JP2012226275A - Electrophotographic photoreceptor, electrophotographic cartridge, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor that contains a binder resin having excellent wear resistance against load in practical use, high mechanical strength, excellent electrical characteristics, high stability of coating liquid for forming a photosensitive layer, and excellent adhesiveness with a substrate.SOLUTION: An electrophotographic photoreceptor has sufficient mechanical strength by having a photosensitive layer containing a polyester resin having a specific chemical structure, high solubility and excellent coating liquid stability to solvent used for coating liquid for forming a photosensitive layer, excellent electrical characteristics, and sufficient adhesiveness of a photosensitive layer with a substrate.

Description

  The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having good mechanical properties such as wear resistance and adhesiveness.

Electrophotographic technology is used in image forming apparatuses such as copiers and various printers because of its immediacy and high quality images. As a photoreceptor which is the core of electrophotographic technology, a photoreceptor using an organic photoconductive material having advantages such as pollution-free, easy film formation, and easy manufacture is used.
As a photoreceptor using an organic photoconductive material, a so-called single-layer photoreceptor in which a charge generation material is dispersed in a binder resin, and a laminate photoreceptor in which a charge generation layer and a charge transfer layer are laminated are known. ing. In particular, the laminated type photoconductor can provide a highly sensitive photoconductor by combining a highly efficient charge generating material and a charge transfer material, and can provide a highly safe photoconductor with a wide range of material selection. In addition, the photosensitive layer can be easily formed by coating, has high productivity, and is advantageous in terms of cost. Therefore, the photosensitive layer is the mainstream, and has been developed and put into practical use.

  Since the electrophotographic photosensitive member is repeatedly used in an electrophotographic process, that is, a cycle of charging, exposure, development, transfer, cleaning, static elimination, etc., it is deteriorated by various stresses during that time. 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 deteriorations such as flowing in, decomposing the photosensitive layer composition due to static elimination light or external light. Furthermore, there is mechanical deterioration such as abrasion of the photosensitive layer surface due to rubbing of a cleaning blade, a magnetic brush or the like, contact with a developer or paper, generation of scratches, peeling of the film, and the like. Such damage due to mechanical deterioration tends to appear on the image, and directly impairs the image quality, which is a major factor that limits the life of the photoreceptor.

In the case of a general photoreceptor not provided with a functional layer such as a surface protective layer, the photosensitive layer is subjected to such a load. The photosensitive layer is usually composed of a binder resin and a photoconductive material, and it is the binder resin that substantially determines the strength, but since the amount of the photoconductive material doped is considerably large, sufficient mechanical strength is provided. Has not reached.
On the other hand, in recent years, further downsizing of the image forming apparatus has been demanded from the viewpoint of space saving. In this case, in order to realize the downsizing of the image forming apparatus, a small-diameter type such as 30 mmφ is used as the photoreceptor. As the diameter of the photosensitive member is reduced, the internal stress in the photosensitive layer increases, and as a result, the adhesiveness between the support and the photosensitive layer is deteriorated, and defects such as peeling and cracking are likely to occur. In addition, when the photosensitive layer is made thicker to extend the life of the photoreceptor, the internal stress increases and the adhesiveness deteriorates. Therefore, today's electrophotographic photosensitive members are required to have not only wear resistance but also sufficient adhesion. Binder resins that significantly affect the abrasion resistance of the photosensitive layer include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, polycarbonate, polyester, polysulfone, phenoxy, epoxy, and silicone. Thermoplastic resins such as resins and various thermosetting resins are used. Among the various binder resins, the polycarbonate resin has relatively excellent performance, and various polycarbonate resins have been developed and put into practical use (see Patent Documents 1 to 3).

On the other hand, it has been reported that an electrophotographic photoreceptor using a polyarylate resin marketed under the trade name “U-polymer” as a binder has improved sensitivity compared to the case of using polycarbonate (Patent Document 4). reference). However, the coating solution prepared by dissolving this resin is low in stability, and coating production may be difficult. In response to this problem, by using a polyarylate resin using a dihydric phenol component having a specific structure as a binder resin, the stability of the coating solution used when producing the electrophotographic photoreceptor is improved, and the electrophotographic photoreceptor Improvements in mechanical strength and wear resistance have been reported (see Patent Documents 5 and 6). It has also been reported that the mechanical strength of the photoreceptor is improved by using a diphenyl ether dicarboxylic acid component as the dicarboxylic acid component of the polyarylate resin (see Patent Documents 7 to 9).

JP 50-098332 A JP 59-071057 A JP 59-184251 JP-A-56-135844 Japanese Patent Laid-Open No. 03-006567 Japanese Patent Laid-Open No. 10-288845 Japanese Patent Laid-Open No. 10-20514 JP 2006-53549 A JP 2008-293006 A

However, according to studies by the present inventors, the techniques described in Patent Documents 4 to 9 show improvements in electrical characteristics, wear resistance, etc., but sufficient performance may not be obtained in the adhesion of the photosensitive layer. There was a problem that peeling occurred when the adhesion to the substrate was insufficient.
The present invention has been made in view of the above problems, and has excellent wear resistance against practical loads, excellent electrical characteristics while maintaining high mechanical strength, and high stability of the coating solution for forming a photosensitive layer. An object of the present invention is to provide an electrophotographic photosensitive member containing a binder resin excellent in adhesiveness to a substrate.

  As a result of intensive studies on an electrophotographic photosensitive member that can solve the above-mentioned problems, the present inventors have sufficient mechanical properties by including a polyester resin having a specific chemical structure in the photosensitive layer. An electrophotographic photoreceptor having high solubility in a solvent used for a coating solution for forming a photosensitive layer, excellent coating solution stability, excellent electrical characteristics, and sufficient adhesion between the substrate and the photosensitive layer. Has been found to be able to be obtained, and the present invention has been completed based on such findings.

  That is, the invention according to claim 1 is an electrophotographic photosensitive member having a conductive support and at least a photosensitive layer formed on the conductive support, wherein the photosensitive layer is represented by the following formula (1). An electrophotographic photosensitive member comprising a polyester resin having a repeating structure represented.

(In the formula (1), 0.2 <{a / (a + b + c)} <0.6, A consists of at least one of the structures shown in the following formula (2) or (3), and B represents the following formula ( 4), C represents the structure represented by the following formula (5), X represents the structure represented by the following formula (6), and Y and Z represent a divalent carboxylic acid residue.

(In Formula (2), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.)

(In Formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group, and R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.)

(In Formula (4), R ⁹ represents an alkyl group having 1 to 3 carbon atoms, and R ¹⁰ and R ¹¹ each independently represents a hydrogen atom or a methyl group.)

