JP2012133111A - Lubricant, image forming apparatus, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide lubricant that suppresses the occurrence of image blur despite repeated image formation in a high humidity environment using a photoreceptor having a protective layer formed on the surface thereof, which is crosslinked with a crosslinking resin containing a polymerizable compound having a charge transport structure, as well as an image forming apparatus, and a process cartridge.SOLUTION: Lubricant used by adding to a photoreceptor contains a lubricative material, and a compound represented by the general formula (I), wherein X and Y are each independently an aryl group optionally substituted by a substituent, and n and m are each independently 1 or 2.

Description

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

  In an image forming apparatus using an electrophotographic process, an image is formed on an organic photoreceptor through a charging process, an exposure process, a development process, and a transfer process. At this time, discharge products generated when the organic photoreceptor is charged and toner remaining without being transferred may exist in the organic photoreceptor. For this reason, after the transfer step, the organic photoreceptor is cleaned to remove discharge products and toner.

  When cleaning an organic photoreceptor, a cleaning blade is generally used because it is inexpensive, has a simple mechanism, and is excellent in cleaning properties.

  However, since the friction between the cleaning blade and the surface of the organic photoconductor is large, the cleaning blade is worn out or the surface of the organic photoconductor is worn out, so that the life of the cleaning blade and the organic photoconductor is shortened. is there.

  Therefore, Patent Document 1 discloses that a latent image on an electrophotographic photosensitive member is developed with a developer, a toner image visualized by development is transferred to a recording material, and toner remaining on the photosensitive member is removed with a cleaning blade. As an image forming method having a step of cleaning using an electrophotographic photosensitive member having a photosensitive layer and a protective layer on a conductive support, the surface of the electrophotographic photosensitive member was measured using an atomic force microscope. A configuration is disclosed in which the average surface roughness (Ra) in all directions is 1.5 nm or more and 0.1 μm or less, and image formation is performed while supplying a fatty acid metal salt to the surface of the electrophotographic photosensitive member.

  However, when an image is repeatedly formed in a high humidity environment, there is a problem that image blur occurs.

  Therefore, Patent Document 2 discloses that a fatty acid metal salt is used in combination with a hindered phenol compound or a hindered amine compound.

  However, when an image is repeatedly formed in a high humidity environment using a photoreceptor having a protective layer on which a crosslinkable resin containing a polymerizable compound having a charge transporting structure is crosslinked, image blurring occurs. There is a problem that occurs.

  In view of the problems of the prior art, the present invention uses a photoreceptor having a protective layer on the surface of which a crosslinkable resin containing a polymerizable compound having a charge transporting structure is crosslinked. An object of the present invention is to provide a lubricant, an image forming apparatus, and a process cartridge capable of suppressing the occurrence of image blur even when images are repeatedly formed.

  The invention according to claim 1 is a lubricant used by being applied to a photoconductor, wherein the lubricant and a general formula

（式中、Ｘ及びＹは、それぞれ独立に、置換基により置換されていてもよいアリール基であり、ｎ及びｍは、それぞれ独立に、１又は２である。）
で表される化合物を含むことを特徴とする。

(In the formula, X and Y are each independently an aryl group optionally substituted by a substituent, and n and m are each independently 1 or 2.)
It is characterized by including the compound represented by these.

  According to a second aspect of the present invention, in the lubricant according to the first aspect, the lubricating material includes a metal salt of a fatty acid.

  The invention according to claim 3 is the lubricant according to claim 2, wherein the fatty acid is at least one selected from the group consisting of stearic acid, palmitic acid, myristic acid and oleic acid, It is at least one selected from the group consisting of zinc, aluminum, calcium, magnesium, iron and lithium.

  Invention of Claim 4 is a lubricant as described in any one of Claims 1 thru | or 3. Content of the compound represented by the said General formula (1) is 0.1 to 40 mass% It is characterized by the following.

  The invention according to claim 5 is characterized in that the lubricant according to any one of claims 1 to 4 is solid.

  The invention according to claim 6 is formed on the photoconductor, a charging unit for charging the photoconductor, an exposure unit for exposing the charged photoconductor to form an electrostatic latent image, and the photoconductor. Developing means for developing the electrostatic latent image with toner to form a toner image, transfer means for transferring the toner image formed on the photoreceptor to a recording medium, and the toner image remaining on the photoreceptor An image forming apparatus having a cleaning blade for removing toner, further comprising a lubricant applying unit that applies the lubricant according to claim 1 to the photoconductor.

  According to a seventh aspect of the present invention, in the image forming apparatus according to the sixth aspect, the photosensitive member is formed with a protective layer on the surface of which a crosslinkable resin containing a polymerizable compound having a charge transporting structure is crosslinked. It is characterized by being.

  According to an eighth aspect of the present invention, in the image forming apparatus according to the sixth or seventh aspect, the charging unit includes a corona charger.

  According to a ninth aspect of the present invention, in the process cartridge, the photosensitive member, a cleaning blade for removing the toner remaining on the photosensitive member to which the toner image has been transferred, and the lubrication according to any one of the first to fifth aspects. A lubricant applying means for applying an agent to the photosensitive member is integrally supported and is detachable from the main body of the image forming apparatus.

  According to the present invention, an image is formed repeatedly in a high humidity environment using a photoconductor having a protective layer formed by crosslinking a crosslinkable resin containing a polymerizable compound having a charge transporting structure on the surface. However, it is possible to provide a lubricant, an image forming apparatus, and a process cartridge capable of suppressing the occurrence of image blur.

It is sectional drawing which shows an example of the layer structure of the photoreceptor to which the lubricant of this invention is provided. FIG. 6 is a cross-sectional view showing a modification of the layer configuration of the photoreceptor in FIG. 1. FIG. 5 is a cross-sectional view showing a modification of the layer configuration of the photoreceptor in FIG. 2. FIG. 4 is a cross-sectional view showing a modification of the layer configuration of the photoreceptor in FIG. 3. It is a figure which shows an example of the image forming apparatus of this invention. It is a figure which shows the cleaning brush and cleaning blade of FIG. 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.

  Next, the form for implementing this invention is demonstrated with drawing.

  The lubricant of the present invention is a lubricant used by being applied to a photoreceptor, and includes a lubricating substance and a compound represented by the general formula (1).

  When the lubricant of the present invention is applied to the surface of the photoconductor, friction between the cleaning blade and the surface of the photoconductor is reduced over a long period of time, and image blurring in a high humidity environment is suppressed. be able to.

  The lubricant of the present invention does not need to be solid, and can be applied to the surface of the photoreceptor even in liquid, powder, or semi-kneaded form.

  The lubricating substance is not particularly limited, and examples thereof include fatty acid metal salts, natural waxes such as carnauba wax, fluorine resins such as polytetrafluoroethylene, melamine cyanurate, and boron nitride. However, the lubricating substance is preferably a solid from the viewpoint of supply stability and ease of handling.

  Here, the lubricating substance preferably contains a metal salt of a fatty acid. Among the metal salts of fatty acids, the fatty acid is at least one selected from the group consisting of stearic acid, palmitic acid, myristic acid and oleic acid, and the metal is a group consisting of zinc, aluminum, calcium, magnesium, iron and lithium. It is preferable that it is 1 or more types selected more. Such a metal salt of a fatty acid has a linear alkyl group, so that slippage between layers is likely to occur, and the lubricity is excellent. Moreover, such a metal salt of a fatty acid is excellent in weather resistance.

  Such metal salts of fatty acids usually melt at 70 to 150 ° C. For this reason, a solid lubricant can be obtained by dissolving or dispersing the compound represented by the general formula (1) in a melted state of the fatty acid metal salt, and then pouring it into an arbitrary mold and cooling it. It is done.

  Although it does not specifically limit as a compound represented by General formula (1), In consideration of compatibility with a lubrication substance, the provision to a photoreceptor, and generation | occurrence | production of an image blur, Chemical formula (1-1)-(1- The compound represented by 5) is preferred.

本発明の潤滑剤中の一般式（１）で表される化合物の含有量は、０．１〜４０質量％であることが好ましく、１〜３０質量％がさらに好ましい。本発明の潤滑剤中の一般式（１）で表される化合物の含有量が０．１質量％未満であると、高湿環境下で繰り返し画像を形成すると、画像ボケが発生することがあり、４０質量％を超えると、潤滑剤中の湿潤性物質の含有量が不足して、クリーニングブレードと感光体の表面との間の摩擦が大きくなって、クリーニングブレード及び感光体の寿命が短くなることがある。

The content of the compound represented by the general formula (1) in the lubricant of the present invention is preferably 0.1 to 40% by mass, and more preferably 1 to 30% by mass. When the content of the compound represented by the general formula (1) in the lubricant of the present invention is less than 0.1% by mass, image blur may occur when images are formed repeatedly in a high humidity environment. If the amount exceeds 40% by mass, the content of the wettable substance in the lubricant is insufficient, the friction between the cleaning blade and the surface of the photoreceptor increases, and the life of the cleaning blade and the photoreceptor is shortened. Sometimes.

  Hereinafter, the photoreceptor to which the lubricant of the present invention is applied will be described in detail.

  The photosensitive member is not particularly limited as long as a photosensitive layer is formed on a conductive support. However, the photosensitive member has optical characteristics such as a wide light absorption wavelength range and a large amount of absorption, high sensitivity, and stable charging characteristics. From the viewpoints of electrical characteristics such as the above, wide selection range of materials, ease of production, and low cost, an organic photoreceptor is preferred. Among these, from the viewpoint of wear resistance, an organic photoreceptor having a protective layer formed on the surface is preferable.

