JP4365961B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  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.
[0002]
[Prior art]
  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.
[0003]
  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.
[0004]
  Especially in electrophotographic photoreceptors that are used repeatedly, electrical and mechanical external forces such as charging, image exposure, toner development, transfer to paper, and cleaning treatment are directly applied to the surface of the electrophotographic photoreceptor. Durability against them 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.
[0005]
  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.
[0006]
  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.
[0007]
  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.
[0008]
  In addition, in charge transport layers composed of organic charge transport materials and binder resins, the dependency of charge transport ability on the resin is large. 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, etc., the charge transport layer contains a monomer having a carbon-carbon double bond, and the carbon-carbon double bond of the charge transport material and the heat Alternatively, an electrophotographic photoreceptor in which a charge transport layer cured film is formed by reacting with the energy of light is disclosed, but the charge transport material is only immobilized in a pendant form on 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.
[0009]
  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.
[0010]
[Problems to be solved by the invention]
  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.
[0011]
  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.
[0012]
  Still another object of the present invention is to improve the wear resistance and scratch resistance of the surface layer of the 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.
[0013]
[Means for Solving the Problems]
  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 comprising a compound obtained by polymerizing a hole transporting compound is provided.
[0014]
[Chemical 9]
[0015]
  In the formula, A represents a hole transporting group; P¹And P²Represents a chain polymerizable functional group of the following general formula (11) or general formula (12);¹And P²Z 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; If a is 2 or more, P¹May be the same or different, and when d is 2 or more, P²May be the same or different, and when b is 2 or more, Z and P²May be the same or different.
[0016]
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[0017]
  In the above general formula (1), A and P¹And a hole transporting compound in which the bonding site to Z is replaced by a hydrogen atom is represented by the following general formula (2) or general formula (4).
[0018]
Embedded image
[0019]
  Where R¹ ,R² And Ar ¹ IsMay have a substituentPhenylGroup R¹And R²Same or different.
However, the general formula (2) has one or more groups represented by the following general formula (3).
[0020]
Embedded image
[0021]
  Where R⁴ as well asAr²May have a substituentPhenylIndicates a group.
[0022]
Embedded image
[0023]
  Where Ar³ , Ar⁴ And R ⁵ May have a substituentPhenylIndicates a group, Ar³And Ar⁴May be the same or different.
However, the compound represented by the general formula (4) has one group represented by the following general formula (5).
[0024]
Embedded image
[0025]
  Where R⁷ as well asAr⁵May have a substituentPhenylIndicates a group.
[0026]
  In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member are provided.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, embodiments of the present invention will be described in detail.
[0028]
  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.
[0029]
  Chain-polymerizable functional group P in the general formula (1)¹And P²Means a functional group capable of the above-described reaction form, and here, a specific example of an unsaturated polymerization or ring-opening polymerizable functional group that occupies most of the functional group and has a wide application range.
[0030]
  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.
[0031]
[Table 1]
[0032]
  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.
[0033]
  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.
[0034]
[Table 2]
[0035]
  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.
[0036]
  Among the chain polymerizable functional groups according to the present invention as described above, an acryloyloxy group of the following general formula (11) or a methacryloyloxy group of the general formula (12) is used from the viewpoint of polymerization characteristics and the like.
[0037]
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[0038]
  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).
[0039]
  In general formula (1), “when a is 2 or more P¹May be the same or different ”means that each of n different types of chain polymerizable functional groups is represented by P¹¹, P¹², P¹³, P¹⁴, P¹⁵.... P¹ⁿFor example, when a = 3, the chain polymerizable functional group P directly bonded to the hole transporting compound A¹May be the same for all three, but the same for two but different for one (for example, P¹¹And P¹¹And P¹²However, each of the three is different (for example, P¹²And P¹⁵And P¹⁷Or the like) (If “d is 2 or more, P²May be the same or different. ”When b is 2 or more, Z and P²"May be the same or different" means the same thing).
