JP4285212B2 - Additive for electrophotographic photoreceptor, electrophotographic photoreceptor, image forming apparatus and process cartridge - Google Patents

Description

  The present invention relates to an additive for an electrophotographic photoreceptor, an electrophotographic photoreceptor, an image forming apparatus, and a process cartridge.

  The electrophotographic process is a process for forming a fixed image through a plurality of steps as follows. That is, in an electrophotographic process, typically, the surface of an electrophotographic photoreceptor using a photoconductive material is uniformly charged, and then a latent image is formed by exposure, and the formed latent image is treated with toner. Development to form a toner image, the toner image on the surface of the photoconductor is transferred to the surface of a transfer material such as paper via an intermediate transfer member, if necessary, and the transferred image is heated and / or pressurized or A plurality of steps of fixing by solvent vapor or the like are provided. In general, the toner remaining on the surface of the photosensitive member is cleaned by a cleaning unit or the like, and is again subjected to the plurality of steps described above.

Such electrophotographic photoconductor used in the electrophotographic process, particularly in its surface, chemical resistance to ozone and NO _X generated during charging, release properties to enhance transfer efficiency, mechanical chestnut - training Various characteristics such as surface lubricity, wear resistance, and hardness are required.

  As a method for improving these, for example, 1) addition of hard fine particles (for example, see Patent Document 1 below), 2) addition of an additive for reducing the surface energy, 3) modification of a binder resin (for example, the following non-reduction) 4) Formation of an overcoat layer on the charge transport layer (for example, see Patent Document 2 below), etc. are known.

Particularly for 2), there is a method of adding silicone oil. Besides this, a method of providing a resin layer in which fluororesin particles such as polytetrafluoroethylene (PTFE) are dispersed as a surface protective layer on the surface of the photoreceptor. Proposed. Here, since the resin layer in which the fluororesin particles are dispersed has a low coefficient of friction on the surface, it is said that the cleaning property and the durability against wear are improved. It is said that the chemical durability is improved because it can be shielded from.
JP-A-6-282093 Japanese Patent Laid-Open No. 6-282092 JP 11-218945 A Japanese Patent Laid-Open No. 5-6010 JP-A-6-25120 Japanese Patent Laid-Open No. 7-126224 Idemitsu Kosan Co., Ltd. Technical Report, 36 (2), 88 (1993)

  However, in the methods 1) to 3), since a low molecular weight compound is basically dispersed in a binder resin, no significant improvement in characteristics can be expected, and the overcoat layer 4) is resistant to wear. Although it can be greatly improved, since conductive powder is used in a dispersed manner, there is a problem that image blur is likely to occur particularly under high humidity.

  In the method 2), there is a problem that bleeding is likely to occur when silicone oil is used, and when fluorine resin particles are used, the electrical characteristics are improved by the fluorine-containing surfactant that is usually added to improve dispersibility. There is a problem of deterioration.

  As a method for improving this, it has been proposed to contain a specific diamine charge transporting material having a fluoroalkyl group and fluororesin fine particles to reduce the coefficient of static friction of the photoreceptor (see, for example, Patent Document 3 above). ), Only a specific diamine charge transporting material having a fluoroalkyl group has low charge transporting properties and deteriorates electrical characteristics, so that sufficient performance is not obtained.

  Further, a fluorine-containing tetraarylbenzidine compound in which a fluoroalkyl group is introduced by a carbon-carbon bond or an ether bond (see, for example, Patent Document 4 above), a fluorine-containing styryl compound in which a fluoroalkyl group is introduced by an ether bond (for example, The above-mentioned patent document 5), a diamine compound having a specific fluoroalkyl group (for example, refer to the above-mentioned patent document 6), and the like have also been proposed, but have sufficient performance to improve surface releasability and lubricity. The fact is that nothing has been obtained.

  Accordingly, an object of the present invention is to provide a material capable of exhibiting releasability and lubricity by being added to a photosensitive layer of an electrophotographic photosensitive member and maintaining them for a long period of time. Another object of the present invention is to provide an electrophotographic photosensitive member using this material, and an image forming apparatus and a process cartridge that are provided with the electrophotographic photosensitive member and can reduce environmental burden and drastically reduce costs.

［式中、Ａは下記一般式（ＩＩ）又は（ＩＩＩ）で表されるアリールアミンから誘導されるｍ価の有機基、Ｔは炭素数１〜１０の２価の炭化水素基、Ｒ_ｆは水素原子の少なくとも１つがフッ素原子に置換された炭素数１〜２０の１価の炭化水素基、ｌは０又は１、ｍは１〜４の整数、をそれぞれ示す。なお、Ｔ又はＲ_ｆとしての炭化水素基は直鎖状でも分岐状でもよい。

（Ａｒ _１ 、Ａｒ _２ 、Ａｒ _３ 、Ａｒ _４ 、Ａｒ _５ 、Ａｒ _６ 及びＡｒ _７ は、それぞれ独立に炭素数６〜２０の置換又は未置換のアリール基、一般式（ＩＩＩ）におけるＸは下記一般式（ＩＶ）、（Ｖ）又は（ＶＩ）で表される２価の有機基、をそれぞれ示す。

）］ In order to achieve the above object, the present invention provides an additive for an electrophotographic photoreceptor represented by the following general formula (I).

[Wherein, A is an m-valent organic group derived from an arylamine represented by the following general formula (II) or (III) , T is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R _f is A monovalent hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, l is 0 or 1, and m is an integer of 1 to 4, respectively. The hydrocarbon group as T or R _f may be linear or branched .

(Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ and Ar ₇ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and X in the general formula (III) is Divalent organic groups represented by the formula (IV), (V) or (VI) are shown respectively.

]]

  In the additive for electrophotographic photoreceptors represented by the general formula (I), as described above, m of the fluorinated hydrocarbon groups having a predetermined number of carbon atoms are bonded to A (or A via an ester bond). It is a structural feature that it is bonded to T), and based on this structure, it exhibits releasability and lubricity when applied to the photosensitive layer of an electrophotographic photoreceptor. Moreover, these characteristics are maintained for a long time.

  By using the additive for an electrophotographic photoreceptor, the occurrence of bleeding (bleeding) is overwhelmingly reduced unlike the silicone oil conventionally used for imparting releasability and lubricity. Further, it is suitable for dispersion of fluororesin fine particles, and even when used for dispersion in fluororesin fine particles, the problem of deterioration of electrical characteristics which has been conventionally caused hardly occurs.

  As described above, the additive for an electrophotographic photosensitive member represented by the general formula (I) can be used as a releasability imparting material or a lubricity imparting material, but this additive has a function as a charge transport material. It can be added to the photosensitive layer of an electrophotographic photosensitive member and used as a charge transport material having both releasability and lubricity. Further, the additive for electrophotographic photoreceptors has a remarkable characteristic that it can reduce ghost (residual image) generated in a fixed image, and charge transport having both releasability and lubricity. In addition to functioning as a material, it also functions as a ghost reducing material that significantly improves the quality of fixed images by reducing ghosts.

  In addition to these, the additive for electrophotographic photoreceptors has good solubility, and exhibits very excellent performance in terms of compatibility with the charge transport layer material and dispersibility of the fluorine-containing fine particles.

  An electrophotographic photoreceptor is provided using the additive for an electrophotographic photoreceptor. That is, an electrophotographic photosensitive member having a photosensitive layer formed on a conductive support, the photosensitive layer containing the additive for an electrophotographic photosensitive member of the present invention is provided. The electrophotographic photoreceptor additive contained in the photosensitive layer may be one type or a combination of two or more types, and the photosensitive layer may further include fluororesin fine particles (polytetrafluoroethylene fine particles, etc.), halogenated gallium phthalocyanine crystals, It may contain at least one charge generating material selected from the group consisting of tin halide phthalocyanine crystals, hydroxygallium phthalocyanine crystals and oxytitanium phthalocyanine crystals.

  By applying the electrophotographic photosensitive member, an image forming apparatus and a process cartridge are further provided. That is, the electrophotographic photosensitive member of the present invention, a charging device for charging the electrophotographic photosensitive member, an exposure device for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and developing the electrostatic latent image An image forming apparatus comprising a developing device for forming a toner image and a transfer device for transferring the toner image to a transfer target is provided, and the electrophotographic photosensitive member of the present invention and the electrophotographic photosensitive member are charged. A process cartridge is provided that includes a charging device, an exposure device that exposes a charged electrophotographic photosensitive member to form an electrostatic latent image, and at least one cleaning device that cleans the electrophotographic photosensitive member.

