JPH08286397A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE: To provide an electrophotographic photoreceptor which has a photosensitive layer formed by uniformedly distributing a charge transport material and a charge generation material on its binding resin and is superior in sensitivity, by combining a specific charge generation material and a specific polyester resin. CONSTITUTION: An organic photosensitive layer containing am least one kind of a charge generation material which is selected from a group composed of nonmetal phthalocyanine, titanyl phthalocyanine, perylenue pigment, bisazo pigment, dithioketopyroropyrrole pigment, nonmetal naphthalocyanine pigment, metal naphthalocyanine pigment, squaline pigment, trisazo pigment, indigo pigment, azulenium pigment, and cyanine pigment, and binding resin which is composed of polyester resin or substantially a linear polymer using at least one kind of dihydroxy compound expressed by formulas I, II, etc., is provided on a conductive substrate. In the formulas I, II, R<1> represents an alkylene group of carbon numbers 2-4, R<2> -R<5> represent hydrogen atoms and an alkyl group of carbon numbers 1-4, and (n) is integer more than 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used in an image forming apparatus utilizing an electrophotographic method such as an electrostatic copying machine and a laser beam printer.

[0002]

2. Description of the Related Art The electrophotographic method such as the Carlson process is a process of uniformly charging the surface of an electrophotographic photosensitive member by corona discharge, and exposing the charged surface of the electrophotographic photosensitive member to an electrostatic latent image on the surface of the photosensitive member. And an exposing step for forming the electrostatic latent image, a developing step for bringing the developer into contact with the formed electrostatic latent image to visualize the electrostatic latent image with a toner contained in the developer, and the toner image on paper or the like. It includes a transfer step of transferring, a fixing step of fixing the transferred toner image, and a cleaning step of removing the toner remaining on the photoconductor.

Recently, the electrophotographic photoconductors used in the above electrophotographic method are replaced with inorganic photoconductors such as selenium and cadmium sulfide, which are difficult to handle due to their toxicity, and organic photoconductors with low toxicity. Various so-called organic photoconductors using a photosensitive compound have been proposed. Such an organic photoreceptor has the advantages that it has good workability, is easy to manufacture, and has a high degree of freedom in functional design.

In such an organic photoreceptor, generally, a function-separated type photosensitive layer containing a charge generating material for generating charges by light irradiation and a charge transporting material for transporting the generated charges is often used. . The binder resin containing a charge generation material and a charge transport material, which is formed in the photosensitive layer, is often used in order to increase the mechanical strength such as abrasion resistance and scratch resistance of the photosensitive layer to prolong the life of the photoreceptor. In particular, polycarbonate resins of bisphenol A type, C type, Z type, fluorine-containing type, biphenyl copolymerization type and the like are widely used (JP-A-60-172045 and JP-A-60-12045).
-192950, JP-A-61-62039, JP-A-63-148263, JP-A-1-27.
3064, JP-A-5-80548, JP-A-5-88396).

It is also known that the mechanical strength of the photosensitive layer is improved by increasing the molecular weight of the above-mentioned polycarbonate resin (Japanese Patent Laid-Open No. 5-113671).
JP-A-5-158249, etc.).

[0006]

However, although the mechanical strength of the photosensitive layer is improved by using the above-mentioned polycarbonate resin as the binder resin, the degree of the improvement is insufficient. Further, since the polycarbonate resin has poor compatibility and dispersibility with the charge transport material and the charge generating material, even if a material having excellent charge transporting characteristics and charge generating characteristics is used, the characteristics cannot be fully utilized. Therefore, there is a problem in that the sensitivity also deteriorates.

Further, in a single-layer type photoreceptor containing a charge transporting material and a charge generating material in a single layer, when a polycarbonate resin is used as a binder resin in the photosensitive layer, the polycarbonate resin is aluminum. Since the adhesiveness to the conductive substrate is poor, the photosensitive layer peels off from the conductive substrate during use. A main object of the present invention is to provide an electrophotographic photoreceptor having a photosensitive layer in which a charge transporting material and a charge generating material are uniformly dispersed in a binder resin and having excellent sensitivity.

Another object of the present invention is to provide an electrophotographic photosensitive member having a photosensitive layer having high mechanical strength such as abrasion resistance and excellent adhesiveness to a substrate.

[0009]

Means and Actions for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by combining a specific charge generating material with a specific polyester resin, Since the compatibility and dispersibility with respect to the polyester resin are improved, the new fact that the high charge generation characteristics of the charge generation material are fully exhibited and the sensitivity of the photoconductor is improved was found, and the present invention was completed. It was

Further, since the above-mentioned specific polyester resin has excellent adhesiveness to the conductive substrate, there is no fear that the photosensitive layer will be peeled off from the conductive substrate during long-term use of the photosensitive member. Since it has excellent mechanical strength such as wear resistance, the life of the photoconductor can be extended. That is, the electrophotographic photoreceptor of the present invention, metal-free phthalocyanine, titanyl phthalocyanine, perylene pigment, bisazo pigment, dithioketopyrrolopyrrole pigment, metal-free naphthalocyanine pigment, metal naphthalocyanine pigment, squaraine pigment, trisazo pigment, indigo pigment. , At least one charge generating material selected from the group consisting of azurenium pigments and cyanine pigments, and at least one dihydroxy compound represented by the following general formulas (1), (2) and (3): An organic photosensitive layer containing a binder resin made of polyester resin, which is a linear polymer, is provided on a conductive substrate.

General formula (1):

[0012]

[Chemical 4]

(In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, R ² , R ³ , R ⁴ and R ⁵ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group. Or an aralkyl group.) General formula (2):

[0014]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is the same as above, and n is an integer of 2 or more. ) General formula (3):

[0016]

[Chemical 6]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is the same as above, and R ⁶ and R ⁷ are the same or different and each represents an alkyl group having 1 to 10 carbon atoms. ) Further, the binder resin is represented by the general formula (1), (2) or
At least one of the dihydroxy compounds represented by (3)
A polyester resin, which is a substantially linear polymer using a seed, and a polycarbonate resin may be mixed and used. This has the advantage that the compatibility can be improved by the polycarbonate resin even when a material having poor compatibility with the polyester resin is combined.

Since the polyester resin in the present invention has excellent adhesiveness to the conductive substrate as described above, the organic photosensitive layer using the polyester resin as a binder resin should be used in the form of a single layer. Suitable for Hereinafter, the electrophotographic photoreceptor of the present invention will be described in detail. The charge generating material used in the present invention is as follows. (1) Metal-free phthalocyanine

[0019]

[Chemical 7]

(2) Titanyl phthalocyanine

[0021]

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(3) Perylene pigment

[0023]

[Chemical 9]

(In the formula, R ²⁰ and R ²¹ are the same or different and each represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, alkanoyl group or aralkyl group having 18 or less carbon atoms.) ) Bisazo pigment

[0025]

[Chemical 10]

[In the formula, A ¹ and A ² are the same or different and each represents a coupler residue, and X is

[0027]

[Chemical 11]

(In the formula, R ⁸ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, the aryl group or the heterocyclic group may have a substituent n.
Represents 0 or 1. )

[0029]

[Chemical 12]

[0030]

[Chemical 13]

(In the formula, R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group, an aryl group or an aralkyl group.)

[0032]

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[0033]

[Chemical 15]

[0034]

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(In the formula, R ¹¹ represents a hydrogen atom, an ethyl group, a chloroethyl group or a hydroxyethyl group.)

[0036]

[Chemical 17]

Or

[0038]

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(In the formula, R ¹² , R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group, an aryl group or an aralkyl group). . ] (5) Dithioketopyrrolopyrrole pigment

[0040]

[Chemical 19]

(In the formula, R ^a and R ^b are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ^c and R ^d are the same or different and are a hydrogen atom, an alkyl group or an aryl group. Group) (6) Metal-free naphthalocyanine pigment

[0042]

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(In the formula, R ^e , R ^f , R ^g and R ^h are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.) (7) Metal naphthalocyanine pigment

[0044]

[Chemical 21]

(In the formula, R ⁱ , R ^j , R ^k and R ^L are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and M represents Ti or V.) (8) Squaraine pigment

[0046]

[Chemical formula 22]

(In the formula, R ^m and R ⁿ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.) (9) Trisazo pigment

[0048]

[Chemical formula 23]

(In the formula, Cp ₁ , Cp ₂ and Cp ₃ are the same or different and represent a coupler residue.) (10) Indigo pigment

[0050]

[Chemical formula 24]

(In the formula, R ^o and R ^p are the same or different and each represents a hydrogen atom, an alkyl group or an aryl group,
Z represents an oxygen atom or a sulfur atom. ) (11) Azurenium pigment

[0052]

[Chemical 25]

(In the formula, R ^q and R ^r are the same or different and each represents a hydrogen atom, an alkyl group or an aryl group.) (12) Cyanine pigment

[0054]

[Chemical formula 26]

(In the formula, R ^s and R ^t are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ^u and R ^v are the same or different and are a hydrogen atom, an alkyl group or an aryl group. Examples of the alkyl group include a methyl group, an ethyl group,
Examples thereof include an alkyl group having 1 to 6 carbon atoms such as a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group.
The alkyl group of 5 is an alkyl group having 1 to 6 carbon atoms excluding a hexyl group. The alkyl group having 1 to 10 carbon atoms is a group containing an octyl group, a nonyl group, a decyl group and the like in addition to the alkyl group having 1 to 6 carbon atoms described above.

Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenylyl group, an o-terphenyl group, a naphthyl group, an anthryl group and a phenanthryl group.

Examples of the alkanoyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, a pentanoyl group and a hexanoyl group. Examples of the aralkyl group include an aralkyl group having a carbon number of 1 to 6 in the alkyl group portion such as a benzyl group, a phenethyl group, a trityl group and a benzhydryl group.

As the alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group and the like having 1 to 6 carbon atoms. The group is raised. Examples of the heterocyclic group include thienyl group, pyrrolyl group, pyrrolidinyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, 2H-imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyranyl group, pyridyl group. Group, piperidyl group, piperidino group, 3-morpholinyl group, morpholino group, thiazolyl group and the like. It may also be a heterocyclic group condensed with an aromatic ring.

Substituents that may be substituted on the above groups include
For example, a halogen atom, an amino group, a hydroxyl group, a carboxyl group which may be esterified, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 2 to 2 carbon atoms. And the alkenyl group of 6 and the like. Examples of the coupler residue represented by A ¹ , A ² and Cp ₁ , Cp ₂ , Cp ₃ include groups represented by the following general formulas (a) to (g).

[0060]

[Chemical 27]

In each formula, R ¹⁵ represents a carbamoyl group, a sulfamoyl group, an allofanoyl group, an oxamoyl group, an anthraniloyl group, a carbazoyl group, a glycyl group, a hydantoyl group, a phthalamoyl group or a succinamoyl group. These groups, a halogen atom, a phenyl group which may have a substituent, a naphthyl group which may have a substituent,
It may have a substituent such as a nitro group, a cyano group, an alkyl group, an alkenyl group, a carbonyl group and a carboxyl group.

R ¹⁶ is an aromatic ring condensed with a benzene ring,
The atomic groups necessary for forming a polycyclic hydrocarbon or a heterocycle are shown, and these rings may have the same substituents as described above. R ¹⁷ represents an oxygen atom, a sulfur atom or an imino group. R ¹⁸ represents a divalent chain hydrocarbon group or an aromatic hydrocarbon group, and these groups may have the same substituents as described above.

R ¹⁹ represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups may have the same substituents as described above. R ²² is a divalent chain hydrocarbon group, an aromatic hydrocarbon group or the following formula in the above general formulas (e) and (f):

[0064]

[Chemical 28]

It represents an atomic group necessary for forming a heterocycle with the moiety represented by, and these rings may have the same substituents as described above. R ²³ is a hydrogen atom, an alkyl group,
It represents an amino group, a carbamoyl group, a sulfamoyl group, an allofanoyl group, a carboxyl group, an alkoxycarbonyl group, an aryl group or a cyano group, and groups other than a hydrogen atom may have the same substituents as described above.

R ²⁴ represents an alkyl group or an aryl group, and these groups may have the same substituents as described above.
Examples of the alkenyl group include vinyl group, allyl group, and 2
-Butenyl group, 3-butenyl group, 1-methylallyl group,
2-pentenyl group, 2-hexenyl group and the like has 2 to 12 carbon atoms.
6 are alkenyl groups.

Examples of the atomic group necessary for forming an aromatic ring by condensing with the benzene ring in R ¹⁶ include alkylene groups such as methylene group, ethylene group, propylene group and butylene group. Examples of the aromatic ring formed by the condensation of R ¹⁶ and the benzene ring include naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, and naphthacene ring.

In R ¹⁶ , the atomic group necessary for condensation with the benzene ring to form a polycyclic hydrocarbon is
Examples thereof include alkylene groups having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group and butylene group. Examples of the atomic group necessary for forming a polycyclic hydrocarbon by condensing with the benzene ring in R ¹⁶ include a carbazole ring, a benzocarbazole ring, a dibenzofuran ring and the like.

The atomic group necessary for forming a heterocycle by condensing with a benzene ring in R ¹⁶ is, for example, benzofuranyl group, benzothiophenyl group, indolyl group, 1H-indolyl group, benzoxazolyl group. Group, benzothiazolyl group, 1H-indaryl group, benzimidazolyl group, chromenyl group, chromanyl group, isochromanyl group, quinolinyl group, isoquinolinyl group, cinnolinyl group, phthalazinyl group, quinazonilyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, xanthenyl group , An acridinyl group, a phenanthridinyl group, a phenazinyl group, a phenoxazinyl group and a thianthrenyl group.

The aromatic heterocyclic group formed by the condensation of R ¹⁶ and the benzene ring is, for example, a thienyl group,
Examples thereof include furyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group and thiazolyl group. It may also be a heterocyclic group condensed with another aromatic ring (for example, a benzofuranyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinolyl group).

In R ¹⁸ and R ²² , the divalent chain hydrocarbon includes ethylene group, propylene group, butylene group, and the like, and the divalent aromatic hydrocarbon includes phenylene group, naphthylene group, Examples thereof include a phenanthrylene group. Examples of the heterocyclic group for R ¹⁹ include a pyridyl group, a pyrazyl group, a thienyl group, a pyranyl group and an indolyl group.

In R ²² , the atomic group necessary to form a heterocycle with the moiety represented by the formula (h) is, for example, phenylene group, naphthylene group, phenanthrylene group, ethylene group, propylene group or butylene. Groups and the like. Examples of the aromatic heterocyclic group formed by R ²² and the portion represented by the formula (h) include a benzimidazole group, a benzo [f] benzimidazole group, and a dibenzo [e, g] benzimidazole group. Group, benzopyrimidine group and the like. These groups may have the same substituents as described above.

Examples of the alkoxycarbonyl group for R ²³ include groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group and a butoxycarbonyl group. The above general formulas (a) to (g)
The coupler residues represented by A ¹ , A ² , Cp ₁ and C
Specific examples of p ₂ and Cp ₃ include the following groups.

[0074]

[Chemical 29]

[0075]

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[0076]

[Chemical 31]

[0077]

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Specific examples of the perylene pigment include the following compound (CG3-1).

[0079]

[Chemical 33]

Specific examples of the bisazo pigment include the following compounds (CG4-1) to (CG4-10).

[0081]

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[0082]

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[0083]

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Specific examples of the dithioketopyrrolopyrrole pigment include the following compounds (CG5-1) to (CG5-2).

[0085]

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Specific examples of the metal-free naphthalocyanine pigment include the following compound (CG6-1).

[0087]

[Chemical 38]

Specific examples of the metal naphthalocyanine pigment include the following compound (CG7-1).

[0089]

[Chemical Formula 39]

Specific examples of the squaraine pigment include:
The following compounds (CG8-1) to (CG8-2) are listed.

[0091]

[Chemical 40]

Specific examples of the trisazo pigment include the following compounds (CG9-1) to (CG9-2).

[0093]

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Specific examples of the indigo pigment include the following compounds (CG10-1) to (CG10-2).

[0095]

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Specific examples of the azurenium pigment are:
The following compounds (CG11-1) to (CG11-2) are listed.

[0097]

[Chemical 43]

Specific examples of the cyanine pigment include the following compounds (CG12-1) to (CG12-2).

[0099]

[Chemical 44]

Next, the polyester resin used as the binder resin in the present invention will be described. The polyester resin in the present invention, as described above, the general formula (1),
It is a substantially linear polymer using the dihydroxy compound represented by (2) or (3). That is, the polyester resin comprises a dicarboxylic acid or an ester-forming derivative thereof, and at least one of the dihydroxy compounds,
It is a copolymer obtained by polycondensation with other diols. Here, the ratio of the dihydroxy compound in the diol component is 10 mol% or more, preferably 30 mol% or more, and more preferably 50 mol% or more. When the proportion of the dihydroxy compound is lower than 10 mol%, the heat resistance is poor and the molded product is easily deformed by heat, and the dispersibility of the colorant and the solubility in an organic solvent tend to be lowered.

The polyester resin of the present invention has an intrinsic viscosity of 0.3 dl measured at 20 ° C. in chloroform.
/ G or more, preferably 0.6 dl / g or more. When the intrinsic viscosity is less than 0.3 dl / g, the mechanical properties of the photoreceptor,
In particular, abrasion resistance and the like are reduced. On the other hand, the intrinsic viscosity is 0.3
If it is dl / g or more, a molded product having sufficient mechanical properties can be obtained. However, as the intrinsic viscosity increases, it takes longer to dissolve it in a solvent, and the viscosity of the solution tends to increase. . In particular, if the viscosity of the solution is too high, it becomes difficult to apply the coating liquid for forming the organic photosensitive layer onto the conductive substrate. Therefore, when the intrinsic viscosity becomes 2 dl / g or more, practical problems occur. A polyester resin having an optimum intrinsic viscosity can be easily obtained by adjusting melt polymerization conditions such as a molecular weight modifier, polymerization time, and polymerization temperature, and conditions of a chain extension reaction in a subsequent step.

