JP2008293006A - Electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having excellent wear resistance and electric characteristic, containing a binder resin and high stability of a coating solution. <P>SOLUTION: The electrophotographic photoreceptor comprises a conductive support and a photosensitive layer formed on the conductive support. The photosensitive layer has a repeating structure represented by the formula (1). In the formula (1), 0.5<äa/(a+b)}<1 is satisfied, where A is a divalent phenol residue of a 250 or less molecular weight, B is a divalent phenol residue, X is a structure represented by the following formula (2), and Y is a divalent carboxylic acid residue. In the formula (2), R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom, an alkyl group, an aryl group, a halogen group or an alkoxy group, and n<SP>1</SP>, m<SP>1</SP>are each independently an integer from 0 to 4. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrophotographic photosensitive member, and more particularly to an electrophotographic photosensitive member having good wear resistance and the like.

The electrophotographic technology is widely used in the fields of 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 photoconductor using an organic photoconductive material, a so-called dispersion type photoconductor in which a photoconductive fine powder is dispersed in a binder resin and a multi-layer type photoconductor in which a charge generation layer and a charge transfer layer are laminated. Are known. 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. In particular, such damage on the surface of the photosensitive layer is likely to appear on the image and directly impairs the image quality, which is a major factor limiting 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. In addition, due to the increasing demand for high-speed printing, materials for a higher-speed electrophotographic process are required. In this case, in addition to high sensitivity and long life, the photosensitive member must have good responsiveness because the time from exposure to development is shortened.

  In addition, each layer constituting these electrophotographic photoreceptors is usually formed by applying a coating solution containing a photoconductive substance, a binder resin, etc. on a substrate by dip coating, spray coating, nozzle coating, bar coating, roll coating, blade It is formed by coating by coating or the like. In these layer forming methods, a known method such as coating is applied as a coating solution obtained by dissolving a substance contained in a layer in a solvent.

  Examples of the binder resin for the photosensitive layer include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, thermoplastic resins such as polycarbonate, polyester, polysulfone, phenoxy, epoxy, and silicone resin, and various kinds of heat. A curable resin is 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). Further, when a polyarylate resin using a dihydric phenol component having a specific structure is used as a binder resin, the stability of the coating solution used for producing the electrophotographic photosensitive member is improved, and the electrophotographic photosensitive member machine is further improved. It has been reported that the mechanical strength and wear resistance are improved (see Patent Document 5 and Patent Document 6).

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

  By the way, the conventional electrophotographic photosensitive member as described above is worn and scratched on the surface of the electrophotographic photosensitive member due to practical loads such as development with toner, friction with paper, and friction with a cleaning member (blade). The present situation is that the printing performance is limited in practical use.

For example, when a commercially available polyarylate resin “U-polymer” is improved in terms of wear resistance and sensitivity, the stability of the coating solution prepared by dissolving this resin is low, and coating production is difficult. There is. In addition, by using a polyarylate resin having a specific structure, solubility, solution stability, mechanical strength, and the like can be improved, but there are insufficient electrical properties, particularly responsiveness. Even when a polyarylate copolymer using bis (4-hydroxy-3,5-dimethylphenyl) methane and 2,2-bis (4-hydroxyphenyl) propane is used as the bisphenol component, the mechanical properties are slightly improved. As can be seen, sufficient performance cannot be obtained in terms of electrical characteristics, sensitivity, and responsiveness, and adhesion to the substrate is often insufficient.
Therefore, as a resin used for an electrophotographic photosensitive member, a binder resin having high mechanical strength, high solubility in a solvent, excellent liquid stability, and excellent adhesiveness and responsiveness is desired. Currently.

The present invention has been made to solve such problems.
That is, an object of the present invention is an electron containing a binder resin that has excellent wear resistance against a practical load, excellent electrical characteristics while maintaining high mechanical strength, and high stability of a coating solution for forming a photosensitive layer. It is to provide a photographic photoreceptor.

  Therefore, as a result of intensive studies, the present inventors have sufficient mechanical properties by including a polyester resin having a specific chemical structure in the photosensitive layer, and are higher than the solvent used in the coating solution for forming the photosensitive layer. It has been found that an electrophotographic photosensitive member having solubility and excellent coating solution stability and excellent electrical characteristics can be obtained, and the present invention has been completed based on such knowledge.

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

(In formula (1), 0.5 <{a / (a + b)} <1, A is a divalent phenol residue having a molecular weight of 250 or less, B is a divalent phenol residue, and X is the following formula (2) And Y is a divalent carboxylic acid residue.)

(In Formula (2), R ¹ and R ² 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) .)

  The invention according to claim 2 is the electrophotographic photosensitive member according to claim 1, wherein A in the formula (1) has a structure represented by the following formula (3).

(In Formula (3), R ³ is a hydrogen atom or an alkyl group, and R ⁴ and R ⁵ are each independently an alkyl group.)

  The invention according to claim 3 is the electrophotographic photosensitive member according to claim 1 or 2, wherein B in the formula (1) has a structure represented by the following formula (4).

(In Formula (4), R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group, or a substituent that may be bonded to each other to form a cyclic structure, and R ⁸ and R ⁹ are each independently And n ² and m ² are each independently an integer of 1 to 4.)

  The invention according to claim 4 is the electrophotographic photoreceptor according to any one of claims 1 to 3, wherein the photosensitive layer further contains a compound represented by the following formula (5). .

(In Formula (5), Ar ^{1 to} Ar ⁶ each independently represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. M ³ , m ⁴ each independently represents 0 or 1. Q represents a direct bond or a divalent residue, R ^{10 to} R ¹⁷ each independently represents a hydrogen atom, 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, each of n ^{3 to} n ⁶ independently represents an integer of 0 to 4. Ar ^{1 to} Ar ⁶ may be bonded to each other to form a ring structure.)

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

  The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

(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.

(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 the formula (1), A is a divalent phenol residue having a molecular weight of 250 or less. This divalent phenol residue indicates a structure in which two hydrogen atoms are removed from two hydroxyl groups of a divalent phenol compound used as a raw material when producing a polyester resin. The molecular weight of A is 250 or less, but 245 or less and 180 or more are particularly preferable.

Specific examples of the dihydric phenol compound for deriving the dihydric phenol residue represented by A in the formula (1) include 4,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy- 1,1′-biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxy-1,1′-biphenyl, bis (4-hydroxyphenyl) methane, (2-hydroxyphenyl) ( 4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) ketone Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (4-hydroxy-3-methylphenyl) methane, 1,1 Bis (4-hydroxy-3-methylphenyl) ethane and the like. These dihydric phenol components can be used in combination.
Moreover, it is preferable that A in said Formula (1) is a compound which has a structure shown to following formula (3).

In formula (3), R ³ is a hydrogen atom or an alkyl group, and R ⁴ and R ⁵ are each independently an alkyl group.

Examples of R ³ in the formula (3) include a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and a divalent phenol compound that derives a divalent phenol residue represented by the formula (3). In view of the simplicity of production, R ³ is 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).

Examples of R ⁴ and R ⁵ in formula (3) include alkyl groups having 1 to 6 carbon atoms, but in the production of a divalent phenol compound that derives a divalent phenol residue represented by formula (3). In view of the simplicity, R ³ is preferably an alkyl group having 4 or less carbon atoms, and particularly preferably an alkyl group having 1 carbon atom (methyl group).

  Specific examples of formula (3) include bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, and the like. These dihydric phenol components can be used in combination.

In formula (1), B is a divalent phenol residue. This divalent phenol residue, like A, has a structure in which two hydrogen atoms are removed from two hydroxyl groups of a divalent phenol compound used as a raw material when producing a polyester resin. The structure of B is not particularly limited as long as it is a divalent phenol residue, and any structure can be used as long as it is a structure possessed by a known resin usually used for binding a photosensitive layer of an electrophotographic photoreceptor. It doesn't matter.
Specific examples of the dihydric phenol compound for deriving the dihydric phenol residue represented by B in the formula (1) include 4,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy- 1,1′-biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxy-1,1′-biphenyl, bis (4-hydroxyphenyl) methane, (2-hydroxyphenyl) ( 4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4- Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) methane, -Bis (4-hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis ( 4-hydroxy-3-methylphenyl) ether, 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, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane and the like can be mentioned. These dihydric phenol components can be used in combination.
Moreover, it is preferable that B in the said Formula (1) is a compound which has a structure shown in following formula (4).

In formula (4), R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group, or a substituent that may be bonded to each other to form a cyclic structure, and R ⁸ and R ⁹ are each independently An alkyl group, and n ² and m ² are each independently an integer of 1 to 4;

Examples of R ⁶ and R ^{7 in} formula (4) include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclohexane ring bonded to each other. In consideration of the convenience in production of the dihydric phenol compound derived from the dihydric phenol residue represented by the formula (4), R ⁶ and R ⁷ may be a hydrogen atom, an alkyl group having 4 or less carbon atoms, or A bonded cyclohexane ring is preferable, and a hydrogen atom, an alkyl group having 1 carbon atom (methyl group), or a cyclohexane ring bonded to each other is particularly preferable.

As R < ⁸ > and R < ⁹ > in Formula (4), a C1-C6 alkyl group is mentioned. In view of the convenience in production of the dihydric phenol compound for deriving the dihydric phenol residue represented by the formula (4), R ⁸ and R ⁹ are preferably alkyl groups having 4 or less carbon atoms, The alkyl group (methyl group) is particularly preferable.

N ² and m ² in the formula (4) are each independently an integer of 1 to 4. Considering the convenience in production of the dihydric phenol compound for deriving the dihydric phenol residue represented by the formula (4), n ² and m ² are preferably 2 or less, particularly preferably 1.

