JP4407490B2 - Electrophotographic photosensitive member and image forming apparatus using the same - Google Patents

Description

The present invention includes a photosensitive layer containing a resin such as polyester having a specific molecular structure and a specific organic compound, and is excellent in surface slipperiness, slidability, durability thereof, and electrical characteristics. The present invention relates to a photoconductor and an image forming apparatus using the electrophotographic photoconductor.

Electrophotographic technology is used not only in conventional copiers, but also in various printers, facsimiles, etc. because of its immediacy and high-quality images. Photoconductors that form the core of electrophotographic technology , Inorganic photoconductive materials such as amorphous silicon and arsenic-selenium, and organic photoconductive materials are used. As the photosensitive layer of the electrophotographic photoreceptor using the organic photoconductive material, a so-called multilayer photoreceptor in which charge generation and charge transport functions are separated and stacked as a charge generation layer and a charge transport layer has high productivity. It has been researched and developed energetically because it has a high degree of safety, a high degree of design freedom, and a photoconductor with higher performance, and is now the mainstream of photoconductors. .

By the way, a photoreceptor in an electrophotographic process is repeatedly subjected to actions such as charging, exposure, development, transfer, cleaning, and static elimination, so that it has various durability and stability such as physical, mechanical, chemical, and electrical. On the other hand, a photoreceptor using an organic photoconductive material, in particular, a developer, a transfer material, a corona discharge product, a cleaning blade, and the like, compared to a photoreceptor using an inorganic photoconductive material. In reality, the durability against mechanical contact is still inferior, and with the recent development of finer developer particles or high sphericity chemical polymerization toners aimed at higher resolution and higher image quality, There is an increasing demand for easy transferability of toner and high-precision cleaning characteristics.

In order to achieve easy transferability of toner and high-precision cleaning characteristics, it is necessary to reduce the surface energy related to the frictional force and adhesion force on the surface of the photoreceptor. And the use of a fluorine-based leveling agent, specifically, a method in which silicone oil, fluorine-based resin powder, ester wax, or the like is included in the outermost surface layer of the photoreceptor is known. The surface modifiers generally used to improve wear resistance, surface slipperiness, etc. are, for example, leveling agents, which are poorly compatible with coating liquid components. During film drying or during relatively short-term storage, the leveling agent migrates to the surface and segregates on the extreme surface of the surface layer, so that the surface energy can be effectively reduced initially. Although a leveling agent will be scraped facilitated while the repetitive surface is rubbed, there was a problem to the effect disappears sustained in a short period of time. The same applies to ester waxes, and it is impossible to add a sufficient amount due to poor compatibility with the coating liquid, and even if a coating film is formed, ester waxes are likely to segregate on the surface, which is effective. Sustainability was difficult to obtain. Also, for example, when resin fine particles such as polytetrafluoroethylene are dispersed in the photosensitive layer, the lubricity is surely improved and the effect seems to be sustained. In some cases, incident light for forming a latent image is scattered and reflected to prevent faithful latent image formation. In particular, in recent years, it has been found that the process using a dot-like minute latent image such as a laser, LED, or liquid crystal shutter controlled by a digital signal has a large influence and greatly reduces the uniformity of the image.

On the other hand, in order to avoid the problem of a decrease in sustainability due to migration of these surface modifiers in the photosensitive layer, in order to give a surface modification function to the binder resin, for example, a polysiloxane block copolymer polycarbonate resin is used as a binder resin. (For example, see Patent Document 1), a method using a fluorine atom-containing polycarbonate resin as a binder resin (for example, see Patent Document 2), and a method using a polycarbonate resin having a long-chain alkyl chain as a side chain as a binder resin (For example, refer to Patent Document 3), a method in which a polycarbonate resin having a long-chain alkoxycarbonyl group as a substituent is used as a binder resin in combination with an ester wax (for example, refer to Patent Document 4), and a long-chain alkoxycarbonyl group is substituted. Polycarbonate resin and polyester resin as base The method used in combination with the ester wax binder resin (e.g., Patent Document 5 reference.) Have been proposed. However, although these methods also have a certain degree of sustainability improvement effect as compared with the above-described method using the surface modifier, it is still difficult to say that they satisfy the market requirements sufficiently. Furthermore, as described above, recent toner developers tend to have finer particles and lower glass transition points in response to higher resolution, higher image quality, and higher speed. This has led to a decrease in transfer efficiency and filming due to the increase in image quality. At present, there is a long-awaited photoreceptor.
JP-A-2-240655 Japanese Patent Laid-Open No. 6-282094 JP 7-13363 A JP 2001-92161 A JP 2001-290288 A

  The present invention has been made in view of the above-described present situation. Therefore, the present invention provides an electrophotographic photoreceptor excellent in surface slipperiness, slidability, durability thereof, and electrical characteristics, and the electronic An object of the present invention is to provide an image forming apparatus using a photographic photoreceptor.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that it is extremely effective by containing a resin such as polyester having a specific molecular structure and a specific organic compound in the photosensitive layer of the electrophotographic photosensitive member. The present invention has been achieved by finding that the surface slipperiness can be improved and the effect is also sustained, that is, the present invention is an electrophotographic photoreceptor having a photosensitive layer on a conductive support. Wherein the surface layer of the photosensitive layer comprises a unit containing an aromatic diol residue represented by the following general formula (III) having a substituent Z represented by the following general formula (I) as a constitutional repeating unit: An electrophotographic photosensitive member containing a resin and a compound represented by the following general formula (V), the electrophotographic photosensitive member, a charging means for charging the electrophotographic photosensitive member, and a charged electron Against photoconductor The gist of the present invention is an image forming apparatus comprising: an image exposure unit that performs image exposure to form an electrostatic latent image; a developing unit that develops the electrostatic latent image with toner; and a transfer unit that transfers the toner to a transfer target. To do.

〔式(III) 中、Ｒ ² は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、ハロゲン原子、又は水素原子を示し、Ｚは前記一般式(I) で表される置換基を示し、ベンゼン環は更に置換基を有していてもよい。〕 [In Formula (I), R ¹ is an alkyl group having 6 to 100 carbon atoms which may have a substituent, an alkenyl group having 6 to 100 carbon atoms which may have a substituent, or a substituent. Represents an alkynyl group having 6 to 100 carbon atoms, and n is an integer of 0 to 10. ]

[In the formula (III), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a hydrogen atom, and Z represents the above general formula ( The substituent represented by I) is shown, and the benzene ring may further have a substituent. ]

[In the formula (V), U represents a p-valent group having two or more aromatic rings which may have a substituent represented by the following general formula (VI), and V represents an oxy group or R ³ represents a divalent linking group of an ester group , R ³ is an alkyl group having 10 to 100 carbon atoms which may have a substituent, and carbon which may have a substituent , having 3 or less branches. An alkenyl group having a number of 10 to 100, or an alkynyl group having a carbon number of 10 to 100 which may have a substituent, wherein the alkyl group, the alkenyl group and the alkynyl group are linear or branched with 3 or less branches And p is an integer of 2-4 . ]

The present invention can provide an electrophotographic photoreceptor excellent in surface slipperiness, slidability, durability thereof, and electrical characteristics, and an image forming apparatus using the electrophotographic photoreceptor.

(1) Resin containing a unit containing an aromatic diol residue having a substituent Z represented by the general formula (I) as a constitutional repeating unit The electrophotographic photoreceptor of the present invention has a photosensitive layer having the following general formula (I It is essential to contain a resin containing a unit containing an aromatic diol residue having a substituent Z represented by:

[In Formula (I), R ¹ is an alkyl group having 6 to 100 carbon atoms which may have a substituent, an alkenyl group having 6 to 100 carbon atoms which may have a substituent, or a substituent. Represents an alkynyl group having 6 to 100 carbon atoms, and n is an integer of 0 to 10. ]

Here, the alkyl group, alkenyl group and alkynyl group of R ¹ in the general formula (I) may be linear or branched, and is preferably an alkyl group. Further, from the viewpoint of the effect on the surface slipperiness and the like, the number of carbon atoms is preferably 10 or more, more preferably 16 or more, particularly preferably 18 or more, and the ease of production. Therefore, it is preferably 50 or less. Further, n is preferably from 0 to 4. Examples of the substituent for these alkyl group, alkenyl group and alkynyl group include halogen atoms such as chlorine, fluorine and bromine.