(In Formula (5), R < ¹² > -R < ¹⁹ > is each independently the hydrogen atom, the alkyl group which may have a C1-C20 substituent, the alkoxyl group, and the aromatic group which may be substituted. X ¹ represents any ^one of a single bond, an alkylene group, —CR ²⁰ R ²¹ —, an oxygen atom, and a sulfur atom, and R ²⁰ and R ²¹ each independently represent a hydrogen atom or a carbon number of 1 to 20 Or an alkyl group which may have a substituent, or a group in which R ²⁰ and R ²¹ are bonded to each other to form a ring which may have a substituent.

(In Formula (6), R ²² and R ²³ each independently represents any of a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group, and n ¹ and m ¹ are each independently 0 to 0. Represents an integer of 4.)
The invention according to claim 2 is characterized in that the formula (2) is a structure represented by the following formula (7) and the formula (3) is a structure represented by the following formula (8). The electrophotographic photosensitive member.

  The invention according to claim 3 is the electrophotographic photoreceptor, wherein the photosensitive layer contains a charge transport material represented by the following formula (9) or the following formula (10).

(In formula (9), Ar ^{1 to} Ar ⁴ may be the same or different and each represents an aryl group which may have a substituent.)

(In Formula (10), Ar ^{5 to} Ar ¹⁰ each independently represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. M ¹ , m ² each independently represents 0 or 1. Q represents a direct bond or a divalent residue, and R ^{24 to} R ³¹ each independently represent a hydrogen atom or an alkyl group which may have a substituent. , An aryl group that may have a substituent, or a heterocyclic group that may have a substituent, n ^{1 to} n ⁴ each independently represents an integer of 0 to ^4. Ar ⁵ to Ar ¹⁰ may be bonded to each other to form a cyclic structure.)
According to a fourth aspect of the present invention, there is provided the electrophotographic photosensitive member, a charging unit for charging the electrophotographic photosensitive member, and an image exposing unit for performing image exposure on the charged electrophotographic photosensitive member to form an electrostatic latent image. An electrophotographic cartridge comprising: a developing unit that develops the electrostatic latent image with toner; and a transfer unit that transfers the toner to a transfer target. The invention according to claim 5 is the electrophotographic photosensitive member, a charging means for charging the electrophotographic photosensitive member, an exposure means for forming an electrostatic latent image by exposing the charged electrophotographic photosensitive member, An image comprising: a developing unit that develops the electrostatic latent image with toner; a transfer unit that transfers the toner to a transfer target; and a fixing unit that fixes the toner transferred to the transfer target. Forming device.

  According to the present invention, an electrophotographic photoreceptor excellent in wear resistance, adhesiveness and the like 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.

Hereinafter, modes for carrying out the present invention (hereinafter, embodiments of the present invention) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
The electrophotographic photoreceptor of the present invention has the following << 1. By using a polyester resin containing a specific dihydric phenol described in detail in Polyester Resin >> at a specific copolymerization ratio, it has high solubility in a solvent used during coating for forming a photosensitive layer, and is excellent. In addition to exhibiting various properties such as wear resistance and electrical properties, the substrate and the photosensitive layer are sufficiently excellent in adhesion. This improvement in adhesion is described in the following << 1. This is considered to be because the residual stress in the photosensitive layer was reduced by including the specific polyester resin described in detail in “Polyester resin”. Although the reason for this is not clear, the resin structure contains a specific amount of a dihydric phenol having a specific structure that is not linear, such as formula (2) or formula (3), which will be described in detail below. This is considered to be reasonably flexible and relieve residual stress.

<< 1. Polyester resin >>
The photosensitive layer of the electrophotographic photoreceptor to which this exemplary embodiment is applied contains a polyester resin having a repeating structure represented by the following formula (1).

In formula (1), A is a dihydric phenol component consisting of at least one of the structures shown in the following formula (2) or (3).

In formula (2), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.
Examples of R ¹ and R ² in the formula (2) include a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, but a dihydric phenol residue represented by the formula (2) is derived. In view of the convenience in the production of the monohydric phenol compound, R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 carbon atom (methyl group). .

  Specific examples of the formula (2) include bis (2-hydroxyphenyl) methane, 1,1-bis (2-hydroxyphenyl) ethane, 1,1-bis (2-hydroxyphenyl) propane, and 2,2-bis. (2-hydroxyphenyl) propane, bis (2-hydroxy-3-methylphenyl) methane, 1,1-bis (2-hydroxy-3-methylphenyl) ethane, 2,2-bis (2-hydroxy-3-) Methylphenyl) propane, bis (2-hydroxy-5-methylphenyl) methane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 2,2-bis (2-hydroxy-5-methylphenyl) Examples include propane. Among these, bis (2-hydroxyphenyl) methane and bis (2-hydroxy-5-methylphenyl) methane are particularly preferable in consideration of the convenience in production. These dihydric phenol components can be used in combination.

In formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group, and R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.
Examples of R ⁵ and R ⁶ in the formula (3) include a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and two derivatives for deriving the dihydric phenol residue represented by the formula (3). In view of the convenience in the production of a monohydric phenol compound, R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 carbon atom (methyl group). .

Specific examples of the formula (3) include (2-hydroxyphenyl) (4-hydroxyphenyl) methane, 1,1- (2-hydroxyphenyl) (4-hydroxyphenyl) ethane, 1,1- (2-hydroxy Phenyl) (4-hydroxyphenyl) propane, 2,2- (2-hydroxyphenyl) (4-hydroxyphenyl) propane, (2-hydroxy-3-methylphenyl) (4-hydroxy-3-methylphenyl) methane, 1,1- (2-hydroxy-3-methylphenyl) (4-hydroxy-3-methylphenyl) ethane, 2,2- (2-hydroxy-3-methylphenyl) (4-hydroxy-3-methylphenyl) Examples include propane. Among these, (2-hydroxyphenyl) (4-hydroxyphenyl) methane is particularly preferable in view of the convenience in production. These dihydric phenol components can be used in combination.
In formula (1), B represents a dihydric phenol having the structure of the following formula (4).

In formula (4), R ⁹ represents an alkyl group having 1 to 3 carbon atoms, and R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group.
Specific examples of the formula (4) include 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) butane, etc. Is mentioned. Among these, 1,1- (4-hydroxyphenyl) ethane and 1,1-bis (4-hydroxy-3-methylphenyl) ethane are preferable in consideration of solubility and wear resistance. These dihydric phenol components can be used in combination.
In the formula (1), C represents a dihydric phenol having a structure represented by the following formula (5).