[0040]
  A in the general formula (1) represents a hole transporting group, and P¹Examples of the hydrogenation compound (hole transport compound) in which the bonding site between Z and Z is replaced with a hydrogen atom include the following general formulas (2) and (4).
[0041]
Embedded image
[0042]
  However, the general formula (2) has one or more groups represented by the following general formula (3).
[0043]
Embedded image
[0044]
  In the general formulas (2) and (3), Ar¹ , Ar ² , R ¹ , R ² And R ⁴ Is optionally substituted phenylGroupShow. R¹And R²May be the same or different.
[0045]
  MaR¹Or R²Or Ar¹Any two of them, or Ar²And R⁴May be bonded directly or via a bonding group, and examples of the bonding group include alkylene groups such as methylene group, ethylene group and propylene group, heteroatoms such as oxygen and sulfur atoms, or CH═CH group. It is done.
[0046]
Embedded image
[0047]
  In the general formula (4), the compound represented by the general formula (4) has one group represented by the following general formula (5).
[0048]
Embedded image
[0049]
  In the general formulas (4) and (5), Ar³, Ar⁴ , Ar ⁵ , R ⁵ And R ⁷ Is optionally substituted phenylGroupShow. Ar³And Ar⁴May be the same or different.
[0050]
  MaR⁵Or Ar³Or Ar⁴Any two of them, or Ar⁵And R⁷May be bonded directly or via a bonding group, and examples of the bonding group include alkylene groups such as methylene group, ethylene group and propylene group, heteroatoms such as oxygen and sulfur atoms, or CH═CH group. It is done.
[0051]
  Z in the general formula (1) is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR⁸= CR⁹(R⁸And R⁹Represents an alkyl group, an aryl group or a hydrogen atom, R⁸And R⁹May be the same or different), C = O, S = O, SO₂Represents an organic residue in which one or any combination of an oxygen atom or a sulfur atom is combined. Among them, those represented by the following general formula (6) are preferable, and those represented by the following general formula (7) are particularly preferable.
[0052]
Embedded image
[0053]
Embedded image
[0054]
  In the general formula (6), X¹~ X³Is an alkylene group having 20 or less carbon atoms such as methylene group, ethylene group and propylene group which may have a substituent, (CR¹⁰= CR¹¹)_m, C = O, S = O, SO₂Represents an oxygen atom or a sulfur atom, Ar⁶And Ar⁷Is an arylene group which may have a substituent (benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran and dibenzothiophene. A group from which atoms are removed). R¹⁰And R¹¹Represents an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group and a thiophenyl group which may have a substituent, or a hydrogen atom;¹⁰And R¹¹May be the same or different. m represents an integer of 1 to 5, pt represents 0 or an integer of 1 to 10 (provided that pt is not simultaneously 0).
[0055]
  In the general formula (7), X⁴And X⁵Is (CH₂)_g, (CH = CR¹²)_h, C = O, or an oxygen atom, Ar⁵Is an arylene group which may have a substituent (benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran and dibenzothiophene. A group from which atoms are removed). R¹²Represents an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group and 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 (in particular, 0 or an integer of 1 to 5 is preferred, provided that u to w are It is never 0 at the same time).
[0056]
  In the above general formulas (1) to (7), R¹, R², R⁴, R⁵, R⁷~ R¹², Ar¹~ Ar⁸, X¹~ X⁵And Z each may have a halogen atom such as fluorine, chlorine, bromine and iodine; or a nitro group or a cyano group or a hydroxyl group; or an alkyl such as a methyl group, an ethyl group, a propyl group and a butyl group. 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; Aryl groups such as phenyl, naphthyl, anthryl and pyrenyl; or substituted amino groups such as dimethylamino, diethylamino, dibenzylamino, diphenylamino and di (p-tolyl) amino; styryl and Aryl vinyl groups such as naphthyl vinyl group, etc. That it is preferable that the other.
