JP4704273B2 - Photoconductor, image forming apparatus, process cartridge, and image forming method - Google Patents

Description

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

  In general, an electrophotographic method is a method in which a photoconductive photosensitive member is first charged in a dark place, for example, by corona discharge, and then exposed to an image to selectively dissipate only the exposed portion of the electrostatic latent image. Image forming method in which the latent image portion is developed with electrophotographic fine particles (toner) composed of a colorant such as a dye or pigment and a binder such as a polymer substance, and visualized to form an image. one of. In such an electrophotographic method, the basic characteristics required of the photoconductor are that it can be charged to an appropriate potential in the dark, has little charge dissipation in the dark, and quickly dissipates the charge by light irradiation. What can be done.

  Conventionally, as a photoconductor used in an electrophotographic method, a conductive support provided with a photosensitive layer mainly composed of selenium or a selenium alloy, an inorganic photoconductive material such as zinc oxide or cadmium sulfide as a binder. Dispersed in water, poly (N-vinylcarbazole) and organic photoconductive materials such as trinitrofluorenone and azo pigments, and those using amorphous silicon materials are generally known. However, in recent years, organic electrophotographic photoreceptors have been widely used because of low cost, high degree of freedom in designing photoreceptors, low pollution, and the like.

  Organic electrophotographic photoreceptors include a photoconductive resin type represented by polyvinylcarbazole (PVK), a charge transfer complex type represented by PVK-TNF (2,4,7-trinitrofluorenone), and a phthalocyanine-binder. Are known, such as a pigment dispersion type, a function separation type photoreceptor using a combination of a charge generation material and a charge transport material, and the function separation type photoreceptor is attracting attention.

  The mechanism of electrostatic latent image formation in the function-separated type photoreceptor is described below. When the photoconductor is charged and then irradiated with light, the light passes through the charge transport layer and is absorbed by the charge generation material in the charge generation layer, and the charge generation material that has absorbed the light generates charge carriers. The charge carriers are injected into the charge transport layer, move in the charge transport layer according to the electric field generated by charging, and form an electrostatic latent image by neutralizing the charge on the surface of the photoreceptor. In the functionally separated type photoreceptor, it is known to use a combination of a charge transport material having absorption mainly in the ultraviolet region and a charge generating material having absorption mainly in the visible region, and satisfy the above basic characteristics. Things have been obtained.

  In recent years, as the speed and size of the electrophotographic process has been increased, in addition to the basic characteristics described above, the photoconductor has reliability and durability that can maintain high image quality even when used for a long period of time. It is strongly demanded.

  The photoreceptor is subjected to various mechanical and chemical loads in the electrophotographic process. Due to such a load, the photoreceptor is worn and an abnormal image is generated due to a decrease in film thickness. As means for improving the durability of the photoconductor, Patent Documents 1 to 5 disclose a technique for adding a filler to the photoconductor and a technique for providing a surface protective layer in which a filler is dispersed on the surface of the photosensitive layer.

  In a photoreceptor containing a filler, the dispersion state of the filler is very important for high durability, high image quality, and high stability.

  When the filler is in a non-uniform state or filler aggregate is present in the film, the transparency of the film is lowered, writing light is scattered by the filler, charge generation is non-uniform, and image characteristics are deteriorated. Further, in such a state, even when the charges generated in the photosensitive layer are transported to the surface of the photoreceptor, the charge transport is hindered by the filler, potential unevenness occurs on the surface of the photoreceptor, and image characteristics are deteriorated. descend. Further, when filler aggregates are present on the surface of the photoreceptor, problems such as poor cleaning and missing cleaning blades also occur.

  These problems can be solved by preparing a highly dispersible coating liquid with reduced filler aggregation. Furthermore, it is important for the coating liquid to increase the dispersion stability of the filler. A coating solution having a low dispersion stability of the filler not only has a problem in storage for a long period of time, but also during the film formation, the filler settles out, making it impossible to produce a stable photoreceptor.

  Patent Documents 6 and 7 disclose techniques for adding a dispersant to the coating liquid as a technique for improving the dispersion and aggregation state of the filler in the film and the dispersion stability of the coating liquid.

  These dispersants modify the surface of the polar filler, improve dispersibility of the coating liquid in a solvent or resin, and improve dispersibility and dispersion stability. And the photoreceptor produced using the coating liquid containing these dispersing agents disperse | distributes a filler uniformly in a film | membrane, and abrasion resistance and an image characteristic improve.

  Patent Document 8 discloses that an image forming member having excellent wear resistance can be obtained by graft-bonding a charge transporting portion with a linking group on the surface of a filler. However, since a linking group or a fixing group is introduced and reacted in the charge transport portion and the filler portion, there is a difficulty in dealing with the diversity of materials.

  Further, Patent Documents 9 to 12 disclose techniques for adding an acrylic-modified polyorganosiloxane to a film containing a filler in order to reduce the surface free energy of the photoreceptor. By adding the acryl-modified polyorganosiloxane, the free energy on the surface of the photoreceptor is lowered and the cleaning property is improved. However, since the polarity difference between the filler and the acrylic-modified polyorganosiloxane is large, a problem remains in the dispersion stability of the filler.

As described above, by including acrylic modified polyorganosiloxane and filler on the surface of the photoreceptor, the durability of the photoreceptor is improved. However, mechanical durability and image quality stability are improved compared to the amorphous silicon photoreceptor. The nature is low. Since further colorization, high speed, and miniaturization will progress in the future, it is desired that the organic electrophotographic photoreceptor be highly durable.
JP-A-1-205171 Japanese Patent Laid-Open No. 7-333881 Japanese Patent Laid-Open No. 8-15887 JP-A-8-123053 Japanese Patent Laid-Open No. 8-146664 JP 2003-149849 A JP 2002-268257 A JP 2006-63341 A Japanese Patent Laid-Open No. 2005-08445 JP 2004-184906 A JP 2003-98714 A JP 2003-202686 A

  The present invention has been made in view of the above-described problems of the prior art, and provides a photoconductor excellent in mechanical durability, electrical stability and image stability, an image forming apparatus and a process cartridge having the photoconductor, and image formation using the photoconductor. It aims to provide a method.

  According to the first aspect of the present invention, there is provided a photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer is grafted with an acrylic-modified polyorganosiloxane and a monomer having a polar group on a polycarbonate resin or a polyarylate resin. It contains a graft copolymer obtained by polymerization and a filler.

  According to a second aspect of the present invention, there is provided the photosensitive member according to the first aspect, wherein the photosensitive layer includes a charge generation layer and a charge transport layer, and the charge transport layer includes the acrylic-modified polyorganosiloxane. And a graft copolymer and a filler.

  According to a third aspect of the present invention, in the photoconductor in which at least a photoconductive layer and a protective layer are laminated on a conductive support, the protective layer comprises an acrylic-modified polyorganosiloxane and a polycarbonate resin or poly It contains a graft copolymer obtained by graft polymerization of a monomer having a polar group to an arylate resin and a filler.

  According to a fourth aspect of the present invention, there is provided the photosensitive member according to the third aspect, wherein the photosensitive layer is formed by laminating a charge generation layer and a charge transport layer.

  According to a fifth aspect of the present invention, in the photoreceptor according to the third or fourth aspect, the protective layer further contains a charge transport material.

  The invention according to claim 6 is the photoreceptor according to any one of claims 1 to 5, wherein the acrylic modified polyorganosiloxane is obtained by grafting an acrylic polymer to the polyorganosiloxane. To do.

  According to a seventh aspect of the present invention, in the photoreceptor according to the sixth aspect, the acrylic-modified polyorganosiloxane has a general formula.

［式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、炭素数が１以上２０以下の炭化水素基又はハロゲン化炭化水素基であり、Ｙは、ラジカル重合性官能基又はメルカプト基若しくはラジカル重合性官能基及びメルカプト基を有する有機基であり、Ｚ^１及びＺ^２は、それぞれ独立に、水素原子、低級アルキル基又は一般式

[Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y is a radical polymerizable functional group or a mercapto group or It is an organic group having a radical polymerizable functional group and a mercapto group, and Z ¹ and Z ² are each independently a hydrogen atom, a lower alkyl group or a general formula

（式中、Ｒ^４及びＲ^５は、それぞれ独立に、炭素数が１以上２０以下の炭化水素基又はハロゲン化炭化水素基であり、Ｒ^６は、炭素数が１以上２０以下の炭化水素基若しくはハロゲン化炭化水素基、ラジカル重合性官能基又はメルカプト基若しくはラジカル重合性官能基及びメルカプト基を有する有機基である。）
で表される官能基であり、ｍは、１以上１００００以下の整数であり、ｎは、１以上の整数である。］
で表されるポリオルガノシロキサンに、一般式

(In the formula, R ⁴ and R ⁵ are each independently a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms. Or a halogenated hydrocarbon group, a radical polymerizable functional group, or a mercapto group or an organic group having a radical polymerizable functional group and a mercapto group.)
M is an integer of 1 or more and 10,000 or less, and n is an integer of 1 or more. ]
The polyorganosiloxane represented by the general formula

（式中、Ｒ^７は、水素原子又はメチル基であり、Ｒ^８は、アルキル基、アルコキシ基で置換されたアルキル基、シクロアルキル基又はアリール基である。）
で表わされるアクリルモノマー７０重量％以上１００重量％以下と、該アクリルモノマーと共重合することが可能なモノマー０重量％以上３０重量％以下の混合物を乳化グラフト重合することにより得られ、該混合物に対する該ポリオルガノシロキサンの重量比は、５／９５以上９５／５以下であることを特徴とする。

(In the formula, R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group, an alkyl group substituted with an alkoxy group, a cycloalkyl group, or an aryl group.)
Obtained by emulsion graft polymerization of a mixture of 70% by weight to 100% by weight of an acrylic monomer represented by the formula (1) and 0% by weight to 30% by weight of a monomer copolymerizable with the acrylic monomer. The weight ratio of the polyorganosiloxane is 5/95 or more and 95/5 or less.

  According to an eighth aspect of the present invention, in the photoreceptor according to any one of the first to seventh aspects, the filler is an inorganic filler.

  The invention according to claim 9 is the photoreceptor according to claim 8, wherein the inorganic filler is a metal oxide.

  According to a tenth aspect of the present invention, in the photoreceptor according to the ninth aspect, the metal oxide contains at least one of silicon oxide, titanium oxide, and aluminum oxide.

  According to an eleventh aspect of the present invention, an image forming apparatus includes at least the photoconductor according to any one of the first to tenth aspects.

  According to a twelfth aspect of the present invention, a process cartridge includes at least the photosensitive member according to any one of the first to tenth aspects.

  According to a thirteenth aspect of the present invention, in the image forming method, an image is formed using the photoconductor according to any one of the first to tenth aspects.

  According to the present invention, it is possible to provide a photoconductor excellent in mechanical durability, electrical stability and image stability, an image forming apparatus and a process cartridge having the photoconductor, and an image forming method using the photoconductor.

  Next, the best mode for carrying out the present invention will be described.

  The first embodiment of the photoreceptor of the present invention has at least a photosensitive layer on a conductive support, and the photosensitive layer includes an acrylic-modified polyorganosiloxane and a monomer having a polar group in a polycarbonate resin or a polyarylate resin. It contains a graft copolymer obtained by graft polymerization and a filler. In the second embodiment of the photoreceptor of the present invention, at least a photosensitive layer and a protective layer are laminated on a conductive support, and the protective layer comprises an acrylic-modified polyorganosiloxane and a polycarbonate resin or a polyarylate resin. Contains a graft copolymer obtained by graft polymerization of a monomer having a polar group, and a filler. In the present invention, the polycarbonate resin and the polyarylate resin mean a resin having a polycarbonate skeleton and a polyarylate skeleton, respectively, and copolymers having these structures are also included.

