JP4518000B2 - Electrophotographic photoreceptor and image forming apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photoreceptor and an image forming apparatus using the electrophotographic photoreceptor. Specifically, the present invention relates to an electrophotographic photosensitive member containing a specific compound and an image forming apparatus using the electrophotographic photosensitive member.

Electrophotographic technology is widely used in copiers, various printers, facsimiles and the like because of its immediacy and high quality images. For the photoreceptors that form the core of electrophotographic technology, inorganic photoconductive materials such as amorphous silicon and arsenic-selenium and organic photoconductive materials are used.
Several layers have been devised as the layer structure of the organic photoreceptor, but a so-called laminated photoreceptor in which the charge generation layer and the charge transport layer are separated by separating the functions of charge generation and charge transport, and a charge generation material In general, a so-called single-layer type photoreceptor containing a charge transporting material and a charge transporting material is used. As a layered structure of a laminated type photoreceptor, a normal laminated type photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and a reverse laminated type photosensitive layer in which layers are reversed are known.

  The electrophotographic process is repeatedly charged, exposed, developed, transferred, cleaned, neutralized, etc., so it has various durability, stability, such as physical, mechanical, chemical, and electrical properties. Sex is required. In particular, the durability of organic photoreceptors against mechanical contact with developers, transfer materials, corona discharge products, cleaning blades and the like is inferior to inorganic photoreceptors. In addition, with the recent development of finer developer particles or high-spherical chemically polymerized toners aimed at higher resolution and higher image quality, there is an increasing demand for easy transferability of toner and high-precision cleaning characteristics. ing.

  In order to achieve easy transferability of toner and high-accuracy cleaning characteristics, it is necessary to reduce the energy related to the frictional force and adhesion force on the surface of the photoconductor. In addition, the use of a silicone leveling agent, specifically, a method of adding silicone oil or the like to the surface layer, or a method of dispersing a surface modifier such as fluororesin or silicon powder in the surface layer is known.

For example, it has been reported that silicone oil is added (for example, see Patent Document 1) or that fluorine resin powder is contained (for example, see Patent Document 2).
JP 11-352707 A JP 2002-40684 A

  However, these commonly used surface modifiers are, for example, leveling agents, which are poorly compatible with the coating liquid components, so that during the coating film drying process or during a relatively short period of storage. The leveling agent easily moves to the surface and segregates on the extreme surface of the surface layer. Therefore, although the surface energy can be effectively reduced in the initial stage, the leveling agent is easily scraped off while the surface is repeatedly rubbed, and the effect is lost immediately and there is a problem in sustainability. . Further, for example, when fluororesin fine particles are dispersed in the photosensitive layer, the lubricity is certainly improved and the effect seems to continue, but these fine particles form a latent image incident on the photosensitive layer. For this reason, there is a case where the light is scattered and reflected to prevent the formation of a faithful latent image. In particular, in recent years, it has been found that this process has a large effect in processes using dot-like micro latent images such as lasers, LEDs, and liquid crystal shutters controlled by digital signals, and the uniformity of the image is greatly reduced.

  On the other hand, as described above, recent toner developers tend to have smaller particle sizes and lower glass transition temperatures for higher resolution, higher image quality, and higher speed. This means that transfer efficiency is reduced due to increased adhesion, and filming is likely to occur. At present, there is a long-awaited demand for photoreceptors with more sophisticated surface characteristics.

  That is, the object of the present invention is a highly durable and highly functional electrophotographic photosensitive member that is free from light scattering and reflection, has low surface energy, is excellent in surface slipperiness and surface releasability, and maintains its surface characteristics. And providing an image forming apparatus using the photoconductor.

  As a result of intensive studies on the above problems, the present inventors include a compound in which a specific aliphatic hydrocarbon having 10 to 100 carbon atoms is bonded to a condensed ring having two or more aromatic rings in the outermost layer of the photoreceptor. Thus, the present inventors have found that the surface energy can be reduced extremely effectively and that the effect is also durable. That is, the gist of the present invention is an electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, wherein the outermost layer of the photoreceptor contains a compound represented by the following general formula (1). An electrophotographic photosensitive member and an image forming apparatus using the photosensitive member.

(In General Formula (1), A represents an n-valent condensed ring having two or more aromatic rings which may have a substituent, X represents a divalent linking group, and B represents carbon. And represents a substituent having an aliphatic hydrocarbon group having a prime number of 10 to 60. n represents an integer of 2 to 4. )

  The electrophotographic photoreceptor containing a specific compound in the outermost layer of the photoreceptor according to the present invention has excellent surface characteristics such as a low surface friction coefficient and a low surface energy. The low coefficient of friction provides the effect that high-quality images can be obtained by suppressing the reversal of the blade, reducing the load on the machine, and further suppressing the jitter of the photoreceptor. In addition, a photoreceptor having a low surface energy exhibits high toner releasability, and a high-quality image can be obtained. Since these characteristics persist even after repeated use, a stable image can always be formed. In addition, there is almost no adverse effect on the photoconductive properties such as sensitivity and photoresponsive properties due to the inclusion of the compound, and it has excellent durability and provides an image forming apparatus such as a high-speed copying machine or a color printer with extremely high quality. I can do it.

Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of the embodiments of the present invention, and is appropriately modified without departing from the spirit of the present invention. can do.
The electrophotographic photoreceptor of the present invention contains a compound represented by the general formula (1).

