JP2018159087A - Polyarylate resin, and electrophotographic photoreceptor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylate having excellent electric characteristics and solubility, and stabilize performance of polyarylate resin when being used repeatedly as binder resin of an electrophotographic photoreceptor and improve a transfer memory.SOLUTION: Polyarylate resin has a specific repeated structure, obtained by polymerization of a raw material monomer containing specific bisphenol, where the content of a specific bisphenol residue in the polyarylate is 10 ppm or less.SELECTED DRAWING: None

Description

The present invention relates to a polyarylate resin having a specific structure obtained by polymerizing a predetermined raw material monomer, specifically, a polyarylate resin obtained by polymerizing a raw material monomer in which the purity of bisphenol having a specific structure is controlled, and further using the same. The present invention relates to an electrophotographic photosensitive member.

A polyarylate resin is known as one of engineering plastics that are excellent in mechanical strength and amorphous. With regard to the structure of this polyarylate resin, various structures have been proposed for the properties required so far. In recent years, transparency in the electrical and electronic fields,
There is an increasing demand for coating film resins having excellent wear resistance, and in particular, in the field of electrophotography, the use of polyarylate resins having various structures as binder resins for organic photoreceptors has been studied.

Polycarbonate used in many electrophotographic photoreceptors by using a commercially available polyarylate resin “U-polymer” as a binder resin for the photosensitive layer as a development of polyarylate resins on electrophotographic photoreceptors. It has been reported that the sensitivity is improved as compared with the case of using a resin (see Patent Document 1). However, the coating solution prepared by dissolving this polyarylate resin has low stability, and coating production may be difficult. In response to this problem, by using a polyarylate resin using a divalent phenol component having a specific structure as a binder resin, the stability of the coating solution used in the production of the electrophotographic photoreceptor is improved, and the electrophotographic photoreceptor Improvements in mechanical strength and wear resistance have been reported (see Patent Documents 2 to 5).

On the other hand, the electrophotographic photosensitive member is repeatedly used in an electrophotographic process, that is, a cycle of charging, exposure, development, transfer, cleaning, static elimination, and the like, and deteriorates due to various stresses. Such deterioration includes, for example, strongly oxidative ozone generated from a corona charger normally used as a charger, chemical damage caused by NOx to the photosensitive layer, and carrier (current) generated by image exposure. There are chemical and electrical degradation such as flowing inside, electrical damage due to charging for transferring toner to paper, and decomposing the photosensitive layer composition by static elimination light or external light. Therefore, these deteriorations have caused the life of the electrophotographic photosensitive member. There is a demand for an electrophotographic photosensitive member with small fluctuations in image characteristics in repeated use. Regarding the electrical characteristics during repeated use, there is no report on the relationship with the by-products in the dihydric phenol component in the polyarylate resin, but once it is polymerized and taken into the polymer, it cannot be removed. The impact should be fully considered.

JP-A-56-135844 Japanese Patent Laid-Open No. 3-6567 JP-A-9-22126 JP-A-9-319129 JP 2006-290959 A

In the techniques described in Patent Documents 2 to 5, it is described that by using a polyarylate resin using a specific bisphenol, an electrophotographic photoreceptor having improved solubility, solvent cracking properties, mechanical properties, and the like can be obtained. However, the electrical characteristics may be deteriorated in repeated use.
The object of the present invention is to provide a polyarylate excellent in electrical properties and solubility,
It is another object of the present invention to stabilize the performance during repeated use when the polyarylate resin is used as a binder resin for an electrophotographic photosensitive member and to improve a transfer memory.

As a result of intensive studies on an electrophotographic photosensitive member that can solve the above problems, the present inventors have found that the ratio of the bisphenol component of the specific structure in the polyarylate resin having the specific structure, the content of by-products, and The inventors have found that by controlling the purity of the raw material monomer used for the polymerization, the electrical properties and solubility of the polyarylate resin, particularly the electrical properties in repeated use, can be improved, and the present invention has been achieved.

That is, the invention according to claim 1 is a polyarylate resin having a repeating structure represented by formula (1), obtained by polymerizing a raw material monomer containing bisphenol represented by formula (2), After hydrolysis of the polyarylate resin, the amount of bisphenol residue represented by the formula (4) detected by a gas chromatograph using a flame ionization detector (FID) is expressed by the formula (2).
, 10 p in terms of intensity ratio with respect to the total amount of bisphenol residues represented by formula (3) and formula (4)
It is a polyarylate resin characterized by having a pm or less.

(In the formulas (1) to (4), Y represents at least one divalent group selected from an m-phenylene group, a p-phenylene group, or a divalent group in which two p-phenylene groups are bonded via an oxygen atom. N represents an integer of 1 or more, X represents a single bond, —CR ¹ R ² —, O, CO, or S. Each of R ¹ and R ² independently represents a hydrogen atom. , A methyl group, an ethyl group, or a cyclohexylidene group formed by combining R ¹ and R ² .
In the invention according to claim 2, the amount of the bisphenol residue represented by the formula (3) detected by a gas chromatograph using a flame ionization detector (FID) is represented by the formulas (2) and (3). The polyarylate resin according to claim 1, wherein the strength ratio is 0.2% or more and 1% or less with respect to the total amount of bisphenol residues represented by the formula (4).

The invention according to claim 3 is the polyarylate resin according to claim 1 or 2, wherein the bisphenol represented by the formula (3) is a bisphenol represented by the formula (3a).

(In the formula (3a), X represents a single bond, —CR ¹ R ² —, O, CO, or S. R ¹
, R ² each independently represents a hydrogen atom, a methyl group, or an ethyl group, or R ¹ and R 2
² represents a cyclohexylidene group formed by bonding with ² ; )
The invention according to claim 4 is the polyarylate resin according to any one of claims 1 to 3, wherein the raw material monomer has a bisphenol purity of 99% or more.

The invention according to claim 5 is a polyarylate resin having a repeating structure represented by formula (1), obtained by polymerizing a raw material monomer containing bisphenol represented by formula (2), wherein the raw material monomer The content of bisphenol represented by formula (4) detected by a gas chromatograph using a hydrogen flame ionization detector (FID) is represented by formula (2), formula (3) and formula (4). It is a polyarylate resin characterized by having a strength ratio of 10 ppm or less with respect to the total amount of bisphenol produced.

(In the formulas (1) to (4), Y represents at least one divalent group selected from an m-phenylene group, a p-phenylene group, or a divalent group in which two p-phenylene groups are bonded via an oxygen atom. N represents an integer of 1 or more, X represents a single bond, —CR ¹ R ² —, O, CO, or S. Each of R ¹ and R ² independently represents a hydrogen atom. , A methyl group, an ethyl group, or a cyclohexylidene group formed by combining R ¹ and R ² .
The invention according to claim 6 is a flame ionization detector (FID) in the raw material monomer.
The content of the bisphenol represented by the formula (3) detected by the gas chromatograph using the ratio of the strength to the total amount of the bisphenol represented by the formula (2), the formula (3) and the formula (4) The polyarylate resin according to claim 5, wherein the polyarylate resin is 0.3% or more and 1% or less.

The invention according to claim 7 is an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains the polyarylate resin according to any one of claims 1 to 6. An electrophotographic photosensitive member is characterized.
The invention according to claim 8 is the electrophotographic photoreceptor according to claim 7, wherein the photosensitive layer is formed by laminating a charge transport layer and a charge generation layer.

The invention according to claim 9 is characterized in that the charge transport layer contains at least one charge transport material selected from the group of compounds represented by the following formulas (7) to (10). Or an electrophotographic photosensitive member according to 8.

A tenth aspect of the present invention is an image forming apparatus using the electrophotographic photosensitive member according to any one of the seventh to ninth aspects.
11. The image according to claim 10, wherein in the electrophotographic process, the toner developed on the photoconductor is directly transferred to a print medium without passing through an intermediate transfer body. Forming device.

A twelfth aspect of the invention is a cartridge for an image forming apparatus using the electrophotographic photosensitive member according to any one of the seventh to ninth aspects.
The invention according to claim 13 is a method for producing a polyarylate resin having a repeating structure represented by the formula (1) according to any one of claims 1 to 6, wherein the formula (2) A method for producing a polyarylate resin, characterized by polymerizing a bisphenol component containing bisphenol and a divalent carboxylic acid component.

According to the present invention, a polyarylate resin having high solubility and storage stability and excellent electrical characteristics and an electrophotographic photoreceptor excellent in transfer memory during repeated use can be obtained.

1 is a conceptual diagram illustrating an embodiment of an image forming apparatus using an electrophotographic photosensitive member of the present invention. FIG. 2 is an X-ray diffraction pattern of hydroxygallium phthalocyanine (A) described in Production Example 1 of the present invention. FIG. 3 is an X-ray diffraction pattern of hydroxygallium phthalocyanine (B) described in Production Example 2 of the present invention.

The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
<< 1. Polyarylate resin >>
The polyarylate resin of the present invention has a repeating structure represented by the formula (1), and the formula (
It is obtained by polymerizing a raw material monomer containing bisphenol represented by 2).

In formula (1), Y represents at least one divalent group selected from an m-phenylene group, a p-phenylene group, or a divalent group in which two p-phenylene groups are bonded via an oxygen atom. That is, examples of the dicarboxylic acid residue of the polyarylate resin represented by the formula (1) include terephthalic acid, isophthalic acid, and diphenyl ether-4,4′-dicarboxylic acid. These dicarboxylic acid residues can be used in combination as required, and among them, terephthalic acid and isophthalic acid are preferably combined from the viewpoint of mechanical properties. When terephthalic acid and isophthalic acid are combined, the content ratio of both is preferably 10/90 to 90/10 (molar ratio) from the viewpoint of solubility and mechanical properties, and 25/75 to 75/25 (molar ratio). It is more preferable to set it as 35/65 to 65/35 (molar ratio).

In formulas (1) and (2), each X represents a single bond, —CR ¹ R ² —, O, CO, or S. R ¹ and R ² each independently represent a hydrogen atom, a methyl group, or an ethyl group, or R 1
¹ and R ^{2 each} represents a cyclohexylidene group formed by combining R ¹ and R ² . n is 1
It represents the above integer.
The polyarylate resin of the present invention only needs to contain the repeating structure represented by the above formula (1) in its molecular structure, for example, it has only the repeating structure represented by the above formula (1). Alternatively, for example, a copolymer having a repeating structure represented by the above formula (1) and a repeating structure other than the repeating structure represented by the formula (1) may be used.

As a repeating unit other than the repeating structure represented by the above formula (1) of the copolymer, the following formula (
And a copolymer containing the repeating structure represented by 6).

(In formula (6), Z represents at least one divalent group selected from an m-phenylene group, a p-phenylene group, or a divalent group in which two p-phenylene groups are bonded via an oxygen atom. R
^{3 to} R ⁶ each independently represents a hydrogen atom or a methyl group. W is a single bond, —CR ⁷ R
⁸ - represents O, CO, and S. R ⁷ and R ⁸ each independently represent a hydrogen atom, a methyl group, or an ethyl group, or a cyclohexylidene group formed by combining R ⁷ and R ⁸ . m represents an integer of 1 or more. )

Examples of the dicarboxylic acid residue of the polyarylate resin represented by the formula (6) include terephthalic acid,
Examples thereof include isophthalic acid and diphenyl ether-4,4′-dicarboxylic acid. These dicarboxylic acid residues can be used in combination as required, and among them, terephthalic acid and isophthalic acid are preferably combined from the viewpoint of mechanical properties. When terephthalic acid and isophthalic acid are combined, the content ratio of both is 10 / from the viewpoint of solubility and mechanical properties.
90-90 / 10 (molar ratio) is preferable, 25 / 75-75 / 25 (molar ratio)
It is more preferable to set it as 35/65 to 65/35 (molar ratio).