  The additive for electrophotographic photoreceptors of the present invention is excellent in compatibility with a binder and the like, and exhibits excellent performance such as electrical characteristics and surface lubricity. Further, it effectively acts as a dispersant for fluororesin particles such as polytetrafluoroethylene, and can exhibit stable performance.

  Hereinafter, preferred embodiments for carrying out the present invention will be described with reference to the drawings as the case may be. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted.

(Additive for electrophotographic photoreceptors)
The additive for electrophotographic photoreceptors of the present invention is a compound represented by the general formula (I), and preferred embodiments of A, T, R _f , l and m in the general formula are as follows.

A in the general formula (I) is particularly preferably an m-valent group derived from an arylamine represented by the general formula (II) or (III). Here, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ and Ar ₇ (hereinafter abbreviated as “Ar _{1 to} Ar ₇ ”) are each independently substituted or non-substituted having 6 to 20 carbon atoms. This means a substituted aryl group, and X is a divalent organic group.

Specific examples of Ar _{1 to} Ar ₇ include substituted or unsubstituted aryl groups having the following structures.

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ (hereinafter abbreviated as “R _{1 to} R ₇ ”) are each independently a hydrogen atom or a C 1-5 carbon atom. A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, or a substituted or unsubstituted aryl group having 1 to 14 carbon atoms, each of R _{1 to} R ₇ May have a plurality of substituted benzene rings.

As T in general formula (I), the C1-C10 bivalent hydrocarbon group which was illustrated below is preferable.

Examples of X in the arylamine represented by the general formula (III) include those selected from the following groups (1) to (7).

In the formula, R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted group having 6 to 15 carbon atoms. A substituted phenyl group, a C6-C15 substituted or unsubstituted aralkyl group, or a halogen atom is represented, and a means 0 or 1.

V may be selected from the following groups (8) to (17). Here, b means an integer of 1 to 10, and c means an integer of 1 to 3.

X may be selected from the following groups (18) to (24) in addition to the above groups.

In the above formula, R ₁₅ and R ₁₆ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a carbon number of 1 to 14 A substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group having 1 to 14 carbon atoms, or a halogen atom, d and e are each independently an integer of 1 to 10, and f and g are each independently An integer of 0 to 2, h and i each independently represents 0 or 1. V has the same meaning as described above.

X preferably has a structure represented by the following structural formula (IV), (V) or (VI) because of high mobility.

R _f in the general formula (I) is a monovalent hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (the number of carbon atoms is preferably 6 to 12). The following groups are mentioned.

  An additive for an electrophotographic photoreceptor represented by the general formula (I), wherein A in the general formula (I) is derived from an arylamine represented by the above general formula (II) or (III) Examples of the compound that is a valent group include an arylamine compound containing an ester group described in JP-A-9-31039 or the like, or an ester exchange reaction with a fluorinated alcohol, or an arylamine compound containing an ester group Can be easily synthesized by esterifying with fluorine-containing alcohol or fluorine-containing hydrocarbon such as chlorine, bromine, or iodide after being converted to a free carboxylic acid by hydrolysis.

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

  The fluorinated alcohol is preferably added in an amount of 1 equivalent or more, preferably 1.2 equivalents or more, more preferably 1.5 equivalents or more, relative to the ester group of the arylamine compound. In addition, inorganic acids such as sulfuric acid and phosphoric acid, titanium alkoxides, acetates or carbonates such as calcium and cobalt, and oxides of zinc and lead may be added as catalysts. The catalyst is used in an amount of 1/10000 to 1 part by weight, preferably 1/1000 to 1/2 part by weight, based on 1 part by weight of the arylamine compound. The reaction is carried out at a reaction temperature of 100 to 300 ° C., preferably above the boiling point of the alcohol to be eliminated. The ester group of the arylamine compound is preferably an ester with a low-boiling alcohol such as methanol or ethanol in order to promote the transesterification reaction. The reaction is preferably performed in an inert gas such as nitrogen or argon, and may be performed using a high boiling point solvent such as p-cymene or 1-chloronaphthalene.

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

  The fluorine-containing alcohol is preferably added in an amount of 1 equivalent or more, preferably 1.2 equivalents or more, more preferably 1.5 equivalents or more with respect to the arylamine compound carboxylic acid. An inorganic acid such as sulfuric acid or phosphoric acid, an acetate or carbonate such as titanium alkoxide, calcium or cobalt, or an oxide of zinc or lead may be added as a catalyst. The catalyst is used in an amount of 1/10000 to 1 part by weight, preferably 1/1000 to 1/2 part by weight, based on 1 part by weight of the arylamine compound. The reaction is carried out at a reaction temperature of 100 to 300 ° C., preferably above the boiling point of the alcohol to be eliminated. The ester group of the arylamine compound is preferably an ester with a low-boiling alcohol such as methanol or ethanol in order to promote the transesterification reaction. The reaction is preferably performed in an inert gas such as nitrogen or argon, and may be performed using a high-boiling solvent such as p-cymene or 1-chloronaphthalene.

  It is preferable to add the fluorinated alcohol in an amount of 1 equivalent or more, preferably 1.2 equivalents or more, more preferably 1.5 equivalents or more with respect to the acid group of the arylamine compound carboxylic acid. As the acid catalyst, sulfuric acid, toluenesulfonic acid, trifluoroacetic acid and the like can be used for ordinary esterification reaction, 1 / 10000-1 / 10 parts by weight with respect to 1 part by weight of the arylamine compound carboxylic acid, Preferably it is used in the range of 1/1000 to 1/50 parts by weight. In order to remove water generated during the polymerization, it is preferable to use a solvent that can be azeotroped with water, and toluene, chlorobenzene, 1-chloronaphthalene, etc. are effective, and fluoroalkyl group-containing compounds (for electrophotographic photoreceptors) 1 to 100 parts by weight, preferably 2 to 50 parts by weight per 1 part by weight of the additive). The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization. After completion of the reaction, the reaction solution is poured into water, extracted with a solvent such as toluene, hexane, or ethyl acetate, washed with water, and further purified using an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay if necessary. May be.

  Further, the fluorine-containing hydrocarbon having a halogen group such as Cl, Br, I and the like, 1 to 5 equivalents, preferably 1.1 to 3 equivalents with respect to the acid group of the arylamine compound carboxylic acid, pyridine, piperidine, triethylamine, Bases such as dimethylaminopyridine, trimethylamine, DBU, sodium hydride, sodium hydroxide, potassium hydroxide and aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, acetone, methyl ethyl ketone, etc. In an organic solvent such as an ether solvent such as diethyl ether or tetrahydrofuran. The base is used in an amount of 1 to 3 equivalents, preferably 1 to 2 equivalents, relative to the carboxylic acid. The aprotic organic solvent used is 1 to 50 parts by weight, preferably 1.5 to 30 parts by weight, based on the carboxylic acid derivative. The reaction temperature can be arbitrarily set between 0 ° C. and the boiling point of the solvent, but 0 ° C. to 150 ° C. is preferable. After completion of the reaction, the reaction solution is poured into water, extracted with a solvent such as toluene, hexane, or ethyl acetate, washed with water, and further purified using an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay if necessary. May be.

Regarding the additive for an electrophotographic photosensitive member when A in the general formula (I) is an m-valent group derived from an arylamine represented by the general formula (II), suitable Ar ₁ , Ar ₂ , Ar ₃ The combinations of T, l, m and R _f are shown in Table 1 below.

Regarding the additive for an electrophotographic photoreceptor in which A in the general formula (I) is an m-valent group derived from an arylamine represented by the general formula (III), suitable Ar ₄ , Ar ₅ , Ar ₆ , Ar ₇ , T, l, m and R _f combinations are shown in Tables 2, 3, 4, 5, 6, 7, 8, 9 and 10 below.

等の記載は結合手がＮ原子のみに結合し、−（Ｔ）_ｌ−ＣＯ_２Ｒ_ｆで表される基には結合していないことを示しており、

等の記載は、結合手の一方がＮ原子に結合しており、他方が−（Ｔ）_ｌ−ＣＯ_２Ｒ_ｆで表される基に結合していることを示している。 In Tables 1-10

And the like indicate that the bond is bonded only to the N atom and not to the group represented by-(T) ₁ -CO ₂ R _f ,

The description such as indicates that one of the bonds is bonded to the N atom and the other is bonded to the group represented by-(T) ₁ -CO ₂ R _f .