Specific examples of the formula (4) include bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxy- 3-methylphenyl) propane, 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, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane and the like. These dihydric phenol components can be used in combination.
X in the formula (1) is a divalent carboxylic acid residue having a structure represented by the following formula (2).

In Formula (2), R ¹ and R ² 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. is there.

Examples of R ¹ and R ^{2 in} formula (2) include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms; an aryl group such as a phenyl group and a naphthyl group; a fluorine atom, a chlorine atom, a bromine atom, and iodine. Halogen groups such as atoms; alkoxy groups such as methoxy, ethoxy and butoxy groups. In view of the convenience in the production of the divalent carboxylic acid compound derived from the divalent carboxylic acid residue represented by the formula (2), R ¹ and R ² are 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 (2) include, for example, diphenyl ether-2,2′-dicarboxylic acid, diphenyl ether-2,4′-dicarboxylic acid, 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 (2) can be used in combination with a plurality of compounds as necessary.

  Y in Formula (1) is a divalent carboxylic acid residue. Specific examples of the divalent carboxylic acid compound that induces Y 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, 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 ether Ether 2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid. Considering the simplicity of production of the dicarboxylic acid component, isophthalic acid, terephthalic acid, and diphenyl ether-4,4'-dicarboxylic acid are particularly preferable. The compounds exemplified as Y in these formulas (1) can be used in combination of a plurality of compounds as necessary.

  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.

(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.

(Conductive support)
Examples of the material for the conductive support used in the electrophotographic photosensitive member to which this embodiment is applied include metal materials such as aluminum, aluminum alloy, stainless steel, copper, and nickel; metal, carbon, tin oxide, and the like. Resin material to which conductivity is imparted by adding conductive powder; resin, glass, paper, etc. deposited or coated with a conductive material such as aluminum, nickel, ITO (indium-tin oxide) on its surface It is done.

  Examples of the form of the conductive support include a drum shape, a sheet shape, and a belt shape. Alternatively, a conductive material having an appropriate resistance value may be coated on a conductive support using a metal material for the purpose of controlling conductivity, surface properties, etc. or covering defects.

  When a metal material such as an aluminum alloy is used as the conductive support, anodization treatment, chemical conversion film treatment, or the like may be performed in advance. In addition, when performing an anodizing process, it is desirable to perform a sealing process by a well-known method.

  The surface of the conductive support may be smooth, or may be roughened by a special cutting method or polishing treatment, or by mixing particles having an appropriate particle size with the material constituting the conductive support. It may be a simplified one. In order to reduce the cost, it is possible to use the drawing tube as it is without performing the cutting process.

(Undercoat layer)
In the electrophotographic photosensitive member to which this exemplary embodiment is applied, an undercoat layer may be provided between the conductive support and the photosensitive layer in order to improve adhesion and blocking properties. As the undercoat layer, for example, a resin, a resin in which particles such as a metal oxide are dispersed, or the like is used. Examples of the metal oxide particles used for the undercoat layer include, for example, metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, and calcium titanate. And metal oxide particles containing a plurality of metal elements such as strontium titanate and barium titanate. As these metal oxide particles, only one type of particle may be used, or a plurality of types of particles may be mixed and used.

  Among these, 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 silicone. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. A thing of a several crystalline state may be contained. In addition, various particle diameters of the metal oxide particles can be used. Among these, from the viewpoint of characteristics and liquid stability, the average primary particle diameter is preferably 10 nm or more and 100 nm or less, and particularly preferably It is 10 nm or more and 50 nm or less.

  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 phenoxy resin, epoxy resin, polyvinyl pyrrolidone resin, polyvinyl alcohol resin, casein, polyacrylic resin, celluloses, gelatin, starch, polyurethane resin, polyimide resin, polyamide resin, etc. alone Alternatively, it can be used in a cured form together with a curing agent. Among these, alcohol-soluble copolymerized polyamide, modified polyamide, and the like are preferable because they exhibit good dispersibility and coating properties.

  The compounding composition ratio of the metal oxide particles with respect to the binder resin is not particularly limited, but it is usually preferable in the range of 10% by weight to 500% by weight in terms of stability of the dispersion and coatability. The thickness of the undercoat layer is not particularly limited, but is preferably 0.1 μm to 20 μm in view of the photoreceptor characteristics and applicability. Further, a known antioxidant or the like may be added to the undercoat layer.

(Photosensitive layer)
Other components contained in the photosensitive layer of the electrophotographic photoreceptor to which the exemplary embodiment is applied will be described.

(Charge generation layer)
When the electrophotographic photosensitive member to which the exemplary embodiment is applied is a laminated type photosensitive member, the charge generating layer constituting the photosensitive layer contains a charge generating substance. Examples of charge generation materials include selenium and its alloys, cadmium sulfide, and other inorganic photoconductive materials; phthalocyanine pigments, azo pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, benzimidazole pigments And various photoconductive materials such as organic pigments. Among these, organic pigments, phthalocyanine pigments, and azo pigments are particularly preferable.

  The fine particles of these charge generation layer materials are, for example, polyvinyl acetate, polyacrylate, polymethacrylate, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, cellulose. Used in a form bound with various binder resins such as esters and cellulose ethers.

  Although the usage-amount of a charge generation substance is not specifically limited, Usually, it is used in 30 weight part-500 weight part with respect to 100 weight part of binder resin. The thickness of the charge generation layer is usually 0.1 μm to 1 μm, preferably 0.15 μm to 0.6 μm.

  When a phthalocyanine compound is used as the charge generation material, specifically, a metal such as metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, or an oxide or halide thereof. Phthalocyanines are used.

  Examples of the ligand to a trivalent or higher metal atom include an oxygen atom, a chlorine atom, a hydroxyl group, an alkoxy group, and the like. In particular, highly sensitive X-type, τ-type metal-free phthalocyanine, A-type, B-type, D-type titanyl phthalocyanine, vanadyl phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, and the like are suitable.

  Of the crystal forms of titanyl phthalocyanine mentioned here, A type and B type are described in W.W. It has been shown by Heller et al. As phase I and phase II, respectively (Zeit. Kristallogr. 159 (1982) 173), and type A is known as a stable type. The D type is a crystal type showing a clear peak at a diffraction angle 2θ ± 0.2 ° of 27.3 ° in powder X-ray diffraction using CuKα rays. As the phthalocyanine compound, only a single compound may be used, or several mixed states may be used. As the mixed state in the phthalocyanine compound or the crystalline state here, the respective constituent elements may be mixed and used later, or a mixed state is generated in the production / treatment process of the phthalocyanine compound such as synthesis, pigmentation, and crystallization. It can also be a As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known.

(Charge transport layer)
When the electrophotographic photosensitive member to which this exemplary embodiment is applied is a laminated type photosensitive member, the charge transporting layer constituting the photosensitive layer contains a charge transporting substance. 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 quinones such as diphenoquinone; carbazole derivatives, indoles Heterocyclic compounds such as derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, oxadiazole derivatives, pyrazoline derivatives, thiadiazole derivatives; aniline derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine compounds or these compounds 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, a carbazole derivative, a hydrazone derivative, an aromatic amine derivative, a stilbene derivative, a butadiene derivative, and a combination of these derivatives are preferable, and a combination of an aromatic amine derivative, a stilbene derivative, and a butadiene derivative is combined. Is preferred.
Among charge transport materials, compounds having a structure represented by the following formula (5) are preferably used.

In formula (5), Ar ^{1 to} Ar ⁶ each independently represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. m ³ and m ⁴ each independently represents 0 or 1. Ar ⁵ in the case of m ³ = 0 and Ar ^{6 in} the case of m ⁴ = 0 each have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It may be a monovalent heterocyclic group. Ar ⁵ in the case of m ³ = 1 and Ar ^{6 in} the case of m ⁴ = 1 each have an alkylene group that may have a substituent, an arylene group that may have a substituent, or a substituent. The divalent heterocyclic group which may be sufficient. Q represents a direct bond or a divalent residue. R ^{10 to} R ¹⁷ 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 ³ ~n ⁶ represents an integer of 0 to 4 each independently. Ar ^{1 to} Ar ⁶ may be bonded to each other to form a cyclic structure.

Further, in formula (5), R ^{10 to} R ¹⁷ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aralkyl group which may be substituted, or a heterocyclic group which may have a substituent.

  In formula (5), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, and a cyclohexyl group. Of these, an alkyl group having 1 to 6 carbon atoms is preferred. When the alkyl group has an aryl substituent, examples thereof include a benzyl group and a phenethyl group, and an alkyl group having 7 to 12 carbon atoms is preferable.

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 12 carbon atoms is preferable.
The 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.
In R ^{10 to} R ¹⁷ , the most preferable are a methyl group and a phenyl group.

In formula (5), Ar ^{1 to} Ar ⁶ each independently represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. m ³ and m ⁴ each independently represents 0 or 1. Ar ⁵ in the case of m ³ = 0 and Ar ^{6 in} the case of m ⁴ = 0 each have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Each represents a monovalent heterocyclic group, Ar ⁵ in the case of m ³ = 1, and Ar ⁶ in the case of m ⁴ = 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. Among these, an aryl group having 6 to 14 carbon atoms is preferable.
Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is preferable.

In the formula (5), 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 are Ar ¹ and Ar ² are phenylene groups, and Ar ³ is a phenyl group.