Specific examples of the bisphenol residue of the polyarylate resin represented by the formula (6) include bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, and bis- (3 , 5-Dimethyl-4-hydroxyphenyl) methane, 1,1
-Bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxy-3-methylphenyl) ethane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl)
Ethane, 1,1-bis- (4-hydroxyphenyl) propane, 1,1-bis- (4-hydrokey 3-methylphenyl) propane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) ) Propane, 2,2-bis- (4-hydroxyphenyl) propane, 2,
2-bis- (4-hydrokey 3-methylphenyl) propane, 2,2-bis- (3,5-
Dimethyl-4-hydroxyphenyl) propane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 1,1-bis- (4-hydrokey 3-methylphenyl) cyclohexane, 1,1-bis- (3,5 -Dimethyl-4-hydroxyphenyl) cyclohexane,
1,1-bis- (4-hydroxyphenyl) -1-phenylethane, 4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenol, 3,3 ', 5,5'-tetra Methyl-4,4′-biphenol, 4,4′-dihydroxydiphenyl ether, 3,3′-
Examples thereof include dimethyl-4,4′-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxybenzophenone, and the like.

Among these, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, bis- ( 3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-
Bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxy-3-methylphenyl) ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4 -Hydrokey 3-methylphenyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 4,4'-biphenol, 3,3′-dimethyl-4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol and 4,4′-dihydroxydiphenyl ether are preferred.

Further, considering mechanical properties, bis- (4-hydroxyphenyl) methane, bis- (4
-Hydroxy-3-methylphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxy-3-methylphenyl) ethane, 2,2-bis- (4 -Hydroxy 3-methylphenyl) propane, 4,4'-biphenol, 3,3
'-Dimethyl-4,4'-biphenol, 3,3', 5,5'-tetramethyl-4,4 '
-Biphenol is more preferred.

The repeating structure represented by the formula (1) constituting the polyarylate resin of the present invention preferably has the following repeating units.

When the polyarylate resin of the present invention is a copolymer, the content of the formula (1) is not particularly specified, but is preferably 30 mol% or more, more preferably 50 mol% or more, and further preferably 60 mol. % Or more. If the content is too small, the electrical properties and solubility may be insufficient.
Further, in the polyarylate resin of the present invention, after hydrolysis of the polyarylate resin, the following formula (
The content in the intensity ratio detected by the flame ionization detector (FID) when measured using the gas chromatograph of bisphenol represented by 4) is expressed by the equations (2), (3), (
The total amount of bisphenol represented by 4) is preferably 10 ppm or less, more preferably 8 ppm or less, still more preferably 5 ppm or less, and particularly preferably not detected. The amount of bisphenol represented by formula (4) is the sum of free bisphenol and bisphenol bonded in the repeating structure. By reducing the amount of bisphenol of the formula (4) in the polyarylate resin, it becomes possible to control the terminal group such as the carboxylic acid chloride terminal and to suppress the accumulation of electric charges simply by reducing the phenol component. Thus, it is considered that the repeated transfer memory is good.

The content of the bisphenol residue represented by the following formula (4) in the polyarylate resin is, for example, that the polyarylate resin having a repeating structure represented by the formula (1) is hydrolyzed under basic or acidic conditions. It can be measured by gas chromatography after decomposing into monomer components and neutralizing. The ratio of the area of each peak to the total area of peaks derived from the raw material monomers is defined as the content. In the hydrolysis method, methanol, ethanol, 1-propanol, 1-butanol, benzyl alcohol or other alcohol or water is used as a solvent. Under basic conditions, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxy are used. In the acidic condition, an acid such as hydrochloric acid or sulfuric acid is used. The reaction temperature for the hydrolysis is preferably 20 ° C to 100 ° C, more preferably 30 ° C to
70 ° C. If the reaction temperature is low, the rate of hydrolysis is slow and cannot be sufficiently decomposed into monomers. On the other hand, if the reaction temperature is too high, decomposition of bisphenol may occur. The completion of the hydrolysis reaction can be confirmed by GPC or NMR.

(In the formula (4), X represents a single bond, —CR ¹ R ² —, O, CO, or S. Also, R ¹ ,
R ² each independently represents a hydrogen atom, a methyl group, or an ethyl group, or R ¹ and R ²
And a cyclohexylidene group formed by bonding to each other. )
In addition, the polyarylate resin of the present invention is a hydrolyzed polyarylate resin that is detected by a flame ionization detector (FID) when measured using a gas chromatograph (following formula (
The amount of bisphenol residues in the strength ratio represented by 3) is determined by the formulas (2), (3) and (4).
) Is 1% or less with respect to the total amount of bisphenol residues represented, and is preferably 0.8% or less, more preferably 0.5% or less, from the viewpoint of electrical characteristics during repeated use. Also,
Usually, it is 0.2% or more, preferably 0.3% or more, more preferably 0.4% or more. In this case, the amount of bisphenol residue is the sum of free bisphenol and bisphenol bonded in the repeating structure.

When the bisphenol residue of the formula (3) is present in the above range in the polyarylate resin, the compatibility between the polyarylate resin and the charge transporting material is increased, and the interaction between the charge generating material is also increased, so that it can be used repeatedly. It is thought that the electrical characteristics of the are improved. The amount of the bisphenol residue represented by the following formula (3) in the polyarylate resin is, for example, the formula (1).
The polyarylate resin having a repeating structure represented by) is hydrolyzed under basic or acidic conditions as described above to be decomposed into monomer components, neutralized, and then measured by gas chromatography.

(In the formula (3), X represents a single bond, —CR ¹ R ² —, O, CO, S. R ¹ and R ² each independently represents a hydrogen atom, a methyl group, or an ethyl group. Or a cyclohexylidene group formed by combining R ¹ and R ^2. )
≪2. Production method of polyarylate resin >>
The method for producing the polyarylate resin of the present invention is not particularly limited as long as it is a method capable of polymerizing a raw material monomer containing a bisphenol represented by the formula (2) described later, and is a known polyarylate. This polymerization method can be applied for production. As a polymerization method of the polyarylate resin, for example, an interfacial polymerization method, a melt polymerization method, a solution polymerization method, or the like can be used. Here, an example of the manufacturing method of polyarylate resin is demonstrated.

In the case of production by the interfacial polymerization method, for example, a solution in which a dihydric phenol compound is dissolved in an alkaline aqueous solution and a halogenated hydrocarbon solution in which an aromatic dicarboxylic acid chloride compound is dissolved are mixed. In this case, a quaternary ammonium salt or a quaternary phosphonium salt can be present as a catalyst. The polymerization temperature ranges from 0 ° C to 40 ° C, and the polymerization time ranges from 2 hours to 2
The range of 0 hour is preferable in terms of productivity. After completion of the polymerization, the aqueous phase and the organic phase are separated,
By washing and collecting the polymer dissolved in the organic phase by a known method, a target resin can be obtained.

Examples of the alkali component used in the interfacial polymerization method include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. As the usage-amount of an alkali component, the range of 1.01 times equivalent-3 times equivalent of the phenolic hydroxyl group contained in a reaction system is preferable.
Examples of the halogenated hydrocarbon include dichloromethane, chloroform, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dichlorobenzene, and the like.

Examples of the quaternary ammonium salt or quaternary phosphonium salt used as the catalyst include, for example, salts of tertiary alkylamines such as tributylamine and trioctylamine such as hydrochloric acid, bromic acid and iodic acid; benzyltriethylammonium chloride, benzyltrimethylammonium Examples include chloride, benzyltributylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylphosphonium bromide, triethyloctadecylphosphonium bromide, N-laurylpyridinium chloride, laurylpicolinium chloride It is done.

In the interfacial polymerization method, a molecular weight regulator can be used. Examples of the molecular weight regulator include phenol, o, m, p-cresol, o, m, p-ethylphenol, o,
alkylphenols such as m, p-propylphenol, o, m, p- (tert-butyl) phenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives;
1-functional phenol such as m, p-phenylphenol; 1 such as acetic acid chloride, butyric acid chloride, octyl acid chloride, benzoyl chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzenephosphonyl chloride, and their substitutes Examples thereof include functional acid halides. Among these molecular weight regulators, o, m, p- (tert-) are preferred because of their high molecular weight controllability and solution stability.
Butyl) phenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives. Particularly preferred are p- (tert-butyl) phenol, 2,3,6-trimethylphenol, and 2,3,5-trimethylphenol.

Moreover, in order not to oxidize dihydric phenol in an alkaline solution, antioxidant can be added. Examples of the antioxidant include sodium sulfite, hydrosulfite (sodium hyposulfite), sulfur dioxide, potassium sulfite, sodium hydrogen sulfite and the like. Among these, hydrosulfite is particularly preferable from the viewpoint of the antioxidant effect and reduction of environmental load. The amount of the antioxidant used is 0.01 with respect to the total dihydric phenol.
The content is preferably from mass% to 10.0 mass%. More preferably, it is 0.1 mass% or more and 5 mass% or less. If the content is too small, the antioxidant effect may be insufficient. If the content is too large, it may remain in the polyarylate and adversely affect the electrical properties.

As the purification method after polymerization of the polyarylate resin, any method can be used as long as the effects of the present invention are not significantly impaired. For example, the polyarylate resin solution is an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide; An aqueous solution of acid such as hydrochloric acid, nitric acid, phosphoric acid, etc .; a method of separating by standing separation, centrifugation, etc. after washing with water or the like.
Other purification methods include, for example, a method of precipitating the produced polyarylate resin solution in a solvent in which the polyarylate resin is insoluble, a method of dispersing the polyarylate resin solution in warm water and distilling off the solvent, Or you may refine | purify by the method etc. which distribute | circulate a polyarylate resin solution to an adsorption column.

The purified polyarylate resin may be precipitated in water, alcohol or other organic solvent in which the polyarylate resin is insoluble, or the polyarylate resin solution is distilled off in warm water or in a dispersion medium in which the polyarylate resin is insoluble. Alternatively, the solvent may be removed by distilling off the solvent by heating, decompression, or the like, and when it is taken out in the form of a slurry, the solid can be taken out by a centrifugal separator or a filter.

The obtained polyarylate resin is usually dried at a temperature not higher than the decomposition temperature of the polyarylate resin, but can be preferably dried at 20 ° C. or higher and below the melting temperature of the resin. At this time, it is preferable to dry under reduced pressure.
Preferably, the drying time is not less than the time until the purity of impurities such as the residual solvent becomes below a certain level, specifically, the residual solvent is usually 1000 ppm or less, preferably 300 ppm or less,
More preferably, it is dried for not less than 100 ppm.

≪3. Raw material monomer >>
In the production of the polyarylate resin of the present invention, a raw material monomer containing bisphenol having a structure represented by the formula (2) is used.

In the formula (2), each X represents a single bond, —CR ¹ R ² —, O, CO, or S. R ¹ and R
² each independently represents a hydrogen atom, a methyl group, or an ethyl group, or a cyclohexylidene group formed by combining R ¹ and R ² .
The specific structure of bisphenol represented by Formula (2) is illustrated below.