In formula (5), R ^{12 to} R ¹⁹ each independently represent a hydrogen atom, an alkyl group that may have a substituent having 1 to 20 carbon atoms, an alkoxyl group, or an aromatic group, X ¹ represents any of a single bond, an alkylene group, —CR ²⁰ R ²¹ —, an oxygen atom, and a sulfur atom. R ²⁰ and R ²¹ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic group which may have a substituent, or R ²⁰ and R ²¹ bonded to each other. It represents one of the groups forming a ring which may have a substituent.

The alkyl group having 1 to 20 carbon atoms which may have a substituent in R ^{12 to} R ¹³ is an alkyl group having usually 20 or less carbon atoms, preferably 6 or less, and more preferably 3 or less. If it exceeds this range, there is a possibility that the wear resistance is lowered.
Specific examples of the alkyl group having 1 to 20 carbon atoms that may have this substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, Examples include a chloromethyl group, a fluorinated alkyl group, and a benzyl group.

Specific examples of the alkoxy group which may have a substituent in R ^{12 to} R ¹⁹ include a methoxy group, an ethoxy group, a propoxy group, a cyclohexoxy group, and the like.
Specific examples of the aromatic group that may have a substituent in R ^{12 to} R ¹⁹ include a phenyl group, a chlorophenyl group, and a fluorophenyl group.
As a preferable combination in R ^{12 to} R ¹⁹ , R ¹³ , R ¹⁵ , R ¹⁶ , and R ¹⁸ are hydrogen atoms, and R ¹² , R ¹⁴ , R ¹⁷ , and R ¹⁹ are hydrogen atoms or having 1 to 3 carbon atoms. It is an alkyl group. From the viewpoint of mechanical properties, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ and R ¹⁹ are particularly preferably hydrogen atoms, and R ¹² and R ¹⁷ are each a hydrogen atom or a methyl group.

Specific examples of the alkylene group for X ¹ include — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ — and the like.
The alkyl group which may have a substituent in R ²⁰ and R ²¹ is usually an alkyl group having 20 or less carbon atoms, preferably 6 or less carbon atoms, more preferably 3 or less carbon atoms, Specific examples include a methyl group, an ethyl group, a propyl group, a cyclohexyl group, and the like.

The aromatic group which may have a substituent in R ²⁰ and R ²¹ is usually a condensed polycyclic group having 20 or less carbon atoms or a phenyl group which may have a substituent. , Phenyl group, naphthyl group, anthryl group, phenanthryl group, tolyl group, and the like.
In R ²⁰ and R ²¹ , the group in which R ²⁰ and R ²¹ are bonded to each other to form a ring which may have a substituent is usually a cycloalkylidene group having 10 or less carbon atoms, preferably 8 carbon atoms. Or less, more preferably 6 or less carbon atoms, and specific examples thereof include a cyclohexylidene group.

In Formula (5), X ¹ is preferably —CR ²⁰ R ²¹ —. Specifically, bis- (4-hydroxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- ( 4-hydrokey 3-methylphenyl) propane, bis- (4-hydroxy-3-methylphenyl) methane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 1,1-bis- (4-hydroxy-3) -Methylphenyl) ethane, bis- (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis- (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis- (4 -Hydroxy-3,5-dimethylphenyl) propane, bis- (4-hydroxy-3,6-dimethylphenyl) methane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl ethane, 1,1-bis - (4-hydroxyphenyl) propane.

  Among these, bis (4-hydroxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 1,1-bis- ( 4-Hydroxy-3-methylphenyl) ethane and bis- (4-hydroxy-3-methylphenyl) methane are particularly preferred. It is also possible to use a combination of a plurality of these dihydric phenol components.

  X in the formula (1) represents a dicarboxylic acid component having a structure represented by the following formula (6).

In Formula (6), R ²² and R ²³ are each independently a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group, and n ¹ and m ¹ are each independently an integer of 0 to 4 To express.
R ²² and R ^{23 in} Formula (6) are, for example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms; an aryl group such as a phenyl group or a naphthyl group; a fluorine atom, a chlorine atom, a bromine atom, iodine Halogen groups such as atoms; alkoxy groups such as methoxy, ethoxy and butoxy groups. In consideration of the convenience in production of the divalent carboxylic acid compound derived from the divalent carboxylic acid residue represented by the formula (6), R ²² and R ²³ are each a hydrogen atom, an alkyl group having 1 carbon atom (methyl Group) is particularly preferred.

n ¹ and m ¹ are each independently an integer of 0 to 4, and particularly preferably n ¹ = m ¹ = 0.
Specific examples of the divalent carboxylic acid compound derived from the divalent carboxylic acid residue represented by the formula (6) include, for example, diphenyl ether-2,2′-dicarboxylic acid, diphenyl ether-2,4′-dicarboxylic acid, and diphenyl ether. Examples include -4,4'-dicarboxylic acid. Among these, diphenyl ether-4,4′-dicarboxylic acid is particularly preferable in view of convenience in production. These compounds exemplified as the formula (6) can be used in combination of a plurality of compounds as necessary.

Y and Z in formula (1) represent a divalent carboxylic acid. Specific examples of the divalent carboxylic acid compound for deriving Y and Z include, for example, adipic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, toluene-2,5-dicarboxylic acid, p-xylene- 2,5-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid Acid, pyridine-3,5-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl- 4,4′-dicarboxylic acid, diphenyl ether-2,2′-dicarboxylic acid, diphenyl ether-2,3′-dicarboxylic acid, diphenyl Examples include ether-2,4′-dicarboxylic acid, diphenylether-3,3′-dicarboxylic acid, diphenylether-3,4′-dicarboxylic acid, and diphenylether-4,4′-dicarboxylic acid. Considering the simplicity of production of the dicarboxylic acid component, isophthalic acid, terephthalic acid, and dicarboxylic acid represented by the formula (6) are preferable, and diphenyl ether-4,4′-dicarboxylic acid is particularly preferable. The compounds exemplified as Y and Z in the formula (1) may be the same, or a plurality of compounds may be used in combination as necessary.

In the formula (1), the lower limit of a / (a + b + c) is greater than 0.2, preferably 0.3 or more, more preferably 0.4 or more, while the upper limit is less than 0.6. Preferably it is 0.55 or less. If a / (a + b + c) is too small, the adhesion may be insufficient. On the other hand, if a / (a + b + c) is too large, the solubility may be insufficient.
The photosensitive layer in the electrophotographic photoreceptor to which the exemplary embodiment is applied can be used by mixing a polyester resin having a repeating structure represented by the above-described formula (1) with another resin. is there. Other resins mixed here include, for example, vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride or copolymers thereof; polycarbonate resin, polyester resin, polyester polycarbonate resin, polysulfone resin, phenoxy resin, epoxy Examples thereof include thermoplastic resins such as resins and silicone resins, and various thermosetting resins. Of these resins, polycarbonate resins and polyester resins are preferred. Moreover, the mixing ratio of the resin to be used in combination is not particularly limited, but it is usually preferable to use the resin in a range not exceeding the ratio of the polyester resin having the repeating structure represented by the formula (1).