(Electrophotographic photoreceptor)
1 to 3 are schematic cross-sectional views showing first to third embodiments of the electrophotographic photosensitive member of the present invention, respectively, in which the electrophotographic photosensitive member 1 is placed in the stacking direction of the conductive support 2 and the photosensitive layer 3. It is cut along.

  The electrophotographic photoreceptor 1 according to the first and second embodiments shown in FIGS. 1 and 2 includes a function-separated type photosensitive layer that is contained in different layers of a charge generation material and a charge transport material. That is, in the photosensitive layer 3, a layer containing a charge generating material (charge generating layer 5) and a layer containing a charge transporting material (charge transporting layer 6) are formed separately and laminated so that they are adjacent to each other. ing.

  On the other hand, the electrophotographic photoreceptor 1 according to the third embodiment shown in FIG. 3 includes a single-layer type photosensitive layer in which the charge generation material and the charge transport material are contained in the same layer. That is, in the photosensitive layer 3, a charge generation / transport layer 8 containing a charge generation material and a charge transport material is formed.

  More specifically, in the electrophotographic photoreceptor 1 according to the first embodiment, the undercoat layer 4, the charge generation layer 5, and the charge transport layer 6 are laminated in this order on the conductive support 2 to form the photosensitive layer 3. In the electrophotographic photoreceptor 1 according to the second embodiment, the undercoat layer 4, the charge generation layer 5, the charge transport layer 6 and the protective layer 7 are laminated in this order on the conductive support 2. Thus, the photosensitive layer 3 is configured. In the electrophotographic photoreceptor 1 according to the third embodiment, the undercoat layer 4 and the charge generation / transport layer 8 are laminated in this order on the conductive support 2 to constitute the photosensitive layer 3.

  In addition, although illustration is abbreviate | omitted, as a deformation | transformation aspect of 2nd Embodiment, the aspect which reversed the lamination | stacking order of the charge generation layer 5 and the charge transport layer 6 in 2nd Embodiment, or a deformation | transformation aspect of 3rd Embodiment Also possible is a mode in which the protective layer 7 made of the same components as in the first and second embodiments is formed on the charge generation / transport layer 8 of the third embodiment. In any of the above embodiments, the photosensitive layer can contain the additive for an electrophotographic photoreceptor of the present invention. That is, both the charge generation layer 5 and the charge transport layer 6 can contain the additive for an electrophotographic photosensitive member of the present invention. However, it is preferable that the additive be included in the charge transport layer 6 to function as a charge transport material. .

  As the conductive support 2, aluminum is used in an appropriate shape such as a drum shape, a sheet shape, or a plate shape, but is not limited thereto. Moreover, you may perform an anodizing process, a boehmite process, a honing process, etc. for the purpose of injection | pouring prevention, adhesive improvement, interference fringe prevention, etc.

  An undercoat layer 4 can be provided between the conductive support 2 and the photosensitive layer 3 or between the conductive support 2 and the charge generation / transport layer 8 as shown in FIGS. As the pulling layer 4, an organic zirconium compound such as a zirconium chelate compound, a zirconium alkoxide compound or a zirconium coupling agent, an organic titanium compound such as a titanium chelate compound, a titanium alkoxide compound or a titanate coupling agent, an aluminum chelate compound or an aluminum coupling agent In addition to organoaluminum compounds such as antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum Organic metal compounds such as um silicon alkoxide compounds, aluminum titanium alkoxide compounds, aluminum zirconium alkoxide compounds, especially organic zirconium compounds, organic titanyl compounds, and organoaluminum compounds are preferably used because of their low residual potential and good electrophotographic characteristics. The

  Also, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxycyclohexyltri It can be used by further containing a silane coupling agent such as methoxysilane.

  Furthermore, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol resin, vinyl chloride- A known binder resin such as a vinyl acetate copolymer, an epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, or polyacrylic acid may be further contained.

  These mixing ratios can be appropriately set as necessary. Further, an electron transporting pigment may be mixed / dispersed in the undercoat layer. Examples of the electron transport pigment include organic pigments such as perylene pigment, bisbenzimidazole perylene pigment, polycyclic quinone pigment, indigo pigment, and quinacridone pigment described in JP-A-47-30330, cyano group, nitro group, Examples thereof include organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitroso groups and halogen atoms, and inorganic pigments such as zinc oxide and titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments, zinc oxide, and titanium oxide are preferably used because of their high electron mobility.

  Further, the surface of these pigments may be surface-treated with the above-mentioned coupling agent or binder for the purpose of controlling dispersibility and charge transporting property. If the amount of the electron transporting pigment is too large, the strength of the undercoat layer is lowered and a coating film defect is caused, so that it is used at 95% by weight or less, preferably 90% by weight or less.

  As a mixing / dispersing method, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent, as long as the organic solvent dissolves an organometallic compound or resin and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. Anything can be used. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene Ordinary organic solvents such as toluene can be used alone or in admixture of two or more.

  The thickness of the undercoat layer is preferably from 0.1 to 30 μm, more preferably from 0.2 to 25 μm. In addition, as the coating method used when the undercoat layer is provided, conventional methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used. The coated layer is dried to obtain an undercoat layer. Usually, the drying is performed at a temperature at which the solvent can be evaporated to form a film. In particular, a base material that has been subjected to an acidic solution treatment or a boehmite treatment is preferably formed with an undercoat layer because the defect concealing power of the base material tends to be insufficient.

  As the charge generation material contained in the charge generation layer 5, known materials such as azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments may be used. In particular, metal and metal-free phthalocyanine pigments are preferred. Among them, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472, and Dichlorotin phthalocyanine disclosed in JP-A-5-140473, titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 are particularly preferred.

  The charge generation layer can be formed by mixing a charge generation material and a binder resin. Such a binder resin can be selected from a wide range of insulating resins, and poly-N-vinylcarbazole. It can also be selected from organic photoconductive polymers such as polyvinyl anthracene, polyvinyl pyrene and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin Insulating resins such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be mentioned, but are not limited thereto. These binder resins can be used alone or in admixture of two or more.

  The blending ratio of the charge generating material to the binder resin (weight ratio) is preferably in the range of 10: 1 to 1:10. In addition, as a method for dispersing these, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. Is done.

  Further, at the time of dispersion, it is effective to make the particle size of the charge generating material 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. Solvents used for the dispersion include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran Ordinary organic solvents such as methylene chloride, chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more.

  The thickness of the charge generation layer is preferably from 0.1 to 5 μm, more preferably from 0.2 to 2.0 μm. In addition, as a coating method used when the charge generation layer is provided, usual methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used.

  As the charge transport layer 6, a layer formed by a known technique can be used, and the charge transport layer 6 is formed containing a charge transport material and a binder resin, or contains a polymer charge transport material. Formed.

As the charge transport material, the additive for electrophotographic photoreceptors represented by the general formula (I) of the present invention can be used. In addition, the charge transport material is an additive for electrophotographic photoreceptors represented by the general formula (I), quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, 2,4, Fluorenone compounds such as 7-trinitrofluorenone, xanthone compounds, benzophenone compounds, cyanovinyl compounds, electron transport compounds such as ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylenes One or more other charge transport materials such as a hole transporting compound such as a benzene compound, a stilbene compound, an anthracene compound, and a hydrazone compound can be used as a mixture, but the invention is not limited thereto. When mixing, from the viewpoint of mobility, compounds represented by the following general formula (Ia), general formula (Ib), and general formula (Ic) are preferable.

In the general formula (Ia), R ₂₁ represents a hydrogen atom or a methyl group. N means 1 or 2. Ar ₈ and Ar ₉ represent a substituted or unsubstituted aryl group, and the substituent includes a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 3 carbon atoms. And a substituted amino group substituted with an alkyl group.

In the general formula (Ib), R ₂₂ and R ₂₂ ′ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ₂₃ , R ₂₃ ′, R ₂₄ , and R ₂₄ ′ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 2 carbon atoms. Represents an amino group substituted with an alkyl group or a substituted or unsubstituted aryl group. p and q are integers of 0-2.

