added dropwise. After completion of dropping, the mixture was stirred for 30 minutes and then returned to room temperature, stirred for 2 hours, further heated to 80 to 85 ° C., and stirred for 15 hours. The reaction solution was poured into 1.5 kg of about 15% aqueous sodium acetate solution and stirred for 12 hours. After neutralization, extraction was performed using toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 23 g of 6.

  To a place where 0.89 g of lithium aluminum hydride was added to 100 ml of dry THF and stirred at room temperature, a solution of 6 (15 g: 0.023 mol) / 100 ml of dry THF was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours, and 200 ml of 5% hydrochloric acid aqueous solution was slowly added dropwise. After completion of dropping, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified using a silica gel column to obtain 13.6 g of 7.

  7 (10 g: 0.015 mol) and triethylamine (6.1 g: 0.06 mol) were added to 120 ml of dry THF and cooled to 0-5 ° C., and then acryloyl chloride (4.1 g: 0.045 mol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature and stirred at room temperature for 6 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified using a silica gel column to obtain 6.4 g of 8 (Compound No. 2-33) (oxidation potential: 0.78 V).

(Synthesis Example 4: Synthesis of Compound No. 2-44)
Synthesized according to the following route.

  Diphenylchlorophosphine (80.0 g: 0.36 mmol) was added to 600 ml of diethylene glycol dimethyl ether, 8 ml of water was further added, and then oily sodium hydride (60%: 23 g: 0.58 mol) was slowly added. After completion of the addition, the mixture was stirred for 1 hour at room temperature, and then a 9 (80 g: 0.28 mol) / 100 ml THF solution was slowly added dropwise. After completion of dropping, the mixture was stirred at 80 ° C. for 15 hours. After cooling, the reaction solution was poured into water, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified using a silica gel column to obtain 58.5 g of 10. The synthesis method from 10 to 13 was performed according to the synthesis method from 5 to 8 in Synthesis Example 3 to obtain 13 (Compound No. 2-44) (oxidation potential: 0.78 V).

(Synthesis Example 5: Synthesis of Compound No. 2-89)
7 (10 g: 15 mmol) obtained in Synthesis Example 3 was added to 50 ml of dry THF, and 1.8 g of oily sodium hydride (about 60%) was slowly added after cooling to 0 to 5 ° C. After completion of the addition, the mixture was returned to room temperature, stirred for 1 hour, cooled again to 0 to 5 ° C., and allyl bromide (7.5 g: 0.062 mol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour and then returned to room temperature for 1 hour. The reaction solution was poured into water, neutralized, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified using a silica gel column to obtain 5.4 g of the objective compound (Compound No. 2-89) (oxidation potential 0.76 V).

  In the present invention, by polymerizing a hole transporting compound having two or more chain-polymerizable functional groups in the same molecule, the compound having a hole transporting ability is crosslinked in the photosensitive layer. A three-dimensional crosslinked structure is formed with points. The hole transporting compound can be polymerized / crosslinked only, or can be mixed with a compound having another chain polymerizable group, and the kind / ratio thereof is arbitrary. As used herein, the compound having another chain polymerizable group includes any monomer or oligomer / polymer having a chain polymerizable group.

  When the functional group of the hole transporting compound and the functional group of the other chain polymerizable compound are the same group or a group that can be polymerized with each other, they both have a three-dimensional cross-linked copolymer structure via a covalent bond. Is possible. When both functional groups are functional groups that do not polymerize with each other, the photosensitive layer is a mixture of two or more three-dimensional cured products, or other chain-polymerizable compound monomer or its component in a three-dimensional cured product as a main component. Although it is comprised as what contains hardened | cured material, it is also possible to form IPN (Inter Penetrating Network), ie, an interpenetrating network structure, by controlling the compounding ratio / film forming method well.

  Further, a photosensitive layer may be formed from a monomer or oligomer / polymer having no chain polymerizable group and a monomer or oligomer / polymer having a polymerizable group other than the chain polymerizable group. Good.

  Further, in some cases, it is possible to contain a hole transporting compound that is not chemically bonded to the three-dimensional crosslinked structure, that is, does not have a chain polymerizable functional group. Further, other various additives, a lubricant such as fluorine atom-containing resin fine particles, and the like may be contained.

