JP4164174B2 - Method for producing electrophotographic photosensitive member - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a method for producing an electrophotographic photosensitive member, and more particularly to a method for producing an electrophotographic photosensitive member having a photosensitive layer containing a specific material.
[0002]
[Prior art]
  Conventionally, inorganic photoconductive materials such as selenium, cadmium sulfide and zinc oxide have been widely used for electrophotographic photoreceptors. On the other hand, as an electrophotographic photoreceptor using an organic photoconductive material, a photoconductive polymer typified by poly-N-vinylcaribazole or 2,5-bis (p-diethylaminophenyl) -1,3,4 is used. Known are those using a low molecular organic photoconductive material such as oxadiazole, and combinations of such organic photoconductive materials with various dyes and pigments.
[0003]
  Since an electrophotographic photosensitive member using an organic photoconductive material has good film forming properties and can be produced by coating, it has an advantage of providing an electrophotographic photosensitive member that is extremely productive and inexpensive. In addition, there has been an advantage that the photosensitive wavelength range can be freely controlled by selecting the dye or pigment to be used, and extensive studies have been made so far.
[0004]
  In particular, the development of a functionally separated type photoreceptor in which a charge generation layer containing an organic photoconductive dye or pigment and a charge transport layer containing a photoconductive polymer or a low molecular organic photoconductive material are laminated has been developed. The sensitivity and durability that have been regarded as the disadvantages of the organic electrophotographic photoreceptors have been remarkably improved, and this has become the mainstream of organic electrophotographic photoreceptors. In the function separation type photoreceptor, the charge generation layer is generally composed of a charge generation material and a binder resin, and the charge transport layer is generally composed of a charge transport material and a binder resin. Central.
[0005]
  However, when a high-sensitivity function-separated type photoconductor is repeatedly used in an electrophotographic apparatus, a decrease in chargeability and a fluctuation in sensitivity occur, which greatly hinders high durability. The decrease in chargeability and sensitivity fluctuations due to repeated use of the photoreceptor are largely influenced by the mechanical characteristics in the environment where the photoreceptor is used.
[0006]
  That is, although there is a difference depending on the friction, method or load with toner or paper, the photosensitive layer is worn by a practical load such as friction due to the cleaning site, and the film thickness is reduced. This reduction in the film thickness of the photoconductor causes a decrease in chargeability and sensitivity fluctuations, and when these fluctuations exceed the range allowable in the development system, the photoconductor reaches the end of its life.
[0007]
  In order to cope with a decrease in chargeability and sensitivity fluctuation due to a decrease in the thickness of the photoreceptor due to wear or the like, a charge transport material is polymerized as disclosed in JP-A-1-134457, or JP-A-2-127852. As disclosed in Japanese Laid-Open Patent Publication No. 2003-260, a technique is disclosed that attempts to take measures by improving the strength of the charge transport layer by using a curable binder resin for the charge transport layer and curing the resin.
[0008]
  However, there are fluctuations in chargeability and sensitivity caused by repeated use of high-sensitivity function-separated photoconductors due to factors other than abrasion due to wear, and the cause is not clear. Was never taken. As long as this remains one of the factors hindering the high durability of the organic photoreceptor, a highly durable and highly stable photoreceptor that does not vary in chargeability and sensitivity even after repeated use cannot be completed. Therefore, further improvement in this regard has been strongly desired.
[0009]
[Problems to be solved by the invention]
  The object of the present invention is to eliminate the above-mentioned drawbacks of the organic function-separated type photoreceptor, and extremely little change and deterioration of the photoreceptor characteristics such as a decrease in chargeability and sensitivity fluctuation during repeated use, and even during repeated use. An object of the present invention is to provide a method for producing a highly sensitive electrophotographic photosensitive member capable of exhibiting stable performance.
[0010]
  Another object of the present invention is to provide a method for producing an electrophotographic photoreceptor having good potential stability during repeated use and high image quality.
[0011]
[Means for Solving the Problems]
  According to the present invention, in an electrophotographic photosensitive member having a conductive support and a photosensitive layer provided on the conductive support,
  The photosensitive layer has a charge generation layer and a charge transport layer in this order.Fucked inLayered structure,
  The charge generation layer comprises a charge generation material andIt is shown by the following general formula (1)In a composition containing a hole transporting compound having two or more chain-polymerizable functional groups in the same molecule, the hole transporting compound is formed through a step of curing by polymerization or crosslinking with heat or ultraviolet rays. Are layered
An electrophotographic photoreceptor manufacturing method is provided.
[0012]
[12]
[0013]
{(In the formula (1), A represents a hole transporting group. P ¹ And P ² Represents a chain polymerizable functional group represented by the following general formula (14) or (15). P ¹ And P ² May be the same or different. Z represents an organic residue which may have a substituent. Y represents a hydrogen atom. a, b and d represent 0 or an integer of 1 or more. However, when a = 0, b + d is an integer of 3 or more, when b or d is 0, a is an integer of 2 or more, and in other cases, a + b + d is an integer of 3 or more. If a is 2 or more, P ¹ May be the same or different. P if d is 2 or more ² May be the same or different. When b is 2 or more, Z may be the same or different. )
[0014]
[13]
[0015]
Also, A, P ¹ A hole transporting compound in which a bonding site with Z and a bonding site with Z are each replaced with a hydrogen atom is any of the following general formulas (2), (3), (4), (5) and (7) Indicated by the indicated compound.
