JP4194606B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus, and more specifically, an electrophotographic photosensitive member having an intermediate layer and a photosensitive layer in this order on a support, and the electrophotographic photosensitive member. The present invention relates to a process cartridge and an electrophotographic apparatus.

  The electrophotographic photosensitive member has an intermediate layer to cover defects on the support, improve adhesion between the photosensitive layer and the support, prevent electrical breakdown of the photosensitive layer, and prevent carrier injection from the support to the photosensitive layer. A layer called a layer (sometimes called an undercoat layer) is interposed.

In the case of a negatively charged electrophotographic photosensitive member that is generally used at present, the intermediate layer is formed from the photosensitive layer to the support in consideration of prevention of increase in residual charge and prevention of cycle-up of surface potential. It is necessary to improve the carrier (electron) injection property. Therefore, it is preferable to use an electron transporting material (electron transport material). For example, JP-A-5-27469 (Patent Document 1), JP-A-9-319128 (Patent Document 2), JP-A 2000-321805. Japanese Patent Publication (Patent Document 3) and the like describe that an electron-accepting substance is contained in the intermediate layer. When an electron transport material is used for this purpose, for example, when it is used for an intermediate layer, it is dissolved in a coating solvent at the time of forming the intermediate layer, and when an additional photosensitive layer is formed on the intermediate layer by coating, the upper layer It is necessary to be insoluble in the solvent of the coating solution used for forming the photosensitive layer. However, it is difficult to satisfy this requirement using the materials described in the above publications, and the electron transport material dissolves during formation by coating the upper layer, the intermediate layer peels off, cracks, etc. occur, and sufficient electron transport is achieved by elution. There was a problem that sex could not be maintained.
JP-A-5-27469 JP-A-9-319128 JP 2000-321805 A

  For the purpose of improving this point, for example, JP-A-11-119458 describes that an electron transport material having an alkoxysilyl group is used for the intermediate layer. However, when a hydrolyzable group is present, the electrophotographic characteristics are easily affected by temperature and humidity, and the coating property is deteriorated due to deterioration of the photoreceptor coating solution, and image defects are caused accordingly. there were.

  The present invention has been made to solve the above-described problems in the prior art.

  That is, firstly, it is an object to provide an electrophotographic photosensitive member having a small residual potential and an extremely small potential fluctuation during repeated use, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  Second, the electrophotographic photosensitive member in which the influence of temperature and humidity on the electrophotographic characteristics is small and the occurrence of image defects due to deterioration of the photosensitive member coating liquid is prevented, the process cartridge having the electrophotographic photosensitive member, and the electronic It is to provide a photographic apparatus.

（式（Ａ−１１）中、Ｒ ^１１１ 、Ｒ ^１１２ およびＲ ^１１３ の少なくとも１つは、非加水分解性重合性官能基を有する基である。ｍ１１は、０以上の整数である。ｍ１１が２以上のとき、Ｒ ^１１１ は、互いに異なる基であってもよい。Ｑ ^１１１ 、Ｑ ^１１２ 、Ｑ ^１１３ 、Ｑ ^１１４ は、それぞれ独立に、酸素原子、硫黄原子、Ｃ（ＣＮ） _２ 、ＣＲ ^Ｑ１ ＣＮ、ＣＹ _２ （Ｙはハロゲン原子）、Ｃ（ＣＯＯＲ ^Ｑ２ ） _２ 、ＣＲ ^Ｑ３ ＣＯＯＲ ^Ｑ４ 、ＮＲ ^Ｑ５ 、および、ＮＣＮのいずれかである。Ｒ ^Ｑ１ 、Ｒ ^Ｑ２ 、Ｒ ^Ｑ３ 、Ｒ ^Ｑ４ 、Ｒ ^Ｑ５ は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、および、置換基を有してもよいアリール基のいずれかを示す。）
であり、
該非加水分解性重合性官能基が、非加水分解性の縮重合性官能基である
ことを特徴とする電子写真感光体である。 The present invention provides an electrophotographic photosensitive member having an intermediate layer and a photosensitive layer in this order on a support,
The intermediate layer contains a polymer of an electron transport material having a non-hydrolyzable polymerizable functional group,
The compound in which the electron transport material having the non-hydrolyzable polymerizable functional group has a structure represented by the following formula (A-11)