[0057]
  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. It has an oxidation potential of 1.2 (V)TheIf exceeded, injection of charges (holes) from the charge generating material is difficult to occur, and problems such as increase in residual potential, deterioration in sensitivity, and increase in potential fluctuation during repeated use are likely to occur, and below 0.4 (V) In addition to problems such as a decrease in charging ability, the compound itself is easily oxidized and thus easily deteriorates, resulting in problems such as sensitivity deterioration, image blurring, and potential fluctuation during repeated use. Because.
[0058]
  The oxidation potential described here is measured by the following method.
[0059]
  (Measurement method of oxidation potential)
  Saturated calomel electrode as reference electrode and 0.1N (n-Bu) as electrolyte₄N⁺ClO₄ ⁻Using an acetonitrile solution, the potential applied to the working electrode (platinum) was swept by a potential sweeper, and the potential when the obtained current-potential curve showed a peak was taken as the oxidation potential. Specifically, the sample is 0.1N (n-Bu)₄N⁺ClO₄ ⁻Dissolve in acetonitrile solution to a concentration of about 5-10 mmol%. 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.
[0060]
  Furthermore, the hole transporting compound having the chain polymerizable functional group has a hole transporting ability of 1 × 10^-7(Cm²/ V. (sec) or higher drift mobility is preferable (however, the applied electric field: 5 × 10⁴V / cm). 1 × 10^-7(Cm²/ V. If it is less than (sec), holes may not sufficiently move from the post-exposure development to the electrophotographic photosensitive member, so that the apparent sensitivity may be reduced and the residual potential may be increased.
[0061]
  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.
[0062]
[22]
[0063]
[Chemical23]
[0064]
[24]
[0065]
[Chemical25]
[0066]
[Chemical26]
[0067]
[27]
[0068]
[Chemical28]
[0069]
[Chemical29]
[0070]
[Chemical30]
[0071]
[Chemical31]
[0072]
[32]
[0073]
[Chemical33]
[0074]
[Chemical34]
[0075]
[Chemical35]
[0076]
[36]
[0077]
[Chemical37]
[0078]
  In the present invention, a typical synthesis method of a hole transporting compound having a chain polymerizable functional group is shown below.
[0079]
  (Synthesis Example 1: Synthesis of Compound No. 1-13)
  Synthesized according to the following route.
[0080]
[Chemical38]
[0081]
  1 (50 g: 0.173 mol), 2 (7.5 g: 81 mmol), anhydrous potassium carbonate (47.8 g) and copper powder (55 g) together with 200 g of 1,2-dichlorobenzene at 180-190 ° C. while heating and stirring. Went for hours. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was purified using a silica gel column to obtain 58 g of 3.
[0082]
  After cooling 35 g of N, N-dimethylformamide (DMF) to 0 to 5 ° C., phosphorus oxychloride (18.4 g: 0.12 mol) was slowly added dropwise so as not to exceed 10 ° C. After stirring for 15 minutes after completion of the dropping, a solution of 3 (50.0 g: 0.12 mol) / DMF 50 g 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 1 hour, further heated to 80 to 85 ° C. and stirred for 5 hours. The reaction solution was poured into 800 g 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 37.8 g of 4.
[0083]
  4 (25 g: 56 mmol) was added to 200 ml of ethanol, and 1,1-diphenylhydrazine hydrochloride (35 g: 159 mmol) was added thereto. After completion of the addition, the mixture was stirred at room temperature for 1 hour and then further heated and stirred at 50 ° C. for 2 hours. The reaction solution was cooled, 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 24.5 g of 5.
[0084]
  5 (20 g: 33 mmol) was added to 200 g of methyl cellosolve, and sodium methylate (12.0 g) was slowly added while stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and further heated and stirred at 40 to 50 ° C. for 8 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 subjected to column purification using a silica gel column to obtain 7.1 g of 6.
[0085]
  6 (7.0 g: 11 mmol) and triethylamine (3.5 g: 35 mmol) were added to 100 ml of dry tetrahydrofuran (THF), cooled to 0-5 ° C., and then acryloyl chloride (2.5 g: 28 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 2.8 g of 7 (Compound No. 1-13) (oxidation potential: 0.69 V).
[0086]
  (Synthesis Example 2: Synthesis of Compound No. 2-1)
  Synthesized according to the following route.