Among these, bis- (4-hydroxy-3-methylphenyl) methane, 1,1-bis- (4-hydroxy-3-methylphenyl) ethane, 2,2-bis- (4-hydroxy-3-methyl) Phenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) butane.
In particular, from the viewpoint of electrical characteristics, 1,1-bis- (4-hydroxy-3-methylphenyl) ethane and 2,2-bis- (4-hydroxy-3-methylphenyl) propane are preferable.

The purity of the bisphenol represented by the above formula (2) in the raw material monomer is preferably 99% or more, more preferably 99.2% or more, and particularly preferably 99.4% or more. When the purity is equal to or higher than the above lower limit, the molecular weight can be effectively controlled when the polymer (polyarylate resin) is used. Moreover, it is 99.8% or less normally, Preferably it is 99.
It is 7% or less, more preferably 99.6% or less. When the purity is not less than the above upper limit, polymerization reproducibility may not be obtained due to the influence of impurities, or electrical characteristics may be deteriorated. The previous purity can be measured by gas chromatography. The ratio of the area of each peak to the total area of peaks derived from the raw material monomers was defined as the content.

The raw material monomer may contain only one type of bisphenol having the structure represented by the above formula (2), and two or more types of bisphenol represented by the above formula (2) having different structures. , And may be contained in any ratio and combination.
Here, in this invention, content of the bisphenol represented by following formula (4) in a raw material monomer is 10 ppm or less, Preferably it is 5 ppm or less, More preferably, it is 1
ppm or less. When the content of bisphenol represented by the following formula (4) exceeds 10 ppm, the electrical properties and polymerization controllability of polyarylate produced by polymerizing the raw material monomer are deteriorated. Since the bisphenol represented by the formula (4) has more ortho-positioned methyl groups than the bisphenol represented by the formula (2), it is difficult to control the polymerization reactivity because the reactivity during polymerization is low. It is considered that polymerization reproducibility becomes difficult. Also,
Since it is difficult to control the terminal group in the produced polyarylate, it is considered that the electrical characteristics are deteriorated. The content of bisphenol represented by the following formula (4) in the raw material monomer can be measured by a gas chromatograph.

(In formula (4), each X represents a single bond, —CR ¹ R ² —, O, CO, S. Also, R ¹ , R
² each independently represents a hydrogen atom, a methyl group, or an ethyl group, or a cyclohexylidene group formed by combining R ¹ and R ² . )
The specific structure of bisphenol represented by Formula (4) is illustrated below.

Among these, (4-hydroxy-3-methylphenyl) (4-hydroxy-3,5
-Dimethylphenyl) methane, 1- (4-hydroxy-3-methylphenyl) -1- (4
-Hydroxy-3,5-dimethylphenyl) ethane, 2- (4-hydroxy-3-methylphenyl) -2- (4-hydroxy-3,5-dimethylphenyl) propane.

In the present invention, the content in the intensity ratio detected by a flame ionization detector (FID) when measured using a gas chromatograph of bisphenol represented by the following formula (3) in the raw material monomer is 1% or less. Preferably 0.8% or less, more preferably 0
. 6% or less. Moreover, it is 0.3% or more normally, Preferably it is 0.35% or more, More preferably, it is 0.4% or more. When the content of bisphenol represented by the following formula (3) exceeds 1%, the mechanical properties and solubility of the polyarylate produced by polymerizing the raw material monomer are deteriorated. On the other hand, when the content is less than 0.2%, the electrical properties of the produced polyarylate resin, particularly the electrical properties during repeated use, deteriorate. Since the bisphenol represented by the formula (3) has fewer methyl groups at the ortho position than the bisphenol represented by the formula (2), the reactivity at the time of polymerization is high, and the polyarylate end group produced is controlled. Therefore, it is considered that the solubility and electrical characteristics are improved. In the raw material monomer,
The content of bisphenol represented by the following formula (3) can be measured by a gas chromatograph. The ratio of the area of each peak to the total area of peaks derived from the raw material monomers is defined as the content.

In formula (3), X represents a single bond, —CR ¹ R ² —, O, CO, or S. R ¹ ,
R ² each independently represents a hydrogen atom, a methyl group, or an ethyl group, or R ¹ and R ²
And a cyclohexylidene group formed by bonding to each other.
The bisphenol represented by the formula (3) is particularly represented by the bisphenol represented by the formula (3a).

(In the formula (3a), X represents a single bond, —CR ¹ R ² —, O, CO, or S. R ¹
, R ² each independently represents a hydrogen atom, a methyl group, or an ethyl group, or R ¹ and R 2
² represents a cyclohexylidene group formed by bonding with ² ; )
The specific structure of bisphenol represented by Formula (3) is illustrated below.

Among these, (4-hydroxyphenyl) (4-hydroxy-3-methylphenyl) methane, (2-hydroxyphenyl) (4-hydroxy-3-methylphenyl) methane, 1- (4-hydroxyphenyl) -1 -(4-hydroxy-3-methylphenyl) ethane, 1- (2-hydroxyphenyl) -1- (4-hydroxy-3-methylphenyl) ethane, 1- (4-hydroxyphenyl) -1- (2- Hydroxy-3-methylphenyl)
Ethane, 2- (4-hydroxyphenyl) -2- (4-hydroxy-3-methylphenyl) propane, 2- (2-hydroxyphenyl) -2- (4-hydroxy-3-methylphenyl) propane, 2- (4-hydroxyphenyl) -2- (2-hydroxy-3-methylphenyl) propane. In particular, 1- (4-hydroxyphenyl) -1-
(4-hydroxy-3-methylphenyl) ethane, 2- (4-hydroxyphenyl) -2
-(4-Hydroxy-3-methylphenyl) propane is preferred.

Here, in the raw material monomer used in the present invention, the starting material is usually ortho-
Impurities contained in cresol (for example, phenol, 2,6-xylenol, toluene,
Xylene and the like), by-products derived therefrom, and regioisomers derived from the dimerization reaction of orthotalk resole.
In the present invention, among these impurities in the raw material monomer, by controlling the amount of by-products derived from phenol, the characteristics when a polyarylate resin is obtained are excellent. In addition, the amount of by-products derived from phenol (the above formula (3) and the bisphenol represented by the above formula (4)) is the amount of ortho-cresol used for the production of the bisphenol represented by the above formula (2). It can be controlled by controlling the production (purification) method or adding a suitable amount of phenol to the purified ortho-cresol.

For example, as a method of controlling the amount of impurities by the production (purification) method of ortho-cresol, a method by rectification of fractional cresol, a method of rectification from mixed cresol which is synthesized by oxidizing cymene, and chlorobenzene is hydrolyzed and synthesized. Rectification from mixed cresol, synthesis by gas phase reaction alkylation with phenol and methanol, rectification, and production of ortho-cresol by hydrolysis of purified ortho-chlorotoluene. .

Among these, from the viewpoint of controlling the content of 2,6-xylenol, a method of rectifying from mixed cresol synthesized by hydrolyzing chlorobenzene, and producing ortho-cresol by hydrolysis of purified ortho-chlorotoluene Is preferred. Compared with the case of using fractional cresol, when chlorobenzene is used, the chlorobenzene raw material itself does not contain xylenol impurities, which is effective for suppression.

<< 4. Physical properties of polyarylate resin of the present invention >>
The viscosity average molecular weight (Mv) of the polyarylate resin of the present invention is usually 5,000 or more, preferably 10,000 or more, more preferably 20,000 or more. Usually 2
00,000 or less, preferably 150,000 or less, more preferably 100
, 000 or less. When the viscosity average molecular weight (Mv) is less than 5,000, the mechanical strength is insufficient and may not be practical. When the viscosity average molecular weight exceeds 200,000, it is difficult to apply to an appropriate film thickness when a coating solution is used. It may become.

In addition, the amount of carboxylic acid chloride group present at the terminal of the polyarylate resin in the present invention is usually 0.1 μequivalent / g or less, preferably 0.05 μequivalent / g or less. When the amount of the terminal carboxylic acid chloride group exceeds the above range, the storage stability when the polyarylate resin is used as a coating solution for an electrophotographic photoreceptor tends to decrease.
The amount of OH groups present at the end of the polyarylate resin in the present invention is usually 50.0 μeq / g or less, preferably 25.0 μeq / g or less, and more preferably 5.0 μeq / g. When the amount of terminal OH groups exceeds the above range, the electrical characteristics when the polyarylate resin is used as an electrophotographic photosensitive member tend to deteriorate.

The amount of carboxylic acid groups present at the end of the polyarylate resin in the present invention is usually 50.0.
μequivalent / g or less, preferably 25.0 μequivalent / g or less, more preferably 15.0 μequivalent / g
g. When the amount of the terminal carboxylic acid group exceeds the above range, the electric characteristics when the polyarylate resin is used as an electrophotographic photosensitive member tend to deteriorate.

≪5. Electrophotographic photoreceptor coating solution >>
The polyarylate resin of the present invention is suitably used for an electrophotographic photoreceptor coating solution. This coating solution for an electrophotographic photoreceptor is usually used for forming a photosensitive layer in an electrophotographic photoreceptor, and particularly preferably used for forming a charge transport layer when the photosensitive layer is a laminated photosensitive layer.

In the electrophotographic photoreceptor coating solution, the polyarylate resin is usually used as a binder resin, and in the electrophotographic photoreceptor coating solution, in addition to the polyarylate resin,
For example, necessary materials are appropriately contained depending on the use of the coating solution for an electrophotographic photosensitive member, such as a charge generation material and a charge transport material. Such a charge generating substance, a charge transporting substance, and the like can be the same as those described in the section of the electrophotographic photosensitive member described later.

In the electrophotographic photoreceptor coating solution, it is also possible to use a mixture of the polyarylate resin having the repeating structure represented by the above-described formula (1) and another resin. Examples of the resin having another structure to be mixed here include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, or copolymers thereof; polycarbonate resins, polyester resins, polyarylate resins, polyester polycarbonate resins, Examples thereof include thermoplastic resins such as polysulfone resins, phenoxy resins, epoxy resins, and silicone resins, and various thermosetting resins. Of these resins, polycarbonate resins and polyarylate resins are preferred.

Specific examples of suitable structures of the resin having the other structure are shown below. These specific examples are shown for illustration, and any known binder resin may be mixed and used as long as it does not contradict the gist of the present invention.

In addition, when using together the polyarylate resin of this invention, and another binder resin, there is no restriction | limiting in a use ratio and it is arbitrary as long as the effect of this invention is acquired.

≪6. Electrophotographic photoreceptor >>
The electrophotographic photoreceptor to which this exemplary embodiment is applied has a photosensitive layer provided on a conductive support,
The photosensitive layer contains a polyarylate resin having a repeating structure represented by the above formula (1). As a specific configuration of the photosensitive layer, for example, a laminate in which a charge generation layer mainly composed of a charge generation material and a charge transport layer mainly composed of a charge transport material and a binder resin are stacked on a conductive support. Type photoreceptor; a dispersion type (single layer type) photoreceptor having a photosensitive layer in which a charge generating substance is dispersed in a layer containing a charge transport substance and a binder resin on a conductive support. The polyarylate resin having a repeating structure represented by the above formula (1) is usually used for a layer containing a charge transport material, and preferably used for a charge transport layer of a multilayer photoreceptor.

As a specific configuration of the photosensitive layer used in the electrophotographic photosensitive member to which the exemplary embodiment is applied, for example, in the case of a laminated type photosensitive member, it contains a charge transport material and a binder resin, and maintains an electrostatic charge. A charge transport layer that transports charges generated by exposure, and a charge generation layer that contains a charge generation material and generates charge pairs by exposure. In addition, if necessary, for example, a charge blocking layer for blocking charge injection from the conductive support, or a light diffusion layer for diffusing light such as laser light to prevent generation of interference fringes, etc. There is. In the case of a dispersion type (single layer type) photoreceptor,
In the photosensitive layer, a charge transfer material and a charge generation material are dispersed in a binder resin.