Of the groups represented by R ^{10 to} R ¹⁷ and Ar ^{1 to} Ar ⁶ in formula (5), 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, sec-butyl group, 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 An aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group; an aryloxy group such as a phenoxy group or a triloxy group; an arylalkoxy group such as a benzyloxy group or a phenethyloxy group; an aryl group such as a phenyl group or a naphthyl group; Aryl vinyl such as styryl group and naphthyl vinyl group Acyl groups such as acetyl group and benzoyl group; dialkylamino groups such as dimethylamino group and diethylamino group; diarylamino groups such as diphenylamino group and dinaphthylamino group; diaralkyls such as dibenzylamino group and diphenethylamino group; An amino group; a diheterocyclic amino group such as a dipyridylamino group or a dithienylamino group; a substituted amino group such as a diallylamino group or a combination of substituents of the amino group described above; a cyano group, a nitro group, a hydroxyl group; Etc. 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, and an alkylthio group having 1 to 6 carbon atoms. , An aryloxy group having 6 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a halogen atom, and having 1 to 6 carbon atoms. An alkyl group and a phenyl group are more preferable, and a methyl group and a phenyl group are particularly preferable.

In formula (5), n ^{3 to} n ⁶ each independently represents an integer of 0 to 4, preferably 0 to 2, and particularly preferably 1. m ³ and m ⁴ represent 0 or 1, and 0 is preferable.

  In formula (5), Q represents a direct bond or a divalent residue, and a preferable divalent residue is a group 16 atom, an alkylene which may have a substituent, or a substituent. A good arylene group, an optionally substituted cycloalkylidene group, or a group in which these are bonded to each other, for example, [—O—Z—O—], [—Z—O—Z—], [—S—Z -S-], [-ZZ-] and the like (provided that O is an oxygen atom, S is a sulfur atom, and Z may have an arylene group or a substituent which may have a substituent). Represents an alkylene group).

  As an alkylene group which comprises Q, a C1-C6 thing is preferable, and a methylene group and ethylene group are still more preferable especially. Moreover, as a cycloalkylidene group, a C5-C8 thing is preferable and especially a cyclopentylidene group and a cyclohexylidene group are still more preferable. 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.

  In addition, these alkylene group, arylene group, and cycloalkylidene group may have a substituent. Preferred examples of the substituent include a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an aryl having 6 to 14 carbon atoms. Groups.

  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-2002-275133, 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.

  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.

(Dispersion (single layer) photosensitive layer)
In the case of a dispersion type photosensitive layer, the above-described charge generating material is dispersed in a charge transport medium comprising the above-described binder resin and a charge transport material. The particle size of the charge generation material needs to be sufficiently small, and is preferably 1 μm or less, more preferably 0.5 μm or less. If the amount of the charge generating material dispersed in the dispersion type photosensitive layer is excessively small, sufficient sensitivity cannot be obtained, and if it is excessively large, there are problems such as a decrease in chargeability and a decrease in sensitivity. The amount of the charge generating material used is preferably in the range of 0.5 wt% to 50 wt%, more preferably 1 wt% to 20 wt%.

  The film thickness of the dispersion type photosensitive layer is usually 5 μm to 50 μm, more preferably 10 μm to 45 μm. Also in this case, known plasticizers for improving film formability, flexibility, mechanical strength, additives for suppressing residual potential, dispersion aids for improving dispersion stability, coatability A leveling agent and a surfactant, for example, silicone oil, fluorine oil, and other additives may be added to improve the above. On the dispersion type photosensitive layer, a protective layer may be provided for the purpose of preventing the wear of the dispersion type photosensitive layer or preventing or reducing the degradation of the dispersion type photosensitive layer due to discharge products generated from a charger or the like. . Further, for the purpose of reducing frictional resistance and wear on the surface of the electrophotographic photosensitive member, the surface layer may contain fluorine resin, silicone resin or the like. Moreover, the particle | grains which consist of these resin, and the particle | grains of an inorganic compound may be included.

(Method for preparing electrophotographic photoreceptor)
The method for preparing the electrophotographic photoreceptor to which the exemplary embodiment is applied is not particularly limited, but usually a photosensitive layer containing a polyester resin having a repeating structure represented by the formula (1) on a conductive support. For example, the forming coating solution is applied by a known method such as a dip coating method, a spray coating method, a nozzle coating method, a bar coating method, a roll coating method, or a blade coating method. Among these, the dip coating method is preferable because of its high productivity.

Next, an example of an image forming apparatus using the electrophotographic photoreceptor to which the exemplary embodiment is applied will be described. FIG. 1 is a diagram illustrating an image forming apparatus. The image forming apparatus 10 shown in FIG. 1 includes an electrophotographic photoreceptor 1 in which a photosensitive layer containing a polyester resin having a repeating structure represented by the above-described formula (1) is provided on a predetermined conductive support. A charging device 2 comprising a charging roller for charging the electrophotographic photosensitive member 1, an exposure device 3 for forming an electrostatic latent image on the photosensitive surface of the electrophotographic photosensitive member 1, and a toner (T And a developing device 4 for feeding
Furthermore, a transfer device 5 that applies a predetermined voltage value (transfer voltage) with a polarity opposite to the charging potential of the toner (T) and transfers the toner image formed on the electrophotographic photosensitive member 1 to the recording paper (P); A cleaning device 6 that scrapes and collects residual toner attached to the electrophotographic photoreceptor 1 and a fixing device 7 that fixes the toner image transferred to the recording paper (P) are provided.

The electrophotographic photoreceptor 1 has a drum shape in which a photosensitive layer containing the above-described polyester resin is provided on the surface of a cylindrical conductive support.
The charging device 2 has a roller-type charging roller. As the charging device 2, for example, a corona charging device such as corotron or scorotron, a contact charging device such as a charging brush, and the like are often used. In many cases, the electrophotographic photoreceptor 1 and the charging device 2 are designed to be removable from the main body of the image forming apparatus 10 as a cartridge having both of them (hereinafter also referred to as a photoreceptor cartridge). ing. For example, when the electrophotographic photoreceptor 1 or the charging device 2 deteriorates, the photoreceptor cartridge can be removed from the main body of the image forming apparatus 10 and another new photosensitive body cartridge can be mounted on the main body of the image forming apparatus 10. (Not shown).

  The type of the exposure apparatus 3 is not particularly limited as long as it can 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. The exposure can also be performed by a photoreceptor internal exposure method. The light used for the exposure is not particularly limited, and examples thereof include monochromatic light having a wavelength of 780 nm, monochromatic light having a wavelength slightly shorter than 600 nm to 700 nm, and monochromatic light having a short wavelength of 380 nm to 500 nm.

  The developing device 4 includes a developing tank 41 in which toner (T) is stored. Further, the developing tank 41 carries an agitator 42 for stirring the toner (T) and the stored toner (T). Then, a supply roller 43 to be supplied to a developing roller 44, which will be described later, and the electrophotographic photosensitive member 1 and the supply roller 43 are brought into contact with each other and carry the toner (T) supplied by the supply roller 43 and A developing roller 44 that is brought into contact with the surface and a regulating member 45 that is in contact with the developing roller 44 are provided. If necessary, a replenishing device (not shown) for replenishing toner (T) from a container such as a bottle or cartridge to the developing tank 41 may be attached. The type of the developing device 4 is not particularly limited, and any device such as a dry development method such as a cascade phenomenon, a one-component conductive toner phenomenon, a two-component magnetic brush development, or a wet development method can be used.

  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 supply roller 43 is formed from, for example, a conductive sponge. 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 a metal roll with a silicone resin, a urethane resin, a fluororesin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary. The regulating member 45 is formed of a resin blade such as a silicone resin or a urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating a metal blade with a resin.

  The regulating member 45 is in contact with the developing roller 44 and 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 charging the toner (T) by frictional charging with the toner (T). The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown).

  The type of the toner (T) is not particularly limited, but normally, besides a powdery toner, a polymerized toner using a suspension polymerization method, an emulsion polymerization method, or the like can be used. In particular, when a polymerized toner is used, a toner having a small particle diameter of about 4 to 8 μm is preferable, and the toner (T) particles have a variety of shapes ranging from a nearly spherical shape to those outside a potato-like spherical shape. Can be used for The polymerized toner is excellent in charging uniformity and transferability and is suitably used for high image quality.

  In many cases, the toner (T) is stored in the toner cartridge and designed to be removable from the main body of the image forming apparatus 10, and when the toner (T) in the used toner cartridge is used up, The toner cartridge can be removed from the main body of the image forming apparatus 10 and another new toner cartridge can be mounted. Further, a cartridge provided with the electrophotographic photoreceptor 1, the charging device 2, and the toner (T) can be used.

  Although not shown, 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 type of the transfer device 5 is not particularly limited. For example, an apparatus using an arbitrary method such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method is used. Can do.

  The cleaning device 6 is not particularly limited, and any cleaning device such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, or the like can be used.

  The fixing device 7 includes an upper fixing member 71 made of a fixing roller, a lower fixing member 72 made of a fixing roller in contact with the upper fixing member 71, and a heating device 73 provided inside the upper fixing member 71. ing. The heating device 73 may be provided inside the lower fixing member 72. The upper fixing member 71 or the lower fixing member 72 is a known heat fixing member such as a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicone rubber, a fixing roll in which Teflon (registered trademark) resin is coated, or a fixing sheet. Can be used. Further, the upper fixing member 71 or the lower fixing member 72 may be configured to supply a release agent such as silicone oil in order to improve the releasability, or may be configured to forcibly apply pressure to each other by a spring or the like. . The type of the fixing device 7 is not particularly limited, and for example, a fixing device using an arbitrary method such as heat roller fixing, flash fixing, oven fixing, pressure fixing, or the like can be provided.

Next, the operation of the image forming apparatus 10 will be described.
The surface (photosensitive surface) of the electrophotographic photosensitive member 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 electrophotographic photosensitive member 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.
Next, development of the electrostatic latent image formed on the photosensitive surface of the electrophotographic photoreceptor 1 is performed by the developing device 4. That is, the developing device 4 thins the toner (T) supplied by the supply roller 43 with a regulating member 45 such as a developing blade and also has a predetermined polarity (here, the same as the charging potential of the electrophotographic photosensitive member 1). Polarity and negative polarity) are triboelectrically charged, conveyed while being carried on the developing roller 44, and brought into contact with the surface of the electrophotographic photosensitive member 1.