[0087]
[Chemical39]
[0088]
  1 (50 g: 0.173 mol), 2 (8.0 g: 86 mmol), anhydrous potassium carbonate (47.8 g), and copper powder (55 g) together with 200 g of 1,2-dichlorobenzene at 180 to 190 ° C. while heating and stirring. Went for hours. After the reaction solution was filtered, the solvent was removed under reduced pressure, and the residue was recrystallized twice with an acetone / methanol mixed solvent to obtain 51 g of 3.
[0089]
  After cooling 35 g of DMF to 0 to 5 ° C., phosphorus oxychloride (18.4 g: 0.12 mol) was slowly added dropwise so as not to exceed 10 ° C. After stirring for 15 minutes after completion of dropping, a solution of 3 (50.0 g: 0.12 mol) / DMF 50 g 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 1 hour, further heated to 80 to 85 ° C. and stirred for 5 hours. The reaction solution was poured into 800 g 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 37.8 g of 4.
[0090]
  4 (30 g: 67 mmol) and 1,1-diphenylmethyldiethyl phosphate (20.5 g: 67 mmol) were dissolved in 200 ml of dry THF, and then oily sodium hydride (about 60%: 2.97 g: about 74 mmol) at room temperature. Was added slowly. After completion of the addition, the mixture was stirred at room temperature for 30 minutes and then heated and stirred for 3 hours. The reaction solution was cooled, 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 21.1 g of 5.
[0091]
  5 (20 g: 33.6 mmol) was added to 200 g of methyl cellosolve, and sodium methylate (7.0 g) was slowly added while 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 15.1 g of 6.
[0092]
  6 (15 g: 29.3 mmol) and triethylamine (8.88 g: 87.9 mmol) were added to 100 ml of dry THF and cooled to 0 to 5 ° C., and then acryloyl chloride (8.0 g: 88.4 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 9.8 g of 7 (Compound No. 2-1) (oxidation potential: 0.76 V).
[0093]
  (Synthesis Example 3: Synthesis of Compound No. 2-34)
  Synthesized according to the following route.
[0094]
[Chemical40]
[0095]
  1 (50 g: 0.173 mol), 8 (31.7 g: 0.173 mol), anhydrous potassium carbonate (50 g) and copper powder (65 g) together with 250 g of 1,2-dichlorobenzene and stirring with heating at 180-190 ° C. 10 Went for hours. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to obtain 49 g of 9.
[0096]
  After cooling DMF40g to 0-5 degreeC, the phosphorus oxychloride (19.9g: 0.13mol) was dripped slowly so that it might not exceed 10 degreeC. After completion of the dropwise addition, the mixture was stirred as it was for 15 minutes, and then a 9 (45 g: 0.013 mol) / DMF 60 g 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 1 hour, further heated to 80 to 85 ° C. and stirred for 5 hours. The reaction solution was poured into 1 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 purified using a silica gel column to obtain 33 g of 10.
[0097]
  10 (30 g: 80 mmol) and 1-phenyl-1- (p-methoxyphenyl) methyldiethyl phosphate (27 g: 80.7 mmol) were dissolved in 200 ml of dry THF, where oily sodium hydride (about 60%: 3.8 g: about 95 mmol) was added slowly. After completion of the addition, the mixture was stirred for 30 minutes at room temperature and then heated and stirred for 3 hours. The reaction mixture was cooled, poured into water, 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 28.1 g of 11.
[0098]
  11 (20 g: 36 mmol) was added to 150 g of methyl cellosolve, and sodium methylate (8.0 g) was slowly added while 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 90 to 100 ° C. for 20 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 15.8 g of 12.
[0099]
  12 (15 g: 23 mmol) and triethylamine (7.0 g: 69 mmol) were added to 100 ml of dry THF and cooled to 0-5 ° C., and then acryloyl chloride (6.3 g: 70 mmol) 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 5.85 g of 13 (Compound No. 2-34) (oxidation potential: 0.78 V).
[0100]
  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.
[0101]
  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.