(In Formula (A-11), at least one of R ¹¹¹ , R ^112, and R ¹¹³ is a group having a non-hydrolyzable polymerizable functional group. M11 is an integer of 0 or more. In the above, R ¹¹¹ may be different from each other , and Q ¹¹¹ , Q ¹¹² , Q ¹¹³ , and Q ¹¹⁴ are each independently an oxygen atom, a sulfur atom, C (CN) ₂ , CR ^Q1 CN, CY ₂ (Y is a halogen atom), C (COOR ^Q2 ) ₂ , CR ^Q3 COOR ^Q4 , NR ^Q5 , or NCN R ^Q1 , R ^Q2 , R ^Q3 , R ^Q4 , R ^Q5 are each Independently, any one of a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and an aryl group which may have a substituent is shown.
And
The electrophotographic photoreceptor , wherein the non-hydrolyzable polymerizable functional group is a non-hydrolyzable polycondensable functional group.

  The present invention also provides a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  The electrophotographic photoreceptor of the present invention has very good electrophotographic characteristics such as environmental potential stability and residual potential, and can exhibit stable performance even during repeated use.

  The effect of the electrophotographic photosensitive member is also exhibited in a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member, and can provide a high-quality image free from defects.

  The electrophotographic photoreceptor of the present invention will be described in detail below.

  The support of the electrophotographic photosensitive member of the present invention may be any material having conductivity, for example, a metal or alloy such as aluminum, copper, chromium, nickel, zinc and stainless steel formed into a drum or sheet shape. Laminated metal foil such as aluminum and copper on plastic film, aluminum, indium oxide and tin oxide deposited on plastic film, conductive material applied alone or with binder resin to provide conductive layer Metal, plastic film, paper, etc. are mentioned.

The intermediate layer of the electrophotographic photoreceptor of the present invention contains a polymer of an electron transport material having a non-hydrolyzable polymerizable functional group that is not a hydrolyzable polymer group such as an alkoxysilyl group.

  The intermediate layer is formed by applying a solution containing the electron transport substance and polymerizing / crosslinking by drying at room temperature or drying by heating, or heat / electromagnetic waves.

Examples of the non-hydrolyzable condensation polymerizable functional groups, for example, water group, an amino group, a carboxyl group, an aldehyde group, and etc. carboxylic acid chloride groups.

Of these condensation-polymerizable functional group, a hydroxyl group, an amino group, a carboxyl group are more preferable.

  When there are two or more polymerizable functional groups in one molecule, they may all be the same or different from each other.

  Among the electron transport materials, an electron transport material selected from the group consisting of the following formulas (A-1) to (A-11) is preferable.

In the above formula, R ¹¹ , at least one of R ²¹ and R ²² , at least one of R ³¹ and R ³² , at least one of R ⁴¹ and R ⁴² , at least one of R ⁵¹ and R ⁵² , and R ⁶¹ And R ⁶² , at least one of R ⁷¹ and R ⁷² , at least one of R ⁸¹ and R ⁸² , at least one of R ⁹¹ and R ⁹² , at least one of R ¹⁰¹ and R ¹⁰² , and R ¹¹¹ , R ¹¹² and R ¹¹³ are groups having a non-hydrolyzable polymerizable functional group. Then, in ^{which, R 11, R 21, R} 22, R 31, R 32, R 41, R 42, R 51, R 52, R 61, R 62, R 71, R 72, R 81, R 82 , R ⁹¹ , R ⁹² , R ¹⁰¹ , R ¹¹¹ have a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, which may have a substituent, or a substituent. Aralkyl group such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group and the like, which may have a substituent, phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group , Aryl groups such as furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group, and methoxy group , Alkoxy groups such as ethoxy group, propoxy group, butoxy group, aryloxy groups such as phenoxy group, naphthoxy group, acyl group, ester group, cyano group, nitro group, amide group, sulfonic acid group Or a sulfonic acid ester group, a sulfonic acid amide group, a hydroxy group, an aldehyde group, or a halogen atom, and R ¹⁰² , R ¹¹² , and R ¹¹³ may have a substituent, methyl group, ethyl Group, propyl group, alkyl group such as butyl group, etc., which may have a substituent, aralkyl group such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group, etc. Phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoxyl Lil group, carbazolyl group, phenothiazinyl group, or an aryl group such as a benzofuryl group, and a benzothiophenyl group, an ester group.