[0016]
[14]
[0017]
(In formula (2), R ¹ , R ² And R ³ Represents a phenyl group which may have a substituent. R ¹ , R ² And R ³ May be the same or different. )
[0018]
[15]
[0019]
(In formula (3), R ⁴ , R ⁵ , R ⁸ And R ⁹ Represents a phenyl group which may have a substituent. R ⁶ And R ⁷ Represents a phenylene group which may have a substituent. R ⁴ , R ⁵ , R ⁸ And R ⁹ And R ⁶ And R ⁷ May be the same or different. Q represents an organic residue which may have a substituent. )
[0020]
[16]
[0021]
(In formula (4), R ¹⁰ , R ¹¹ , R ¹² And R ¹³ Represents a phenyl group which may have a substituent. R ¹⁰ , R ¹¹ , R ¹² And R ¹³ May be the same or different. Ar ¹ And Ar ² Represents a phenylene group which may have a substituent. Ar ¹ And Ar ² May be the same or different. m represents 0 or 1; However, when m = 0, Ar ² Becomes a phenyl group which may have a substituent. )
[0022]
[17]
[0023]
(In the formula (5), Ar ³ And Ar ⁴ Represents a phenyl group which may have a substituent. Ar ³ And Ar ⁴ May be the same or different. R ¹⁴ Represents a phenyl group which may have a substituent.
However, Ar ³ , Ar ⁴ And R ¹⁴ At least one of them has one substituent represented by the following general formula (6). )
[0024]
[18]
[0025]
(In formula (6), R ¹⁶ Represents a phenyl group which may have a substituent. Ar ⁵ Represents a phenyl group which may have a substituent. )
[0026]
[19]
[0027]
(In formula (7), R ¹⁷ And R ¹⁸ Represents a phenyl group which may have a substituent. R ¹⁷ And R ¹⁸ May be the same or different. Ar ⁶ Represents a phenyl group which may have a substituent. However, the compound represented by the general formula (7) has one or more substituents represented by the following general formula (8). )
[0028]
[20]
[0029]
(In formula (8), R ²⁰ Represents a phenyl group which may have a substituent. Ar ⁷ Represents a phenyl group which may have a substituent. )}
[0030]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, embodiments of the present invention will be described in detail.
[0031]
  As a result of intensive studies to solve the above-mentioned drawbacks, the present inventors have determined that the photosensitive layer has a charge generation layer and a charge transport layer in this order.Fucked inThe charge generation layer is composed of a charge generation material and a charge generation layer.It is shown by the above general formula (1)In a composition containing a hole transporting compound having two or more chain-polymerizable functional groups in the same molecule, the hole transporting compound is formed through a step of curing by polymerization or crosslinking with heat or ultraviolet rays. The present inventors have found that the problem can be solved by the layer being formed.
[0032]
  As described above, the function-separated type photoreceptor has a structure in which a charge generation layer and a charge transport layer are laminated, the charge generation layer is composed of a charge generation material and a binder resin, and the charge transport layer is composed of a charge transport material and a charge transport material. Generally, it is composed of a binder resin. In this configuration, the photosensitivity is expressed by first absorbing light by the charge generation material in the charge generation layer, thereby generating photocarriers. Next, it is considered that sensitivity is developed by injecting photocarriers from the charge generating material into the charge transport material in the charge transport layer and further transporting the charge transport layer. However, the details of the phenomenon of generation and injection of this photocarrier are very complicated, and change slightly depending on, for example, the positional relationship between the charge generation material and the charge transport material.
[0033]
  In recent years, various detailed studies on the generation and injection of optical carriers have been carried out. For example, as reported in the Journal of the Electrophotographic Society, Vol. 35, No. 2 (1996) p110-115, only carrier injection is performed. In addition, the importance of the positional relationship between the charge generation material and the charge transport material has been shown even in the generation of carriers. In the function-separated type photoconductor of the charge generation layer / charge transport layer lamination type prepared by the wet coating method, It has been reported that the charge transport material soaked in the charge generation layer plays an important role for carrier generation. Based on the above-mentioned facts, the present inventors have investigated the cause of the change in chargeability and sensitivity of the photosensitive member during repeated use other than the above-mentioned wear scraping, and studied countermeasures.
[0034]
  As a result, although not fully understood yet, it is suggested that the cause of the above-mentioned fluctuation is also due to the spatial positional relationship between the charge generation material and the charge transport material changing during repeated use. As a countermeasure, charge generation materialsIt is shown by the above general formula (1)In a composition containing a hole transporting compound having two or more chain-polymerizable functional groups in the same molecule, the hole transporting compound is cured by polymerization or crosslinking with heat or ultraviolet rays to form a charge generation layer Has been found to be very effective.
[0035]
  That is, the present invention relates to an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer includes a charge generation layer and a charge transport layer in this order.Fucked inThe charge generation layer is composed of a charge generation material and a charge generation layer.It is shown by the above general formula (1)In a composition containing a hole transporting compound having two or more chain-polymerizable functional groups in the same molecule, the hole transporting compound is formed through a step of curing by polymerization or crosslinking with heat or ultraviolet rays. It is characterized by being a layer formed.
[0036]
  Next, the structure of the electrophotographic photosensitive member manufactured by the manufacturing method of the present invention will be described in detail. The structure of the photoreceptor produced by the production method of the present invention has a photosensitive layer on a conductive support, and the photosensitive layer comprises a charge generation layer / a charge transport layer in this order.Fucked inIt is a layered configuration. Since the charge transport layer is generally hole transportable, the stacked structure in the order of charge generation layer / charge transport layer is used.NaruWith negatively charged photoreceptorBecome.