  The viscosity average molecular weight (Mv) of the polyester resin having a repeating structure represented by the formula (1) is usually 10,000 to 300,000, preferably 20,000 to 200,000, particularly preferably 25, The range is from 000 to 150,000. When the viscosity average molecular weight (Mv) is excessively small, the mechanical strength when obtained as a film for forming a photoconductor tends to decrease. Moreover, when a viscosity average molecular weight (Mv) is too large, the viscosity as a coating liquid rises and it tends to become difficult to apply | coat to a suitable film thickness.

≪2. Production method of polyester resin >>
Next, the manufacturing method of the polyester resin which has a repeating structure represented by Formula (1) used for the electrophotographic photosensitive member to which this Embodiment is applied is demonstrated. As a method for producing the polyester resin, for example, a known polymerization method such as an interfacial polymerization method, a melt polymerization method, or a solution polymerization method can be used. Here, an example of the manufacturing method of a polyester 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 is preferably in the range of 0 ° C. to 40 ° C., and the polymerization time is preferably in the range of 2 hours to 20 hours from the viewpoint of productivity. After the completion of the polymerization, the water phase and the organic phase are separated, and the polymer dissolved in the organic phase is washed and recovered by a known method to obtain the intended resin.

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, m, p-propylphenol, o, m, p- (tert-butyl) phenol, and pentyl. Alkylphenols such as phenol, hexylphenol, octylphenol, nonylphenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives; monofunctional phenols such as o, m, p-phenylphenol; acetic acid chloride, butyric acid chloride, octyl Examples thereof include monofunctional acid halides such as acid chloride, benzoyl chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzenephosphonyl chloride and substituted products thereof. Among these molecular weight regulators, o, m, p- (tert-butyl) phenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives are preferred because of their high molecular weight controllability and solution stability. It is. Particularly preferred are p- (tert-butyl) phenol, 2,3,6-trimethylphenol, and 2,3,5-trimethylphenol.

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

  The polyester resin after purification is precipitated in water, alcohol or other organic solvent in which the polyester resin is insoluble, or the solvent of the polyester resin solution is distilled off in warm water or in a dispersion medium in which the polyester resin is insoluble, or heated and reduced in pressure. For example, the solvent may be removed by distilling off the solvent, and when the slurry is taken out, the solid can be taken out by a centrifuge or a filter.

The obtained polyester resin is usually dried at a temperature equal to or lower than the decomposition temperature of the polyester resin, but can be preferably dried at a temperature not lower than 20 ° C. and not higher than the melting temperature of the resin. At this time, it is preferable to dry under reduced pressure.
Preferably, the drying time is longer 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 lower, preferably 300 ppm or lower, more preferably 100 ppm or lower. dry.

≪3. Electrophotographic photoreceptor >>
The electrophotographic photosensitive member to which this exemplary embodiment is applied has a photosensitive layer provided on a conductive support, and the photosensitive layer contains a polyester resin having a repeating structure represented by the above formula (1). To do. 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 polyester 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, a charge transfer material and a charge generation material are dispersed in a binder resin in the photosensitive layer.

<3-1. 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. In order to reduce the cost, it is possible to use the drawing tube as it is without performing the cutting process.

<3-2. Undercoat layer>
An undercoat layer may be provided between the conductive support and the photosensitive layer described later for improving adhesion and blocking properties. 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.

Examples of metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, titanium Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium acid 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. Moreover, the thing of a several crystal state may be contained.

In addition, various particle sizes of metal oxide particles can be used. Among these, from the viewpoint of characteristics and liquid stability, the average primary particle size is preferably 10 nm or more and 100 nm or less, and particularly 10 nm or more and 50 nm or less. 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 in combination of two or more in any combination and ratio. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamides, modified polyamides, and the like are preferable because they exhibit good dispersibility and coatability.

The use ratio of the inorganic particles to the binder resin used in the undercoat layer can be arbitrarily selected. From the viewpoint of the stability of the dispersion and the coating property, the binder resin is usually 10% by mass or more, It is preferable to use in the range of 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.

<3-3. 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.
<3-3-1. Multilayer photosensitive layer>
-Charge generation layer In the case of a multilayer type photoreceptor (function-separated type photoreceptor), the charge generation layer is formed by binding a charge generation substance 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. Particularly, titanyl phthalocyanines (also known as oxytitanium) such as X-type, τ-type metal-free phthalocyanine, A-type (also known as β-type), B-type (also known as α-type), and D-type (also known as Y-type), which are highly sensitive crystal types Phthalocyanine), vanadyl phthalocyanine, chloroindium phthalocyanine, 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, type II, etc. The [mu] -oxo-aluminum phthalocyanine dimer 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 °. D-type (Y-type) titanyl phthalocyanine, II-type chlorogallium phthalocyanine, V-type and 28.1 ° have the strongest peaks, and 26.2 ° have peaks Hydroxygallium phthalocyanine having a clear peak at 28.1 ° and a full width at half maximum W of 25.9 ° of 0.1 ° ≦ W ≦ 0.4 °, G-type μ-oxo -Gallium phthalocyanine dimer and the like are particularly preferable. Among these, D-type (Y-type) titanyl phthalocyanine is most preferable because it shows 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, Modified ether type polyester resin, Phenoxy resin, Polyvinyl chloride resin, Polyvinylidene chloride resin, Polyvinyl acetate resin, Polystyrene resin, Acrylic resin, Methacrylic resin, Polyacrylamide resin, Polyamide Resin, polyvinyl pyridine resin, cellulosic resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, casein, vinyl chloride -Vinyl acetate-vinyl acetate copolymers such as vinyl acetate copolymers, hydroxy-modified vinyl chloride-vinyl acetate copolymers, carboxyl-modified vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, etc. Insulating resins such as polymers, styrene-butadiene copolymers, vinylidene chloride-acrylonitrile copolymers, styrene-alkyd resins, silicon-alkyd resins, phenol-formaldehyde resins, poly-N-vinylcarbazole, polyvinyl anthracene, polyvinyl And organic photoconductive polymers such as perylene. Any one of these binder resins may be used alone, or two or more thereof may be mixed and used in any combination.