In the present invention, the dispersibility of the polyester resin and the charge generating material is good because the polyester resin is prepared by using the dihydroxy compounds (1), (2) and (3) as copolymerization components. It is presumed that the solubility of the solvent is improved without impairing the moldability of. Further, the reason why the adhesive property with the conductive substrate is good is considered that the ester bond part in the molecule of the polyester resin contributes to the adhesive property with the metal. Furthermore, it is speculated that the abrasion resistance of the photosensitive layer is improved because the copolymerization of the dihydroxy compound increases the entanglement of polymer molecular chains and increases the elastic modulus.

Examples of the dicarboxylic acid or its ester-forming derivative include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid,
1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,
6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,7-
Naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4 '
-Biphenyldicarboxylic acid, aromatic dicarboxylic acid such as 9,9-bis (4-carboxyphenylene) fluorene,
Alternatively, an aliphatic dicarboxylic acid such as maleic acid, adipic acid, sebacic acid, decamethylene dicarboxylic acid, or an ester-forming derivative thereof may be used. These may be used alone or in combination of two or more.

Examples of the fluorene-based dihydroxy compound represented by the general formula (1) include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 9,9-bis [4- ( 2-hydroxyethoxy)-
3-methylphenyl] fluorene, 9,9-bis [4-
(2-Hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-ethylphenyl] fluorene, 9,9
-Bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] fluorene, 9,9-bis [4- (2
-Hydroxyethoxy) -3-propylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] fluorene, 9,
9-bis [4- (2-hydroxyethoxy) -3-isopropylphenyl] fluorene, 9,9-bis [4-
(2-Hydroxyethoxy) -3,5-diisopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-n-butylphenyl] fluorene, 9,9-bis [4- (2 -Hydroxyethoxy)-
3,5-di-n-butylphenyl] fluorene, 9,9-
Bis [4- (2-hydroxyethoxy) -3-isobutylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diisobutylphenyl]
Fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3- (1-methylpropyl) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy)
-3,5-bis (1-methylpropyl) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxy) Ethoxy) -3,5-diphenylphenyl] fluorene, 9,9-bis [4- (2-
Hydroxyethoxy) -3-benzylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy)
-3,5-Dibenzylphenyl] fluorene, 9,9-
Examples thereof include bis [4- (3-hydroxypropoxy) phenyl] fluorene and 9,9-bis [4- (4-hydroxybutoxy) phenyl] fluorene. You may use these individually or in mixture of 2 or more types. Among these, 9,9-bis [4- (2-hydroxyethoxy)]
Phenyl] fluorene is preferable in terms of optical characteristics and moldability.

The cycloalkane-based dihydroxy compound represented by the general formula (2) may be any compound synthesized from cycloalkanone, for example, 1,1-bis [4- (2-hydroxyethoxy) Phenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3-methylphenyl] cyclohexane, 1,1-
Bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] cyclohexane, 1,1-bis [4-
(2-Hydroxyethoxy) -3-ethylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxy) Ethoxy)-
3-propylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] cyclohexane, 1,1-bis [4- (2
-Hydroxyethoxy) -3-isopropylphenyl]
Cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3-n-butylphenyl] cyclohexane, 1,
1-bis [4- (2-hydroxyethoxy) -3,5-
Di-n-butylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl] cyclohexane, 1,1-bis [4- (2-
Hydroxyethoxy) -3,5-diisobutylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3- (1-methylpropyl) phenyl] cyclohexane, 1,1-bis [4- (2 -Hydroxyethoxy) -3,5-bis (1-methylpropyl)
Phenyl] cyclohexane, 1,1-bis [4- (2-
Hydroxyethoxy) -3-phenylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diphenylphenyl] cyclohexane,
1,1-bis [4- (2-hydroxyethoxy) -3-
Benzylphenyl] cyclohexane, 1,1-bis [4
-(2-Hydroxyethoxy) -3,5-dibenzylphenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -4-methylcyclohexane, 1,1-bis [4- (2 -Hydroxyethoxy)
Phenyl] -2,4,6-trimethylcyclohexane,
Dihydroxy compounds derived from cyclohexanone such as 1,1-bis [4- (2-hydroxypropoxy) phenyl] cyclohexane and 1,1-bis [4- (2-hydroxybutoxy) phenyl] cyclohexane, 1,1
-Bis [4- (2-hydroxyethoxy) phenyl] cyclopentane, 1,1-bis [4- (2-hydroxyethoxy) -3-methylphenyl] cyclopentane, 1,
1-bis [4- (2-hydroxyethoxy) -3,5-
Dimethylphenyl] cyclopentane, 1,1-bis [4
-(2-Hydroxyethoxy) -3-ethylphenyl]
Cyclopentane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] cyclopentane, 1,1-bis [4- (2-hydroxyethoxy)-
3-propylphenyl] cyclopentane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] cyclopentane, 1,1-bis [4- (2
-Hydroxyethoxy) -3-isopropylphenyl]
Cyclopentane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] cyclopentane, 1,1-bis [4- (2-hydroxyethoxy) -3-n-butylphenyl] A dihydroxy compound derived from cyclopentanone such as cyclopentane,
1,1-bis [4- (2-hydroxyethoxy) phenyl] cycloheptane, 1,1-bis [4- (2-hydroxyethoxy) -3-methylphenyl] cycloheptane, 1,1-bis [4- (2-hydroxyethoxy)-
3,5-Dimethylphenyl] cycloheptane, 1,1-
Bis [4- (2-hydroxyethoxy) -3-ethylphenyl] cycloheptane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] cycloheptane, 1,1-bis [ 4- (2-hydroxyethoxy) -3-propylphenyl] cycloheptane, 1,
1-bis [4- (2-hydroxyethoxy) -3,5-
Dipropylphenyl] cycloheptane, 1,1-bis [4- (2-hydroxyethoxy) -3-isopropylphenyl] cycloheptane, 1,1-bis [4- (2-
Dihydroxy compounds derived from cycloheptanone such as hydroxyethoxy) -3,5-diisopropylphenyl] cycloheptane and 1,1-bis [4- (2-hydroxyethoxy) -3-n-butylphenyl] cycloheptane, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclooctane, 1,1-bis [4-
(2-Hydroxyethoxy) -3-methylphenyl] cyclooctane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] cyclooctane, 1,1-bis [4- (2 -Hydroxyethoxy)-
3-Ethylphenyl] cyclooctane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] cyclooctane, 1,1-bis [4- (2-
Hydroxyethoxy) -3-propylphenyl] cyclooctane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] cyclooctane,
1,1-bis [4- (2-hydroxyethoxy) -3-
Isopropylphenyl] cyclooctane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] cyclooctane, 1,1-bis [4-
Examples include, but are not limited to, dihydroxy compounds derived from cyclooctanone such as (2-hydroxyethoxy) -3-n-butylphenyl] cyclooctane.

The cycloalkane-based dihydroxy compounds synthesized from these cycloalkanones can be used alone or in combination of two or more kinds. Among these, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 1,1-bis [4- (2-hydroxyethoxy) -3-methylphenyl] cyclohexane, 1,1-bis [ 4- (2-hydroxyethoxy)
-3,5-Dimethylphenyl] cyclohexane, 1,1
-Bis [4- (2-hydroxyethoxy) phenyl] cyclopentane, 1,1-bis [4- (2-hydroxyethoxy) -3-methylphenyl] cyclopentane, 1,
1-bis [4- (2-hydroxyethoxy) -3,5-
Dimethylphenyl] cyclopentane, 1,1-bis [4
-(2-hydroxyethoxy) phenyl] cyclooctane, 1,1-bis [4- (2-hydroxyethoxy)-
3-Methylphenyl] cyclooctane, 1,1-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] cyclooctane and the like are preferable from the viewpoint of moldability.