  Specific examples of aromatic diols that form an aromatic diol residue having a substituent Z represented by the general formula (I) include pyrocatechol, resorcinol, hydroquinone, xylylene glycol, and the like. Dihydroxybenzenes, bis (4-hydroxyphenyl), bis (3-methyl-4-hydroxyphenyl), bis (3,5-dimethyl-4-hydroxyphenyl) and other bis (hydroxyphenyl) s, bis (2 -Hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane [bisphenol F], 2-hydroxyphenyl-4-hydroxyphenyl-methane, bis (3-methyl-4-hydroxyphenyl) methane [dimethylbisphenol F], bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3 6-dimethyl-4-hydroxyphenyl) methane, bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (4′-hydroxyphenyl) ethane [bisphenol E], 1,1-bis (3 ′ -Methyl-4'-hydroxyphenyl) ethane, 1,1-bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) ethane, 1,1-bis (3', 6'-dimethyl-4'-) Hydroxyphenyl) ethane, 1,1-bis (3′-phenyl-4′-hydroxyphenyl) ethane, 1,1-bis (4′-hydroxyphenyl) propane, 1,1-bis (3′-phenyl-4) '-Hydroxyphenyl) propane, 2,2-bis (4'-hydroxyphenyl) propane [bisphenol A], 2,2-bis (3'-methyl-4'-hydroxyphene) ) Propane [bisphenol C], 2,2-bis (3′-ethyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-i-propyl-4′-hydroxyphenyl) propane, 2, 2-bis (3′-s-butyl-4′-hydroxyphenyl) propane, 2,2-bis (3 ′, 5′-dimethyl-4′-hydroxyphenyl) propane [tetramethylbisphenol A], 2,2 -Bis (3'-phenyl-4'-hydroxyphenyl) propane [bisphenol Q], 2,2-bis (4'-hydroxyphenyl) butane, 2,2-bis (4'-hydroxyphenyl) -3-methylbutane 2,2-bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxyphenyl) -4-methylpentane, 2,2-bis (4 ' Bis (hydroxyphenyl) alkanes such as hydroxyphenyl) hexane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4′-hydroxyphenyl) -1-phenylethane [Bisphenol P], 1,1-bis (4′-hydroxyphenyl) -1-phenylpropane, bis (hydroxyphenyl) phenyl such as 2,2-bis (4′-hydroxyphenyl) -1,3-diphenylpropane Alkanes, 1,1-bis (4′-hydroxyphenyl) cyclopentane, bis (hydroxyphenyl) cycloalkanes such as 1,1-bis (4′-hydroxyphenyl) cyclohexane [bisphenol Z], bis (4 ′ -Hydroxyphenyl) -1,4-phenylenedimethyle Bis (2 ′, 6′-dimethyl-4′-hydroxyphenyl) -1,4-phenylenedimethylene, bis (2 ′, 6′-dimethyl-4′-hydroxyphenyl) -1,4-phenylenebis (Α-methylethylidene), bis (4′-hydroxyphenyl) -1,4-phenylenebis (α-methylvinylidene), bis (2′-methyl-4′-hydroxyphenyl) -1,4-phenylenebis ( Bis (hydroxyphenyl) such as bis (hydroxyphenyl) phenylene dimethylenes such as α-methylvinylidene), bis (4-hydroxyphenyl) ether [bisphenol O], bis (3,5-dimethyl-4-hydroxyphenyl) ether ) Ethers, bis (4-hydroxyphenyl) ketone, bis (3,5-dimethyl-4-hydroxyphenyl) And bis (hydroxyphenyl) ketones such as phenolphthalein, bis (4-hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis ( Bis (hydroxyphenyl) sulfoxides such as 4-hydroxyphenyl) sulfoxide and bis (3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone [bisphenol S], bis (3,5- And bis (hydroxyphenyl) sulfones such as dimethyl-4-hydroxyphenyl) sulfone.

  In the present invention, the aromatic diol residue having the substituent Z represented by the general formula (I) is preferably a bis (hydroxyphenyl) compound residue represented by the following general formula (II). .

  [In the formula (II), X represents an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, a phenylenedimethylene group which may have a substituent, oxy Group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, or a single bond, and the benzene ring may further have a substituent. However, the substituent Z when X is an alkylene group, a cycloalkylene group, or a phenylenedimethylene group, or the substituent Z of the benzene ring has the substituent Z represented by the general formula (I). ]

  Furthermore, the bis (hydroxyphenyl) compound residue represented by the general formula (II) is preferably a bis (hydroxyphenyl) alkane residue represented by the following general formula (III).

[In the formula (III), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a hydrogen atom, and Z represents the above general formula ( The substituent represented by I) is shown, and the benzene ring may further have a substituent. ]

When X in the general formula (II) is an alkylene group, a cycloalkylene group, or a phenylenedimethylene group, when R ² in the general formula (III) is an alkyl group or an aryl group, and Examples of the substituent other than the substituent Z represented by the general formula (I) in the benzene ring in the general formulas (II) and (III) include, for example, 1 to 1 carbon atoms which may further have a substituent. Examples include about nine alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, alkoxy groups, aryl groups which may have further substituents, and halogen atoms. Among them, an alkyl group is preferable, and a methyl group is particularly preferable.

  Preferable specific examples of the aromatic diol that forms the aromatic diol residue represented by the above general formula (III) include, for example, 3,3-bis (4′-hydroxyphenyl) propionic acid hexyl ester 3,3-bis (4′-hydroxyphenyl) propionic acid octyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid nonyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid Decyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid undecenyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid dodecyl ester, 3,3-bis (4′-hydroxyphenyl) Propionic acid tetradecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid hexadecy Ester, 3,3-bis (4'-hydroxyphenyl) propionic acid octadecyl ester, 3,3-bis (4'-hydroxyphenyl) propionic acid eicosyl ester, 3,3-bis (4'-hydroxyphenyl) propion Acid docosyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -ethylhexyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -hexyldecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -octyldodecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -decyltetradecyl ester, 3,3 -Bis (4′-hydroxyphenyl) propionic acid-2 ″ -tetradecyloctadecyl ester Tere, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -tetradecyleicosyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -hexadecyl octadecyl ester 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -hexadecyleicosyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid hexyl ester, 4,4-bis (4 '-Hydroxyphenyl) butanoic acid octyl ester, 4,4-bis (4'-hydroxyphenyl) butanoic acid nonyl ester, 4,4-bis (4'-hydroxyphenyl) butanoic acid undecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid undecenyl ester, 4,4-bis (4′-hydroxyphenyl) butane Tanoic acid dodecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid tetradecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid hexadecyl ester, 4,4-bis (4′- Hydroxyphenyl) butanoic acid octadecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid eicosyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid docosyl ester, 4,4-bis ( 4′-hydroxyphenyl) butanoic acid-2 ″ -ethylhexyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid-2 ″ -hexyldecyl ester, 4,4-bis (4′-hydroxyphenyl) ) Butanoic acid-2 ''-octyldodecyl ester, 4,4-bis (4'-hydroxyphenyl) butanoic acid- '' -Decyltetradecyl ester, 4,4-bis (4'-hydroxyphenyl) butanoic acid-2 ''-tetradecyloctadecyl ester, 4,4-bis (4'-hydroxyphenyl) butanoic acid-2 '' -Tetradecyl eicosyl ester, 4,4-bis (4'-hydroxyphenyl) butanoic acid-2 "-hexadecyl octadecyl ester, 4,4-bis (4'-hydroxyphenyl) butanoic acid-2"- Hexadecyl eicosyl ester, 3,3-bis (4′-hydroxyphenyl) butanoic acid octadecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid hexyl ester, 4,4-bis (4′-hydroxy) Phenyl) pentanoic acid octyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid nonyl ester 4,4-bis (4′-hydroxyphenyl) pentanoic acid undecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid undecenyl ester, 4,4-bis (4′-hydroxyphenyl) Pentanoic acid dodecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid tetradecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid hexadecyl ester, 4,4-bis (4′- Hydroxyphenyl) pentanoic acid octadecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid eicosyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid docosyl ester, 4,4-bis ( 4′-hydroxyphenyl) pentanoic acid-2 ″ -ethylhexyl ester, 4,4-bis ( 4′-hydroxyphenyl) pentanoic acid-2 ″ -hexyldecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid-2 ″ -octyldodecyl ester, 4,4-bis (4′-hydroxy) Phenyl) pentanoic acid-2 ″ -decyltetradecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid-2 ″ -tetradecyloctadecyl ester, 4,4-bis (4′-hydroxyphenyl) Pentanoic acid-2 ″ -tetradecyleicosyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid-2 ″ -hexadecyloctadecyl ester, 4,4-bis (4′-hydroxyphenyl) pentane Acid-2 ″ -hexadecyleicosyl ester, 3,3-bis (4′-hydroxyphenyl) pentanoic acid Kutadecyl ester, 5,5-bis (4′-hydroxyphenyl) pentanoic acid octadecyl ester, 5,5-bis (4′-hydroxyphenyl) hexanoic acid octadecyl ester, 6,6-bis (4′-hydroxyphenyl) Heptanoic acid octadecyl ester, 7,7-bis (4′-hydroxyphenyl) octanoic acid octadecyl ester, 8,8-bis (4′-hydroxyphenyl) nonanoic acid octadecyl ester, 9,9-bis (4′-hydroxyphenyl) ) Decanoic acid octadecyl ester, 10,10-bis (4′-hydroxyphenyl) undecanoic acid octadecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid hexyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pe Octanoic acid tanyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid nonyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid undecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid undecenyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid dodecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid tetradecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid hexadecyl ester, 4,4-bis (4′- Hydroxy-3'-methylphenyl) pentanoic acid octadecyl ester, 4,4-bis (4'-hydroxy-3'-methylphenyl) ) Pentanoic acid eicosyl ester, 4,4-bis (4'-hydroxy-3'-methylphenyl) pentanoic acid docosyl ester, 4,4-bis (4'-hydroxy-3'-methylphenyl) pentanoic acid- 2 ″ -ethylhexyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -hexyldecyl ester, 4,4-bis (4′-hydroxy-3′-methyl) Phenyl) pentanoic acid-2 ″ -octyldodecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -decyltetradecyl ester, 4,4-bis (4 ′) -Hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -tetradecyloctadecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) Nyl) pentanoic acid-2 ″ -tetradecyleicosyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -hexadecyloctadecyl ester, 4,4-bis ( 4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -hexadecyleicosyl ester, 3,3-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid octadecyl ester, 5,5- Bis (4′-hydroxy-3′-methylphenyl) pentanoic acid octadecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid hexyl ester, 4,4-bis (4 '-Hydroxy-3', 5'-dimethylphenyl) pentanoic acid octyl ester, 4,4-bis (4'-hydroxy-3 ', 5 -Dimethylphenyl) pentanoic acid nonyl ester, 4,4-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) pentanoic acid undecyl ester, 4,4-bis (4'-hydroxy-3', 5 '-Dimethylphenyl) pentanoic acid undecenyl ester, 4,4-bis (4'-hydroxy-3', 5'-dimethylphenyl) pentanoic acid dodecyl ester, 4,4-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) pentanoic acid tetradecyl ester, 4,4-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) pentanoic acid hexadecyl ester, 4,4-bis (4'-hydroxy-3) ', 5'-dimethylphenyl) pentanoic acid octadecyl ester, 4,4-bis (4'-hydroxy-3', 5'-dimethylphenyl) Pentanoic acid eicosyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid docosyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethyl) Phenyl) pentanoic acid-2 ″ -ethylhexyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid-2 ″ -hexyldecyl ester, 4,4-bis (4 '-Hydroxy-3', 5'-dimethylphenyl) pentanoic acid-2 ''-octyldodecyl ester, 4,4-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) pentanoic acid-2' ' -Decyl tetradecyl ester, 4,4-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) pentanoic acid-2' '-tetradecyl octadecyl ester, , 4-Bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid-2 ″ -tetradecyleicosyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethyl) Phenyl) pentanoic acid-2 ″ -hexadecyloctadecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid-2 ″ -hexadecyleicosyl ester, 3,3 -Bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid octadecyl ester, 5,5-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid octadecyl ester, etc. .