In general formula (Ic), R ₂₅ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH—CH═. Represents C (Ar ₁₀ ) ₂ . Here, Ar ₁₀ represents a substituted or unsubstituted aryl group. R ₂₆ and R ₂₇ may be the same or different, and are an amino group substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. Represents a group, a substituted or unsubstituted aryl group.

  The binder resin used for the charge transport layer is polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile. Copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinyl Carbazole, polysilane, and polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used alone or in admixture of two or more. The blending ratio (weight ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  A polymer charge transport material can also be used alone. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, the polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material alone can be used as the charge transport layer, but it may be formed by mixing with the binder resin.

  The thickness of the charge transport layer is preferably 5 to 50 μm, more preferably 10 to 30 μm. As a coating method, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used.

  Solvents used when providing the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenated fats such as methylene chloride, chloroform and ethylene chloride. Ordinary organic solvents such as aromatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether or linear ethers can be used alone or in admixture of two or more.

  In addition, for the purpose of preventing deterioration of the photoreceptor due to ozone, oxidizing gas, or light or heat generated in the image forming apparatus (copying machine), an antioxidant, a light stabilizer, a heat stabilizer, etc. are contained in the photosensitive layer. Additives can be added.

  For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine.

Moreover, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like. Usable electron acceptors include, for example, succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m- Examples thereof include dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, and phthalic acid. Of these, benzene derivatives having an electron-withdrawing substituent such as fluorenone, quinone and Cl, CN, NO ₂ are particularly preferred.

The electrophotographic photoreceptor of the present invention may be provided with a protective layer (surface layer) as described above. However, in order to provide resistance to abrasion, scratches, etc., the protective layer is a high-strength protective layer (high-strength surface layer). ) Is preferable. As this high-strength protective layer, a conductive resin dispersed in a binder resin, a fluororesin (polytetrafluoroethylene, etc.) dispersed in a charge transport material, a lubricating fine particle such as an acrylic resin, silicone, A hard coating agent such as acrylic can be used. From the viewpoints of strength, electrical characteristics, image quality maintenance, etc., those having a charge transporting property and comprising a siloxane-based resin having a crosslinked structure are preferable, and among these, the structure represented by the following general formula (VII) is particularly preferable. Those having excellent strength and stability are preferred.
G-D-F (VII)

  In general formula (VII), G represents an inorganic glassy network subgroup, D represents a flexible organic subunit, and F represents a charge transporting subunit. F has a structure having photocarrier transport properties, such as triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, and quinone compounds. Examples thereof include compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, and ethylene compounds.

  G in the general formula (VII) is preferably a reactive Si group, which causes a cross-linking reaction with each other to form an inorganic glassy network that is a three-dimensional Si—O—Si bond.

  D in the general formula (VII) is for directly binding F for imparting charge transporting properties to a three-dimensional inorganic glassy network. In addition, the inorganic glassy network, which has firmness but is brittle, is imparted with appropriate flexibility and has an effect of improving the strength as a film.

The group bonded to the compound represented by the general formula (VII) by a bond in D means a group capable of binding to a silanol group generated when the compound represented by the general formula (VII) is hydrolyzed; _{Si (R 8) (3-} r) a group represented by Q _r, epoxy group, isocyanate group, carboxyl group, hydroxy group, good group such as a halogen atom. Of _{these, -Si (R 8) (3} -r) a group represented by Q _r, epoxy group, compounds having isocyanate group is preferable because it has a stronger mechanical strength. Q is a hydrolyzable group. Furthermore, those having two or more of these groups in the molecule are preferable because the crosslinked structure of the cured film becomes three-dimensional and has higher mechanical strength.

It is preferable that the compound represented by the general formula (VII) has a structure represented by the following general formula (VIII) because it is excellent in charge transport property, light resistance, discharge generated gas resistance and the like.

In general formula (VIII), Ar ₃ ′, Ar ₄ ′, Ar ₅ ′ and Ar ₆ ′ each independently represent a substituted or unsubstituted aryl group, and Ar ₇ ′ represents a substituted or unsubstituted aryl group or arylene group. 1 to _{4 of} Ar ₃ ′, Ar ₄ ′, Ar ₅ ′ and Ar ₆ ′ have a bond that can be bonded to the bond group represented by -DG, Combined with D. D is derived from a flexible organic subunit (for example, a divalent aliphatic group), G is derived from a substituted silicon group having a hydrolyzable group represented by —Si (R ₈ ) _(3-r) Q _r , R ₈ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, r represents an integer of 1 to 3, t represents an integer of 1 to 4, and k represents an integer of 0 to 1.

From the viewpoint of charge transport properties, light resistance, and discharge generated gas resistance, the compound represented by the general formula (VII) is more preferably a compound represented by the following general formula (VIIIa).

In general formula (VIIIa), Ar ₃ ″, Ar ₄ ″, Ar ₅ ″ and Ar ₆ ″ each independently represent a substituted or unsubstituted arylene group (preferably a substituted or unsubstituted phenylene group), and Ar ₇ ′ Is as defined above (preferably a divalent group derived from substituted or unsubstituted biphenyl). Z is a hydrogen atom or a group represented by -D'-G '. However, at least one of Z must be a group represented by -D'-G '. D ′ is a divalent aliphatic group (which may have an ester group, an ether group, a thioether group, etc., and preferably has 1 to 12 carbon atoms), and G ′ is —Si 2 (R _{8 (3-r)} means a group represented by Q _r ′. R ₈ , k and r are as defined above, and Q ′ is a halogen atom, an alkoxy group (preferably an alkoxy group having 1 to 3 carbon atoms), an acyloxy group, an alkenyloxy group, an amino group, a mercapto group, It represents a hydrolyzable group selected from a ketoximate group, an aminooxy group and a carbamoyl group.

  In the protective layer, for the purpose of adjusting the film formability and flexibility of the film, it may be used by mixing with other coupling agents and fluorine compounds. As such a compound, various silane coupling agents and commercially available silicone hard coat agents can be used.

  As silane coupling agents, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, Dimethyldimethoxysilane and the like can be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (above, manufactured by Shin-Etsu Silicone), AY42-440, AY42-441, AY49-208 (above, Toray Dow Corning) Etc.) can be used.

The protective layer also has (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) to provide water repellency and low adhesion. Trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H , Fluorinated compounds such as 2H, 2H-perfluorooctyltriethoxysilane may be added. The silane coupling agent can be used in any amount, but the amount of the fluorine-containing compound is desirably 0.25 or less by weight with respect to the compound not containing fluorine. Beyond this, there may be a problem with the film formability of the crosslinked film. In order to improve the strength of the membrane, it is used _{-Si (R 8) (3-} r) Q r to compounds that have a substituted silicon group having 2 or more having a hydrolyzable group represented simultaneously More preferred.

  These coating solutions are prepared without solvent or, if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether and dioxane. Although it can be used, it preferably has a boiling point of 100 ° C. or lower. These can also be used as a mixture. The amount of the solvent can be arbitrarily set, but if it is too small, the compound represented by the general formula (VII) is likely to precipitate. Therefore, 0.5 to 30 parts, preferably 1 part of the compound represented by the general formula (VII) 1-20 parts. While the reaction temperature and time vary depending on the type of raw material, it is generally 0-100 ° C, preferably 10-70 ° C, particularly preferably 15-50 ° C. Although there is no restriction | limiting in particular in reaction time, Since it will become easy to produce gelation when reaction time becomes long, it is preferable to carry out in 10 minutes to 100 hours.

  Curing catalysts include proton acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, bases such as ammonia and triethylamine, organotin compounds such as dibutyltin diacetate, dibutyltin dioctoate and stannous oxalate, tetra-n-butyl Examples include titanates, organotitanium compounds such as tetraisopropyl titanate, organoaluminum compounds such as aluminum tributoxide, aluminum triacetylacetonate, iron salts of organic carboxylic acids, manganese salts, cobalt salts, zinc salts, zirconium salts, etc. From the viewpoint of storage stability, a metal compound is preferable, and further, metal acetylacetonate or acetylacetate is preferable, and aluminum triacetylacetonate is particularly preferable.

  The amount of the curing catalyst used can be arbitrarily set, but is preferably 0.1 to 20% by weight with respect to the total amount of materials containing hydrolyzable silicon substituents in terms of storage stability, properties, strength, etc. More preferably, it is 3 to 10% by weight. The curing temperature can be arbitrarily set, but is set to 60 ° C. or higher, more preferably 80 ° C. or higher in order to obtain a desired strength. Although hardening time can be arbitrarily set as needed, 10 minutes-5 hours are preferable. It is also effective to stabilize the characteristics after the curing reaction by maintaining a high humidity state. Further, depending on the application, it can be hydrophobized by surface treatment with hexamethyldisilazane, trimethylchlorosilane or the like.