The dihydroxy compound represented by the general formula (3) may be any compound synthesized from alkanone. That is, there is a dihydroxy compound represented by the general formula: C _m H _2m O (where m is an integer) and derived from a linear alkanone containing a branch.
Examples of such a dihydroxy compound (3) include 2,2-bis [4- (2-hydroxyethoxy) phenyl] -4-methylpentane and 2,2-bis [4- (2-
Hydroxyethoxy) -3-methylphenyl] -4-methylpentane, 2,2-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] -4-methylpentane, 2,2-bis [4 -(2-hydroxyethoxy) -3-ethylphenyl] -4-methylpentane,
2,2-bis [4- (2-hydroxyethoxy) -3,
5-Diethylphenyl] -4-methylpentane, 2,2
-Bis [4- (2-hydroxyethoxy) -3-propylphenyl] -4-methylpentane, 2,2-bis [4
-(2-Hydroxyethoxy) -3,5-dipropylphenyl] -4-methylpentane, 2,2-bis [4-
(2-Hydroxyethoxy) -3-isopropylphenyl] -4-methylpentane, 2,2-bis [4- (2-
Dihydroxy compounds derived from 4-methyl-2-pentanone such as hydroxyethoxy) -3,5-diisopropylphenyl] -4-methylpentane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] -3 -Methylbutane, 2,2-bis [4- (2-hydroxyethoxy) -3-methylphenyl] -3-methylbutane,
2,2-bis [4- (2-hydroxyethoxy) -3,
5-Dimethylphenyl] -3-methylbutane, 2,2-
Bis [4- (2-hydroxyethoxy) -3-ethylphenyl] -3-methylbutane, 2,2-bis [4- (2
-Hydroxyethoxy) -3,5-diethylphenyl]
A dihydroxy compound derived from 3-methyl-2-butanone such as -3-methylbutane, 3,3-bis [4-
(2-hydroxyethoxy) phenyl] pentane, 3,
3-bis [4- (2-hydroxyethoxy) -3-methylphenyl] pentane, 3,3-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] pentane, 3,3-bis [ 4- (2-hydroxyethoxy)-
3-ethylphenyl] pentane, 3,3-bis [4-
Dihydroxy compounds derived from 3-pentanone such as (2-hydroxyethoxy) -3,5-diethylphenyl] pentane, 3,3-bis [4- (2-hydroxyethoxy) phenyl] -2,4-dimethylpentane , 3,
3-bis [4- (2-hydroxyethoxy) -3-methylphenyl] -2,4-dimethylpentane, 3,3-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] -2 , 4-dimethylpentane, 3,3-bis [4- (2-hydroxyethoxy) -3-ethylphenyl] -2,4-dimethylpentane, 3,3-bis [4
Dihydroxy compounds derived from 2,4-dimethyl-3-pentanone such as-(2-hydroxyethoxy) -3,5-diethylphenyl] -2,4-dimethylpentane, 3,3-bis [4- (2 -Hydroxyethoxy) phenyl] -2,4-dimethylhexane, 3,3-bis [4- (2-hydroxyethoxy) -3-methylphenyl] -2,4-dimethylhexane, 3,3-bis [4-
(2-Hydroxyethoxy) -3,5-dimethylphenyl] -2,4-dimethylhexane, 3,3-bis [4-
(2-Hydroxyethoxy) -3-ethylphenyl]-
2,4-dimethylhexane, 3,3-bis [4- (2-
Hydroxyethoxy) -3,5-diethylphenyl]-
2,4-dimethyl-3-, such as 2,4-dimethylhexane
Dihydroxy compounds derived from hexanone, 3,3
-Bis [4- (2-hydroxyethoxy) phenyl]-
2,5-dimethylhexane, 3,3-bis [4- (2-
Hydroxyethoxy) -3-methylphenyl] -2,5
-Dimethylhexane, 3,3-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] -2,5
-Dimethylhexane, 3,3-bis [4- (2-hydroxyethoxy) -3-ethylphenyl] -2,5-dimethylhexane, 3,3-bis [4- (2-hydroxyethoxy) -3,5 Examples include dihydroxy compounds derived from 2,4-dimethyl-3-hexanone such as -diethylphenyl] -2,5-dimethylhexane. These compounds may be used alone or in combination of two or more.

Examples of the other diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1, Aliphatic glycols such as 5-pentanediol, 1,4-pentanediol and 1,3-pentanediol, 1,1-bis [4- (2-hydroxyethoxy) phenyl] -1-
A diol having an aromatic ring in its main chain or side chain such as phenylethane, a compound having an aromatic ring and sulfur in its main chain such as bis [4- (2-hydroxyethoxy) phenyl] sulfone, or another dihydroxy compound, For example, bis- [4- (2-hydroxyethoxy) phenyl]-
Sulfone, tricyclodecane dimethylol, etc. can be used.

To produce the polyester resin of the present invention, an appropriate method can be selected from known methods such as a transesterification method, a melt polymerization method such as a direct polymerization method, a solution polymerization method and an interfacial polymerization method. . Further, as the reaction conditions such as the polymerization catalyst at that time, a conventionally known method can be used. To produce the polyester resin of the present invention by the transesterification method of the melt polymerization method, general formulas (1), (2) and
At least one dihydroxy compound selected from (3) is preferably 10 to 95 mol% of the glycol component in the resin. If the proportion of the glycol component exceeds 95 mol%, problems such as the melt polymerization reaction not proceeding and the polymerization time becoming extremely long occur. However, even when it is more than 95 mol%, it can be easily produced by the solution polymerization method or the interfacial polymerization method.

Further, dicarboxylic acid or its derivative,
The polyester resin (amorphous) obtained by copolymerizing the above dihydroxy compound (1), (2) or (3) has a polystyrene-equivalent weight average molecular weight of 100,000 (0.6 dl / g in intrinsic viscosity in chloroform). This is a limit that can be easily obtained by a conventionally known polymerization method. In order to obtain a high molecular weight polyester resin having an intrinsic viscosity of 0.6 dl / g or more, it is preferable to polymerize by the above-mentioned method and then react with diisocyanate. By this post-treatment, the molecular chain of polyester is elongated, and the intrinsic viscosity in chloroform is easily adjusted to 0.6 dl /
g or more, and mechanical properties such as abrasion resistance can be improved.

The diisocyanate used in the present invention includes 2
Included are all compounds in which two isocyanate groups are present on the same molecule. More specifically, for example, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, methylene-
4,4'-bisphenyl diisocyanate, xylylene diisocyanate, 3-isocyanatomethyl-3,
Examples include 5,5-trimethylcyclohexyl isocyanate. You may use these individually or in mixture of 2 or more types. Among these, especially methylene-4,
4'-Bisphenyl diisocyanate is preferred.

The amount of diisocyanate to be reacted with the polyester polymer is usually 0.5 to 1.3 times, preferably 0.8 to 1 times, the number of moles of the polyester calculated based on the number average molecular weight. The range of 1 time is preferable.
The end of the polyester molecule is alcoholic OH,
The diisocyanate reacts with the alcohol to form a urethane bond, whereby chain extension of the polyester is achieved. At this time, since the amount of urethane bonds introduced into the polyester is usually 1% or less in terms of mole fraction, physical properties such as refractive index, birefringence, glass transition point and transparency of the resin as a whole are not treated. It is no different from the polyester resin.

If necessary in the above chain extension reaction, a suitable catalyst may be used. As the catalyst, a metal catalyst such as tin octylate, dibutyltin dilaurate, and lead naphthenate, diazobiscyclo [2,2,2] octane, and tri-N-butylamine are preferable. The amount of the catalyst added depends on the chain extension reaction temperature, but is usually 0.01 mol or less, preferably 0.001 mol per mol of diisocyanate.
It is added in an amount of not more than mol.

The reaction proceeds by adding an appropriate amount of the catalyst and diisocyanate to the above polyester in a molten state and stirring the mixture under a stream of dry nitrogen. Although the reaction temperature of the chain extension reaction varies depending on the conditions, it is preferably set to a temperature not higher than the boiling point of the solvent when the reaction is carried out in an organic solvent, and a temperature not lower than the glass transition point of the polyester when the organic solvent is not used. Since the molecular weight that can be reached and the degree of coloration due to side reactions are determined by the reaction temperature, the optimum reaction system and the reaction temperature suitable for it can be selected in consideration of the target molecular weight and the molecular weight of the polyester before the reaction. . For example, when trichlorobenzene is used as the organic solvent, the reaction can be carried out in the range of 130 to 150 ° C., and there is almost no coloring due to side reaction.

The chain extension reaction of the polyester described above significantly increases the molecular weight and achieves an increase in intrinsic viscosity.
The final attainable molecular weight varies depending on the molecular weight before the reaction, but usually, the molecular weight of the chain-extended polyester can be adjusted to a desired value by changing the reaction temperature and the reaction time and the amount of diisocyanate. Since this is different depending on the case, it is difficult to specify the reaction temperature and the reaction time, but generally, the higher the temperature and the longer the reaction time, the higher the molecular weight. Further, the amount of diisocyanate is the most equivalent to the number of moles of the polyester determined from the number average molecular weight or 1.1 equivalent, and the effect of chain extension is the highest.

Usually, a dicarboxylic acid or its ester-forming derivative and a dihydroxy compound (1), (2) or
The molecular weight of the polyester obtained by copolymerizing (3) is about 50,000 (0.4 dl / g in intrinsic viscosity), and at most 100,000 (0.6 dl / g in intrinsic viscosity). For example, when the chain extension reaction is carried out using about 50,000 polyesters that can be most easily produced as a raw material, a high molecular weight polyester having an intrinsic viscosity of 0.7 to 1.5 dl / g is obtained.

The chain-extended polyester generally has a wide molecular weight distribution. The molecular weight distribution of the amorphous polyester copolymerized with the above-mentioned special dihydroxy compound produced by melt polymerization is usually about 2 in terms of the ratio of the weight average molecular weight to the number average molecular weight, although it varies depending on various reaction conditions. After the chain extension reaction, it usually becomes about 4 or more. When the molecular weight distribution is not preferable, the molecular weight distribution can be controlled, if necessary, by using a generally known molecular weight fractionation method. Examples of such a molecular weight fractionation method include a reprecipitation method with a poor solvent, a method of passing through a column filled with a gel and sieving according to the size of the molecule, and an Analysis of
The methods described in polymers, TR Crompton, Pergamon Press can be used.

Further, in the present invention, a polycarbonate resin represented by the following general formula (A) can be contained as the binder resin in addition to the above polyester resin.

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(In the formula, R ^Q and R ^R are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an aryl group which may have a substituent, and R ^Q and R ^R
May combine with each other to form a ring. R ^S , R ^T , R
^U , R ^V , R ^W , R ^X , R ^Y and R ^Z represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group which may have a substituent or a halogen atom. ) Such a polycarbonate resin may be a homopolymer using a single monomer or a copolymer using two or more kinds of monomers represented by the above general formula.