[0037]
  As the support of the electrophotographic photosensitive member, any material can be used as long as it has conductivity, for example, a metal or alloy such as aluminum, copper, chromium, nickel, zinc and stainless steel formed into a drum or a sheet, A metal foil such as aluminum and copper laminated on a plastic film, a metal film deposited with aluminum, indium oxide and tin oxide, etc. Moreover, a plastic film, paper, etc. are mentioned.
[0038]
  In the present invention, an undercoat layer having a barrier function and an adhesive function may be provided between the conductive layer and the photosensitive layer. The undercoat layer can be formed of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, alcohol-soluble amide, polyurethane, gelatin or the like. The film thickness of the undercoat layer is suitably from 0.1 μm to 3 μm.
[0039]
  The charge generation layer, which is the most characteristic layer of the photoreceptor manufactured by the manufacturing method of the present invention, includes a charge generation material andIt is shown by the above general formula (1)In a composition containing a hole transporting compound having two or more chain-polymerizable functional groups in the same molecule, the hole transporting compound is formed through a step of curing by polymerization or crosslinking with heat or ultraviolet rays. Layer. As the charge generation material, azo pigments such as Sudan Red and Diane Blue, quinone pigments such as pyrenequinone and anthanthrone, quinocinian pigments, perylene pigments, indigo pigments such as indigo and thioindigo, phthalocyanine pigments and the like can be used.
[0040]
  Next, although it is a hole transportable compound which has a chain-polymerizable functional group, the chain-polymerizable functional group in this invention is demonstrated first. 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.
[0041]
  The chain-polymerizable functional group P in the general formula (1) means a functional group capable of the above-mentioned reaction form, and here, it occupies most of the functional group and is an unsaturated polymerization or ring-opening polymerizable functional group having a wide application range. A specific example is shown.
[0042]
  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. The majority is due to. Specific examples of the unsaturated polymerizable functional group are shown in Table 1, but are not limited thereto.
[0043]
[Table 1]
[0044]
  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 or an anthryl group, or a hydrogen atom may be used.
[0045]
  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.
[0046]
[Table 2]
[0047]
  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 or an anthryl group, or a hydrogen atom may be used.
[0048]
  Chain-polymerizable functional group according to the present invention as described aboveIsThe following general formula (14)Or (15)Indicated byIsThe
[0049]
[Chemical21]
[0050]
  Next, the hole transport material in the present invention will be described. 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 preferably the following general formula (1).
[0051]
[Chemical22]
[0052]
  In formula (1), P¹And P²IsIt is represented by the above general formula (14) or (15)A chain polymerizable functional group is shown. P¹And P²May be the same or different. Z represents an organic residue which may have a substituent. Y represents a hydrogen atom. a, b and d represent 0 or an integer of 1 or more. However, when a = 0, b + d is an integer of 3 or more, when b or d is 0, a is an integer of 2 or more, and in other cases, a + b + d is an integer of 3 or more. If a is 2 or more, P¹May be the same or different. P if d is 2 or more²May be the same or different. When b is 2 or more, Z may be the same or different.
[0053]
  Here, “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, P²“May be the same or different” and “when b is 2 or more, Z may be the same or different” means the same thing).
[0054]
  A in the general formula (1) represents a hole transporting group., P ¹Or as a hydrogenation compound (hole transport compound) in which the bonding site with Z is replaced with a hydrogen atom,underGeneral formulas (2), (3), (4), (5) and (7)The
[0055]
[Chemical23]
[0056]
  In formula (2), R¹, R²And R³ IsOptionally substituted phenylGroupShow.
[0057]
  R ¹, R²And R³May be the same or different. MaR of the general formula (2)¹Or R²Or R³Any two of them may be bonded directly or via a bonding group. Examples of the bonding group include alkylene groups such as a methylene group, ethylene group, and propylene group, heteroatoms such as oxygen and sulfur atoms, and CH═CH groups.
[0058]
[Chemical24]
[0059]
  In formula (3), R⁴, R⁵, R⁸And R⁹ IsOptionally substituted phenylGroupShow. R⁴, R⁵, R⁸And R⁹May be the same or different. R⁶And R⁷ IsMay have a substituentPhenylene groupIndicates. R⁶And R⁷May be the same or different. Q represents an organic residue which may have a substituent.
[0060]
  MaR of the general formula (3)⁴Or R⁵Or R⁶Any two of R or R⁷Or R⁸Or R⁹Any two of them may be bonded directly or via a bonding group. Examples of the bonding group include alkylene groups such as a methylene group, ethylene group, and propylene group, heteroatoms such as oxygen and sulfur atoms, and CH═CH groups.
[0061]
[Chemical25]
[0062]
  In formula (4), R¹⁰, R¹¹, R¹²And R¹³ IsOptionally substituted phenylGroupShow. R¹⁰, R¹¹, R¹²And R¹³May be the same or different.
[0063]
  Ar¹May have a substituentPhenylene groupIndicates. m represents 0 or 1; Ar²May be substituted phenyl when m = 0GroupShow. When m = 1, the above Ar¹Similar toPhenyleneIndicates a group. When m = 1, Ar¹And Ar²May be the same or different.
[0064]
  MaR in the general formula (4)¹⁰And R¹¹Or R¹²And R¹³Or Ar¹And Ar²May be bonded directly or via a bonding group. Examples of the bonding group include alkylene groups such as a methylene group, ethylene group, and propylene group, heteroatoms such as oxygen and sulfur atoms, and CH═CH groups.
[0065]
[Chemical26]
[0066]
  In formula (5), Ar ³ And Ar ⁴ Represents a phenyl group which may have a substituent. Ar ³ And Ar ⁴ May be the same or different. R ¹⁴ Represents a phenyl group which may have a substituent.