In the general formula (1), A represents an n-valent condensed ring having 2 or more aromatic rings which may have a substituent, and preferably has 2 or more and 5 or less aromatic rings. N-valent condensed ring. If the number of aromatic rings in A is large, the affinity with the photosensitive layer component is improved, which is advantageous. However, if the number is too large, it becomes a disadvantage because it traps charges when particles are formed and deteriorates electrical characteristics.
Examples of the condensed ring constituting A in the general formula (1) include those having 8 to 60 carbon atoms, such as pentalene, indene, naphthalene, azulene, heptalene, biphenylene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, Examples include triphenylene, pyrene, chrysene, naphthacene, picene, perylene, pentacene, tetraphenylene, hexacene, rubicene, coronene, trinaphthylene, heptaphene, heptacene, pyrantolene, ovalene, fullerene and the like. Considering factors such as the affinity with the photosensitive layer, the availability of raw materials, and the ease of synthesis, those having a large number of carbon atoms are disadvantageous because of their low solubility. Preferred examples include those having 8 to 20 carbon atoms, such as pentalene, indene, naphthalene, azulene, heptalene, biphenylene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, and perylene. Among them, naphthalene, anthracene, pyrene, perylene, and fluorene are preferable. Further, a heteroatom may be contained in the condensed ring, and examples of the heteroatom that may be contained include oxygen, nitrogen, and sulfur.

  In the condensed ring, in the general formula (1)

In addition to the above, it may have a substituent bonded directly. The substituent represents a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted amino group. When the number of the substituents is 2 or more, the substituents may be bonded to the same or different aromatic rings, and may be the same or different. Further, the substituents may be bonded to each other to form a ring structure.

In consideration of the influence on electric characteristics, it is preferable that A in the general formula (1) has aliphatic and aromatic hydrocarbons that do not contain a hetero atom as the substituent, or does not have a substituent. .
In the general formula (1), various kinds of X can be used as long as they are divalent linking groups, but oxygen, sulfur, sulfonyl group, sulfone group, sulfenyl group, carbonyl group, ester group, thioester group, phosphorus Among these, an acid ester group, a methylene group, or a linking group obtained by combining these groups is preferable, particularly a linking group having 6 or less atoms. Among these, a divalent linking group containing an oxygen atom or an alkylene group is particularly preferable, and among them, an ether bond, an ester bond, and a methylene group are particularly preferable because of easy synthesis.

X is preferably bonded to the aromatic ring portion of A, and X is preferably not bonded to two aromatic rings of A at the same time.
In general formula (1), B represents a linear or branched aliphatic hydrocarbon group having 10 to 100 carbon atoms.
When the carbon number of B is small, the compatibility with the photosensitive layer tends to be improved. On the other hand, there is a tendency for the surface energy reduction effect to be small. Conversely, when the carbon number is large, the surface energy reduction effect is high. However, since the compatibility with the photosensitive layer, the stability of the coating solution when forming the photosensitive layer, and the compatibility tend to deteriorate, the carbon number of the B portion in the formula is usually 10 Above, preferably 14 or more, more preferably 18 or more, usually 100 or less, preferably 80 or less, more preferably 60 or less.

  In general formula (1), the number of branches at the B portion is preferably 3 or less. This is because the surface energy is effectively reduced. Among them, a straight chain having no branch or one having 1 branch is particularly preferable. Although unsaturated bonds may be present, it is preferable that they are all saturated. Here, the number of branches refers to the number of molecular chains directly bonded to a series molecular chain having the largest number of carbon atoms as a main chain.

  The effect is obtained with 1 to 10 as n, but preferably an integer of 2 to 8, more preferably 2 to 4. If n is too small, a sufficient sliding effect cannot be obtained, and if it is too large, the compatibility with the photosensitive layer is lowered and the bleed out is increased. When n is 2 to 10, in the general formula (1)

The structures of the parts represented by may be the same or different.
Preferred examples of the compound represented by the general formula (1) according to the present invention include compounds as shown in Table 1, but are not limited to these compounds. Table 1 shows only the portions corresponding to A, X, and B of the compound represented by the general formula (1). Among X in the table, the left and right orientations of the ester group and the —CH ₂ O— group are different, but A is present on the left side with respect to the ester group and the —CH ₂ O— group arranged as shown in the table. Suppose that B is bonded to the right side.

  The compound represented by the general formula (1) may be used in any combination as one kind or a mixture of two or more kinds. Normally, one compound is used, but each compound often has a gradient in dispersibility in the film due to the difference in compatibility with the binder. In this case, by combining two or more compounds well, the compound can be uniformly distributed in the film. It is also possible to form a dispersed state.

The compound represented by the general formula (1) is contained in the outermost surface layer of the photoreceptor. In the case of a sequentially laminated type photosensitive layer, the charge transport layer preferably contains, and in this case, usually 0.01 to 30 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the binder resin contained in the charge transport layer. 0.1
It is used in an amount of 20 parts by weight, more preferably 0.3 to 20 parts by weight. When the single-layer type photosensitive layer is contained, it is usually 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0. 0 parts by weight with respect to the binder resin usually contained in the entire photosensitive layer. It is used in the range of 3 to 20 parts by weight.

  In the case of a reverse lamination type photosensitive layer, it is preferable to have an overcoat layer as the outermost surface layer. In that case, the overcoat layer contains the compound represented by the general formula (1) according to the present invention, and the addition amount is 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin component of the overcoat layer. It is preferable to use in the range. The film thickness of the overcoat layer is usually 0.01 to 100 μm, preferably 1 to 10 μm.