Specific examples of the polycarbonate resin represented by the general formula (A) are shown below.

[0122]

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The blending ratio of the polycarbonate resin (A) to the polyester resin is 10% by weight.
The polycarbonate resin (A) is 1 to 9 parts by weight relative to 0 parts by weight.
Suitably 9 parts by weight. The photoconductor of the present invention can be applied to both a single layer type and a laminated type photosensitive layer.

In order to obtain a single-layer type photoreceptor, a photosensitive layer containing the charge generating material, a predetermined charge transporting material, a polyester resin as a binder resin, etc. is formed on a conductive substrate by means of coating or the like. do it. Further, in order to obtain a laminated type photoreceptor, a charge generation layer containing a charge generation material and a binder resin is formed on a conductive substrate by means of coating or the like, and a charge transport layer is formed on the charge generation layer. A charge transport layer containing a material and a binder resin may be formed. On the contrary, the charge transport layer may be formed on the conductive substrate, and then the charge generation layer may be formed.

As the charge generating material, in addition to the above, other conventionally known charge generating materials may be used for the purpose of expanding the sensitivity region of the electrophotographic photosensitive member so as to have an absorption wavelength region in a desired region. Can also be used together. Other charge generating materials include azo pigments other than the above, perylene pigments, anthanthrone pigments, phthalocyanine pigments,
Examples thereof include naphthalocyanine pigments, indigo pigments, triphenylmethane pigments, slene pigments, toluidine pigments, pyrazoline pigments, quinacridone pigments, and dithioketopyrrolopyrrole pigments.

Various conventionally known charge transport materials can be used as the charge transport material, and such charge transport materials include electron transport materials and hole transport materials. As the electron-transporting material, for example, ^{2,6-dimethyl-2,, 6,}
-Diphenoquinone derivatives such as ditert-dibutyldiphenoquinone, malononitrile, thiopyran compounds, fluorenone compounds such as tetracyanoethylene, 2,4,8-trinitrothioxanthone, 3,4,5,7-tetranitro-9-fluorenone Compounds, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride,
Examples thereof include maleic anhydride and dibromomaleic anhydride.

As the hole transport material, for example, N,
Benzidine compounds such as N, N ', N'-tetra (4-methylphenyl) benzidine, N, N, N', N'-
Phenylenediamine compounds such as tetra (3-methylphenyl) -m-phenylenediamine, 2,5-di (4-
Methylaminophenyl), oxadiazole compounds such as 1,3,4-oxadiazole, styryl compounds such as 9- (4-diethylaminostyryl) anthracene,
Carbazole compounds such as polyvinylcarbazole, 1
-Pyrazoline compounds such as phenyl-3- (p-dimethylaminophenyl) pyrazolin, hydrazone compounds,
Triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazole compounds and other nitrogen-containing cyclic compounds, fused polycyclic compounds Compounds are exemplified.

The above-mentioned polyester resin used as the binder resin has a high adhesiveness to the conductive substrate, and is therefore preferably used particularly as the binder resin for the single-layer photoreceptor. In the case of a laminated photoreceptor, the abrasion resistance of the photosensitive layer is improved by using the polyester resin as the binder resin for the surface layer. In that case, the polyester resin may be used for the layer on the substrate side, or another binder resin may be used.

Other binder resins include, for example, the above-mentioned polycarbonate resins, styrene-based polymers, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-acrylic acid copolymers, polyethylene and ethylene. -Vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, alkyd resin, polyvinyl butyral, polyamide and the like can be mentioned.

The single-layer type organic photosensitive layer and the laminated type organic photosensitive layer include
Additives such as sensitizers, antioxidants, deterioration inhibitors such as ultraviolet absorbers, and plasticizers may be included. Further, in order to improve the sensitivity of the charge generation layer, known sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generation material.

In the laminated photoreceptor, the charge generating material and the binder resin which constitute the charge generating layer can be used in various ratios, but the charge generating material 5 to 5 parts by weight relative to 100 parts by weight of the binder resin. It is preferably used in an amount of 1000 parts by weight, particularly 30 to 500 parts by weight. The charge transport material constituting the charge transport layer and the binder resin can be used in various proportions within a range that does not hinder the transport of charges and a range that does not crystallize, but they are generated in the charge generation layer by light irradiation. 10 to 500 parts by weight of the charge transport material, particularly 25 to 100 parts by weight of the binder resin so that the charges can be easily transported.
It is preferably used in a proportion of 200 parts by weight.

The thickness of the laminated photosensitive layer is preferably 0.01 to 10 μm, particularly 0.1 to 5 μm, and 2 to 100 μm for the charge transport layer.
m, particularly preferably about 5 to 50 μm.
In a single-layer type photoreceptor, the charge generation material is 0.1 to 50 parts by weight, particularly 0.5 to 100 parts by weight with respect to the binder resin.
30 parts by weight, 20 to 500 parts by weight of the charge transport material, particularly 30 to 200 parts by weight are suitable. The thickness of the single-layer type photosensitive layer is 5 to 100 μm, particularly 10 to 50 μm.
It is preferable that the thickness is about m.

In the case of a single-layer type photoreceptor, it is between a conductive substrate and a photosensitive layer, and in the case of a laminated type photoreceptor, it is between a conductive substrate and a charge generating layer, and a conductive substrate. A barrier layer may be formed between the charge transport layer and the charge transport layer or between the charge generation layer and the charge transport layer to the extent that the characteristics of the photoreceptor are not impaired. It may be formed.

As the conductive substrate on which the above layers are formed, various conductive materials can be used.
For example, simple metals such as aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, plastic materials in which the above metals are vapor-deposited or laminated, iodide Examples thereof include glass coated with aluminum, tin oxide, indium oxide, or the like.

The conductive substrate may be in the form of a sheet, a drum or the like, as long as the substrate itself has conductivity or the surface of the substrate has conductivity. Further, it is preferable that the conductive substrate has sufficient mechanical strength when used. When each of the above layers is formed by a coating method, the charge generating material, charge transporting material, binder resin and the like exemplified above are combined with a suitable solvent by a known method, for example, a roll mill, a ball mill, an attritor, a paint shaker. Alternatively, an ultrasonic disperser or the like may be used for dispersion and mixing to prepare a coating solution, which may be coated and dried by a known means.

As the solvent for forming the coating solution, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol and butanol,
Aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, dimethyl ether, diethyl ether, tetrahydrofuran, Examples thereof include ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and methyl acetate, dimethylformaldehyde, dimethylformamide and dimethyl sulfoxide. These solvents can be used alone or in combination of two or more.

Further, in order to improve the dispersibility of the charge transport material or the charge generating material and the smoothness of the surface of the photosensitive layer, a surface active agent, a leveling agent, etc. may be used.

[0138]

The present invention will be described in detail below with reference to Reference Examples, Examples and Comparative Examples. Reference example 1 terephthalic acid dimethyl ester 10.68 kg (55 mol), 9,9-bis [4- (2-hydroxyethoxy)]
Phenyl] fluorene 16.88 kg (38.5 mol)
And ethylene glycol 7.2 kg (116 mol) as raw materials, and calcium acetate 15.99 g as a catalyst
(0.091 mol), and charged these into the reaction tank,
The transesterification reaction was carried out by gradually heating from 190 ° C. to 230 ° C. according to a conventional method with stirring. After extracting a predetermined amount of methanol out of the system, 6.9 g (0.066 mol) of germanium oxide as a polymerization catalyst and 14 g (0.1 mol) of phosphoric acid trimethyl ester for preventing coloring.
And gradually increase the temperature and reduce the pressure, and while removing the generated ethylene glycol, the heating tank temperature is 280 ° C.,
The degree of vacuum was made to reach 1 Torr or less. This condition was maintained, the increase in viscosity was waited, the reaction was terminated after reaching a predetermined stirring torque (after about 2 hours), and the reaction product was extruded into water to obtain pellets.

The intrinsic viscosity of this copolymer is 0.38 dl /
g. The weight average molecular weight determined by GPC is 550.
And the number average molecular weight was 25,000. The glass transition temperature was 145 ° C. 30 g of the above polyester copolymer was dissolved in trichlorobenzene to prepare a 40% by weight solution. To the above solution, 0.337 g of methylenebis (4-phenylisocyanate) 1.1 times the number of moles of the polyester copolymer calculated from the number average molecular weight and 0.175 mg of diazobiscyclo [2,2,2] octane were added. In addition, the mixture was heated and stirred at 150 ° C. for 10 hours under a nitrogen stream. The obtained reaction product was reprecipitated in methanol and washed with a large amount of methanol and distilled water to obtain a chain-extended polyester resin (1-1).