Specifically, the charge generation layer is prepared by dispersing the halogen-substituted indium phthalocyanine of the present invention and other charge generation materials used in some cases in a solution obtained by dissolving the above-described binder resin in an organic solvent. Is applied on a conductive support (or an undercoat layer when an undercoat layer is provided).
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, chloronaphthalene, amide solvents such as dimethylformamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-butanol, benzyl alcohol, etc. Alcohol solvents, aliphatic polyhydric alcohols such as glycerin and polyethylene glycol, chain or cyclic ketone solvents such as acetone, cyclohexanone, methyl ethyl ketone, ester solvents such as methyl formate, ethyl acetate, n-butyl acetate, dichloromethane, The Halogenated hydrocarbon solvents such as roform, 1,2-dichloroethane, chain or cyclic ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, acetonitrile, dimethyl Aprotic polar solvents such as sulfoxide, sulfolane, hexamethylphosphoric triamide, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine and other nitrogen-containing compounds, ligroin and other mineral oils, water, etc. Can be mentioned. 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 (weight) 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 photoconductor 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.

  Among charge transport materials, a compound having a structure represented by the following general formula (9) or the following general formula (10) is preferably used.

In formula (9), Ar ^{1 to} Ar ⁴ may be the same or different and each represents an aryl group which may have a substituent.
In the formula (9), Ar ^{1 to} Ar ⁴ are preferably aryl groups having 6 to 20 carbon atoms, which may be the same or different. For example, phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, pyrenyl. From the viewpoint of production cost, aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl are particularly preferable.
Furthermore, the charge transport material is preferably a compound represented by the following formula (11).

In formula (11), Ar ^{19 to} Ar ²⁴ may be the same or different and each represents an aryl group which may have a substituent, and n represents an integer of 2 or more. Z represents a monovalent organic residue, and m represents an integer of 0 to 4.
In formula (11), Ar ^{19 to} Ar ²⁴ are preferably aryl groups having 6 to 20 carbon atoms, and may be the same or different. For example, phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, pyrenyl. From the viewpoint of production cost, aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl are particularly preferable.

Further, when it has a substituent, the substituent is preferably a substituent having 1 to 10 carbon atoms and having a substituent constant σp of 0.20 or less according to Hammett's rule. Z represents a monovalent organic residue, and a substituent having a substituent constant σp in the Hammett rule of 0.20 or less is preferable.
Examples of such a substituent or monovalent organic residue Z include, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylamino group having 2 to 4 carbon atoms, and 6 to 10 carbon atoms. Examples thereof include an aryl group, and specifically include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, butoxy, N, N-dimethylamino, N, N -Diethylamino, phenyl, 4-tolyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, naphthyl and the like. Among these, a hydrocarbon group having 1 to 4 carbon atoms is particularly preferable from the viewpoint of electrical characteristics.

  In the general formula (11), n is preferably an integer of 2 or more. From the viewpoint of compatibility and manufacturing cost, n = 2 is particularly preferable. As m, an integer of 0 to 1 is preferable, but in view of manufacturing cost, m = 0 is particularly preferable.

In formula (10), Ar ^{5 to} Ar ¹⁰ each independently represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. m ¹ and m ² each independently represents 0 or 1. Ar ⁹ in the case of m ¹ = 0 and Ar ^{10 in} the case of m ² = 0 each have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. It may be a monovalent heterocyclic group. Ar ⁹ in the case of m ¹ = 1 and Ar ^{10 in} the case of m ² = 1 each have an alkylene group that may have a substituent, an arylene group that may have a substituent, or a substituent. It represents an optionally divalent heterocyclic group. Q represents a direct bond or a divalent residue. R
^{24 to} R ³¹ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. n ¹ ~n ⁴ represents each independently integers from 0-4. Ar ^{5 to} Ar ¹⁰ may be bonded to each other to form a cyclic structure.

Further, in the general formula (10), R ^{24 to} R ³¹ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It represents an aralkyl group which may have a heterocyclic group which may have a substituent.
In the general formula (10), when R ^{24 to} R ³¹ are alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, cyclopentyl group, cyclohexyl group Among these, an alkyl group having 1 to 6 carbon atoms is preferable. When the alkyl group has an aryl substituent, examples thereof include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 12 carbon atoms is preferable.

When R ²⁴ to R ³¹ is an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, pyrenyl group, preferably an aryl group having 6 to 12 carbon atoms. When R ^{24 to} R ³¹ are a heterocyclic group, an aromatic heterocyclic ring is preferable, and examples thereof include a furyl group, a thienyl group, and a pyridyl group, and a monocyclic aromatic heterocyclic ring is more preferable.
Among R ^{24 to} R ³¹ , the most preferable are a methyl group and a phenyl group.

In General Formula (10), Ar ^{5 to} Ar ¹⁰ each independently represent an arylene group that may have a substituent or a divalent heterocyclic group that may have a substituent. m ¹ and m ² each independently represents 0 or 1. Ar ⁹ in the case of m ¹ = 0 and Ar ^{10 in} the case of m ² = 0 each have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a monovalent heterocyclic group, and Ar ⁹ in the case of m ¹ = 1 and Ar ¹⁰ in the case of m ² = 1 each have an alkylene group and a substituent which may have a substituent. An arylene group which may be substituted, or a divalent heterocyclic group which may have a substituent. Specifically, examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a pyrenyl group, and an aryl group having 6 to 14 carbon atoms is preferable; the arylene group includes a phenylene group and a naphthylene group. A phenylene group is preferable.

In the general formula (10), the monovalent heterocyclic group is preferably an aromatic heterocyclic ring, and examples thereof include a furyl group, a thienyl group, and a pyridyl group, and a monocyclic aromatic heterocyclic ring is more preferable. . As the divalent heterocyclic group, an aromatic heterocyclic ring is preferable, and examples thereof include a pyridylene group and a thienylene group, and a monocyclic aromatic heterocyclic ring is more preferable. Of these, the most preferred is Ar ⁵ and Ar ⁶ are phenylene groups.