In addition, since the compound of the present invention can be a compound that is transparent to the entire visible light range, the exposure light source can be used not only with a normally used near-infrared laser or LED but also with a visible light source. Therefore, exposure with white light or exposure with a blue LED or laser having a relatively short wavelength is also possible.
Further, in the electrophotographic photoreceptor of the present invention, it is more preferable that the outermost layer of the photoreceptor contains a resin having an aromatic diol residue having a substituent Y represented by the following general formula (2) as a constituent component. By using such a resin having a long-chain hydrocarbon group, the bleed-out of the wax from the resin surface can be suppressed, and a photoreceptor having a good surface state over a long period of time can be obtained even when used repeatedly.

In general formula (2), R represents a hydrocarbon group having 6 to 100 carbon atoms which may have a substituent, and m is an integer of 0 to 10.
Here, the hydrocarbon group of R 1 in the general formula (2) may be linear or branched, and is preferably linear. 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, m is preferably 0-4. Examples of the substituent of the hydrocarbon group include halogen atoms such as chlorine, fluorine and bromine.

Specific examples of aromatic diols that form an aromatic diol residue having the substituent Y represented by the general formula (2) 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'-hydroxyphenyl) propane [bisphenol] Enol 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 (hydride) such as bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxyphenyl) -4-methylpentane, 2,2-bis (4'-hydroxyphenyl) hexane Loxyphenyl) alkanes, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4′-hydroxyphenyl) -1-phenylethane [bisphenol P], 1,1 -Bis (hydroxyphenyl) phenylalkanes such as bis (4'-hydroxyphenyl) -1-phenylpropane and 2,2-bis (4'-hydroxyphenyl) -1,3-diphenylpropane, 1,1-bis Bis (hydroxyphenyl) cycloalkanes such as (4′-hydroxyphenyl) cyclopentane and 1,1-bis (4′-hydroxyphenyl) cyclohexane [bisphenol Z], bis (4′-hydroxyphenyl) -1,4 -Phenylenedimethylene, bis (2 ', 6'-dimethyl-4'-hydroxypheny ) -1,4-phenylenedimethylene, bis (2 ′, 6′-dimethyl-4′-hydroxyphenyl) -1,4-phenylenebis (α-methylethylidene), bis (4′-hydroxyphenyl) -1 Bis (hydroxyphenyl) phenylenedimethylenes such as 1,4-phenylenebis (α-methylvinylidene), bis (2′-methyl-4′-hydroxyphenyl) -1,4-phenylenebis (α-methylvinylidene), Bis (hydroxyphenyl) ethers such as bis (4-hydroxyphenyl) ether [bisphenol O], bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, bis (3 Bis (hydroxyphenyl) keto such as 5-dimethyl-4-hydroxyphenyl) ketone and phenolphthalein Bis (4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide and other bis (hydroxyphenyl) sulfides, bis (4-hydroxyphenyl) sulfoxide, bis (3,5- Bis (hydroxyphenyl) sulfoxides such as dimethyl-4-hydroxyphenyl) sulfoxide, bis (hydroxy) such as bis (4-hydroxyphenyl) sulfone [bisphenol S], bis (3,5-dimethyl-4-hydroxyphenyl) sulfone Phenyl) sulfones and the like.

In the present invention, the aromatic diol residue having the substituent Y represented by the general formula (2) is preferably a bis (hydroxyphenyl) compound residue represented by the following general formula (4). .

In the general formula (4), K represents an organic divalent group or a single bond. Examples of the organic divalent group include an alkylene group which may have a substituent, and a substituent. Represents a cycloalkylene group which may have a substituent, a phenylenedimethylene group which may have a substituent, an oxy group, a carbonyl group, a thio group, a sulfinyl group or a sulfonyl group, and the benzene ring may further have a substituent. . However, the substituent Y when K is an alkylene group, a cycloalkylene group, or a phenylenedimethylene group, or the substituent Y of the benzene ring has the substituent Y represented by the general formula (2).

Furthermore, the bis (hydroxyphenyl) compound residue represented by the general formula (4) is preferably a bis (hydroxyphenyl) alkane residue represented by the following general formula (5).

In the general formula (5), 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 L represents the above general formula ( 2) The benzene ring may further have a substituent.
In addition, when K in the general formula (4) is an alkylene group, a cycloalkylene group, or a phenylenedimethylene group, when R ² in the general formula (5) is an alkyl group or an aryl group, and Examples of the substituent other than the substituent Y represented by the general formula (2) on the benzene ring in the general formulas (4) and (5) 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 (5) 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 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) 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, 3,3-bis (4′-hydroxy) Phenyl) propionic acid-2 ″ -tetradecyleicosyl ester, 3,3-bis (4′-hydroxyphenyl) propionic acid-2 ″ -hexadecyloctadecyl 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) butanoic acid dodecyl ester, 4,4-bis (4′-hydroxyphenyl) Enyl) 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-2 ″ -decyltetradecyl ester, 4,4-bis (4′-hydroxyphenyl) bu Acid-2 ″ -tetradecyloctadecyl ester, 4,4-bis (4′-hydroxyphenyl) butanoic acid-2 ″ -tetradecyleicosyl ester, 4,4-bis (4′-hydroxyphenyl) butane Acid 2 ″ -hexadecyl octadecyl 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 hexyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid octyl ester, 4,4-bis (4′-hydroxyphenyl) pentane Acid nonyl ester, 4,4-bis (4′-hydroxyphenyl) pentanoic acid undecyl ester, 4,4-bis (4′-hydro) Cyphenyl) 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) pentane -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'' Hexadecyl octadecyl 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 Kutadecyl 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) pentanoic acid octyl ester, 4,4-bis (4'-hydroxy-3'-methylphenyl) Pentanoic acid nonyl ester, 4,4-bis (4′-hydroxy-3′-methylphenyl) pen Tanoic 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′-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''-tetradecyloctadecyl 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′-methyl) Phenyl) pentanoic acid octadecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid hexyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethyl) Phenyl) pentanoic acid octyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid nonyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethyl) Phenyl) 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′-dimethylphenyl) 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 ″ -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′-dimethylphenyl) pentanoic acid-2 ″ -hexadecyloctadecyl ester, 4,4-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid-2 ″- Hexadecyl ester Cosyl ester, 3,3-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid octadecyl ester, 5,5-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) pentanoic acid An octadecyl ester etc. are mentioned.