  It is preferable to add an antioxidant to the protective layer of the electrophotographic photosensitive member for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated by a charger. When the mechanical strength of the surface of the photoconductor is increased and the photoconductor has a long life, the photoconductor is in contact with the oxidizing gas for a long time, and therefore, stronger oxidation resistance is required than before.

  Antioxidants are preferably hindered phenols or hindered amines, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. , Etc., may be used. The addition amount of the antioxidant is preferably 20% by weight or less, and more preferably 10% by weight or less.

  Examples of hindered phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N'-hexamethylenebis (3,5-diphenyl). -t-butyl-4-hydroxyhydrocinnamide, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, 2, 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4 , 4'-Butylidenebis (3-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-t-butylphenol), and the like.

  Also, a resin that dissolves in alcohol can be added for the purposes of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. Examples of resins soluble in alcohol solvents include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal or acetoacetal (for example, manufactured by Sekisui Chemical Co., Ltd.). ESREC B, K, etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics. The molecular weight of the resin is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. If the molecular weight is less than 2000, the desired effect cannot be obtained. If the molecular weight is more than 100,000, the solubility becomes low and the addition amount is limited, or the film formation is poor at the time of coating. The addition amount is preferably 1 to 40%, more preferably 1 to 30%, and most preferably 5 to 20%. If it is less than 1%, it is difficult to obtain the desired effect, and if it exceeds 40%, image blurring under high temperature and high humidity tends to occur.

  Furthermore, various fine particles can be added to the protective layer in order to improve the antifouling substance adhesion and lubricity on the surface of the electrophotographic photosensitive member. They can be used alone or in combination. Examples of the fine particles include silicon-containing fine particles. The silicon-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon-containing fine particles is selected from acidic or alkaline aqueous dispersions having an average particle diameter of 1 to 100 nm, preferably 10 to 30 nm, or those dispersed in organic solvents such as alcohols, ketones and esters. A commercially available product can be used. The solid content of colloidal silica in the outermost surface layer is not particularly limited, but is 0.1 to 50% by weight in the total solid content of the outermost surface layer in terms of film forming properties, electrical characteristics, and strength. Preferably, 0.1 to 30% by weight is used.

  Silicone fine particles used as silicon-containing fine particles are spherical and have an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. Can be used. Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain more sufficient properties is low, the crosslinking reaction is not hindered. The surface properties of the photographic photoreceptor can be improved.

  That is, it can improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the outermost surface layer in the electrophotographic photosensitive member is preferably 0.1 to 30% by weight, more preferably 0.5 to 10% by weight in the total solid content of the outermost surface layer.

Other fine particles include fluorine-based fine particles such as ethylene tetrafluoride, ethylene trifluoride, hexafluoropropylene, vinyl fluoride, and vinylidene fluoride, and “8th Polymer Materials Forum Lecture Proceedings, p89”. As shown, fine particles made of a resin obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ Examples thereof include semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO.

  For the same purpose, an oil such as silicone oil can be added to the protective layer. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Reactive silicone oils such as modified polysiloxanes, phenol-modified polysiloxanes, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3, 5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9 Cyclic methylphenylcyclosiloxanes such as pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane, cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane, 3- (3,3,3-trifluoro Fluorine-containing cyclosiloxanes such as propyl) methylcyclotrisiloxane, methylhydrosiloxane mixtures, hydrosilyl group-containing cyclosiloxanes such as pentamethylcyclopentasiloxane and phenylhydrocyclosiloxane, and vinyl groups such as pentavinylpentamethylcyclopentasiloxane And cyclic siloxanes such as cyclosiloxanes.

  In the case of a single-layer type photosensitive layer, the single-layer type photosensitive layer can be formed containing the charge generation material, the charge transport material, and a binder resin. The charge transport material may be a polymer charge transport material. As the binder resin, the same binder resin as that used in the charge generation layer and the charge transport layer can be used. The content of the charge generating material in the single-layer type photosensitive layer is 10 to 85% by weight, preferably 20 to 50% by weight. The content of the charge transport material is preferably 5 to 50% by weight. The solvent and coating method used for coating can be the same as described above. The film thickness of the single-layer type photosensitive layer is preferably 5 to 50 μm, more preferably 10 to 40 μm.

  Further, an aqueous dispersion of a modified resin containing a fluorine-based resin as an essential component is applied or immersed in the outermost layer disposed at the position farthest from the conductive support of the electrophotographic photosensitive member. You can also. This is preferable because the transfer efficiency can be improved. In addition, it is possible to sufficiently suppress the progress of abrasion of the photosensitive layer that occurs in the repeated processes of charging, exposure, development, transfer, and cleaning, thereby extending the life of the photoreceptor.

  An aqueous dispersion of a modified resin containing a fluororesin as an essential component applied to the outermost layer of the electrophotographic photoreceptor will be described below. Fluorocarbon resins include tetrafluoroethylene homopolymers or copolymers of tetrafluoroethylene and olefins, fluorine-containing olefins, perfluoroolefins, fluoroalkyl vinyl ethers, vinylidene fluoride homopolymers or vinylidene fluoride and olefins, fluorine-containing Copolymers with olefins, perfluoroolefins, fluoroalkyl vinyl ethers, homopolymers of chlorotrifluoroethylene or copolymers of chlorotrifluoroethylene with olefins, fluorine-containing olefins, perfluoroolefins, fluoroalkyl vinyl ethers, etc. , Tetrafluoroethylene homopolymers or copolymers are preferred, and tetrafluoroethylene homopolymers and various copolymers are In 95: 5-10: It is also preferred to use a mixture with 90.

  The modified resin containing a fluorine-based resin as an essential component is used as an aqueous dispersion, and the aqueous dispersion may further contain a wax and / or silicone. By containing wax and / or silicone, it is preferable to promote penetration of the fluorine-based resin into the blade.

  Here, examples of the wax include paraffin wax, microcrystalline wax, and perotratam. Examples of the silicone include silicone oil, silicone grease, oil compound, and silicone varnish.

  If necessary, the aqueous dispersion of the modified resin containing a fluorine resin as an essential component may be a fluorine-based or other nonionic, cationic, anionic or amphoteric surfactant, pH adjuster, solvent, polyhydric alcohol, flexible An agent, a viscosity modifier, a light stabilizer, an antioxidant and the like can also be mixed. The penetration layer can be formed by immersing the blade member in an aqueous dispersion of a modified resin containing a fluorine-based resin as an essential component. In order to promote penetration of the fluorine-based resin into the blade member. Further, it can be carried out under reduced pressure. The pressure at this time is 0.9 atm or less, preferably 0.8 atm or less, more preferably 0.7 atm or less.

  In addition, heating the aqueous dispersion to 40 ° C. or higher, preferably 50 ° C. or higher is effective in promoting penetration. Further, it is effective to treat at 0.1 atm or higher, preferably 0.2 atm or higher, more preferably 0.3 atm or higher, and it is also effective to combine decompression, pressurization and heat treatment. is there. Moreover, after making it adhere to a blade member by spraying or the apply | coating method, it can heat to 40 degreeC or more, Preferably it is 50 degreeC or more, and a osmosis | permeation layer can also be formed. Further, after attaching an aqueous dispersion of a modified resin containing a fluorine-based resin as an essential component, wiping or washing can be performed before or after heat drying.

(Image forming device)
FIG. 4 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 200 shown in FIG. 4 includes an electrophotographic photosensitive member 207 of the present invention, a charging device 208 that charges the electrophotographic photosensitive member 207 by a contact charging method, a power supply 209 connected to the charging device 208, and a charging device. An exposure device 210 that exposes the electrophotographic photosensitive member 207 charged by 208 to form an electrostatic latent image, and a developing device that develops the electrostatic latent image formed by the exposure device 210 with toner to form a toner image 211, a transfer device 212 that transfers the toner image formed by the developing device 211 to the transfer target 500, a cleaning device 213, a static eliminator 214, and a fixing device 215.