  The electrophotographic photosensitive member of the present invention has a structure in which a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material are laminated in this order on a conductive support, or vice versa. It is possible to adopt any configuration including a single layer in which the charge generation material and the charge transport material are dispersed in the same layer. In the former stacked type, the charge transport layer may be composed of two or more layers. In the latter single layer type, the charge transport layer may be further formed on the photosensitive layer containing the same charge generating material and charge transport material. Further, a protective layer can be formed on the charge generation layer or the charge transport layer.

  In any of these cases, the photosensitive layer only needs to contain one or both of a hole transporting compound having a chain polymerizable group and a polymer obtained by polymerizing, crosslinking, or curing the previous hole transporting compound. However, from the viewpoint of characteristics as an electrophotographic photoreceptor, particularly electrical characteristics such as residual potential, and durability, a function-separated photoreceptor structure in which a charge generation layer / charge transport layer are laminated in this order is preferable. The advantage is that the surface layer can be made highly durable without lowering the charge transport ability.

  Next, a method for producing an electrophotographic photoreceptor according to the present invention will be specifically described.

  The support of the electrophotographic photosensitive member may have any conductivity, for example, a metal or alloy such as aluminum, copper, chromium, nickel, zinc and stainless steel formed into a drum or sheet, aluminum and Metal foil such as copper laminated on plastic film, aluminum, indium oxide and tin oxide deposited on plastic film, metal with conductive layer applied alone or with binder resin, plastic Examples include films and paper.

  In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided on the conductive support. The undercoat layer is used for improving the adhesion of the photosensitive layer, improving the coatability, protecting the support, covering defects on the support, improving the charge injection from the support, and protecting the photosensitive layer from electrical breakdown. Formed for.

  Materials for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, glue and gelatin Etc. are known. These are dissolved in a solvent suitable for each and coated on a support. The film thickness at that time is preferably 0.1 to 2 μm.

  When the electrophotographic photoreceptor of the present invention is a function-separated type electrophotographic photoreceptor, a charge generation layer and a charge transport layer are laminated. Examples of charge generation materials used in the charge generation layer include selenium-tellurium, pyrylium, thiapyrylium dyes, various central metals and crystal systems, such as α, β, γ, ε, and X-type crystals. Type phthalocinine compounds, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetrical quinocyanine pigments, quinocyanines and JP-A No. 54-143645 Amorphous silicon and the like.

  In the case of a function-separated type electrophotographic photosensitive member, the charge generation layer comprises a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an attritor, and a roll mill together with the charge generation material 0.3 to 4 times the binder resin and solvent. The film is well dispersed by a method such as the above, and a dispersion is applied and dried, or is formed as a single composition film such as a vapor deposition film of the charge generation material. The film thickness is preferably 5 μm or less, and particularly preferably in the range of 0.1 to 2 μm.

  When using a binder resin, for example, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic ester, methacrylic ester, vinylidene fluoride, trifluoroethylene, polyvinyl alcohol, polyvinyl acetal, polycarbonate , Polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin and epoxy resin.

  In the present invention, the hole transporting compound having a chain polymerizable functional group has a charge transport layer formed on the charge generation layer or a charge transport layer made of a charge transport material and a binder resin on the charge generation layer. Later, it can be used as a surface protective layer having a hole transporting ability (this surface protective layer also has a hole transporting ability and is therefore a photosensitive layer). In any case, the surface layer is generally formed by applying a solution containing the hole transporting compound, followed by a polymerization / crosslinking reaction. It is also possible to form a surface layer using a material obtained by reacting to obtain a cured product and then again dispersing or dissolving in a solvent. As a method for applying these solutions, for example, a dip coating method, a spray coating method, a curtain coating method, a spin coating method, and the like are known. From the viewpoint of efficiency and productivity, the dip coating method is preferable. Also, vapor deposition, plasma, and other known film forming methods can be appropriately selected.

  In the present invention, the hole transporting compound having a chain polymerizable group is preferably polymerized and crosslinked by radiation. The greatest advantage of radiation polymerization is that it does not require a polymerization initiator, which makes it possible to produce a very high-purity three-dimensional photosensitive layer matrix and ensure good electrophotographic properties. . In addition, because it is a short and efficient polymerization reaction, the productivity is high, and further, because of its good radiation transmission, it inhibits curing when a thick film or a shielding material such as an additive is present in the film. The influence of the is very small. However, depending on the type of the chain polymerizable group and the type of the central skeleton, the polymerization reaction may not easily proceed, and in this case, the polymerization initiator can be added within a range that does not affect the polymerization reaction. The radiation used at this time is an electron beam and a gamma ray.