  When the charged toner (T) carried on the developing roller 44 comes into contact with the surface of the electrophotographic photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the electrophotographic photoreceptor 1. Subsequently, the toner image is transferred to the recording paper (P) by the transfer device 5. Thereafter, the toner (T) remaining on the photosensitive surface of the electrophotographic photosensitive member 1 without being transferred is removed by the cleaning device 6. When the toner (T) 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 (T) is heated to a molten state, After passing, it is cooled and the toner (T) is fixed on the recording paper (P), and a final image is obtained.

  In addition to the above-described configuration, the image forming apparatus 10 may have a configuration capable of performing a static elimination process, for example. The neutralization process is a process of neutralizing the electrophotographic photosensitive member 1 by exposing the electrophotographic photosensitive member 1, 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 10 may be further modified. For example, the image forming apparatus 10 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 configuration using the toner (T) may be used.

  Hereinafter, the present embodiment will be described more specifically based on examples. Note that this embodiment is not limited to the examples. In the examples and comparative examples, parts and% are based on weight unless otherwise specified.

(1) Viscosity average molecular weight Flowing down of the resin in dichloromethane (concentration: C = 6.00 g / L) at 20.0 ° C. using an Ubbelohde capillary viscometer (dichloromethane flow time t0: 135.40 seconds) The time (t) was measured, and the viscosity average molecular weight (Mv) of the resin was calculated based on the following formula. η _sp = (t / t ₀ ) −1
X = (0.2092 × η _sp ) +1.0734
Y = 100 × η _sp / C
C = 6.00
η = Y / X
Mv = 3207 × (η ^1.205 )

(2) Preparation of photoreceptor sheet 10 parts by weight of oxytitanium phthalocyanine and 150 parts by weight of 4-methoxy-4-methyl-2-pentanone are mixed and pulverized and dispersed in a sand grind mill to obtain a pigment dispersion. Manufactured. Oxytitanium phthalocyanine has Bragg angles (2θ ± 0.2) of 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.5 ° in X-ray diffraction by CuKα ray. Strong diffraction peaks are shown at 1 °, 20.8 °, 23.3 °, 26.3 °, and 27.1 °.

  To this pigment dispersion, 50 parts by weight of a 5 wt% 1,2-dimethoxyethane solution of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name Denkabutyral # 6000C), 50 parts by weight of a 5% by weight 1,2-dimethoxyethane solution of PKHH) is added, and an appropriate amount of 1,2-dimethoxyethane is added to prepare a coating solution for forming a charge generation layer having a solid content concentration of 4.0%. did. This charge generation layer forming coating solution was applied on a polyethylene terephthalate sheet having aluminum deposited on the surface so that the film thickness after drying was 0.4 μm and dried to provide a charge generation layer.

  Next, a coating solution for forming a charge transport layer is applied onto the charge generation layer so that the film thickness after drying is 20 μm, and dried at 125 ° C. for 20 minutes to form a charge transport layer. A body sheet was prepared. The coating solution for forming the charge transport layer comprises 100 parts by weight of each resin shown in Tables 1 and 2 described later, 8 parts by weight of an antioxidant (Irganox 1076), 0.03 parts by weight of silicone oil as a leveling agent, and 50 parts by weight of the charge transport material produced by the method described in Example 1 of JP-A No. 2002-080432, comprising isomers mainly composed of the charge transport material (1) having the chemical structure shown below, was added to tetrahydrofuran. / Toluene mixed solvent (tetrahydrofuran 80 wt%, toluene 20 wt%) 640 parts by weight was prepared.

(3) Electrical characteristics test Using an electrophotographic characteristic evaluation apparatus (basic and applied electrophotographic technology, edited by the Electrophotographic Society, Corona, pages 404 to 405) based on the Electrophotographic Society measurement standard, The prepared photosensitive sheet is affixed to an aluminum drum to form a cylinder, and the aluminum drum and the aluminum base of the photosensitive sheet are connected to each other. Then, the drum is rotated at a constant rotational speed to charge, expose, and potential. An electrical property evaluation test was performed by a cycle of measurement and static elimination.
The initial surface potential was −700 V, the exposure light was 780 nm, the neutralization light was 660 nm, and the surface potential (VL) was measured when the exposure light was irradiated at 2.4 μJ / cm ² . In the VL measurement, the time required from the exposure to the potential measurement was 139 ms. The measurement environment was a temperature of 25 ° C. and a relative humidity of 50% (NN environment), and a temperature of 5 ° C. and a relative humidity of 10% (LL environment). The smaller the absolute value of the VL value, the better the response (unit: -V).

(4) Wear test A photoconductor sheet prepared in advance was cut into a circle having a diameter of 10 cm to prepare a test piece, and this was subjected to a wear test using a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.). The test condition is to compare the weight before and after the test after 1000 rotations with no load (wear wheel's own weight) using wear wheel CS-10F in an atmosphere of temperature 23 ° C and relative humidity 50%. It was measured by. The smaller the amount of wear, the better the wear resistance (unit: mg).

(5) Production Example of Polyester Resin A resin was produced by the following method.
Production Example 1 (Resin 1)
Sodium hydroxide (10.81 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, bis (4-hydroxyphenyl) methane (hereinafter referred to as BP-a), (2-hydroxyphenyl) (4-hydroxyphenyl) methane (hereinafter referred to as BP-b), bis (2-hydroxyphenyl) methane (hereinafter referred to as “BP”) BP-c) (mixing ratio, BP-a: BP-b: BP-c = about 35:48:17 (hereinafter referred to as BP-d)) (14.28 g, divalent phenol residue in the repetitive structure After adding, stirring and dissolving the base molecular weight 198) and bis (4-hydroxy-3-methylphenyl) methane (hereinafter BP-e) (6.98 g, divalent phenol residue molecular weight 226 in the repeating structure) The aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2699 g) and p- (tert-butyl) phenol (0.5662 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (30.65 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.92 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 1. The obtained resin 1 had a viscosity average molecular weight of 25,000. The repeating structure of Resin 1 is shown below.

Production Example 2 (Resin 2)
Sodium hydroxide (9.06 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-d (14.07 g, divalent phenol residue molecular weight 198 in the repetitive structure) and 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as BP-f) (7 .72 g, divalent phenol residue molecular weight 254) in the repeating structure was added, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2687 g) and p- (tert-butyl) phenol (0.7236 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.75 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (1.29 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 2. The obtained resin 2 had a viscosity average molecular weight of 25,000. The repeating structure of Resin 2 is shown below.

Production Example 3 (Resin 3)
Sodium hydroxide (10.70 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, BP-a (14.15 g, divalent phenol residue molecular weight 198 in the repeating structure) and 1,1-bis (4-hydroxy-3-methylphenyl) ethane (hereinafter referred to as BP-g) (7 .34 g, divalent phenol residue molecular weight 240) in the repetitive structure was added, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2674 g) and p- (tert-butyl) phenol (0.5609 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (30.36 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.88 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 3. The obtained resin 3 had a viscosity average molecular weight of 44,800. The repeating structure of resin 3 is shown below.

Production Example 4 (Resin 4)
Sodium hydroxide (10.71 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-a (14.16 g, divalent phenol residue molecular weight 198 in the repeating structure) and BP-f (7.77 g, divalent phenol residue molecular weight 254 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2676 g) and p- (tert-butyl) phenol (0.5614 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.78 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.89 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 4. The obtained resin 4 had a viscosity average molecular weight of 51,600. The repeating structure of the resin 4 is shown below.

Production Example 5 (Resin 5)
Sodium hydroxide (10.71 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, BP-a (14.16 g, divalent phenol residue molecular weight 198 in the repetitive structure) and bis (4-hydroxy-3,5-dimethylphenyl) methane (hereinafter referred to as BP-h) (7.77 g) After adding, stirring and dissolving the divalent phenol residue molecular weight 254) in the repeating structure, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2676 g) and p- (tert-butyl) phenol (0.5614 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.78 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.89 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 5. The obtained resin 5 had a viscosity average molecular weight of 40,600. The repeating structure of the resin 5 is shown below.

Production Example 6 (Resin 6)
Sodium hydroxide (10.61 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-a (14.03 g, divalent phenol residue molecular weight 198 in the repeating structure) and 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane (hereinafter referred to as BP-i). (8.12 g, divalent phenol residue molecular weight 268 in the repetitive structure) was added, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2651 g) and p- (tert-butyl) phenol (0.5561 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.50 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.85 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 6. The obtained resin 6 had a viscosity average molecular weight of 52,500. The repeating structure of the resin 6 is shown below.

Production Example 7 (Resin 7)
Sodium hydroxide (10.52 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-a (13.90 g, divalent phenol residue molecular weight 198 in the repeating structure) and 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane (hereinafter referred to as BP-j) After adding, stirring and dissolving (8.46 g, divalent phenol residue molecular weight 282 in the repetitive structure), this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2626 g) and p- (tert-butyl) phenol (0.5510 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.23 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.81 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 7. The resulting resin 7 had a viscosity average molecular weight of 48,200. The repeating structure of the resin 7 is shown below.

Production Example 8 (Resin 8)
Sodium hydroxide (10.43 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. There, BP-a (13.79 g, divalent phenol residue molecular weight 198 in the repeating structure) and 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (hereinafter referred to as BP-k) (8 .75 g of divalent phenol residue molecular weight 294) in the repetitive structure was added, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2606 g) and p- (tert-butyl) phenol (0.5466 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.00 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.78 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 8. The viscosity average molecular weight of the obtained resin 8 was 52,000. The repeating structure of the resin 8 is shown below.