[0067]
  However,In formula (5), Ar³, Ar⁴And R¹⁴At least one of them has one or more substituents represented by the following general formula (6).
[0068]
[Chemical27]
[0069]
  formula(6) Medium, Ar⁵Is optionally substituted phenylGroupShow. R ¹⁶ IsFeni which may have a substituentLe groupShowThe
[0070]
  MaThe, Ar⁵And R¹⁶May be bonded directly or via a bonding group. Examples of the bonding group include alkylene groups such as methylene group, ethylene group and propylene group, heteroatoms such as oxygen and sulfur atoms, and CH═CH group.The
[0071]
[Chemical28]
[0072]
  In formula (7), R ¹⁷ And R ¹⁸ Represents a phenyl group which may have a substituent. R ¹⁷ And R ¹⁸ May be the same or different. Ar ⁶ Represents a phenyl group which may have a substituent.
[0073]
  However, the general formula (7)The compound represented byIt has one or more substituents represented by the following general formula (8).
[0074]
[29]
[0075]
  formula(8) Medium, Ar⁷Is optionally substituted phenylGroupShow. R ²⁰ IsOptionally substituted phenylGroupIndicationThe
[0076]
  MaThe, Ar⁷And R²⁰May be bonded directly or via a bonding group. Examples of the bonding group include alkylene groups such as methylene group, ethylene group and propylene group, heteroatoms such as oxygen and sulfur atoms, and CH═CH group.The
[0077]
  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, CR²¹= CR²²(R²¹And R²²Represents an alkyl group, an aryl group or a hydrogen atom. R²¹And R²²May be the same or different. ), C = O, S = O, SO₂, An oxygen atom or a sulfur atom, or a combination organic residue thereof. Among them, those represented by the following general formula (9) are preferable, and those represented by the following general formula (10) are particularly preferable.
[0078]
[Chemical30]
[0079]
  In the general formula (9), X¹, X²And X³Is an alkylene having 1 to 20 carbon atoms, such as a methylene group, an ethylene group or a propylene group, which may have a substituent, (CR²³= CR²⁴) M¹(R²³And R²⁴Represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. R²³And R²⁴May be the same or different. m¹Represents an integer of 1 to 5. ), C = O, S = O, SO₂Represents an oxygen atom or a sulfur atom. Ar⁸And Ar⁹Is an arylene group (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc.) An arylene group from which a hydrogen atom has been removed. p, q, r, s, and t show the integer of 0-10. However, p, q, r, s, and t are not 0 at the same time.
[0080]
[Conversion 31]
[0081]
  In the general formula (10), X⁴And X⁵Is (CH₂)_g(G represents an integer of 1 to 10), (CH = CR²⁵)_h(R²⁵Represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. h represents an integer of 1 to 5. ), C═O, or an oxygen atom. Ar¹⁰Is an arylene group (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc.) An arylene group from which a hydrogen atom has been removed. u, v, and w represent an integer of 0-10. Particularly preferred is an integer from 0 to 5. However, u, v, and w are not 0 at the same time.
[0082]
  In the above general formulas (1) to (10), R¹~R ¹⁴ , R ¹⁶ ~ R ¹⁸ , R ²⁰ ~R²⁵, Ar¹~ Ar¹⁰, X¹~ X⁵, Z and Q each may have a halogen atom such as fluorine, chlorine, bromine or iodine, a nitro group, a cyano group, a hydroxyl group or a methyl group, an alkyl group such as an ethyl group, a propyl group or a butyl group Group or methoxy group, ethoxy group, propoxy group or other alkoxy group or phenoxy group, naphthoxy group or other aryloxy group or benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group or other aralkyl group or phenyl group, naphthyl Group, anthryl group, aryl group such as pyrenyl group or the like, substituted amino group such as dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, di (p-tolyl) amino group, styryl group, naphthylvinyl group, etc. An aryl vinyl group etc. are mentioned.
[0083]
  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. That is, the hole transporting compound having a chain polymerizable functional group represented by the general formula (1) and the hydrogen adduct of the hole transporting group A preferably have 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 it exceeds, injection of charges (holes) from the charge generating material hardly occurs, causing problems such as an increase in residual potential, deterioration in sensitivity and potential fluctuation during repeated use, and charging below 0.4 (V). In addition to problems such as reduced performance, the compound itself is easily oxidized and thus easily deteriorates, resulting in problems such as sensitivity deterioration, image blurring, and potential fluctuations during repeated use. .
[0084]
  The oxidation potential described here is measured by the following method.
[0085]
  (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 when the current value showed a peak (or the first peak when there were a plurality of peaks) was defined as the oxidation potential.
[0086]
  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.
[0087]
  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.
[0088]
[32]
[0089]
[Chemical33]
[0090]
[Chemical34]
[0091]
[35]
[0092]
[36]
[0093]
[Chemical37]
[0094]
[38]
[0095]
[Chemical39]
[0096]
[40]
[0097]
[41]
[0098]
[Chemical42]
[0099]
[Chemical43]
[0100]
[44]
[0101]
[45]
[0102]
[46]
[0103]
[47]
[0104]
[Chemical48]
[0105]
[49]
[0106]
[50]
[0107]
[Chemicalization 51]
[0108]
[Chemical52]
[0109]
[53]
[0110]
[54]
[0111]
[Chemical55]
[0112]
[Chemical56]
[0113]
[Chemical57]
[0114]
[Conversion]
[0115]
[Chemical59]
[0116]
[60]
[0117]
[61]
[0118]
[62]
[0119]
[Chemical63]
[0120]
[64]
[0121]
[65]
[0122]
[66]
[0123]
[Chemical67]
[0124]
[68]
[0125]
[Chemical69]
[0126]
[70]
[0127]
[71]
[0128]
[72]
[0129]
[73]
[0130]
[74]
[0131]
[75]
[0132]
[Chemical76]
[0133]
[Chemical77]
[0134]
[78]
[0135]
[79]
[0136]
[80]
[0137]
[81]
[0138]
[82]
[0139]
  In the present invention, a typical synthesis method of a hole transporting compound having a chain polymerizable functional group is shown below.