  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 Tanoic 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′- Dimethylphenyl) 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 the aromatic diol residue having the substituent Y represented by the general formula (2) as a structural unit is not particularly limited as long as the resin contains the aromatic diol residue. For example, a polyester resin containing a structural unit consisting of the aromatic diol residue having a substituent Y represented by the general formula (2) and a dicarboxylic acid residue, the general formula (
2) A polycarbonate resin containing a structural unit composed of the aromatic diol residue and the carbonate residue having the substituent Y represented by the formula (6) is exemplified. Among them, represented by the following general formula (6) A polyester resin containing units as constituent units is preferred.

In the general formula (6), 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 L represents the above general formula ( 2) represents a substituent Y represented by the following formula, the benzene ring may further have a substituent, and M may have an alkylene group which may have a substituent, or may have a substituent. A cycloalkylene group or an arylene group which may have a substituent is shown.

  Here, examples of dicarboxylic acids that form a dicarboxylic acid residue containing an alkylene group, cycloalkylene group, or arylene group of M in the general formula (6) include malonic acid, succinic acid, glutaric acid, adipic acid, and pimeline. Acids, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, aliphatic dicarboxylic acids such as dodecadicarboxylic acid, alicyclic dicarboxylic acids 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′-Diphenylsulfonedicarboxylic acid, 2,6-na Aromatic dicarboxylic acids such as data dicarboxylic acid, 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 (6) as a structural repeating unit has the substituent Y represented by the general formula (2) in the general formula (6). In place of the aromatic diol residue, a diol residue having no substituent Y represented by the general formula (2) 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 those other than the aromatic diols having no substituent Y represented by the general formula (2) In addition,
For example, ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, Aliphatic diols such as polyethylene glycol and polytetramethylene ether glycol, and 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, 2,5 -Alicyclic diols, such as norbornane dimethylol, etc. are mentioned.

  In the present invention, the polyester resin containing the unit represented by the general formula (6) as a constituent 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 Y represented by the general formula (2) 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%.
<Support>
The photosensitive layer of the present invention is provided on a conductive support. Examples of the conductive support include a drum made of a metal material such as aluminum, stainless steel, copper, and nickel, and a polyester film provided with a conductive layer such as aluminum, copper, palladium, tin oxide, and indium oxide on the surface. In addition, an insulating support such as paper made into a sheet, belt, drum, or roll, or a material obtained by kneading conductive fine particles such as carbon or copper powder with plastic or paper is used.

When an aluminum drum is used, an extruded or drawn tube of an aluminum alloy or a material obtained by cutting them is used, and the maximum surface roughness Rmax is preferably 2.5 μm or less.
A known blocking layer, which 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. Is used.

When the aluminum anodic oxide coating is used, the film thickness is preferably 1 to 10 μm, for example, 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, a metal oxide such as titania, alumina, silica and zirconium oxide, or a metal fine powder such as copper, silver and aluminum may be used alone or mixed and dispersed. The particle size of these fine powders can be selected as appropriate. For example, it is preferable to use a primary particle size of several tens of nm to several μm, and they may be used in combination.
The film thickness of these barrier layers can be set as appropriate, but it is preferably 0.05 to 50 μm, preferably 0.1 to 10 μm.

<Photosensitive layer>
The constitution of the photosensitive layer that can carry out the present invention may be a single layer type photosensitive layer or a laminated type photosensitive layer. Further, in the laminated photosensitive layer, either a forward laminated photosensitive layer or a reverse laminated photosensitive layer can be employed.
<Charge generating material>
As the charge generation material used in the photosensitive layer, any known charge generation material can be used. For example, azo pigments, phthalocyanine pigments, perylene pigments, quinacridone pigments, polycyclic quinone pigments, indigo pigments, Benzimidazole pigments, pyrylium salts, thiapyrylium salts, squalium salts and the like can be used. Among these, it is preferable to use a phthalocyanine pigment.

<Charge generation layer>
For the charge generation layer in the laminated photosensitive layer, these pigments and / or salts are used, for example, polyester resin, polyvinyl acetate, polyacrylic ester, polymethacrylic ester, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl. You may use by the dispersion layer of the form bound | bonded with various binder resins, such as a butyral, a phenoxy resin, an epoxy resin, a urethane resin, a cellulose ester, and a cellulose ether.
The use ratio in this case is used in the 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 μm to 2 μm, preferably 0.15 μm to 0.005.
8 μm is preferred.
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 as necessary. Furthermore, a vapor deposition film of the above substance may be used.