  Among these, 3,3-bis (4′-hydroxyphenyl) propionic acid undecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid undecenyl ester, 3,3 are more preferable. -Bis (4'-hydroxyphenyl) propionic acid dodecyl ester, 3,3-bis (4'-hydroxyphenyl) propionic acid tetradecyl ester, 3,3-bis (4'-hydroxyphenyl) propionic acid hexadecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid octadecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid eicosyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid doco Silester, 3,3-bis (4′-hydroxyphenyl) propiyl Acid-2 ″ -hexyldecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -octyldodecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 '' -Decyltetradecyl ester, 3,3-bis (4'-hydroxyphenyl) propionic acid-2 ''-tetradecyloctadecyl ester, 3,3-bis (4'-hydroxyphenyl) propionic acid-2 '' -Tetradecyl eicosyl ester, 3,3-bis (4'-hydroxyphenyl) propionic acid-2 "-hexadecyl octadecyl ester, 3,3-bis (4'-hydroxyphenyl) propionic acid-2"- Hexadecyl eicosyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid undecyl ester, , 4-Bis (4′-hydroxyphenyl) butanoic acid undecenyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid dodecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid tetradecyl ester Ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid hexadecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid octadecyl ester, 4,4-bis (4′-hydroxyphenyl) butane Acid eicosyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid docosyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid-2 ″ -hexyldecyl ester, 4,4- Bis (4′-hydroxyphenyl) butanoic acid-2 ″ -octyldodecyl ester, 4,4-bis (4′-hydro) Droxyphenyl) butanoic acid-2 ″ -decyltetradecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid-2 ″ -tetradecyloctadecyl ester, 4,4-bis (4′-hydroxy) Phenyl) butanoic acid-2 ″ -tetradecyleicosyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid-2 ″ -hexadecyloctadecyl ester, 4,4-bis (4′-hydroxyphenyl) ) Butanoic acid-2 ″ -hexadecyleicosyl ester, 3,3-bis (4′-hydroxyphenyl) butanoic acid octadecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid undecyl ester, 4 , 4-Bis (4′-hydroxyphenyl) pentanoic acid undecenyl ester, 4,4-bis (4′-hydro Cyphenyl) pentanoic acid dodecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid tetradecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid hexadecyl ester, 4,4-bis (4 '-Hydroxyphenyl) pentanoic acid octadecyl ester, 4,4-bis (4'-hydroxyphenyl) pentanoic acid eicosyl ester, 4,4-bis (4'-hydroxyphenyl) pentanoic acid docosyl ester, 4,4- Bis (4′-hydroxyphenyl) pentanoic acid-2 ″ -hexyldecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid-2 ″ -octyldodecyl ester, 4,4-bis (4 ′ -Hydroxyphenyl) pentanoic acid-2 ''-decyltetradecyl ester, 4,4-bis 4′-hydroxyphenyl) pentanoic acid-2 ″ -tetradecyloctadecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid-2 ″ -tetradecyleicosyl ester, 4,4-bis (4 '-Hydroxyphenyl) pentanoic acid-2 ″ -hexadecyloctadecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid-2 ″ -hexadecyleicosyl ester, 3,3-bis (4 ′) -Hydroxyphenyl) pentanoic acid octadecyl ester, 5,5-bis (4'-hydroxyphenyl) pentanoic acid octadecyl ester, 5,5-bis (4'-hydroxyphenyl) hexanoic acid octadecyl ester, 6,6-bis (4 '-Hydroxyphenyl) heptanoic acid octadecyl ester, 7,7-bis (4'- Hydroxyphenyl) octanoic acid octadecyl ester, 8,8-bis (4′-hydroxyphenyl) nonanoic acid octadecyl ester, 9,9-bis (4′-hydroxyphenyl) decanoic acid octadecyl ester, 10,10-bis (4 ′) -Hydroxyphenyl) undecanoic acid octadecyl ester, 4,4-bis (4'-hydroxy-3'-methylphenyl) pentanoic acid undecyl ester, 4,4-bis (4'-hydroxy-3'-methylphenyl) pentane Acid undecenyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid dodecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid tetradecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pen Acid hexadecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid octadecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid eicosyl ester 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid docosyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -hexyldecyl Ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -octyldodecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid— 2 ″ -decyltetradecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -tetradecyl Kutadecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -tetradecyleicosyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) ) Pentanoic acid-2 ″ -hexadecyloctadecyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid-2 ″ -hexadecyleicosyl ester, 3,3-bis (4) '-Hydroxy-3'-methylphenyl) pentanoic acid octadecyl ester, 5,5-bis (4'-hydroxy-3'-methylphenyl) pentanoic acid octadecyl ester, 4,4-bis (4'-hydroxy-3') , 5′-dimethylphenyl) pentanoic acid undecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) Pentaic acid undecenyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid dodecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) ) Pentanoic acid tetradecyl ester, 4,4-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) pentanoic acid hexadecyl ester, 4,4-bis (4'-hydroxy-3', 5'-) Dimethylphenyl) pentanoic acid octadecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid eicosyl ester, 4,4-bis (4′-hydroxy-3 ′, 5 ′) -Dimethylphenyl) pentanoic acid docosyl ester, 4,4-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) pentanoic acid-2' ' Hexyldecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid-2 ″ -octyldodecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5 '-Dimethylphenyl) pentanoic acid-2' '-decyltetradecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid-2 ″ -tetradecyloctadecyl ester, 4 , 4-Bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid-2 ″ -tetradecyleicosyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethyl) Phenyl) pentanoic acid-2 ″ -hexadecyloctadecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid-2 '-Hexadecyleicosyl ester, 3,3-bis (4'-hydroxy-3', 5'-dimethylphenyl) pentanoic acid octadecyl ester, 5,5-bis (4'-hydroxy-3 ', 5'- And dimethylphenyl) -pentanoic acid octadecyl ester.