In general formula (10), among the groups represented by R ^{24 to} R ³¹ and Ar ^{5 to} Ar ¹⁰ , the alkyl group, aryl group, aralkyl group, and heterocyclic group may further have a substituent. . Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, and tert-butyl. Group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and other alkyl groups; methoxy group, ethoxy group, propyloxy group and other alkoxy groups; methylthio group, ethylthio group and other alkylthio groups; vinyl group, allyl group and other alkenyl groups Groups; aralkyl groups such as benzyl, naphthylmethyl, and phenethyl groups; aryloxy groups such as phenoxy and triloxy groups; arylalkoxy groups such as benzyloxy and phenethyloxy groups; aryl groups such as phenyl and naphthyl groups; Aryl vinyl groups such as styryl groups and naphthyl vinyl groups; Acyl groups such as til group and benzoyl group; Dialkylamino groups such as dimethylamino group and diethylamino group; Diarylamino groups such as diphenylamino group and dinaphthylamino group; Diaralkylamino groups such as dibenzylamino group and diphenethylamino group A diheterocyclic amino group such as a group, a dipyridylamino group or a dithienylamino group; a substituted amino group such as a diallylamino group or a disubstituted amino group obtained by combining substituents of the amino group described above; and a cyano group, a nitro group, A hydroxyl group etc. are mentioned. These substituents may be bonded to each other to form a cyclic hydrocarbon group or a heterocyclic group via a single bond, a methylene group, an ethylene group, a carbonyl group, a vinylidene group, an ethylenylene group or the like.

  Among these, preferred substituents include a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and 6 to 12 carbon atoms. An arylthio group having 6 to 12 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms, more preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group, and a methyl group and a phenyl group. Is particularly preferred.

In General Formula (10), n ^{1 to} n ⁴ each independently represents an integer of 0 to 4, preferably 0 to 2, and particularly preferably 1. m ¹ and m ² represent 0 or 1, and 0 is preferable.
In general formula (10), Q represents a direct bond or a divalent residue, and a divalent residue is preferably a group 16 atom, an alkylene which may have a substituent, or a substituent. An arylene group which may be substituted, a cycloalkylidene group which may have a substituent, or a group in which these are bonded to each other, for example, [—O—Z—O—], [—Z—O—Z—], [—S— Z—S—], [—Z—Z—] and the like (provided that O is an oxygen atom, S is a sulfur atom, and Z may have an arylene group or substituent which may have a substituent). Represents a good alkylene group).

  As an alkylene group which comprises Q, a C1-C6 thing is preferable and a methylene group and an ethylene group are still more preferable especially. Moreover, as a cycloalkylidene group, a C5-C8 thing is preferable and a cyclopentylidene group and a cyclohexylidene group are still more preferable especially. As the arylene group, those having 6 to 14 carbon atoms are preferable, and among them, a phenylene group and a naphthylene group are more preferable.

These alkylene groups, arylene groups, and cycloalkylidene groups may have a substituent. Preferred substituents include a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number. Examples thereof include an alkenyl group having 1 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms.
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. 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.

Moreover, the binder resin of the charge transport layer used in the electrophotographic photoreceptor of the present invention is a polyester resin having a repeating structure represented by the above formula (1). The binder resin may be a mixture of the polyester resin used in the present invention and other resins. Examples of the other resins include butadiene resin, styrene resin, vinyl acetate resin, vinyl chloride resin, acrylic ester resin, methacrylic ester resin, Polymers and copolymers of vinyl compounds such as acid ester resin, vinyl alcohol resin, ethyl vinyl ether, polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal, polycarbonate resin, polyester resin, polyarylate resin, polyamide resin, polyurethane resin , Cellulose ester resin, phenoxy resin, silicon resin, silicon-alkyd resin, poly-N-vinylcarbazole resin, and the like. These binder resins can also be used after being crosslinked by heat, light or the like using an appropriate curing agent.

  The ratio of the binder resin composed of the polyester resin having the repeating structure represented by the formula (1) and the charge transport material is usually 30 parts by weight to 200 parts by weight, preferably 100 parts by weight of the binder resin. , 40 parts by weight to 150 parts by weight. The film thickness of the charge transport layer is usually 5 μm to 50 μm, preferably 10 μm to 45 μm.

  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. You may contain additives, such as a compound, dye, a pigment, and a leveling agent. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds. Examples of dyes and pigments include various pigment compounds and azo compounds.

<3-3-2. 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 photoreceptor, 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, and on a conductive support (or an undercoat layer when an undercoat layer is provided). It can be obtained by coating and drying.

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. It is used in the range of usually 0.5% by mass or more, preferably 1% by mass or more, and usually 50% by mass or less, preferably 20% by mass or less based on the whole layer-type photosensitive layer.
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 μm or less, preferably 50 μm or less. Also in this case, known plasticizers for improving film formability, flexibility, mechanical strength, additives for suppressing residual potential, dispersion aids for improving dispersion stability, coatability Leveling agents and surfactants such as silicone oil, fluorine oil and other additives may be added to improve the viscosity.

<3-4. Other functional layers>
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.

<3-5. 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. The viscosity of the coating solution is usually 0.01 cps or more, preferably 0.1 cps or more, and usually 20 cps or less, preferably 10 cps or less.
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.
<4. Image forming apparatus>
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention (an image forming apparatus of the present invention) will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, and a developing device 4, and further, a transfer device 5, a cleaning device 6 and a fixing device as necessary. A device 7 is provided.
The electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-described electrophotographic photoreceptor of the present invention, but in FIG. 1, as an example, a drum in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. The photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are 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 type 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. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a short wavelength of 380 nm to 500 nm. . 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 an arbitrary device such as a dry development method such as cascade development, one-component insulating toner development, one-component conductive toner development, or two-component magnetic brush development, or a wet development method is used. be able to. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

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

  The 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 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

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

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

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. 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 to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.
Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

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

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

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

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.
[Production of polyester resin]
Production Example 1 (Method for producing polyester resin (1))
Sodium hydroxide (10.98 g) and H ₂ O (470 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.43 g), bis (2-hydroxyphenyl) methane (hereinafter referred to as BP-a), (2-hydroxyphenyl) (4-hydroxyphenyl) methane (hereinafter referred to as BP-). b), a mixture of bis (4-hydroxyphenyl) methane (hereinafter referred to as BP-c) (mixing ratio, BP-a: BP-b: BP-c = 17: 45: 38 (hereinafter referred to as BP-d)) ( 15.80 g), 1,1-bis (4-hydroxy-3, methylphenyl) ethane (8.20 g) (hereinafter, BP-e) and benzyltriethylammonium chloride (0.30 g) were added in this order, and dissolved with stirring. Then, this alkaline aqueous solution was transferred to a 2 L reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (33.90 g) and dichloromethane (235 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 (392 mL) was added and stirring was continued for 10 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 (471 mL) three times, and further washed with demineralized water (471 mL) twice.

  The washed organic layer was diluted with 590 ml of dichloromethane, poured into methanol (4000 ml), and the resulting precipitate was filtered off and dried to obtain the desired polyester resin (1). The viscosity average molecular weight of the obtained polyester resin (1) was 37,000. The structural formula of the obtained polyester resin (1) is shown below.