Production Example 9 (Resin 9)
Sodium hydroxide (10.68 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, 1,1-bis (4-hydroxyphenyl) ethane (hereinafter referred to as BP-1) (15.10 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-e (6.90 g, repeating) After adding, stirring and dissolving the divalent phenol residue molecular weight 226) in the structure, this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2668 g) and p- (tert-butyl) phenol (0.5596 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.69 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.87 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 9. The obtained resin 9 had a viscosity average molecular weight of 56,500. The repeating structure of the resin 9 is shown below.

Production Example 10 (Resin 10)
Sodium hydroxide (10.58 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-1 (14.96 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-g (7.25 g, divalent phenol residue molecular weight 240 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2643 g) and p- (tert-butyl) phenol (0.5544 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.41 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.84 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 10. The obtained resin 10 had a viscosity average molecular weight of 54,300. The repeating structure of the resin 10 is shown below.

Production Example 11 (Resin 11)
Sodium hydroxide (10.48 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-1 (14.83 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-f (7.60 g, divalent phenol residue molecular weight 254 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2618 g) and p- (tert-butyl) phenol (0.5493 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.14 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.80 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 11. The obtained resin 11 had a viscosity average molecular weight of 46,300. The repeating structure of the resin 11 is shown below.

Production Example 12 (Resin 12)
Sodium hydroxide (10.40 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-1 (14.71 g, divalent phenol residue molecular weight 212 in the repeating structure) and 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BP-m) (7.89 g, repeating) After adding, stirring, and dissolving the divalent phenol residue molecular weight 266) in the structure, this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2598 g) and p- (tert-butyl) phenol (0.5450 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.91 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.77 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 12. The obtained resin 12 had a viscosity average molecular weight of 45,200. The repeating structure of the resin 12 is shown below.

Production Example 13 (Resin 13)
Sodium hydroxide (10.39 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. BP-l (14.69 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-i (7.94 g, divalent phenol residue molecular weight 268 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2594 g) and p- (tert-butyl) phenol (0.5442 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.87 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.77 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 13. The obtained resin 13 had a viscosity average molecular weight of 55,600. The repeating structure of the resin 13 is shown below.

Production Example 14 (Resin 14)
Sodium hydroxide (10.29 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. BP-l (14.56 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-j (8.28 g, divalent phenol residue molecular weight 282 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2571 g) and p- (tert-butyl) phenol (0.5393 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.61 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.73 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 14. The resulting resin 14 had a viscosity average molecular weight of 45,100. The repeating structure of the resin 14 is shown below.

Production Example 15 (Resin 15)
Sodium hydroxide (10.21 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-1 (14.44 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-k (8.56 g, divalent phenol residue molecular weight 294 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2551 g) and p- (tert-butyl) phenol (0.5351 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.39 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.70 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 15. The obtained resin 15 had a viscosity average molecular weight of 59,700. The repeating structure of the resin 15 is shown below.

Production Example 16 (Resin 16)
Sodium hydroxide (10.45 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BP-n) (15.75 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-e (6.75 g, repeating) After adding, stirring and dissolving the divalent phenol residue molecular weight 226) in the structure, this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2610 g) and p- (tert-butyl) phenol (0.5476 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.05 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.79 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 16. The obtained resin 16 had a viscosity average molecular weight of 51,500. The repeating structure of the resin 16 is shown below.

Production Example 17 (Resin 17)
Sodium hydroxide (10.36 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-n (15.60 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-g (7.10 g, divalent phenol residue molecular weight 240 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2586 g) and p- (tert-butyl) phenol (0.5426 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.79 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.76 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 17. The obtained resin 17 had a viscosity average molecular weight of 47,000. The repeating structure of the resin 17 is shown below.

Production Example 18 (Resin 18)
Sodium hydroxide (10.26 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. BP-n (15.46 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-f (7.44 g, divalent phenol residue molecular weight 254 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2563 g) and p- (tert-butyl) phenol (0.5377 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.53 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.72 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 18. The obtained resin 18 had a viscosity average molecular weight of 43,500. The repeating structure of the resin 18 is shown below.

Production Example 19 (Resin 19)
Sodium hydroxide (10.26 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. BP-n (15.46 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-h (7.44 g, divalent phenol residue molecular weight 254 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2563 g) and p- (tert-butyl) phenol (0.5377 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.53 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.72 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 19. The resulting resin 19 had a viscosity average molecular weight of 48,400. The repeating structure of the resin 19 is shown below.

Production Example 20 (Resin 20)
Sodium hydroxide (10.18 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-n (15.34 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-m (7.73 g, divalent phenol residue molecular weight 266 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2543 g) and p- (tert-butyl) phenol (0.5335 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.31 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.69 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 20. The obtained resin 20 had a viscosity average molecular weight of 42,000. The repeating structure of the resin 20 is shown below.

Production Example 21 (Resin 21)
Sodium hydroxide (10.17 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-n (15.32 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-i (7.78 g, divalent phenol residue molecular weight 268 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2540 g) and p- (tert-butyl) phenol (0.5329 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.27 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.69 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 21. The obtained resin 21 had a viscosity average molecular weight of 48,800. The repeating structure of the resin 21 is shown below.

Production Example 22 (Resin 22)
Sodium hydroxide (10.00 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. BP-n (15.07 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-k (8.39 g, divalent phenol residue molecular weight 294 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2498 g) and p- (tert-butyl) phenol (0.5241 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (27.81 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.63 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 22. The obtained resin 22 had a viscosity average molecular weight of 45,400. The repeating structure of the resin 22 is shown below.

Production Example 23 (Resin 23)
Sodium hydroxide (10.66 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-e (16.06 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-a (6.04 g, divalent phenol residue molecular weight 198 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2662 g) and 2,3,5-trimethylphenol (0.5064 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.63 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.87 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 23. The resulting resin 23 had a viscosity average molecular weight of 51,800. The repeating structure of the resin 23 is shown below.

Production Example 24 (Resin 24)
Sodium hydroxide (10.54 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, BP-e (15.88 g, divalent phenol residue molecular weight 226 in the repeating structure) and bis (4-hydroxyphenyl) ether (hereinafter referred to as BP-o) (6.03 g, 2 in the repeating structure) After adding, stirring and dissolving the valent phenol residue molecular weight 200), this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2632 g) and 2,3,5-trimethylphenol (0.5006 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.89 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.82 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 24. The obtained resin 24 had a viscosity average molecular weight of 29,700. The repeating structure of the resin 24 is shown below.

Production Example 25 (Resin 25)
Sodium hydroxide (10.56 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-e (15.91 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-l (6.40 g, divalent phenol residue molecular weight 212 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2637 g) and 2,3,5-trimethylphenol (0.5017 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.36 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.83 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 25. The obtained resin 25 had a viscosity average molecular weight of 57,600. The repeating structure of the resin 25 is shown below.

Production Example 26 (Resin 26)
Sodium hydroxide (10.46 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, BP-e (15.76 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-n (6.76 g, divalent phenol residue molecular weight 226 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2613 g) and 2,3,5-trimethylphenol (0.4970 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.08 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.79 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 26. The obtained resin 26 had a viscosity average molecular weight of 59,400. The repeating structure of the resin 26 is shown below.

Production Example 27 (Resin 27)
Sodium hydroxide (10.37 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, BP-e (15.62 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-g (7.11 g, divalent phenol residue molecular weight 240 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2589 g) and 2,3,5-trimethylphenol (0.4925 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.82 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.76 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 27. The obtained resin 27 had a viscosity average molecular weight of 63,400. The repeating structure of the resin 27 is shown below.

Production Example 28 (Resin 28)
Sodium hydroxide (10.27 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-e (15.48 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-f (7.45 g, divalent phenol residue molecular weight 254 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2566 g) and 2,3,5-trimethylphenol (0.4880 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.56 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.73 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 28. The obtained resin 28 had a viscosity average molecular weight of 53,800. The repeating structure of the resin 28 is shown below.

Production Example 29 (Resin 29)
Sodium hydroxide (10.27 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-e (15.48 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-h (7.45 g, divalent phenol residue molecular weight 254 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2566 g) and 2,3,5-trimethylphenol (0.4880 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.56 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.73 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 29. The obtained resin 29 had a viscosity average molecular weight of 54,300. The repeating structure of the resin 29 is shown below.

Production Example 30 (Resin 30)
Sodium hydroxide (10.19 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. There, BP-e (15.36 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-m (7.74 g, divalent phenol residue molecular weight 266 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2546 g) and 2,3,5-trimethylphenol (0.4843 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.34 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.70 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 30. The resulting resin 30 had a viscosity average molecular weight of 49,300. The repeating structure of the resin 30 is shown below.

Production Example 31 (Resin 31)
Sodium hydroxide (10.18 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-e (15.34 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-i (7.79 g, divalent phenol residue molecular weight 268 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2543 g) and 2,3,5-trimethylphenol (0.4837 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.30 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.69 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 31. The obtained resin 31 had a viscosity average molecular weight of 56,200. The repeating structure of the resin 31 is shown below.

Production Example 32 (Resin 32)
Sodium hydroxide (8.83 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (16.68 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-d (5.91 g, divalent phenol residue molecular weight 198 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Subsequently, benzyltriethylammonium chloride (0.2605 g) and 2,3,5-trimethylphenol (0.4955 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.00 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (1.26 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 32. The obtained resin 32 had a viscosity average molecular weight of 48,600. The repeating structure of the resin 32 is shown below.

Production Example 33 (Resin 33)
Sodium hydroxide (10.43 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. BP-g (16.68 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-a (5.91 g, divalent phenol residue molecular weight 198 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Subsequently, benzyltriethylammonium chloride (0.2605 g) and 2,3,5-trimethylphenol (0.4955 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.00 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.78 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 33. The obtained resin 33 had a viscosity average molecular weight of 40,000. The repeating structure of the resin 33 is shown below.