  The charging device 208 shown in FIG. 4 brings a contact-type charging member (for example, a charging roll) into contact with the surface of the photoconductor 207, applies a voltage uniformly to the photoconductor, and charges the surface of the photoconductor to a predetermined potential. Is.

  As the contact-type charging member, a roller-shaped member in which an elastic layer, a resistance layer, a protective layer and the like are provided on the outer peripheral surface of the core material is preferably used. The shape of the contact-type charging member may be any of the above-described roller shape, brush shape, blade shape, pin electrode shape, and the like, and can be arbitrarily selected according to the specifications and form of the image forming apparatus.

  As a material of the core material in the roller-shaped contact type charging member, a conductive material such as iron, copper, brass, stainless steel, aluminum, nickel or the like is used. Also, a resin molded product in which conductive particles or the like are dispersed can be used. As the material of the elastic layer, a conductive or semiconductive material, for example, a rubber material in which conductive particles or semiconductive particles are dispersed can be used. As the material for the resistance layer and the protective layer, conductive particles or semiconductive particles are dispersed in a binder resin to control the resistance.

  When charging the photoreceptor using these contact-type charging members, a voltage is applied to the contact-type charging member. The applied voltage may be either a DC voltage or a DC voltage superimposed with an AC voltage.

  Note that a non-contact type corona charging device such as a corotron or a scorotron may be used instead of the contact type charging member in FIG. These can be arbitrarily selected according to the specifications and form of the image forming apparatus.

  As the exposure apparatus 210, an optical system apparatus that can expose a light source such as a semiconductor laser, an LED (light emitting diode), and a liquid crystal shutter on the surface of the electrophotographic photosensitive member in a desired image-like manner can be used.

  As the developing device 211, a conventionally known developing device using a regular or reversal developer such as a one-component system or a two-component system can be used. The shape of the toner used in the developing device 211 is not particularly limited, but a spherical toner is preferable from the viewpoint of high image quality and ecology.

  Examples of the transfer device 212 include a roller-type contact charging member, a contact-type transfer charger using a belt, a film, a rubber blade, or the like, or a scorotron transfer charger or a corotron transfer charger using corona discharge. It is done.

The cleaning device 213 is for removing residual toner adhering to the surface of the electrophotographic photosensitive member after the transfer process. The cleaned electrophotographic photosensitive member is repeatedly used for the image forming process described above. . As the cleaning device, brush cleaning, roll cleaning, and the like can be used in addition to the cleaning blade. Among these, it is preferable to use the cleaning blade. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.
Although the above embodiment has one image forming unit, an image forming apparatus according to another embodiment can be a tandem type image forming apparatus having a plurality of image forming units.

  For example, when there are four image forming units, for example, yellow, magenta, cyan, and blank color component toners can be used in the developing devices of the four image forming units. The tandem image forming apparatus includes a belt that is common to the four image forming units and conveys a recording material, a conveyance device that conveys the belt, a toner supply device that supplies a toner image to each developing device, and a color toner. A fixing device for fixing the image to the recording material is preferably provided.

  The above-described image forming apparatus of the present invention exhibits particularly excellent durability in the case of an electrophotographic photosensitive member having a strong mechanical strength, when contact charging with a large stress on the electrophotographic photosensitive member is used. Further, the image forming apparatus of the present invention preferably has a mechanism capable of supplying only the toner alone when the photographic photosensitive member is used for 200000 cycles or more, further 250,000 cycles or 300000 cycles or more.

Here, the toner used in the image forming apparatus of the present invention will be described.
The toner used in the present invention comprises toner particles and other external additives, and the toner particles are a mixture of a binder resin, a colorant, a template, and, if necessary, silica or a charge control agent.

  The toner particles are not particularly limited as long as they satisfy the desired shape index and particle size. For example, a binder resin, a colorant, a template agent, and a charge control agent as necessary. What is obtained by kneading and pulverizing method of kneading, pulverizing, and classifying; What is obtained by changing the shape of particles obtained by kneading and pulverizing method with mechanical impact force or thermal energy; Emulsion polymerization of the polymer, and the resulting dispersion is mixed with a dispersion of a colorant, template, and, if necessary, a charge control agent, and agglomerated and heat-fused to obtain toner particles. What can be obtained by the agglomeration method; a suspension weight in which a polymerizable monomer, a colorant, a release agent, and a charge control agent, if necessary, are suspended in an aqueous solvent to obtain a binder resin. Obtained by legal method; binder resin and colorant, release agent, belt if necessary A solution such as the control agent is suspended in an aqueous solvent, and the like that obtained by a solution suspension method and granulated. In addition, toner particles obtained by a known method such as a production method in which the toner particles obtained by the above method are used as a core, and agglomerated particles are further adhered and heat-fused to have a core-shell structure can be used. Among those obtained by these production methods, from the viewpoint of shape control and particle size distribution control, suspension polymerization methods, emulsion polymerization aggregation methods, and dissolution suspension methods, which are produced in an aqueous solvent, are preferred, emulsion polymerization aggregation methods Is more preferred.

  When toner particles are produced by a wet process, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner particles in the present invention may be either magnetic toner particles containing a magnetic material or non-magnetic toner particles not containing a magnetic material.

  Binder resins include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate, and methyl acrylate. Α-methylene aliphatic monocarboxylic esters such as ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, vinyl Homopolymers and copolymers of vinyl ethers such as methyl ether, vinyl ethyl ether, and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone can be exemplified. Typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. Examples thereof include coalescence, polyethylene, and polypropylene. Furthermore, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can be mentioned. Coloring agents include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, duPont oillet, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, and lamp black. , Rose Bengal, CI Pigment Red 48: 1, CI Pigment Red 122, C.1. Pigment Red 57: 1, CI Pigment Yellow 97, CI Pigment Yellow 17, CI Pigment Blue 15: 1, CI And CI Pigment Blue 15: 3.

  Examples of the release agent include low-molecular polyethylene, low-molecular polypropylene, Fischer tropical wax, montan wax, cartewax, rice wax, and candelilla wax.

  In addition, a charge control agent may be added to the toner particles as necessary. Known charge control agents can be used, and examples thereof include azo metal complex compounds, metal complex compounds of salicylic acid, and resin-type charge control agents containing polar groups. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination.

  The toner particles include the above-described binder resin, a colorant, and a template, and a mixture of silica and the above-described charge control agent is used as necessary. The average particle diameter of the toner particles is 2 to 12 μm, preferably 3 to 9 μm. Further, it is preferable to use toner particles having an average shape index (ML2 / A) of 100 to 140. Thereby, high development sensitivity and transferability can be obtained, and a high-quality image can be obtained.

  Examples of the external additive added to the toner particles include lubricating particles, inorganic fine particles, organic fine particles, composite fine particles, and other inorganic oxides.

  The lubricating particles are for imparting lubricity to the surface of the photoreceptor. Lubricating particles include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids and fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, silicones having a softening point upon heating, oleic amides Aliphatic amides such as erucic acid amide, ricinoleic acid amide, stearic acid amide, etc., plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animals such as beeswax Minerals such as waxes, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc., petroleum waxes, and their modified products can be used alone or in combination. May be. The average particle size of the slippery particles may be in the range of 0.1 to 10 μm, and the particles having the above chemical structure may be pulverized to have the same particle size. The amount added to the toner is preferably 0.05 to 2.0 parts by weight and more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the toner.

  In addition, inorganic fine particles, organic fine particles, composite fine particles obtained by adhering inorganic fine particles to the organic fine particles, and the like can be added to the toner for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photosensitive member. Among these, inorganic fine particles are particularly preferable in terms of excellent abrasiveness.

  Inorganic fine particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used. For the above inorganic fine particles, titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecyl benzen sulfonate titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, γ- (2 -Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltri Methoxysilane hydrochloride, hexamethylcisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxy Silane, dodecyl trimethoxy silane, phenyl trimethoxy silane, o- methylphenyl trimethoxy silane, may be subjected to a treatment with such as a silane coupling agent such as p- methylphenyl trimethoxy silane. In addition, those hydrophobized with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate and calcium stearate are also preferably used.

  Examples of the organic fine particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  As the particle size of these inorganic fine particles and organic fine particles, if it is too small, it lacks the polishing ability, and if it is too large, it tends to cause scratches on the surface of the electrophotographic photosensitive member, so the average particle size is 5 nm to 1000 nm, It is preferably 800 nm, and more preferably 5 nm to 700 nm. Further, the sum of the addition amount of the lubricating particles is preferably 0.6% by weight or more.