  In the above formula, m1, m2, n2, m3, n3, m4, n4, m5, n5, m6, n6, m7, n7, m8, n8, m9, n9, m10, m11 are integers of 0 or more. is there.

In the above formula, when m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11 are 2 or more, R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ , R ⁶¹ , R ⁷¹ , R ⁸¹ , R ⁹¹ , R ¹⁰¹ , and R ¹¹¹ may be groups different from each other.

In the above formula, when n2, n3, n4, n5, n6, n7, n8, n9 is 2 or more, R ²² , R ³² , R ⁴² , R ⁵² , R ⁶² , R ⁷² , R ⁸² , R ⁹² may be a group different from each other.

  M2 and n2, m3 and n3, m4 and n4, m5 and n5, m6 and n6, m7 and n7, m8 and n8, and m9 and n9 are not 0 at the same time. .

In the above formula, Q ¹¹ , Q ¹² , Q ²¹ , Q ²² , Q ³¹ , Q ³² , Q ⁴¹ , Q ⁵¹ , Q ⁶¹ , Q ⁷¹ , Q ⁷² , Q ⁸¹ , Q ⁸² , Q ⁹¹ , Q ⁹² , Q ¹⁰¹ , Q ¹⁰² , Q ¹¹¹ , Q ¹¹² , Q ¹¹³ , Q ¹¹⁴ are each independently an oxygen atom, a sulfur atom, C (CN) ₂ , CR ^Q1 CN, CY ₂ (Y is fluorine, chlorine, bromine) Or a halogen atom such as C (COOR ^Q2 ) ₂ , CR ^Q3 COOR ^Q4 , NR ^Q5 , and NCN.

In the above formula, R ^Q1 , R ^Q2 , R ^Q3 , R ^Q4 , and R ^Q5 are each independently a hydrogen atom or a substituent that may have a methyl group, an ethyl group, a propyl group, or a butyl group. Aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group, etc., which may have a substituent, phenyl group, naphthyl group, which may have a substituent , Anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group and the like.

Further, in the above ^{formula, Q 42} is either an oxygen atom, sulfur atom and SO _2.

In the above formula, A ² , A ³ , B ³ , A ⁴ , B ⁴ , A ⁵ , A ⁶ , B ⁶ , A ⁸ , B ⁸

Is an aryl ring such as a benzene ring, a naphthalene ring, an anthracene ring, a thiophene ring, a furan ring, or a pyridine ring, which may have a substituent.

R ¹¹ , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ , R ⁴² , R ⁵¹ , R ⁵² , R ⁶¹ , R ⁶² , R ⁷¹ , R ⁷² , R ⁸¹ , R ⁸² , R ⁹¹ , ^{R 92, R 101, R 102} , R 111, R 112, R 113, Q 11, Q 12, Q 21, Q 22, Q 31, Q 32, Q 41, Q 51, Q 61, Q 71, Q 72 Q ⁸¹ , Q ⁸² , Q ⁹¹ , Q ⁹² , Q ¹⁰¹ , Q ¹⁰² , Q ¹¹¹ , Q ¹¹² , Q ¹¹³ , Q ¹¹⁴ , R ^Q1 , R ^Q2 , R ^Q3 , R ^Q4 , R ^Q5 , A ² , A ³ , B ³ , A ⁴ , B ⁴ , A ⁵ , A ⁶ , B ⁶ , A ⁸ , B ⁸ may have a substituent such as halogen atoms such as fluorine, chlorine, bromine, iodine, nitro Group, cyano group, hydroxyl group, methyl group Alkyl groups such as ethyl group, propyl group and butyl group, alkoxy groups such as methoxy group, ethoxy group and propoxy group, aryloxy groups such as phenoxy group and naphthoxy group, benzyl group, phenethyl group and naphthylmethyl group Aralkyl groups such as a furfuryl group and a thienyl group, and aryl groups such as a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group.