[0140]
  (Synthesis Example 1: Synthesis of Compound No. 6)
  Synthesized according to the following route.
[0141]
[Chemical83]
[0142]
  1 (50 g: 0.47 mol), 2 (406 g: 1.4 mol), anhydrous potassium carbonate (193 g) and copper powder (445 g) were heated and stirred at 180-190 ° C. with 1.2 kg of 1,2-dichlorobenzene. 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 132 g of 3.
[0143]
  3 (120 g: 0.28 mol) was added to 1.5 kg of methyl cellosolve, and sodium methylate (150 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 10 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 78 g of 4.
[0144]
  4 (70 g: 0.2 mol) and triethylamine (40 g: 0.4 mol) were added to 400 ml of dry tetrahydrofuran (THF), cooled to 0-5 ° C., and then acryloyl chloride (55 g: 0.6 mol) 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 42 g of 5 (Compound No. 6) (oxidation potential: 0.83 V).
[0145]
  (Synthesis example2: Compound No. 152)
  Synthesized according to the following route.
[0146]
[Chemical84]
[0147]
  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.
[0148]
  3 (80 g: 0.26 mol) was added to 300 g of N, N-dimethylformamide (DMF), 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 refluxed.3Stirring was performed for hours. After cooling, the reaction mixture was poured into water, acidified with dilute hydrochloric acid and extracted with ethyl acetate, the organic layer was further extracted with 1.2N aqueous sodium hydroxide solution, the aqueous layer was acidified with dilute hydrochloric acid and extracted with ethyl acetate, After drying over anhydrous sodium sulfate, the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 64 g of 4.
[0149]
  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.
[0150]
  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 stirring for 15 minutes after completion of the dropwise addition, a 5 (42.2 g: 0.07 mol) / 102 g DMF solution was slowly added dropwise. After completion of the dropwise addition, 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.
[0151]
  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.
[0152]
  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 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 subjected to column purification using a silica gel column to obtain 6.4 g of 8 (Compound No. 152) (oxidation potential: 0.78 V).
[0153]
  (Synthesis example3: Compound No. Synthesis of H.263)
  Synthesized according to the following route.
[0154]
[Chemical85]
[0155]
  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.
[0156]
  After cooling DMF242g to 0-5 degreeC, the phosphorus oxychloride (84.8g: 553.2mmol) was dripped slowly so that it might not exceed 10 degreeC. 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.
[0157]
  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 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.
[0158]
  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. 263) (oxidation potential: 0.80 V).
[0159]
  In the present invention, the hole transporting compound having two or more chain polymerizable functional groups in the same molecule is polymerized / crosslinked, so that the compound having hole transporting ability is positioned in the photosensitive layer. In particular, in the case of having two or more chain polymerizable functional groups, since it is incorporated into the three-dimensional crosslinked structure through a covalent bond with two or more crosslinking points, it has an effect on potential stability. Becomes even larger. The hole transporting compound can be polymerized / crosslinked only or mixed with a compound having another chain polymerizable group, and the type / ratio thereof is arbitrary.
[0160]
  The compound having another chain polymerizable group mentioned here 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.
[0161]
  In the present invention, for the polymerization / crosslinking reaction of the chain polymerizable group, either heat or ultraviolet light can be used. When conducting a polymerization reaction with heat, a polymerization initiator may be required to proceed with thermal energy alone, but a polymerization initiator may be required, but in order to advance the reaction efficiently at a lower temperature, addition of an initiator Is desirable.
[0162]
  The polymerization initiator used in this case may be any initiator having a half-life at room temperature or higher. Specific examples thereof include ammonium persulfate, dicumyl peroxide, benzoyl peroxide, cyclohexane peroxide, and t-butyl hydro gen. Peroxides such as peroxide and di-t-butyl peroxide, and azo-based compounds such as azobisbutyronitrile. The addition amount is about 0.01 to 10 parts by weight with respect to 100 parts by weight of the total weight of the compound having a chain polymerizable group, and the temperature of the reaction system is appropriately selected between room temperature and 200 ° C. depending on the initiator. it can.
[0163]
  In the present invention, polymerization / crosslinking in the case of using ultraviolet rays is extremely rare when the reaction proceeds only with ultraviolet (light) energy, and a photopolymerization initiator is generally used in combination. In this case, the polymerization initiator mainly refers to those that absorb ultraviolet rays having a wavelength of 400 nm or less to generate active species such as radicals and ions and initiate polymerization, and specific examples thereof include acetophenone, benzoin, Examples thereof include radical polymerization initiators such as benzophenone and thioxanthone, and ion polymerization initiators such as diazonium compounds, sulfonium compounds, iodonium compounds, and metal complex compounds.
[0164]
  The addition amount of the initiator is about 0.01 to 50 parts by weight with respect to 100 parts by weight of the total weight of the compound having a chain polymerizable group. In the present invention, the above-described heat and photopolymerization initiators can be used in combination.