  Further, other inorganic oxides can be attached to the toner. The inorganic oxide is preferably a small-diameter inorganic oxide having a primary particle size of 40 nm or less in terms of powder flowability, charge control, etc., and larger in diameter in terms of adhesion reduction and charge control. It is preferable to further add the inorganic oxide. Known inorganic oxides can be used as these inorganic oxides, but it is preferable to add silica and titanium oxide in combination in order to perform precise charge control. Further, it is preferable that the small-diameter inorganic fine particles are surface-treated in order to improve dispersibility and powder flowability.

  As a method of mixing the toner particles and the external additive, a method of manufacturing the toner particles and the external additive by mixing them with a angel mixer or a V blender can be used. In addition, when the toner particles are produced by a wet method, they can be mixed by a wet method.

  The toner obtained by the above-described method is used by mixing a carrier in use. Examples of the carrier include iron powder, glass beads, ferrite powder, nickel powder, or those having a resin coating on the surface thereof. The mixing ratio with the carrier can be set as appropriate.

  In recent years, high-definition image writing using a laser having a wavelength of about 380 to 450 nm has been performed in an image forming apparatus for the purpose of improving image quality. In this case, the exposure spot is condensed to about 30 nm. The influence of the photoconductor driving accuracy is remarkably increased. When the rotational torque of the photoconductor is high, image density unevenness due to vibration of the photoconductor, so-called “banding” is likely to occur. However, the use of the electrophotographic photoconductor of the present invention provides a remarkable effect. In order to clean a spherical toner having an average shape index (ML2 / A) of the toner of 100 to 140, it is effective to improve the releasability of the surface of the photoreceptor. The electrophotographic photoreceptor is also effective in this respect.

  Note that the wear amount and the surface roughness are preferably controlled appropriately. As this means, the blade member is brought into contact with the electrophotographic photosensitive member, the contact pressure and angle thereof are adjusted, the surface layer material is made suitable, the control by the material of the blade member, the adjustment by using in combination with the polishing roll and the brush member, Examples include strength control using the surface layer material of the electrophotographic photosensitive member, and control by adding inorganic fine particles such as aluminum oxide, cerium oxide, and barium sulfate to the toner, and control to an appropriate range by combining these controls. To do.

  As an appropriate range for the wear rate, if the wear rate is 0.1 nm or less per 1000 revolutions, contaminants on the surface of the electrophotographic photosensitive member cannot be sufficiently removed, so that image flow is likely to occur particularly at high temperatures and high humidity. It is difficult to extend the service life due to much wear. Further, if the surface roughness Rz exceeds 2 μm, the toner slips through and causes image quality defects. Therefore, it is preferable that the wear rate is 0.1 to 80 nm per 1000 revolutions and the surface roughness Rz is 2 μm or less.

(Process cartridge)
FIG. 5 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of a process cartridge including the electrophotographic photosensitive member of the present invention. In addition to the electrophotographic photosensitive member 207, the process cartridge 300 is provided with a charging device 208, a developing device 211, a cleaning device (cleaning means) 213, an opening 218 for exposure, and an opening 217 for static elimination exposure. Are combined and integrated with each other.

  The process cartridge 300 is used for an image forming apparatus main body including a transfer device 212 that transfers a toner image formed by the developing device 211 to the transfer target 500, a fixing device 215, and other components not shown. The image forming apparatus is configured together with the image forming apparatus main body.

  Although the preferred embodiments of the present invention have been described above, the present invention can be modified and changed in various ways within the scope of the gist thereof.

  The present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

(Example 1)
5 g of the compound represented by the following structural formula (A), 10 g of perfluorocyclohexyl methanol, and 0.1 g of tetrabutoxy titanium were placed in a 50 ml flask and reacted at 150 ° for 10 hours in a nitrogen atmosphere. The reaction solution was dissolved in toluene and purified by silica gel column chromatography to obtain 7.1 g of compound 34 shown in Table 4 as a pale yellow oil. The IR spectrum of compound 34 is shown in FIG.

(Example 2)
5 g of the compound represented by the structural formula (A), 11 g of 1H, 1H, 2H, 2H-perfluorooctanol and 0.1 g of tetrabutoxytitanium were placed in a 50 ml flask and reacted at 160 ° C. for 10 hours in a nitrogen atmosphere. The reaction solution was dissolved in toluene and purified by silica gel column chromatography to obtain 8.6 g of compound 52 shown in Table 6 as a pale yellow oil. The IR spectrum of compound 52 is shown in FIG.

(Example 3)
3 g of a compound represented by the following structural formula (B), 1H, 1H, 2H, 2H-perfluorododecanol 12.4 g and tetrabutoxytitanium 0.1 g were placed in a 50 ml flask and reacted at 160 ° for 10 hours in a nitrogen atmosphere. . The reaction solution was dissolved in a mixed solvent of tetrahydrofuran and toluene and purified by silica gel column chromatography. After concentration, the product was dissolved in tetrahydrofuran and precipitated by adding hexane to obtain 6.3 g of Compound 9 shown in Table 1 as a pale yellow powder. The IR spectrum of Compound 9 is shown in FIG.

(Preparation of electrophotographic photoreceptor-1)
100 parts by weight of zinc oxide (SMZ-017N: manufactured by Teica) was stirred and mixed with 500 parts by weight of toluene, 2 parts by weight of a silane coupling agent (A1100: manufactured by Nihon Unicar) was added, and the mixture was stirred for 5 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the Si element strength was 1.8 × 10 ⁻⁴ of the zinc element strength.

  35 parts by weight of the above zinc oxide subjected to surface treatment, 15 parts by weight of blocked isocyanate (Sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) as a curing agent, 6 parts by weight of butyral resin (BM-1, manufactured by Sekisui Chemical Co., Ltd.) 44 parts by weight of methyl ethyl ketone was mixed, and dispersion was obtained by dispersing for 2 hours in a sand mill using glass beads having a diameter of 1 mm. As a catalyst, 0.005 part by weight of dioctyltin dilaurate and 17 parts by weight of Tospearl 130 (manufactured by GE Toshiba Silicon Co., Ltd.) were added to the obtained dispersion as a catalyst to obtain an undercoat layer coating solution. This coating solution was applied on a drawn tube base material having a diameter of 84 mm made of JIS A3003 alloy by a dip coating method, followed by drying and curing at 160 ° C. for 100 minutes to obtain an undercoat layer having a thickness of 20 μm.

  One part by weight of chlorogallium phthalocyanine with strong diffraction peaks at 7.4 °, 16.6 °, 25.5 °, and 28.3 ° in the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum was added to polyvinyl butyral (ESREC BM-S, Sekisui Chemical) 1 part by weight and 100 parts by weight of n-butyl acetate were mixed, treated with a glass shaker with a paint shaker for 1 hour to disperse, and the resulting coating solution was dip coated on the undercoat layer. A charge generation layer having a thickness of about 0.15 μm was formed by heating and drying at 10 ° C. for 10 minutes.

2 parts of a benzidine compound represented by the following structure (C), 0.1 part of compound 34, 3 parts of a polymer compound (viscosity average molecular weight 39,000) shown in the following basic unit 1 were dissolved in 20 parts of chlorobenzene, A coating solution in which 0.3 part of fluoroethane fine particles (Daikin Industries: Lubron L-2) is dispersed is applied onto the charge generation layer by a dip coating method, heated at 110 ° C. for 40 minutes, and transported with a thickness of 20 μm. A layer was formed. This is referred to as an electrophotographic photoreceptor-1.

(Preparation of electrophotographic photoreceptor-2)
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member-1, except that Lubron L-2 was not added. This is referred to as an electrophotographic photoreceptor-2.

(Preparation of electrophotographic photoreceptors 3 and 4)
An electrophotographic photosensitive member was produced in the same manner as in the electrophotographic photosensitive member-1, except that compound 34 was replaced with compound 9 and compound 52. These are designated as electrophotographic photoreceptors 3 and 4, respectively.

(Preparation of electrophotographic photoreceptor-5)
An electrophotographic photosensitive resin except that the benzidine compound represented by the structure (C) and the polymer compound represented by the basic unit 1 are replaced with the compound represented by the following structure (D) and the polymer compound represented by the basic unit 2. An electrophotographic photosensitive member was produced in the same manner as the photoconductor-1. This is designated as an electrophotographic photoreceptor-5.