<6-1. Conductive support>
There is no particular limitation on the conductive support, but for example, metal materials such as aluminum, aluminum alloy, stainless steel, copper, and nickel, and conductive powder such as metal, carbon, and tin oxide are added to impart conductivity. A resin material, a resin, glass, paper, or the like on which a conductive material such as aluminum, nickel, or ITO (indium tin oxide) is deposited or applied on the surface is mainly used. These may be used alone or in combination of two or more in any combination and ratio. As a form of the conductive support, a drum form, a sheet form, a belt form or the like is used. Further, a conductive material having an appropriate resistance value may be used on a conductive support made of a metal material in order to control conductivity and surface properties and to cover defects.

Moreover, when using metal materials, such as an aluminum alloy, as an electroconductive support body, you may use, after giving an anodic oxide film. When an anodized film is applied, it is desirable to perform a sealing treatment by a known method.
The surface of the support may be smooth, or may be roughened by using a special cutting method or performing a polishing treatment. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support. Also, for cost reduction,
It is also possible to use the drawing tube as it is without performing the cutting treatment.

<6-2. Undercoat layer>
Between the conductive support and the photosensitive layer to be described later, for the improvement of adhesiveness, blocking property, etc.,
An undercoat layer may be provided. As the undercoat layer, a resin or a resin in which particles such as a metal oxide are dispersed is used. The undercoat layer may be a single layer or a plurality of layers. In the case where the undercoat layer is composed of a plurality of layers, it may be configured to comprise a conductive layer (interference fringe prevention layer) and an intermediate layer on the conductive support.

Examples of metal oxide particles used for the undercoat layer include metals containing one kind of metal element such as titanium oxide, indium oxide, tin oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, barium sulfate, etc. Examples thereof include metal oxide particles containing a plurality of metal elements such as oxide particles, calcium titanate, strontium titanate, and barium titanate. One kind of these particles may be used alone, or a plurality of kinds of particles may be mixed and used. Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicon. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. Also,
A thing of a several crystalline state may be contained.

Various particle sizes of the metal oxide particles can be used. Among them, the average primary particle size is preferably 10 nm or more and 100 nm or less, particularly from the viewpoint of characteristics and liquid stability.
0 nm or more and 50 nm or less are preferable. This average primary particle size can be obtained from a TEM photograph or the like.
The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin.
The binder resin used for the undercoat layer is epoxy resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, chloride resin. Cellulose esters such as vinylidene resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, polyurethane resin, polyacryl resin, polyacrylamide resin, polyvinyl pyrrolidone resin, polyvinyl pyridine resin, water-soluble polyester resin, nitrocellulose Resin, cellulose ether resin, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, zirconium chelate compound, zirconium The organic zirconium compound alkoxide compounds, titanyl chelate compounds, organic titanyl compounds such as titanium alkoxide compounds include known binder resins such as a silane coupling agent. These may be used alone or 2
You may use a seed | species or more together by arbitrary combinations and ratios. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, resol type phenol resins, alcohol-soluble copolymer polyamides, modified polyamides, and the like are preferable because they exhibit good dispersibility and coating properties.

The use ratio of the inorganic particles to the binder resin used for the undercoat layer can be arbitrarily selected. However, from the viewpoint of the stability of the dispersion and the coating property, it is usually 1 for the binder resin.
It is preferable to use in the range of 0 mass% or more and 500 mass% or less.
The thickness of the undercoat layer is arbitrary as long as the effects of the present invention are not significantly impaired, but the viewpoint of improving the electrical characteristics, strong exposure characteristics, image characteristics, repeat characteristics, and coating properties during production of the electrophotographic photosensitive member. Therefore, it is usually 0.01 μm or more, preferably 0.1 μm or more, and usually 30 μm or less, preferably 20 μm or less. A known antioxidant or the like may be mixed in the undercoat layer. For the purpose of preventing image defects, pigment particles, resin particles and the like may be included.

<6-3. Photosensitive layer>
As a type of the photosensitive layer, a charge generation material and a charge transport material are present in the same layer and are dispersed in a binder resin, a charge generation layer in which a charge generation material is dispersed in a binder resin, and a charge. A functional separation type (laminated type) composed of two layers of a charge transport layer in which a transport material is dispersed in a binder resin can be mentioned, but any type may be used.
In addition, as the laminated photosensitive layer, a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and a charge transport layer and a charge generation layer are laminated in this order. There are reverse laminated type photosensitive layers, and any of them can be adopted, but a forward laminated type photosensitive layer capable of exhibiting the most balanced photoconductivity is preferable.

<6-3-1. Multilayer photosensitive layer>
[Charge generation layer]
In the case of a laminated type photoreceptor (function separation type photoreceptor), the charge generation layer is formed by binding a charge generation material with a binder resin.

Examples of the charge generation material include inorganic photoconductive materials such as selenium and its alloys, cadmium sulfide, and organic photoconductive materials such as organic pigments, but organic photoconductive materials are preferred, especially organic pigments. Is preferred. Examples of organic pigments include phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium) pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments. . Among these, phthalocyanine pigments or azo pigments are particularly preferable. When organic pigments are used as the charge generating substance, usually, fine particles of these organic pigments are used in the form of a dispersion layer bound with various binder resins.

When a metal-free phthalocyanine compound or a metal-containing phthalocyanine compound is used as the charge generation material, a photosensitive member having a high sensitivity to a laser beam having a relatively long wavelength, for example, a laser beam having a wavelength around 780 nm, is obtained. When an azo pigment such as diazo or trisazo is used, it is sufficient for white light, laser light having a wavelength around 660 nm, or laser light having a relatively short wavelength, for example, laser having a wavelength around 450 nm or 400 nm. A photosensitive member having a high sensitivity can be obtained.

When an organic pigment is used as the charge generating material, a phthalocyanine pigment or an azo pigment is particularly preferable. The phthalocyanine pigment provides a photosensitive material with high sensitivity to a laser beam having a relatively long wavelength, and the azo pigment has a sufficient sensitivity to white light and a laser beam having a relatively short wavelength. , Each is excellent.
When using a phthalocyanine pigment as a charge generation material, specifically, metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, aluminum or other metal or oxide thereof, halide, water Those having crystal forms of coordinated phthalocyanines such as oxides and alkoxides, and phthalocyanine dimers using oxygen atoms as bridging atoms are used. In particular, X is a highly sensitive crystal form.
Type, τ-type metal-free phthalocyanine, A-type (also known as β-type), B-type (also known as α-type), D-type (also known as Y-type), etc. Hydroxyindium phthalocyanine, chlorogallium phthalocyanine such as type II, hydroxygallium phthalocyanine such as type V, μ-oxo-gallium phthalocyanine dimer such as type G and type I, μ-oxo-aluminum phthalocyanine dimer such as type II Is preferred.

Among these phthalocyanines, A-type (also known as β-type), B-type (also known as α-type), and powder X-ray diffraction angle 2θ (± 0.2 °) are 27.1 ° or 27.3 °. Having strong peaks at D-type (Y-type) titanyl phthalocyanine, II-type chlorogallium phthalocyanine, V-type, and 28.1 °, and 26.2 °
No peak at 0 °, a clear peak at 28.1 °, and a full width at half maximum W of 25.9 ° is 0.00.
Hydroxygallium phthalocyanine characterized by 1 ° ≦ W ≦ 0.4 °, G-type μ
-Oxo-gallium phthalocyanine dimer and the like are more preferable. Among these, V-type hydroxygallium phthalocyanine and D-type (Y-type) titanyl phthalocyanine are particularly preferable because they exhibit good sensitivity.

The phthalocyanine compound may be a single compound or several mixed or mixed crystal states. As the mixed state that can be put in the phthalocyanine compound or crystal state here, those obtained by mixing the respective constituent elements later may be used, or they may be mixed in the production / treatment process of the phthalocyanine compound such as synthesis, pigmentation, and crystallization. It may be the one that caused the condition. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known. In order to generate a mixed crystal state, as described in JP-A-10-48859, two types of crystals are mixed, mechanically ground and made amorphous, and then converted into a specific crystal state by solvent treatment. The method of doing is mentioned.

When an azo pigment is used as the charge generation material, various bisazo pigments and trisazo pigments are preferably used.
When an organic pigment is used as the charge generation material, one kind may be used alone, or two or more kinds of pigments may be mixed and used. In this case, it is preferable to use a combination of two or more kinds of charge generating materials having spectral sensitivity characteristics in different spectral regions of the visible region and the near red region. Among them, a disazo pigment, a trisazo pigment and a phthalocyanine pigment are preferably used in combination. More preferred.

The binder resin used for the charge generation layer is not particularly limited, but examples include polyvinyl butyral resin, polyvinyl formal resin, polyvinyl acetal type such as partially acetalized polyvinyl butyral resin in which a part of butyral is modified with formal, acetal, or the like. Resin, polyarylate resin, polycarbonate resin, polyester resin, polyarylate resin, modified ether-based polyester resin, phenoxy resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin, acrylic resin, methacrylic resin, poly Acrylamide resin, polyamide resin, polyvinyl pyridine resin, cellulose resin, polyurethane resin, epoxy resin, silicon resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, Vinyl chloride such as zein, vinyl chloride-vinyl acetate copolymer, hydroxy-modified vinyl chloride-vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer -Insulating resin such as vinyl acetate copolymer, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-alkyd resin, silicon-alkyd resin, phenol-formaldehyde resin, and poly-N-vinylcarbazole , Organic photoconductive polymers such as polyvinyl anthracene and polyvinyl perylene. Any one of these binder resins may be used alone, or two or more thereof may be mixed and used in any combination.

The solvent used for preparing the coating solution is not particularly limited as long as it dissolves the binder resin. For example, saturated aliphatic solvents such as pentane, hexane, octane, and nonane, and aromatics such as toluene, xylene, and anisole. Group solvents, halogenated aromatic solvents such as chlorobenzene, dichlorobenzene and chloronaphthalene, amide solvents such as dimethylformamide and N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n
-Alcohol solvents such as butanol and benzyl alcohol, aliphatic polyhydric alcohols such as glycerin and polyethylene glycol, chain or cyclic ketone solvents such as acetone, cyclohexanone and methyl ethyl ketone, methyl formate, ethyl acetate, n-butyl acetate, etc. Ester solvents, halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane, chain chains such as diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, etc. Cyclic ether solvents, aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylene Amine, triethylenediamine, nitrogen-containing compounds such as triethylamine, mineral oil ligroin, and water. Any one of these may be used alone, or two or more of these may be used in combination. In addition, when providing the above-mentioned undercoat layer, what does not melt | dissolve this undercoat layer is preferable.

In the charge generation layer, the mixing ratio (mass) of the binder resin and the charge generation material is usually 10 parts by mass or more, preferably 30 parts by mass or more, and usually 1000 parts by mass with respect to 100 parts by mass of the binder resin. Part or less, preferably 500 parts by mass or less, and the film thickness is usually 0.1 μm or more, preferably 0.15 μm or more, and usually 10 μm or less, preferably 0.6 μm or less. If the ratio of the charge generation material is too high, the stability of the coating solution may be reduced due to aggregation of the charge generation material, while if the ratio of the charge generation material is too low, the sensitivity as a photoreceptor may be decreased. There is.