  By using such a photoconductor, it is possible to provide an image forming apparatus having excellent mechanical durability, electrical stability, and image stability.

  In the present invention, the photosensitive layer or the protective layer contains a filler having a high mechanical strength and an acrylic-modified polyorganosiloxane having a low surface free energy. Generally, an acrylic-modified polyorganosiloxane is non-polar and has a filler. Has a polarity, and when it is mixed with a binder resin (polycarbonate, polyarylate, etc.) in the photosensitive layer or protective layer, severe aggregation of the filler occurs and a smooth film cannot be obtained. Therefore, the affinity between the filler and the binder resin can be improved by graft-polymerizing the binder resin with a monomer having a polar group having a high affinity for the filler.

  In the present invention, the graft copolymer obtained by graft polymerization of a monomer having a polar group to a binder resin (polycarbonate resin or polyarylate resin) has a polar site and a nonpolar site, and therefore, as shown in FIG. In addition, when the filler 11, the graft copolymer 12, the acrylic modified polyorganosiloxane 13 and the binder resin 14 are added to the photosensitive layer (or protective layer) 10, the surface of the filler 11 is tightly wrapped in the graft copolymer 12. As a result, contact with the acrylic-modified polyorganosiloxane 13 can be avoided. Thereby, aggregation of the filler 11 can be suppressed and dispersed uniformly in the binder resin 14. As a result, photoconductor cleaning defects and abnormal images that occur when filler is added to the photosensitive layer (or protective layer), and photoconductor that occurs when acrylic modified polyorganosiloxane is added to the photosensitive layer (or protective layer). Thus, it is possible to obtain a photoconductor that solves the shortage of mechanical strength and is excellent in mechanical durability and electrical stability and image stability.

  In the present invention, the acrylic-modified polyorganosiloxane is not particularly limited, but it is preferable that an acrylic polymer is grafted to the polyorganosiloxane from the viewpoint of compatibility with a binder resin such as polycarbonate and polyarylate.

  Moreover, there is no restriction | limiting in particular in a filler, Although any of an organic filler and an inorganic filler may be sufficient, an inorganic filler is preferable from a viewpoint of mechanical strength.

  Next, the wear mechanism of the photosensitive layer or protective layer containing the filler will be described (see FIG. 2). In the electrophotographic process, the photosensitive layer (or protective layer) 10 is subjected to a mechanical load at the cleaning unit. In the cleaning unit, the toner 15, the cleaning blade, and the cleaning brush come into contact with the photosensitive layer (or protective layer) 10 and gradually wear away from a portion having low mechanical strength. When the photosensitive layer (or protective layer) 10 contains the filler 11 and the acryl-modified polyorganosiloxane 13, it selectively wears from the acryl-modified polyorganosiloxane 13 and the binder resin 14. In FIG. 2A, the filler 11 does not exist on the surface of the photosensitive layer (or protective layer) 10, the acrylic modified polyorganosiloxane 13 and the binder resin 14 are worn, and at the same time, the soft acrylic modified polyorganosiloxane 13 in the form of particles. Is spread on the surface of the photosensitive layer (or protective layer) 10, and the surface free energy of the photosensitive layer (or protective layer) 10 decreases. In FIG. 2B, the filler 11 having a higher hardness than the acrylic modified polyorganosiloxane 13 and the binder resin 14 does not wear, and the acrylic modified polyorganosiloxane 13 and the binder resin 14 around the filler 11 wear. . However, the filler 11 becomes a steric hindrance, and the wear rate of the acrylic modified polyorganosiloxane 13 and the binder resin 14 decreases. In FIG. 2C, the filler 11 protrudes, the binder resin 14 around the filler 11 is gradually worn, the contact area between the filler 11 and the binder resin 14 decreases, and the filler 11 and the binder resin 14 are attached. Adhesive force decreases and the filler 11 is detached. By repeating the processes of A, B and C, the photosensitive layer (or protective layer) 10 is reduced in film thickness while keeping the surface free energy low.

  Here, the surface free energy of the photosensitive layer or the protective layer varies depending on the composition and the addition amount of the acrylic-modified polyorganosiloxane. The acrylic-modified polyorganosiloxane exhibits slipperiness and removal of foreign matters by reducing the surface energy at the polyorganosiloxane portion, but the acrylic-modified polyorganosiloxane preferably has a long polydimethylsiloxane chain. At this time, if normal silicone oil or silicone resin is used, it will not be uniformly dispersed in the film, or it will segregate on the surface and will be detached during the process operation, and supply from the film will not be performed, causing slippage. And the ability to remove foreign substances cannot be maintained. In addition, the acrylic-modified polyorganosiloxane has an acrylic polymer part, but in order to improve the compatibility with the binder resin, the acrylic polymer part is distributed to some extent uniformly. The coalescence is preferably grafted. In the present invention, the acrylic-modified polyorganosiloxane has good compatibility with the binder resin, so that the adhesiveness with the binder resin increases, does not easily disengage, and exhibits an effect over a long period of time. be able to. In addition, when the acrylic-modified polyorganosiloxane is distributed in the form of particles, the surface of the photosensitive layer or the protective layer is more easily exhibited than the case where it is uniformly distributed in the binder resin, since it has a lower free energy characteristic. It is considered that the free energy can be kept low continuously.

  Here, the wear amount of the photosensitive layer or the protective layer varies depending on the mechanical strength of the binder resin, the mechanical strength of the filler, the filler amount, the filler diameter, and the like. In FIG. 2C, the adhesive force between the filler and the binder resin greatly contributes to the abrasion of the photosensitive layer or the protective layer, and the wear resistance is improved by improving the affinity between the filler and the binder resin. In addition, if the affinity between the filler and the binder resin is increased, the dispersibility of the filler in the coating solution is also improved, and the filler dispersion stability of the coating solution and the photosensitive material actually produced using the coating solution are also improved. Dispersibility of the filler in the layer or protective layer is improved.

  Conventionally, the photosensitive layer or the protective layer is made of a heat-sensitive material such as polymethyl methacrylate, polystyrene, or a vinyl polymer such as polyolefin, or a copolymer thereof, polycarbonate resin, polyarylate (polyester) resin, phenoxy resin, epoxy resin, or silicone resin. A plastic resin or a thermosetting resin is used. Among them, a polycarbonate resin or a polyarylate resin is preferable because of excellent manufacturing characteristics, mechanical strength, and particularly abrasion resistance as a photoreceptor. In the present invention, a polar group is added to the polycarbonate resin or the polyarylate resin. By graft polymerization of a monomer having, the affinity between the filler and the resin can be increased and the dispersibility of the filler can be improved. As a result, the mechanical strength of the photosensitive layer or the protective layer can be improved.

  Next, a graft copolymer obtained by graft polymerization of a monomer having a polar group to the polycarbonate resin or polyarylate resin used in the present invention will be described.

  In the present invention, the graft polymerization is accompanied by a hydrogen abstraction reaction from a polycarbonate resin or a polyarylate resin, and usually oxygen radicals, electron beam irradiation, light irradiation to an aromatic ketone, or the like can be used. Among these, the method using oxygen radicals is convenient and suitable for use in the photoreceptor. Oxygen radicals are generated by the decomposition of peroxides, and as the peroxides, diacyl peroxides, peroxyesters, and hydroperoxides can be used.

  Moreover, as a monomer which has a polar group used for graft polymerization, the vinyl monomer which has a polar group is preferable. Specifically, acrylic acid and its esters, methacrylic acid and its esters, itaconic acid and its esters, itaconic anhydride, acrylonitrile, acrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl pyrazine, vinyl imidazole, vinyl benzoic acid and Examples thereof include vinyl esters and vinyl benzyl chloride. These monomers may be polymerized alone or in combination of two or more. Further, in the case of copolymerization, a monomer having no polar group such as styrene or vinyl toluene may be used.

  About the graft amount of the vinyl monomer which has a polar group, it is preferable that 1 unit is grafted per 100-2000 units of a polycarbonate structure or a polyarylate structure. If the amount of grafting is larger than the above range, the electrostatic characteristics of the photoreceptor are affected, and in the case of an acidic monomer, the chargeability may be lowered, and in the case of a basic monomer, the residual potential may be increased. When the graft amount is smaller than the above range, the effect on the dispersibility of the filler may be reduced.

  Examples of the hydrogen abstraction reaction include a reaction of abstracting hydrogen such as a substituent of the phenyl nucleus and an alkyl group on the phenyl nucleus. Among these, a reaction in which hydrogen of the alkyl group is withdrawn is preferable because of easy reaction.

From the above, the polycarbonate resin or polyarylate resin has the general formula (1)
HO-X-OH
[Wherein X is a general formula

｛式中、Ｒ_１０１、Ｒ_１０２、Ｒ_１０３及びＲ_１０４は、それぞれ独立に、ハロゲン基、炭素数１〜６の無置換若しくは置換のアルキル基又は無置換若しくは置換のアリール基であり、Ｒ_１０１、Ｒ_１０２、Ｒ_１０３及びＲ_１０４がそれぞれ複数個存在するときは、同一であっても異なっていてもよく、ｏ及びｐは、それぞれ独立に、０〜４の整数であり、ｑ及びｒは、それぞれ独立に、０〜３の整数であり、Ｙは、単結合、炭素数２〜４の直鎖状のアルキレン基、オキシ基、チオ基、一般式

_{{Wherein, R 101, R 102, R} 103 and _{R 104} each independently a halogen group, an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group having 1 to 6 carbon _{atoms, R 101} , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ may be the same or different, and o and p are each independently an integer of 0 to 4, q and r are Each independently represents an integer of 0 to 3, and Y represents a single bond, a linear alkylene group having 2 to 4 carbon atoms, an oxy group, a thio group, or a general formula.

（式中、Ｒ_１０５は、ハロゲン基、炭素数１〜６の無置換若しくは置換のアルキル基、炭素数１〜６の無置換若しくは置換のアルコキシ基又は無置換若しくは置換のアリール基であり、ｓは、０〜４の整数であり、ｔは、１〜３の整数である。）
で表される２価基、一般式

(Wherein R ₁₀₅ represents a halogen group, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, or an unsubstituted or substituted aryl group; Is an integer from 0 to 4, and t is an integer from 1 to 3.)
A divalent group represented by the general formula

（式中、Ｒ_１０６及びＲ_１０７は、それぞれ独立に、水素原子、ハロゲン基、炭素数１〜６の無置換若しくは置換のアルキル基、炭素数１〜６の無置換若しくは置換のアルコキシ基又は無置換若しくは置換のアリール基であり、Ｒ_１０６及びＲ_１０７が結合して炭素数５〜１２の炭素環を形成していてもよい。）
で表される２価基、一般式

(Wherein R ₁₀₆ and R ₁₀₇ are each independently a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, or (It is a substituted or substituted aryl group, and R ₁₀₆ and R ₁₀₇ may combine to form a carbocyclic ring having 5 to 12 carbon atoms.)
A divalent group represented by the general formula

（式中、Ｒ_１０８、Ｒ_１０９、Ｒ_１１０及びＲ_１１１は、それぞれ独立に、水素原子、ハロゲン基、炭素数１〜６の無置換若しくは置換のアルキル基、炭素数１〜６の無置換若しくは置換のアルコキシ基又は無置換若しくは置換のアリール基である。）
で表される２価基又は構造式

Wherein R ₁₀₈ , R ₁₀₉ , R ₁₁₀ and R ₁₁₁ are each independently a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted or substituted group having 1 to 6 carbon atoms, A substituted alkoxy group or an unsubstituted or substituted aryl group.)
A divalent group or a structural formula

で表される２価基である。｝
で表される２価基である。］
で表されるアルキル基を有するビフェノール化合物又はビスフェノール化合物を用いて合成されていることが好ましい。

It is a bivalent group represented by these. }
It is a bivalent group represented by these. ]
It is preferable to synthesize | combine using the biphenol compound or bisphenol compound which has the alkyl group represented by these.