[0102]
  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.
[0103]
  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.
[0104]
  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.
[0105]
  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.
[0106]
  Next, a method for producing an electrophotographic photoreceptor according to the present invention will be specifically described.
[0107]
  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.
[0108]
  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.
[0109]
  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.
[0110]
  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.
[0111]
  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.
[0112]
  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.
[0113]
  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.
[0114]
  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.
[0115]
  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 should be noted that when the dose is less than 1 Mrad, the crosslinking tends to be insufficient, and when the dose exceeds 100 Mrad, the electrophotographic photosensitive member characteristics are likely to deteriorate.
[0116]
  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 more 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.
[0117]
  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 and polystyrylanthracene. A polymer compound having a heterocyclic ring or condensed polycyclic aromatic, a heterocyclic compound such as pyrazoline, imidazole, oxazole, triazole and carbazole, a triarylalkane derivative such as triphenylmethane, a triarylamine derivative 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) is described above. Apply and dry by known methods It can be formed.
[0118]
  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.
[0119]
  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.
[0120]
  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.
[0121]
  FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
[0122]
  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.
[0123]
  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.
[0124]
  The transfer material 7 that has received the image transfer is separated from the surface of the electrophotographic photosensitive member, introduced into the fixing means 8, and subjected to fixing to be printed out as a copy (copy).
[0125]
  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.
[0126]
  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 with the electrophotographic photosensitive member 1 to form a cartridge, and is attached to and detached from the apparatus main body using guide means such as a rail 12 of the apparatus main body. A flexible process cartridge 11 can be obtained.
[0127]
  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.
[0128]
  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. .
[0129]
【Example】
  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” means part by mass.
[0130]
  (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 1 mmφ glass beads. This paint was applied onto 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.
[0131]
  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.
[0132]
  Next, 5 parts of a bisazo pigment represented by the following structural formula (18), 2 parts of polyvinyl butyral resin and 35 parts of cyclohexanone are dispersed in a sand mill apparatus using 1 mmφ glass beads for 24 hours, and tetrahydrofuran is further added to form a charge generation layer. The paint was used. This paint was applied onto 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.
[0133]
[Chemical41]
[0134]
  Compound Example No. 60 parts of the 1-13 hole transporting compound was dissolved in a mixed solvent of 30 parts of monochlorobenzene / 30 parts of 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 with an electron beam under the conditions of an acceleration voltage of 150 kV and a dose of 30 Mrad to form a charge transport layer having a film thickness of 15 μm to obtain an electrophotographic photosensitive member. It was.
[0135]
  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 electrophotographic photosensitive member, 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.
[0136]
  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 −700 V is set) and residual potential Vsl (light amount three times the light attenuation sensitivity light amount) )), 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.
[0137]
  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 shows very stable and good characteristics such as
[0138]
  (Example 1-2, 1-5, 1-10~ 1-12, 1-18)
  In Example 1-1, the hole transporting compound No. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-1 except that 1-13 was replaced with the compounds shown in Table 4. The results are shown in Table 3.
[0139]
  (Example 1-22)
  In Example 1-1, the hole transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1 except that the amount of 1-13 was 48 parts and 12 parts of an acrylic monomer represented by the following structural formula (19) was added. The results are shown in Table 3.
[0140]
[Chemical42]
[0141]
  (Example 1-23)
  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 1-13 was 48 parts and 12 parts of an acrylic oligomer represented by the following structural formula (20) was added. The results are shown in Table 3.
[0142]
[Chemical43]
[0143]
  (Examples 1-24 to 1-28)
  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.
[0144]
  (Example 1-29)
  After forming the charge generation layer in Example 1-1, 20 parts of a styryl compound represented by the following structural formula (21) and 10 parts of a polycarbonate resin having a repeating unit represented by the following structural formula (22) 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.
[0145]
[Chemical44]
[0146]
[Chemical45]
[0147]
  Subsequently, the hole transporting compound No. 60 parts of 1-13 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 the conditions of an acceleration voltage of 150 kV and a dose of 30 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.