As a method for dispersing the charge generation material, a known dispersion method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be used. At this time, it is effective to refine the particles to a particle size in the range of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.

[Charge transport layer]
The charge transport layer of the multilayer photoreceptor contains a charge transport material and usually contains a binder resin and other components used as necessary. Specifically, such a charge transport layer is prepared by, for example, preparing a coating solution by dissolving or dispersing a charge transport material and a binder resin in a solvent. In addition, in the case of a reverse lamination type photosensitive layer, it can be obtained by coating and drying on a conductive support (or on the undercoat layer when an undercoat layer is provided).

The charge transport material is not particularly limited, and any material can be used. Examples of charge transport materials include aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, electron withdrawing materials such as quinone compounds such as diphenoquinone, carbazole derivatives, indoles Derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, thiadiazole derivatives, heterocyclic compounds such as benzofuran derivatives, aniline derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives and multiple types of these compounds bind Or an electron donating substance such as a polymer having a group consisting of these compounds in the main chain or side chain. Among these, carbazole derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and those in which a plurality of these compounds are bonded are preferable. Specific examples of suitable structures of the charge transport material are shown below. Specific examples are shown below for illustration, and any known charge transport material may be used as long as it is not contrary to the gist of the present invention.

Specific examples of the charge transport material contained in the charge transport layer constituting the photosensitive layer of the electrophotographic photoreceptor to which the exemplary embodiment is applied include, for example, arylamine-based compounds described in JP-A-9-244278. Compounds, arylamine compounds described in JP-A No. 2002-275133, enamine compounds described in JP-A 2009-20504, and the like. These charge transport materials may be used alone or in combination. Among these, it is preferable that the charge transport material contains at least one charge transport material selected from the group of compounds represented by the following formulas (7) to (10).

The charge transport layer is formed in such a form that these charge transport materials are bound to the binder resin. The charge transport layer may be composed of a single layer, or may be a stack of a plurality of layers having different constituent components or composition ratios.
The polyarylate resin having a repeating structure represented by the above formula (1) is preferably used as a binder resin for the charge transport layer. The binder resin may be a mixture of the polyarylate resin used in the present invention and a resin having another structure, and the other resin described in the resin having another structure mixed in the photosensitive layer. Is mentioned.

The ratio of the polyarylate resin having a repeating structure represented by the formula (1) and the charge transport material is usually 10 parts by weight or more with respect to 100 parts by weight of the binder resin. Among these, 20 parts by mass or more is preferable from the viewpoint of residual potential reduction, and more preferably 30 parts by mass or more from the viewpoint of stability and charge mobility when repeatedly used. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, the charge transport material is usually used at a ratio of 120 parts by mass or less. Among these, 100 parts by mass or less is preferable from the viewpoint of compatibility between the charge transport material and the binder resin, 70 parts by mass or less is more preferable from the viewpoint of printing durability, and 50 parts by mass or less is particularly preferable from the viewpoint of scratch resistance.

The thickness of the charge transport layer is usually 5 μm to 50 μm, preferably 10 μm to 45 μm.
It is.
It should be noted that the charge transport layer has well-known plasticizers, antioxidants, ultraviolet absorbers, and electron withdrawing properties in order to improve film forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. Compounds, dyes, pigments,
You may contain additives, such as a leveling agent. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds. Examples of dyes and pigments include
Various dye compounds, azo compounds and the like can be mentioned.

<6-3-2. Single-layer type photosensitive layer>
The single-layer type photosensitive layer is formed using a binder resin in order to ensure film strength, in the same manner as the charge transport layer of the multilayer photoconductor, in addition to the charge generation material and the charge transport material. Specifically, a charge generation material, a charge transport material, and various binder resins are dissolved or dispersed in a solvent to prepare a coating solution.
It can be obtained by coating and drying on a conductive support (on the undercoat layer when an undercoat layer is provided).

The types of the charge transport material and the binder resin and the use ratios thereof are the same as those described for the charge transport layer of the multilayer photoreceptor. The charge generating material is further dispersed in the charge transport medium comprising these charge transport material and binder resin.
As the charge generation material, the same materials as those described for the charge generation layer of the multilayer photoreceptor can be used. However, in the case of a photosensitive layer of a single-layer type photoreceptor, it is necessary to sufficiently reduce the particle size of the charge generating material. Specifically, the range is usually 1 μm or less, preferably 0.5 μm or less.

If the amount of the charge generating material dispersed in the single-layer type photosensitive layer is too small, sufficient sensitivity cannot be obtained, but if it is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. Usually 0.5% by mass or more, preferably 1% by mass or more, and usually 50% by mass with respect to the entire layer-type photosensitive layer.
Hereinafter, it is preferably used in the range of 20% by mass or less.
In addition, the usage ratio of the binder resin and the charge generation material in the single-layer type photosensitive layer is such that the charge generation material is usually 0.1 parts by weight or more, preferably 1 part by weight or more, based on 100 parts by weight of the binder resin. It is 30 mass parts or less, Preferably it is set as the range of 10 mass parts or less.

The film thickness of the single-layer type photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100
It is not more than μm, preferably not more than 50 μm. Also in this case, film formability, flexibility,
Known plasticizers for improving mechanical strength, additives for suppressing residual potential, dispersion aids for improving dispersion stability, leveling agents for improving coatability, surfactants, for example Silicone oil, fluorine oil and other additives may be added.

<6-4. Other functional layers and additives>
For the purpose of improving film forming properties, flexibility, coating properties, contamination resistance, gas resistance, light resistance, etc., in both the photosensitive layer and the layers constituting the photosensitive layer, both of the multilayer type photosensitive member and the single layer type photosensitive member. Additives such as well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds, leveling agents, and visible light shielding agents may be included.

Further, in both the laminated type photoreceptor and the single layer type photoreceptor, the photosensitive layer formed by the above procedure may be the uppermost layer, that is, the surface layer, but another layer may be provided on the photosensitive layer and used as the surface layer. Good.
For example, a protective layer may be provided for the purpose of preventing the photosensitive layer from being worn out or preventing or reducing the deterioration of the photosensitive layer due to discharge products generated from a charger or the like. The protective layer is formed by containing a conductive material in an appropriate binder resin, or disclosed in JP-A-9-190004 and JP-A-10-10.
A copolymer using a compound having a charge transporting ability such as a triphenylamine skeleton described in each publication of No. 252377 can be used.

Examples of the conductive material used for the protective layer include aromatic amino compounds such as TPD (N, N′-diphenyl-N, N′-bis- (m-tolyl) benzidine), antimony oxide, indium oxide, tin oxide, and oxide. Metal oxides such as titanium, tin oxide-antimony oxide, aluminum oxide, and zinc oxide can be used, but are not limited thereto.
As the binder resin used for the protective layer, known resins such as polyamide resin, polyurethane resin, polyester resin, polyarylate resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, and siloxane resin are used. In addition, JP-A-9-190004, JP-A-1
A copolymer of the resin and a skeleton having a charge transporting ability such as a triphenylamine skeleton as described in JP-A-0-252377 can also be used.

The electrical resistance of the protective layer is preferably in the range of usually 10 ⁹ Ω · cm or more and 10 ¹⁴ Ω · cm or less. If the electric resistance is higher than the above range, the residual potential may increase and an image with much fogging may be formed. On the other hand, if the value is lower than the above range, there is a possibility that the image is blurred and the resolution is lowered. Further, the protective layer is preferably configured so as not to substantially prevent transmission of light irradiated during image exposure.

Further, for the purpose of reducing the frictional resistance and wear on the surface of the photoconductor, and increasing the transfer efficiency of the toner from the photoconductor to the transfer belt and paper, etc., the surface layer is made of fluorine resin, silicon resin, polyethylene resin, Particles made of this resin or inorganic compound particles may be contained in the surface layer.
Alternatively, a layer containing these resins and particles may be newly formed as a surface layer.
Furthermore, it goes without saying that a layer for improving electrical properties and mechanical properties, such as an intermediate layer such as a barrier layer, an adhesive layer and a blocking layer, and a transparent insulating layer, may be provided as necessary.

<6-5. Formation method of each layer>
Each layer constituting these photoreceptors is formed by immersing, coating, spraying, nozzle coating, bar coating, roll coating, blade coating, etc., on a support, a coating solution obtained by dissolving or dispersing a substance to be contained in a solvent. In this method, the coating and drying steps are sequentially repeated for each layer.

There are no particular restrictions on the solvent or dispersion medium used in the preparation of the coating solution, but specific examples include alcohols such as methanol, ethanol, propanol and 2-methoxyethanol, tetrahydrofuran, 1,4-dioxane, dimethoxyethane and the like. Ethers, esters such as methyl formate and ethyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, chloroform, 1,2-dichloroethane, 1,1, Chlorinated hydrocarbons such as 2-trichloroethane, 1,1,1-trichloroethane, tetrachloroethane, 1,2-dichloropropane, trichloroethylene, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine , Nitrogen-containing compounds such as triethylenediamine, acetonitrile, N- methylpyrrolidone, N, N- dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like. Moreover, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and kinds.

The amount of the solvent or dispersion medium used is not particularly limited, but considering the purpose of each layer and the properties of the selected solvent / dispersion medium, it is appropriate so that the physical properties such as solid content concentration and viscosity of the coating liquid are within a desired range. It is preferable to adjust.
For example, in the case of a charge transport layer layer of a single layer type photoreceptor and a function separation type photoreceptor, the solid content concentration of the coating solution is usually 5% by mass or more, usually 5% by mass or more, preferably 10% by mass or more, Moreover, it is 40 mass% or less normally, Preferably it is set as the range of 35 mass% or less. Further, the viscosity of the coating solution is usually in the range of 10 cps or more, preferably 50 cps or more, and usually 500 cps or less, preferably 400 cps or less.

In the case of a charge generation layer of a multilayer photoreceptor, the solid content concentration of the coating solution is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass. % Or less. Further, the viscosity of the coating solution is usually 0.01 cps or more, preferably 0.1 cps.
The range is not less than ps and usually not more than 20 cps, preferably not more than 10 cps.
Examples of the coating method include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, and a curtain coating method. Other known coating methods can also be used.
The coating solution is preferably dried by touching at room temperature, followed by heating or drying in a temperature range of usually 30 ° C. or more and 200 ° C. or less for 1 minute to 2 hours, while still or blowing. The heating temperature may be constant or the heating may be performed while changing the temperature during drying.

≪7. Image forming device >>
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 disposed 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. Examples of the charging device include a corona charging device such as a corotron and a scorotron, a direct charging device (contact type charging device) that charges a direct charging member to which a voltage is applied by contacting the photosensitive member surface, and a contact charging device such as a charging brush 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 an alternating current on a 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. As a specific example,
Examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, and LEDs. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary, but for example, monochromatic light with a wavelength of 780 nm,
The exposure may be performed with monochromatic light having a wavelength slightly shorter than 700 nm, monochromatic light with a short wavelength of 380 nm to 500 nm, or the like. Among these, it is preferable to use light having a short wavelength of 380 to 500 nm because the resolution becomes high. Among these, 405 nm monochromatic light is preferable.

The type of the developing device 4 is not particularly limited, and cascade development, one-component insulating toner development,
Any apparatus such as a dry development system such as a one-component conductive toner development or a two-component magnetic brush development, or a wet development system can be used. 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
It is 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 regulating 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 abuts on the developing roller 44 and is pressed with a predetermined force against the developing roller 44 by a spring or the like (a general blade linear pressure is 5 to 5).
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. This transfer device 5 uses toner T
The toner image formed on the electrophotographic photosensitive member 1 is transferred onto a recording paper (paper, medium) P by applying a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of.