  FIG. 1 shows an example of the layer structure of a photoreceptor to which the lubricant of the present invention is applied. In the photoreceptor 10 </ b> A, a photosensitive layer 12 is formed on a conductive support 11. At this time, an undercoat layer may be formed between the conductive support 11 and the photosensitive layer 12, or a protective layer may be formed on the photosensitive layer 12.

  FIG. 2 shows another example of the layer structure of the photoreceptor to which the lubricant of the present invention is applied. The photoconductor 10B has the same configuration as the photoconductor 10A except that the photoconductive layer 12 in which the charge generation layer 12a and the charge transport layer 12b are sequentially stacked is formed. At this time, the order in which the charge generation layer 12a and the charge transport layer 12b are stacked may be reversed.

  FIG. 3 shows another example of the layer structure of the photoreceptor to which the lubricant of the present invention is applied. The photoconductor 10C has the same configuration as the photoconductor 10B, except that the undercoat layer 13 is formed between the conductive support 11 and the charge generation layer 12a.

  FIG. 4 shows another example of the layer structure of the photoreceptor to which the lubricant of the present invention is applied. The photoconductor 10D has the same configuration as the photoconductor 10C except that the protective layer 14 is formed on the charge transport layer 12b.

  The protective layer 14 (see FIG. 4) can be formed by crosslinking a crosslinkable resin.

  Although it does not specifically limit as a crosslinkable resin, The precursor of a urethane resin, a silicone resin, a phenol resin, an epoxy resin, an acrylic resin etc. are mentioned. Among these, from the viewpoint of electrostatic properties, the crosslinkable resin preferably contains a polymerizable compound having a charge transporting structure. For example, as the crosslinkable resin, the protective layer 14 containing a urethane resin is formed by crosslinking a charge transport material having a hydroxyl group and a compound having an isocyanate group.

  Although it does not specifically limit as a charge transport material which has a hydroxyl group, The compound represented by Chemical formula (2-1)-(2-18) is mentioned.

水酸基を有する電荷輸送性物質は、例えば、特許第３５４００５６号公報等に開示されている合成方法を用いて合成することができる。

The charge transporting substance having a hydroxyl group can be synthesized using, for example, a synthesis method disclosed in Japanese Patent No. 3540056.

  The crosslinkable resin preferably contains a trifunctional or higher functional radical polymerizable compound having no charge transport structure and a monofunctional radical polymerizable compound having a charge transport structure from the viewpoint of wear resistance and electrostatic characteristics. .

  If a charge transport material is used instead of a monofunctional radically polymerizable compound having a charge transport structure, the charge transport material may precipitate or become cloudy, resulting in a decrease in wear resistance or a decrease in electrostatic characteristics. Sometimes.

  In addition, if a bifunctional or higher functional radical polymerizable compound having a charge transport structure is used instead of a monofunctional radical polymerizable compound having a charge transport structure, the charge transport structure is bulky, so that the protective layer 14 is distorted. May occur, the internal stress may increase, cracks or scratches may occur due to carrier adhesion, or the electrostatic characteristics may deteriorate.

  A trifunctional or higher functional radical polymerizable compound having no charge transporting property is a hole transporting structure such as triarylamine, hydrazone, pyrazoline, carbazole, or an electron such as condensed polycyclic quinone, diphenoquinone, cyano group, nitro group, etc. It means a compound that does not have an electron transporting structure such as an aromatic ring substituted by an attractive group and has three or more radically polymerizable groups. The radical polymerizable group means a group having a carbon-carbon double bond and capable of radical polymerization. In addition, the 3 or more radically polymerizable group which the trifunctional or more radically polymerizable compound which does not have charge transportability may have may be the same, or may differ.

  Although it does not specifically limit as a radically polymerizable group, 1-substituted ethylene group, 1, 1-substituted ethylene group, etc. are mentioned.

As the 1-substituted ethylene functional group, the general formula CH ₂ ═CH—X ₁ —
Wherein X ₁ is an arylene group which may be substituted with a substituent, an alkenylene group which may be substituted with a substituent, a carbonyl group, a carbonyloxy group, a general formula —CON (R ₁ ) —
(In the formula, R ₁ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group.)
Or a thio group. )
The group represented by these is mentioned.

Examples of the arylene group for X ₁ include a phenylene group and a naphthylene group. In addition, examples of the alkenylene group in X ₁ include a vinylene group.

Examples of the alkyl group for R ₁ include a methyl group and an ethyl group. Moreover, examples of the aralkyl group in R ₁ include a benzyl group, a naphthylmethyl group, and a phenethyl group. Furthermore, examples of the aryl group in R ₁ include a phenyl group and a naphthyl group.

  Specific examples of the 1-substituted ethylene functional group include vinyl group, styryl group, 2-methyl-1,3-butadienyl group, vinylcarbonyl group, acryloyloxy group, acryloylamide group, vinylthio group and the like.

As the 1,1-substituted ethylene group, the general formula CH ₂ ═C (Y) —X ₂ —
Wherein X ₂ is a group, a single bond or an alkylene group described in X ₁ above, and Y is an alkyl group which may be substituted with a substituent, or may be substituted with a substituent. Aralkyl group, aryl group optionally substituted by a substituent, halogen group, cyano group, nitro group, alkoxy group, general formula -COOR ₂
(In the formula, R ₂ represents a hydrogen atom, an alkyl group which may be substituted with a substituent, an aralkyl group which may be substituted with a substituent, or an aryl group which may be substituted with a substituent. .)
Or a group represented by the general formula -CONR ₃ R ₄
(R ₃ and R ₄ may each independently be a hydrogen atom, an alkyl group that may be substituted with a substituent, an aralkyl group that may be substituted with a substituent, or a substituent. An aryl group.)
It is group represented by these. )
It is group represented by these. However, Y is either a cyano group or an aryl group, a X ₂ is a carbonyl group, an alkenylene group or an arylene group. )
The group represented by these is mentioned.

Examples of the alkyl group for Y, R ₂ , R ₃ and R ₄ include a methyl group and an ethyl group. Examples of the aralkyl group in Y, R ₂ , R ₃ and R ₄ include a benzyl group, a naphthylmethyl group, a phenethyl group and the like. Furthermore, examples of the aryl group in Y, R ₂ , R ₃ and R ₄ include a phenyl group and a naphthyl group. Further, examples of the alkoxy group for Y include a methoxy group and an ethoxy group.

  Specific examples of the 1,1-substituted ethylene group include an α-chloroacryloyloxy group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, and an α-cyanoethylenephenylene group.

In addition, as a substituent in X ₁ , X ₂ , Y, R ₂ , R ₃ and R _4, an alkyl group such as a halogen group, a nitro group, a cyano group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, etc. Examples thereof include aryloxy groups such as alkoxy groups and phenoxy groups, aryl groups such as phenyl groups and naphthyl groups, and aralkyl groups such as benzyl groups and phenethyl groups.

  The trifunctional or higher functional radical polymerizable compound having no charge transporting property preferably has an acryloyloxy group and / or a methacryloyloxy group.

  A compound having 3 or more acryloyloxy groups and not having a charge transporting property is obtained by esterifying or transesterifying a compound having 3 or more hydroxyl groups with acrylic acid (salt), acrylic acid halide, and acrylic acid ester. It can be synthesized by reacting. A compound having three or more methacryloyloxy groups and having no charge transporting property can be synthesized in the same manner.

  Although it does not specifically limit as a trifunctional or more radically polymerizable compound which does not have charge transport property, A trimethylol propane triacrylate (TMPTA), a trimethylol propane trimethacrylate, EO modified | denatured trimethylol propane triacrylate, PO modified | denatured trimethylol Propane triacrylate, caprolactone modified trimethylolpropane triacrylate, HPA modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH modified glycerol triacrylate, EO modified glycerol triacrylate, PO Modified glycerol triacrylate, tris (acryloxyethyl) isocyanurate Dipentaerythritol hexaacrylate (DPHA), caprolactone modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl modified dipentaerythritol pentaacrylate, alkyl modified dipentaerythritol tetraacrylate, alkyl modified dipentaerythritol triacrylate, dimethylol Examples include propanetetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, EO-modified phosphoric acid triacrylate, 2,2,5,5, -tetrahydroxymethylcyclopentanone tetraacrylate, and two or more of them may be used in combination. .

  The EO modification and PO modification mean ethyleneoxy modification and propyleneoxy modification, respectively.

  The trifunctional or higher functional radical polymerizable compound having no charge transporting property preferably has a molecular weight ratio of 250 or less to the number of radical polymerizable groups. Further, when the ratio of the molecular weight to the number of radical polymerizable groups exceeds 250, the wear resistance may be lowered.

  The content of the trifunctional or higher functional radical polymerizable compound having no charge transport property in the protective layer 14 is usually 20 to 80% by mass, and preferably 35 to 65% by mass. When the content of the trifunctional or higher functional radical polymerizable compound having no charge transporting property in the protective layer 14 is less than 20% by mass, the wear resistance may be deteriorated. The content of the monofunctional radically polymerizable compound having a charge transport structure in the layer 14 may be lowered, and the electrostatic characteristics may be lowered.