  In addition, the alkyl group in the above expression is preferably an alkyl group having 10 or less carbon atoms.

  Further, the electron transport material having this non-hydrolyzable polymerizable functional group has a reduction potential (corresponding to the electron affinity Ea) of −0.2 V with respect to the potential of the reference electrode SCE (SCE: saturated carmello electrode). To -1.2V. More preferably, it is in the range of -0.3V to -1.0V. If the voltage exceeds −1.0 V, injection of charges (electrons) from the charge generating material is difficult to occur, and problems such as an increase in residual potential, deterioration in sensitivity, and potential fluctuation during repeated use may occur. If it is less than −0.3 V, problems such as a decrease in charging ability may occur.

  In the present invention, the reduction potential is measured by the following method.

(Measurement method of reduction potential)
Using a saturated calomel electrode as a reference electrode, a 0.1 N (n-Bu) ₄ N + ClO ₄ -dichloromethane solution as an electrolyte, sweeping the potential applied to the working electrode (platinum) by a potential sweeper, and the obtained current-potential The potential when the curve showed a peak was taken as the oxidation potential.

Specifically, the sample is dissolved in a 0.1 N (n-Bu) ₄ N + ClO ₄ -dichloromethane solution to a concentration of about 1 mmol%. A voltage is applied to the sample solution by a working electrode, and the voltage is linearly changed from 0 V to -1.5 V (the potential at the peak top position where the current value shows a peak in this current-potential curve is E1). Furthermore, the current change when linearly changing from -1.5 V to 0 V is measured (the potential at the peak top position where the current value showed a peak in this current-potential curve is E2), and the current-potential Get a curve. The obtained (E1 + E2) / 2 was defined as the reduction potential here.

Furthermore, the electron transport material having the non-hydrolyzable polymerizable functional group preferably has a drift mobility of 1 × 10 ⁻⁷ cm ² / V · s or more as its electron transport ability ( (Applied electric field: 5 × 10 ⁴ V / cm). If it is less than 1 × 10 ⁻⁷ cm ² / V · s, the electrophotographic photosensitive member may not be able to sufficiently move electrons until development after exposure, resulting in a problem that the apparent sensitivity is reduced and the residual potential is increased. May occur.

  The following are representative examples of the electron transport material having a non-hydrolyzable polymerizable functional group of the present invention, but the present invention is not limited to these (the numbers below the compound numbers are examples of each compound). The reduction potential of (−V).

Of these, compounds 4, 20 , 22 , 30 , 30, 31 , 34 , 35 , 4 , 2 , 58 , 60 are preferred, and 2 0 , 3, 4 , 5, 8 , 60 are more preferred.

  The intermediate layer of the electrophotographic photoreceptor of the present invention may have one or more electron transport materials having a non-hydrolyzable polymerizable functional group. In addition to the electron transport material having a non-hydrolyzable polymerizable functional group, a compound having a crosslinkable functional group and a non-hydrolyzable polymerizable functional group of the electron transport material may be used in combination. The content ratio in the intermediate layer of the electron transport material having a non-hydrolyzable polymerizable functional group and the compound having a non-hydrolyzable polymerizable functional group and a crosslinkable functional group in the electron transport material is expressed by mass ratio. 9/1 to 1/9 is preferable, and 7/3 to 3/7 is more preferable.

  In addition, the intermediate layer may be mixed with a known material. Examples thereof include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, polycarbonate, polyvinyl acetal, etc. Resin.