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,
If 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.
The fixing member 71 or 72 is provided with a heating device 73. In addition,
FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. Each of the upper and lower fixing members 71 and 72 includes a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, and a fixing sheet. A member can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve 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 with a predetermined potential (for example, −60) by the charging device 2.
0V). 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. The toner image is transferred to the transfer device 5.
Is transferred onto the recording paper P. 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.

Specific embodiments of the present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist.
The purity of the raw material monomer containing bisphenol and the amount of by-products used in Examples and the like were measured by the following methods.

[Method of analyzing raw material monomers]
The purity of the raw material monomer was determined by gas chromatography using each sample as a 1% acetone solution. The ratio of the area of each peak to the total area of peaks derived from the raw material monomers was defined as the content.

Equipment: Shimadzu GC17A
Column: DB-5 (30 mx 0.25 mmφ 0.25 µm)
Detector: FID
In addition, GC / MS was measured to identify by-products.
Equipment: Agilent 6890/5975
Column: DB-1HT (15 mx 0.25 mmφ 0.1 µm)
Detector: MSD SCAN method (EI)
The analysis and analysis results are shown in Table-1.

The raw material bisphenol structure, monomethyl structure, and trimethyl structure in the table are shown below.

[Manufacture of polyarylate resin]
[Example 1] (Production method of polyarylate resin (1))
Sodium hydroxide (6.20 g) and H ₂ O (235 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.36g)
Raw material monomers Bis-C (1) {2,2-bis (3-methyl-4-hydroxyphenyl) propane} (16.18 g) and benzyltriethylammonium chloride (0.1
68 g) in this order, and dissolved by stirring, and then the aqueous alkaline solution was transferred to a 1 L reaction vessel.

Separately, terephthalic acid chloride (6.55 g) and isophthalic acid chloride (6.55)
A mixed solution of g) and dichloromethane (117 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the reaction vessel at 20 ° C., the dichloromethane solution was dropped from the dropping funnel over 30 minutes while stirring the alkaline aqueous solution in the reaction vessel. After further stirring for 1 hour, dichloromethane (196 mL) was added and stirring was continued for 4 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1 N hydrochloric acid (240 mL).
Further, washing was performed twice with demineralized water (240 mL).

The organic layer after washing was diluted with 230 ml of methylene chloride and diluted with methanol (2100 ml).
The precipitate obtained by pouring the solution is taken out by filtration and dried to obtain the desired polyarylate resin (1
) The analytical values of the resulting polyarylate resin (1) are shown in Table 2. The structural formula of the polyarylate resin (1) is shown below.

[Example 2] (Production method of polyarylate resin (2))
Sodium hydroxide (5.01 g) and H ₂ O (235 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.346 g
), Raw material monomer Bis-C (1) (13.02 g) and benzyltriethylammonium chloride (0.136 g) in this order, dissolved with stirring,
Transferred to reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (15.38 g) and dichloromethane (117 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (196 mL) was added and stirring was continued for 7 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1 N hydrochloric acid (240 mL).
Further, washing was performed twice with demineralized water (240 mL).

The organic layer after washing was diluted with 230 ml of methylene chloride and diluted with methanol (2100 ml).
The precipitate obtained by pouring the solution is taken out by filtration and dried to obtain the desired polyarylate resin (2
) The analytical value of the obtained polyarylate resin (2) is shown in Table 2. The structural formula of the polyarylate resin (2) is shown below.

[Example 3] (Production method of polyarylate resin (3))
The raw material monomer Bis-C (1) (16.18 g) of Example 1 was converted into the raw material monomer Bis-C.
Synthesis was performed in the same manner except that the mixture was changed to a mixture of (1) (11.33 g) and raw material monomer Bis-C (2) (4.85 g) to obtain a polyarylate resin (3). The analytical value of the obtained polyarylate resin (3) is shown in Table 2.

[Comparative Example 1] (Production method of polyarylate resin (4))
A polyarylate resin (4) was obtained in the same manner as in Example 1 except that the raw material monomer Bis-C (1) was changed to the raw material monomer Bis-C (2). The analytical value of the obtained polyarylate resin (4) is shown in Table-2.
[Comparative Example 2] (Method for producing polyarylate resin (5))
A polyarylate resin (5) was obtained in the same manner as in Example 2 except that the raw material monomer Bis-C (1) was changed to the raw material monomer Bis-C (2). The analytical value of the obtained polyarylate resin (5) is shown in Table-2.

[Comparative Example 3] (Method for producing polyarylate resin (6))
Raw material monomer Bis-C (1) of Example 1 (16.18 g) was converted to raw material monomer Bis-
A polyarylate resin (6) was obtained by the same synthesis except that the mixture was changed to a mixture of C (1) (4.85 g) and raw material monomer Bis-C (2) (11.33 g). The analytical values of the resulting polyarylate resin (6) are shown in Tables 2-1 and 2-2.

[analysis]
Viscosity average molecular weight of each polyarylate resin obtained, carboxylic acid chloride end group amount, O
The amount of H end groups and the amount of carboxylic acid end groups were measured by the following methods.
[Measurement of viscosity average molecular weight (Mv)]
The polyarylate resin was dissolved in dichloromethane to prepare a solution having a concentration C of 6.00 g / L. The flow time t of the sample solution was measured in a constant temperature water bath set at 20.0 ° C. using an Ubbelohde capillary viscometer with a flow time t ₀ of the solvent (dichloromethane) of 136.16 seconds. The viscosity average molecular weight (Mv) was calculated according to the following formula.
a = 0.438 × η _sp +1 η _sp = t / t ₀ −1
b = 100 × η _sp / C C = 6.00 (g / L)
η = b / a
Mv = 3207 × η ^1.205

[Measurement of Carboxylic Acid Chloride End Group Amount [CF (μ equivalent / g)]]
About 1.5 g of polyarylate was precisely weighed, and 20 mL of methylene chloride was added and dissolved. To this was added 2 mL of a 1% methylene chloride solution of 4- (p-nitrobenzyl) pyridine to bring the total volume to 25.
Adjusted to mL. After coloring over 30 minutes, spectrophotometer (manufactured by Shimadzu Corporation, U
V-1200) was used to measure the absorbance at a wavelength of 450 nm. Separately, an extinction coefficient was obtained using a methylene chloride solution of benzoyl chloride, and the amount of CF groups in the resin was quantified.

[Measurement of OH end group amount [OH (μ equivalent / g)]]
About 0.2 g of polyarylate was precisely weighed and dissolved in 10 mL of methylene chloride. To this, 5 mL of 5% acetic acid / methylene chloride solution was added, and further 10 mL of titanium tetrachloride solution (* 1) was added for color development, and then the total liquid volume was adjusted to 25 mL. The absorbance of the solution at a wavelength of 480 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-1200). (* 1: Mixed solution of methylene chloride 200 mL, 5% acetic acid / methylene chloride solution 22 mL, titanium chloride 5.5 mL).
Separately, the extinction coefficient was determined using a methylene chloride solution of a bisphenol compound (composition) having the same composition as the polyarylate resin to be measured, and the amount of OH groups in the resin was quantified.

[Measurement of Amount of Carboxylic Acid End Group [COOH (μ equivalent / g)]]
About 0.4 g of polyarylate resin is precisely weighed in a tall beaker and benzyl alcohol 25
mL was added and dissolved by heating in an oil bath at 195 ° C. After confirming complete dissolution, the solution was removed from the oil bath and cooled. After cooling, 2 mL of ethyl alcohol was gently introduced along the wall of the tall beaker. Using this solution, an automatic titrator (GT100, manufactured by Mitsubishi Chemical Corporation)
Titrated with 01N NaOH benzyl alcohol solution. Separately, only the solvent benzyl alcohol was titrated with a 0.01 N NaOH benzyl alcohol solution to obtain a blank value. Moreover, the factor of 0.01N-NaOH benzyl alcohol solution was calculated | required with the following method.

(1) 0.01N hydrochloric acid (HCL) (volumetric reagent known defined solution (F _HCL = 1)) 1,
2, 4 mL is accurately weighed into a titration beaker with a whole pipette.
(2) Add 25 mL of benzyl alcohol and 2 mL of ethyl alcohol to each.
(3) Using an automatic titrator (GT100, manufactured by Mitsubishi Chemical), titration was performed with a 0.01 N NaOH benzyl alcohol solution.
(4) Calculation: Plot the amount of NaOH benzyl alcohol titrant (Y-axis) against the amount of hydrochloric acid-adjusted solution (X-axis) in (1).
Factor of 0.01N-NaOH benzyl alcohol solution F = F _HCL / S
COOH group = {(A−B) × F × 10} / W (μ equivalent / g)
A: Measurement titration volume (mL)
B: Blank titration (mL)
F: Factor of 0.01N NaOH benzyl alcohol solution W: Polyarylate resin amount (g)
[Hydrolysis of polyarylate and purity analysis of bisphenol]
About 0.1 g of polyarylate was weighed and 4.9 g of methanol was added. To this, 0.1 g of 28% sodium methoxide / methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by stirring at 50 ° C. for 7 hours to carry out a hydrolysis reaction. Subsequently, after cooling to room temperature, acetic acid is added at 0.05-0.
1g was added and neutralized.

The bisphenol purity of the solution after hydrolysis was determined by gas chromatographic measurement. The ratio of the area of each peak to the total area of peaks derived from bisphenol monomers was taken as the content. The peak derived from the bisphenol monomer was identified from the analysis result of the raw material bisphenol.
Equipment: Shimadzu GC17A
Column: DB-5 (30 mx 0.25 mmφ 0.25 µm)
Detector: Hydrogen flame ionization detector (FID)

<Preparation of photoreceptor sheet>
[Example 4]
The undercoat layer dispersion was prepared as follows. High-speed fluidized mixing of rutile type titanium oxide having an average primary particle diameter of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by mass of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) Kneading machine (
Surface treatment titanium oxide obtained by mixing at high speed at a rotational peripheral speed of 34.5 m / sec and dispersing with a ball mill of methanol / 1-propanol, It was set as the dispersion slurry of chemical-treatment titanium oxide. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene, and ε-caprolactam [compound represented by the following formula (A)] / bis (4-amino-3-methylcyclohexyl) methane [the following formula ( Compound represented by B)] / hexamethylenediamine [compound represented by the following formula (C)] / decamethylene dicarboxylic acid [compound represented by the following formula (D)] / octadecamethylene dicarboxylic acid [following formula The compound molar ratio of the compound represented by (E) is 75% / 9.5%
/3%/9.5%/3% of the copolyamide pellets heated and stirred and mixed to dissolve the polyamide pellets, and then subjected to ultrasonic dispersion treatment to obtain methanol / 1-propanol. An undercoating layer dispersion having a solid content concentration of 18.0% and containing a hydrophobic / titanium mass ratio of 7/1/2 and a hydrophobically treated titanium oxide / copolymerized polyamide at a mass ratio of 3/1.

The charge generation layer forming coating solution was prepared as follows. As a charge generation material, 20 parts of Y-type (also known as D-type) oxytitanium phthalocyanine and 1,2- 1, which show a strong diffraction peak at 27.3 ° in the Bragg angle (2θ ± 0.2) in X-ray diffraction by CuKα rays. 280 parts of dimethoxyethane were mixed and pulverized with a sand grind mill for 1 hour for atomization dispersion treatment. Subsequently, polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “
Denkabutyral "# 6000C) 10 parts, 255 parts of 1,2-dimethoxyethane and 4 parts
-A binder solution obtained by dissolving in 85 parts of methoxy-4-methyl-2-pentanone and 230 parts of 1,2-dimethoxyethane were mixed to obtain a coating solution β for forming a charge generation layer. Prepared.