  A monofunctional radically polymerizable compound having a charge transporting structure is a hole transporting structure such as triarylamine, hydrazone, pyrazoline or carbazole, or an electron such as condensed polycyclic quinone, diphenoquinone, cyano group or nitro group. It means a compound having an electron transport structure such as an aromatic ring having an attractive group and one radical polymerizable group. The radical polymerizable group is the same as the radical polymerizable group of a tri- or higher functional radical polymerizable compound having no charge transporting property, and is preferably an acryloyloxy group or a methacryloyloxy group.

  The monofunctional radically polymerizable compound having a charge transporting structure preferably has a triarylamine structure from the viewpoint of electrostatic properties.

（式中、Ｒ_１は、水素原子、ハロゲン基、置換基により置換されていてもよいアルキル基、置換基により置換されていてもよいアラルキル基、置換基により置換されていてもよいアリール基、シアノ基、ニトロ基、アルコキシ基、一般式
−ＣＯＯＲ_２
（式中、Ｒ_２は、水素原子、置換基により置換されていてもよいアルキル基、置換基により置換されていてもよいアラルキル基又は置換基により置換されていてもよいアリール基である。）
で表される基、ハロカルボニル基、又は、一般式
−ＣＯＮＲ_３Ｒ_４
（式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子、ハロゲン基、置換基により置換されていてもよいアルキル基、置換基により置換されていてもよいアラルキル基又は置換基により置換されていてもよいアリール基である。）
で表される基であり、Ａｒ_１は、置換基により置換されていてもよい二価の芳香族基であり、Ａｒ_２及びＡｒ_３は、それぞれ独立に、置換基により置換されていてもよい一価の芳香族基であり、Ｘは、単結合又は一般式
−Ｙ−Ａｒ_４−
（式中、Ｙは、単結合、置換基により置換されていてもよいアルキレン基、置換基により置換されていてもよいシクロアルキレン基、置換基により置換されていてもよいアルキレンオキシ基、オキシ基、チオ基又はビニレン基であり、Ａｒ_４は、置換基により置換されていてもよい二価の芳香族基である。）
で表される基であり、Ｚは、置換基により置換されていてもよいアルキレン基、置換基により置換されていてもよいアルキレンオキシ基、アルキレンオキシカルボニル基であり、ｎは、０〜３の整数である。）
で表される化合物がさらに好ましい。

(In the formula, R ₁ represents a hydrogen atom, a halogen group, an alkyl group which may be substituted with a substituent, an aralkyl group which may be substituted with a substituent, an aryl group which may be substituted with a substituent, Cyano group, nitro group, alkoxy group, general formula -COOR ₂
(In the formula, R ₂ represents a hydrogen atom, an alkyl group which may be substituted with a substituent, an aralkyl group which may be substituted with a substituent, or an aryl group which may be substituted with a substituent.)
Or a halocarbonyl group represented by the general formula —CONR ₃ R ₄
(Wherein R ₃ and R ₄ are each independently substituted with a hydrogen atom, a halogen group, an alkyl group optionally substituted with a substituent, an aralkyl group optionally substituted with a substituent, or a substituent. An aryl group that may be present.)
Ar ₁ is a divalent aromatic group that may be substituted with a substituent, and Ar ₂ and Ar ₃ may each independently be substituted with a substituent. A monovalent aromatic group, X is a single bond or a general formula —Y—Ar ₄ —.
Wherein Y is a single bond, an alkylene group which may be substituted with a substituent, a cycloalkylene group which may be substituted with a substituent, an alkyleneoxy group which may be substituted with a substituent, or an oxy group. , A thio group or a vinylene group, and Ar ₄ is a divalent aromatic group which may be substituted with a substituent.)
Z is an alkylene group which may be substituted with a substituent, an alkyleneoxy group which may be substituted with a substituent, or an alkyleneoxycarbonyl group, and n is 0-3. It is an integer. )
Is more preferable.

Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, and a butyl group. Further, examples of the aralkyl group in R ₁ include a benzyl group, a phenethyl group, and a naphthylmethyl group. Furthermore, examples of the aryl group in R ₁ include a phenyl group and a naphthyl group. Examples of the alkoxy group for R ₁ include a methoxy group, an ethoxy group, and a propoxy group.

Examples of the substituent in R ₁ include halogen groups, nitro groups, cyano groups, alkyl groups such as methyl groups and ethyl groups, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, phenyl groups and naphthyl groups. And aryl groups such as benzyl group and phenethyl group.

R ₁ is preferably a hydrogen atom or a methyl group.

Examples of the monovalent aromatic group in Ar ₂ and Ar ₃ include a monovalent condensed polycyclic hydrocarbon group, a monovalent non-condensed cyclic hydrocarbon group, and a monovalent heterocyclic group.

  The monovalent condensed polycyclic hydrocarbon group includes a pentanyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group, an s-indacenyl group, a fluorenyl group, an acenaphthylenyl group, and a preadenyl group. Acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylyl group, pyrenyl group, chrysenyl group, naphthacenyl group and the like. The monovalent condensed polycyclic hydrocarbon group preferably has 18 or less carbon atoms constituting the ring.

  Monovalent non-condensed cyclic hydrocarbon groups include groups derived from monocyclic hydrocarbon compounds such as benzene, diphenyl ether, polyethylene diphenyl ether, diphenyl thioether, diphenyl sulfone, biphenyl, polyphenyl, diphenylalkane, diphenylalkene, diphenylalkyne. , Groups derived from non-condensed polycyclic hydrocarbon compounds such as triphenylmethane, distyrylbenzene, 1,1-diphenylcycloalkane, polyphenylalkane and polyphenylalkene, and ring-assembled hydrocarbons such as 9,9-diphenylfluorene Examples include groups derived from compounds.

  Examples of the heterocyclic group include groups derived from heterocyclic aromatic compounds such as carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.

The substituents for Ar ₂ and Ar ₃ are shown below.

[1] Halogen atom, cyano group, nitro group [2] Alkyl group The carbon number of the alkyl group is usually 1 to 12, preferably 1 to 8, and more preferably 1 to 4. The alkyl group is a fluoro group, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It may be substituted with a substituted phenyl group.

  As the alkyl group, methyl group, ethyl group, n-butyl group, isopropyl group, t-butyl group, s-butyl group, n-propyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-ethoxyethyl group 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-phenylbenzyl group and the like.

[3] Alkoxy group The alkyl group in the alkoxy group is the same as the alkyl group in [2].

  Alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, n-butoxy, s-butoxy, isobutoxy, 2-hydroxyethoxy, benzyloxy, trifluoro A methoxy group etc. are mentioned.

[4] Aryloxy group Examples of the aryl group in the aryloxy group include a phenyl group and a naphthyl group. The aryloxy group may be substituted by an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a halogen group.

  Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.

[5] Alkyl mercapto group or aryl mercapto group Examples of the alkyl mercapto group include a methylthio group and an ethylthio group. Examples of the aryl mercapto group include a phenylthio group and a p-methylphenylthio group.

[6] Amino group optionally substituted by a substituent The amino group optionally substituted by a substituent has the general formula —NR ₁ R _2.
[Wherein, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group or an aryl group in [2], and R ₁ and R ₂ may jointly form a ring. ]
It is represented by

Examples of the aryl group in R ₁ and R ₂ include a phenyl group, a biphenyl group, and a naphthyl group. The aryl group is an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a halogen group. May be substituted.

  Examples of the amino group optionally substituted by a substituent include an amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-ditolylamino group, dibenzylamino group, Examples include a piperidino group, a morpholino group, a pyrrolidino group, and the like.

[7] Alkylenedioxy group or alkylenedithio group Examples of the alkylenedioxy group include a methylenedioxy group. Examples of the alkylenedithio group include a methylenedithio group.

[8] Others Examples include a styryl group that may be substituted with a substituent, a β-phenylstyryl group that may be substituted with a substituent, a diphenylaminophenyl group, a ditolylaminophenyl group, and the like.

Examples of the divalent aromatic group in Ar ₁ and Ar ₄ include a group derived from a monovalent aromatic group in Ar ₂ and Ar ₃ .

  Carbon number of the alkylene group in Y is 1-12 normally, 1-8 are preferable and 1-4 are more preferable. The alkylene group is a fluoro group, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It may be substituted with a substituted phenyl group.

  Examples of the alkylene group include methylene group, ethylene group, n-butylene group, isopropylene group, t-butylene group, s-butylene group, n-propylene group, trifluoromethylene group, 2-hydroxyethylene group, and 2-ethoxyethylene. Group, 2-cyanoethylene group, 2-methoxyethylene group, benzylidene group, phenylethylene group, 4-chlorophenylethylene group, 4-methylphenylethylene group, 4-biphenylethylene group and the like.

  Carbon number of the cycloalkylene group in Y is 5-7 normally. The cycloalkylene group may be substituted with a fluoro group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

  Examples of the cycloalkylene group include a cyclohexylidene group, a cyclohexylene group, and a 3,3-dimethylcyclohexylidene group.

The alkyleneoxy group for Y is represented by the chemical formula —CH ₂ CH ₂ O—.
A group represented by the formula: —CH ₂ CH ₂ CH ₂ O—
A group represented by the general formula _{- (OCH 2 CH 2) n} O-
(In the formula, n is an integer of 1 to 4.)
A group represented by the formula:-(OCH ₂ CH ₂ CH ₂ ) _m O-
(In the formula, m is an integer of 1 to 4.)
The group etc. which are represented by these are mentioned.

  The alkyleneoxy group may be substituted with a substituent such as a hydroxyl group, a methyl group, or an ethyl group.