In R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ , examples of the halogen group include a fluoro group, a chloro group, a bromo group, and an iodo group.

  Examples of the alkyl group having 1 to 6 carbon atoms include linear, branched or cyclic alkyl groups, and examples of the substituent for the alkyl group having 1 to 6 carbon atoms include a fluoro group, a cyano group, a phenyl group, and a halogen group. Or the phenyl group substituted by the C1-C6 linear, branched, and cyclic alkyl group is mentioned. Specific examples of the unsubstituted or substituted alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, s-butyl group, n-butyl group, and isobutyl group. Trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, cyclopentyl group, cyclohexyl group and the like.

  Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the substituent of the aryl group include the same halogen groups as those described above and unsubstituted or substituted alkyl groups having 1 to 6 carbon atoms.

  In Y, examples of the linear alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group.

In R _{105 to} R ₁₁₁ , the halogen group, the unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, and the unsubstituted or substituted aryl group are the same as R ₁₀₁ , R ₁₀₂ , R _103, and R ₁₀₄ .

  Examples of the unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms include alkoxy groups having the above-described unsubstituted or substituted alkyl group having 1 to 6 carbon atoms. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, Examples include benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.

Examples of the carbocyclic ring having 5 to 12 carbon atoms formed by combining R ₁₀₆ and R ₁₀₇ include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, and cyclooctadecane.

  Specific examples of the biphenol compound or bisphenol compound having an alkyl group represented by the general formula (1) include bis (4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) methane, and bis (3- Methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis (4-hydroxyphenyl) -1,1-dimethylpropane, 2,2-bis (4-hydroxyphenyl) propane, 2- (4-hydroxy Phenyl) -2- (3-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2- Tylpropane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) ) Nonane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) Propane, 2,2-bis (3-s-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxypheny) ) Propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxy) Phenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5- Dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxy) Cyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4- Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cycloheptane, 2,2-bis (4-hydroxyphenyl) norbornane, 2,2-bis (4-hydroxyphenyl) Adamantane, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide, 3,3,3 ′, 3 ′ -Tetramethyl-6,6'-dihydroxyspiro (bis) indane, 3,3 ', 4,4'-tetrahydro-4 4,4 ', 4'-tetramethyl-2,2'-spirobi- (2H-1-benzopyran) 7,7'-diol, and the like.

  Next, the acrylic-modified polyorganosiloxane used in the present invention will be described.

  The acrylic-modified polyorganosiloxane preferably has an acrylic polymer grafted on the polyorganosiloxane (main chain).

［式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜２０の炭化水素基又はハロゲン化炭化水素基であり、Ｙは、ラジカル重合性官能基又はメルカプト基若しくはラジカル重合性官能基及びメルカプト基を有する有機基であり、Ｚ^１及びＺ^２は、それぞれ独立に、水素原子、低級アルキル基又は一般式

[Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y is a radical polymerizable functional group, a mercapto group or radical polymerization. An organic group having a functional functional group and a mercapto group, and Z ¹ and Z ² are each independently a hydrogen atom, a lower alkyl group or a general formula

（式中、Ｒ^４及びＲ^５は、それぞれ独立に、炭素数１〜２０の炭化水素基又はハロゲン化炭化水素基であり、Ｒ^６は、炭素数が１〜２０の炭化水素基若しくはハロゲン化炭化水素基、ラジカル重合性官能基又はメルカプト基若しくはラジカル重合性官能基及びメルカプト基を有する有機基である。）
で表される官能基であり、ｍは、１〜１００００の整数であり、ｎは、１以上の整数である。］
で表されるポリオルガノシロキサンに、一般式（３）

(In the formula, R ⁴ and R ⁵ are each independently a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a hydrocarbon group or halogenated group having 1 to 20 carbon atoms. It is a hydrocarbon group, a radical polymerizable functional group or a mercapto group or an organic group having a radical polymerizable functional group and a mercapto group.)
M is an integer of 1 to 10000, and n is an integer of 1 or more. ]
In the polyorganosiloxane represented by general formula (3)

（式中、Ｒ^７は、水素原子又はメチル基であり、Ｒ^８は、アルキル基、アルコキシ基で置換されたアルキル基、シクロアルキル基又はアリール基である。）
で表わされるアクリルモノマー及び必要に応じて用いられるアクリルモノマーと共重合することが可能なモノマーを、乳化重合法でグラフト重合（以下、乳化グラフト重合という）することにより製造されていることが特に好ましい。

(In the formula, R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group, an alkyl group substituted with an alkoxy group, a cycloalkyl group, or an aryl group.)
It is particularly preferred to be produced by graft polymerization (hereinafter referred to as emulsion graft polymerization) of an acrylic monomer represented by the formula (1) and a monomer that can be copolymerized with an acrylic monomer used as necessary. .

In R ¹ , R ² and R ³ , examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; phenyl group, tolyl group, xylyl group, naphthyl group and the like Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include functional groups in which at least one hydrogen atom bonded to the carbon atom of the above hydrocarbon group is substituted with a halogen atom. .

  In Y, examples of the radical polymerizable functional group include a vinyl group, an allyl group, a γ-acryloyloxypropyl group, a γ-methacryloyloxypropyl group, and the organic group having a mercapto group includes a γ-mercaptopropyl group and the like. Is mentioned.

In Z ¹ and Z ² , examples of the lower alkyl group include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group.

In R ⁴ , R ⁵ and R ⁶ , the organic group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, a radical polymerizable functional group, a mercapto group or a radical polymerizable functional group and a mercapto group is It is the same.

  Furthermore, m is preferably an integer of 500 to 8000, and n is preferably an integer of 1 to 500.

  The polyorganosiloxane represented by the general formula (2) is a cyclic polyorganosiloxane, a liquid polydimethylsiloxane having both ends blocked with hydroxyl groups, a liquid polydimethylsiloxane having both ends blocked with alkoxy groups, and both ends having trimethylsilyl. A polydimethylsiloxane blocked with a group, a silane for introducing at least one of a radical polymerizable functional group and a mercapto group, and a hydrolyzate thereof, and the purpose of the present invention is not impaired, if necessary. It can be produced by reacting using an amount of trialkoxysilane and its hydrolyzate.

  Next, another example of the method for producing the polyorganosiloxane represented by the general formula (2) will be described.

  First, as a first production method, as a raw material, for example, a low molecular weight cyclic siloxane such as octamethylcyclotetrasiloxane, a dialkoxysilane compound having at least one of a radical polymerizable functional group and a mercapto group, and hydrolysis thereof The method of manufacturing polyorganosiloxane by polymerizing in the presence of a strongly alkaline or strongly acidic catalyst is used. The polyorganosiloxane thus obtained is subjected to a process of emulsifying and dispersing in an aqueous medium in the presence of an emulsifier in order to carry out emulsion graft polymerization.

  Next, as a second production method, for example, a low molecular weight polyorganosiloxane, a dialkoxysilane having at least one of a radical polymerizable functional group and a mercapto group, and a hydrolyzate thereof are used as raw materials. Examples include a method of emulsion polymerization in an aqueous medium in the presence of an anionic surfactant such as an acid surfactant or a sulfate ester surfactant. In the case of such emulsion polymerization, the same raw materials are used, and after emulsifying and dispersing in an aqueous medium with a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, potassium hydroxide, sodium hydroxide It can also superpose | polymerize by adding strong alkaline compounds, such as.

  When the polyorganosiloxane represented by the general formula (2) thus obtained has a low molecular weight, the effect of imparting continuous slidability, abrasion resistance, etc. to the photosensitive layer or protective layer is reduced. Therefore, a higher molecular weight is preferable. For this reason, in the first production method, it is preferable that the polyorganosiloxane has a high molecular weight in the emulsion graft polymerization. In the second production method, the polyorganosiloxane can be made to have a high molecular weight by setting the aging temperature to 30 ° C. or lower, preferably 15 ° C. or lower in the aging treatment performed after emulsion polymerization. it can.

  In the present invention, examples of the acrylic monomer represented by the general formula (3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Alkyl (meth) acrylate; Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; cyclohexyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Examples include benzyl acid. These acrylic monomers may be used independently and may be used in combination of 2 or more type.

  Moreover, a polyfunctional monomer, an ethylenic monomer, etc. are mentioned as a monomer which can be copolymerized with the acrylic monomer represented by General formula (3).

  Examples of the polyfunctional monomer include amide monomers such as (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and the like. The alkylol or alkoxyalkylated product thereof; oxirane group-containing monomer such as glycidyl (meth) acrylate and allyl glycidyl ether; hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Carboxyl group-containing monomers such as (meth) acrylic acid, maleic anhydride, crotonic acid and itaconic acid; amino groups such as 2-dimethylaminoethyl (meth) acrylate and 2-diethylaminoethyl (meth) acrylate Nomer; Polyoxyalkylene group-containing monomers such as ethylene oxide adduct and propylene oxide adduct of (meth) acrylic acid; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. Examples include complete esters of polyhydric alcohol and (meth) acrylic acid; allyl (meth) acrylate and divinylbenzene. These polyfunctional monomers have an effect of imparting elasticity, durability, heat resistance and the like to the molded body by participating in crosslinking between polymers in the acrylic-modified polyorganosiloxane.

  On the other hand, examples of the ethylenic monomer include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, and vinyl versatate.

  These monomers may be used independently and may be used in combination of 2 or more type. Moreover, you may use combining an ethylenic monomer and a polyfunctional monomer.

  The amount of the monomer that can be copolymerized with the acrylic monomer represented by the general formula (3) is usually 90% by weight or less based on the total weight of the acrylic monomer represented by the general formula (3). Preferably, it is 30 wt% or less. When this amount exceeds 90% by weight, the miscibility between the resulting acrylic-modified polyorganosiloxane and the binder resin may be lowered.

  Further, in order to impart excellent slidability and abrasion resistance to the photosensitive layer or protective layer, the glass transition temperature of the acrylic polymer to be grafted is usually 20 ° C. or higher, and preferably 30 ° C. or higher.

  In the present invention, when emulsion graft polymerization is performed, the weight of the polyorganosiloxane represented by the general formula (2) with respect to the mixture of the acrylic monomer represented by the general formula (3) and a monomer copolymerizable therewith. The ratio is preferably 5/95 to 95/5 or less, and more preferably 51/49 to 95/5. When this weight ratio is less than 5/95, the acrylic-modified polyorganosiloxane cannot sufficiently exhibit the effect of the polyorganosiloxane itself, and the acrylic polymer may have a sticky feeling. On the other hand, if the ratio is greater than 95/5, the acrylic modified polyorganosiloxane is less miscible with the binder resin and tends to bleed on the surface of the photosensitive layer or protective layer. May be easily reduced.

  In the present invention, the emulsion graft polymerization can be carried out by a known emulsion polymerization method using an aqueous emulsion of polyorganosiloxane and a normal radical polymerization initiator. In addition, the manufacturing method of acrylic modified polyorganosiloxane is described in the 4th-8th pages and the 9th-10th pages of Japanese Patent Publication No. 7-5808.

  In the present invention, if impurities such as an emulsifier and an aggregating agent used in emulsion graft polymerization remain, the electrical properties of the photoreceptor may be impaired. Therefore, the acrylic-modified polyorganosiloxane may be purified as necessary. It is preferable to use it. Examples of the purification method include a method of stirring and washing with an acid, an aqueous alkali solution, water, alcohol and the like, and a solid-liquid extraction method such as Soxhlet extraction.