  Further, among these, 3,3-bis (4′-hydroxyphenyl) propionic acid octadecyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid eicosyl ester, 4-bis (4′-hydroxyphenyl) butanoic acid octadecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid eicosyl ester, 3,3-bis (4′-hydroxyphenyl) butanoic acid octadecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid octadecyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid eicosyl ester, 3,3-bis (4′-hydroxyphenyl) pentanoic acid octadecyl ester Ester, 5,5-bis (4′-hydroxyphenyl) pentanoic acid Tadecyl ester, 5,5-bis (4′-hydroxyphenyl) hexanoic acid octadecyl ester, 6,6-bis (4′-hydroxyphenyl) heptanoic acid octadecyl ester, 7,7-bis (4′-hydroxyphenyl) Octanoic acid octadecyl ester, 8,8-bis (4′-hydroxyphenyl) nonanoic acid octadecyl ester, 9,9-bis (4′-hydroxyphenyl) decanoic acid octadecyl ester, 10,10-bis (4′-hydroxyphenyl) ) Undecanoic acid octadecyl ester, 4,4-bis (4'-hydroxy-3'-methylphenyl) pentanoic acid octadecyl ester, 4,4-bis (4'-hydroxy-3'-methylphenyl) pentanoic acid eicosyl ester 3,3-bis (4′-hydroxy-3′-methyl) Phenyl) pentanoic acid octadecyl ester, 5,5-bis (4′-hydroxy-3′-methylphenyl) pentanoic acid octadecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentane Acid octadecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid eicosyl ester, 3,3-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) And pentadecanoic acid octadecyl ester, 5,5-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid octadecyl ester, and the like. Among these, from the viewpoint of polymerizability and availability, 4, 4-bis (4′-hydroxyphenyl) pentanoic acid octadecyl ester is most preferred.

  In the present invention, the resin containing a unit containing the aromatic diol residue having the substituent Z represented by the general formula (I) as a constituent repeating unit is particularly limited as long as the resin contains the aromatic diol residue. For example, a polyester resin containing a structural repeating unit composed of the aromatic diol residue having a substituent Z represented by the general formula (I) and a dicarboxylic acid residue, the general formula (I) A polycarbonate resin containing a structural repeating unit consisting of the aromatic diol residue and the carbonate residue having the substituent Z represented by the formula (IV). Among them, a unit represented by the following general formula (IV) It is preferable that it is a polyester resin which contains as a structural repeating unit.

[In the formula (IV), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a hydrogen atom, and Z represents the general formula ( I) represents a substituent represented by formula (I), the benzene ring may further have a substituent, and Y represents an alkylene group which may have a substituent, or a cyclo which may have a substituent. An alkylene group or an arylene group which may have a substituent is shown. ]

Here, examples of the dicarboxylic acid that forms a dicarboxylic acid residue containing an alkylene group, a cycloalkylene group, or an arylene group of Y in the general formula (IV) include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelin. Acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, aliphatic dicarboxylic acid such as dodecadicarboxylic acid, alicyclic dicarboxylic acid such as hexahydroterephthalic acid, hexahydroisophthalic acid, and phthalic acid, isophthalic acid Terephthalic acid, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-diphenylketone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4 , 4'-Diphenylsulfone dicarboxylic acid, 2,6-naphthalene Aromatic dicarboxylic acids such as carboxylic acids, and acid halides such as these acid chlorides and the like. In the present invention, aromatic dicarboxylic acids and their acid halides are preferable, and terephthalic acid, isophthalic acid, and their acid halides are particularly preferable.

  In the present invention, the polyester resin containing the unit represented by the general formula (IV) as a constituent repeating unit has the substituent Z represented by the general formula (I) in the general formula (IV). In place of the aromatic diol residue, a diol residue having no substituent Z represented by the general formula (I) is used as a copolymerization component, and the constitutional repetition consisting of the diol residue and the dicarboxylic acid residue Copolymers containing units may be used, and the diols forming the diol residue at that time include, in addition to the aromatic diols having no substituent Z represented by the general formula (I) For example, ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol Aliphatic diols such as neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, polyethylene glycol, polytetramethylene ether glycol, and 1,2-cyclohexanediol, 1,4-cyclohexanediol, Examples thereof include alicyclic diols such as 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, and 2,5-norbornane dimethylol.

  In the present invention, the polyester resin containing the unit represented by the general formula (IV) as a constitutional repeating unit can be produced by a known production method such as an interfacial polymerization method, a melt polymerization method, or a solution polymerization method. For example, in the case of the production by the interfacial polymerization method, a solution in which one or more diol components are dissolved in an alkaline aqueous solution and a halogenated hydrocarbon solution in which one or more dicarboxylic acid components are dissolved are added as necessary. In the presence of a catalyst such as a quaternary ammonium salt or a quaternary phosphonium salt, usually in a temperature range of 0 to 40 ° C., mixed in a range of 2 to 12 hours for polycondensation. The target resin can be obtained by washing and collecting the polymer dissolved and dissolved in the organic phase by a known method.

Examples of the alkali component in the aqueous alkali solution used herein include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of the alkali component used is the phenolic hydroxyl group contained in the reaction system. A range of 1 to 3 equivalents is preferred. Examples of the halogenated hydrocarbon used here include dichloromethane, chloroform, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dichlorobenzene and the like. In addition, examples of quaternary ammonium salts or quaternary phosphonium salts used as catalysts include salts of tertiary alkylamines such as tributylamine and trioctylamine such as hydrochloric acid, bromic acid and iodic acid, benzyltrimethylammonium chloride, and benzyltriethyl. Ammonium chloride, benzyltributylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylphosphonium bromide, triethyloctadecylphosphonium bromide, N-laurylpyridinium chloride, laurylpicolinium chloride, etc. Can be mentioned.

  In this polycondensation, phenol, o-, m-, p-cresol, 2,4,6-trimethylphenol, 2,3,6-trimethylphenol, o-, m-, p are used as molecular weight regulators. -Ethylphenol, o-, m-, p-propylphenol, o-, m-, pt-butylphenol, 2,6-dimethyl-4-tert-butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, etc. Monofunctional phenols such as alkylphenols, o-, m-, p-phenylphenol, acetic chloride, butyric chloride, octyl chloride, benzoyl chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzenephosphonyl chloride, Monofunctional acids such as their substitutes Androgenic product may be present.

  As a method for purifying the resin after polycondensation, the resin solution is washed with an alkaline aqueous solution such as sodium hydroxide and potassium hydroxide, an aqueous acid solution such as hydrochloric acid, nitric acid and phosphoric acid, water, etc. Liquid separation may be performed by centrifugation or the like. Also, by the method of precipitating the produced resin solution in a solvent in which the resin is insoluble, the method of dispersing the resin solution in warm water and distilling off the solvent, or the method of circulating the resin solution through an adsorption column, etc. The resin may be purified. The purified resin is a method in which the resin is precipitated in water, alcohol, or other organic solvent, a method in which the resin solution is mixed with warm water or a dispersion medium in which the resin is insoluble, and the solvent is distilled off. It is possible to take out by using a method such as distilling off the solvent. When the produced resin is in the form of a slurry, it can be taken out as a solid by a centrifuge, a filter or the like. The obtained resin is usually dried at a temperature not higher than the decomposition temperature of the resin, but is preferably dried under reduced pressure at a temperature not lower than 20 ° C. and not higher than the melting temperature of the resin. The drying time is longer than the time until the purity of impurities such as the remaining solvent becomes below a certain level. Usually, the drying is performed for more than the time until the remaining solvent reaches 1,000 ppm or less, preferably 300 ppm or less, more preferably 100 ppm or less.

  In the present invention, as the resin containing the unit containing the aromatic diol residue having the substituent Z represented by the general formula (I) as a constituent repeating unit, all the units containing the aromatic diol residue are constituted. The content is preferably 1 to 90 mol% of the repeating unit, more preferably 10 to 70 mol%, and particularly preferably 20 to 60 mol%.

(2) Compound Represented by General Formula (V) In the electrophotographic photoreceptor of the present invention, it is essential that the photosensitive layer also contains a compound represented by the following general formula (V).

[In formula (V), U represents a p-valent group having two or more aromatic rings which may have a substituent, V represents a divalent linking group, and R ³ represents a substituent. An optionally substituted alkyl group having 10 to 100 carbon atoms, an optionally substituted alkenyl group having 10 to 100 carbon atoms, or an optionally substituted alkyl group having 10 to 100 carbon atoms. An alkynyl group is shown, and p is an integer of 1 to 10. ]

  Here, the p-valent group having two or more aromatic rings of U is preferably a group represented by the following general formula (VI).