  Moreover, 0.1-15 micrometers is preferable and, as for the film thickness of an intermediate | middle layer, 0.4-10 micrometers is more preferable.

  The photosensitive layer of the photoreceptor of the present invention has a structure in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated (function separation type, lamination type), and the charge generation material and charge transport. Any configuration of a single layer in which a substance is dispersed in the same layer (single layer type) can be adopted.

  Among these configurations, a laminated photosensitive layer having a configuration in which a charge generation layer and a charge transport layer are laminated in this order is preferable in terms of electrophotographic characteristics. Hereinafter, the case of this configuration will be described as an example.

  Examples of the charge generation material used in the charge generation layer include selenium-tellurium, pyrylium, thiapyrylium dyes, various central metals and crystal systems, specifically, crystals such as α, β, γ, ε, and X type Examples thereof include phthalocyanine compounds having a type, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanine and amorphous silicon.

  The charge generation layer is well dispersed by a method such as homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor and roll mill together with 0.3 to 4 times the amount of binder resin and solvent. It is formed by applying a liquid and drying, or formed as a single composition film such as a vapor deposition film of the charge generation material.

  The thickness of the charge generation layer is preferably 5 μm or less, and more preferably in the range of 0.1 to 2 μm.

  When a binder resin is used, examples of the resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene, polyvinyl Examples include alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.

  The charge transport layer comprises a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene and phenanthrene in the main chain or side chain; a nitrogen-containing ring compound such as indole, carbazole, oxadiazole and pyrazoline; a hydrazone compound and a styryl compound It is formed by applying a solution in which a charge transport material such as a resin is dissolved in a resin having a film forming property and drying.

  Examples of the resin having a film forming property include polyester, polycarbonate, polystyrene, polymethacrylic acid ester, and polyarylate.

  The thickness of the charge transport layer is preferably 5 to 40 μm, and more preferably 8 to 30 μm.

  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 / productivity, the dip coating method is preferable.

  Also, vapor deposition, plasma, and other known film forming methods can be appropriately selected.

  Various additives can be added to the photosensitive layer in the invention. Such additives include deterioration inhibitors such as antioxidants and ultraviolet absorbers, and lubricants such as tetrafluoroethylene resin particles and carbon fluoride.

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

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

  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 that is synchronously taken out and fed. 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).

  Further, the surface of the photoreceptor 1 after image transfer may be cleaned by removing residual toner after cleaning by the cleaning means 9.

  The primary charging means 3 and the transfer means 6 may be contact means such as a charging roller or non-contact means such as a corona charger.

  Further, after performing the charge removal process with the pre-exposure light 10 from the pre-exposure means (not shown), it may be used repeatedly for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.

  In the present invention, among the above-described components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9, a plurality of components are integrally coupled as a process cartridge. You may comprise so that attachment or detachment with respect to electrophotographic apparatus main bodies, such as a copying machine and a laser beam printer, is possible. 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.

  Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is a reflected light or transmitted light from a document, or a sensor that reads the document with a sensor and scans the laser beam according to this signal. The light emitted by driving the LED array and the liquid crystal shutter array.

  The electrophotographic photoreceptor 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, and laser plate making.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  “Part” means “part by mass”.

( Reference Example 1)
First, the coating material for the conductive layer was prepared according to the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide (mass parts, hereinafter the same), phenol resin 25 parts, methyl cellosolve 20 parts, methanol 5 parts and silicone oil (polydimethylsiloxane poly) An oxyalkylene copolymer (average molecular weight 3000) was prepared by dispersing 0.002 part in a sand mill using glass beads having a diameter of 1 mm for 2 hours. This paint was applied by dip coating on an aluminum cylinder having a diameter of 30 mm and a length of 260 mm, and dried at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

Next, the following Exemplified Compound Nos. 19 (The number under Compound No. is the reduction potential (−V) of this compound)

30 parts, 0.5 part of a compound (AIBN) having a structure represented by the following formula,

  An intermediate layer paint consisting of 30 parts of monochlorobenzene and 20 parts of THF was prepared, applied to the conductive layer by a dip coating method so that the film thickness after drying was 3 μm, and dried at 160 ° C. for 60 minutes. A layer was formed.