  The content of the acrylic-modified polyorganosiloxane in the photosensitive layer is preferably 20% by weight or less, and more preferably 10% by weight or less. If the content exceeds 20% by weight, the mechanical strength of the photoreceptor may be lowered, the residual potential may be raised, and the like.

  Examples of the method for dispersing the acrylic-modified polyorganosiloxane in the binder resin include a method of stirring in a general-purpose solvent, a ball milling method, a vibration milling method, a high-pressure liquid collision method, and an ultrasonic method. In addition, a method of mechanically mixing the acryl-modified polyorganosiloxane and the binder resin using a device such as a Banbury mixer, a roll mill, or a twin screw extruder, and shaping the pellets can be used. Extruded pellets can be molded over a wide temperature range, and a normal injection molding machine is used for molding. The acrylic-modified polyorganosiloxane and binder resin shaped into pellets can be further applied to the above solution dispersion method.

  As a commercial item of acrylic modified polyorganosiloxane, for example, Charine R-170S, R-170, NR-150, NR-130, R-210 (above, manufactured by Nissin Chemical Industry Co., Ltd.), X-22-8084, X-22-8171 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  Next, the filler used in the present invention will be described.

  The filler is added to the photosensitive layer or the protective layer for the purpose of improving the wear resistance, and may be either an organic filler or an inorganic filler. Examples of organic fillers include fluororesin powders such as polytetrafluoroethylene, silicone resin powders, and carbon powders. Inorganic fillers include metals such as copper, tin, aluminum, and indium, silicon oxide, tin oxide, and zinc oxide. , Titanium oxide, indium oxide, antimony oxide, bismuth oxide, tin oxide doped with antimony, metal oxides such as tin-doped indium oxide, and inorganic materials such as potassium titanate. Among these, from the viewpoint of the hardness of the filler, inorganic fillers are preferable, metal oxides are more preferable, and silicon oxide, aluminum oxide, and titanium oxide are particularly preferable. These fillers may be used alone or in combination of two or more.

  The average primary particle size of the filler is preferably 0.01 to 0.5 μm from the viewpoint of light transmittance and wear resistance of the photosensitive layer or protective layer. When the average primary particle size of the filler is less than 0.01 μm, it may cause a decrease in abrasion resistance, a decrease in dispersibility, etc., and when it exceeds 0.5 μm, sedimentation of the filler is promoted in the dispersion. Or toner filming may occur.

  The higher the filler concentration in the photosensitive layer or protective layer, the higher the wear resistance. However, if it exceeds 80% by weight, side effects such as an increase in residual potential and a decrease in the writing light transmittance of the photosensitive layer or protective layer. May occur. Therefore, the filler concentration is usually 80% by weight or less, preferably 50% by weight or less, based on the total solid content. The lower limit of the filler concentration is usually 5% by weight.

From the viewpoint of filler dispersibility, the filler is preferably surface-treated with at least one surface treatment agent. Decreasing the dispersibility of the filler not only increases the residual potential, but also decreases the transparency of the coating film, causes defects in the coating film, and decreases the wear resistance. There is a possibility that it will develop into a big problem. As the surface treatment agent, a conventionally used surface treatment agent can be used, but a surface treatment agent capable of maintaining the insulating properties of the filler is preferable. For example, titanate coupling agents, aluminum coupling agents, zircoaluminate coupling agents, higher fatty acids, etc., and these silane coupling agents are mixed; Al ₂ O ₃ , TiO ₂ , ZrO ₂ , silicone, stearin These mixing treatments such as aluminum acid are preferable from the viewpoint of filler dispersibility and image blur. The surface treatment with the silane coupling agent may have a strong influence on image blur, but the influence can be suppressed by performing a mixing treatment of the surface treatment agent and the silane coupling agent. The surface treatment amount varies depending on the average primary particle size of the filler, but is preferably 3 to 30% by weight, more preferably 5 to 20% by weight. If the surface treatment amount is less than 3% by weight, the effect of improving the dispersibility of the filler may not be obtained. If the surface treatment amount is more than 30% by weight, the residual potential may increase.

  Next, the layer structure of the photoreceptor of the present invention will be described.

  FIG. 3 shows a photosensitive copolymer containing an acrylic modified polyorganosiloxane, a graft copolymer obtained by graft polymerization of a monomer having a polar group on a polycarbonate resin or polyarylate resin, and a filler on a conductive support 21. This is a configuration example in which a layer 22 is provided.

  FIG. 4 shows a graft copolymer obtained by graft-polymerizing a charge generation layer 22a and an acrylic-modified polyorganosiloxane on a conductive support 21 and a monomer having a polar group in a polycarbonate resin or polyarylate resin. This is a configuration example in which a charge transport layer 22b containing a filler is provided.

  FIG. 5 shows a graft copolymer obtained by graft polymerization of a photosensitive layer 22 and an acrylic-modified polyorganosiloxane on a conductive support 21 and a monomer having a polar group on a polycarbonate resin or polyarylate resin, and a filler. It is the structural example which provided the protective layer 23 containing this.

  FIG. 6 shows a graft obtained by graft polymerization of a charge generation layer 22a, a charge transport layer 22b and an acrylic-modified polyorganosiloxane on a conductive support 21 and a monomer having a polar group in a polycarbonate resin or polyarylate resin. This is a configuration example in which a protective layer 23 containing a copolymer and a filler is provided.

  In the above photoreceptor, an undercoat layer may be formed on the conductive support for the purpose of preventing moire and preventing charge injection from the conductive support to the photosensitive layer.

  The photoreceptor of the present invention comprises an acrylic-modified polyorganosiloxane, a graft copolymer obtained by graft polymerization of a monomer having a polar group on a polycarbonate resin or polyarylate resin, and a photosensitive layer or protective layer containing a filler. As long as it has at least, other layers etc. may be combined arbitrarily.

Examples of the conductive support include those having a volume resistivity of 10 ¹⁰ Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, indium oxide Metal oxides such as film or cylindrical plastic or paper coated by vapor deposition or sputtering; aluminum, aluminum alloy, nickel, stainless steel plates, etc., and extruding, drawing, etc. After the conversion, surface-treated pipes such as cutting, superfinishing, and polishing are exemplified. Further, endless nickel belts and endless stainless steel belts disclosed in JP-A-52-36016 can also be used as the conductive support.

  In addition, a material obtained by coating a conductive layer in which conductive powder is dispersed in a binder resin on the above support can also be used as the conductive support. Examples of the conductive powder include carbon black and acetylene black; metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver; metal oxide powder such as conductive tin oxide and ITO. Examples of the binder resin include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyacetic acid. Vinyl, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly (N-vinylcarbazole), acrylic resin, silicone resin, epoxy resin, melamine resin , Urethane resins, phenol resins, alkyd resins, and other thermoplastic resins, thermosetting resins, and photocurable resins. The conductive layer can be provided by dispersing and applying conductive powder and a binder resin in a solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, it is conductive using a heat shrinkable tube containing conductive powder in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a cylindrical substrate. Those provided with a conductive layer can also be used as a conductive support.

  Next, the photosensitive layer will be described. The photosensitive layer may have a single layer structure or a laminated structure. First, the case where the photosensitive layer has a laminated structure composed of a charge generation layer and a charge transport layer will be described.

  The charge generation layer contains a charge generation material, and may further contain a binder resin, if necessary. A known charge generation material can be used for the charge generation layer. Examples of the charge generation material include monoazo pigments, disazo pigments, trisazo pigments, perylene pigments, perinone pigments, quinacridone pigments, and quinone condensation polymers. Examples thereof include ring compounds, squalic acid dyes, other phthalocyanine pigments, naphthalocyanine pigments, azulenium salt dyes, and the like. These may be used alone or in combination. Of these, azo pigments and / or phthalocyanine pigments are preferred, and have the general formula

［式中、Ｒ_２０１及びＲ_２０２は、それぞれ独立に、水素原子、ハロゲン基、アルキル基、アルコキシ基又はシアノ基である。Ｃｐ_１及びＣｐ_２は、それぞれ独立に、一般式

[Wherein, R ₂₀₁ and R ₂₀₂ each independently represent a hydrogen atom, a halogen group, an alkyl group, an alkoxy group, or a cyano group. Cp ₁ and Cp ₂ are each independently a general formula

（式中、Ｒ_２０３は、水素原子、メチル基、エチル基等のアルキル基又はフェニル基等のアリール基である。Ｒ_２０４、Ｒ_２０５、Ｒ_２０６、Ｒ_２０７及びＲ_２０８は、それぞれ独立に、水素原子、ニトロ基、シアノ基、フルオロ基、クロロ基、ブロモ基、ヨード基等のハロゲン基、トリフルオロメチル基、メチル基、エチル基等のアルキル基、メトキシ基、エトキシ基等のアルコキシ基、ジアルキルアミノ基又は水酸基であり、Ｚは、置換若しくは無置換の芳香族炭化水素環又は置換若しくは無置換の芳香族複素環を構成するのに必要な原子群である。）
で表されるカップラー残基である。］
で表されるアゾ顔料及びチタニルフタロシアニン（特に、ＣｕＫαの特性Ｘ線（波長１．５１４Å）に対するブラッグ角２θの回折ピーク（±０．２゜）として、少なくとも２７．２゜に最大回折ピークを有するチタニルフタロシアニン）が特に好ましい。

(Wherein R ₂₀₃ is a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group. R ₂₀₄ , R ₂₀₅ , R ₂₀₆ , R ₂₀₇ and R ₂₀₈ are each independently Hydrogen atom, nitro group, cyano group, fluoro group, chloro group, bromo group, iodo group and other halogen groups, trifluoromethyl group, methyl group, ethyl group and other alkyl groups, methoxy group, ethoxy group and other alkoxy groups, (It is a dialkylamino group or a hydroxyl group, and Z is an atomic group necessary for constituting a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocyclic ring.)
It is a coupler residue represented by these. ]
As a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray of CuKα (wavelength 1.514Å), the maximum diffraction peak is at least 27.2 °. Titanyl phthalocyanine) is particularly preferred.

  Binder resins include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly (N-vinylcarbazole), polyacrylamide, and polyvinyl benzal. , Polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulose resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone and the like. The amount of the binder resin added is usually 0 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the charge generation material.

  The thickness of the charge generation layer is usually from 0.01 to 5 μm, preferably from 0.1 to 2 μm.

  For the charge generation layer, a coating solution in which a charge generation material is dispersed in a solvent together with a binder resin, if necessary, using a ball mill, an attritor, a sand mill, an ultrasonic wave, or the like is applied onto a conductive support. It can be formed by drying.

  Examples of the solvent include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, ligroin, etc. Solvents, ester solvents, and ether solvents are preferred. As a coating method of the coating solution, a dip coating method, a spray coating method, a bead coating method, a nozzle coating method, a spinner coating method, a ring coating method, or the like can be used.

  The charge transport layer contains a charge transport material and a binder resin. As the charge transport material, a hole transport material and an electron transport material can be used.

  Electron transport materials include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4, 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-trinitro Examples include dibenzothiophene-5,5-dioxide, benzoquinone derivatives, and the like.

  Examples of the hole transport material include poly (N-vinylcarbazole) and derivatives thereof, γ-carbazolyl ethyl polyglutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, etc. It is.

  These charge transport materials can be used alone or in combination of two or more. Also, a polymer charge transport material having both a charge transport function and a binder function can be used.

  When the charge transport layer is the outermost layer, the charge transport layer is composed of an acrylic-modified polyorganosiloxane, a graft copolymer obtained by graft polymerization of a monomer having a polar group on a polycarbonate resin or polyarylate resin, and a filler. Contains a charge transport material. These graft copolymers may be used alone or in combination of two or more. At this time, a graft copolymer derived from a polycarbonate resin and a graft copolymer derived from a polyarylate resin may be mixed and used. Furthermore, you may mix and use with another polycarbonate resin and / or polyarylate resin.