<Charge transport material>
As the charge transport material, a binder resin having a charge transport function alone may be used, but a configuration in which the charge transport material is dispersed in the binder resin is more preferable.
Examples of the charge transport material 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-diphenyl Hydrazone compounds such as hydrazone, N-methylcarbazole-3-carbaldehyde-N, N-diphenylhydrazone, and 5- (4- (di-p-tolylamino) benzylidene) -5H-dibenzo (a, d) cycloheptene. Styryl compounds, triarylamine compounds such as p-tolylamine, benzidine compounds such as N, N, N ′, N′-tetraphenylbenzidine, butadiene compounds, di- (p-ditolylaminophenyl) methane, etc. Triphenyl meta Such system compounds. Among them, since it is desired that the mobility is fast, it is preferable that benzidine compounds such as N, N, N ′, N′-tetraphenylbenzidine, butadiene compounds, di- (p-ditolylaminophenyl) methane, etc. A triphenylmethane compound, more preferably a benzidine compound such as N, N, N ′, N′-tetraphenylbenzidine.

<Charge transport layer>
As the charge transport layer in the multilayer photosensitive layer, a material obtained by binding the above charge transport material with a binder resin is used. Examples of the binder resin to be used include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, polycarbonate, polyester, polyester carbonate, polysulfone, polyimide, phenoxy, epoxy, silicone resin, and the like. These partially cross-linked cured products can also be used.

  The ratio of the binder resin to the charge transport material is usually 30 to 200 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. Further, 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. The charge transport layer has a thickness of 10 to 60 μm, preferably 10 to 45 μm.

<Single layer type photosensitive layer>
When the photosensitive member has a single-layer type photosensitive layer, the charge generation material is dispersed in the matrix mainly composed of the binder resin and the charge transport material having the above-described mixing ratio. The particle diameter must be sufficiently small, preferably 1 μm or less, more preferably 0.5 μm or less.
If the amount of the charge generating material dispersed in the photosensitive layer is too small, sufficient sensitivity cannot be obtained. If the amount is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. %, Preferably 0.5 to 25% by weight, more preferably 1.0 to 20% by weight. The film thickness of the photosensitive layer is usually 5 to 50 μm, more preferably 10 to 45 μm. Also in this case, known plasticizers for improving film formability, flexibility, mechanical strength, additives for suppressing residual potential, dispersion aids for improving dispersion stability, coatability Leveling agents, surfactants, silicone oils, fluorine oils and other additives may be added to improve the properties.

<Other functional layers>
As the outermost surface layer, a conventionally known overcoat layer mainly composed of, for example, a thermoplastic or thermosetting polymer may be provided. In this case, the overcoat layer or both the overcoat layer and the photosensitive layer contain the compound represented by the general formula (1). The film thickness of the overcoat layer is usually 0.01 to 100 μm, preferably 1 to 10 μm.

<Layer formation method>
Each layer of the photoreceptor is formed by sequentially applying and forming a coating solution obtained by dissolving or dispersing a substance to be contained in a layer using a known method such as a dip coating method, a spray coating method, or a ring coating method. Is done.
<Image forming apparatus>
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention (an image forming apparatus of the present invention) will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, and a developing device 4, and further, a transfer device 5, a cleaning device 6 and a fixing device as necessary. A device 7 is provided.
The electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-described electrophotographic photoreceptor of the present invention, but in FIG. 1, as an example, a drum in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. The photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5 and a cleaning device 6 are arranged along the outer peripheral surface of the electrophotographic photosensitive member 1.

  The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. As the charging device, a corona charging device such as corotron or scorotron, a direct charging device (contact type charging device) for charging a charged member directly in contact with the surface of the photosensitive member, and the like are often used. Examples of direct charging means include contact chargers such as charging rollers and charging brushes. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2. As the direct charging means, either charging with air discharge or injection charging without air discharge is possible. Moreover, as a voltage applied at the time of charging, it is possible to use only a direct current voltage or to superimpose alternating current on direct current.

  The type of the exposure apparatus 3 is not particularly limited 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. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a short wavelength of 380 nm to 500 nm. .

  The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component insulating toner development, one-component conductive toner development, or two-component magnetic brush development, or a wet development method is used. be able to. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicon resin, a urethane resin, a fluorine resin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary. The developing roller 44 is disposed between the electrophotographic photoreceptor 1 and the supply roller 43 and is in contact with the electrophotographic photoreceptor 1 and the supply roller 43, respectively. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown).
The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photosensitive member 1.

  The restricting member 45 is formed of a resin blade such as silicon resin or urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such a metal blade with resin. The regulating member 45 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.
The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like that are disposed to face the electrophotographic photoreceptor 1. The transfer device 5 applies 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 a recording paper (paper, medium) P. Is.

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner. However, when there is little or almost no toner remaining on the surface of the photoreceptor, the cleaning device 6 may be omitted.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. As the upper and lower fixing members 71 and 72, known heat fixing members such as a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll coated with a fluororesin, or a fixing sheet are used. be able to. Further, the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve the releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.
The type of the fixing device is not particularly limited, and a fixing device of any type such as heat roller fixing, flash fixing, oven fixing, pressure fixing, etc. can be provided including those used here.

In the electrophotographic apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.
Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.
When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6.