The charge transport layer coating solution was prepared as follows. The charge transport material is represented by the following formula (7) produced by the method described in Example 1 of JP-A-2002-080432, which is composed of a group of geometric isomers having the following structure as a main component. 50 parts by weight of the mixture
100 parts by mass of a polyarylate resin (1) produced in the above, an antioxidant (Irganox 10
76) 8 parts by mass, 0.05 part by mass of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed with 640 parts by mass of a tetrahydrofuran / toluene mixed solvent (80% by mass of tetrahydrofuran, 20% by mass of toluene), and charge transport is performed. A layer coating solution was prepared.

Subsequently, the coating solution for forming the undercoat layer obtained as described above was applied onto a polyethylene terephthalate sheet having aluminum deposited on the surface so that the film thickness after drying was about 1.5 μm and dried at room temperature. Thus, an undercoat layer was provided.
Further, the charge generation layer forming coating solution β obtained as described above is applied on the undercoat layer so that the film thickness after drying is about 0.4 μm, and is dried at room temperature. A generation layer was provided.
Subsequently, the coating film for forming the charge transport layer is coated on the charge generation layer with a film thickness after drying of 25.
It applied using an applicator so that it might become micrometer, and it dried at 125 degreeC for 20 minute (s), and formed the charge transport layer, and produced the photoreceptor sheet. Table 3 shows the results of initial electrical property evaluation and repeated electrical property evaluation.

[Example 5]
50 parts by mass of the charge transport material represented by the above formula (7) was changed to 10 parts by mass of the charge transport material represented by the following formula (8) and 80 parts by mass of the charge transport material represented by the following formula (9). A photoreceptor sheet was prepared in the same manner as Example 4 except for the above. Table 3 shows the results of initial electrical property evaluation and repeated electrical property evaluation.

[Comparative Example 4]
A photoreceptor sheet was prepared in the same manner as in Example 4 except that the polyarylate resin (1) was changed to the polyarylate resin (4). Table 3 shows the results of initial electrical property evaluation and repeated electrical property evaluation.
[Comparative Example 5]
A photoreceptor sheet was produced in the same manner as in Example 5 except that the polyarylate resin (1) was changed to the polyarylate resin (4). Table 3 shows the results of initial electrical property evaluation and repeated electrical property evaluation.

[Initial electrical property evaluation; electrical property evaluation 1]
Using an electrophotographic characteristic evaluation apparatus (basic and applied electrophotographic technology, edited by Electrophotographic Society, Corona, pages 404-405) prepared in accordance with the electrophotographic society measurement standard, the photoconductor sheet is made of an aluminum drum. After the aluminum drum and the aluminum substrate of the photoconductor are connected to each other, the drum is rotated at a constant rotational speed to charge, expose,
An electrical property evaluation test was performed by a cycle of potential measurement and static elimination. At that time, the initial surface potential is-
700 V, exposure is 780 nm, charge removal is 660 nm monochromatic light, exposure light is 0.92
The surface potential (VL) at the time of irradiation with μJ / cm 2 was measured. In the VL measurement, the time required from the exposure to the potential measurement was 139 ms. In addition, the surface potential is half the initial surface potential (-
350V) irradiation energy (half exposure energy: μJ / cm ² ) sensitivity (E _1/2 )
). The smaller the absolute value of the value of VL, the better the electrical characteristics,
_A smaller value of _1/2 indicates higher sensitivity. Measurement environment is temperature 25 ° C, relative humidity 50
% Under (N / N).

[Repetitive electrical property evaluation; Electrical property evaluation 2]
An electrophotographic characteristic evaluation apparatus manufactured according to the electrophotographic society measurement standard (basic and applied electrophotographic technology, edited by the Electrophotographic Society, Corona, pages 404 to 405) is used, and the photosensitive sheet is 80 mm in diameter. The drum is attached to an aluminum drum to form a cylindrical shape, and electrical connection between the aluminum drum and the aluminum substrate of the photosensitive sheet is made.
The sample was rotated at rpm, and the cycle of charging, exposure, potential measurement, and charge removal was repeated 30000 times to evaluate the characteristics before and after. At that time, the charging (scorotron charger) conditions are fixed so that the initial surface potential of the photosensitive member is about −700 V at the beginning of the test, and the difference (ΔV) in the observed surface potential (V0).
0) was measured. The smaller the absolute value of ΔV0, the better the chargeability during repeated use. The measurement environment was a temperature of 25 ° C. and a relative humidity of 50%.

When Examples 4 and 5 and Comparative Examples 4 and 5 are compared, the photoconductor produced with the polyarylate (1) using the raw material bisphenol Bis-C (1) has good initial electrical characteristics, and has repeated electrical characteristics. It can be seen that the charging property is good. On the other hand, a photoconductor produced with polyarylate (4) using Bis-C (2) has good initial electrical characteristics, but the chargeability of repeated electrical characteristics tends to deteriorate.

[Transfer memory evaluation]
After carrying out the initial electrical characteristic test, the static eliminator was removed, and a corotron to which +6.5 kV was applied was installed instead to simulate the transfer load. In this state, after repeating the charge-exposure-transfer load cycle 4000 times, the VL is measured again, and the difference ΔV from the initial value ΔV
L was determined. The measurement environment was 25 ° C. and 50% RH. The smaller the absolute value of ΔVL,
Indicates that the transfer memory is good.

[Example 6]
Using the photoreceptor sheet prepared in Example 4, transfer memory evaluation was performed according to the above evaluation method. The results are shown in Table-4.
[Comparative Example 6]
Using the photosensitive sheet produced in Comparative Example 4, transfer memory evaluation was performed according to the above evaluation method. The results are shown in Table-4.

As shown in Table 4, the photoconductor of Example 6 produced with polyarylate (1) using Bis-C (1) has a small absolute value of ΔVL, and a good image can be obtained even when used repeatedly. . On the other hand, in the photoconductor of Comparative Example 6 made of polyarylate (4) using Bis-C (2), Δ
Since the absolute value of VL is large, repeated use makes it easier for image defects to occur due to memory generation.

[Example 7]
Except that the polyarylate (1) was changed to the polyarylate (2), the same as in Example 6,
A photoreceptor sheet was prepared and a transfer memory was evaluated. The results are shown in Table-5.
[Comparative Example 7]
Except that the polyarylate (1) was changed to the polyarylate (5), the same as in Example 6,
A photoreceptor sheet was prepared and a transfer memory was evaluated. The results are shown in Table-5.

As shown in Table-5, the photoconductor produced with polyarylate (5) using Bis-C (2) compared to the photoconductor produced with polyarylate (2) using Bis-C (1). ΔVL
The absolute value of is large and image defects are likely to occur. By using Bis-C (1), it is possible to improve image defects due to generation of memory due to repeated use.

[Production of hydroxygallium phthalocyanine]
Production Example 1
3,4.6 g of 1,3-diiminoisoindoline and 10 g of gallium trichloride were placed in 200 ml of dimethyl sulfoxide and reacted at 160 ° C. for 4 hours. After cooling the reaction solution to room temperature, 4.6 g of 5.0 wt% aqueous sodium hypochlorite solution was added. This reaction solution was filtered off, and the resulting crystals were washed with 300 ml of methanol and 100 ml of ion exchange water, and then dried to obtain 21.2 g of chlorogallium phthalocyanine.

After 4.0 g of the obtained chlorogallium phthalocyanine was dissolved in 160 g of concentrated sulfuric acid at −10 ° C., this solution was dropped into 1200 g of distilled water at 5 ° C. to precipitate crystals. After washing with distilled water, dilute ammonia water or the like, it was dried to obtain 3.6 g of hydroxygallium phthalocyanine.
2.0 g of the obtained hydroxygallium phthalocyanine was added to 30 m of dimethylformamide.
l, Milling treatment was carried out for 30 hours in a sand ground mill together with 55 g of glass beads. After filtration, it was washed twice with 100 ml of methanol and dried to obtain 1.9 g of V-type hydroxygallium phthalocyanine (A). Obtained hydroxygallium phthalocyanine (A)
The powder X-ray diffraction pattern of is shown in FIG.

Production Example 2
Under a nitrogen atmosphere, 32 g of o-phthalodinitrile and 10 g of gallium trichloride were placed in 164 g of α-chloronaphthalene and reacted at 205 ° C. for 5 hours. The reaction solution was cooled to 150 ° C. and filtered, and the resulting crystals were washed with 150 ml of N-methylpyrrolidone and further with 150 ml of methanol, and then dried to obtain chlorogallium phthalocyanine 11.5.
g was obtained.
The obtained chlorogallium phthalocyanine was treated with concentrated sulfuric acid and milled in the same manner as in Production Example 1 to obtain 1.9 g of V-type hydroxygallium phthalocyanine (B). The powder X-ray diffraction pattern of the resulting hydroxygallium phthalocyanine (B) is shown in FIG.

[Example 8]
A coating solution for forming a charge generation layer was prepared by mixing 20 parts by mass of hydroxygallium phthalocyanine (A) prepared in Preparation Example 1 and 280 parts by mass of 1,2-dimethoxyethane as a charge generation substance, and using a sand grind mill for 1 hour. The mixture was pulverized and subjected to atomization dispersion treatment. Subsequently, 10 parts by mass of polyvinyl butyral (trade name “Denka Butyral” # 6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 255 parts by mass of 1,2-dimethoxyethane and 4-
A binder liquid obtained by dissolving in a mixed solution of 85 parts by mass of methoxy-4-methyl-2-pentanone and 230 parts by mass of 1,2-dimethoxyethane were mixed to form a coating solution for forming a charge generation layer. Prepared.

The coating solution for the charge transport layer includes 40 parts by mass of a compound represented by the following formula (9) as a charge transport material, 40 parts by mass of the compound represented by the following formula (10), and the polyarylate produced in Example 1. 100 parts by weight of (1), 8 parts by weight of an antioxidant (Ciba Specialty Chemicals, trade name: Irganox 1076), silicone oil (Shin-Etsu Chemical Co., Ltd., trade name: KF)
96) 0.05 part by mass of tetrahydrofuran / toluene mixed solvent (tetrahydrofuran 8
(0% by mass, 20% by mass of toluene) was mixed with 640 parts by mass to prepare a coating solution for charge transport layer.

Subsequently, the coating solution for forming the undercoat layer obtained as described above was applied onto a polyethylene terephthalate sheet vapor-deposited on the surface so that the film thickness after drying was about 1.5 μm and dried at room temperature. Then, an undercoat layer similar to that used in Example 4 was provided.
Further, the charge generation layer forming coating solution obtained as described above is applied on the undercoat layer so that the film thickness after drying is about 0.3 μm, and dried at room temperature to generate charge. A layer was provided.
Subsequently, the coating film for forming the charge transport layer is coated on the charge generation layer with a film thickness after drying of 25.
It applied using an applicator so that it might become micrometer, and it dried at 125 degreeC for 20 minute (s), the charge transport layer was formed, and the photoreceptor sheet was produced.