[0165]
  The amount of the hole transporting compound when the hole transporting compound having a chain polymerizable group is used in the charge transporting layer is the above general formula (with respect to the total weight of the charge transporting layer film after polymerization curing) The hydrogen adduct of the hole transporting group A having a chain polymerizable functional group represented by 1) is preferably 10 to 90% in terms of molecular weight, more preferably 20 to 80%. If the amount is too large, the ability to transport electrons in the charge generation layer decreases, causing problems such as a decrease in sensitivity and an increase in residual potential. If the amount is too small, the effect of stabilizing the potential becomes insufficient.
[0166]
  Further, a charge generation layer is formed from the hole transporting compound and a monomer or oligomer / polymer having no chain polymerizable group or a monomer or oligomer / polymer having a polymerizable group other than the chain polymerizable group. Also 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.
[0167]
  In the method for producing a charge generation layer of a photoreceptor produced by the production method of the present invention, the charge generation material and a hole transport compound having a chain polymerizable functional group are mixed with a solvent and, if necessary, a polymerization initiator, and further, 0 if necessary. It is formed by dispersing well together with 3 to 4 times the amount of binder resin by a method such as homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor and roll mill, and applying the dispersion and drying. The film thickness is preferably 5 μm or less, and particularly preferably in the range of 0.1 to 2 μm.
[0168]
  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, epoxy resin and the like.
[0169]
  The charge generation layer is formed by applying the charge generation material and the hole transporting compound having the chain polymerizable group, a polymerization initiator if necessary, and a solution containing a binder resin if necessary, followed by a polymerization / crosslinking reaction. LetShapeCompleteTheAs 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.
[0170]
  The charge transport layer of the multilayer photoconductor is a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene, or phenanthrene in the main chain or side chain, and a nitrogen-containing heterocyclic compound such as indole, carbazole, oxadiazole, or pyrazoline. , Hydrazone compounds, styryl compounds, and the like, are formed using a coating solution in which a film transportable resin is dissolved.
[0171]
  Examples of the resin having such a film forming property include polyester, polycarbonate, polystyrene, polymethacrylic acid ester and the like. The thickness of the charge transport layer is preferably 5 to 40 μm, more preferably 10 to 30 μm.
[0172]
  In the present invention, when the polymer charge transport compound disclosed in JP-A-1-134457 and JP-A-9-319101 is used as the charge transport material, the overall durability of the photoreceptor is dramatically improved. Improves both wear abrasion reduction and chargeability and sensitivity fluctuations. Furthermore, the charge transport layer is identical to the charge generation layer.Shown by the general formula (1)When one or both of a hole transporting compound having two or more chain-polymerizable functional groups in the same molecule and one obtained by polymerizing, crosslinking, or curing the hole transporting compound are contained, the improvement effect is remarkable. In particular, the photoconductor is excellent in stability and durability. Also in this case, the hole transporting compound having a chain polymerizable group is preferably polymerized / crosslinked by heat or ultraviolet rays.
[0173]
  Various additives can be added to the photosensitive layer (charge generation layer / charge transport layer) in the present invention. Additives include anti-degradation agents such as antioxidants and ultraviolet absorbers, and lubricants such as fluorine atom-containing resin fine particles.
[0174]
  FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member manufactured by the manufacturing method of the present invention.
[0175]
  In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member manufactured by the manufacturing method of the present invention, which is rotated about a shaft 2 in the direction of the arrow at a predetermined peripheral speed. In the rotating process, the photosensitive member 1 is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the primary charging unit 3, and then an image from an image 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 photoreceptor 1.
[0176]
  The formed electrostatic latent image is then developed with toner by the developing unit 5, and the developed toner developed image is rotated between the photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown). The image is sequentially transferred by the transfer means 6 to the transfer material 7 taken out synchronously and fed.
[0177]
  The transfer material 7 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, thereby being printed out as a copy (copy).
[0178]
  After the image transfer, the surface of the photoreceptor 1 is cleaned by removing the transfer residual toner by the cleaning unit 9 and further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown), and then repeatedly. Used 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.
[0179]
  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 can be attached to and detached 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.
[0180]
  In addition, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is a reflected light or transmitted light from a document, or a signal is read by a sensor and converted into a signal, and laser beam scanning performed according to this signal is performed. Light emitted by driving the LED array, driving the liquid crystal shutter array, or the like.
[0181]
  The electrophotographic photosensitive member produced by the production method of the present invention is not only used in electrophotographic copying machines but also widely used in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. Can be used.
[0182]
【Example】
  Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” indicates parts by weight.
[0183]
  Example 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 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.
[0184]
  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.
[0185]
  Next, 5 parts of a bisazo pigment of the following structural formula (21), Compound Example No. 6 parts of the hole transporting compound 6 and 60 parts of cyclohexanone were dispersed for 24 hours in a sand mill apparatus using 1 mmφ glass beads, and 60 parts of tetrahydrofuran and 0.6 part of the photopolymerization initiator of the following structural formula (22) were added. Then, a charge generation layer coating material was prepared. This paint is coated on the intermediate layer, and 500 mW / cm using a metal halide lamp.²A charge generation layer having a film thickness of 0.2 μm was formed by irradiating with ultraviolet light at a light intensity of 60 seconds for curing.
[0186]
[Chemical86]
[0187]
[Chemical87]
[0188]
  Next, 60 parts of a hole transporting compound of the following structural formula (23) and 80 parts of a Z-type polycarbonate resin (weight average molecular weight 20000) are dissolved in a mixed solvent of 30 parts of monochlorobenzene / 10 parts of dichloromethane, and used for a charge transport layer. A paint was prepared. This paint was coated on the charge generation layer and dried at 120 ° C. for 30 minutes to form a charge transport layer having a thickness of 15 μm, whereby an electrophotographic photosensitive member was obtained.