[In the formula (VI), W represents a q-valent linking group, and R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or hydrogen. An atom is shown, q is an integer of 2-4 , r is an integer of 0-4 . Each multiple is R ⁴ and r may be the same or different and when r is 2 or more, plural R ⁴ may be the same or different and the cyclic structure R ⁴ together It may be formed. However, q value is equal to p value. ]

  Here, as the q-valent linking group of W, for example, an alkylene group, a cycloalkylene group, an arylene group, or the like, or these are an oxy group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, an ester group, a carbonate ester And a single bond or the like in combination with or without a group, a sulfate ester group, a phosphate ester group or the like.

  Among these, as a p-valent group having two or more aromatic rings of U, a unit containing an aromatic diol residue having a substituent Z represented by the general formula (I) is used as a constitutional repeating unit. It is preferable to use the same aromatic diols as mentioned in the resin to be included and hindered phenols as a phenolic antioxidant as the basic skeleton, and to effectively exhibit the effect of reducing the surface energy. From the viewpoint, the formula weight is preferably 2,000 or less.

  Examples of the divalent linking group for V include, for example, an alkylene group, an oxy group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, an ester group, a carbonate ester group, a sulfate ester group, and a phosphate ester group. Of these, an oxy group and an ester group are preferable, and an oxy group is particularly preferable. V is preferably all bonded to an aromatic ring of U.

The alkyl group, alkenyl group and alkynyl group of R ³ may be linear or branched, but the number of branches is preferably 3 or less, and is linear. Particularly preferred is an alkyl group. Further, the carbon number is preferably 16 or more from the viewpoint of the effect on the surface slipperiness, more preferably 18 or more, and 60 or less from the viewpoint of compatibility in the photosensitive layer. preferable. Examples of the substituent for these alkyl group, alkenyl group and alkynyl group include halogen atoms such as chlorine, fluorine and bromine.

P is an integer of 1 to 10, preferably 2 to 10, particularly preferably 2 to 4. When p is 2 or more, V and R ³ may be the same or different.

Suitable specific examples of the compound represented by the above general formula (V) are shown in the following Table 1 for each of U, V, R ³ , and p. In the table, the ester group as V has different left and right orientations, but the left side is bonded to U and the right side to R ³ with respect to the ester group arranged as shown in the table.

(3) Electrophotographic Photoreceptor Next, the electrophotographic photoreceptor of the present invention will be described in detail below. The above-mentioned resin containing a unit containing an aromatic diol residue having a substituent Z represented by the general formula (I) as a constitutional repeating unit, and the compound represented by the general formula (V) are conductive. In an electrophotographic photosensitive member having a photosensitive layer on a support, by incorporating it in the photosensitive layer, effects excellent in surface slipperiness, slidability, durability thereof, electrical characteristics and the like are exhibited.

(3a) Conductive support In the electrophotographic photosensitive member of the present invention, the conductive support on which the photosensitive layer is provided is, for example, a metal material such as aluminum, aluminum alloy, stainless steel, copper, or nickel in the form of a drum. Resin film such as polyester provided with a conductive layer such as aluminum, copper, palladium, tin oxide and indium oxide on the surface, insulating support such as paper, or conductive fine particles such as carbon and copper powder A plastic, etc., kneaded and mixed into a sheet, belt, drum, or roll is used. Among them, aluminum and its alloys are preferable, and when an aluminum drum is used, the material is, for example, 3000 series, 5000 series, 6000 series aluminum alloy extrusion / pulling pipes or the like that are specified by JIS. The surface roughness is preferably 2.5 μm or less in terms of the maximum surface roughness Rmax.

  A known blocking layer that is usually used may be provided between the conductive support and the photosensitive layer. Examples of the blocking layer include inorganic layers such as aluminum anodized film, aluminum oxide, and aluminum hydroxide, organic layers such as polyvinyl alcohol, casein, polyvinyl pyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, and polyamide. Layers are used. The film thickness in the case of using an aluminum anodized film is preferably 1 to 10 μm, and is preferably sealed with nickel acetate or the like in order to further improve the blocking function.

  When the organic layer is used as a blocking layer, it can be used alone or in combination with metal oxides such as titania, alumina, silica and zirconium oxide, or metal fine powders such as copper, silver and aluminum. Also good. The particle diameter of these fine metal powders can be selected as appropriate. For example, it is preferable to use a primary particle diameter of several tens of nanometers to several micrometers, and they may be used in combination. Although the thickness of these blocking layers can be set as appropriate, it is preferably in the range of 0.05 to 20 μm, preferably 0.1 to 10 μm.

(3b) Photosensitive layer
(i) Layer structure As a specific structure of the photosensitive layer, (A1) a charge generation layer mainly composed of a charge generation material on a conductive support, and a charge transport material and a binder resin as a main component A layered photosensitive layer in which charge transport layers are laminated in this order, (A2) a charge transport layer mainly composed of a charge transport material and a binder resin on a conductive support, and a charge generation material as a main component. A layer containing a charge transporting substance and a binder resin is laminated on (A) a laminated photosensitive member such as a reverse laminated photosensitive layer in which charge generation layers are laminated in this order, and (B) a conductive support. Examples of a basic layer structure include a monolayer type (dispersion type) photosensitive layer in which a charge generation material is dispersed in this layer. Each of the outermost surface layers may be provided with a conventionally known overcoat layer mainly composed of, for example, a thermoplastic resin or a thermosetting resin.

(ii) Multilayer type photosensitive layer
(a) Charge generation layer In the case of a multilayer photosensitive layer, examples of the charge generation material used in the charge generation layer include azo pigments, phthalocyanine pigments, perylene pigments, quinacridone pigments, polycyclic quinone pigments, indigo pigments, and benzimidazole pigments. , Pyrylium salt, thiapyrylium salt, squalium salt and the like. As the charge generation layer, these pigments or / and salts are usually used, for example, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, Used in a form bound with various binder resins such as epoxy resin, urethane resin, cellulose ester, cellulose ether and the like. In this case, the charge generation material is used in a range of 30 to 500 parts by weight with respect to 100 parts by weight of the binder resin, and the film thickness is usually 0.1 to 2 μm, preferably 0.15 to 0.8 μm. It is said.

  In addition, the charge generation layer may contain various additives such as a leveling agent, an antioxidant, and a sensitizer for improving the coating property, if necessary.

(b) Charge Transport Layer The charge transport layer may be formed of a binder resin having a charge transport function alone, but it is preferable that the charge transport material is dispersed in the binder resin. Examples of the charge transporting substance include polycyclic aromatic compounds such as pyrene and anthracene, heterocyclic compounds such as carbazole, indole, oxazole, thiazole, pyrazoline, oxathiazole, thiadiazole, and triazole, p-diethylaminobenzaldehyde-N, N Hydrazone compounds such as -diphenylhydrazone, N-methylcarbazole-3-carbaldehyde-N, N-diphenylhydrazone, 5- (4- (di-p-tolylamino) benzylidene) -5H-dibenzo (a, d) cycloheptene Styryl compounds such as p-tritolylamine, benzidine compounds such as N, N, N, N-tetraphenylbenzidine, butadiene compounds, di- (p-ditolylaminophenyl) methane, etc. Triphenyl Tan-based compounds, and the like.

  Further, as the binder resin, a resin containing a unit containing an aromatic diol residue having a substituent Z represented by the general formula (I) described above as a constitutional repeating unit is used, and if necessary, For example, homopolymers or copolymers of vinyl compounds such as methyl methacrylate, styrene, vinyl chloride, polycarbonate, polyester, polyester carbonate, polysulfone, polyimide, phenoxy resin, epoxy resin, silicone resin, and the like may be used in combination. The use ratio of the charge transport material is usually 30 to 200 parts by weight, preferably 40 to 150 parts by weight, and the film thickness is usually 10 to 60 μm, preferably 100 parts by weight of the binder resin. Is 10 to 45 μm.

  In addition, the charge transport layer may contain various additives such as antioxidants such as hindered phenols and hindered amines, ultraviolet absorbers, sensitizers, leveling agents, and electron-withdrawing substances as necessary. .

(iii) Single-layer type photosensitive layer In the case of a single-layer type photosensitive layer, a resin containing a unit containing an aromatic diol residue having the substituent Z represented by the general formula (I) as a constituent repeating unit. Furthermore, if necessary, the same charge generation as in the multilayer photosensitive layer is performed in the charge transport medium in which the same charge transport material as that in the multilayer photosensitive layer is dispersed in the binder resin combined with other resins. The material is dispersed. In this case, the particle size of the charge generation material needs to be sufficiently small, preferably 1 μm or less, more preferably 0.5 μm or less. The amount of the charge generating material dispersed in the single-layer type photosensitive layer is preferably in the range of 0.5 to 50% by weight, more preferably 1 to 20% by weight from the viewpoints of sensitivity and chargeability. Used in range. The film thickness of the single-layer type photosensitive layer is usually 5 to 50 μm, more preferably 10 to 45 μm.