(Preparation of electrophotographic photoreceptor-6)
A charge transport layer was prepared in the same manner as in the electrophotographic photoreceptor-1 except that Compound 34 and Lubron L-2 were not added. A compound represented by the following structure (E) is dissolved in 5 parts of isopropyl alcohol, 3 parts of tetrahydrofuran and 0.3 part of distilled water together with the following constituent materials, and 0.5 part of ion exchange resin (Amberlyst 15E) is added and stirred at room temperature. Then, hydrolysis was performed for 24 hours.
Construction material structure (E) 2 parts methyltrimethoxysilane 2 parts tetramethoxysilane 0.5 parts colloidal silica 0.3 parts

0.1 parts of aluminum trisacetylacetonate (Al (aqaq) ₃ ), 3,5-di-t-butyl-4-hydroxytoluene (BHT) 0.4 for the liquid obtained by filtering and separating the ion exchange resin from the hydrolyzed product 0.05 parts of compound 5, 0.05 parts of Lubron L-2 and 0.02 part of Lubron were added, and this coating solution was applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, It was cured by heat treatment for a time, and a surface layer having a thickness of about 3 μm was formed. This is designated as an electrophotographic photoreceptor-6.

(Preparation of electrophotographic photoreceptor-7)
A photoconductor was prepared in the same manner as the electrophotographic photoconductor-6 except that the material used for the surface layer was the following structure (F) instead of the structure (E). This is designated as an electrophotographic photoreceptor-7.

(Preparation of electrophotographic photoreceptor-8)
A charge transport layer was prepared in the same manner as in the electrophotographic photoreceptor-1 except that Compound 34 and Lubron L-2 were not added.

(Preparation of electrophotographic photoreceptor-9)
A charge transport layer was prepared in the same manner as in the electrophotographic photoreceptor-5 except that Compound 34 and Lubron L-2 were not added.

(Preparation of electrophotographic photoreceptor-10)
A charge transport layer was prepared in the same manner as in the electrophotographic photoreceptor-6 except that Compound 5 and Lubron L-2 were not added.

(Preparation of electrophotographic photoreceptor-11)
A charge transport layer was prepared in the same manner as in the electrophotographic photoreceptor-7 except that Compound 5 and Lubron L-2 were not added.

(Examples 8 to 20)
The settings of the Fuji Xerox printer DocuCentre Color 500 are as shown in Table 11 for the setting parameters of the photoconductor and cleaning blade (setting angle (BSA: degree), blade weight (N / F: g / mm)). Except for modification, the image formation test of 10,000 sheets was performed in the environment of high temperature and high humidity (30 ℃, 80% RH), and then 10,000 sheets of paper were tested in the environment of low temperature and low humidity (10 ℃, 20% RH). Photoreceptor wear rate, surface roughness, presence or absence of adhesion to the photoconductor after image formation test, and toner cleaning performance under high temperature and high humidity (30 ° C, 80% RH) (charging due to poor cleaning) Container stains and image quality degradation), transferability, and image quality.
Adhesion was determined by visual observation, and ◯: no adhesion, Δ: partial (about 30% or less of the total), and x: adhesion.
The cleaning property was judged by visual observation, and ○: good, Δ: partial (about 10% or less of the whole) image defects such as streaks, x: extensive image defect.
Transferability is determined by peeling the transfer residual toner on the surface of the photoconductor with an adhesive tape and measuring the weight. ○: Transfer efficiency 90% or more, △: Transfer efficiency 85-90%, X: Transfer efficiency less than 85% It was.
The image quality was judged by visual observation.
Further, the ghost was determined by printing the chart of the pattern shown in FIG. 9 and determining the appearance of the letter G on the solid black portion as follows: ○: good to slight, Δ: slightly conspicuous, x: clearly visible.
In addition, the phenomenon was shown when there was a defect. The cleaning blade was set at 23 °, 3 g / mm doctor direction.

  In addition, the photoconductor torque before and after performing the print test using the above unit was measured with a Heidon Tribogear Type 94I manufactured by Shinto Kagaku in an environment of high temperature and high humidity (30 ° C., 80% RH) without being set in the printer. . The results are shown in Table 11.

(Examples 21 to 27)
The Fuji Xerox printer DocuCentre Color 500 was used, the exposure light source was replaced with a laser with an oscillation wavelength of 405 nm, and the print speed was set to 1/2 to evaluate only the initial image quality. The results are shown in Table 11.

(Comparative Examples 1-4)
Evaluations similar to those in Example 8 were performed using combinations of the photoreceptor, developer, and blade in Table 11.

1 is a schematic cross-sectional view of an electrophotographic photosensitive member according to a first embodiment. It is a schematic cross section of the electrophotographic photosensitive member according to the second embodiment. It is a schematic cross section of the electrophotographic photosensitive member according to the third embodiment. 1 is a schematic configuration diagram of an image forming apparatus according to an embodiment. It is a schematic block diagram of the process cartridge which concerns on embodiment. 4 is an IR spectrum of Compound 34. 4 is an IR spectrum of Compound 52. 4 is an IR spectrum of Compound 9. It is a figure which shows the evaluation pattern and evaluation criteria of a ghost, (a) shows determination (circle), (b) shows determination (triangle | delta), (c) shows determination x.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photoreceptor, 2 ... Conductive support body, 3 ... Photosensitive layer, 4 ... Undercoat layer, 5 ... Charge generation layer, 6 ... Charge transport layer, 7 ... Protective layer, 8 ... Charge generation / transport layer, DESCRIPTION OF SYMBOLS 200 ... Image forming apparatus, 207 ... Electrophotographic photosensitive member, 208 ... Charging device, 209 ... Power source, 210 ... Exposure device, 211 ... Developing device, 212 ... Transfer device, 213 ... Cleaning device, 214 ... Static eliminator, 215 ... Fixing Apparatus, 216... Mounting rail, 217... Opening for static elimination exposure, 218... Opening for exposure, 300... Process cartridge, 500.

Claims (10)

An additive for an electrophotographic photoreceptor represented by the following general formula (I).

[Wherein, A is an m-valent organic group derived from an arylamine represented by the following general formula (II) or (III) , T is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R _f is A monovalent hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, l is 0 or 1, and m is an integer of 1 to 4, respectively .

(Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ and Ar ₇ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and X in the general formula (III) is Divalent organic groups represented by the formula (IV), (V) or (VI) are shown respectively.

]] The additive for an electrophotographic photosensitive member according to claim 1, which functions as a releasability imparting material by being added to the photosensitive layer of an electrophotographic photosensitive member having a photosensitive layer. The additive for an electrophotographic photosensitive member according to claim 1 or 2, which functions as a lubricity-imparting material when added to the photosensitive layer of an electrophotographic photosensitive member having a photosensitive layer. The additive for an electrophotographic photoreceptor according to any one of claims 1 to 3 , which functions as a charge transport material by being added to the photosensitive layer of an electrophotographic photoreceptor having a photosensitive layer. The additive for an electrophotographic photosensitive member according to any one of claims 1 to 4 , which functions as a ghost reducing material by being added to the photosensitive layer of the electrophotographic photosensitive member provided with the photosensitive layer. An electrophotographic photosensitive member having a photosensitive layer formed on a conductive support,
The said photosensitive layer is an electrophotographic photoreceptor containing the additive for electrophotographic photoreceptors as described in any one of Claims 1-5 . The electrophotographic photoreceptor according to claim 6 , wherein the photosensitive layer further contains fluororesin fine particles. The photosensitive layer is further halogenated gallium phthalocyanine crystal, a halogenated tin phthalocyanine crystal, according to claim 6 or 7, wherein at least one kind of charge generating material selected from the group consisting of hydroxy gallium phthalocyanine crystal and oxytitanium phthalocyanine crystal Electrophotographic photoreceptor. The electrophotographic photosensitive member according to any one of claims 6 to 8 ,
A charging device for charging the electrophotographic photoreceptor;
An exposure apparatus that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image;
A developing device for developing the electrostatic latent image to form a toner image;
An image forming apparatus comprising: a transfer device that transfers the toner image to a transfer target. The electrophotographic photosensitive member according to any one of claims 6 to 8 ,
At least one selected from a charging device for charging the electrophotographic photosensitive member, an exposure device for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and a cleaning device for cleaning the electrophotographic photosensitive member; A process cartridge.

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