Production Example 34 (Resin 34)
Sodium hydroxide (10.31 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (16.49 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-o (5.90 g, divalent phenol residue molecular weight 200 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2576 g) and 2,3,5-trimethylphenol (0.4900 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.26 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.74 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 34. The obtained resin 34 had a viscosity average molecular weight of 36,000. The repeating structure of the resin 34 is shown below.

Production Example 35 (Resin 35)
Sodium hydroxide (10.34 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (16.53 g, divalent phenol residue molecular weight 240 in the repeating structure) and 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl (hereinafter referred to as BP-) p) (6.26 g, molecular weight 212 of the divalent phenol residue in the repeating structure) was added, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2581 g) and 2,3,5-trimethylphenol (0.4910 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.73 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.75 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 35. The obtained resin 35 had a viscosity average molecular weight of 29,300. The repeating structure of the resin 35 is shown below.

Production Example 36 (Resin 36)
Sodium hydroxide (10.34 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (16.53 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-1 (6.26 g, divalent phenol residue molecular weight 212 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2581 g) and 2,3,5-trimethylphenol (0.4910 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.73 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.75 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 36. The obtained resin 36 had a viscosity average molecular weight of 43,900. The repeating structure of the resin 36 is shown below.

Production Example 37 (Resin 37)
Sodium hydroxide (10.24 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-g (16.38 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-n (6.61 g, divalent phenol residue molecular weight 226 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2558 g) and 2,3,5-trimethylphenol (0.4866 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.47 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.71 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 37. The obtained resin 37 had a viscosity average molecular weight of 47,900. The repeating structure of the resin 37 is shown below.

Production Example 38 (Resin 38)
Sodium hydroxide (10.24 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (16.25 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-e (6.56 g, divalent phenol residue molecular weight 226 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.
Then, benzyltriethylammonium chloride (0.2575 g) and 2,3,5-trimethylphenol (0.6785 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.46 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.71 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 38. The obtained resin 38 had a viscosity average molecular weight of 43,100. The repeating structure of the resin 38 is shown below.

Production Example 39 (Resin 39)
Sodium hydroxide (10.15 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. BP-g (16.23 g, divalent phenol residue molecular weight 240 in the repeating structure), 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxy-1,1′- Biphenyl (hereinafter referred to as BP-q) (6.96 g, molecular weight 240 of the divalent phenol residue in the repeating structure) was added, stirred and dissolved, and then the aqueous alkaline solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2535 g) and 2,3,5-trimethylphenol (0.4822 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.22 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.68 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 39. The obtained resin 39 had a viscosity average molecular weight of 45,800. The repeating structure of the resin 39 is shown below.

Production Example 40 (Resin 40)
Sodium hydroxide (10.06 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (15.97 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-f (7.24 g, divalent phenol residue molecular weight 254 in the repeating structure) were added and stirred. After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2529 g) and 2,3,5-trimethylphenol (0.6665 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (27.96 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.65 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 40. The obtained resin 40 had a viscosity average molecular weight of 38,000. The repeating structure of the resin 40 is shown below.

Production Example 41 (Resin 41)
Sodium hydroxide (10.06 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-g (15.97 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-h (7.24 g, divalent phenol residue molecular weight 254 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2529 g) and 2,3,5-trimethylphenol (0.6665 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (27.96 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.65 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 41. The obtained resin 41 had a viscosity average molecular weight of 39,800. The repeating structure of the resin 41 is shown below.

Production Example 42 (Resin 42)
Sodium hydroxide (9.98 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-g (15.85 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-m (7.52 g, divalent phenol residue molecular weight 266 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2511 g) and 2,3,5-trimethylphenol (0.6615 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (27.75 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.62 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 42. The resulting resin 42 had a viscosity average molecular weight of 35,400. The repeating structure of the resin 42 is shown below.

Production Example 43 (Resin 43)
Sodium hydroxide (10.03 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-h (16.97 g, divalent phenol residue molecular weight 254 in the repeating structure) and BP-n (6.48 g, divalent phenol residue molecular weight 226 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Subsequently, benzyltriethylammonium chloride (0.2505 g) and 2,3,6-trimethylphenol (0.4765 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (27.88 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.64 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 43. The obtained resin 43 had a viscosity average molecular weight of 45,700. The repeating structure of the resin 43 is shown below.

Production Example 44 (Resin 44)
Sodium hydroxide (9.78 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-h (16.55 g, divalent phenol residue molecular weight 254 in the repeating structure) and BP-m (7.43 g, divalent phenol residue molecular weight 266 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.
Then, benzyltriethylammonium chloride (0.2444 g) and 2,3,6-trimethylphenol (0.4648 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (27.20 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.55 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 44. The obtained resin 44 had a viscosity average molecular weight of 39,900. The repeating structure of the resin 44 is shown below.

Production Example 45 (Resin 45)
Sodium hydroxide (9.45 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-m (16.73 g, divalent phenol residue molecular weight 266 in the repeating structure) and BP-k (7.92 g, divalent phenol residue molecular weight 294 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2360 g) and p- (tert-butyl) phenol (0.4951 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (26.26 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.43 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 45. The obtained resin 45 had a viscosity average molecular weight of 47,300. The repeating structure of the resin 45 is shown below.

Production Example 46 (Resin 46)
Sodium hydroxide (10.15 g) and H ₂ O (423 mL) were weighed in a 500 mL beaker and dissolved with stirring. Thereto, BP-1 (10.17 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-i (12.84 g, divalent phenol residue molecular weight 268 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel.

Then, benzyltriethylammonium chloride (0.2552 g) and 2,3,6-trimethylphenol (0.6725 g) were sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.20 g) and dichloromethane (211 mL) was transferred into the dropping funnel.

While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.68 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 46. The obtained resin 46 had a viscosity average molecular weight of 35,400. The repeating structure of the resin 46 is shown below.

(Examples 1 to 42, Comparative Examples 1 to 4)
Electrical characteristics tests and abrasion tests were performed on the photoreceptor sheets prepared using the above-described resins 1 to 46. The results are shown in Tables 1 and 2 together with the viscosity average molecular weights (Mv) of Resin 1 to Resin 46. Table 3 shows the compound names of the divalent phenol compound that gives the divalent phenol residue A and the divalent phenol compound that gives the divalent phenol residue B shown in abbreviations.

From the results shown in Tables 1 and 2, a polyester resin (resin 1 to resin 42) using a divalent phenol residue having a molecular weight of 250 or less and {a / (a + b)} in the formula (1) being 0.7. ) -Containing photoreceptor sheets (Examples 1 to 42) show good performance in electrical properties and wear tests.
On the other hand, a polyester resin (resin 43, resin 44, resin 45) using a divalent phenol residue having a molecular weight of 250 or more and {a / (a + b)} in the formula (1) is 0.7. The photosensitive sheet contained (Comparative Examples 1 to 3) does not give sufficient results in the wear test. Further, a photoreceptor sheet containing a polyester resin (resin 46) using a divalent phenol residue having a molecular weight of 250 or less and {a / (a + b)} in formula (1) being 0.5 (Comparative Example 4) ) Also shows that sufficient results cannot be obtained in the wear test.

Production Example 47 (Resin 47)
Sodium hydroxide (10.57 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-l (14.86 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-g (7.20 g, divalent phenol residue molecular weight 240 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel. Then, benzyltriethylammonium chloride (0.2655 g) and p- (tert-butyl) phenol (0.7292 g) were sequentially added to the reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.38 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.83 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 47. The obtained resin 47 had a viscosity average molecular weight of 42,100. The repeating structure of the resin 47 is shown below.

Production Example 48 (Resin 48)
Sodium hydroxide (10.38 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-1 (14.58 g, divalent phenol residue molecular weight 212 in the repeating structure) and BP-i (7.89 g, divalent phenol residue molecular weight 268 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel. Subsequently, benzyltriethylammonium chloride (0.2608 g) and p- (tert-butyl) phenol (0.7301 g) were sequentially added to the reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.85 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.76 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 48. The resulting resin 48 had a viscosity average molecular weight of 46,200. The repeating structure of the resin 48 is shown below.

Production Example 49 (Resin 49)
Sodium hydroxide (10.66 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-e (16.03 g, divalent phenol residue molecular weight 226 in the repeating structure) and BP-d (6.03 g, divalent phenol residue molecular weight 198 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel. Then, benzyltriethylammonium chloride (0.2666 g) and 2,3,5-trimethylphenol (0.5465 g) were sequentially added to the reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (29.63 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.86 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered off and dried to obtain the desired resin 49. The obtained resin 49 had a viscosity average molecular weight of 40,600. The repeating structure of the resin 49 is shown below.

Production Example 50 (Resin 50)
Sodium hydroxide (10.27 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (18.75 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-l (4.14 g, divalent phenol residue molecular weight 212 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel. Then, benzyltriethylammonium chloride (0.25569 g) and 2,3,5-trimethylphenol (0.5268 g) were sequentially added to the reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.55 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.73 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 50. The obtained resin 50 had a viscosity average molecular weight of 45,700. The repeating structure of the resin 50 is shown below.

Production Example 51 (Resin 51)
Sodium hydroxide (10.40 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (14.23 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-1 (8.39 g, divalent phenol residue molecular weight 212 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel. Then, benzyltriethylammonium chloride (0.2601 g) and 2,3,5-trimethylphenol (0.5332 g) were sequentially added to the reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.90 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.77 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 51. The obtained resin 51 had a viscosity average molecular weight of 43,400. The repeating structure of the resin 51 is shown below.

Production Example 52 (Resin 52)
Sodium hydroxide (9.97 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (15.88 g, divalent phenol residue molecular weight 240 in the repeating structure) and BP-i (7.59 g, divalent phenol residue molecular weight 268 in the repeating structure) were added thereto, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel. Then, benzyltriethylammonium chloride (0.2500 g) and 2,3,5-trimethylphenol (0.5738 g) were sequentially added to the reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (27.72 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.62 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 52. The obtained resin 52 had a viscosity average molecular weight of 45,000. The repeating structure of the resin 52 is shown below.