The intrinsic viscosity of this polyester resin is 0.7.
The weight average molecular weight determined by GPC is 6 dl / g and is 12
And the number average molecular weight was 38,000.
The glass transition temperature was 145 ° C. Reference Example 2 A chain was prepared in the same manner as in Reference Example 1 except that 2,6-naphthalenedicarboxylic acid was used as the acid component and ethylene glycol and bis [4- (2-hydroxyethoxy) phenyl] fluorene were used as the diol component. An extended polyester resin (1-2) was obtained. The intrinsic viscosity of this polyester resin was 0.7 dl / g. Reference Example 3 Succinic acid was used as the acid component, and ethylene glycol, bis [4- (2-hydroxyethoxy) phenyl] fluorene and 1,1-bis [4- were used as the diol component.
A chain-extended polyester resin (1-3) was obtained in the same manner as in Reference Example 1 except that (2-hydroxyethoxy) phenyl] cyclohexane was used. The intrinsic viscosity of this polyester resin was 0.8 dl / g. Reference Example 4 10.68 kg (55 mol) of dimethyl terephthalate, 1,1-bis [4- (2-hydroxyethoxy)]
Phenyl] cyclohexane 13.71 kg (38.5 mol) and ethylene glycol 7.2 kg (116 mol) as raw materials, and calcium acetate 15.99 as a catalyst.
Using g (0.091 mol), these were put into a reaction tank and gradually heated from 190 ° C. to 230 ° C. according to a conventional method with stirring to carry out a transesterification reaction. After extracting a predetermined amount of methanol out of the system, 6.9 g (0.066 mol) of germanium oxide as a polymerization catalyst and 14 g (0.1 mol) of phosphoric acid trimethyl ester for preventing coloration were added. Then, gradually raise the temperature and reduce the pressure, and remove the ethylene glycol that is generated while keeping the heating bath temperature at 280
The degree of vacuum and the degree of vacuum reached 1 Torr or less. This condition was maintained, the increase in viscosity was waited, the reaction was terminated after reaching a predetermined stirring torque (after about 2 hours), and the reaction product was extruded into water to obtain pellets.

The intrinsic viscosity of this copolymer is 0.39 dl /
g. The weight average molecular weight determined by GPC is 550.
And the number average molecular weight was 25,000. The glass transition temperature was 145 ° C. 30 g of the above polyester copolymer was dissolved in trichlorobenzene to prepare a 40% by weight solution. To the above solution, 0.337 g of methylenebis (4-phenylisocyanate) 1.1 times the number of moles of the polyester copolymer calculated from the number average molecular weight and 0.175 mg of diazobiscyclo [2,2,2] octane were added. In addition, the mixture was heated and stirred at 150 ° C. for 10 hours under a nitrogen stream. The obtained reaction product was reprecipitated in methanol and washed with a large amount of methanol and distilled water to obtain a chain-extended polyester resin (2-1).

The intrinsic viscosity of this polyester resin is 0.7.
The weight average molecular weight determined by GPC is 6 dl / g and is 12
And the number average molecular weight was 38,000.
The glass transition temperature was 115 ° C. Reference Example 5 2,6-naphthalenedicarboxylic acid was used as the acid component, and ethylene glycol and 1, as the diol component.
1-bis [4- (2-hydroxyethoxy) phenyl]
A chain-extended polyester resin (2-2) was obtained in the same manner as in Reference Example 4 except that cyclohexane was used. The intrinsic viscosity of this polyester resin was 0.8 dl / g. Reference Example 6 2,6-naphthalenedicarboxylic acid was used as the acid component, and ethylene glycol and 1, as the diol component.
1-bis [4- (2-hydroxyethoxy) -3,5-
Dimethylphenyl] cyclohexane was used,
Chain-extended polyester resin (2-
3) was obtained. The intrinsic viscosity of this polyester resin is 0.8
It was dl / g. Reference example 7 terephthalic acid dimethyl ester 10.68 kg (55 mol), 2,2-bis [4- (2-hydroxyethoxy)
Phenyl] -4-methylpentane 13.60 kg (3
8.5 mol) and 7.2 kg of ethylene glycol (1
16 mol) as a raw material, and calcium acetate as a catalyst 1
Using 5.99 g (0.091 mol), these were put into a reaction tank and stirred at 190 ° C. to 23 ° C. according to a conventional method.
The transesterification reaction was performed by gradually heating to 0 ° C. After extracting a predetermined amount of methanol out of the system, 6.9 g (0.066 mol) of germanium oxide as a polymerization catalyst and 14 g of phosphoric acid trimethyl ester for preventing coloring
(0.1 mol) was added, the temperature was raised and the pressure was gradually reduced, and the heating tank temperature was 280 ° C. and the degree of vacuum was 1 Torr or less while removing the generated ethylene glycol. This condition was maintained, the increase in viscosity was waited, the reaction was terminated after reaching a predetermined stirring torque (after about 2 hours), and the reaction product was extruded into water to obtain pellets.

The intrinsic viscosity of this copolymer is 0.39 dl /
g. The weight average molecular weight determined by GPC is 550.
And the number average molecular weight was 25,000. The glass transition temperature was 145 ° C. 30 g of the above polyester copolymer was dissolved in trichlorobenzene to prepare a 40% by weight solution. To the above solution, 0.337 g of methylenebis (4-phenylisocyanate) 1.1 times the number of moles of the polyester copolymer calculated from the number average molecular weight and 0.175 mg of diazobiscyclo [2,2,2] octane were added. In addition, the mixture was heated and stirred at 150 ° C. for 10 hours under a nitrogen stream. The obtained reaction product was reprecipitated in methanol and washed with a large amount of methanol and distilled water to obtain a chain-extended polyester resin (3-1).

The intrinsic viscosity of this polyester resin is 0.7.
The weight average molecular weight determined by GPC is 6 dl / g and is 12
And the number average molecular weight was 38,000.
The glass transition temperature was 105 ° C. Reference Example 8 2,6-naphthalenedicarboxylic acid was used as the acid component, ethylene glycol and 2, as the diol component.
2-bis [4- (2-hydroxyethoxy) -3-methylphenyl] -4-methylpentane was used,
A chain-extended polyester resin (3-
2) was obtained. The intrinsic viscosity of this polyester resin is 0.8
It was dl / g. Reference Example 9 Same as Reference Example 7 except that succinic acid was used as the acid component and ethylene glycol and 2,2-bis [4- (2-hydroxyethoxy) phenyl] -4-methylpentane were used as the diol component. To obtain a chain-extended polyester resin (3-3). The intrinsic viscosity of this polyester resin was 0.8 dl / g. Examples 1 to 162 [Single layer photoreceptor for digital light source (positive charging type)] Any one of the pigments represented by the general formulas (CG1), (CG2), (CG5) to (CG12) as a charge generating material. used. In addition, a diphenoquinone-based compound (E
T1) was used as a hole transport material, and a benzidine compound (HT1) represented by the following formula was used. further,
Polyester resins (1-1) to (1-3), (2-1) to (2-3) obtained in Reference Examples 1 to 9 as binder resins,
Any of (3-1) to (3-3) or a mixture of this polyester resin and a polycarbonate resin was used. Further, tetrahydrofuran was used as a solvent for dissolving these components.

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[Chemical 47]

[0146]

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The charge generating materials and binder resins used are shown in Table 1 by using the above compound numbers. The blending amount of each material is as follows. (Component) (parts by weight) Charge generating material 5 Hole transport material 50 Electron transport material 30 (or 0) Binder resin 90 Solvent 800 When the binder resin is the above mixture, the mixing ratio is 70 parts by weight of polyester resin and polycarbonate resin It was 20 parts by weight.

The components were mixed and dispersed in a ball mill for 50 hours to prepare a coating solution for a single layer type photosensitive layer. This coating solution is applied on an aluminum tube by dip coating,
Dry with hot air at 100 ° C for 60 minutes to obtain a film thickness of 15 to 20 μm
A single-layer type photoreceptor for a digital light source having the single-layer type photosensitive layer was manufactured. Comparative Example 1 A single-layer photoreceptor was manufactured in the same manner as in Examples 1 to 162 except that a polycarbonate resin composed of the repeating unit of the formula (A-4) was used alone as the binder resin. Comparative Example 2 Examples 1 to 162 except that copper phthalocyanine represented by the following formula (CG13-1) was used as the charge generation material.
A single-layer photoconductor was manufactured in the same manner as in.

[0149]

[Chemical 49]

The following tests were carried out on the obtained electrophotographic photoreceptors of Examples and Comparative Examples to evaluate their characteristics. <Evaluation of Positively Charged Photoreceptor for Digital Light Source> Photosensitivity Test Using a drum sensitivity tester manufactured by GENTEC, an applied voltage was applied to the surface of the photoconductor obtained in each of Examples and Comparative Examples, The surface was charged to + 700V. Then, the wavelength of 780 nm was extracted from the white light of the halogen lamp, which is the exposure light source, using a bandpass filter.
(Half width 20 nm), the monochromatic light having a light intensity of 16 μW / cm ² is applied to the surface of the photoconductor (irradiation time 80 ms), and the surface potential at the time when 330 ms has elapsed from the start of exposure is
It was measured as the potential VL (V) after exposure. Abrasion resistance test The photoconductors obtained in the respective examples and comparative examples were attached to an imaging unit of a plain paper facsimile (model number LDC-650 manufactured by Mita Kogyo Co., Ltd.), and 150,000 without paper passing.
After rotating once, the change in film thickness of the photosensitive layer was measured. Adhesion Test Adhesion of the photosensitive layer was evaluated according to the cross-cut test described in JIS K 5400 (General Test Method for Paints). The adhesiveness (%) was calculated by the following formula.

[0151]

[Equation 1]

These test results are shown in Tables 1 to 3 together with the above-mentioned compound numbers of the binder resin and the charge generating material used.
It shows in Table 9.