  After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P. In addition to the above-described configuration, the image forming apparatus may have a configuration capable of performing, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.
The electrophotographic photosensitive member 1 is combined with one or more of the charging device 2, the exposure device 3, the developing device 4, the transfer device 5, the cleaning device 6, and the fixing device 7 to form an integrated cartridge ( The electrophotographic photosensitive member cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. In this case, for example, when the electrophotographic photosensitive member 1 and other members are deteriorated, the electrophotographic photosensitive member cartridge is removed from the main body of the image forming apparatus, and another new electrophotographic photosensitive member cartridge is mounted on the main body of the image forming apparatus. This facilitates maintenance and management of the image forming apparatus.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
Synthesis Example-1
200 g of a mixture of branched primary alcohols having 32, 34, and 36 carbon atoms (trade name NJECOAL C32-36, manufactured by Shin Nippon Rika Co., Ltd.), 400 cm ³ of toluene were charged into a reactor equipped with a thermometer and a reflux condenser. While heating to 60 ° C. and stirring, 55 g of phosphorus tribromide was added dropwise. After reacting for 1 hour, the solution was neutralized by adding an aqueous sodium carbonate solution, and the entire amount was released into 3000 cm ³ of methanol, and the resulting precipitate was collected by filtration to obtain a branched alkyl bromide having 32 to 36 carbon atoms (hereinafter referred to as engecol bromide). There was 98 g).

  2.89 g of 2,7-dihydroxynaphthalene, 20.1 g of enjechol bromide and 1.16 g of tetrabutylammonium bromide were reacted at about 120 ° C. for 4 hours with stirring in 120 ml of toluene, 60 ml of dimethyl sulfoxide and 120 g of 50% aqueous sodium hydroxide. I let you. The mixture was neutralized with an appropriate amount of 5% hydrochloric acid while being cooled in an ice bath, and extracted with 100 ml of toluene. The obtained organic phase was washed twice with 100 ml of a saturated aqueous solution of sodium chloride, dried over sodium sulfate, and then the solvent was distilled off to give crude 2,7-bis (C32-36 branched alkyloxy) naphthalene. The product was obtained. This was purified by column chromatography using silica gel to obtain 11.3 g of 2,7-bis (C32-C36 branched alkyloxy) naphthalene.

Synthesis Example-2
A mixture of branched primary alcohols having 32, 34, and 36 carbon atoms (trade name NJECOAL C32-36, manufactured by Shin Nippon Rika Co., Ltd.), 3.6 g of triethylamine, 40 cm ³ of tetrahydrofuran, a thermometer, and a reflux condenser. Charge to the attached reactor and stir 2, 6
-1.5 g of naphthalenedicarboxylic acid dichloride was added. This was heated to 60 ° C. and reacted for 4 hours, and then the total amount was released into 500 ml of methanol. The resulting precipitate was collected by filtration and purified by column chromatography using silica gel to obtain 2,6- 2.9 g of naphthalenedicarboxylic acid (C32-C36 branched alkyl) diester was obtained.

Synthesis example-3
Energol bromide 8.1 g, fluorene 0.8 g, and dimethylformamide 30 ml obtained in the same manner as in Synthesis Example 1 were charged into a reactor equipped with a thermometer and a reflux condenser, and potassium tert-butoxide was stirred at room temperature. 1.7 g was added little by little and stirred for 1 hour. The reaction solution was discharged into 1000 ml of methanol, and the precipitated solid was separated by filtration. This was purified by column chromatography using silica gel to obtain 3.7 g of 9,9-di (C32-36 branched alkyl) fluorene.

Synthesis example 4
9.4 g of docosyl bromide, 1.7 g of fluorene, 25 ml of dimethylformamide, and 35 ml of tetrahydrofuran were charged into a reactor equipped with a thermometer and a reflux condenser, and 3.4 g of potassium tert-butoxide was added little by little at room temperature while stirring. Added and stirred for 1 hour. The reaction solution was discharged into 1000 mL of methanol, and the precipitated solid was separated by filtration. This was purified by column chromatography using silica gel to obtain 4.7 g of 9,9-didocosylfluorene.

Synthesis example-5
16.7 g of stearyl bromide, 3.8 g of fluorene and 40 ml of dimethylformamide were charged into a reactor equipped with a thermometer and a reflux condenser, and 8.4 g of potassium tert-butoxide was added little by little at room temperature while stirring. Stir for hours. The reaction solution was discharged into 200 mL of methanol, and the precipitated solid was separated by filtration. This was purified by column chromatography using silica gel to obtain 16 g of 9,9-distearylfluorene.
The compounds represented by the general formula (1) obtained in Synthesis Examples 1 to 5 are collectively shown in the following table.

Example-1
2 parts by weight of oxytitanium phthalocyanine having a powder X-ray diffraction spectrum by CuKα characteristic X-ray shown in FIG. To the part, 500 parts by weight of 1,2 dimethoxyethane was added and pulverized and dispersed by a sand grind mill. The dispersion thus obtained was applied onto a polyethylene terephthalate film having aluminum deposited on the surface by a bar coater so that the film thickness after drying was 0.4 μm, thereby providing a charge generation layer.

  On this charge generation layer, 50 parts by weight of the charge transport material shown below, 20 parts by weight of the compound synthesized in Synthesis Example 1, and 70 parts by weight of the following polycarbonate resin 1 (copolymerization ratio is molar ratio) Using a film applicator, a solution obtained by dissolving 30 parts by weight of polyarylate resin 1 and 0.05 parts by weight of silicone oil in a mixed solvent of tetrahydrofuran and toluene (weight ratio 8: 2) to a solid content concentration of 23% was obtained. The charge transport layer was provided so that the film thickness after coating and drying was 25 μm. The photoreceptor thus prepared is referred to as a photoreceptor A.