Production Example 53 (Resin 53)
Sodium hydroxide (10.22 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. Thereto, BP-h (17.40 g, divalent phenol residue molecular weight 254 in the repeating structure) and BP-d (5.83 g, divalent phenol residue molecular weight 198 in the repeating structure) were added, stirred, After dissolution, this alkaline aqueous solution was transferred to a 1 L reaction vessel. Then, benzyltriethylammonium chloride (0.2535 g) and 2,3,6-trimethylphenol (0.3038 g) were sequentially added to the reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.40 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the aqueous alkali solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.70 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further with H ₂ O (424 mL). Washing was performed twice.
The washed organic layer was poured into methanol (2,820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin 53. The resulting resin 53 had a viscosity average molecular weight of 42,800. The repeating structure of the resin 53 is shown below.

[Manufacture of photosensitive drum]
<Manufacture of dispersion for charge generation layer>
Bragg angles (2θ ± 0.2) 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.1 °, 20.8 ° in X-ray diffraction by CuKα ray , 10 parts by weight of oxytitanium phthalocyanine showing strong diffraction peaks at 23.3 °, 26.3 °, and 27.1 ° are added to 150 parts by weight of 1,2-dimethoxyethane, and pulverized and dispersed in a sand grind mill. And a pigment dispersion was produced.
5 parts by weight of polyvinyl butyral (trade name Denkabutyral # 6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) was dissolved in 95 parts by weight of 1,2-dimethoxyethane to produce a binder solution 1 having a solid content concentration of 5%.

  5 parts by weight of phenoxy resin (trade name PKHH, manufactured by Union Carbide Co., Ltd.) was dissolved in 95 parts by weight of 1,2-dimethoxyethane to produce a binder solution 2 having a solid content concentration of 5%. To 160 parts by weight of the previously prepared pigment dispersion, 50 parts by weight of binder solution 1, 50 parts by weight of binder solution 2, an appropriate amount of 1,2-dimethoxyethane, and an appropriate amount of 4-methoxy-4-methyl-2- Pentanone was added to prepare a charge generation layer dispersion α having a solid content concentration of 4.0% and 1,2-dimethoxyethane: 4-methoxy-4-methyl-2-pentanone = 9: 1.

Example 43
The surface of a cylinder made of an aluminum alloy having an outer diameter of 30 mm, a length of 285 mm, and a wall thickness of 1.0 mm, which has a mirror-finished surface, is anodized and then sealed with a sealing agent mainly composed of nickel acetate. By performing the treatment, an anodic oxide coating (alumite coating) of about 6 μm was formed. The charge generation layer dispersion α produced earlier was dip coated on this cylinder, and the charge generation layer was formed so that the film thickness after drying was about 0.3 μm.
Next, the cylinder in which the charge generation layer is formed is charged with 50 parts by weight of a charge transport material composed of an isomer mixture containing the charge transport material (1) as a main component and 100 parts by weight of resin 4 as a binder resin for the charge transport layer. Part, a silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF96) 0.05 part by weight is immersed in a coating solution for forming a charge transport layer dissolved in a tetrahydrofuran / toluene mixed solvent (tetrahydrofuran 80% by weight, toluene 20% by weight). By applying, a charge transport layer having a thickness of 20 μm after drying was provided. The photoreceptor drum thus obtained is designated L4.

Example 44
A photosensitive drum L11 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 11.

Example 45
A photoconductive drum L47 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 47.

Example 46
A photoconductor drum L48 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 48.

Example 47
A photosensitive drum L18 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 18.

Example 48
A photoconductive drum L49 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 49.

Example 49
A photoconductive drum L25 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 25.

Example 50
A photosensitive drum L26 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 26.

Example 51
A photoconductor drum L27 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 27.

Example 52
A photoconductor drum L28 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 28.

Example 53
A photoconductor drum L29 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 29.

Example 54
A photosensitive drum L30 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 30.

Example 55
A photosensitive drum L32 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 32.

Example 56
A photosensitive drum L33 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 33.

Example 57
A photoconductor drum L50 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 50.

Example 58
A photoconductor drum L36 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 36.

Example 59
A photosensitive drum L51 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 51.

Example 60
A photoconductor drum L37 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 37.

Example 61
A photoconductor drum L38 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 38.

Example 62
A photoconductor drum L40 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 40.

Example 63
A photoconductor drum L41 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 41.

Example 64
A photosensitive drum L42 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 42.

Example 65
A photoconductive drum L52 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 52.

Comparative Example 5
A photosensitive drum L53 was produced in the same manner as in Example 43 except that the resin 4 was changed to the resin 53.

[Measurement of film loss by wear test]
These photosensitive drums are mounted on a commercially available color laser printer (Epson LP3000C, scorotron charging, non-magnetic one-component jumping development, intermediate transfer method, four-cycle method), and monochrome (black) mode under normal temperature and humidity conditions 6,000 prints were made. The amount of film reduction was calculated from the difference in film thickness before and after printing. The results are shown in Table 4. The smaller the amount of film loss, the better the wear resistance.

<Preparation of dispersion for undercoat layer>
Rutile-type white titanium oxide with an average primary particle size of 40 nm (product name: TTO55N, manufactured by Ishihara Sangyo Co., Ltd.) and 3% by weight of methyldimethoxysilane (product name: TSL8117, manufactured by Toshiba Silicone Co., Ltd.) The mixture was introduced into a mixing and kneading machine (product name: SMG300, manufactured by Kawata Co., Ltd.), and high speed mixing (rotational peripheral speed: 34.5 m / sec) was performed to obtain surface-treated titanium oxide.
The surface-treated titanium oxide is dispersed in a mixed solvent of methanol / n-propanol = 7/3 by a ball mill, and the titanium oxide slurry is mixed with a copolymerized polyamide solution of the following structural formula (1). A sonic dispersion treatment was performed, and a dispersion having a solvent composition of methanol / n-propanol = 7/3, titanium oxide / polyamide = 3/1 and a solid content concentration of 16% by weight was prepared, and a dispersion for an undercoat layer Was made.

<Preparation of dispersion for charge generation layer>
10 parts by weight of oxytitanium phthalocyanine, which shows a maximum diffraction peak at a Bragg angle (2θ ± 0.2) of 27.3 ° in X-ray diffraction using CuKα rays, is added to 150 parts by weight of 1,2-dimethoxyethane, and is added to a sand grind mill. Then, a pulverization dispersion treatment was performed to prepare a pigment dispersion.

  In 160 parts by weight of this pigment dispersion, 5 parts by weight of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Butyral # 6000C) was dissolved in 95 parts by weight of 1,2-dimethoxyethane, and the solid content concentration was 5% by weight. 100 parts by weight of the binder solution, an appropriate amount of 1,2-dimethoxyethane and an appropriate amount of 4-methoxy-4-methyl-2-pentanone were added, and the solid content concentration was 4.0% by weight, 1,2-dimethoxyethane: 4- A dispersion β1 for charge generation layer with methoxy-4-methyl-2-pentanone = 9: 1 was prepared.

  Bragg angles (2θ ± 0.2) 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.1 °, 20.8 ° in X-ray diffraction by CuKα ray , 10 parts by weight of oxytitanium phthalocyanine showing strong diffraction peaks at 23.3 °, 26.3 °, and 27.1 ° are added to 150 parts by weight of 1,2-dimethoxyethane, and pulverized and dispersed in a sand grind mill. And a pigment dispersion was prepared.

In 160 parts by weight of this pigment dispersion, 5 parts by weight of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Butyral # 6000C) was dissolved in 95 parts by weight of 1,2-dimethoxyethane, and the solid content concentration was 5% by weight. 100 parts by weight of the binder solution, an appropriate amount of 1,2-dimethoxyethane and an appropriate amount of 4-methoxy-4-methyl-2-pentanone were added, and the solid content concentration was 4.0%, 1,2-dimethoxyethane: 4-methoxy A charge generating layer dispersion β2 of -4-methyl-2-pentanone = 9: 1 was prepared.
Charge generation layer dispersion β1 and charge generation layer dispersion β2 were mixed at a ratio of 8: 2 to prepare charge generation layer dispersion β.

<Production of photosensitive drum>
Example 66
A cylinder made of an aluminum alloy having an outer diameter of 30 mm, a length of 254 mm, and a wall thickness of 0.75 mm, whose surface is roughly cut (Rmax = 0.8), is dip-coated in the previously prepared dispersion for the undercoat layer to form a film. An undercoat layer having a thickness of about 1.3 μm was formed. This cylinder was dip-coated in the charge generation layer dispersion β prepared earlier, and a charge generation layer was formed so that the weight after drying was 0.3 g / m ² (film thickness: about 0.3 μm).
Next, the cylinder in which the charge generation layer is formed is charged with 50 parts by weight of a charge transport material composed of an isomer mixture containing the charge transport material (1) as a main component and 100 parts by weight of resin 4 as a binder resin for the charge transport layer. Dip coating in a solution obtained by dissolving 0.05 part by weight of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.) in 640 parts by weight of a tetrahydrofuran / toluene mixed solvent (tetrahydrofuran 80% by weight, toluene 20% by weight). Thus, a charge transport layer having a thickness of 25 μm after drying was provided. The photosensitive drum thus obtained is designated S4.

Example 67
A photosensitive drum S11 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 11.

Example 68
A photosensitive drum S47 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 47.

Example 69
A photosensitive drum S48 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 48.

Example 70
A photosensitive drum S18 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 18.

Example 71
A photosensitive drum S49 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 49.