[0153]

[Table 1]

[0154]

[Table 2]

[0155]

[Table 3]

[0156]

[Table 4]

[0157]

[Table 5]

[0158]

[Table 6]

[0159]

[Table 7]

[0160]

[Table 8]

[0161]

[Table 9]

In each table, the one marked with * in the example number means that the photoconductor is one in which the electron transport material is not added. Examples 163 to 279 [Single-layer photoconductor for analog light source (positive charging type)] Examples 1 to 1
Instead of the charge generation material used in 162, the general formula (CG3),
Single-layer photoconductors for analog light sources were produced in the same manner as in Examples 1-162 except that the perylene pigment or bisazo pigment represented by (CG4) was used. Comparative Example 3 A single-layer photosensitive member was produced in the same manner as in Examples 163 to 279, except that 90 parts by weight of a polycarbonate resin composed of the repeating unit of the above formula (A-4) was used alone as the binder resin. Comparative Example 4 Examples 163 to 279 except that a bisazo pigment represented by the following formula (CG13-2) was used as the charge generation material.
A single-layer photoconductor was manufactured in the same manner as in.

[0163]

Embedded image

The following tests were conducted on the obtained electrophotographic photoreceptors of Examples and Comparative Examples to evaluate the characteristics. <Evaluation of positively charged photoreceptor for analog light source> Photosensitivity test Using a drum sensitivity tester manufactured by GENTEC, an applied voltage was applied to the surface of the photoreceptor obtained in each of Examples and Comparative Examples, The surface was charged to + 700V. Then, the surface of the photoconductor is irradiated with white light (light intensity 147 lux.sec.) Of a halogen lamp which is an exposure light source (irradiation time 50 msec), and the surface potential at the time when 330 msec has elapsed from the start of exposure, It was measured as the potential VL (V) after exposure. Abrasion resistance test The photoconductors obtained in each of the examples and comparative examples were mounted on an electrostatic copying machine (model number DC-2556 manufactured by Mita Kogyo Co., Ltd.) and rotated 150000 times with no paper passing. After that, the change in the film thickness of the photosensitive layer was measured. Adhesion test: Measured in the same manner as above.

The results of these tests are shown in Table 10 together with the above-mentioned compound numbers of the binder resin and the charge generating material used.
~ Shown in Table 18.

[0166]

[Table 10]

[0167]

[Table 11]

[0168]

[Table 12]

[0169]

[Table 13]

[0170]

[Table 14]

[0171]

[Table 15]

[0172]

[Table 16]

[0173]

[Table 17]

[0174]

[Table 18]

In each table, the one marked with * in the example number means that the photoconductor is one in which the electron transport material is not added. Examples 280 to 306 [Layered photoreceptor for digital light source (positive charging type)] 2 parts by weight of the pigment represented by any of the formulas (CG1) and (CG2) as a charge generating material, and a reference example as a binder resin. 1 to
9, the polyester resins (1-1) to (1-3),
120 parts by weight of tetrahydrofuran, which is a solvent, is any one of (2-1) to (2-3) and (3-1) to (3-3), or 1 part by weight of a mixture of the polyester resin and the polycarbonate resin. At the same time, they were mixed and dispersed in a ball mill to prepare a coating liquid for the charge generation layer. This coating solution is applied on an aluminum tube by dip coating,
It was dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of 0.5 μm.

When the mixture of the polyester resin and the polycarbonate resin was used as the binder resin, 70 parts by weight of the polyester resin and 20 parts by weight of the polycarbonate resin were mixed and used. Then, 80 parts by weight of the diphenoquinone compound represented by the formula (ET1) and 90 parts by weight of the polyester resin (1-1) obtained in Reference Example 1 as a binder resin were added to tetrahydrofuran 800
Mix and disperse in a ball mill for 50 hours together with parts by weight,
A coating liquid for charge transport layer was prepared. This coating solution is applied on the charge generation layer by a dip coating method, and the temperature is 90 ° C.
After drying with hot air for 15 minutes, a charge transport layer having a film thickness of 15 μm was formed to produce a laminated / positively charged photoreceptor for a digital light source.

When a mixture of polyester resin and polycarbonate resin is used as the binder resin instead of the above polyester resin alone, the polyester resin 7
0 parts by weight and 20 parts by weight of a polycarbonate resin were mixed and used. Comparative Example 5 A laminate for a digital light source was prepared in the same manner as in Examples 280 to 306 except that 1 part by weight of a polycarbonate resin composed of the repeating unit of the formula (A-4) was used alone as the binder resin for the charge generation layer. -A positively charged photoreceptor was manufactured. Comparative Example 6 Examples 280 to 30 except that the copper phthalocyanine represented by the above formula (CG13-1) was used as the charge generation material.
In the same manner as in 6, a laminated / positive charging type photoconductor for a digital light source was manufactured.

With respect to the obtained electrophotographic photoreceptors of Examples and Comparative Examples, a photosensitivity test and an abrasion resistance test were conducted in accordance with the above-described evaluation method for positively charged photoreceptors for digital light sources. The results are shown in Table 19 together with the above-mentioned compound numbers of the binder resin and the charge generating material used.

[0179]

[Table 19]

Examples 307 to 333 [Layered photoreceptor for digital light source (positive charging type)] 80 parts by weight of a benzidine compound represented by the above formula (HT1) as a hole transport material, and a formula as a binder resin. 90 parts by weight of the polycarbonate resin represented by (A-1) and 800 parts by weight of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill to prepare a coating liquid for the charge transport layer.
This coating solution was applied onto an aluminum tube by a dip coating method and dried with hot air at 100 ° C. for 60 minutes to give a film thickness of 15
A μm charge transport layer was formed.

Then, as the charge generating material, the above formula (CG
1) or 2 parts by weight of the pigment represented by (CG2), and the polyester resin (1-
1) to (1-3), (2-1) to (2-3), (3-
1) to (3-3) or 1 part by weight of a mixture of this polyester resin and a polycarbonate resin was mixed and dispersed with 120 parts by weight of tetrahydrofuran in a ball mill to prepare a charge generation layer coating liquid. This coating solution is applied on the charge transport layer by a dip coating method,
It was dried with hot air at 90 ° C. for 60 minutes to form a charge generation layer having a film thickness of 10 μm, and a laminated / positively charged photoreceptor for a digital light source was manufactured.

When a mixture of polyester resin and polycarbonate resin was used as the binder resin, 0.7 part by weight of polyester resin and 0.3 part by weight of polycarbonate resin were mixed and used. Comparative Example 7 A laminate for a digital light source was prepared in the same manner as in Examples 307 to 333 except that 1 part by weight of a polycarbonate resin composed of the repeating unit of the formula (A-4) was used alone as the binder resin for the charge generation layer. -A positively charged photoreceptor was manufactured. Comparative Example 8 Examples 307 to 33 except that the copper phthalocyanine represented by the above formula (CG13-1) was used as the charge generation material.
In the same manner as in 3, a laminated / positively charged photoreceptor for digital light source was manufactured.

Photosensitivity tests and abrasion resistance tests were carried out on the obtained electrophotographic photoreceptors of Examples and Comparative Examples in accordance with the above-mentioned evaluation method for positively charged photoreceptors for digital light sources. The results are shown in Table 20 together with the compound numbers of the binder resin and the charge generating material used.

[0184]

[Table 20]

Examples 334 to 360 [Laminate Photoreceptor for Digital Light Source (Negative Charge Type)] 2 parts by weight of the pigment represented by the formula (CG1) or (CG2) as a charge generating material, and a reference as a binder resin. Polyester resins (1-1) to (1-3) and (2-1) obtained in Examples 1 to 9
To (2-3), (3-1) to (3-3), or 1 part by weight of a mixture of the polyester resin and the polycarbonate resin is mixed and dispersed with 120 parts by weight of tetrahydrofuran in a ball mill, A charge generation layer coating solution was prepared. This coating solution was applied onto an aluminum tube by a dip coating method and dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of 0.5 μm.

If a mixture of polyester resin and polycarbonate resin is used as the binder resin,
0.7 parts by weight of polyester resin and 0.3 parts by weight of polycarbonate resin were mixed and used. Then, 80 parts by weight of a benzidine compound represented by the above formula (HT1) as a hole transport material and 90 parts by weight of the polyester resin (1-1) obtained in Reference Example 1 as a binder resin were added to tetrahydrofuran. It was mixed and dispersed in a ball mill together with 800 parts by weight to prepare a coating liquid for the charge transport layer. This coating solution is applied onto the charge generation layer by dip coating,
It was dried with hot air at 0 ° C. for 60 minutes to form a charge transport layer having a film thickness of 15 μm, and a laminated / negatively charged photoreceptor for a digital light source was manufactured. Comparative Example 9 A laminate for a digital light source was prepared in the same manner as in Examples 334 to 360, except that 1 part by weight of a polycarbonate resin containing the repeating unit of the formula (A-4) was used alone as the binder resin for the charge generation layer. -A negative charging type photoconductor was manufactured. Comparative Example 10 A laminated / negatively charged photoreceptor for a digital light source was manufactured in the same manner as in Examples 334 to 360 except that the pigment represented by the formula (CG13-1) was used as the charge generation material.