[0189]
[Chemical88]
[0190]
  The produced electrophotographic photoreceptor was evaluated for electrophotographic characteristics and stability during repeated use. The electrophotographic characteristics and stability during repeated use were evaluated by mounting this photoreceptor on a machine obtained by removing the cleaner and the developer from LBP-SX manufactured by Canon Inc. Initial photoconductor 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 a non-sheet-passing durability test for 10000 sheets is performed, and each change value ΔVd, ΔVl (the amount of light equal to the amount of light at which Vl initially becomes −150 V is irradiated after endurance) Change amount of Vl) and ΔVsl.
[0191]
  The results are shown in Table 3. The photoconductor produced by the production method of the present invention has good initial photoconductor characteristics, and the photoconductor characteristics hardly change even after repeated use. It shows good characteristics.
[0192]
  (Examples 2 to 5)
  In Example 1, the hole transporting compound No. 6 is compound example No. 6, respectively. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that 139, 151, 265 and 356 were used. The results are shown in Table 3.
[0193]
  Example 9
  In the same manner as in Example 1, a support, a conductive layer, and an undercoat layer were formed. Next, 3 parts of oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of the Bragg angle (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction , Polyvinyl butyral (trade name: ESREC BM2, Sekisui Chemical Co., Ltd.) resin, 1 part, compound example No. Disperse 5 parts of 358 and 35 parts of cyclohexanone in a sand mill using φ1 mm glass beads for 2 hours, and then add 60 parts of ethyl acetate and 0.6 part of a photopolymerization initiator represented by the structural formula (22). It melt | dissolved and the coating material for charge generation layers was prepared. This paint is applied on the intermediate layer by a dip coating method, and 500 mW / cm using a metal halide lamp.²A charge generation layer having a film thickness of 0.2 μm was formed by irradiating with ultraviolet light at a light intensity of 60 seconds for curing.
[0194]
  Next, a charge transport layer coating was applied on the charge generation layer using the charge transport layer paint in the same manner as in Example 1, followed by heat drying at 120 ° C. for 30 minutes to form a charge transport layer having a thickness of 20 μm. Formed. This photoreceptor was evaluated in the same manner as in Example 1, and the results are shown in Table 3.
[0195]
  (Examples 10 to 14)
  In Example 9, the hole transporting compound No. 358, Compound Example No. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that 139, 154, 222, 344 and 410 were used. The results are shown in Table 3.
[0196]
  (Example 15)
  In Example 9, the amount of the hole transporting compound in the charge generation layer was 3 parts, and further 2 parts of an acrylic monomer having the structure of the following structural formula (25) was added. A body was made and evaluated. The results are shown in Table 3.
[0197]
[Chemical89]
[0198]
  (Example 16)
  In Example 9, the photopolymerization initiator represented by the structural formula (22) was replaced with a thermal polymerization initiator represented by the following structural formula (26), and instead of an ultraviolet curing reaction, a thermosetting reaction was performed at 140 ° C. for 1 hour. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that. The results are shown in Table 3.
[0199]
[Chemical90]
[0200]
  (Example 17)
  The charge generation layer was molded in the same manner as in Example 9. Next, Compound Example No. 358 hole transporting compounds of 358 were dissolved in a mixed solvent of 30 parts monochlorobenzene / 30 parts dichloromethane to prepare a coating material for a charge transport layer. After coating the paint on the charge generation layer and drying at 50 ° C. for 10 minutes, an acceleration voltage of 150kAn electron beam was irradiated under the conditions of V and an irradiation dose of 20 Mrad, the resin in the charge transport layer was cured, and a charge transport layer having a thickness of 17 μm was formed to obtain an electrophotographic photosensitive member.
[0201]
  As a result of evaluating this photoreceptor in the same manner as in Example 1, both the initial characteristics and the stability during repeated use were very good. The results are shown in Table 3.
[0202]
  (Example 18)
  After the formation of the charge generation layer in the same manner as in Example 9, 20 parts of a polycarbonate resin of the following structural formula (27) synthesized according to the production method described in P10-11 of JP-A-8-248649 was added to 80 parts of tetrahydrofuran. A charge transport layer was formed on the charge generation layer using a paint for a charge transport layer prepared by dissolving in the solution. The film thickness of the charge transport layer at this time was 17 μm. This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. As a result, both initial characteristics and stability during repeated use were satisfactory. The results are shown in Table 3.
[0203]
[Chemical91]
[0204]
  (Comparative Example 1)
  Using the same amount of polyvinyl butyral (trade name: ESREC BM2, Sekisui Chemical Co., Ltd.) resin in place of the hole transporting compound having a chain polymerization group used in the charge generation layer in Example 1, the charge transport layer was applied. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the subsequent electron beam irradiation was not performed. As a result, as shown in Table 3, the initial characteristics were good, but the absolute value of the dark portion potential Vd after repeated use decreased, the absolute values of Vl and Vsl both increased, and the stability was poor. It was.
[0205]
  (Comparative Example 2)
  An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the charge generation material in the charge generation layer in Comparative Example 1 was replaced with that of Example 9. As a result, as shown in Table 3, the initial characteristics were good, but the absolute values of the dark part potentials Vd, Vl, and Vsl all decreased during repeated use, resulting in poor stability.