  When the charge transport layer is not the outermost layer, the binder resin is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride- Vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate resin, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly (N-vinylcarbazole), acrylic resin Further, thermoplastic or thermosetting resins such as silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin can be used.

  The amount of the charge transport material added is usually 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin.

  Moreover, you may add a plasticizer, a leveling agent, etc. to a charge transport layer as needed. Examples of the plasticizer include those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate. The amount used is usually 0 to 30% by weight based on the binder resin. is there. Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount used is usually 0 with respect to the binder resin. ˜1% by weight.

  The film thickness of the charge transport layer is preferably 25 μm or less from the viewpoint of resolution and responsiveness. The lower limit value varies depending on the system to be used (particularly, charging potential), but is preferably 5 μm or more.

  The charge transport layer is formed by coating a charge transport layer and a binder resin on a charge generation layer by applying or dissolving a coating liquid in a solvent such as tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, It can be formed by drying.

  Next, the case where the photosensitive layer has a single layer structure will be described.

  The photosensitive layer may include a binder resin and the above-described charge generation material, and may further include the above-described charge transport material to be a function separation type.

  When the photosensitive layer is the outermost layer, the photosensitive layer is composed of an acrylic modified polyorganosiloxane, a graft copolymer obtained by graft polymerization of a monomer having a polar group on a polycarbonate resin or polyarylate resin, a filler, a charge, It contains a generating material and may further contain a charge transport material. These graft copolymers may be used alone or in combination of two or more. At this time, a graft copolymer derived from a polycarbonate resin and a graft copolymer derived from a polyarylate resin may be mixed and used. Furthermore, you may mix and use with another polycarbonate resin and / or polyarylate resin.

  When the photosensitive layer is not the outermost layer, as the binder resin, the binder resin used in the aforementioned charge transport layer may be used alone, or mixed with the binder resin used in the aforementioned charge generation layer. It may be used.

  The amount of the charge generation material added is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the binder resin. The amount of the charge transport material added is preferably 0 to 190 parts by weight and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the binder resin.

  Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added to a photosensitive layer as needed.

  The film thickness of the photosensitive layer is usually 5 to 25 μm.

  The photosensitive layer is formed by a dip coating method, a spray coating method, or a coating solution in which a charge generating material and a binder resin are dissolved or dispersed in a solvent such as tetrahydrofuran, dioxane, dichloroethane, cyclohexane, or the like, if necessary. It can be formed by applying and drying by a bead coating method or the like.

  The photoreceptor of the present invention can further have an undercoat layer between the conductive support and the photosensitive layer.

  In general, the undercoat layer is mainly composed of a resin. However, considering that a coating solution containing a solvent is applied on the undercoat layer, the resin may have high solvent resistance to general organic solvents. preferable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a fine powder pigment of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, or indium oxide may be added to the undercoat layer in order to prevent moire and reduce residual potential. .

  Furthermore, as the undercoat layer, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used.

As these other undercoat layers, Al ₂ O ₃ provided by anodic oxidation, organic substances such as polyparaxylylene (parylene), inorganic substances such as SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ are used. What was provided by the vacuum thin film preparation method etc. can also be used.

  The thickness of the undercoat layer is usually 0 to 5 μm.

  The undercoat layer can be formed using the same solvent and coating method as those for the photosensitive layer described above.

  The photoreceptor of the present invention can have a protective layer on the photosensitive layer for the purpose of improving mechanical durability.

  The protective layer contains an acrylic-modified polyorganosiloxane, a graft copolymer obtained by graft polymerization of a monomer having a polar group on a polycarbonate resin or polyarylate resin, and a filler. These graft copolymers may be used alone or in combination of two or more. At this time, a graft copolymer derived from a polycarbonate resin and a graft copolymer derived from a polyarylate resin may be mixed and used. Furthermore, you may mix and use with another polycarbonate resin and / or polyarylate resin.

  The protective layer preferably contains a charge transport material in order to reduce residual potential and improve responsiveness. As the charge transport material, the charge transport material used in the above-described charge transport layer can be used. Note that when a low-molecular charge transport material is used as the charge transport material, the protective layer may have a concentration gradient. At this time, in order to improve the wear resistance, it is preferable to reduce the concentration on the surface side of the charge transport material. In addition, a polymer charge transport material having a function as a charge transport material and a function of a binder can also be used for the protective layer.

  The thickness of the protective layer is preferably 1.0 to 8.0 μm.

  In general, a photoconductor that is used repeatedly over a long period of time is mechanically durable and difficult to wear. However, in an actual machine, ozone, NOx gas, and the like are generated from a charging member and the like. It adheres to the surface and causes image flow. In order to suppress image flow, it is necessary to wear the photosensitive layer at a certain speed or higher. For this reason, when considering long-term repeated use, the thickness of the protective layer is preferably 1.0 μm or more. On the other hand, when the thickness of the protective layer is greater than 8.0 μm, the residual potential may increase or the fine dot reproducibility may decrease.

  As the coating method of the protective layer, a dip coating method, a spray coating method, a bead coating method, a nozzle coating method, a spinner coating method, a ring coating method and the like can be used, but in general, a coating solution from a nozzle having a minute opening. A spray coating method is used in which fine droplets generated by spraying and atomizing are deposited on the photosensitive layer to form a coating film.

  In the present invention, for the purpose of improving the environmental resistance, in particular, for the purpose of suppressing a decrease in sensitivity and an increase in residual potential, an antioxidant, a plasticizer, a lubricant, an ultraviolet absorber, a low molecular charge transport material, a leveling Additives such as agents can be added to each layer. Further, a dispersion stabilizer can be added in order to improve the dispersibility of the filler in the coating solution. Specific examples of these additives are shown below.

Examples of the antioxidant that can be added to each layer include, but are not limited to, the following.
(A) Phenol compound 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (4′- Hydroxy-3 ', 5'-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4 -Hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [meth] -3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3′-t-butylphenyl) buty Rick acid] glycol ester, tocopherols and the like.
(B) p-phenylenediamines N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-s-butyl-p-phenylenediamine, N-phenyl-Ns-butyl-p- Phenylenediamine, N, N′-diisopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.
(C) Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2 -(2-octadecenyl) -5-methylhydroquinone and the like.
(D) Organic sulfur compounds Dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, ditetradecyl 3,3′-thiodipropionate, and the like.
(E) Organophosphorus compounds Triphenylphosphine, tris (nonylphenyl) phosphine, tris (dinonylphenyl) phosphine, tricresylphosphine, tris (2,4-dibutylphenoxy) phosphine and the like.

Examples of the plasticizer that can be added to each layer include the following, but are not limited thereto.
(A) Phosphate ester plasticizer Triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tris phosphate (2-ethylhexyl) , Triphenyl phosphate and the like.
(B) Phthalate ester plasticizers Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, bis (2-ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, Dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, octyl decyl phthalate, dibutyl fumarate, fumaric acid Dioctyl etc.
(C) Aromatic carboxylic acid ester plasticizers Trioctyl trimellitic acid, tri-n-octyl trimellitic acid, octyl oxybenzoate and the like.
(D) Aliphatic dibasic ester plasticizer dibutyl adipate, di-n-hexyl adipate, bis (2-ethylhexyl) adipate, di-n-octyl adipate, n-octyl-n-decyl adipate , Diisodecyl adipate, dicapryl adipate, bis (2-ethylhexyl) azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, bis (2-ethylhexyl) sebacate, bis sebacate (2-ethoxyethyl), dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, di-n-octyl tetrahydrophthalate and the like.
(E) Fatty acid ester derivatives butyl oleate, glycerin monooleate, methyl acetylricinoleate, pentaerythritol ester, dipentaerythritol hexaester, triacetin, tributyrin and the like.
(F) Oxyacid ester plasticizers Methyl acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, tributyl acetyl citrate and the like.
(G) Epoxy plasticizer Epoxidized soybean oil, epoxidized linseed oil, epoxy butyl stearate, decyl epoxy stearate, octyl epoxy stearate, benzyl epoxy stearate, dioctyl epoxy hexahydrophthalate, didecyl epoxy hexahydrophthalate, etc. .
(H) Dihydric alcohol ester plasticizers Diethylene glycol dibenzoate, triethylene glycol bis (2-ethylbutyrate) and the like.
(I) Chlorinated plasticizer Chlorinated paraffin, chlorinated diphenyl, chlorinated fatty acid methyl, methoxychlorinated fatty acid methyl, and the like.
(J) Polyester plasticizer Polypropylene adipate, polypropylene sebacate, polyester, acetylated polyester and the like.
(K) Sulfonic acid derivatives p-toluenesulfonamide, o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-ethyl-o-toluenesulfonamide, N-cyclohexyl-p-toluenesulfonamide and the like.
(L) Citric acid derivatives Triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, tris (2-ethylhexyl) citrate, n-octyldecyl acetyl citrate and the like.
(M) Others Terphenyl, partially hydrogenated terphenyl, camphor, 2-nitrodiphenyl, dinonylnaphthalene, methyl abietate and the like.

Examples of the lubricant that can be added to each layer include, but are not limited to, the following.
(A) Hydrocarbon compound Liquid paraffin, paraffin wax, microwax, low-polymerized polyethylene and the like.
(B) Fatty acid compounds Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like.
(C) Fatty acid amide compounds Stearylamide, palmitylamide, oleylamide, methylenebis (stearylamide), ethylenebis (stearylamide) and the like.
(D) Ester compounds Lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, and the like.
(E) Alcohol compounds Cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol, polyglycerol and the like.
(F) Metal soap Lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, magnesium stearate and the like.
(G) Natural wax Carnauba wax, candelilla wax, beeswax, whale wax, ibotarou, montan wax and the like.
(H) Others Silicone compounds, fluorine compounds, etc.

Examples of the ultraviolet absorber that can be added to each layer include the following, but are not limited thereto.
(A) Benzophenone series 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4 -Methoxybenzophenone and the like.
(B) salicylate-based phenyl salicylate, 3,5-di-t-butyl-4-hydroxybenzoate 2,4-di-t-butylphenyl, and the like.
(C) Benzotriazole series (2′-hydroxyphenyl) benzotriazole, (2′-hydroxy-5′-methylphenyl) benzotriazole, (2′-hydroxy-5′-methylphenyl) benzotriazole, (2′- Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole and the like.
(D) Cyanoacrylate-based ethyl 2-cyano-3,3-diphenylacrylate.
(E) Quencher (metal complex)
Nickel (2,2′-thiobis (4-t-octylphenolate) n-butylamine, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate and the like.
(F) HALS (hindered amine)
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2, 6,6-tetramethylpyridine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyl Oxy-2,2,6,6-tetramethylpiperidine and the like.

  Next, the image forming method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.

  FIG. 7 is a diagram showing an example of the image forming apparatus of the present invention, and modifications as will be described later also belong to the category of the present invention.

  In FIG. 7, a photoconductor 31 is the photoconductor of the present invention. The photoconductor 31 has a drum shape, but may have a sheet shape or an endless belt shape. As the charging member (roller) 32, the pre-transfer charger 33, and the pre-cleaning charger 34, known means such as a corotron, a scorotron, a solid state charger (solid state charger), and a charging roller are used. As the charging member 32, a member that is in contact with or close to the photosensitive member 31 is preferably used. Further, when charging the photosensitive member 31 by the charging member 32, charging unevenness can be reduced by charging the photosensitive member 31 with an electric field in which an alternating current component is superimposed on a direct current component of the charging member 32. It is effective. At this time, unnecessary charges are erased by the eraser 35.

  As the transfer means, in addition to the transfer belt 36, the above charger can be used, but a combination of a transfer charger and a separation charger is effective.