[Example 9]
In Example 8, a photoreceptor sheet was produced in the same manner as in Example 8, except that the charge generation material was changed to hydroxygallium phthalocyanine (B) produced in Production Example 2.
[Comparative Example 8]
In Example 8, polyarylate (4) produced in Comparative Example 1 was prepared as polyarylate (1).
A photoreceptor sheet was prepared in the same manner as in Example 1 except that
[Comparative Example 9]
In Example 9, polyarylate (4) produced in Comparative Example 1 was prepared as polyarylate (1).
A photoreceptor sheet was prepared in the same manner as in Example 2 except that

[Comparative Example 10]
In Example 8, polyarylate (1) produced in Comparative Example 3 was prepared as polyarylate (1).
A photoreceptor sheet was prepared in the same manner as in Example 1 except that
[Example 10]
In Example 8, the polyarylate (3) produced in Example 3 was prepared as the polyarylate (1).
A photoreceptor sheet was prepared in the same manner as in Example 1 except that

[Example 11]
In Example 8, instead of 40 parts by mass of the charge transport material represented by formula (9) and 40 parts by mass of the charge transport material represented by formula (10), the charge transport material represented by formula (9) 70 parts by weight,
A photoreceptor sheet was prepared in the same manner as in Example 8 except that the charge transport material was changed to 10 parts by mass represented by the following formula (8).

[Example 12]
In Example 8, instead of 40 parts by mass of the charge transport material represented by formula (9) and 40 parts by mass of the charge transport material represented by formula (10), the charge represented by the following formula (7) A photoreceptor sheet was produced in the same manner as in Example 8 except that 50 parts by mass of the transport material was used.

Initial electrical property evaluation, repeated electrical property evaluation, and transfer memory evaluation were measured in the same manner as in Examples 4 and 6. The results are shown in Table-6.

When Examples 8 and 9 and Comparative Examples 8 to 10 are compared, the photoconductor produced with the polyarylate resins (1) and (3) has a good bright potential (VL), chargeability in repeated electrical characteristics, and transfer. It can be seen that the memory is good. On the other hand, the photoreceptors made of the polyarylate resins (4) and (6) are not inferior in the initial electrical characteristics, but the chargeability of the repeated electrical characteristics and the transfer memory are likely to deteriorate.

[Example 13]
<Manufacture of photosensitive drum>
The surface was rough-cut and cleaned to a clean outer diameter of 30 mm, a length of 376 mm, and a wall thickness of 0.
On a 75 mm aluminum cylinder, the coating solution for forming the undercoat layer, the coating solution for forming the charge generation layer, and the coating solution for forming the charge transport layer used in the production of the photoreceptor of Example 8 were sequentially applied by dip coating and dried. Then, an undercoat layer, a charge generation layer, and a charge transport layer were formed so that the film thicknesses after drying were 1.3 μm, 0.4 μm, and 25 μm, respectively, and a photosensitive drum was manufactured. The charge transport layer was dried at 125 ° C. for 20 minutes.

[Measurement of residual amount of α-chloronaphthalene]
Immerse the photoreceptor drum in acetone, dissolve acetone-soluble components in the charge transport layer,
Insoluble matter and swollen binder resin are peeled off. Subsequently, the charge generation layer 100 cm ²
A corresponding portion was immersed in 1,2-dimethoxyethane and subjected to ultrasonic treatment to form a dispersion of the charge generation layer, and the dissolved polyvinyl butyral resin was filtered off to isolate a hydroxygallium phthalocyanine pigment that was insoluble. The isolated pigment sample was identified and quantified by GC / MS (SIM) method. First, a calibration curve (peak area vs. detected intensity) was prepared with a known concentration of α-chloronaphthalene sample, and α-chloronaphthalene was calculated from the calibration curve and the peak area of the measurement sample. In addition, before isolating the measurement sample, a standard product was added to check the recovery rate, and the solvent detection amount was corrected from the recovery rate.

Residual α-chloronaphthalene was not detected from the hydroxygallium phthalocyanine in the charge generation layer.
<Image test>
For the image test, a tandem full-color printer MICROLINE9800 manufactured by Oki Data Co., Ltd., which is a dry development type electrophotographic method, a printing speed of 243 mm / s, a non-magnetic one-component development, a charging roller, and a direct transfer method from a photoconductor to a paper by a conveyance belt. Used.

The prepared photosensitive drums (four equivalents) are mounted on cyan, magenta, yellow, and black electrophotographic photosensitive cartridges, and 1000 sheets of A4 paper are fed vertically in an environment of 25 ° C. and 50% RH. Printed. Thereafter, A4 paper was fed sideways and a full-tone halftone image was printed. However, no image defects such as a decrease in density at both ends of the photoreceptor were observed. In addition, halftone printing was performed by changing the test environment to 25 ° C. and 10% RH, but no decrease in density was observed.

[Example 14]
<Manufacture of photosensitive drum>
A photoconductor drum was manufactured in the same manner as in Example 13 except that the coating solution was changed to the coating solution used for manufacturing the photoconductor of Example 9. From the hydroxygallium phthalocyanine of the charge generation layer, 0
. 2 ng / cm ² of residual α-chloronaphthalene was detected.

<Image test>
In the same manner as in Example 13, the above photosensitive drums (four equivalents) were mounted on cyan, magenta, yellow, and black electrophotographic photosensitive member cartridges, and A4 was used in an environment of 25 ° C. and 50% RH. 1000 sheets of paper were printed in the vertical feed. Thereafter, A4 paper was fed sideways and a halftone image was printed on the entire surface. However, image defects such as a density difference at the edge were not observed so much as to cause no problem. In addition, halftone printing was performed by changing the test environment to 25 ° C. and 10% RH, but no decrease in density was observed.

[Comparative Example 11]
<Manufacture of photosensitive drum>
A photoconductor drum was manufactured in the same manner as in Example 13 except that the coating solution was changed to the coating solution used for manufacturing the photoconductor of Comparative Example 8. Residual α-chloronaphthalene was not detected from hydroxygallium phthalocyanine in the charge generation layer.

<Image test>
In the same manner as in Example 13, the above photosensitive drums (four equivalents) were mounted on cyan, magenta, yellow, and black electrophotographic photosensitive member cartridges, and A4 was used in an environment of 25 ° C. and 50% RH. 1000 sheets of paper were printed in the vertical feed. Thereafter, the A4 paper was fed sideways and a halftone image was printed on the entire surface. As a result, a decrease in density was observed in the portion where the transfer load at the end portion was repeatedly strongly received, and an image defect of a density step was observed. Further, full-tone printing was performed with the test environment changed to 25 ° C. and 10% RH, but no density reduction was observed.

[Comparative Example 12]
<Manufacture of photosensitive drum>
A photoconductor drum was manufactured in the same manner as in Example 13 except that the coating solution was changed to the coating solution used for manufacturing the photoconductor of Comparative Example 9. From the hydroxygallium phthalocyanine of the charge generation layer, 0
. Residual α-chloronaphthalene of ³ ng / cm ² was detected.

<Image test>
In the same manner as in Example 13, the above photosensitive drums (four equivalents) were mounted on cyan, magenta, yellow, and black electrophotographic photosensitive member cartridges, and A4 was used in an environment of 25 ° C. and 50% RH. 1000 sheets of paper were printed in the vertical feed. Thereafter, the A4 paper was fed sideways and a halftone image was printed on the entire surface. As a result, a decrease in density was observed in the portion where the transfer load at the end portion was repeatedly strongly received, and an image defect of a density step was observed. Further, full-tone printing was performed with the test environment changed to 25 ° C. and 10% RH, but no density reduction was observed.

As shown in the present invention, it has been clarified that the polyarylate resin having a specific structure is excellent in electrical characteristics. It has been clarified that such polyarylate resin can be used in an electrophotographic photosensitive member, and in particular, has excellent electrical characteristics during repeated use.

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

Claims (13)

Formula (1) obtained by polymerizing a raw material monomer containing bisphenol represented by Formula (2)
The polyarylate resin having a repetitive structure represented by formula (4), which is detected by a gas chromatograph using a flame ionization detector (FID) after hydrolysis of the polyarylate resin. The polyarylate resin is characterized in that the amount of bisphenol residues is 10 ppm or less in terms of the strength ratio with respect to the total amount of bisphenol residues represented by formula (2), formula (3) and formula (4).

(In the formulas (1) to (4), Y represents at least one divalent group selected from an m-phenylene group, a p-phenylene group, or a divalent group in which two p-phenylene groups are bonded via an oxygen atom. N represents an integer of 1 or more, X represents a single bond, —CR ¹ R ² —, O, CO, or S. Each of R ¹ and R ² independently represents a hydrogen atom. , A methyl group, an ethyl group, or a cyclohexylidene group formed by combining R ¹ and R ² . The equation (3) detected by gas chromatograph using a flame ionization detector (FID).
The amount of bisphenol residues represented by the formula (2), the formula (3) and the total amount of bisphenol residues represented by the formula (4) is 0.2% or more and 1% or less. The polyarylate resin according to claim 1, wherein: The polyarylate resin according to claim 1 or 2, wherein the bisphenol represented by the formula (3) is a bisphenol represented by the formula (3a).

(In the formula (3a), X represents a single bond, —CR ¹ R ² —, O, CO, or S. R ¹
, R ² each independently represents a hydrogen atom, a methyl group, or an ethyl group, or R ¹ and R 2
² represents a cyclohexylidene group formed by bonding with ² ; ) The polyarylate resin according to any one of claims 1 to 3, wherein the raw material monomer has a bisphenol purity of 99% or more. Formula (1) obtained by polymerizing a raw material monomer containing bisphenol represented by Formula (2)
The polyarylate resin having a repeating structure represented by formula (4), which is detected by a gas chromatograph using a flame ionization detector (FID) in the raw material monomer
The polyarylate resin is characterized in that the content of bisphenol represented by the formula (2), the formula (3) and the total amount of bisphenol represented by the formula (4) is 10 ppm or less in strength ratio .

(In the formulas (1) to (4), Y represents at least one divalent group selected from an m-phenylene group, a p-phenylene group, or a divalent group in which two p-phenylene groups are bonded via an oxygen atom. N represents an integer of 1 or more, X represents a single bond, —CR ¹ R ² —, O, CO, or S. Each of R ¹ and R ² independently represents a hydrogen atom. , A methyl group, an ethyl group, or a cyclohexylidene group formed by combining R ¹ and R ² . The content of bisphenol represented by the formula (3) detected by gas chromatography using a flame ionization detector (FID) in the raw material monomer is expressed by the formula (2), formula (3) and formula (4). The polyarylate resin according to claim 5, wherein the strength ratio is 0.3% or more and 1% or less with respect to the total amount of bisphenol represented by the formula (1). An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains the polyarylate resin according to any one of claims 1 to 6. . The electrophotographic photosensitive member according to claim 7, wherein the photosensitive layer is formed by laminating a charge transport layer and a charge generation layer. The electrophotographic photosensitive member according to claim 7 or 8, wherein the charge transport layer contains at least one charge transport material selected from the group of compounds represented by the following formulas (7) to (10). body.

  An image forming apparatus using the electrophotographic photosensitive member according to claim 7. The image forming apparatus according to claim 10, wherein in the electrophotographic process, the toner developed on the photoconductor is directly transferred to a print medium without an intermediate transfer member. A cartridge for an image forming apparatus using the electrophotographic photosensitive member according to any one of claims 7 to 9. It is a manufacturing method of the polyarylate resin which has a repeating structure represented by the said Formula (1) of any one of Claims 1-6, Comprising: The bisphenol component containing the bisphenol represented by the said Formula (2) And a divalent carboxylic acid component. A method for producing a polyarylate resin.

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