Example-2
Photoreceptor B was prepared in the same manner as in Example 1 except that the compound synthesized in Synthesis Example-2 was used instead of the compound synthesized in Synthesis Example-1.
Example-3
Photoreceptor C was prepared in the same manner as in Example 1 except that the compound synthesized in Synthesis Example-3 was used instead of the compound synthesized in Synthesis Example-1.
Example-4
Photoreceptor D was prepared in the same manner as in Example 1 except that the compound synthesized in Synthesis Example-4 was used instead of the compound synthesized in Synthesis Example-1.
Example-5
Photoreceptor E was prepared in the same manner as in Example 1 except that the compound synthesized in Synthesis Example-5 was used instead of the compound synthesized in Synthesis Example-1.
Comparative Example-1
In Example-1, Comparative Photosensitive Member F was prepared in the same manner as Example-1 except that the compound synthesized in Synthesis Example-1 was not added.
Comparative Example-2
In Example-1, a comparative photoreceptor G was prepared in the same manner except that the ester wax represented by the following structural formula was used instead of the compound synthesized in Synthesis Example-1.

CH ₃ (CH ₂ ) ₁₇ OCO (CH ₂ ) ₈ COO (CH ₂ ) ₉ OCO (CH ₂ ) ₈ COO (CH ₂ ) ₁₇ CH ₃

(Evaluation of electrical characteristics)
These electrophotographic photoreceptors were cut into a size of 100 mm in width and 250 mm in length, wound around an aluminum tube having a diameter of 80 mm so that the photosensitive layer was on the outside, and fixed using a double-sided adhesive tape. At this time, the four corners of the photosensitive layer are removed with a cloth soaked in tetrahydrofuran to expose the aluminum vapor-deposited surface. One end of the conductive adhesive tape is attached to this portion, and one end of the tape is attached to the aluminum tube. Then, the conductive support of the photoreceptor and the aluminum tube were made conductive.

The performance evaluation sample thus obtained was mounted on a photoreceptor characteristic evaluation apparatus installed in an environmental test room at a temperature of 25 ° C. and a relative humidity of 50%. After charging the surface potential of the electrophotographic photosensitive member to be −700 V, irradiation with 780 nm light was performed while changing the irradiation intensity, and the surface potential after 100 milliseconds was measured. Table 2 shows the measured values of the surface potential (hereinafter sometimes referred to as VLmax) when irradiated with light having an intensity of 1.0 μJ / cm ² . Further, the exposure intensity at which the surface potential of the photoreceptor after −100 msec after exposure to 780 nm light is −350 V is defined as half exposure intensity, and this value is shown in Table-2.

From this result, the electrophotographic photosensitive member containing the compound of the present invention (photosensitive members A, B, C, D and E) and the electrophotographic photosensitive member not containing the compound of the present invention (comparative photosensitive member F) are equivalent. It turns out that it has the electrical property of. Further, the electrophotographic photosensitive member G of Comparative Example 2 containing a wax that is not of the present invention has a high half-exposure amount, that is, a low sensitivity, and has a VLmax.
It was inferior in the high electrical characteristics.

(Evaluation of surface properties)
The above-mentioned electrophotographic photosensitive member was cut into a size of 60 mm in width and 130 mm in length, and fixed with an adhesive tape on a reciprocating table of a FR-2 type abrasion tester manufactured by Suga Test Instruments Co., Ltd. A load of 7.8 N was applied, and polishing was performed by reciprocating 300 times on the electrophotographic photosensitive member with a 3M company's Wetdry Tri-M-ite Paper 2000. Thereafter, a load of 7.8 N was applied, and polishing was performed by reciprocating 300 times on the electrophotographic photosensitive member with JK Wiper (registered trademark) 150-S manufactured by Crecia Corporation.

About these electrophotographic photoreceptors before and after surface polishing, a friction coefficient was measured using a Heidon-14 type surface property tester manufactured by Shinto Kagaku Co., Ltd. At this time, a nonwoven fabric SOFPADS manufactured by Dynic Co., Ltd. having a width of 10 mm and a length of 12 mm was used as the friction body, and the measurement was performed under a load of 2.9 N and a sweep speed of 100 mm / min. The results are shown in Table-3.
Furthermore, the contact angle with pure water was measured for the electrophotographic photoreceptor before and after surface polishing using a FACE CA-D contact angle meter manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table-3.

  From these results, the photoconductor of the present invention has a small coefficient of friction and excellent durability compared to the comparative photoconductor both in the initial use and after polishing, and has a large contact angle with pure water and low adhesion. I understood.

From the above results, the photoreceptors (Examples 1 to 5) of the present invention have a reduced coefficient of friction as compared with the photoreceptor of Comparative Example 1 that does not have the synthetic compound of the present invention without deteriorating electrical characteristics. And it was found to have a large contact angle. Although the photoconductor in Comparative Example 2 has a low coefficient of friction, it has a small contact angle and is difficult to use as a photoconductor in order to deteriorate electrical characteristics. From the above points, it can be seen that the photoreceptor in the present invention is an excellent photoreceptor having improved surface properties without deteriorating electrical characteristics.
Example-6
A photoconductor H was prepared in the same manner as in Example 1, except that the compound synthesized in Synthesis Example 1 used for the charge transport layer was changed to 10 parts by weight.
Example-7
Photoreceptor I was prepared in the same manner as in Example-6 except that the resin used for the charge transport layer in place of polycarbonate resin 1 and polyarylate resin 1 was 100 parts by weight of polycarbonate resin 1.
Example-8
Photoreceptor J was prepared in the same manner as in Example-6 except that the resin used for the charge transport layer in place of polycarbonate resin 1 and polyarylate resin 1 was 100 parts by weight of polycarbonate resin 2 shown below. did.