  Light sources such as the image exposure unit 37 and the charge removal lamp 38 are fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LED), semiconductor lasers (LD), electroluminescence (EL), and the like. In general, light emitting diodes and semiconductor lasers are preferable. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

  In addition to the steps shown in FIG. 7, such a light source may be provided with a transfer step using light irradiation, a static elimination step, a cleaning step, a pre-exposure step, etc. to irradiate the photoreceptor 31 with light. .

  The toner developed on the photosensitive member 31 by the developing unit 39 is transferred by the registration roller 40 to the transfer paper 41 sent in time with the image formation on the photosensitive member 31, and transferred by the separation claw 42. The paper 40 is separated. At this time, not all of the toner on the photoconductor 31 is transferred, and some toner remains on the photoconductor 31. Such toner is removed from the photoreceptor 31 by the cleaning brush 43 and the cleaning blade 44. The cleaning may be performed only by the cleaning brush 43, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush 43.

  When the photosensitive member is positively (or negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. If this is developed with a negative (or positive) toner (electric detection fine particles), a positive image is obtained, and if developed with a positive (or negative) toner, a negative image is obtained.

  A known method is applied to such a developing unit, and a known method is also applied to the charge eliminating unit.

  FIG. 8 shows another example of the image forming apparatus of the present invention. The photoconductor 51 is the photoconductor of the present invention. The photoconductor 51 is driven by driving rollers 52a and 52b, and is charged by a charger 53, image exposure by a light source 54, development (not shown), transfer using the charger 54, pre-cleaning exposure by a light source 55, Cleaning with the cleaning brush 56 and static elimination with the light source 57 are repeated. In FIG. 8, the photoreceptor 51 is irradiated with light for exposure before cleaning from the side of the conductive support. In this case, the conductive support is translucent.

  The image forming method shown in FIG. 8 exemplifies an embodiment of the present invention, and other embodiments are possible. For example, in FIG. 8, the pre-cleaning exposure is performed from the conductive support side, but it may be performed from the photosensitive layer side, or image exposure and neutralizing light irradiation may be performed from the conductive support side.

  On the other hand, as the light irradiation process, image exposure, pre-cleaning exposure, and static elimination exposure are illustrated, but in addition to these, exposure before transfer and pre-exposure of image exposure may be performed, An irradiation step may be provided to irradiate the photoconductor with light.

  The image forming means as described above may be fixedly incorporated in an image forming apparatus such as a copying apparatus, a facsimile machine, or a printer, but may be incorporated in the image forming apparatus in the form of a process cartridge. A process cartridge is a single device (part) that contains a photoreceptor and includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, a charge eliminating unit, and the like. There are many shapes and the like of the process cartridge, but a general example is shown in FIG. The process cartridge shown in FIG. 9 includes a photoreceptor 61, a charging member 62, an image exposure unit 63, a developing roller 64, a transfer roller 65, and a cleaning brush 66. The photoreceptor 61 is the photoreceptor of the present invention.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this does not limit the aspect of this invention. In addition, a part means a weight part.
(Synthesis Example 1) Synthesis of vinylpyridine-grafted bisphenol Z-type polycarbonate 3.0 g of bisphenol Z-type polycarbonate TS2050 (manufactured by Teijin Ltd.), 0.3 g of 4-vinylpyridine, 0.1 g of dry BPO (benzoyl peroxide) and 40 ml of dehydrated toluene Then, the mixture was heated and stirred at 100 ° C. for 5 hours under an argon gas atmosphere. After standing at room temperature, it was diluted with dichloromethane and reprecipitated with methanol. Next, it was dissolved in dichloromethane, water was added, the organic layer was washed with water, reprecipitated again with methanol, and isolated and dried to obtain 2.97 g of an ultrathin yellowish white vinylpyridine grafted bisphenol Z-type polycarbonate.

The weight average molecular weight by GPC was 146300. Further, when the graft amount was measured by ¹ H-NMR analysis, 1 unit of vinylpyridine was grafted to 688 units of bisphenol Z carbonate. The graft amount was calculated from the integral value of 4 protons of the vinylpyridine ring and the integral value of 8 protons of the benzene ring. In addition, the weight average molecular weight by GPC of the raw material bisphenol Z-type polycarbonate was 147000.
(Synthesis Example 2) Synthesis of acrylic acid grafted bisphenol Z type polycarbonate 3.0 g of bisphenol Z type polycarbonate TS2050 (manufactured by Teijin Ltd.), 0.3 g of acrylic acid and 0.1 g of dry BPO (benzoyl peroxide) were dissolved in 40 ml of dehydrated toluene. The mixture was heated and stirred at 100 ° C. for 5 hours under an argon gas atmosphere. After standing at room temperature, it was diluted with dichloromethane and reprecipitated with methanol. Next, it was dissolved in dichloromethane, water was added, the organic layer was washed with water, reprecipitated again with methanol, isolated and dried to obtain 2.95 g of white acrylic acid grafted bisphenol Z type polycarbonate. The weight average molecular weight by GPC was 146700.
Synthesis Example 3 Synthesis of Vinylpyridine Grafted Bisphenol Z-Type Polyarylate 2.68 g (10 mmol) of 1,1′-bis (4-hydroxyphenyl) cyclohexane was placed in a reaction vessel, and 15.0 mg of 4-t-butylphenol (0 .1 mmol) and 1.52 g (38 mmol) of sodium hydroxide were dissolved in 50 ml of water, and then 13.6 mg (0.06 mmol) of BTEAC (benzyltriethylammonium chloride) as a phase transfer catalyst was added and dissolved ( Water phase). Separately, 2.03 g (10.02 mmol) of a 1: 1 mixture of teraphthalic acid chloride and isophthalic acid chloride was dissolved in 40 ml of dichloromethane (organic phase). The organic phase was added while keeping the reaction vessel at 20 ° C. and stirring the aqueous phase at 650 rpm. After performing the reaction in this state for 5 hours, stirring was stopped and the aqueous phase and the organic phase were separated. The organic phase was neutralized with an acetic acid aqueous solution, and the organic phase was washed with water three times. Next, it was reprecipitated with methanol and isolated and dried to obtain 3.81 g of white bisphenol Z-type polyarylate. The polymerization yield was 95.4%. Moreover, the weight average molecular weight by GPC was 153500.

  Bisphenol Z-type polyarylate (3.0 g), 4-vinylpyridine (0.3 g) and dry BPO (benzoyl peroxide) (0.1 g) were dissolved in dehydrated toluene (40 ml), and the mixture was heated and stirred at 100 ° C. for 5 hours in an argon gas atmosphere. . After standing at room temperature, it was diluted with dichloromethane and reprecipitated with methanol. Next, after dissolving in dichloromethane, adding water, washing the organic layer with water, reprecipitating with methanol again and drying it to obtain 2.96 g of ultra-light yellowish white vinylpyridine grafted bisphenol Z polyarylate. It was.

The weight average molecular weight by GPC was 153200. Further, when the graft amount was measured by ¹ H-NMR analysis, 1 unit of vinylpyridine was grafted to 635 units of bisphenol Z arylate. The graft amount was calculated from the integral value of 4 protons of the vinylpyridine ring and the integral value of 12 protons of the benzene ring.
(Synthesis Example 4) Synthesis of acrylic acid grafted bisphenol Z type polyarylate 3.0 g of bisphenol Z type polyarylate, 0.3 g of acrylic acid and 0.1 g of dry BPO (benzoyl peroxide) were dissolved in 40 ml of dehydrated toluene, and argon gas was added. Under an atmosphere, the mixture was heated and stirred at 100 ° C. for 5 hours. After standing at room temperature, it was diluted with dichloromethane and reprecipitated with methanol. Next, it was dissolved in dichloromethane, water was added, the organic layer was washed with water, then reprecipitated again with methanol and isolated and dried to obtain 2.93 g of white acrylic acid grafted bisphenol Z polyarylate. The weight average molecular weight by GPC was 153100.
(Synthesis Example 5) Synthesis of Vinylpyridine Grafted Bisphenol E Type Polycarbonate 4.28 g (20 mmol) of 4,4′-ethylidine bisphenol was placed in a reaction vessel, and 30.0 mg (0.2 mmol) of 4-t-butylphenol and hydroxylated. Sodium 6.00 g (150 mmol) and hydrosulfite 9.0 mg (0.5 mmol) were dissolved in 120 ml of water at room temperature. Next, a triphosgene solution in which 3.56 g (12 mmol) of triphosgene was dissolved in 10 ml of dichloromethane was added at 15 ° C., and the mixture was stirred as it was for 15 minutes. Further, 20.2 mg (0.2 mmol) of triethylamine was added as a catalyst, reacted at room temperature for 90 minutes, diluted with dichloromethane, and the organic phase was separated. This organic phase was washed once with water, then washed with a 2% by weight aqueous hydrochloric acid solution, washed three times with water, and reprecipitated with methanol to obtain 4.16 g of a bisphenol E type polycarbonate. The polymerization yield was 97.5%. Moreover, the weight average molecular weight by GPC was 151500.

  Bisphenol E-type polycarbonate (3.0 g), 4-vinylpyridine (0.3 g), and dry BPO (benzoyl peroxide) (0.1 g) were dissolved in dehydrated toluene (40 ml), and the mixture was heated and stirred at 100 ° C. for 5 hours in an argon gas atmosphere. After standing at room temperature, it was diluted with dichloromethane and reprecipitated with methanol. Next, it was dissolved in dichloromethane, water was added, the organic layer was washed with water, reprecipitated again with methanol, and isolated and dried to obtain 2.95 g of an ultrathin yellowish white vinylpyridine grafted bisphenol E type polycarbonate.

The weight average molecular weight by GPC was 150500. Further, when the graft amount was measured by ¹ H-NMR analysis, 1 unit of vinylpyridine was grafted to 630 units of bisphenol E-type carbonate. The graft amount was calculated from the integral value of 4 protons of the vinylpyridine ring and the integral value of 8 protons of the benzene ring.
(Synthesis Example 6) Synthesis of acrylic acid grafted tetrabromobisphenol A / bisphenol Z copolymer polycarbonate 5.43 g (10 mmol) of tetrabromobisphenol A and 1.68 g of 1,1′-bis (4-hydroxyphenyl) cyclohexane (10 mmol) was placed in a reaction vessel, and 30.0 mg (0.2 mmol) of 4-t-butylphenol, 6.00 g (150 mmol) of sodium hydroxide and 9.0 mg (0.5 mmol) of hydrosulfite were added to 120 ml of water at room temperature. Dissolved. Next, a triphosgene solution in which 3.56 g (12 mmol) of triphosgene was dissolved in 10 ml of dichloromethane was added at 15 ° C., and the mixture was stirred as it was for 15 minutes. Further, 20.2 mg (0.2 mmol) of triethylamine was added as a catalyst, reacted at room temperature for 90 minutes, diluted with dichloromethane, and the organic phase was separated. The organic phase was washed once with water, washed with a 2% by weight aqueous hydrochloric acid solution, washed with water three times, and reprecipitated with methanol to obtain 7.86 g of a tetrabromobisphenol A / bisphenol Z copolymer polycarbonate. The polymerization yield was 97.0%. Moreover, the weight average molecular weight by GPC was 161000.