  As an accelerator for electron beam irradiation, any type such as a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type can be used. In the case of irradiating an electron beam, the irradiation condition is very important in the electrophotographic photosensitive member of the present invention in order to develop electric characteristics and durability. In the present invention, 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 exceeds 300 kV, the damage of the electron beam irradiation on the electrophotographic photosensitive member characteristics tends to increase. In addition, it is necessary to be careful because the crosslinking is likely to be insufficient when the dose is less than 1 Mrad, and the electrophotographic photoreceptor characteristics are likely to deteriorate when the dose exceeds 100 Mrad.

  The amount of the hole transporting compound when the hole transporting compound having the chain polymerizable group is used as a charge transporting layer is the above general formula (with respect to the total mass of the charge transporting layer film after polymerization crosslinking). The hydrogenated product of the hole transporting group A having a chain polymerizable functional group represented by 1) is preferably 20% by mass or more, and particularly preferably 40% by mass or more. If it is less than that, the charge transport ability is lowered, and problems such as a decrease in sensitivity and an increase in residual potential are likely to occur. In this case, the thickness of the charge transport layer is preferably 1 to 50 μm, and particularly preferably 3 to 30 μm.

  When the hole transporting compound is used as a surface protective layer on the charge generation layer / charge transport layer, the charge transport layer corresponding to the lower layer is formed of a suitable charge transport material such as poly-N-vinylcarbazole, polystyrylanthracene, etc. Polymer compounds having a heterocyclic ring or condensed polycyclic aromatic, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole, carbazole, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, A solution in which a low molecular weight compound such as a phenylenediamine derivative, an N-phenylcarbazole derivative, a stilbene derivative, or a hydrazone derivative is dispersed / dissolved in a solvent together with an appropriate binder resin (which can be selected from the aforementioned resin for charge generation layer) Apply and dry by known methods It can be.

  In this case, the ratio of the charge transport material to the binder resin is suitably selected so that the mass of the charge transport material is preferably from 30 to 100, more preferably from 50 to 100, assuming that the total mass of both is 100. When the amount of the charge transport material is less than that, the charge transport ability is lowered, and problems such as a decrease in sensitivity and an increase in residual potential are likely to occur. The film thickness of the charge transport layer is determined so that the total film thickness combined with the upper surface protective layer is 1 to 50 μm, and is preferably adjusted in the range of 5 to 30 μm.

  In the present invention, in any of the cases described above, the charge transport material can be contained in the photosensitive layer containing the cured product of the hole transport compound. In the case of a single-layer type photosensitive layer, a charge generation material is simultaneously contained in the solution containing the hole transporting compound, and this solution may be provided with an appropriate undercoat layer or intermediate layer. The hole transporting compound formed on a single layer type photosensitive layer formed of a charge generating material and a charge transporting material provided on a conductive support, when formed by polymerization and crosslinking after coating on the support Any of the cases of polymerizing and cross-linking after applying a solution containing sucrose is possible.

  Various additives can be added to the photosensitive layer in the invention. Additives include anti-degradation agents such as antioxidants and ultraviolet absorbers, and lubricants such as fluorine atom-containing resin fine particles.

  FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

  In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotating process, the electrophotographic photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on the peripheral surface thereof by the primary charging unit 3, and then from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. Exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.

  The formed electrostatic latent image is then developed with toner by the developing unit 5, and the developed toner image is transferred between the electrophotographic photosensitive member 1 and the transfer unit 6 from a paper supply unit (not shown). The transfer means 6 sequentially transfers the transfer material 7 taken out in synchronization with the rotation of the paper and fed.

  The transfer material 7 that has received the image transfer is separated from the surface of the electrophotographic photosensitive member, introduced into the image fixing means 8, and subjected to image fixing to be printed out as a copy (copy).

  After the image transfer, the surface of the electrophotographic photosensitive member 1 is cleaned by removing the transfer residual toner by the cleaning unit 9, and is further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown). Used repeatedly for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.