As the vinylene group for Y, the general formula — (C (R ₁ ) ═CH) _n —
(In the formula, R ₁ represents a hydrogen atom, an alkyl group (similar to the alkyl group in the above [2]), or a divalent aromatic group (the divalent aromatic group in Ar ₂ and Ar ₃ described above). And n is 1 or 2.)
A group represented by the formula: —C (R ₂ ) ═CH— (CH═CH) _m —
(In the formula, R ₂ represents a hydrogen atom, an alkyl group (similar to the alkyl group in the above [2]), or a divalent aromatic group (the divalent aromatic group in Ar ₂ and Ar ₃ described above). And m is an integer of 1 to 3.)
The group etc. which are represented by these are mentioned.

  The alkylene group for Z is the same as the alkylene group for Y.

  The alkyleneoxy group in Z is the same as the alkyleneoxy group in Y.

  Examples of the alkyleneoxycarbonyl group for Z include a caprolactone-modified group.

  A monofunctional radically polymerizable compound having a charge transporting structure has a general formula

（式中、Ｒ_１は、水素原子又はメチル基であり、Ｒ_２及びＲ_３は、それぞれ独立に、置換基により置換されていてもよい炭素数１〜６のアルキル基であり、Ｚは、単結合、メチレン基、エチレン基、化学式
−ＣＨ_２ＣＨ_２Ｏ−
で表される基、化学式
−ＣＨ（ＣＨ_３）ＣＨ_２Ｏ−
で表される基、又は、化学式

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 6 carbon atoms which may be substituted with a substituent, and Z is Single bond, methylene group, ethylene group, chemical formula -CH ₂ CH ₂ O-
A group represented by the formula: —CH (CH ₃ ) CH ₂ O—
Or a group represented by the chemical formula

で表される基であり、ｏ、ｐ及びｑは、それぞれ独立に、０又は１であり、ｓ及びｔは、それぞれ独立に、０〜３の整数である。）
で表される化合物であることが好ましい。

O, p, and q are each independently 0 or 1, and s and t are each independently an integer of 0 to 3. )
It is preferable that it is a compound represented by these.

R ₂ and R ₃ are preferably each independently a methyl group or an ethyl group.

  The content of the monofunctional radically polymerizable compound having a charge transporting structure in the protective layer 14 is usually 20 to 80% by mass, and preferably 35 to 65% by mass. When the content of the monofunctional radically polymerizable compound having a charge transporting structure in the protective layer 14 is less than 20% by mass, the electrostatic properties may be deteriorated. The content of the trifunctional or higher functional radical polymerizable compound having no structure may be lowered, and the wear resistance may be lowered.

  The crosslinkable resin may further contain a monofunctional radically polymerizable compound having no charge transporting structure, a bifunctional radically polymerizable compound having no charge transporting structure, and / or a radically polymerizable oligomer. .

  Examples of the monofunctional radical polymerizable compound having no charge transport structure include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxy Examples include butyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, and styrene monomer.

  Examples of the bifunctional radically polymerizable compound having no charge transporting structure include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexane. Examples include diol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, and neopentyl glycol diacrylate.

  Examples of the radical polymerizable oligomer include epoxy acrylate oligomer, urethane acrylate oligomer, polyester acrylate oligomer and the like.

  The addition amount of the monofunctional radically polymerizable compound having no charge transporting structure, the bifunctional radically polymerizable compound having no charge transporting structure and the radically polymerizable oligomer is usually from the point of wear resistance. It is 50 mass% or less with respect to the trifunctional or more radically polymerizable compound which does not have a charge transport structure, and 30 mass% or less is preferable.

  When crosslinking a crosslinkable resin containing a trifunctional or higher functional radical polymerizable compound having no charge transport structure and a monofunctional radical polymerizable compound having a charge transport structure, a polymerization initiator may be used.

  Examples of the thermal polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di ( Peroxybenzoyl) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, peroxide initiators such as lauroyl peroxide, azobisisobutylnitrile, azobiscyclohexanecarbonitrile Azo initiators such as methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, 4,4′-azobis-4-cyanovaleric acid, and the like may be used in combination.

  Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Acetophenone-based or ketal-based photopolymerization initiators such as methyl-2-morpholino (4-methylthiophenyl) propan-1-one and 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, Benzoin ether photopolymerization initiators such as benzoin isopropyl ether, benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, 1 Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene, thioxanthone photopolymerization such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone An initiator etc. are mentioned, You may use 2 or more types together. Other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, and bis (2,4,6-trimethylbenzoyl) phenyl. Examples include phosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compound, triazine compound, imidazole compound, and the like. It is done.

  A compound having a photopolymerization-promoting effect when a crosslinkable resin containing a trifunctional or higher functional radical polymerizable compound having no charge transport structure and a monofunctional radical polymerizable compound having a charge transport structure is crosslinked. Can be used alone or in combination with a photopolymerization initiator.

  Examples of the compound having an effect of promoting photopolymerization include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylamino. Examples include benzophenone.

  The addition amount of a polymerization initiator is 0.5-40 mass% with respect to crosslinkable resin, and 1-20 mass% is preferable.

  The protective layer 14 may further contain a binder resin that does not have crosslinkability without crosslinking the crosslinkable resin. Binder resins include polycarbonate, polyester, methacrylic resin, acrylic resin, polyethylene, polyvinyl chloride, polyvinyl acetate, polystyrene, polyvinylidene chloride, silicone resin, polyvinyl carbazole, polyvinyl butyral, polyvinyl formal, polyacrylate, polyacrylamide, phenoxy Resins etc. are mentioned, and two or more kinds may be used in combination.

  The protective layer 14 can be formed by applying a coating solution containing a crosslinkable resin. The coating liquid may further contain a plasticizer, a leveling agent, a charge transport material, and the like.

  Examples of the plasticizer include dibutyl phthalate and dioctyl phthalate.

  The addition amount of the plasticizer is usually 20% by mass or less and preferably 10% by mass or less with respect to the solid content of the coating solution.

  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 addition amount of the leveling agent is usually 3% by mass or less with respect to the solid content of the coating solution.

  The coating liquid may further contain a solvent.

  Solvents include alcohol solvents such as methanol, ethanol, propanol and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran, dioxane and propyl ether. Solvent, halogen solvent such as dichloromethane, dichloroethane, trichloroethane, chlorobenzene, aromatic solvent such as benzene, toluene, xylene, cellosolve solvent such as methyl cellosolve, ethyl cellosolve, cellosolve acetate, etc. May be.

  Examples of the method for applying the coating solution include a dip coating method, a spray coating method, a bead coating method, and a ring coating method.

  When crosslinking the crosslinkable resin, it is preferable to irradiate light. As the light source, a light source that emits ultraviolet light such as a high-pressure mercury lamp or a metal halide lamp can be used, but a light source that emits visible light can also be used. Moreover, it is preferable that the temperature of the surface of the coating film containing a crosslinkable resin at the time of irradiating light is 20-170 degreeC. It is preferable to control the surface temperature of the coating film using a heat medium.

  Next, a compound having three acryloyloxy groups is used as a trifunctional or higher functional radical polymerizable compound having no charge transport structure, and an acryloyloxy group is used as a monofunctional radical polymerizable compound having a charge transport structure. An example of a method for forming the protective layer 14 in the case of using a triarylamine compound having one of the above.

  The mass ratio of the triarylamine compound having one acryloyloxy group to the compound having three acryloyloxy groups is usually 3/7 to 7/3. In addition, 3 to 20% of the polymerization initiator is added to the total mass of the compound having three acryloyloxy groups and the triarylamine compound having one acryloyloxy group, and a solvent is added to the coating solution. To prepare.

  In the charge transport layer 12b on which the protective layer 14 is formed, a triarylamine-based donor is used as the charge transport material, and polycarbonate is used as the binder resin. Examples of the liquid solvent include tetrahydrofuran, 2-butanone, and ethyl acetate. Moreover, the addition amount of a solvent is 3 to 10 times with respect to the total mass of the compound which has three acryloyloxy groups, and the triarylamine compound which has one acryloyloxy group.

  After sequentially laminating the undercoat layer 13, the charge generation layer 12a, and the charge transport layer 12b on the conductive support 11 such as an aluminum cylinder, a coating solution is applied using a spray coating method, and after touch drying, Irradiate light to crosslink the crosslinkable resin.

When irradiating ultraviolet light using a metal halide lamp, the illuminance is preferably 50 to 1000 mW / cm ² . For example, when the illuminance is 700 mW / cm ² , ultraviolet light is uniformly applied to all surfaces for about 2 minutes while rotating the drum. At this time, a heat medium is used to control the surface temperature of the coating film so as not to increase. After crosslinking the crosslinkable resin, in order to reduce the solvent remaining in the coating film, the photosensitive member 10D is obtained by heating at 100 to 150 ° C. for 10 to 30 minutes.

  In order to promote the crosslinking of the crosslinked resin, it is preferable to lower the oxygen concentration in the atmosphere when heating or irradiating with ultraviolet light. Thereby, since inhibition of radical polymerization by oxygen can be reduced, the protective layer 14 having a high crosslinking density can be formed.

  In addition, it is also effective to apply a coating solution using a spray coating method or to dry it by touching in an atmosphere in which the oxygen concentration is reduced by substitution with nitrogen.

  The thickness of the protective layer 14 is usually 1 to 30 μm, preferably 2 to 20 μm, and more preferably 4 to 15 μm. When the thickness of the protective layer 14 is less than 1 μm, the wear resistance may be lowered, and when it exceeds 30 μm, the electrostatic characteristics may be lowered.