  Next, 3 parts of a hydroxygallium phthalocyanine compound having a crystal type having strong peaks at 7.4 ° and 28.2 ° with a Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα and polyvinyl butyral resin (degree of butyralization) 2 parts of 65 mol%, number average molecular weight 35000) are added to 80 parts of cyclohexanone, dispersed in a sand mill for 4 hours together with glass beads, diluted with 80 parts of ethyl acetate, and dried on the intermediate layer. The film was applied by a dip coating method so that the film thickness was 0.15 μm, and dried at 100 ° C. for 10 minutes to form a charge generation layer.

  Next, 10 parts of a hole transport material having a structure represented by the following formula:

Further, 15 parts of Z-type polycarbonate resin is dissolved in a mixed solvent of 50 parts of monochlorobenzene and 20 parts of THF to prepare a coating material for a hole transport layer, and the film thickness after drying on the charge generation layer is 20 μm. Was applied by a dip coating method, and dried at 120 ° C. for 45 minutes to form a hole transport layer, thereby producing an electrophotographic photoreceptor.

  This photoreceptor is mounted on a printer LBP1760 manufactured by Canon Inc., and charged DC (direct current) component and light intensity under normal temperature and normal humidity (23 ° C./50%) and low temperature and low humidity (15 ° C./10%) conditions. Were evaluated.

Initial photoreceptor characteristics [dark portion potential Vd, light attenuation sensitivity (light amount necessary to attenuate light to −150 V when dark portion potential is set to −600 V), residual potential Vsl (light amount of 1.5 μJ / cm ² when irradiated) Potential)], and a 5000-sheet endurance test was performed, and the characteristics of the photoconductor after the endurance were measured, and the change values ΔVd and ΔVl (the same amount of light as when Vl was initially −150 V) were measured. ΔVsl was obtained by determining the amount of change in Vl when irradiated with a certain amount of light after endurance. Moreover, the presence or absence of the film | membrane defect and image defect by visual observation was observed.

  The surface potential of the photoconductor is measured by modifying the LBP cartridge, attaching a potential probe (model 6000B-8: manufactured by Trek) to the development position, and using a surface potential meter (model 344: manufactured by Trek). went. The results are shown in Table 2.

(Example 21)
In Reference Example 1, Exemplified Compound No. An intermediate layer paint comprising 25 parts of 34, 12 parts of melamine resin (Uban 20HS: manufactured by Mitsui Chemicals), 50 parts of THF, and 50 parts of methoxypropanol was prepared, and the film thickness after drying on the conductive layer The electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that the intermediate layer was formed by applying the film by a dip coating method so that the thickness was 1 μm and drying at 150 ° C. for 60 minutes. The results are shown in Table 2.

(Example 2 2)
In Example 21, Exemplified Compound No. 34 , No o. Except that instead of the 6 0 similarly to produce the electrophotographic photosensitive member in Example 21, was evaluated. The results are shown in Table 2.

(Example 24)
In Example 21, Exemplified Compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 21 except that 34 was 12 parts and melamine resin was 25 parts. The results are shown in Table 2.

( Reference Example 25)
In Reference Example 1, Exemplified Compound No. 25 parts of phenol, 12 parts of phenol resin (Priofen J325: manufactured by Dainippon Ink and Chemicals), 25 parts of methanol, 25 parts of butanol, 50 parts of methoxypropanol The electrophotographic photosensitive member is the same as in Reference Example 1 except that it is applied on the conductive layer by a dip coating method so that the film thickness after drying becomes 1 μm, and dried at 150 ° C. for 60 minutes to form an intermediate layer. Were made and evaluated. The results are shown in Table 2.

( Reference Example 26)
In Reference Example 25, Exemplified Compound No. No. 22 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 25 except that 54 was used. The results are shown in Table 2.