Tetrabromobisphenol A / bisphenol Z copolymer polycarbonate (3.0 g), acrylic acid (0.3 g), and dry BPO (benzoyl peroxide) (0.1 g) are dissolved in dehydrated toluene (40 ml), and argon gas atmosphere is at 100 ° C. for 5 hours. Heating and stirring were performed. After standing at room temperature, it was diluted with dichloromethane and reprecipitated with methanol. Next, after dissolving in dichloromethane, adding water, washing the organic layer with water, reprecipitating again with methanol, isolating and drying, white acrylic acid grafted tetrabromobisphenol A type / bisphenol Z type copolycarbonate2. 94 g was obtained. The weight average molecular weight by GPC was 159500.
(GPC measurement method)
GPC is HLC-8120 type (manufactured by Tosoh Corporation), pre-column is TSK grandcolumn SuperH-H (manufactured by Tosoh Corporation), column is TSKgelSuperH5000, H4000, H3000, H3000 (above, manufactured by Tosoh Corporation) Can be used. The measurement temperature is 40 ° C., the carrier is tetrahydrofuran, the flow rate is 0.6 ml / min, and the average molecular weight can be calculated using a polystyrene standard sample.
Example 1
An undercoat layer coating liquid A was dip-coated on a conductive support made of aluminum having an outer diameter of 30 mm and dried by heating to form an undercoat layer having a thickness of 3.5 μm.
(Coating liquid A for undercoat layer)
Alkyd resin Beccosol 1307-60-EL (manufactured by Dainippon Ink and Chemicals) 3 parts Melamine resin Super Becamine G-821-60 (manufactured by Dainippon Ink and Chemicals) 2 parts Titanium oxide CR-EL (made by Ishihara Sangyo) ) 20 parts methyl ethyl ketone 100 parts On the undercoat layer, the charge generation layer coating liquid A was dip-coated and dried by heating to form a charge generation layer having a thickness of 0.2 μm.
(Coating liquid A for charge generation layer)
Structural formula

で表されるアゾ顔料５部
ポリビニルブチラールＸＹＨＬ（ＵＣＣ社製）１部
２−ブタノン１００部
シクロヘキサノン２００部
電荷発生層上に、電荷輸送層用塗工液Ａを浸漬塗工し、加熱乾燥させ、膜厚が２７μｍの電荷輸送層を形成し、感光体を作製した。
（電荷輸送層用塗工液Ａ）
ビスフェノールＺ型ポリカーボネートＴＳ２０５０（帝人社製）（以下、Ｚ−Ｐｃという）１部
１部の構造式

5 parts of an azo pigment represented by the following formula: 1 part of polyvinyl butyral XYHL (UCC) 1 part 2-butanone 100 parts cyclohexanone 200 parts On the charge generation layer, the charge transport layer coating liquid A is dip coated, dried by heating, A charge transport layer having a thickness of 27 μm was formed to produce a photoreceptor.
(Coating liquid A for charge transport layer)
Bisphenol Z-type polycarbonate TS2050 (manufactured by Teijin Limited) (hereinafter referred to as Z-Pc) 1 part 1 part structural formula

で表される正孔輸送物質Ａ
テトラヒドロフラン１０部
電荷輸送層上に、保護層用塗工液Ａをスプレー塗工し、１５０℃で２０分間加熱乾燥させ、膜厚が５μｍの保護層を形成し、感光体を作製した。
（保護層用塗工液Ａ）
合成例１で合成したビニルピリジングラフトビスフェノールＺ型ポリカーボネート（以下、ＶＰ−Ｐｃという）４部
３部の正孔輸送物質Ａ
シリカ粒子ＫＭＰＸ１００（信越化学工業社製）３部
平均一次粒径が０．２μｍ、平均粒径が３０μｍ、オルガノポリシロキサン成分が７０重量％、アクリル成分が３０重量％の請求項７で定められたアクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）０．７部
テトラヒドロフラン１７０部
シクロヘキサノン５０部
（実施例２）
保護層用塗工液Ａの代わりに、保護層用塗工液Ｂを用いたこと以外は、実施例１と同様にして、感光体を作製した。
（保護層用塗工液Ｂ）
合成例２で合成したアクリル酸グラフトビスフェノールＺ型ポリカーボネート（以下、ＡＣ−Ｐｃという）４部
３部の正孔輸送物質Ａ
シリカ粒子ＫＭＰＸ１００（信越化学工業社製）３部
アクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）０．７部
テトラヒドロフラン１７０部
シクロヘキサノン５０部
（実施例３）
保護層用塗工液Ａの代わりに、保護層用塗工液Ｃを用いたこと以外は、実施例１と同様にして、感光体を作製した。
（保護層用塗工液Ｃ）
合成例３で合成したビニルピリジングラフトビスフェノールＺ型ポリアリレート（以下、ＶＰ−Ｐａという）４部
３部の正孔輸送物質Ａ
シリカ粒子ＫＭＰＸ１００（信越化学工業社製）３部
アクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）０．７部
テトラヒドロフラン１７０部
シクロヘキサノン５０部
（実施例４）
保護層用塗工液Ａの代わりに、保護層用塗工液Ｄを用いたこと以外は、実施例１と同様にして、感光体を作製した。
（保護層用塗工液Ｄ）
合成例４で合成したアクリル酸グラフトビスフェノールＺ型ポリアリレート（以下、ＡＣ−Ｐａという）４部
３部の正孔輸送物質Ａ
シリカ粒子ＫＭＰＸ１００（信越化学工業社製）３部
アクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）０．７部
テトラヒドロフラン１７０部
シクロヘキサノン５０部
（実施例５）
シリカ粒子ＫＭＰＸ１００の代わりに、アルミナ粒子ＡＡ０３（住友化学社製）を用いたこと以外は、実施例１と同様にして、感光体を作製した。
（実施例６）
シリカ粒子ＫＭＰＸ１００の代わりに、アルミナ粒子ＡＡ０３（住友化学社製）を用いたこと以外は、実施例２と同様にして、感光体を作製した。
（実施例７）
シリカ粒子ＫＭＰＸ１００の代わりに、アルミナ粒子ＡＡ０３（住友化学社製）を用いたこと以外は、実施例３と同様にして、感光体を作製した。
（実施例８）
シリカ粒子ＫＭＰＸ１００の代わりに、アルミナ粒子ＡＡ０３（住友化学社製）を用いたこと以外は、実施例４と同様にして、感光体を作製した。
（実施例９）
保護層用塗工液Ａの代わりに、保護層用塗工液Ｅを用いたこと以外は、実施例１と同様にして、感光体を作製した。
（保護層用塗工液Ｅ）
０．５部のＶＰ−Ｐｃ
３．５部のＺ−Ｐｃ
３部の正孔輸送物質Ａ
アルミナ粒子ＡＡ０３（住友化学社製）３部
アクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）０．７部
テトラヒドロフラン１７０部
シクロヘキサノン５０部
（実施例１０）
保護層用塗工液Ａの代わりに、保護層用塗工液Ｆを用いたこと以外は、実施例１と同様にして、感光体を作製した。
（保護層用塗工液Ｆ）
０．５部のＡＣ−Ｐｃ
３．５部のＺ−Ｐｃ
３部の正孔輸送物質Ａ
アルミナ粒子ＡＡ０３（住友化学社製）３部
アクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）０．７部
テトラヒドロフラン１７０部
シクロヘキサノン５０部
（実施例１１）
保護層用塗工液Ａの代わりに、保護層用塗工液Ｇを用いたこと以外は、実施例１と同様にして、感光体を作製した。
（保護層用塗工液Ｇ）
０．５部のＶＰ−Ｐａ
３．５部のＺ−Ｐｃ
３部の正孔輸送物質Ａ
アルミナ粒子ＡＡ０３（住友化学社製）３部
アクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）０．７部
テトラヒドロフラン１７０部
シクロヘキサノン５０部
（実施例１２）
保護層用塗工液Ａの代わりに、保護層用塗工液Ｈを用いたこと以外は、実施例１と同様にして、感光体を作製した。
（保護層用塗工液Ｈ）
０．５部のＡＣ−Ｐａ
３．５部のＺ−Ｐｃ
３部の正孔輸送物質Ａ
アルミナ粒子ＡＡ０３（住友化学社製）３部
アクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）０．７部
テトラヒドロフラン１７０部
シクロヘキサノン５０部
（実施例１３）
外径３０ｍｍアルミニウム製の導電性支持体に、下引き層用塗工液Ａを浸漬塗工し、加熱乾燥させ、膜厚が３．５μｍの下引き層を形成した。

Hole transport material A represented by
Tetrahydrofuran 10 parts On the charge transport layer, the coating liquid A for protective layer was spray-coated and dried by heating at 150 ° C. for 20 minutes to form a protective layer having a film thickness of 5 μm to prepare a photoreceptor.
(Coating liquid A for protective layer)
4 parts of vinylpyridine grafted bisphenol Z-type polycarbonate (hereinafter referred to as VP-Pc) synthesized in Synthesis Example 1 3 parts of hole transport material A
Silica particles KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts The average primary particle size is 0.2 μm, the average particle size is 30 μm, the organopolysiloxane component is 70% by weight, and the acrylic component is 30% by weight. Acrylic-modified polyorganosiloxane Charine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 part Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Example 2)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution B was used instead of the protective layer coating solution A.
(Coating liquid B for protective layer)
4 parts of acrylic acid grafted bisphenol Z-type polycarbonate (hereinafter referred to as AC-Pc) synthesized in Synthesis Example 2 3 parts of hole transport material A
Silica particles KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Acrylic-modified polyorganosiloxane Charine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 parts Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Example 3)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution C was used instead of the protective layer coating solution A.
(Coating liquid C for protective layer)
4 parts of vinylpyridine grafted bisphenol Z-type polyarylate (hereinafter referred to as VP-Pa) synthesized in Synthesis Example 3 3 parts of hole transport material A
Silica particles KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Acrylic-modified polyorganosiloxane Charine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 parts Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Example 4)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution D was used instead of the protective layer coating solution A.
(Coating liquid D for protective layer)
Acrylic acid grafted bisphenol Z type polyarylate synthesized in Synthesis Example 4 (hereinafter referred to as AC-Pa) 4 parts 3 parts of hole transport material A
Silica particles KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Acrylic-modified polyorganosiloxane Charine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 parts Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Example 5)
A photoconductor was prepared in the same manner as in Example 1 except that alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) were used instead of silica particles KMPX100.
(Example 6)
A photoconductor was prepared in the same manner as in Example 2 except that alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) were used instead of silica particles KMPX100.
(Example 7)
A photoconductor was prepared in the same manner as in Example 3 except that alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) were used instead of silica particles KMPX100.
(Example 8)
A photoconductor was prepared in the same manner as in Example 4 except that alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) were used instead of silica particles KMPX100.
Example 9
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution E was used instead of the protective layer coating solution A.
(Coating fluid E for protective layer)
0.5 part VP-Pc
3.5 parts of Z-Pc
3 parts of hole transport material A
Alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) 3 parts Acrylic modified polyorganosiloxane Sharine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 part Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Example 10)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution F was used instead of the protective layer coating solution A.
(Coating fluid F for protective layer)
0.5 part of AC-Pc
3.5 parts of Z-Pc
3 parts of hole transport material A
Alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) 3 parts Acrylic-modified polyorganosiloxane Sharine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 part Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Example 11)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution G was used instead of the protective layer coating solution A.
(Coating liquid G for protective layer)
0.5 part VP-Pa
3.5 parts of Z-Pc
3 parts of hole transport material A
Alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) 3 parts Acrylic modified polyorganosiloxane Sharine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 part Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Example 12)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution H was used instead of the protective layer coating solution A.
(Coating liquid H for protective layer)
0.5 part AC-Pa
3.5 parts of Z-Pc
3 parts of hole transport material A
Alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) 3 parts Acrylic-modified polyorganosiloxane Sharine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 parts Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Example 13)
An undercoat layer coating liquid A was dip-coated on a conductive support made of aluminum having an outer diameter of 30 mm and dried by heating to form an undercoat layer having a thickness of 3.5 μm.