  The protective layer 14 preferably further contains a filler. Thereby, abrasion resistance can be improved. Furthermore, since fine irregularities are formed on the surface of the protective layer 14, the lubricant is easily applied to the photoconductor 10.

  Although it does not specifically limit as a material which comprises an organic filler, Fluorine resin, such as polytetrafluoroethylene, silicone resin, amorphous carbon, etc. are mentioned, You may use 2 or more types together.

  The material constituting the inorganic filler is not particularly limited, but may be a metal such as copper, tin, aluminum, or indium, silicon oxide, tin oxide, aluminum oxide, zinc oxide, titanium oxide, indium oxide, antimony oxide, bismuth oxide, or the like. A metal oxide, potassium titanate, etc. are mentioned, You may use 2 or more types together.

  The filler is preferably an inorganic filler from the viewpoint of hardness, and the material constituting the filler is preferably a metal oxide from the viewpoint of electrostatic characteristics, and more preferably silicon oxide, aluminum oxide, or titanium oxide. At this time, colloidal silica, colloidal alumina, or the like can be used as the inorganic filler.

  The average primary particle size of the filler is preferably 0.01 to 0.5 μm. When the average primary particle size of the filler is less than 0.01 μm, the wear resistance may be lowered, and when it exceeds 0.5 μm, the light transmittance of the protective layer 14 may be lowered.

  Content of the filler in the protective layer 14 is 5-50 mass% normally, and 5-30 mass% is preferable. If the content of the filler in the protective layer 14 is less than 5% by mass, the wear resistance may be reduced. If the content exceeds 30% by mass, the electrostatic characteristics may be reduced or the light transmitted through the protective layer 14 may be reduced. The rate may decrease.

  The filler may be surface-treated with a surface treatment agent. Thereby, the dispersibility of the filler in the protective layer 14 can be improved.

  Although it does not specifically limit as a surface treating agent, Titanate coupling agent, aluminum coupling agent, zircoaluminate coupling agent, higher fatty acid, aluminum oxide, titanium dioxide, zirconium dioxide, silicone resin, aluminum stearate, etc. And two or more of them may be used in combination. Further, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, a higher fatty acid, and a silane coupling agent may be used in combination.

  The amount surface-treated with the surface treatment agent is usually 3 to 30% by mass, preferably 5 to 20% by mass, based on the filler. When the amount of the surface treatment with the surface treatment agent is less than 3% by mass with respect to the filler, the dispersibility of the filler in the protective layer 14 may not be improved, and when it exceeds 30% by mass. In some cases, electrostatic characteristics may deteriorate.

  The charge generation layer 12a (see FIGS. 2 to 4) includes a charge generation material and may further include a binder resin.

  The charge generation material is not particularly limited, but inorganic materials such as crystalline selenium, amorphous selenium, selenium-tellurium compound, selenium-tellurium-halogen compound, selenium-arsenic compound, phthalocyanine pigments such as metal phthalocyanine, metal-free phthalocyanine, Azulhenium salt pigment, squalic acid methine pigment, azo pigment having carbazole skeleton, azo pigment having triphenylamine skeleton, azo pigment having diphenylamine skeleton, azo pigment having dibenzothiophene skeleton, azo pigment having fluorenone skeleton, oxadi Azo pigment having azole skeleton, azo pigment having bis stilbene skeleton, azo pigment having distyryl oxadiazole skeleton, azo pigment having distyryl carbazole skeleton, perylene pigment, anthraquinone or polycyclic Non-based pigments, quinone imine pigments, diphenylmethane or triphenylmethane pigments, benzoquinone or naphthoquinone pigments, cyanine and azomethine pigments, indigoid pigments, bisbenzimidazole pigments, and the like may be used in combination. .

  The binder resin contained in the charge generation layer 12a is not particularly limited, but polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly (N-vinyl). Carbazole), polyacrylamide and the like, and two or more of them may be used in combination.

  The charge generation layer 12a may further contain a charge transport material. The charge generation layer 12a may further contain a polymer charge transport material.

  Methods for forming the charge generation layer 12a include glow discharge polymerization, vacuum deposition, CVD, sputtering, reactive sputtering, ion plating, accelerated ion injection, and other vacuum thin film fabrication methods, dip coating, and the like. And casting methods such as spray coating and bead coating.

  Solvents contained in the coating solution used when forming the charge generation layer 12a using the casting method include acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, dichloroethane, dichloropropane, Examples include trichloroethane, trichlorethylene, tetrachloroethane, tetrahydrofuran, dioxolane, dioxane, methanol, ethanol, isopropyl alcohol, butanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve, ethyl cellosolve, propyl cellosolve, etc. Also good. Among these, tetrahydrofuran, methyl ethyl ketone, dichloromethane, methanol, and ethanol having a boiling point of 40 to 80 ° C. are preferable from the viewpoint of the drying property of the coating film.

  The coating solution can be prepared by dissolving or dispersing the charge generation material in a solvent.

  Examples of the method for dissolving or dispersing the charge generating substance in the solvent include a method using a dispersion medium such as a ball mill, a bead mill, a sand mill, and a vibration mill, and a high-speed liquid collision dispersion method.

  The thickness of the charge generation layer 12a is usually 0.01 to 5 μm, and preferably 0.05 to 2 μm.

  The charge transport layer 12b (see FIGS. 2 to 4) includes a charge transport material and a binder resin.

  As hole transport materials, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyrylanthracene), 1,1-bis- (4-dibenzylaminophenyl) propane, styryl Anthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, etc. may be mentioned, and two or more may be used in combination .

The polymer charge transport materials are shown below.
(A) Polymer having carbazole ring For example, poly-N-vinylcarbazole, JP-A-50-82056, JP-A-54-9632, JP-A-54-11737, JP-A-4-175337 And the compounds described in JP-A-4-183719 and JP-A-6-234841.
(B) Polymer having a hydrazone structure For example, JP-A-57-78402, JP-A-61-20953, JP-A-61-296358, JP-A-1-134456, JP-A-1-134456 179164, JP-A-3-180851, JP-A-3-180852, JP-A-3-50555, JP-A-5-310904, JP-A-6-234840, and the like. Is done.
(C) Polysilylene polymer For example, JP-A-63-285552, JP-A-1-88461, JP-A-4-264130, JP-A-4-264131, JP-A-4-264132, Examples thereof include compounds described in Kaihei 4-264133 and JP-A-4-289867.
(D) Polymer having a triarylamine structure For example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-134457, JP-A-2-282264, JP-A-2- Examples include compounds described in JP-A-304456, JP-A-4-133605, JP-A-4-133066, JP-A-5-40350, and JP-A-5-202135.
(E) Other polymers For example, formaldehyde condensation polymer of nitropyrene, JP-A-51-73888, JP-A-56-150749, JP-A-6-234836, JP-A-6-234837 The described compounds and the like are exemplified.

  Examples of other polymer charge transport materials include polycarbonate having a triarylamine structure, polyurethane having a triarylamine structure, polyester having a triarylamine structure, and a polyether having a triarylamine structure.

  Examples of such a polymer charge transporting material include JP-A 64-1728, JP-A 64-13061, JP-A 64-19049, JP-A-4-11627, JP-A 4-116627. JP 2225014, JP 4-230767, JP 4-320420, JP 5-232727, JP 7-56374, JP 9-127713, JP 9-222740. Examples thereof include polymers having an electron donating group as disclosed in JP-A-9-265197, JP-A-9-211877, JP-A-9-30495, and the like.

  The polymer having an electron donating group may be a copolymer with a known monomer, a block polymer, a graft polymer, a star polymer, or the like. Further, the polymer having an electron donating group may be a crosslinked polymer having an electron donating group disclosed in JP-A-3-109406.

  The electron transport material is not particularly limited, and examples thereof include fluorene compounds such as trinitrofluorenone and fluorenylidenemethane derivatives, and quinone compounds such as diphenoquinone and anthraquinone derivatives, and two or more of them may be used in combination.

  Examples of the binder resin contained in the charge transport layer 12b include polycarbonate, polyester, methacrylic resin, acrylic resin, polyethylene, polyvinyl chloride, polyvinyl acetate, polystyrene, phenol resin, epoxy resin, polyurethane, polyvinylidene chloride, alkyd resin, and silicone. Resin, polyvinyl carbazole, polyvinyl butyral, polyvinyl formal, polyacrylate, polyacrylamide, phenoxy resin and the like may be mentioned, and two or more kinds may be used in combination.

  2 and 3 may be formed by crosslinking a crosslinkable binder resin and a crosslinkable charge transport material.

  The charge transport layer 12b can be formed by applying a coating solution in which a charge transport material and a binder resin are dissolved or dispersed in a solvent on the charge generation layer 12a.

  The charge transport layer 12b may further include a plasticizer, an antioxidant, a leveling agent, and the like.

  The thickness of the charge transport layer 12b is usually 5 to 100 μm, and 5 to 30 μm is preferable in order to achieve high image quality of 1200 dpi or more.

  The photosensitive layer 12 (see FIG. 1) includes a charge generation material, a charge transport material, and a binder resin.

  The photosensitive layer 12 can be formed by applying a coating solution in which a charge generating substance, a charge transporting substance, and a binder resin are dissolved or dispersed in a solvent.

  The photosensitive layer 12 may further contain a plasticizer.

  The thickness of the photosensitive layer 12 is usually 5 to 100 μm, preferably 5 to 50 μm. When the thickness of the photosensitive layer 12 is less than 5 μm, the chargeability may be lowered, and when it exceeds 100 μm, the sensitivity may be lowered.