[0148]
  (Example 1-30)
  In Example 1-29, the hole transporting compound No. 1-13 is compound No. 1-13. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-29 except that 1-34 was used. The results are shown in Table 3.
[0149]
  (Example 1-31)
  In Example 1-29, the hole transporting compound No. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-29 except that 1-13 was changed to 30 parts and 30 parts of the acrylic monomer represented by the structural formula (19) was added. The results are shown in Table 3.
[0150]
  (Example 1-32)
  In Example 1-29, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-29 except that 1-13 was changed to 30 parts and the acrylic oligomer represented by the structural formula (20) was used. The results are shown in Table 3.
[0151]
[Table 3]
[0152]
[Table 4]
[0153]
[Table 5]
[0154]
  (Example 2-1)
  In Example 1-1, the hole transporting compound No. 1-13 is compound No. 1-13. Instead of 2-1, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-1 except that the electron beam was irradiated under the conditions of an acceleration voltage of 150 kV and a dose of 20 Mrad. The results are shown in Table 6.
[0155]
  (Example 2-22-5, 2-122-14, 2-20)
  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 2-1 was replaced with the compounds shown in Table 7. The results are shown in Table 6.
[0156]
  (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 2-1 was 48 parts and 12 parts of an acrylic monomer represented by the structural formula (19) was added. The results are shown in Table 6.
[0157]
  (Example 2-25)
  In Example 2-4, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-4 except that the amount of 2-24 was 48 parts and 12 parts of an acrylic monomer represented by the following structural formula (23) was added. The results are shown in Table 6.
[0158]
[Chemical46]
[0159]
  (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 2-1 was 48 parts and 12 parts of an acrylic oligomer represented by the structural formula (20) was further added. The results are shown in Table 6.
[0160]
  (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.
[0161]
  (Example 2-32)
  After forming the charge generation layer in Example 2-1, 20 parts of a styryl compound represented by the structural formula (21) and 10 parts of a polycarbonate resin having a repeating unit represented by the structural formula (22) 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 prepared by dissolving in 20 parts of a mixed solvent. At this time, the thickness of the charge transport layer was 10 μm.
[0162]
  Subsequently, the hole transporting compound No. 2-1 60 parts was dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating 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 an electron beam under the conditions of an acceleration voltage of 150 kV and a dose of 20 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.
[0163]
  (Example 2-33)
  In Example 2-32, the hole transporting compound No. 2-1, compound no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2-32, except that 2-46 was used. The results are shown in Table 6.
[0164]
  (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 2-1 was 30 parts and 30 parts of the acrylic monomer represented by the structural formula (19) was added. The results are shown in Table 6.
[0165]
  (Example 2-35)
  In Example 2-32, the hole transporting compound No. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2-32, except that 2-1 was 30 parts and the acrylic oligomer represented by the structural formula (20) was used. The results are shown in Table 6.
[0166]
[Table 6]
[0167]
[Table 7]
[0168]
[Table 8]
[0169]
  (Comparative Example 1)
  After forming the charge generation layer in Example 1-1, 15 parts of a styryl compound represented by the structural formula (21) and 15 parts of a polymethyl methacrylate resin having a repeating unit represented by the following structural formula (24) 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.
[0170]
[Chemical47]
[0171]
  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.
[0172]
  (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 (22) was used instead of the polymethyl methacrylate resin represented by the structural formula (24) in Comparative Example 1. As a result of 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.
[0173]
  (Comparative Example 3)
  An electrophotographic photoreceptor 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 (21) and 15 parts of the polycarbonate resin represented by Structural Formula (22) 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 reduced due to the increase in the distance between the charge transport materials, and the sensitivity was lowered and the residual potential was increased. As a result, generation of ghost was observed in the image. The results are shown in Table 9.
[0174]
  (Comparative Example 4)
  After forming the charge transport layer in Example 1-29, 10 parts of the styryl compound represented by the structural formula (21) and 15 parts of the polycarbonate resin represented by the structural formula (22) 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 onto the previous 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 to 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 amount of scraping 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.