  In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9 described above are integrally coupled as a process cartridge. May be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photosensitive member 1 to form a cartridge, and is detachable from the apparatus main body using guide means such as a rail 12 of the apparatus main body. The process cartridge 11 can be obtained.

  Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is a reflected light or transmitted light from the original, or the original is read by a sensor, converted into a signal, and a laser beam scanning performed in accordance with this signal, Light emitted by driving the LED array, driving the liquid crystal shutter array, or the like.

  The electrophotographic photosensitive member of the present invention can be used not only in electrophotographic copying machines but also widely in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, FAX and laser plate making. .

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” means part by mass.

(Example 1-1)
First, the coating material for conductive layers was prepared by the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average 0.002 part of molecular weight 3000) was prepared by dispersing for 2 hours in a sand mill using φ1 mm glass beads. This paint was applied on a 30 mmφ aluminum cylinder by a dip coating method and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

  Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare an intermediate layer coating material. This paint was applied on the conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.6 μm.

  Next, 5 parts of a bisazo pigment represented by the following structural formula (16), 2 parts of polyvinyl butyral resin, and 35 parts of cyclohexanone are dispersed for 24 hours in a sand mill using φ1 mm glass beads, and tetrahydrofuran is further added to form a charge generation layer. The paint was used. This paint was applied on the intermediate layer by a dip coating method and dried at 100 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.2 μm.

  Compound Example No. 60 parts of the 1-24 hole transporting compound was dissolved in a mixed solvent of 30 parts monochlorobenzene / 30 parts dichloromethane to prepare a charge transport layer coating material. This paint is coated on the charge generation layer, and the resin is cured by irradiating an electron beam under the conditions of an acceleration voltage of 150 kV and a dose of 25 Mrad to form a charge transport layer having a film thickness of 15 μm to obtain an electrophotographic photosensitive member. It was.

  The produced electrophotographic photoreceptor was evaluated for precipitation with time, electrophotographic characteristics, and durability. With respect to precipitation over time, a urethane rubber cleaning blade for a copying machine was pressed against the surface of the photoreceptor, stored at 75 ° C., and an accelerated test for precipitation was performed. In the evaluation, the surface of the electrophotographic photosensitive member was observed with a microscope after 14 days, and the presence or absence of precipitation was determined. When there was no precipitation, the test was continued until 30 days later.

  The electrophotographic characteristics and durability were evaluated by mounting the electrophotographic photosensitive member on LBP-SX manufactured by Canon Inc. Initial electrophotographic characteristics [dark portion potential Vd, light attenuation sensitivity (light amount necessary for light attenuation to −150 V when dark portion potential is set to −700 V) and residual potential Vsl (light amount three times the light attenuation sensitivity light amount was irradiated) )), And further, a 10,000 sheet passing durability test was performed to visually observe the presence or absence of image defects, the amount of shaving of the electrophotographic photosensitive member, and the electrophotographic characteristics after the durability, The respective change values ΔVd and ΔVl (the amount of change in Vl when an amount of light equal to the amount of light at which Vl initially becomes −150 V after irradiation) and ΔVsl were obtained.

  The results are shown in Table 3. No precipitation occurs in the electrophotographic photosensitive member of the present invention, the electrophotographic characteristics are good, the amount of abrasion is small, and the electrophotographic characteristics are hardly changed even in the durability. It is very stable and has good characteristics, such as not being seen.

(Examples 1-2 to 1-18)
In Example 1-1, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1 except that 1-24 was replaced with the compounds shown in Table 4. The results are shown in Table 3.

(Example 1-19)
In Example 1-1, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1 except that the amount of 1-24 was 48 parts and 12 parts of an acrylic monomer represented by the following structural formula (17) was further added. The results are shown in Table 3.

(Example 1-20)
In Example 1-2, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-2, except that the amount of 1-25 was 48 parts and 12 parts of an acrylic monomer represented by the following structural formula (18) was added. The results are shown in Table 3.

(Example 1-21)
In Example 1-1, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1 except that the amount of 1-24 was 48 parts and 12 parts of an acrylic oligomer represented by the following structural formula (19) was added. The results are shown in Table 3.

(Examples 1-22 to 1-26)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1 except that the irradiation conditions of the electron beam in Example 1-1 were changed as shown in Table 5. As a result, the shaving amount and durability were good, but a slight decrease in sensitivity and an increase in residual potential were observed in the initial electrophotographic characteristics by increasing the dose. The results are shown in Table 3.