[Measurement of viscosity average molecular weight]
The polyester 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
Production Example 2 (Production Method of Polyester Resin (2))
Sodium hydroxide (10.98 g) and H ₂ O (470 ml) were weighed in a 500 mL beaker and dissolved with stirring. There, a mixture of 2,3,5-trimethylphenol (0.39 g), BP-a, BP-b (mixing ratio, BP-a: BP-b = 60: 40 (hereinafter referred to as BP-f)) (15 .82 g), BP-e (8.20 g) and benzyltriethylammonium chloride (0.30 g) were added in this order and dissolved by stirring, and the aqueous alkaline solution was transferred to a 2 L reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (33.90 g) and dichloromethane (235 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 (392 mL) was added and stirring was continued for 10 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 3 times with 0.1N hydrochloric acid (471 mL), and further washed twice with demineralized water (471 mL).

  Diluted by adding 590 ml of dichloromethane to the washed organic layer, poured into methanol (4000 ml), the precipitate obtained was filtered off and dried to obtain the desired polyester resin (2). The viscosity average molecular weight of the obtained polyester resin (2) was 42,000. The structural formula of the obtained polyester resin (2) is shown below.

Production Example 3 (Method for producing polyester resin (3))
Sodium hydroxide (10.99 g) and H ₂ O (470 ml) were weighed in a 500 mL beaker and dissolved with stirring. There, a mixture of 2,3,5-trimethylphenol (0.21 g), BP-a, BP-b (mixing ratio, BP-a: BP-b = 60: 40 (hereinafter referred to as BP-f)) (15 .91 g), BP-e (8.25 g) and benzyltriethylammonium chloride (0.29 g) were added in this order and dissolved by stirring, and then the aqueous alkaline solution was transferred to a 2 L reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (33.91 g) and dichloromethane (235 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 (700 mL) was added and stirring was continued for 10 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 3 times with 0.1 N hydrochloric acid (700 mL), and further washed twice with demineralized water (700 mL).

  The organic layer after washing was diluted with 900 ml of dichloromethane, poured into methanol (8000 ml), and the resulting precipitate was filtered off and dried to obtain the desired polyester resin (3). The viscosity average molecular weight of the obtained polyester resin (3) was 70,000. The structural formula of the obtained polyester resin (3) is shown below.

Production Example 4 (Production Method of Polyester Resin (4))
Sodium hydroxide (10.60 g) and H ₂ O (470 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.588 g), BP-d (6.49 g), BP-e (18.33 g) and benzyltriethylammonium chloride (0.29 g) were added in that order and dissolved by stirring. Then, this alkaline aqueous solution was transferred to a 2 L reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (32.57 g) and dichloromethane (235 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 (391 mL) was added and stirring was continued for 10 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 3 times with 0.1N hydrochloric acid (471 mL), and further washed twice with demineralized water (471 mL).

  Diluted by adding 590 ml of dichloromethane to the washed organic layer, poured into methanol (4000 ml), the precipitate obtained was filtered and dried to obtain the desired polyester resin (4). The viscosity average molecular weight of the obtained polyester resin (4) was 37,000. The structural formula of the obtained polyester resin (4) is shown below.

Production Example 5 (Method for producing polyester resin (5))
Sodium hydroxide (11.30 g) and H ₂ O (470 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.32 g), BP-d (23.3 g) and benzyltriethylammonium chloride (0.30 g) were added in that order and dissolved by stirring. Moved to.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (35.17 g) and dichloromethane (235 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 (391 mL) was added and stirring was continued for 10 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 3 times with 0.1N hydrochloric acid (471 mL), and further washed twice with demineralized water (471 mL).

  Diluted by adding 590 ml of dichloromethane to the organic layer after washing, poured into methanol (4000 ml), and the resulting precipitate was taken out by filtration and dried to obtain the desired polyester resin (5). The viscosity average molecular weight of the obtained polyester resin (5) was 39,000. The structural formula of the obtained polyester resin (5) is shown below.

<Manufacture of photosensitive drum>
[Example 1]
<Preparation of dispersion for undercoat layer>
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 weight of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) Disperse the surface-treated titanium oxide obtained by mixing in a kneading machine (“SMG300” manufactured by Kawata Co., Ltd.) and mixing at high speed at a rotational peripheral speed of 34.5 m / sec using a ball mill of methanol / 1-propanol. Thus, a dispersion slurry of hydrophobized titanium oxide was obtained. 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 represented by (E)] has a composition molar ratio of 75% / 9.5% / 3% / 9.5% / 3%, and is stirred and mixed while heating with the copolyamide pellets. After dissolving the polyamide pellets, by carrying out ultrasonic dispersion treatment, the weight ratio of methanol / 1-propanol / toluene is 7/1/2, and hydrophobically treated titanium oxide / copolymerized poly Containing bromide at a weight ratio of 3/1, it was undercoat layer dispersion having a solid concentration of 18.0%.

<Preparation of dispersion for charge generation layer>
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, 10 parts of polyvinyl butyral (trade name “Denka Butyral” # 6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) was added to 255 parts of 1,2-dimethoxyethane and 4-methoxy-4-methyl. A binder liquid obtained by dissolving in 85 parts of 2-pentanone and 230 parts of 1,2-dimethoxyethane were mixed to prepare a coating solution for forming a charge generation layer.

<Preparation of coating solution for charge transport layer>
The charge transport layer coating solution was prepared as follows. A mixture (CTM-1) produced by the method described in Example 1 of JP-A-2002-080432, comprising a group of geometric isomers having the following structure as a main component as a charge transport material (75) 100 parts by mass of polyester resin (1) produced in Production Example 1, 4 parts by mass of antioxidant (Irganox 1076), 0.05 part by mass of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.) Was mixed with 640 parts by mass of a tetrahydrofuran / toluene mixed solvent (tetrahydrofuran 80 wt%, toluene 20 wt%) to prepare a charge transport layer coating solution.

On the 3003 series aluminum alloy tube having a diameter of 30 mm, a length of 246 mm, and a wall thickness of 0.75 mm, the coating film for forming the undercoat layer obtained as described above has a film thickness after drying of about 1.5 μm. In this way, it was dip coated and dried at room temperature to provide an undercoat layer.
Subsequently, the charge generation layer forming coating solution obtained as described above is dip-coated on the undercoat layer so that the film thickness after drying is about 0.3 μm, and dried at room temperature. A charge generation layer was provided.

Subsequently, the charge transport layer forming coating solution was dip-coated on the charge generation layer so that the film thickness after drying was about 20 μm to prepare a photosensitive drum.
[Example 2]
75 parts by mass of the charge transport material (CTM-1) is changed to 50 parts by mass of the charge transport material (CTM-2) produced by the method described in Example 4 of JP2009-20504A, which is represented by the following formula. A photosensitive drum was prepared in the same manner as in Example 1 except that.