  Examples of the material constituting the conductive support 11 (see FIGS. 1 to 4) include metals or alloys such as Al, Ni, Fe, Cu, and Au. The conductive support 11 is made of a metal, such as Al, Ag, Au, or a metal oxide such as indium (III) oxide or tin (IV) oxide, polyester, polycarbonate, polyimide, Insulating supports such as glass, metals such as carbon black, graphite, Al, Cu, and Ni, resin-made supports in which conductive particles such as conductive glass are dispersed, paper subjected to conductive treatment, etc. There may be.

  Examples of the shape of the conductive support 11 include a plate shape, a drum shape, and a belt shape. Among these, a drum shape is preferable from the viewpoint of rigidity.

  The undercoat layer 13 (see FIGS. 3 and 4) contains a resin. At this time, considering that the coating solution is applied when forming the charge generation layer 12a or the photosensitive layer 12 on the undercoat layer 13, the undercoat layer 13 contains a resin having excellent dissolution resistance. Is preferred.

  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 resins, alkyd-melamine resins, and epoxy resins. Examples thereof include a curable resin that forms a three-dimensional network structure.

  The undercoat layer 13 may further include powders of metal oxides such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, and indium oxide, metal sulfides, and metal nitrides.

  The undercoat layer 13 can be formed by applying a coating solution in which a resin is dissolved or dispersed in a solvent.

  The undercoat layer 13 is formed by using a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like, a metal oxide formed by a sol-gel method, an aluminum oxide formed by anodization, a polyparaffin. Xylylene (parylene), tin oxide (IV) formed by a vacuum thin film manufacturing method, titanium dioxide, ITO, cerium oxide, or the like may be used.

  The thickness of the undercoat layer 13 is usually 0.1 to 10 μm, preferably 1 to 5 μm.

  The image forming apparatus of the present invention has a cleaning blade for removing the toner remaining on the photoreceptor to which the toner image has been transferred, and a lubricant applying means for applying the lubricant of the present invention to the photoreceptor. There is no particular limitation.

  The cleaning blade and the lubricant applying means are not particularly limited, and known cleaning blades and lubricant applying means can be used.

  FIG. 5 shows an example of the image forming apparatus of the present invention. In the image forming apparatus 100A, the photosensitive member 10 has a drum shape and is driven to rotate counterclockwise in the drawing.

  Hereinafter, a method for forming an image using the image forming apparatus 100A will be described. First, after the surface of the photoconductor 10 is neutralized by the neutralization lamp 101, the surface of the photoconductor 10 is charged by the charger 102. Next, an exposure device (not shown) irradiates the surface of the photoconductor 10 with exposure light L to form an electrostatic latent image, and then the developing device 103 develops the electrostatic latent image with toner. An image is formed. Further, after the toner image formed on the surface of the photoconductor 10 is charged by the pre-transfer charger 104, the toner image is transferred to the recording paper P supplied from the registration roller 105 by the transfer charger 106. Next, after the recording paper P on which the toner image has been transferred is charged by the separation charger 107, the recording paper P is separated from the photoreceptor 10 by the separation claw 108. On the other hand, after the toner remaining on the surface of the photoconductor 10 is charged by the pre-cleaning charger 109, the toner remaining on the surface of the photoconductor 10 is removed by the cleaning brush 110 and the surface of the photoconductor 10 is also removed. Lubricant is applied. Next, the toner remaining on the surface of the photoreceptor 10 is removed by the cleaning blade 111, and the amount of lubricant applied to the surface of the photoreceptor 10 is made uniform.

  FIG. 6 shows the cleaning brush 110 and the cleaning blade 111. Since the rod-like solid lubricant 110a is pressed against the cleaning brush 110, the lubricant is scraped off when the cleaning brush 110 rotates. As a result, the lubricant adhering to the cleaning brush 110 is applied to the surface of the photoreceptor 10. For this reason, the friction between the cleaning blade 111 and the surface of the photosensitive member can be reduced over a long period of time.

  A lubricant application unit independent of the cleaning unit may be installed. In this case, the lubricant application unit is preferably installed on the downstream side of the cleaning unit with respect to the direction in which the photoreceptor 10 rotates. Also, by installing a plurality of lubricant application units and operating the plurality of lubricant application units simultaneously or sequentially, it is possible to improve the lubricant application efficiency and control the consumption.

  As a light source for the static elimination lamp 101 and the exposure unit (not shown), a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), an electroluminescence (EL), or the like is used. Can do. At this time, a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, a color temperature conversion filter, or the like may be used to irradiate only light in a desired wavelength range.

  As the charger 102, the pre-transfer charger 104, the transfer charger 106, the separation charger 107, and the pre-cleaning charger 109, a corotron, a scorotron, a solid charger (solid state charger), a charging roller, or the like may be used. it can.

  The lubricant application brush 110 is not particularly limited, and a fur brush, a mag fur brush, or the like can be used.

  The material constituting the cleaning blade 111 is not particularly limited, and examples thereof include urethane resin, silicone resin, fluororesin, urethane elastomer, silicone elastomer, and fluoroelastomer. Of these, urethane elastomers are preferred from the viewpoints of wear resistance, ozone resistance, and contamination resistance.

  The cleaning blade 111 preferably has a hardness (JIS-A) of 65 to 85 degrees. The cleaning blade 111 preferably has a thickness of 0.8 to 3.0 mm and a protrusion amount of 3 to 15 mm.

  As the toner, a known toner, that is, a toner having a base particle containing a binder resin and a colorant and an external additive can be used. At this time, the base particles may further contain a release agent, a charge control agent, and the like.

  In a high-humidity environment, the surface of the photoreceptor 10D on which the protective layer 14 cross-linked with a crosslinkable resin containing a polymerizable compound having a charge transporting structure is formed has a fatty acid as a lubricant. When an image is repeatedly formed while applying a metal salt, image blur occurs.

  The reason for this is not clear, but the surface of the protective layer 14 is formed by the combination of the fatty acid metal salt deteriorated by the discharge from the charger, the moisture in the air, and the discharge product generated by the discharge from the charger. This is probably because the resistance is lowered and the electrostatic latent image flows. Further, it is considered that the deteriorated fatty acid metal salt is difficult to remove from the protective layer 14.

  Here, even if a metal salt of a fatty acid and a hindered phenol or hindered amine are used in combination, a photosensitive layer having a protective layer 14 on which a crosslinkable resin containing a polymerizable compound having a charge transporting structure is crosslinked is formed on the surface. When an image is repeatedly formed in a high humidity environment using the body 10D, image blur occurs. This may be due to the possibility that hindered phenol or hindered amine deteriorated by discharge from the charger, moisture in the air, and further discharge products.

  FIG. 7 shows another example of the image forming apparatus of the present invention. In the image forming apparatus 100B, the photosensitive member 10 has a belt shape, is stretched by a driving roller 121 and driven rollers 122 and 123, and is rotationally driven by the driving roller 121 in the clockwise direction in the drawing.

  Hereinafter, a method for forming an image using the image forming apparatus 100B will be described. First, after the surface of the drum-shaped photoconductor 10 is neutralized by the static elimination lamp 101, the surface of the photoconductor 10 is charged by the charger 102. Next, an exposure device (not shown) irradiates the surface of the photoconductor 10 with exposure light L to form an electrostatic latent image, and then the developing device 103 develops the electrostatic latent image with toner. An image is formed. Further, after the toner image is transferred to the recording paper (not shown) by the transfer charger 106, the toner remaining on the surface of the photoconductor 10 is removed by the cleaning brush 110 and the surface of the photoconductor 10 is lubricated. The agent is applied. Next, the toner remaining on the surface of the photoreceptor 10 is removed by the cleaning blade 111, and the amount of lubricant applied to the surface of the photoreceptor 10 is made uniform. Further, the toner remaining on the surface of the photoreceptor 10 is removed by the cleaning brush 124.

  The cleaning brush 124 has the same configuration as the cleaning brush 110.

  The process cartridge of the present invention integrally supports a photosensitive member, a cleaning blade for removing toner remaining on the photosensitive member to which a toner image has been transferred, and a lubricant applying means for applying the lubricant of the present invention to the photosensitive member. It is detachable from the main body of the image forming apparatus.

  The cleaning blade and the lubricant applying means are not particularly limited, and known cleaning blades and lubricant applying means can be used.

  FIG. 8 shows an example of the process cartridge of the present invention. The process cartridge 200 is supported integrally with the photoreceptor 10, the charger 102, the developing device 104, the cleaning brush 110, and the cleaning blade 111, and is detachable from the main body of the image forming apparatus. At this time, the cleaning brush 110 removes the toner remaining on the surface of the photoconductor 10 and applies a lubricant to the surface of the photoconductor 10. The cleaning blade 111 removes toner remaining on the surface of the photoconductor 10 and makes the amount of lubricant applied to the surface of the photoconductor 10 uniform.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to an Example. In addition, a part means a mass part.

[Example 1]
First, 85 parts of zinc stearate and 15 parts of the compound represented by the chemical formula (1-1) were melted with stirring at 140 ° C. to obtain a melt. Next, after pouring the melt into the cavity of an aluminum mold having a cavity of 8 mm width x depth 8 mm x length 500 mm preheated at 140 ° C., a preheated heat insulating lid is placed on the upper part of the mold. did. Further, the mold was allowed to cool until the temperature of the mold reached 50 ° C., and the molded product was taken out from the mold. The molded product was processed into a shape having a width of 8 mm, a thickness of 8 mm, and a length of 380 mm to obtain a rod-shaped solid lubricant 110a that can be mounted on RICOH Pro C900.