(Example 1-27)
After forming the charge generation layer in Example 1-1, 20 parts of a styryl compound represented by the following structural formula (20) and 10 parts of a polycarbonate resin having a repeating unit represented by the following structural formula (21) were mixed with 50 parts of monochlorobenzene. A charge transport layer was formed on the charge generation layer using a charge transport layer coating material prepared by dissolving in 20 parts of a mixed solvent / dichloromethane. At this time, the thickness of the charge transport layer was 10 μm.

  Subsequently, the hole transporting compound No. 60 parts of 1-24 were dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating material for the surface protective layer. This paint is applied onto the previous charge transport layer by spray coating, and the resin is cured by irradiating with an electron beam under conditions of an acceleration voltage of 150 kV and a dose of 25 Mrad to form a surface protective layer having a thickness of 5 μm. A photoreceptor was obtained. This electrophotographic photosensitive member was evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

(Example 1-28)
In Example 1-27, the hole transporting compound No. 1-24 to compound no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-27 except that 1-28 was used. The results are shown in Table 3.

(Example 1-29)
In Example 1-27, the hole transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-27 except that 1-24 was changed to 30 parts and 30 parts of the acrylic monomer represented by the structural formula (17) was added. The results are shown in Table 3.

(Example 1-30)
In Example 1-27, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-27 except that 1-24 was 30 parts and the acrylic oligomer represented by the structural formula (19) was used. The results are shown in Table 3.

(Example 2-1)
In Example 1-1, the hole transporting compound No. 1-24 to compound no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-1 except that 2-90 was used. The results are shown in Table 6.

(Examples 2-2 to 2-23)
In Example 2-1, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1, except that 2-90 was replaced with the compounds shown in Table 7. The results are shown in Table 6.

(Example 2-24)
In Example 2-1, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1, except that the amount of 2-90 was 48 parts and 12 parts of the acrylic monomer represented by the structural formula (17) was further added. The results are shown in Table 6.

(Example 2-25)
In Example 2-5, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1, except that the amount of 2-32 was 48 parts and 12 parts of the acrylic monomer represented by the structural formula (18) was further added. The results are shown in Table 6.

(Example 2-26)
In Example 2-1, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1, except that the amount of 2-90 was 48 parts and 12 parts of the acrylic oligomer represented by the structural formula (19) was further added. The results are shown in Table 6.

(Examples 2-27 to 2-31)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1, except that the electron beam irradiation conditions in Example 2-1 were changed as shown in Table 8. As a result, the shaving amount and durability were good, but a slight decrease in sensitivity and an increase in residual potential were observed in the initial electrophotographic characteristics by increasing the dose. The results are shown in Table 6.

(Example 2-32)
After forming the charge generation layer in Example 2-1, 20 parts of a styryl compound represented by the structural formula (20) and 10 parts of a polycarbonate resin having a repeating unit represented by the structural formula (21) were mixed with 50 parts of monochlorobenzene / dichloromethane. A charge transport layer was formed on the charge generation layer using a charge transport layer coating material prepared by dissolving in 20 parts of a mixed solvent. At this time, the thickness of the charge transport layer was 10 μm.

  Subsequently, the hole transporting compound No. 2-90 60 parts were dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating material for the surface protective layer. This paint is applied onto the previous charge transport layer by spray coating, and the resin is cured by irradiating with an electron beam under conditions of an acceleration voltage of 150 kV and a dose of 25 Mrad to form a surface protective layer having a thickness of 5 μm. A photoreceptor was obtained. This electrophotographic photoreceptor was evaluated in the same manner as in Example 2-1. The results are shown in Table 6.

(Example 2-33)
In Example 2-32, the hole transporting compound No. 2-90 is compound no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2-32, except that 2-91 was used. The results are shown in Table 6.

(Example 2-34)
In Example 2-32, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-32, except that 2-90 was 30 parts and 30 parts of the acrylic monomer represented by the structural formula (17) was added. The results are shown in Table 6.

(Example 2-35)
In Example 2-32, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-32, except that 2-90 was 30 parts and the acrylic oligomer represented by the structural formula (19) was used. The results are shown in Table 6.