  Also in the single-layer type photosensitive layer, from the viewpoint of improving film formability, flexibility, mechanical strength, etc., a known plasticizer, slipperiness imparting agent, additive for suppressing residual potential, dispersion A dispersion aid for improving the stability, a leveling agent for improving the coating property, and a surfactant such as silicone oil, fluorine oil and other additives may be added.

(iv) Other additives Further, in the present invention, the compound represented by the general formula (V) is contained in the photosensitive layer, basically the outermost surface layer of the photosensitive layer. When contained in the layer, it is added to the charge transport layer and is usually 0.01 to 40 parts by weight, preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight of the binder resin contained in the layer. Is used in the range of 1 to 30 parts by weight. Moreover, when it is contained in a single-layer type photosensitive layer, it is usually 0.01 to 40 parts by weight, preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight of the binder resin contained in the entire photosensitive layer. Is used in the range of 1 to 30 parts by weight. Moreover, when using for an overcoat layer, it is used in 0.1-50 weight part normally with respect to 100 weight part of resin components of an overcoat layer.

  Examples of the electron-withdrawing substance added to the photosensitive layer include chloranil, 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, Quinones such as phenanthrenequinone, aldehydes such as 4-nitrobenzaldehyde, 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetra Ketones such as nitrofluorenone, 3,3 ′, 5,5′-tetranitrobenzophenone, acid anhydrides such as phthalic anhydride and 4-chloronaphthalic anhydride, tetracyanoethylene, terephthalalmalononitrile, 9-an Tolylmethylidene malononitrile, 4-nitrobenzalmalononitrile Cyano compounds such as 4- (p-nitrobenzoyloxy) benzalmalononitrile, 3-benzalphthalide, 3- (α-cyano-p-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4, Examples thereof include phthalides such as 5,6,7-tetrachlorophthalide. Examples of dye pigments added to the photosensitive layer include triphenylmethane dyes such as methyl violet, brilliant green, and crystal violet, thiazine dyes such as methylene blue, quinone dyes such as quinizarin, cyanine dyes, pyrylium salts, and thiapyrylium. Salt, benzopyrylium salt and the like.

(V) Formation method of each layer Each photosensitive layer of the electrophotographic photosensitive member is obtained by dissolving or dispersing a substance contained in the layer in a solvent, for example, a dip coating method, a spray coating method, a ring coating method, etc. These are formed by sequentially applying and drying using a known method.

(4) Image forming apparatus An image forming apparatus such as a copying machine or a printer using the electrophotographic photosensitive member of the present invention performs charging of the electrophotographic photosensitive member and image exposure to the charged electrophotographic photosensitive member. At least an image exposure unit that forms an electrostatic latent image, a developing unit that develops the electrostatic latent image with toner, and a transfer unit that transfers the toner to a transfer medium.

  An image forming apparatus using the electrophotographic photoreceptor of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing an embodiment of the image forming apparatus of the present invention. Is a conductive support, 12 is a photosensitive layer, 2 is a charging means, 3 is an image exposing means, 4 is a developing means, 41 is a developing tank, 42 is an agitator, 43 is a supply roller, 44 is a developing roller, and 45 is a regulating member. 5 is a transfer unit, 6 is a cleaning unit, 7 is a fixing unit, 71 is an upper fixing roller, 72 is a lower fixing roller, 73 is a heating device, T is toner, P is recording paper, charging unit 2, image exposure The means 3, the developing means 4, the means device 5, and the cleaning means 6 are arranged in this order along the outer peripheral surface of the drum-shaped electrophotographic photosensitive member 1.

  Here, the electrophotographic photosensitive member 1 has an aromatic diol residue having the substituent Z represented by the general formula (I) on the electrophotographic photosensitive member of the present invention described above, that is, a conductive support. It comprises an electrophotographic photoreceptor having a photosensitive layer containing a resin containing a unit containing as a constituent repeating unit and containing a compound represented by the general formula (V). In FIG. Made of a conductive metal and made up of a cylindrical support 11 that can be rotated in the direction of the arrow in the drawing by a rotational drive mechanism (not shown), and a photosensitive layer 12 formed on the outer peripheral surface thereof. A photographic photoreceptor 1 is shown.

  The charging means 2 uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. For example, a corona charging system such as corotron or scorotron using corona discharge, a conductive roller applied with voltage, Alternatively, a direct charging method in which a direct charging member such as a brush or a film is brought into contact with the surface of the photosensitive member and charging is performed by charging with air discharge or injection charging without accompanying is used. Among these, in the corona discharge method, scorotron charging is preferable in order to keep the dark portion potential constant. In the case of the contact charging method using a conductive roller or the like, either DC charging or AC superimposed DC charging can be used. In FIG. 1, as an example, a direct contact charging unit 2 using a conductive roller disposed in contact with the outer peripheral surface of the photoreceptor 1 is shown.

  In many cases, the electrophotographic photosensitive member 1 and the charging unit 2 are detachably provided in the main body of the image forming apparatus as a cartridge in which both are integrated (hereinafter referred to as “photosensitive cartridge”). For example, when the electrophotographic photosensitive member 1 or the charging means 2 has reached the replacement time due to deterioration or the like, the photosensitive member cartridge can be removed from the image forming apparatus main body and replaced with another new photosensitive member cartridge. ing.

  The image exposure means 3 is not particularly limited in its light source as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. For example, a halogen lamp, a fluorescent lamp, a laser such as a semiconductor laser or a He—Ne laser, an LED, a photoconductor internal exposure method, or the like is used. As a digital electrophotographic method, a laser, an LED, an optical shutter array, or the like is used. It is preferable. The wavelength at which image exposure is performed is arbitrary, but for example, monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength of 600 to 700 nm slightly shorter, monochromatic light with a wavelength of 380 to 500 nm, or the like is used. Can do.

  The developing means 4 develops and visualizes the electrostatic latent image formed by the image exposure means 3, and includes, for example, cascade development, one-component insulating toner development, one-component conductive toner development, and two-component magnetic brush development. A dry development method, a wet development method, or the like is used. As the toner, in addition to the pulverized toner, a polymerized toner such as suspension polymerization or emulsion polymerization aggregation method can be used. In particular, in the case of the polymerized toner, the toner having a small particle diameter of about 4 to 8 μm is used. Can be used, and those having a shape that is close to a spherical shape but deviating from a spherical shape such as a potato shape can also be used, which is excellent in charging uniformity and transferability, and is suitably used for high image quality. In FIG. 1, as an example, the developing unit 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45. The developing unit 4 stores toner T inside the developing tank 41. Is shown. In this case, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary.

  Here, the agitator 42 is composed of a plurality of blade-shaped blades that can be rotated in the direction of the arrow in the drawing by a rotation drive mechanism (not shown). The agitator 42 agitates the toner T stored in the developing tank 41 and T is conveyed to the supply roller 43 side. The supply roller 43 is made of a conductive sponge or the like and is disposed so as to be in contact with the developing roller 44 and to be rotated by a rotation driving mechanism (not shown). Supply to the surface. The developing roller 44 is coated with a metal roll such as iron, stainless steel, aluminum, or nickel, which is smoothed or roughened as required, or a metal roll coated with silicon resin, urethane resin, fluororesin, or the like. The toner T is disposed in contact with the electrophotographic photosensitive member 1 and the supply roller 43 so as to be rotatable in a direction indicated by an arrow in the drawing by a rotation drive mechanism (not shown). It is carried and brought into contact with the surface of the electrophotographic photoreceptor 1. The regulating member 45 is made of a resin blade such as silicon resin or urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze or the like, or a blade coated with a resin on the metal blade, and is in contact with the developing roller 44. The blade is pressed against the developing roller 44 with a predetermined force by a spring or the like (general blade linear pressure is 5 to 500 g / cm). The toner T may be charged by friction charging, and the layer thickness of the toner T supplied to the outer peripheral surface of the developing roller 44 is regulated.

  In many cases, the developing unit 4 is also provided as a cartridge (hereinafter referred to as “toner cartridge”) in a detachable manner on the main body of the image forming apparatus, and for example, when the toner in the cartridge runs out. In addition, the toner cartridge can be removed from the main body of the image forming apparatus and replaced with another new toner cartridge. Furthermore, the electrophotographic photosensitive member 1, the charging means 2, and the developing means 4 can be integrated into a cartridge form.

  The transfer means 5 is applied with a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to the recording paper (paper, medium) P. Electrostatic transfer methods such as corona transfer, roller transfer, and belt transfer, pressure transfer methods, adhesive transfer methods, and the like are used. In FIG. 1, as an example, a transfer unit 5 including a transfer charger, a transfer roller, a transfer belt, and the like disposed to face the electrophotographic photoreceptor 1 is shown.