[Example 3]
A photosensitive drum was prepared in the same manner as in Example 1 except that the polyester resin 1 was changed to the polyester resin 2.
[Example 4]
A photosensitive drum was prepared in the same manner as in Example 1 except that the polyester resin 1 was changed to the polyester resin 3.

[Comparative Example 1]
A photosensitive drum was prepared in the same manner as in Example 1 except that the polyester resin 1 was changed to the polyester resin 4.
[Comparative Example 2]
The same as Example 1 except that the polyester resin 1 was changed to the polyester resin 6 (viscosity average molecular weight 40,000) having the structure shown below produced by the method described in Example 6 of JP-A-2006-53549. Thus, a photosensitive drum was prepared.

[Comparative Example 3]
A coating solution for forming a charge transport layer was prepared in the same manner as in Example 1 except that the polyester resin 1 was changed to the polyester resin 5. However, the coating solution became cloudy because the solubility of the polyester resin 5 was poor and the coating solution became cloudy. Not done.
[Electrical characteristics]
An electrophotographic characteristic evaluation apparatus manufactured according to the electrophotographic society measurement standard (basic and applied electrophotographic technology, edited by the Electrophotographic Society, Corona, page 404-405) is used, and the photoreceptor is rotated at a constant rotation speed of 120 rpm. Then, an electrical property evaluation test was performed by a cycle of charging, exposure, potential measurement, and static elimination. At that time, the photosensitive member was charged so that the initial surface potential was − (minus, the same applies hereinafter) to 700 V, and the light from the halogen lamp was converted to monochromatic light of 780 nm with an interference filter and exposed at 1.0 μJ / cm ² . The surface potential measured later (hereinafter sometimes referred to as VL) was defined as the residual potential. The measurement results are shown in Table 1. The lower the residual potential, the better the electrical characteristics.

[Measurement of film loss by wear test]
These photoconductors were mounted on a commercially available color printer COREFIDO C711dn (manufactured by Oki Data Co., Ltd.), and 40,000 sheets were printed under normal temperature and humidity. The film loss per sheet was calculated and the results are shown in Table 1. The smaller the film decrease, the better the wear resistance.

[Adhesion test]
These photoreceptors were subjected to a 5 mm square 9 grid pattern test in accordance with JIS standards (JIS K5400), and the number of grids remaining after the tape was adhered and peeled was measured.
○: The number of remaining grids is 7 to 9 (good)
Δ: Number of remaining grids 2-6 (practical)
X: Number of remaining grids 0 to 1 (unsuitable)
The results are shown in Table 1.

From the results shown in Table 1, it can be seen that when a polyester resin within the scope of the present invention is used, a photoreceptor having good electrical properties and wear resistance and further good adhesion can be obtained. On the other hand, when a / (a + b + c) in formula (1) is smaller than 0.2, it can be seen that sufficient results cannot be obtained in the adhesion test. Further, it can be seen from Comparative Example 3 that when a / (a + b + c) in the formula (1) is larger than 0.6, sufficient solubility as a charge transport layer forming coating solution cannot be obtained.

From the above results, the use of a polyester resin within the scope of the present invention provides a high-performance photoconductor that has not only good electrical properties, wear resistance, solubility, but also sufficient adhesion. It was clarified that it was possible.

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 (5)

An electrophotographic photosensitive member having a conductive support and at least a photosensitive layer formed on the conductive support, wherein the photosensitive layer comprises a polyester resin having a repeating structure represented by the following formula (1): An electrophotographic photosensitive member containing the electrophotographic photosensitive member.

(In the formula (1), 0.2 <{a / (a + b + c)} <0.6, A consists of at least one of the structures shown in the following formula (2) or (3), and B represents the following formula ( 4), C represents the structure represented by the following formula (5), X represents the structure represented by the following formula (6), and Y and Z represent a divalent carboxylic acid residue.

(In Formula (2), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.)

(In Formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group, and R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.)

(In Formula (4), R ⁹ represents an alkyl group having 1 to 3 carbon atoms, and R ¹⁰ and R ¹¹ each independently represents a hydrogen atom or a methyl group.)

(In Formula (5), R < ¹² > -R < ¹⁹ > is each independently the hydrogen atom, the alkyl group which may have a C1-C20 substituent, the alkoxyl group, and the aromatic group which may be substituted. X ¹ represents any ^one of a single bond, an alkylene group, —CR ²⁰ R ²¹ —, an oxygen atom, and a sulfur atom, and R ²⁰ and R ²¹ each independently represent a hydrogen atom or a carbon number of 1 to 20 Or an alkyl group which may have a substituent, or a group in which R ²⁰ and R ²¹ are bonded to each other to form a ring which may have a substituent.

(In Formula (6), R ²² and R ²³ each independently represents any of a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group, and n ¹ and m ¹ are each independently 0 to 0. Represents an integer of 4.) 2. The electron according to claim 1, wherein the formula (2) is a structure represented by the following formula (7), and the formula (3) is a structure represented by the following formula (8). Photoconductor.

The electrophotographic photoreceptor according to claim 1, wherein the photosensitive layer contains a charge transport material represented by the following formula (9) or the following formula (10).

(In formula (9), Ar ^{1 to} Ar ⁴ may be the same or different and each represents an aryl group which may have a substituent.)

(In Formula (10), Ar ^{5 to} Ar ¹⁰ each independently represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. M ¹ , m ² each independently represents 0 or 1. Q represents a direct bond or a divalent residue, and R ^{24 to} R ³¹ each independently represent a hydrogen atom or an alkyl group which may have a substituent. , An aryl group that may have a substituent, or a heterocyclic group that may have a substituent, n ^{1 to} n ⁴ each independently represents an integer of 0 to ^4. Ar ⁵ to Ar ¹⁰ may be bonded to each other to form a cyclic structure.)   The electrophotographic photosensitive member according to any one of claims 1 to 3, charging means for charging the electrophotographic photosensitive member, and image exposure of the charged electrophotographic photosensitive member to form an electrostatic latent image. An electrophotographic cartridge comprising: an image exposure unit; a developing unit that develops the electrostatic latent image with toner; and a transfer unit that transfers the toner to a transfer target.   4. The electrophotographic photosensitive member according to claim 1, charging means for charging the electrophotographic photosensitive member, and exposure means for forming an electrostatic latent image by exposing the charged electrophotographic photosensitive member. And a developing unit that develops the electrostatic latent image with toner, a transfer unit that transfers the toner to a transfer target, and a fixing unit that fixes the toner transferred to the transfer target. An image forming apparatus.

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