[Example 2]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that the compound represented by the chemical formula (1-2) was used instead of the compound represented by the chemical formula (1-1).

[Example 3]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that the compound represented by the chemical formula (1-3) was used instead of the compound represented by the chemical formula (1-1).

[Example 4]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that the compound represented by the chemical formula (1-4) was used instead of the compound represented by the chemical formula (1-1).

[Example 5]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that the compound represented by the chemical formula (1-5) was used instead of the compound represented by the chemical formula (1-1).

[Example 6]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that the addition amounts of zinc stearate and the compound represented by the chemical formula (1-1) were 98 parts and 2 parts, respectively.

[Example 7]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that the addition amounts of zinc stearate and the compound represented by the chemical formula (1-1) were 75 parts and 25 parts, respectively.

[Example 8]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that the addition amounts of zinc stearate and the compound represented by the chemical formula (1-1) were 60 parts and 40 parts, respectively.

[Example 9]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 2 except that calcium stearate was used instead of zinc stearate.

[Example 10]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 2 except that aluminum stearate was used instead of zinc stearate.

[Example 11]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 2 except that lithium stearate was used instead of zinc stearate.

[Example 12]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 2 except that magnesium stearate was used instead of zinc stearate.

[Example 13]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 2 except that zinc palmitate was used instead of zinc stearate.

[Example 14]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that a mixture of zinc stearate and iron stearate in a mass ratio of 4: 1 was used instead of zinc stearate.

[Example 15]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that a mixture of zinc stearate and zinc palmitate in a mass ratio of 1: 1 was used instead of zinc stearate.

[Example 16]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1 except that a mixture of zinc stearate and zinc myristate in a mass ratio of 3: 2 was used instead of zinc stearate.

[Example 17]
A rod-shaped solid lubricant 110a was obtained in the same manner as in Example 1, except that a mixture of zinc stearate and zinc oleate in a mass ratio of 9: 1 was used instead of zinc stearate.

[Comparative Example 1]
A rod-shaped solid lubricant was obtained in the same manner as in Example 1 except that the compound represented by the chemical formula (1-1) was not added.

[Comparative Example 2]
A rod-like solid lubricant was obtained in the same manner as in Example 1 except that hindered phenol sanol LS-2626 (manufactured by Sankyo Co., Ltd.) was used instead of the compound represented by the chemical formula (1-1).

[Comparative Example 3]
A rod-like solid lubricant was obtained in the same manner as in Example 1 except that the hindered amine Sanol LS-744 (Sankyo Co., Ltd.) was used instead of the compound represented by the chemical formula (1-1).

[Comparative Example 4]
A rod-shaped solid lubricant was obtained in the same manner as in Example 1, except that hindered phenol IRGANOX-MD1024 (manufactured by Ciba Specialty Chemicals) was used instead of the compound represented by the chemical formula (1-1). .

  Table 1 shows the characteristics of the rod-like solid lubricant.

［感光体１の作製］
アルキッド樹脂ベッコゾール１３０７−６０−ＥＬ（ＤＩＣ社製）６部、メラミン樹脂スーパーベッカミンＧ−８２１−６０（大日本インキ化学工業社製）４部、酸化チタンＣＲ−ＥＬ（石原産業社製）４０部及びメチルエチルケトン５０部からなる下引き層用塗布液を調製した。

[Preparation of Photoreceptor 1]
6 parts alkyd resin Beccosol 1307-60-EL (manufactured by DIC), 4 parts melamine resin super becamine G-821-60 (manufactured by Dainippon Ink & Chemicals), 40 parts titanium oxide CR-EL (manufactured by Ishihara Sangyo) A coating solution for the undercoat layer comprising 50 parts of methyl ethyl ketone was prepared.

  After applying the coating solution for the undercoat layer on the aluminum conductive support 11 having an outer diameter of 100 mm and a length of 380 mm using the dip coating method, the coating solution is dried at 130 ° C. for 20 minutes, and the thickness is 3 An undercoat layer 13 of 5 μm was formed.

  A coating solution for a charge generation layer comprising 6 parts of Y-type titanyl phthalocyanine, 4 parts of butyral resin BX-1 (manufactured by Sekisui Chemical Co., Ltd.) and 200 parts of 2-butanone was prepared.

  A charge generation layer coating solution was applied onto the undercoat layer 13 using a dip coating method, and then dried at 90 ° C. for 20 minutes to form a charge generation layer 12 a having a thickness of 0.2 μm.

  Bisphenol Z-type polycarbonate 10 parts, chemical formula

で表される電荷輸送物質１０部及びテトラヒドロフラン８０部からなる電荷輸送層用塗布液を調製した。

A coating solution for a charge transport layer consisting of 10 parts of a charge transport material and 80 parts of tetrahydrofuran was prepared.

  A charge transport layer coating solution was applied onto the charge generation layer 12a using a dip coating method, and then dried at 135 ° C. for 20 minutes to form a charge transport layer 12b having a thickness of 22 μm.

  10 parts of trimethylolpropane triacrylate KAYARAD TMPTA (manufactured by Nippon Kayaku Co., Ltd.) having a molecular weight of 296, chemical formula

で表される化合物（Ａ）１０部、光重合開始剤イルガキュア１８４（チバ・スペシャルティ・ケミカルズ社製）１部、紫外線硬化型レベリング剤の１質量％テトラヒドロフラン溶液ＢＹＫ−ＵＶ３５７０（ビックケミー社製）５部及びテトラヒドロフラン１００部からなる保護層用塗布液を調製した。

10 parts of a compound (A) represented by the formula, 1 part of a photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals), 5 parts of a 1% by weight tetrahydrofuran solution of UV curable leveling agent BYK-UV3570 (manufactured by BYK Chemie) And the coating liquid for protective layers which consists of 100 parts of tetrahydrofuran was prepared.

The coating liquid for protective layer was applied on the charge transport layer 12b using a spray coating method in a nitrogen stream, and then left to stand for 10 minutes to dry by touch. Next, in an ultraviolet light irradiation booth substituted with nitrogen gas so that the oxygen concentration becomes 2% or less, using a metal halide lamp with a lamp power of 160 W / cm, an irradiation distance of 120 mm, an illuminance of 700 mW / cm ² , an irradiation time After irradiating with ultraviolet light under conditions of 60 seconds, the film was dried at 130 ° C. for 20 minutes to form a protective layer 13 having a thickness of 8 μm.

  The rod-shaped solid lubricants of Examples 1 to 17 or Comparative Examples 1 to 4 are adhered to the metal support for the lubricant application unit mounted on the full color printer RICOH Pro C900 (manufactured by Ricoh) with a double-sided tape. The photoconductor 1 was mounted on the black station of the modified machine, and image blurring, abrasion resistance, and scratch resistance were evaluated.

<Image blur>
In a high-humidity environment of 27 ° C. and 85% RH, 5000 black single color test charts having an image area ratio of 5% were output continuously, and then the full-color printer was turned off. Next, after leaving in a high humidity environment of 27 ° C. and 85% RH for 24 hours, the full color printer is turned on and a black half-tone image of black monochrome of 1200 dpi 2 by 2 is output, and the presence or absence of blur due to image blur is evaluated. did. Note that ◎ when image blur does not occur, slightly image blur occurs just below the charger, but practically almost no problem, ○, slightly image just below and around the charger. The case where the blur occurred but the level was practically acceptable was evaluated as Δ, and the case where the image blur occurred almost on the entire surface and the level was unacceptable was judged as x.

<Abrasion resistance>
The thickness of the photosensitive layer before and after running, which continuously outputs 100,000 black single-color test charts with an image area ratio of 15% in an environment of 25 ° C. and 50% RH, is the eddy current film thickness meter Fischer scope MMS. (Fischer) was used to calculate the amount of abrasion of the photosensitive layer. The thickness of the photosensitive layer is a value measured in an arbitrary main scanning direction (in the drum axis direction) of the photoreceptor from a position where the distance from one end is 50 mm to a position where the distance is 330 mm at intervals of 10 mm. Is the average value.

  In addition, it is thought that the coating property of a lubricant is so favorable that there is little abrasion amount of a photosensitive layer.

<Scratch resistance>
The presence or absence of streak-like scratches in the sub-scanning direction (drum circumferential direction) on the surface of the photoreceptor after evaluating the wear resistance was visually observed.

  Note that the smaller the number of streak-like scratches on the surface of the photoreceptor, the better the coating property of the lubricant.

  Table 2 shows the evaluation results of image blur, abrasion resistance, and scratch resistance.

表２から、実施例１〜１７の棒状固体潤滑剤１１０ａ及び感光体１を用いて、高湿環境下で繰り返し画像を形成しても、画像ボケの発生を抑制できることがわかる。また、耐摩耗性や耐キズ性も、実使用上問題とはならないレベルを維持していることがわかる。

From Table 2, it can be seen that even if the rod-shaped solid lubricant 110a of Examples 1 to 17 and the photoreceptor 1 are used to form images repeatedly in a high humidity environment, the occurrence of image blur can be suppressed. It can also be seen that the wear resistance and scratch resistance are maintained at a level that does not cause a problem in actual use.

  In contrast, when the rod-shaped solid lubricants of Comparative Examples 1 to 4 were used to repeatedly form images in a high humidity environment, image blur occurred.