  In addition to the electrophotographic photosensitive member 1, the charging unit 2, the image exposure unit 3, the developing unit 4, and the transfer unit 5, the image forming apparatus of the present invention shown in FIG. The fixing means 7 is also provided.

  Here, the cleaning means 6 scrapes off the residual toner T adhering to the photoreceptor 1 and collects the residual toner T. For cleaning, a brush, a magnetic brush, an electrostatic brush, a magnetic roller, Any cleaning member such as a blade can be used.

  The fixing means 7 fixes the toner T transferred onto the recording paper P onto the recording paper P. For example, a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber or fluorine resin. Any method such as heat roller fixing using a heat fixing member such as a fixing sheet, flash fixing, oven fixing, and pressure fixing can be used. In FIG. 1, as an example, a fixing unit 7 using a heat roller system including an upper fixing roller 71 and a lower fixing roller 72 each having a heating device 73 therein is shown. Each of the fixing rollers 71 and 72 may be configured to be able to supply a release agent such as silicone oil to the surface in order to improve the releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

  Although not shown in FIG. 1, a means for removing static electricity by exposure may be provided, and as the exposure light source, a fluorescent lamp, an LED, or the like is used. An exposure energy that is three times or more of the exposure light in the image exposure means is used. Further, a pre-exposure unit, an auxiliary charging unit, and the like may be provided, and a configuration in which offset printing is performed or a full-color tandem configuration using a plurality of types of toners may be employed.

  In the image forming apparatus of the present invention, the cylindrical electrophotographic photosensitive member 1 having the photosensitive layer 12 on the outer peripheral surface of the conductive support 11 is rotated at a constant peripheral speed, and the surface thereof is predetermined by the charging unit 2. It is uniformly charged to a potential (for example, −600 V), and then the charged photosensitive layer 12 of the photosensitive member 1 is exposed by the image exposure unit 3 in accordance with the image to be recorded. An image is formed, and then the toner T supplied by the supply roller 43 is thinned by the regulating member 45 by the developing unit 4 and at a predetermined polarity (here, the same potential as the charged potential of the photoreceptor 1). , Negatively charged), transported while being carried on the developing roller 44, brought into contact with the surface of the photosensitive member 1, and adhered with toner T, thereby visualizing and developing the electrostatic latent image. Obtained The toner image was transferred to the recording paper P by the transfer means 5, heating the toner T transferred on the recording paper P by the fixing means 7, is intended to be fixed on the recording paper P pressurized. On the other hand, the toner T remaining on the photosensitive layer 12 of the photoreceptor 1 is removed by the cleaning means 6 and then the same operation as described above is repeated.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Production Example of Resin A Including Unit Containing Aromatic Diol Residue Having Substituent Z Represented by General Formula (I) as a Constitutional Repeating Unit]
In a 500 mL beaker, 6.83 g of sodium hydroxide and 170 mL of water were weighed and stirred and dissolved while bubbling nitrogen, and then 0.1467 g of benzyltriethylammonium chloride and bis (4-hydroxy-3,5-dimethylphenyl) were added thereto. ) 7.22 g of methane was added in order, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel, followed by 15.17 g of 4,4-bis (4-hydroxyphenyl) pentanoic acid octadecyl ester, 2, 3 , 6-Trimethylphenol 0.1534 g and dichloromethane 170 mL were sequentially added to the reaction vessel. Next, a dichloromethane solution in which 5.78 g of isophthalic acid chloride and 5.78 g of terephthalic acid chloride were dissolved in 170 mL of dichloromethane from a dropping funnel while stirring the aqueous alkali solution in the reaction tank while maintaining the external temperature of the reaction vessel at 20 ° C. Was added dropwise over 1 hour, and stirring was continued for 6 hours. Then, 3.58 mL of acetic acid, 230 mL of dichloromethane, and 230 mL of water were added and stirred for 30 minutes, and then stirring was stopped. The reaction solution is centrifuged to separate the organic phase and the aqueous phase, and the organic phase is gradually put into 400 mL of a stirring 0.1N sodium hydroxide aqueous solution, and the stirring is continued for 30 minutes for washing. The organic phase and the aqueous phase are separated by centrifugation, this washing operation is performed twice, then the same washing operation with 400 mL of 0.1N hydrochloric acid is performed twice, and the same washing operation with 400 mL of water is further performed twice. It was. A precipitate obtained by pouring the washed organic phase into 6000 mL of methanol was filtered out and dried under reduced pressure at 80 ° C. for 24 hours to obtain the desired polyester resin A.

In the obtained resin A, R ² in the general formula (IV) is a —CH ₃ group, Z is a — (CH ₂ ) ₂ —CO—O—C ₁₈ H ₃₇ group, and Y is an isophthaloyl group and a terephthaloyl group. The following constitutional repeating unit (50 mol%), which is a 1: 1 mixture of: bis (4-hydroxy-3,5-dimethylphenyl) methane residue, 1: 1 of isophthalic acid residue and terephthalic acid residue It was a polyester resin composed of 50 mol% of the following constitutional repeating units made of a mixture.

Further, with respect to the obtained resin A, the viscosity average molecular weight was measured by the method shown below, and it was 37,000.
<Viscosity average molecular weight>
The resin was dissolved in dichloromethane to prepare a solution having a concentration c of 6.00 g / L, and a constant temperature set to 20.0 ° C. using an Ubbelohde capillary viscometer with a dichloromethane flow time t ₀ of 136.16 seconds. The flow time t ₁ of the resin solution was measured in a water bath, and the viscosity average molecular weight was calculated according to the following formula.
(a) Relative viscosity η _rel = t ₁ / t ₀
(b) Specific viscosity η _sp = η _rel −1
(c) a = 0.438 × η _sp +1
(d) b = 100 × η _sp / c
(e) Viscosity η = b / a
(f) Viscosity average molecular weight M _v = 3207 × η ^1.205

[Production Example of Compound B Represented by General Formula (V)]
200 g of a mixture of branched primary alcohols having 32, 34, and 36 carbon atoms (“NJECOAL C32-36” manufactured by Nippon Nippon Chemical Co., Ltd.) and 400 mL of toluene were charged into a reactor equipped with a thermometer and a reflux condenser, and the temperature was adjusted to 60 ° C. While heating and stirring, 55 g of phosphorus tribromide was added dropwise and reacted for 1 hour, and then neutralized by adding an aqueous sodium carbonate solution. The entire amount was poured into 3 L of methanol, and the resulting precipitate was collected by filtration. 98 g of branched alkyl bromide of several 32 to 36 was obtained. Meanwhile, 20.5 g of bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F], 15.5 g of tetrabutylammonium bromide, 13.5 g of potassium hydroxide, and 250 mL of tetrahydrofuran were thermometered and refluxed. A reactor equipped with a condenser tube was charged and heated to 60 ° C. with stirring. To this was added 98 g of the branched alkyl bromide having 32 to 36 carbon atoms obtained above, and the mixture was reacted under reflux for 6 hours. After adding 300 mL of toluene to the reaction solution and washing with water three times, the organic phase was reprecipitated with 3 L of methanol to obtain 101 g of a pale yellow crude tetramethylbisphenol F branched alkyl 2-adduct. The crude product was purified by column chromatography using silica gel, further dissolved in 200 mL of toluene, 12.5 g of activated clay was added, and the mixture was stirred at 60 ° C. for 30 minutes, and then the activated clay was removed by filtration. Treatment was carried out once at 0.5 g, once with 2.5 g of activated carbon, and twice with 12.5 g of activated clay, and the solvent was distilled off to obtain a colorless viscous liquid purified compound B. The ¹ H-NMR spectrum of Compound B is shown in FIG.

Example 1
As a charge generation material, 10 parts by weight of oxotitanium phthalocyanine showing a clear peak at a diffraction angle 2θ ± 0.2 ° of 27.3 ° in a powder X-ray diffraction spectrum by CuKα ray, and polyvinyl butyral (electric Chemical Co., Ltd. “Denkabutyral # 6000C”) 5 parts by weight, 500 parts by weight of 1,2 dimethoxyethane was added, and the coating solution for charge generation layer, which was ground and dispersed by a sand grind mill, was deposited on the surface with aluminum. The film was coated on a polyethylene terephthalate film having a thickness of 0.3 μm after drying, and dried to form a charge generation layer.

  Next, on the formed charge generation layer, 60 parts by weight of the charge transport material shown below, 100 parts by weight of the polyester resin A obtained in the above production example as a binder resin, and 10 parts by weight of the compound B obtained in the above production example, In addition, a charge transport layer coating solution prepared by dissolving 0.03 parts by weight of silicone oil as a leveling agent in a mixed solvent of toluene and tetrahydrofuran was applied so that the film thickness after drying was 20 μm, and after air drying, the coating solution was 125 ° C. A charge transport layer was formed by drying for 20 minutes to produce an electrophotographic photoreceptor.