[0206]
  (Comparative Example 3)
  Example 9 except that the hole transporting compound having a chain polymerizable group used in the charge generation layer in Example 9 was replaced with a hole transporting compound having no polymerizable group represented by the structural formula (23). In the same manner as above, an electrophotographic photoreceptor was prepared and evaluated. As a result, as shown in Table 3, the initial characteristics were good, but the stability of repeated use was more stable than Comparative Example 2, but unstable compared to Example 9, and the stability was sufficient. It wasn't.
[0207]
[Table 3]
[0208]
【The invention's effect】
  The electrophotographic photosensitive member produced by the production method of the present invention has an excellent effect on potential stability during repeated use. Furthermore, the electrophotographic characteristics such as sensitivity and residual potential are also very good, and stable performance can always be exhibited. 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.
[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 manufactured by a manufacturing method of the present invention.

Claims (4)

In an electrophotographic photosensitive member having a conductive support and a photosensitive layer provided on the conductive support,
Photosensitive layer is a structure in which the product layer the charge generation layer and a charge transport layer in this order,
In the composition in which the charge generation layer contains a charge generation material and a hole transporting compound having two or more chain polymerizable functional groups in the same molecule represented by the following general formula (1), A method for producing an electrophotographic photoreceptor, which is a layer formed through a step of curing a hole transporting compound by polymerization or crosslinking with heat or ultraviolet rays.
{(In formula (1), A represents a hole transporting group. P ¹ and P ² represent a chain polymerizable functional group represented by the following general formula (14) or (15). P ¹ and P ^2. May be the same or different, Z represents an organic residue which may have a substituent, Y represents a hydrogen atom, a, b and d represent 0 or an integer of 1 or more. However, when a = 0, b + d is an integer of 3 or more, when b or d is 0, a is an integer of 2 or more, and in other cases, a + b + d is an integer of 3 or more. P ¹ may be the same or different when a is 2 or more, P ² may be the same or different when d is 2 or more, and Z when Z is 2 or more May be the same or different.)
A hole transporting compound in which the bonding site of A to P ¹ and the bonding site to Z are each replaced by a hydrogen atom is represented by the following general formulas (2), (3), (4), (5) and It is shown by the compound shown by either (7).
(In the formula (2), R ¹ , R ² and R ³ represent phenyl groups which may have a substituent. R ¹ , R ² and R ³ may be the same or different. )
(In Formula (3), R ⁴ , R ⁵ , R ⁸ and R ⁹ represent a phenyl group which may have a substituent. R ⁶ and R ⁷ represent a phenylene group which may have a substituent. R ⁴ , R ⁵ , R ⁸ and R ⁹ and R ⁶ and R ⁷ may be the same or different, and Q represents an organic residue which may have a substituent.
(In formula (4), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent a phenyl group which may have a substituent. R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same. shows the .Ar ¹ and Ar ² may optionally be the same or different each .m is 0 or 1 indicates a phenylene group which may .Ar ¹ and Ar ² optionally are substituted differently (However, when m = 0, Ar ² is an optionally substituted phenyl group.)
(In the formula (5), the Ar ³ and Ar ⁴ are .Ar ³ and Ar ⁴ may ^{.R 14} also has not each be the same or different shows also a phenyl group substituted substituent The phenyl group which may have is shown.
However, at least one of Ar ³ , Ar ⁴ and R ¹⁴ has one substituent represented by the following general formula (6). )
(In formula (6), R ¹⁶ represents a phenyl group which may have a substituent. Ar ⁵ represents a phenyl group which may have a substituent.)
(In Formula (7), R ¹⁷ and R ¹⁸ represent a phenyl group which may have a substituent. R ¹⁷ and R ¹⁸ may be the same or different. Ar ⁶ represents a substituent. (A phenyl group that may be present, provided that the compound represented by the general formula (7) has one or more substituents represented by the following general formula (8).)
(In Formula (8), R ²⁰ represents a phenyl group which may have a substituent. Ar ⁷ represents a phenyl group which may have a substituent.)} 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 ²¹ = CR ²² (R ²¹ and R ²² represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom, and R ²¹ and R ²² may be the same or different. ), C = O, S = O, SO 2, oxygen atom or sulfur atom, or method of producing an electrophotographic photosensitive member according to claim 1, wherein the organic residue of a combination of these. The method for producing an electrophotographic photosensitive member according to claim 1 , wherein Z in the general formula (1) or Q in the general formula (3) is a group represented by the following general formula (9) or (10).
(In the formula ^(9), X 1 ~X ³ is an alkylene group which may have a ^{substituent, (CR 23 = CR 24)} m 1 (R 23 and ^{R 24} an optionally substituted alkyl group Represents an aryl group or a hydrogen atom which may have a substituent, R ²³ and R ²⁴ may be the same or different, and m ¹ represents an integer of ¹ to 5), C = O, S═O, SO ₂ , an oxygen atom or a sulfur atom, Ar ⁸ and Ar ⁹ each represent an arylene group which may have a substituent, and p, q, r, s and t are 0 to 10 Represents an integer, provided that p, q, r, s, and t are not 0 at the same time.)
(In the formula (10), Ar ¹⁰ represents an arylene group which may have a substituent. X ⁴ and X ⁵ represent (CH ₂ ) _g (g represents an integer of 1 to 10), (CH = CR ₂₅ ) _h (R ²⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. H represents an integer of 1 to 5), C═O Or an oxygen atom, u, v and w are integers of 0 to 10, provided that u, v and w are not 0 at the same time. The electrophotography according to any one of claims 1 to 3 , wherein an oxidation potential of the hole transporting compound having two or more chain polymerizable functional groups in the same molecule is 0.4 to 1.2 (V). A method for producing a photoreceptor.