The following evaluation tests were carried out on the obtained electrophotographic photoreceptors of Examples and Comparative Examples. <Evaluation of Negatively Charged Photoreceptor for Digital Light Source> Photosensitivity Test Using a drum sensitivity tester manufactured by GENTEC, an applied voltage was applied to the surface of the photoconductor obtained in each of Examples and Comparative Examples, The surface was charged to -700V. Then, the wavelength of 780 nm was extracted from the white light of the halogen lamp, which is the exposure light source, using a bandpass filter.
(Half width 20 nm), the monochromatic light having a light intensity of 16 μW / cm ² is applied to the surface of the photoconductor (irradiation time 80 ms), and the surface potential at the time when 330 ms has elapsed from the start of exposure is
It was measured as the potential VL (V) after exposure. Abrasion resistance test The photoconductors obtained in each of the examples and comparative examples were mounted on an imaging unit of an electrostatic laser printer (model LP-2080 manufactured by Mita Kogyo Co., Ltd.), and no paper was passed through 1500.
After being rotated 00 times, the change in film thickness of the photosensitive layer was measured.

The results of these tests are shown in Table 21 together with the above-mentioned compound numbers of the binder resin and the charge generating material used.
Shown in

[0189]

[Table 21]

Examples 361 to 387 [Laminated photoreceptor for analog light source (positive charging type)] 2 parts by weight of the pigment represented by the formula (CG3-1) or (CG4-1) was used as the charge generating material. Example 280
In the same manner as described above, a laminated / positive charging type photoreceptor for analog light source was manufactured. Comparative Example 11 A laminate for an analog light source was prepared in the same manner as in Examples 280 to 306 except that 1 part by weight of a polycarbonate resin composed of the repeating unit of the formula (A-4) was used alone as the binder resin for the charge generation layer. -A positively charged photoreceptor was manufactured. Comparative Example 12 A laminated / positive charging type photoreceptor for analog light sources was manufactured in the same manner as in Examples 280 to 306 except that the pigment represented by the formula (CG13-2) was used as the charge generation material.

The electrophotographic photoreceptors of the respective Examples and Comparative Examples thus obtained were subjected to respective tests of photosensitivity and abrasion resistance in the same manner as in Examples 163 to 279. The results of these tests are shown in Table 22 together with the above-mentioned compound numbers of the binder resin and the charge generating material used.

[0192]

[Table 22]

Examples 388 to 414 [Laminated photoreceptor for analog light source (positive charging type)] 2 parts by weight of the pigment represented by the above formula (CG3-1) or (CG4-1) was used as the charge generating material. Example 307
In the same manner as described in (1) to (333), laminated / positive charging type photoreceptors for analog light sources were manufactured. Comparative Example 13 A laminate for an analog light source was prepared in the same manner as in Examples 307 to 333 except that 90 parts by weight of a polycarbonate resin composed of the repeating unit of the formula (A-4) was used alone as the binder resin for the charge transport layer. -A positively charged photoreceptor was manufactured. Comparative Example 14 A laminated / positive charging type photoreceptor for an analog light source was manufactured in the same manner as in Examples 307 to 333 except that the pigment represented by the formula (CG13-2) was used as the charge generation material.

Each of the obtained electrophotographic photosensitive members of Examples and Comparative Examples was subjected to each test of photosensitivity and abrasion resistance in the same manner as in Examples 163 to 279. The results of these tests are shown in Table 23 together with the above-mentioned compound numbers of the binder resin and the charge generating material used.

[0195]

[Table 23]

Examples 415 to 441 [Laminate Photoreceptor for Analog Light Source (Negative Charging Type)] 2 parts by weight of the pigment represented by the formula (CG3-1) or (CG4-1) was used as the charge generating material. Example 334
In the same manner as described above, a laminated / negatively charged photoreceptor for analog light source was manufactured. Comparative Example 15 A laminate for an analog light source was prepared in the same manner as in Examples 334 to 360, except that 1 part by weight of a polycarbonate resin containing the repeating unit of the formula (A-4) was used alone as the binder resin for the charge generation layer. -A negative charging type photoconductor was manufactured. Comparative Example 16 A laminated / negatively charged photoreceptor for an analog light source was manufactured in the same manner as in Examples 334 to 360 except that the pigment represented by the formula (CG13-2) was used as the charge generation material.

The following tests were carried out on the obtained electrophotographic photosensitive members of Examples and Comparative Examples to evaluate their characteristics. <Evaluation of Negatively Charged Photoreceptor for Analog Light Source> Photosensitivity Test Using a drum sensitivity tester manufactured by GENTEC, an applied voltage was applied to the surface of the photoreceptor obtained in each Example and Comparative Example, The surface was charged to -700V. Then, the surface of the photoconductor is irradiated with white light (light intensity 147 lux.sec.) Of a halogen lamp which is an exposure light source (irradiation time 50 msec), and the surface potential at the time when 330 msec has elapsed from the start of exposure, It was measured as the potential VL (V) after exposure. Abrasion resistance test Electrostatic copying machine (model DC-2 manufactured by Mita Kogyo Co., Ltd.) in which the photoconductors obtained in the respective examples and comparative examples were modified to have negative charging specifications.
556), after rotating the sheet for 150000 times in a paperless state, the change in film thickness of the photosensitive layer was measured.

The results of these tests are shown in Table 24 together with the above-mentioned compound numbers of the binder resin and the charge generating material used.
Shown in

[0199]

[Table 24]

[0200]

According to the present invention, by combining a specific charge generating material and a specific polyester resin,
Since the compatibility and dispersibility of the charge generating material with respect to the polyester resin are improved, the high charge generating characteristics of the charge generating material are fully exhibited, and the sensitivity of the photoreceptor is improved.

Further, since the polyester resin of the present invention has excellent adhesiveness to the conductive substrate, there is no fear that the photosensitive layer will be peeled off from the conductive substrate during long-term use of the photosensitive member. Since it has excellent mechanical strength such as wear resistance, the life of the photoconductor can be extended.

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[Procedure amendment]

[Submission date] July 27, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

[0032]

Embedded image

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050]

[Chemical formula 24]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

[0052]

[Chemical 25]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

[0054]

[Chemical formula 26]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03G 5/06 384 G03G 5/06 384 (72) Inventor Mitsuo Ihara 1 Takumazo, Chuo-ku, Osaka-shi, Osaka Chome 2-28 Mita Industry Co., Ltd. (72) Inventor Ichiro Yamazato 1-Tamazo, Chuo-ku, Osaka-shi, Osaka 1-22-Sanda Industry Co., Ltd. (72) Inventor Yuka Nakamura 1-Tamazo, Chuo-ku, Osaka-shi, Osaka 2-28, Mita Industry Co., Ltd.

Claims (5)

[Claims] 1. A metal-free phthalocyanine, titanyl phthalocyanine, perylene pigment, bisazo pigment, dithioketopyrrolopyrrole pigment, metal-free naphthalocyanine pigment, metal naphthalocyanine pigment, squaraine pigment, trisazo pigment, indigo pigment, azurenium pigment and cyanine pigment. At least one charge generating material selected from the group consisting of: and a compound represented by the general formula (1): (In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, R ² or R ² .
³ , R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom,
An alkyl group, an aryl group or an aralkyl group having 1 to 4 carbon atoms is shown. And a binder resin made of a polyester resin, which is a substantially linear polymer using a dihydroxy compound represented by the formula (1), is provided on an electrically conductive substrate. body. 2. Metal-free phthalocyanine, titanyl phthalocyanine, perylene pigment, bisazo pigment, dithioketopyrrolopyrrole pigment, metal-free naphthalocyanine pigment, metal naphthalocyanine pigment, squaraine pigment, trisazo pigment, indigo pigment, azurenium pigment and cyanine pigment. At least one charge generating material selected from the group consisting of: and a general formula (2): (In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, R ² or R ² .
³ , R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom,
An alkyl group, an aryl group or an aralkyl group having 1 to 4 carbon atoms is shown. n is an integer of 2 or more. And a binder resin made of a polyester resin, which is a substantially linear polymer using a dihydroxy compound represented by the formula (1), is provided on an electrically conductive substrate. body. 3. Metal-free phthalocyanine, titanyl phthalocyanine, perylene pigment, bisazo pigment, dithioketopyrrolopyrrole pigment, metal-free naphthalocyanine pigment, metal naphthalocyanine pigment, squaraine pigment, trisazo pigment, indigo pigment, azurenium pigment and cyanine pigment. At least one charge-generating material selected from the group consisting of: and a compound represented by the general formula (3): (In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, R ² or R ² .
³ , R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, an aryl group or an aralkyl group, R ⁶ and R ⁷ are the same or different and have 1 carbon atom;
10 represents an alkyl group. And a binder resin made of a polyester resin, which is a substantially linear polymer using a dihydroxy compound represented by the formula (1), is provided on an electrically conductive substrate. body. 4. A polyester resin in which the binder resin is a substantially linear polymer using a dihydroxy compound represented by the general formula (1), (2) or (3), and a polycarbonate resin. The electrophotographic photosensitive member according to claim 1, comprising: 5. The organic photosensitive layer is a single layer.
Alternatively, the electrophotographic photoconductor of item 3.