(Comparative Example 1)
After forming the charge generation layer in Example 1-1, 15 parts of a styryl compound represented by the structural formula (20) and 15 parts of a polymethyl methacrylate resin having a repeating unit represented by the following structural formula (22) were added to monochlorobenzene 50. A charge transport layer was formed by coating on the charge generation layer using a paint for charge transport layer prepared by dissolving in a mixed solvent of 20 parts by weight / dichloromethane and drying at 110 ° C. for 1 hour. The thickness of the charge transport layer at this time was 15 μm.

  As a result of evaluating this electrophotographic photoreceptor in the same manner as in Example 1-1, precipitation was observed after 14 days. On the other hand, the initial electrophotographic characteristics were good, but the amount of abrasion of the surface layer in durability was large, and image defects such as fogging and scratches occurred. Further, after 8000 sheets, the thickness of the charge transport layer was reduced by scraping, resulting in poor charging, and image formation became impossible. The results are shown in Table 9.

(Comparative Example 2)
An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 1 except that the polycarbonate resin represented by the structural formula (21) was used instead of the polymethyl methacrylate resin represented by the structural formula (22) in Comparative Example 1. As a result of the evaluation, precipitation was observed after 30 days. Further, although the durability was slightly improved as compared with the case of the polymethyl methacrylate resin, it was not sufficient, and an image defect after durability was generated. The results are shown in Table 9.

(Comparative Example 3)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Comparative Example 2, except that 10 parts of the styryl compound represented by Structural Formula (20) and 15 parts of the polycarbonate resin represented by Structural Formula (21) were used in Comparative Example 2. As a result, although the durability was improved as compared with Comparative Example 2, the charge transport ability was lowered and the sensitivity was lowered and the residual potential was increased by increasing the distance between the charge transport materials. As a result, ghosts were observed in the image. The results are shown in Table 9.

(Comparative Example 4)
After forming the charge transport layer in Example 1-27, 10 parts of a styryl compound represented by the structural formula (20) and 15 parts of the polycarbonate resin represented by the structural formula (21) were mixed in 50 parts of monochlorobenzene / 30 parts of dichloromethane. It melt | dissolved in the solvent and prepared the coating material for surface protection layers. This paint was applied on the charge transport layer by spray coating and dried at 120 ° C. for 1 hour to form a surface protective layer having a thickness of 5 μm. Compared with Comparative Example 3, since the charge transport layer having a high charge transport capability is in the lower layer, the sensitivity decreased, the residual potential increased slightly, and the shaving amount was improved, but the image after durability still has scratches / fogging. It occurred, and sufficient durability could not be secured. The results are shown in Table 9.

(Comparative Example 5)
Hole transporting compound No. 1 in Example 1-1. An electrophotographic photosensitive member was produced in the same manner as in Example 1-1 except that a compound represented by the following structural formula (23) disclosed in JP-A-5-216249 was used instead of 1-24. And evaluated. As a result, the initial electrophotographic characteristics were good, but the durability was significantly lowered as compared with Example 1-1. The results are shown in Table 9.

(Comparative Example 6)
Hole transporting compound No. 1 in Example 1-19 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-19 except that the compound represented by the structural formula (23) was used instead of 1-24. Results The initial electrophotographic characteristics were good, but the durability was significantly reduced as compared with Example 1-19. The results are shown in Table 9.

(Comparative Example 7)
After forming the charge generation layer in Example 1-1, 20 parts of a polycarbonate resin represented by the following structural formula (24) synthesized according to the production method described in P10 to 11 of JP-A-8-248649 was added to tetrahydrofuran. A charge transport layer was formed on the charge generation layer using a charge transport layer coating prepared by dissolving in 80 parts. The thickness of the charge transport layer at this time was 15 μm. As a result of evaluating this electrophotographic photosensitive member in the same manner as in Example 1-1, the mechanical strength was improved as compared with Comparative Examples 1 and 2, but sufficient durability could not be ensured. The results are shown in Table 9.

1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Rail

Claims (9)

In an electrophotographic photoreceptor having a photosensitive layer on a conductive support,
The electrophotographic photoreceptor, wherein the photosensitive layer contains a compound obtained by polymerizing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule as represented by the following general formula (1) .