Example-9
The resin used for the charge transport layer in Example-6 was replaced with the structural repeating unit 70 consisting of a bis (4-hydroxy-3,5-dimethylphenyl) methane residue and a terephthalic acid residue instead of the polycarbonate resin 1. 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 Photoreceptor K was prepared in the same manner except that 70 parts by weight of the polyester resin (polyarylate resin 2) composed of 30 mol% of repeating units and 30 parts by weight of the polyarylate resin 1 were used.
Example-10
In Example-6, the resin used for the charge transport layer was the same except that instead of the polycarbonate resin 1 and the polyarylate resin 1, 100 parts by weight of the polyarylate resin 2 used in Example-9 was used. Thus, a photoreceptor L was prepared.
Comparative Example-3
In Example-6, a comparative photoconductor M was prepared in the same manner as in Example-6 except that the compound synthesized in Synthesis Example-1 was not added.
Comparative Example-4
In Example-7, a comparative photoconductor N was prepared in the same manner as in Example-7 except that the compound synthesized in Synthesis Example-1 was not added.
Comparative Example-5
In Example-8, a comparative photoconductor O was prepared in the same manner as in Example-8 except that the compound synthesized in Synthesis Example-1 was not added.
Comparative Example-6
In Example-9, a comparative photoconductor P was prepared in the same manner as in Example-9 except that the compound synthesized in Synthesis Example-1 was not added.
Comparative Example-7
In Example-10, a comparative photoconductor Q was prepared in the same manner as in Example-10 except that the compound synthesized in Synthesis Example-1 was not added.

  The results of evaluating the electrical characteristics and surface properties of the above photoreceptors in the same manner as in Example 1-5 are shown in the following table.

  From the above results, the photoconductors of the present invention (Examples 6 to 10) did not deteriorate the electrical characteristics, and the friction coefficient was higher than that of the photoconductors of Comparative Examples 3 to 7 having no synthetic compound of the present invention. It has been found to have a reduced and yet high contact angle. In particular, as can be seen from the comparison between Examples 6 and 7 and the comparison between Examples 9 and 10, it can be seen that when a binder resin having a long-chain alkyl group is used, more excellent surface characteristics are exhibited.

Example-11
In Example-1, the charge generation layer coating solution and the charge transport layer coating solution were similarly used except that oxytitanium phthalocyanine having a powder X-ray diffraction spectrum by CuKα rays shown in FIG. 3 was used instead as the charge generation material. Produced. This coating solution is sequentially dipped in an aluminum tube having a diameter of 30 mm and a length of 285 mm, and a charge generation layer having a thickness of 0.4 μm after drying and a charge transport layer having a thickness of 20 μm are laminated. To form a photoconductor.

  This photoreceptor was mounted on a laser printer LP3000C manufactured by Seiko Epson Corporation, and the first and 1000th printed images were compared, but no change was observed. Further, no change was observed in the friction coefficient and contact angle of the photoreceptor, and it was confirmed that the surface modification effect was sustained.

It is a figure which shows an example of the image forming apparatus of this invention. It is a figure which shows the X-ray-diffraction spectrum of the oxytitanium phthalocyanine of Example-1. It is a figure which shows the X-ray-diffraction spectrum of the oxytitanium phthalocyanine of Example-6.

Explanation of symbols

1 Photoconductor
2 Charging device (charging roller)
3 Exposure equipment
4 Development device
5 Transfer device
6 Cleaning device
7 Fixing device
41 Developer tank
42 Agitator
43 Supply roller
44 Developing roller
45 Restriction member
71 Upper fixing member (fixing roller)
72 Lower fixing member (fixing roller)
73 Heating device
T Toner
P Recording paper

Claims (5)

An electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, wherein the outermost layer of the photoreceptor contains a compound represented by the following general formula (1).

(In the formula (1), A may have a substituent, represents a fused having 2 or more aromatic rings, X is a divalent linking group. Further, B is carbon number 10 Represents a substituent having an aliphatic hydrocarbon group of 60. n represents an integer of 2 to 4. ) In the compound represented by the general formula (1), X is bonded to the aromatic ring of A, and X is not bonded to two or more aromatic rings at the same time. Electrophotographic photoreceptor. 3. The electrophotographic photoreceptor according to claim 1, wherein in the compound represented by the general formula (1), B is a linear or branched aliphatic hydrocarbon group having 3 or less. In the electrophotographic photoreceptor, an outermost layer of the photoreceptor is substituted with an aromatic diol residue represented by the general formula (5), which is substituted with a substituent Y represented by the following general formula (2). The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member according to claim 1 is contained.

(In the formula (2), R represents a hydrocarbon group which may carbon atoms 6-50 may have a substituent, m is an integer of 0.)

(In the general formula (5), 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 L represents the above general formula. The substituent Y represented by (2) is shown, and the benzene ring may further have a substituent. 5. The electrophotographic photosensitive member according to claim 1, charging means for charging the photosensitive member, and image exposure means for performing image exposure on the charged photosensitive member to form an electrostatic latent image. 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