Example 72
A photosensitive drum S25 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 25.

Example 73
A photosensitive drum S26 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 26.

Example 74
A photosensitive drum S27 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 27.

Example 75
A photoconductor drum S28 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 28.

Example 76
A photosensitive drum S29 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 29.

Example 77
A photosensitive drum S30 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 30.

Example 78
A photosensitive drum S32 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 32.

Example 79
A photosensitive drum S33 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 33.

Example 80
A photosensitive drum S50 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 50.

Example 81
A photosensitive drum S36 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 36.

Example 82
A photosensitive drum S51 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 51.

Example 83
A photosensitive drum S37 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 37.

Example 84
A photosensitive drum S38 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 38.

Example 85
A photosensitive drum S40 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 40.

Example 86
A photosensitive drum S41 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 41.

Example 87
A photosensitive drum S42 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 42.

Example 88
A photosensitive drum S52 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 52.

Comparative Example 6
A photosensitive drum S53 was produced in the same manner as in Example 66 except that the resin 4 was changed to the resin 53.

[Measurement of film loss by wear test]
Mount these photosensitive drums on a commercially available monochrome laser printer (manufactured by Lexmark, Optra S2450, 24 sheets per minute at A4 vertical feed, roller charging with DC voltage application, non-magnetic one-component contact development, roller transfer) 30,000 sheets were printed under normal temperature and humidity. The amount of film reduction was calculated from the difference in film thickness before and after printing. The results are shown in Table 5. The smaller the amount of film loss, the better the wear resistance.

Example 89
The surface of a cylinder made of an aluminum alloy having an outer diameter of 30 mm, a length of 346 mm, and a wall thickness of 1.0 mm, whose surface has been roughly cut (Rmax = 1.0), is subjected to anodizing treatment, and then nickel acetate as a main component. By performing sealing treatment with a sealing agent, an anodic oxide coating (alumite coating) of about 6 μm was formed.
This cylinder was dip-coated in the previously prepared dispersion for the undercoat layer to form an undercoat layer having a thickness of about 1.3 μm after drying.
Further, the charge generation layer was formed by dip-coating in the charge generation layer dispersion β1 prepared earlier so that the weight after drying was 0.3 g / m ² (film thickness: about 0.3 μm).

  Next, the cylinder in which the charge generation layer is formed is charged with 30 parts by weight of a charge transport material composed of an isomer mixture containing the charge transport material (1) as a main component and 4 weights of an antioxidant (Irganox 1076, manufactured by Ciba Geigy). 100 parts by weight of resin 11 as a binder resin for the charge transport layer, 0.05 parts by weight of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.), tetrahydrofuran / toluene mixed solvent (80% by weight of tetrahydrofuran, 20% by weight of toluene) ) A charge transport layer having a thickness of 25 μm after drying was provided by dip coating in a solution dissolved in 640 parts by weight. The photosensitive drum thus obtained is designated as D11.

Example 90
A photosensitive drum D48 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 48.

Example 91
A photosensitive drum D18 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 18.

Example 92
A photosensitive drum D49 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 49.

Example 93
A photosensitive drum D25 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 25.

Example 94
A photosensitive drum D26 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 26.

Example 95
A photoconductive drum D27 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 27.

Example 96
A photoconductor drum D28 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 28.

Example 97
A photoconductive drum D29 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 29.

Example 98
A photosensitive drum D30 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 30.

Example 99
A photosensitive drum D32 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 32.

Example 100
A photosensitive drum D50 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 50.

Example 101
A photosensitive drum D36 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 36.

Example 102
A photosensitive drum D51 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 51.

Example 103
A photoconductive drum D37 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 37.

Example 104
A photosensitive drum D38 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 38.

Example 105
A photosensitive drum D40 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 40.

Example 106
A photosensitive drum D41 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 41.

Example 107
A photosensitive drum D42 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 42.

Comparative Example 7
A photoconductive drum D53 was produced in the same manner as in Example 89 except that the resin 11 was changed to the resin 53.

[Measurement of film loss by wear test]
These photoconductors are mounted on a commercially available digital multifunction machine (manufactured by Panasonic Communications, WORKIO3200, A4 horizontal feed 32 sheets / minute, roller charging with AC superimposed DC voltage applied, magnetic single component jumping development, resolution 600 dpi × 600 dpi). 30,000 sheets were printed under normal temperature and humidity. The amount of film reduction per 10,000 sheets was calculated from the difference in film thickness before and after printing. The results are shown in Table 6. The smaller the amount of film loss, the better the wear resistance.

Example 108
The surface of an aluminum cylinder having an outer diameter of 30 mm, a length of 246 mm, and a wall thickness of 0.75 mm, which has a mirror-finished surface, is anodized, and then sealed with a sealant mainly composed of nickel acetate. By performing, an anodic oxide film (alumite film) of about 6 μm was formed. This cylinder was dip-coated in the charge generation layer dispersion β1 prepared previously, and the charge generation layer was formed so that the film thickness after drying was about 0.4 μm.

Next, 50 parts by weight of a charge transport material comprising an isomer mixture containing the charge transport material (1) as a main component, 100 parts by weight of resin 47 as a binder resin for a charge transport layer, an antioxidant (Irganox 1076, manufactured by Ciba Geigy) ) 8 parts by weight, 0.05 part by weight of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed with 640 parts by weight of a tetrahydrofuran / toluene mixed solvent (tetrahydrofuran 80% by weight, toluene 20% by weight), and charge transport is performed. A layer forming coating solution was prepared.
The cylinder on which the charge generation layer was previously formed was dip-coated in this charge transport layer forming coating solution to form a 18 μm thick charge transport layer after drying. The photoreceptor drum thus obtained is designated as C47.

Example 109
A photoconductive drum C48 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 48.

Example 110
A photosensitive drum C18 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 18.

Example 111
A photoconductive drum C49 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 49.

Example 112
A photosensitive drum C25 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 25.

Example 113
A photoconductive drum C26 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 26.

Example 114
A photosensitive drum C27 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 27.

Example 115
A photosensitive drum C28 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 28.

Example 116
A photosensitive drum C29 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 29.

Example 117
A photosensitive drum C30 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 30.

Example 118
A photosensitive drum C32 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 32.

Example 119
A photosensitive drum C50 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 50.

Example 120
A photosensitive drum C36 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 36.

Example 121
A photosensitive drum C51 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 51.

Example 122
A photoconductive drum C37 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 37.

Example 123
A photoconductive drum C38 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 38.

Example 124
A photoconductor drum C40 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 40.

Example 125
A photoconductive drum C41 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 41.

Example 126
A photoconductive drum C42 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 42.

Example 127
A photosensitive drum C52 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 52.

Comparative Example 8
A photosensitive drum C53 was produced in the same manner as in Example 108 except that the resin 47 was changed to the resin 53.

  These photoreceptors are mounted on a commercially available color tandem printer (C3100 manufactured by Oki Data Corporation, contact roller charging with DC voltage application, 600 dpi, LED exposure, non-magnetic one-component contact development) and 10,000 at normal temperature and humidity. Sheets were printed, and the amount of film reduction was calculated from the difference in film thickness before and after printing. The results are shown in Table 7. The smaller the amount of film loss, the better the wear resistance.

From the results shown in Table 4, Table 5, Table 6, and Table 7, a divalent phenol residue having a molecular weight of 250 or less was used, and {a / (a + b)} in the general formula (1) was 0.6-0. It can be seen that the photosensitive drum containing the polyester resin No. 8 (Example 43 to Example 127) shows good performance in the abrasion test.
In contrast, a photosensitive drum using a divalent phenol residue having a molecular weight of 250 or more and containing a polyester resin having {a / (a + b)} of 0.7 in the general formula (1) (Comparative Example 5) It can be seen that Comparative Example 8) does not provide sufficient results in the wear test.

It is a figure explaining an image forming apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photosensitive member, 2 ... Charging device, 3 ... Exposure device, 4 ... Developing device, 5 ... Transfer device, 6 ... Cleaning device, 7 ... Fixing device, 41 ... Developing tank, 42 ... Agitator, 43 ... Supply roller , 44 ... developing roller, 45 ... regulating member, 71 ... upper fixing member, 72 ... lower fixing member, 73 ... heating device, T ... toner, P ... recording paper

Claims (4)

A conductive support;
A photosensitive layer formed on the conductive support,
The electrophotographic photoreceptor, wherein the photosensitive layer contains a polyester resin having a repeating structure represented by the following formula (1).

(In formula (1), 0.5 <{a / (a + b)} <1, A is a divalent phenol residue having a molecular weight of 250 or less, B is a divalent phenol residue, and X is the following formula (2) And Y is a divalent carboxylic acid residue.)

(In Formula (2), R ¹ and R ² 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) .) 2. The electrophotographic photosensitive member according to claim 1, wherein A in the formula (1) has a structure represented by the following formula (3).

(In Formula (3), R ³ is a hydrogen atom or an alkyl group, and R ⁴ and R ⁵ are each independently an alkyl group.) The electrophotographic photosensitive member according to claim 1 or 2, wherein B in the formula (1) has a structure represented by the following formula (4).

(In Formula (4), R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group, or a substituent that may be bonded to each other to form a cyclic structure, and R ⁸ and R ⁹ are each independently And n ² and m ² are each independently an integer of 1 to 4.) The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein the photosensitive layer further contains a compound represented by the following formula (5).

(In Formula (5), Ar ^{1 to} Ar ⁶ each independently represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. M ³ , m ⁴ each independently represents 0 or 1. Q represents a direct bond or a divalent residue, R ^{10 to} R ¹⁷ each independently represents a hydrogen atom, 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, each of n ^{3 to} n ⁶ independently represents an integer of 0 to 4. Ar ^{1 to} Ar ⁶ may be bonded to each other to form a ring structure.)

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