[Preparation of Photoreceptor 2]
Instead of trimethylolpropane triacrylate KAYARAD TMPTA (manufactured by Nippon Kayaku Co., Ltd.) having a molecular weight of 296, dipentaerythritol caprolactone-modified hexaacrylate KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.) is used as a protective layer. A photoconductor 2 was obtained in the same manner as the photoconductor 1, except that a coating solution for coating was prepared.

[Preparation of Photoreceptor 3]
Instead of trimethylolpropane triacrylate KAYARAD TMPTA (made by Nippon Kayaku Co., Ltd.) having a molecular weight of 296, dipentaerythritol caprolactone-modified hexaacrylate KAYARAD DPCA-120 (made by Nippon Kayaku Co., Ltd.) having a molecular weight was used to form a protective layer. A photoconductor 3 was obtained in the same manner as the photoconductor 1 except that a coating solution for coating was prepared.

[Preparation of Photoreceptor 4]
Instead of compound (A), a chemical formula

で表される化合物を用いて、保護層用塗布液を調製した以外は、感光体１と同様にして、感光体４を得た。

A photoconductor 4 was obtained in the same manner as the photoconductor 1, except that a protective layer coating solution was prepared using the compound represented by formula (1).

[Preparation of Photoreceptor 5]
Instead of compound (A), a chemical formula

で表される化合物を用いて、保護層用塗布液を調製した以外は、感光体１と同様にして、感光体５を得た。

A photoconductor 5 was obtained in the same manner as the photoconductor 1 except that a coating solution for a protective layer was prepared using the compound represented by formula (1).

[Production of Photosensitive Member 6]
Instead of compound (A), a chemical formula

で表される化合物を用いて、保護層用塗布液を調製した以外は、感光体１と同様にして、感光体６を得た。

A photoconductor 6 was obtained in the same manner as the photoconductor 1 except that a coating solution for a protective layer was prepared using the compound represented by formula (1).

[Preparation of Photoreceptor 7]
In the same manner as the photoreceptor 1, an undercoat layer 13, a charge generation layer 12a, and a charge transport layer 12b were sequentially laminated on the conductive support 11.

  3 parts of alumina AA-03 (manufactured by Sumitomo Chemical Co., Ltd.) having an average primary particle size of 0.3 μm, 0.06 parts of unsaturated polycarboxylic acid polymer BYK-P104 (manufactured by BYK Chemie), and a molecular weight of 296, trimethylolpropane tri 5 parts acrylate SR-351 (manufactured by Sartomer), 5 parts dipentaerythritol caprolactone-modified hexaacrylate KAYARAD DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.) having a molecular weight of 1947, 10 parts compound (A), photopolymerization initiator Irgacure 184 A protective layer coating solution comprising 100 parts of tetrahydrofuran (manufactured by Ciba Specialty Chemicals) and tetrahydrofuran was prepared.

A coating solution for the protective layer was applied on the charge transport layer 12b using a spray coating method in a nitrogen stream, and then allowed to stand for 1 minute to dry naturally. Next, in an ultraviolet light irradiation booth substituted with nitrogen gas so that the oxygen concentration becomes 2% or less, using a metal halide lamp with a lamp power of 160 W / cm, an irradiation distance of 120 mm, an illuminance of 500 mW / cm ² , an irradiation time After irradiating with ultraviolet light under the condition of 45 seconds, the film was dried at 130 ° C. for 20 minutes to form a protective layer 13 having a thickness of 4 μm.

[Preparation of Photoreceptor 8]
Coating for protective layer using silica KMPX100 (manufactured by Shin-Etsu Chemical Co., Ltd.) having an average primary particle diameter of 0.1 μm instead of alumina AA-03 (manufactured by Sumitomo Chemical Co., Ltd.) having an average primary particle diameter of 0.3 μm A photoconductor 8 was obtained in the same manner as the photoconductor 7 except that the solution was prepared.

[Preparation of Photoreceptor 9]
Instead of alumina AA-03 (manufactured by Sumitomo Chemical Co., Ltd.) having an average primary particle size of 0.3 μm, titanium oxide CR-97 (manufactured by Ishihara Sangyo Co., Ltd.) having an average primary particle size of 0.25 μm is used to form a protective layer. A photoconductor 9 was obtained in the same manner as the photoconductor 7, except that a coating solution for coating was prepared.

[Production of Photoreceptor 10]
In the same manner as the photoreceptor 1, an undercoat layer 13, a charge generation layer 12a, and a charge transport layer 12b were sequentially laminated on the conductive support 11.

  3 parts of alumina AA-03 (manufactured by Sumitomo Chemical Co., Ltd.) having an average primary particle size of 0.3 μm, 0.06 part of unsaturated polycarboxylic acid polymer BYK-P104 (manufactured by BYK Chemie), polycarbonate Z polycarbonate (manufactured by Teijin Chemicals Ltd.) ) A protective layer coating solution comprising 10 parts, 0.06 part of dibutylhydroxytoluene, 0.2 part of the antioxidant Sanol LS-2626 (manufactured by Sankyo), 230 parts of tetrahydrofuran and 70 parts of cyclohexanone was prepared.

  Using a spray coating method, a protective layer coating solution was applied onto the charge transport layer 12b and then dried at 150 ° C. for 20 minutes to form a protective layer 13 having a thickness of 5 μm.

[Preparation of Photoreceptor 11]
In the same manner as the photoreceptor 1, an undercoat layer 13, a charge generation layer 12a, and a charge transport layer 12b were sequentially laminated on the conductive support 11.

  20 parts of polyol LZR-170 (Fujikura Kasei Co., Ltd.) having a solid content of 41% by mass, 20 parts of a compound represented by the chemical formula (2-9), and polyisocyanate coronate L (Nippon Polyurethane Industry) having a solid content of 75% by mass A protective layer coating solution consisting of 5 parts of a 1% by weight tetrahydrofuran solution of silicone oil KF50-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.), 50 parts of cyclohexanone and 200 parts of tetrahydrofuran.

  After applying the coating solution for the protective layer on the charge transport layer 12b by using the spray coating method, the coating layer is naturally dried for 1 minute and heated at 150 ° C. for 30 minutes to form the protective layer 13 having a thickness of 5 μm. A photoreceptor 11 was obtained.

  In the black station of a modified machine in which the rod-shaped solid lubricant 110a of Example 1 is bonded to the metal support for the lubricant application unit mounted on the full-color printer RICOH Pro C900 (manufactured by Ricoh) with double-sided tape. Photoconductors 2 to 11 were mounted, and image blur, abrasion resistance, and scratch resistance were evaluated.

  Table 3 shows evaluation results of image blur, abrasion resistance, and scratch resistance.

表３から、実施例１の棒状固体潤滑剤１１０ａ及び感光体２〜１１を用いて、高湿環境下で繰り返し画像を形成しても、画像ボケの発生を抑制できることがわかる。また、耐摩耗性や耐キズ性も、実使用上問題とはならないレベルを維持していることがわかる。

From Table 3, it can be seen that the occurrence of image blur can be suppressed even when the rod-shaped solid lubricant 110a of Example 1 and the photoreceptors 2 to 11 are used to repeatedly form images in a high-humidity environment. It can also be seen that the wear resistance and scratch resistance are maintained at a level that does not cause a problem in actual use.

DESCRIPTION OF SYMBOLS 10 Photoconductor 100A, 100B Image forming apparatus 102 Charging device 103 Developing device 106 Transfer charging device 110 Cleaning brush 110a Bar-shaped solid lubricant 111 Cleaning blade L Exposure light P Recording paper

JP 2001-265040 A JP 2004-258177 A

Claims (9)

A lubricant used by being applied to a photoreceptor,
Lubricating substances and general formula

(In the formula, X and Y are each independently an aryl group optionally substituted by a substituent, and n and m are each independently 1 or 2.)
A lubricant comprising a compound represented by the formula:   The lubricant according to claim 1, wherein the lubricating substance contains a metal salt of a fatty acid. The fatty acid is one or more selected from the group consisting of stearic acid, palmitic acid, myristic acid and oleic acid,
The lubricant according to claim 2, wherein the metal is at least one selected from the group consisting of zinc, aluminum, calcium, magnesium, iron, and lithium.   4. The lubricant according to claim 1, wherein the content of the compound represented by the general formula (1) is 0.1% by mass or more and 40% by mass or less.   The lubricant according to any one of claims 1 to 4, wherein the lubricant is solid. A photosensitive member; a charging unit that charges the photosensitive member; an exposure unit that exposes the charged photosensitive member to form an electrostatic latent image; and the electrostatic latent image formed on the photosensitive member is developed with toner. An image having developing means for forming a toner image, transfer means for transferring the toner image formed on the photosensitive member to a recording medium, and a cleaning blade for removing toner remaining on the photosensitive member to which the toner image has been transferred. A forming device,
An image forming apparatus, further comprising a lubricant applying unit that applies the lubricant according to claim 1 to the photoconductor.   The image forming apparatus according to claim 6, wherein the photosensitive member has a protective layer formed by crosslinking a crosslinkable resin including a polymerizable compound having a charge transporting structure on a surface thereof.   The image forming apparatus according to claim 6, wherein the charging unit includes a corona charger.   6. A photosensitive member, a cleaning blade for removing toner remaining on the photosensitive member to which a toner image has been transferred, and a lubricant applying means for applying the lubricant according to any one of claims 1 to 5 to the photosensitive member. A process cartridge which is integrally supported and detachable from a main body of an image forming apparatus.

Images