{(In the formula, A represents a hole transporting group; P ¹ and P ² represent a chain-polymerizable functional group of the following general formula (9) or general formula (10); P ¹ and P ² Z may be the same or different; Z represents an organic residue which may have a substituent; a, b and d represent 0 or an integer of 1 or more; a + b × d represents an integer of 2 or more; When a is 2 or more, P ¹ may be the same or different. When d is 2 or more, P ² may be the same or different. When b is 2 or more, Z and P ² are the same or different. May be)

Further, a hole transporting compound in which the bonding site between A and P ¹ and Z is replaced with a hydrogen atom is represented by the following general formula (2) or general formula (3).

(Wherein R ¹ , R ² , R ³ and R ⁴ represent an aryl group which may have a substituent; and R ¹ , R ² , R ³ and R ⁴ are the same or different, respectively. Ar ¹ and Ar ² represent an arylene group which may have a substituent (provided that when m = 0, Ar ² represents an aryl group which may have a substituent), They may be the same or different; m represents 0 or 1)

Wherein R ⁵ , R ⁶ , R ⁹ and R ¹⁰ represent an aryl group which may have a substituent, and R ⁷ and R ⁸ represent an arylene group which may have a substituent; R ⁵ , R ⁶ , R ⁹ and R ¹⁰ and R ⁷ and R ⁸ may be the same or different; Q represents an organic residue which may have a substituent)} The electrophotographic photosensitive member according to claim 1, wherein the hole transporting compound in which the bonding site between A, P ¹ and Z is replaced with a hydrogen atom in the general formula (1) is represented by the general formula (2). The electrophotographic photoreceptor according to claim 1, wherein the hole transporting compound in which the bonding site between A, P ¹ and Z is replaced with a hydrogen atom in the general formula (1) is represented by the general formula (3). Z in the general formula (1) or Q in the general formula (3) is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR ¹¹ = CR ¹² (R ¹¹ and R ¹² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom, and R ¹¹ and R ¹² may be the same or different), C═O, S═O The electrophotographic photoreceptor according to any one of claims 1 to 3, which represents an organic residue which is one or any combination of SO ₂ , SO ₂ , oxygen atom or sulfur atom. The electrophotographic photosensitive member according to claim 1, wherein Z in the general formula (1) or Q in the general formula (3) is represented by the following general formula (4).

(In the formula, X ^{1 to} X ³ represent an alkylene group which may have a substituent, (CR ¹³ = CR ¹⁴ ) m ¹ , C═O, S═O, SO ₂ , an oxygen atom or a sulfur atom, Ar ³ and Ar ⁴ represent an arylene group which may have a substituent; R ¹³ and R ¹⁴ represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. R ¹³ and R ¹⁴ may be the same or different; m ¹ represents an integer of ¹ to 5, p to t represents 0 or an integer of 1 to 10; provided that p to t are not simultaneously 0. ) The electrophotographic photosensitive member according to claim 1, wherein Z in the general formula (1) or Q in the general formula (3) is represented by the following general formula (5).

(In the formula, Ar ⁵ represents an arylene group which may have a substituent; X ⁴ and X ⁵ represent (CH ₂ ) g, (CH═CR ¹⁵ ) h, C═O or an oxygen atom; R ¹⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom, g is an integer of 1 to 10, h is an integer of 1 to 5, and u to w are 0. Or an integer of 1 to 10; provided that u to w are not 0 at the same time) The electrophotographic photosensitive member according to any one of claims 1 to 6, wherein the hole transporting compound having two or more chain polymerizable functional groups in the same molecule has an oxidation potential of 0.4 to 1.2 (V). body. The electrophotographic photosensitive member according to claim 1, a charging means for charging the electrophotographic photosensitive member, a developing means for developing the electrophotographic photosensitive member on which an electrostatic latent image is formed with toner, and a transfer Process cartridge characterized in that it is integrally supported with at least one means selected from the group consisting of cleaning means for collecting toner remaining on the electrophotographic photosensitive member after the process, and is detachable from the electrophotographic apparatus main body. . An electrophotographic photosensitive member according to any one of claims 1 to 7, a charging means for charging the electrophotographic photosensitive member, an exposure means for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, An electrophotographic apparatus comprising: a developing unit that develops an electrophotographic photosensitive member having a latent image formed thereon with toner; and a transfer unit that transfers a toner image on a transfer material.