[0175]
  (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 (25) disclosed in JP-A-5-216249 was used instead of 1-13. And evaluated. As a result, the initial electrophotographic characteristics were good, but the durability was significantly reduced compared to Example 1-1. The results are shown in Table 9.
[0176]
[Chemical48]
[0177]
  (Comparative Example 6)
  Hole transporting compound No. 1 in Example 1-22 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-22 except that the compound represented by the structural formula (25) was used instead of 1-13. Results The initial electrophotographic characteristics were good, but the durability was significantly reduced as compared with Example 1-22. The results are shown in Table 9.
[0178]
  (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 (26) 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.
[0179]
[Chemical49]
[0180]
[Table 9]
[0181]
【The invention's effect】
  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. In addition, the effect of the electrophotographic photosensitive member is naturally exhibited in a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member, and high image quality is maintained for a long time.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
1 Electrophotographic photoreceptor
2 axis
3 Charging means
4 exposure light
5 Development means
6 Transfer means
7 Transfer material
8 Fixing means
9 Cleaning means
10 Pre-exposure light
11 Process cartridge
12 rails

Claims (9)

An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer has two or more chain polymerizable functional groups in the same molecule as represented by the following general formula (1) An electrophotographic photosensitive member comprising a compound obtained by polymerizing the above.
{(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 (11) or general formula (12); 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)
In the above general formula (1), the hole transporting 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) or general formula (4).
^(Wherein, R 1, ^{R 2} and Ar ¹ is a phenyl group which may have a location substituent, ^{R 1} and ^{R 2} but it may also be the same or different)
However, the general formula (2) has one or more groups represented by the following general formula (3).
(In the formula, R ⁴ and Ar ² represent a phenyl group which may have a substituent)
^(Wherein, Ar 3, Ar ⁴ and ^{R 5} is a phenyl group which may have a substituent, Ar ³ and Ar ⁴ but it may also be the same or different)
However, the compound represented by the general formula (4) has one group represented by the following general formula (5).
(Wherein R ⁷ and Ar ⁵ represent a phenyl group which may have a substituent)} In the above general formula (1), a hole transporting compound was replaced the binding site of the A and P ¹ and Z a hydrogen atom, an electrophotographic photosensitive according to claim 1 represented by the above following general formula (2) body. The electrophotographic photoreceptor according to claim 1, wherein the hole transporting compound in which the bonding site of A, P ¹ and Z is replaced with a hydrogen atom in the general formula (1) is represented by the general formula (4). Z in the general formula (1) is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR ⁸ = CR ⁹ (R ⁸ and R ⁹ have a substituent, An alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom, and R ⁸ and R ⁹ may be the same or different), C═O, S═O, SO ₂ , oxygen atom or sulfur The electrophotographic photosensitive member according to any one of claims 1 to 3, which shows an organic residue which is one or arbitrarily combined with atoms. The electrophotographic photosensitive member according to claim 1, wherein Z in the general formula (1) is represented by the following general formula (6).
^(Wherein, X 1 to X ³ is an alkylene group which may have a _{^{substituent, (CR 10 = CR 11)}} m, C = O, S = O, SO 2, an oxygen atom or a sulfur atom, Ar ⁶ and Ar ⁷ represent an arylene group which may have a substituent; R ¹⁰ and R ¹¹ represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. , R ¹⁰ and R ¹¹ may be the same or different; m 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 0 at the same time) The electrophotographic photoreceptor according to claim 1, wherein Z in the general formula (1) is represented by the following general formula (7).
(In the formula, Ar ⁸ represents an arylene group which may have a substituent; X ⁴ and X ⁵ represent (CH ₂ ) _g , (CH═CR ¹² ) _h , C═O or an oxygen atom; R ¹² 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 any one of claims 1 to 7 , 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. . The electrophotographic photosensitive member according to any one of claims 1 to 7 charging means for charging the electrophotographic photoreceptor, exposing means for forming an electrostatic latent image was exposed to the charged electrophotographic photosensitive member, electrostatic 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.