The produced electrophotographic photosensitive member is fixed on a reciprocating table of a wear tester “FR-2 type” manufactured by Suga Test Instruments Co., Ltd., a load of 7.8 N is applied, and “Weddingry Tri-M-ite” manufactured by 3M is applied.
Paper 2000 "is reciprocated 300 times on the photoconductor, and a load of 7.8 N is applied.
Polishing was performed by reciprocating 300 times on the photosensitive member with “JK Wiper Tissue 150-S” manufactured by Crecia. Thereafter, for the electrophotographic photosensitive member after the polishing treatment, the surface slipperiness and the contact angle were measured by the following methods, and the results are shown in Table 2 together with the surface slipperiness and the contact angle before the polishing treatment. Indicated.

<Slip property>
The toner is uniformly placed on the electrophotographic photosensitive member so as to be 0.1 mg / cm ^2, and the surface to be contacted is made of urethane rubber having a thickness of 2 mm, which is the same material as the cleaning blade, cut to a width of 1 cm, at an angle of 45 degrees. The dynamic friction coefficient was measured using a fully automatic friction wear tester “DFPM-SS” manufactured by Kyowa Interface Chemical Co., Ltd. under the conditions of a load of 2.0 N, a speed of 5 mm / second, and a stroke of 20 mm.

<Contact angle>
Using an automatic contact angle meter “CA-VP type” manufactured by Kyowa Interface Chemical Co., Ltd., pure water was dropped from an approximately 1 μL glass cylinder onto an electrophotographic photoreceptor in an environment of a temperature of 25 ° C. and a relative humidity of 50%. The contact angle after 2 seconds was measured, and an average value of three times of this measurement was taken.

Furthermore, the electrical characteristics of the produced electrophotographic photosensitive member were evaluated by the method shown below, and the results are shown in Table 2.
<Electrical characteristics>
The electrophotographic photosensitive member is mounted on a photosensitive member characteristic evaluation apparatus installed in an environmental test room at a temperature of 25 ° C. and a relative humidity of 50%, charged so that the surface potential of the photosensitive member becomes −700 V, and then monochromatic at 780 nm. The light was irradiated and exposed while changing the irradiation intensity, and the electrical characteristics were evaluated by a cycle of charging, exposure, potential measurement, and static elimination, using 660 nm LED light as static elimination light. At that time, the exposure intensity at which the surface potential after −100 ms becomes −350 V is reduced by half the exposure amount [E _1/2 ] (μJ / cm ² ).
In addition, the surface potential after the static elimination irradiation was measured as a residual potential [Vr] (V).

Example 2
As a binder resin in the charge transport layer, a structural repeating unit 70 comprising 50 parts by weight of the polyester resin A obtained in the above production example, a bis (4-hydroxy-3,5-dimethylphenyl) methane residue and a terephthalic acid residue. A composition comprising a terephthalic acid residue and a mixture of mol%, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, and 2-hydroxyphenyl-4-hydroxyphenyl-methane residues An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that 50 parts by weight of a polyester resin composed of 30 mol% of repeating units was used, and evaluated in the same manner.

Example 3
The binder resin in the charge transport layer is composed of 20 parts by weight of the polyester resin A obtained in the above production example, 2,2-bis (4′-hydroxy-3′-methylphenyl) propane residue and carbonate residue. Using 51 mol% of repeating units and 80 parts by weight of a polycarbonate resin consisting of 49 mol% of a repeating unit composed of 1,1-bis (4′-hydroxyphenyl) -1-phenylethane residue and carbonate residue In the same manner as in Example 1, an electrophotographic photosensitive member was prepared and evaluated in the same manner.

Comparative Example 1
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 100 parts by weight of the polycarbonate resin used in Example 3 was used as the binder resin in the charge transport layer.

Comparative Example 2
In the charge transport layer, 20 parts by weight of the polyester resin A obtained in the above production example and 80 parts by weight of the polycarbonate resin used in the above Example 3 were used as the binder resin, and obtained in the above production example. An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that Compound B was not used, and evaluated in the same manner.

  As is apparent from the results in Table 2, in the examples, the coefficient of dynamic friction is low after polishing as well as before polishing, and thus it is understood that the characteristics are maintained. The same applies to the contact angle. On the other hand, in a comparative example, it turns out that the dynamic friction coefficient and contact angle after grinding | polishing deteriorate, and there is no sustainability. Regarding electrical characteristics, both the examples and comparative examples were good.

Example 4
The coating solution for the charge generation layer and the coating solution for the charge transport layer used in Example 1 were sequentially dip-coated on an aluminum tube having a diameter of 30 mm and a length of 346 mm, and the film thickness after drying was charged. The electrophotographic photosensitive member was produced by applying the generation layer 0.4 μm and the charge transport layer 25 μm and drying to form a charge generation layer and a charge transport layer. When this electrophotographic photosensitive member was mounted on a digital copying machine “DP3200” manufactured by Matsushita Electric Industrial Co., Ltd. and printed, a good image could be obtained. Further, the first and 1,000th images were visually compared, but no change was observed.

  According to the present invention, the slipperiness and slidability of the surface of an electrophotographic photosensitive member can be remarkably improved without adversely affecting the electrical characteristics, so that excellent image quality is maintained and electrical characteristics excellent in durability are maintained. An electrophotographic photosensitive member can be obtained, and the electrophotographic photosensitive member of the present invention can provide an image forming apparatus such as a high-speed copying machine, a color printer, and a facsimile machine with extremely high quality.

1 is a schematic view showing an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention. ¹ is a ¹ H-NMR spectrum of Compound B obtained in Production Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 11 Conductive support body 12 Photosensitive layer 2 Charging means 3 Image exposure means 4 Developing means 41 Developing tank 42 Agitator 43 Supply roller 44 Developing roller 45 Control member 5 Transfer means 6 Cleaning means 7 Fixing means 71 Upper fixing roller 72 Lower fixing roller 73 Heating device T Toner P Recording paper

Claims (4)

In an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the surface layer of the photosensitive layer has a fragrance represented by the following general formula (III) having a substituent Z represented by the following general formula (I) An electrophotographic photoreceptor comprising a polyester resin containing a unit containing a group diol residue as a constitutional repeating unit and a compound represented by the following general formula (V).

[In Formula (I), R ¹ is an alkyl group having 6 to 100 carbon atoms which may have a substituent, an alkenyl group having 6 to 100 carbon atoms which may have a substituent, or a substituent. Represents an alkynyl group having 6 to 100 carbon atoms, and n is an integer of 0 to 10. ]

[In the formula (III), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a hydrogen atom, and Z represents the above general formula ( The substituent represented by I) is shown, and the benzene ring may further have a substituent. ]

[In the formula (V), U represents a p-valent group having two or more aromatic rings which may have a substituent represented by the following formula (VI), and V represents a divalent oxy group or R ³ represents an ester group, and R ³ has an optionally substituted alkyl group having 10 to 100 carbon atoms, an optionally substituted alkenyl group having 10 to 100 carbon atoms, or a substituent. And an alkyl group, an alkenyl group and an alkynyl group are linear or branched with 3 or less branches, and p is an integer of 2 to 4. ]

[In the formula (VI), W represents a q-valent linking group, and R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or hydrogen. An atom is shown, q is an integer of 2-4, r is an integer of 0-4. The plurality of R ⁴ and r may be the same or different, and when r is 2 or more, the plurality of R ⁴ may be the same or different, and R ⁴ forms a cyclic structure. You may do it. However, q value is equal to p value. ] The polyester resin containing a unit containing an aromatic diol residue having a substituent Z represented by the general formula (I) as a constitutional repeating unit contains a unit represented by the following general formula (IV) as a constitutional repeating unit. The electrophotographic photosensitive member according to claim 1, which is a polyester resin.

[In the formula (IV), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a hydrogen atom, and Z represents the general formula ( I) represents a substituent represented by formula (I), the benzene ring may further have a substituent, and Y represents an alkylene group which may have a substituent, or a cyclo which may have a substituent. An alkylene group or an arylene group which may have a substituent is shown. ] A polyester resin containing, as a constituent repeating unit, a unit containing an aromatic diol residue represented by the general formula (III) having a substituent Z represented by the general formula (I). the electrophotographic photosensitive member according to claim 1 or 2 units are those containing 1 to 90 mol% of all the structural repeating unit containing. An electrophotographic photosensitive member according to any one of claims 1 to 3, image exposure to form a charging means for charging the electrophotographic photoreceptor, an electrostatic latent image performs image exposure to the charged electrophotographic photoreceptor An image forming apparatus comprising: a developing unit that develops the electrostatic latent image with toner; and a transfer unit that transfers the toner to a transfer target.

Images