( Reference Example 27)
In Reference Example 26, an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 26 except that the prepared intermediate layer coating solution was allowed to stand for 7 days in a normal temperature and humidity environment and then the intermediate layer was applied. did. The results are shown in Table 2.

(Comparative Example 1)
In Reference Example 1, a compound having a structure represented by the following formula as an electron transport material for an intermediate layer

An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that was used. The results are shown in Table 3.

( Comparative Example 3)
In Example 21, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 21 except that no electron transport material was added. The results are shown in Table 3 .

(Comparative Example 4)
In Example 26, an electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 26 except that no electron transport material was added. The results are shown in Table 3 .

(Comparative Example 5)
In Reference Example 1, 0.4 part of the following compound disclosed in JP-A-11-119458,

An electrophotographic photosensitive member was prepared in the same manner as in Reference Example 1, except that an intermediate layer coating material prepared by mixing 0.5 parts of a zirconium monoacetylacetonate compound (Orgatics ZC540: manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 3 parts of isopropanol was prepared. Prepared and evaluated. The results are shown in Table 3.

(Comparative Example 6)
In Comparative Example 5, an electrophotographic photoreceptor was prepared and evaluated in the same manner as Comparative Example 5 except that the prepared intermediate layer coating solution was allowed to stand for 7 days in a normal temperature and humidity environment, and then the intermediate layer was applied. . The results are shown in Table 3.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photosensitive member of this invention 2 Axis 3 Primary charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Image fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Rail

Claims (7)

In an electrophotographic photosensitive member having an intermediate layer and a photosensitive layer in this order on a support,
The intermediate layer contains a polymer of an electron transport material having a non-hydrolyzable polymerizable functional group,
The compound in which the electron transport material having the non-hydrolyzable polymerizable functional group has a structure represented by the following formula (A-11)

(In Formula (A-11), at least one of R ¹¹¹ , R ^112, and R ¹¹³ is a group having a non-hydrolyzable polymerizable functional group. M11 is an integer of 0 or more. In the above, R ¹¹¹ may be different from each other , and Q ¹¹¹ , Q ¹¹² , Q ¹¹³ , and Q ¹¹⁴ are each independently an oxygen atom, a sulfur atom, C (CN) ₂ , CR ^Q1 CN, CY ₂ (Y is a halogen atom), C (COOR ^Q2 ) ₂ , CR ^Q3 COOR ^Q4 , NR ^Q5 , or NCN R ^Q1 , R ^Q2 , R ^Q3 , R ^Q4 , R ^Q5 are each Independently, any one of a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and an aryl group which may have a substituent is shown.
And
The non-hydrolyzable polymerizable functional group is a non-hydrolyzable polycondensable functional group
Electrophotographic photosensitive member, wherein a call.   2. The electrophotographic apparatus according to claim 1, wherein the intermediate layer is a layer formed by polymerizing an intermediate layer solution containing an electron transport material having a non-hydrolyzable polymerizable functional group on the support. Photoconductor. The electrophotographic photosensitive member according to claim 1 or 2 , wherein a reduction potential of the electron transport material having a non-hydrolyzable polymerizable functional group is in a range of -0.3V to -1.0V with respect to a potential of a reference electrode. body. The electron transporting material, a non-hydrolyzable polymerizable electrophotographic photosensitive member according to any one of claims 1 to 3, an electron transport material having two or more functional groups in the same molecule. Said photosensitive layer, an electrophotographic photosensitive member according to any one of the claims 1-4 from the intermediate layer side is a layer formed by laminating a charge generation layer and a hole transport layer in this order. An electrophotographic photosensitive member according to any one of claims 1 to 5 the charging means, and at least one means selected from the group consisting of the developing means and the cleaning means integrally supported, detachably attached to an electrophotographic apparatus main body Process cartridge characterized by being. The electrophotographic photosensitive member according to any one of claims 1 to 5, a charging means, an exposure means, the electrophotographic apparatus, characterized in that it comprises a developing means and transfer means.

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