On the undercoat layer, the photosensitive layer coating solution A was dip-coated and dried by heating to form a photosensitive layer having a film thickness of 25 μm to produce a photoreceptor.
(Coating solution A for photosensitive layer)
10 parts VP-Pc
6 parts of hole transport material A
4 parts structural formula

で表される電子輸送物質Ａ
０．４部のオキソチタニウムフタロシアニンＡ（ＣｕＫαの特性Ｘ線（波長１．５１４Å）に対するブラッグ角２θの回折ピーク（±０．２゜）として、少なくとも２７．２゜に最大回折ピークを有するオキソチタニウムフタロシアニン）
シリカ粒子ＫＭＰＸ１００（信越化学工業社製）５部
アクリル変性ポリオルガノシロキサンのシャリーヌＲ−１７０Ｓ（日信化学工業社製）１.１部
テトラヒドロフラン１００部
（実施例１４）
外径３０ｍｍのアルミニウム製の導電性支持体に、下引き層用塗工液Ａを浸漬塗工し、加熱乾燥させ、膜厚が３．５μｍの下引き層を形成した。

Electron transport material A
0.4 part of oxotitanium phthalocyanine A (an oxotitanium having a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.514１．５) of CuKα) Phthalocyanine)
Silica particles KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Acrylic-modified polyorganosiloxane Charine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 1.1 parts Tetrahydrofuran 100 parts (Example 14)
An undercoat layer coating solution A was dip-coated on an aluminum conductive support with an outer diameter of 30 mm and dried by heating to form an undercoat layer having a thickness of 3.5 μm.

  On the undercoat layer, the charge generation layer coating solution A was dip coated and dried by heating to form a charge generation layer having a thickness of 0.2 μm.

On the charge generation layer, the charge transport layer coating solution B was dip coated and dried by heating to form a charge transport layer having a thickness of 27 μm, thereby preparing a photoreceptor.
(Coating liquid B for charge transport layer)
10 parts VP-Pc
10 parts of hole transport material A
Silica particles KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts Acrylic-modified polyorganosiloxane Sharine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.9 parts Tetrahydrofuran 110 parts (Comparative Example 1)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution I was used instead of the protective layer coating solution A.
(Coating liquid I for protective layer)
4 parts of Z-Pc
3 parts of hole transport material A
Silica particles KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Acrylic-modified polyorganosiloxane Charine R-170S (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 parts Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Comparative Example 2)
A photoconductor was prepared in the same manner as in Comparative Example 1 except that alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) were used instead of silica particles KMPX100.
(Comparative Example 3)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution J was used instead of the protective layer coating solution A.
(Coating liquid J for protective layer)
4 parts of Z-Pc
3 parts of hole transport material A
Silica particles KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Dispersant BYK-P104 (manufactured by Big Chemie) 0.06 parts Sharine R-170S of acrylic-modified polyorganosiloxane (manufactured by Nissin Chemical Industry Co., Ltd.) 0.7 parts Tetrahydrofuran 170 Part 50 parts cyclohexanone (Comparative Example 4)
A photoconductor was prepared in the same manner as in Comparative Example 3 except that alumina particles AA03 (manufactured by Sumitomo Chemical Co., Ltd.) were used instead of silica particles KMPX100.
(Comparative Example 5)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution K was used instead of the protective layer coating solution A.
(Coating liquid K for protective layer)
4 parts of Z-Pc
3 parts of hole transport material A
Alumina particles AA03 (Sumitomo Chemical Co., Ltd.) 3 parts Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Comparative Example 6)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solution L was used instead of the protective layer coating solution A.
(Coating liquid L for protective layer)
4 parts of Z-Pc
3 parts of hole transport material A
Acrylic modified polyorganosiloxane Charine R-170S (manufactured by Nissin Chemical Industry) 0.7 part Tetrahydrofuran 170 parts Cyclohexanone 50 parts (Comparative Example 7)
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer was not provided and the thickness of the charge transport layer was 27 μm.
(Evaluation method and evaluation results)
In order to evaluate the dispersion stability of the particles of the protective layer coating liquids A to L (Examples 1 to 12, Comparative Examples 1 to 6), a sedimentation test was performed. 10 ml of the protective layer coating solution was placed in a settling tube (10 ml) and allowed to stand for 1 hour. Evaluation was made by observing the suspension state of the liquid in the settling tube after 1 hour. The upper part of the liquid surface is suspended and the dispersion stability is good. The upper part of the liquid surface is transparent and the dispersion liquid is slightly bad. The whole liquid is transparent. The dispersion stability. Was judged as x. The results are shown in Table 1.

表１より、実施例の保護層塗工液は、何れも優れる分散安定性を示した。ポリカーボネート又はポリアリレートにグラフト重合を行ったグラフト重合体を使用することによって、極性のフィラーと非極性のアクリル変性ポリオルガノシロキサンが同時に安定に存在する分散液が得られた。

From Table 1, all of the protective layer coating solutions of Examples showed excellent dispersion stability. By using a graft polymer obtained by graft polymerization on polycarbonate or polyarylate, a dispersion in which a polar filler and a nonpolar acrylic-modified polyorganosiloxane are present stably at the same time was obtained.

  Next, a 100,000 sheet passing test (A4) was conducted by mounting a photoconductor on an Imagio NEO271 whose image exposure light source was modified to a 655 nm semiconductor laser (writing by a polygon mirror). Then, the halftone image characteristics and the wear amount after the initial and post-run were evaluated.

  The image characteristics were judged as ◯ when the image was good, Δ when the image unevenness occurred locally, and x when the image unevenness occurred overall. The results are shown in Table 2.

摩耗量は、渦電流式膜厚計ＦｉｓｈｅｒｓｃｏｐｅＭＭＳを用いて、感光体上の２０点の膜厚を測定し、初期からの膜厚減少量を求めることにより、評価した。結果を表３に示す。

The amount of wear was evaluated by measuring the film thickness at 20 points on the photoconductor using an eddy current film thickness meter Fisherscope MMS and determining the film thickness reduction from the initial stage. The results are shown in Table 3.

上記の評価結果より、保護層が無い場合は膜削れ量が大きく、寿命が短かった。また、フィラーのみを保護層に添加した場合は、耐摩耗性が向上するものの、クリーニング性が悪くなり、感光体上にトナー及び現像剤成分と思われる物質のフィルミングが起こり、画像ムラが発生した。また、アクリル変性ポリオルガノシロキサンのみを保護層に添加した場合は、保護層の無い場合と同様に、摩耗による画像ムラが発生し、寿命が短かった。また、グラフト共重合体を含有せず、フィラーとアクリル変性ポリオルガノシロキサンを含有する保護層塗工液は、分散安定性が悪く、得られた感光体は、画像特性と耐久性は共に劣っている。さらに、グラフト共重合体を含有せず、フィラーとアクリル変性ポリオルガノシロキサンと分散剤を含有する保護層用塗工液も分散安定性が依然十分ではないので、得られた感光体は、画像安定性と耐久性の両立ができない。これらに対し、実施例の保護層用塗工液は、分散安定性に優れ、得られた感光体は、高い摩耗性と持続的な画像安定性を両立することができる。

From the above evaluation results, when there was no protective layer, the amount of film scraping was large and the life was short. In addition, when only the filler is added to the protective layer, the wear resistance is improved, but the cleaning property is deteriorated, and the filming of a substance that seems to be a toner and a developer component occurs on the photosensitive member, resulting in image unevenness. did. Further, when only the acrylic-modified polyorganosiloxane was added to the protective layer, image unevenness due to abrasion occurred and the life was short, as in the case without the protective layer. Further, the protective layer coating liquid containing no graft copolymer and containing a filler and an acrylic-modified polyorganosiloxane has poor dispersion stability, and the obtained photoreceptor is inferior in both image characteristics and durability. Yes. Furthermore, since the dispersion stability of the coating solution for the protective layer, which does not contain a graft copolymer and contains a filler, an acrylic-modified polyorganosiloxane, and a dispersant, is still insufficient, the obtained photoreceptor has image stability. Compatibility and durability cannot be achieved. On the other hand, the protective layer coating liquids of the examples are excellent in dispersion stability, and the obtained photoreceptor can achieve both high wear resistance and continuous image stability.

It is a figure explaining the photosensitive layer or protective layer used by this invention. It is a figure explaining the abrasion mechanism of the photosensitive layer or protective layer containing a filler. It is a figure which shows an example of the laminated constitution of the photoreceptor of this invention. It is a figure which shows the other example of the laminated constitution of the photoreceptor of this invention. It is a figure which shows the other example of the laminated constitution of the photoreceptor of this invention. It is a figure which shows the other example of the laminated constitution of the photoreceptor of this invention. It is a figure which shows an example of the image forming apparatus of this invention. It is a figure which shows the other example of the image forming apparatus of this invention. It is a figure which shows an example of the process cartridge of this invention.

Explanation of symbols

10 Photosensitive layer (or protective layer)
DESCRIPTION OF SYMBOLS 11 Filler 12 Graft copolymer 13 Acrylic modified polyorganosiloxane 14 Binder resin 15 Toner 16 Photoconductor moving direction 21 Conductive support 22 Photosensitive layer 22a Charge generation layer 22b Charge transport layer 23 Protective layer

Claims (13)

In a photoreceptor having at least a photosensitive layer on a conductive support,
The photosensitive layer contains an acrylic modified polyorganosiloxane, a graft copolymer obtained by graft polymerization of a monomer having a polar group on a polycarbonate resin or polyarylate resin, and a filler. The photosensitive layer has a charge generation layer and a charge transport layer laminated,
The photoconductor according to claim 1, wherein the charge transport layer contains the acrylic-modified polyorganosiloxane, a graft copolymer, and a filler. In a photoreceptor in which at least a photosensitive layer and a protective layer are laminated on a conductive support,
The photoreceptor comprises an acrylic-modified polyorganosiloxane, a graft copolymer obtained by graft polymerization of a monomer having a polar group on a polycarbonate resin or polyarylate resin, and a filler.   The photoreceptor according to claim 3, wherein the photosensitive layer is formed by laminating a charge generation layer and a charge transport layer.   The photoconductor according to claim 3, wherein the protective layer further contains a charge transport material.   6. The photoreceptor according to claim 1, wherein the acrylic modified polyorganosiloxane is obtained by grafting an acrylic polymer to the polyorganosiloxane. The acrylic-modified polyorganosiloxane has a general formula

[Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y is a radical polymerizable functional group or a mercapto group or It is an organic group having a radical polymerizable functional group and a mercapto group, and Z ¹ and Z ² are each independently a hydrogen atom, a lower alkyl group or a general formula

(In the formula, R ⁴ and R ⁵ are each independently a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms. Or a halogenated hydrocarbon group, a radical polymerizable functional group, or a mercapto group or an organic group having a radical polymerizable functional group and a mercapto group.)
M is an integer of 1 or more and 10,000 or less, and n is an integer of 1 or more. ]
The polyorganosiloxane represented by the general formula

(In the formula, R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group, an alkyl group substituted with an alkoxy group, a cycloalkyl group, or an aryl group.)
Is obtained by emulsion graft polymerization of a mixture of 70% by weight or more and 100% by weight or less of an acrylic monomer and 0% by weight or more and 30% by weight or less of a monomer copolymerizable with the acrylic monomer,
7. The photoreceptor according to claim 6, wherein a weight ratio of the polyorganosiloxane to the mixture is 5/95 or more and 95/5 or less.   The photoconductor according to claim 1, wherein the filler is an inorganic filler.   The photoconductor according to claim 8, wherein the inorganic filler is a metal oxide.   The photoreceptor according to claim 9, wherein the metal oxide contains at least one of silicon oxide, titanium oxide, and alumina.   An image forming apparatus comprising at least the photosensitive member according to claim 1.   A process cartridge comprising at least the photosensitive member according to claim 1.   An image forming method, wherein an image is formed using the photosensitive member according to claim 1.

Images