JP2007191646A - Coating agent composition, electrophotographic photoreceptor, image forming device, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating agent composition capable of achieving both of the improvement of mechanical strength and the prevention of delamination when used as a constituent material of an electrophotographic photoreceptor; to provide the electrophotographic photoreceptor using the coating agent composition as the constituent material; and to provide an image-forming device and a process cartridge, having the electrophotographic photoreceptor. <P>SOLUTION: The coating agent composition contains an aromatic compound having an aromatic ring, a hydroxy group bonded to the aromatic ring, and an organic group bonded to the aromatic ring and containing an ethylenically unsaturated bond, and a charge-transporting organic compound and/or an electroconductive inorganic particles. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a coating agent composition, an electrophotographic photoreceptor, an image forming apparatus, and a process cartridge.

  A so-called xerographic image forming apparatus includes an electrophotographic photosensitive member (hereinafter sometimes referred to as “photosensitive member”), a charging device, an image exposing device, a developing device, and a transfer device, and forms an image by an electrophotographic process using them. I do.

  2. Description of the Related Art In recent years, xerographic image forming apparatuses have been further increased in speed and life due to technological progress of each member and system. As a result, the demand for high-speed compatibility and high reliability of each subsystem is increasing. In particular, since the photoconductor used for image writing is more susceptible to stress than other members due to sliding with a cleaning device that cleans the photoconductor, from the viewpoint of high-speed compatibility and high reliability, It is desirable to suppress the occurrence of scratches and wear on the photoreceptor that cause image defects.

As a means for suppressing the occurrence of scratches and wear on the photoreceptor, a method of providing a protective layer on the photoreceptor surface using a resin material has been proposed. For example, Patent Document 1 discloses a photoreceptor in which a protective layer containing a phenol resin is provided on the surface of the photoreceptor.
JP 2002-82469 A

  However, when a protective layer containing a phenolic resin is provided on the surface of the photoconductor as in the photoconductor described in Patent Document 1, although the mechanical strength is improved, the generation of scratches and wear on the surface is suppressed, but the protective layer is protected. There is a problem that a phenomenon in which the protective layer is peeled off (hereinafter referred to as “peeling”) occurs due to insufficient adhesion between the layer and the lower layer, and a trace of peeling appears in the image. In particular, when the lower layer contains a thermoplastic resin, it becomes difficult to maintain sufficient adhesion, and the occurrence of peeling becomes significant.

  The present invention has been made in view of such circumstances, and when used as a constituent material of an electrophotographic photoreceptor, a coating agent composition capable of achieving both improvement in mechanical strength and suppression of peeling. The purpose is to provide goods. Another object of the present invention is to provide an electrophotographic photosensitive member using the coating agent composition as a constituent material, and an image forming apparatus and a process cartridge including the electrophotographic photosensitive member.

  In order to solve the above problems, the present invention relates to an aromatic compound having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an organic group including an ethylenically unsaturated bond bonded to the aromatic ring, and charge transport. A coating agent composition comprising a conductive organic compound and / or conductive inorganic particles is provided.

  According to the coating agent composition of the present invention, when it is used as a constituent material of an electrophotographic photoreceptor by containing the above aromatic compound, a charge transporting organic compound and / or conductive inorganic particles, It is possible to achieve both improvement in mechanical strength and suppression of peeling.

  The reason why the coating composition of the present invention can achieve both improvement in mechanical strength and suppression of peeling is not necessarily clear, but the present inventors speculate as follows. That is, the aromatic compound has a structure in which an organic group containing a hydroxyl group and an ethylenically unsaturated bond is bonded to an aromatic ring, and in the curing reaction, the reaction between the hydroxyl groups, the hydroxyl group and the organic group The reaction with the ethylenically unsaturated bond of the group proceeds. Therefore, it is considered that the structure of the obtained cured product becomes more complicated than that of the conventional phenol resin, and the balance between hardness and flexibility is kept well, and as a result, the mechanical strength is improved. In addition, introduction of an organic group containing an ethylenically unsaturated bond into an aromatic compound contributes to suppression of thermal shrinkage during curing of the coating agent composition and improvement of affinity for a thermoplastic resin and the like. It is considered that the adhesion to thermoplastic resin and the like is improved by such a substituent effect, and peeling can be suppressed.

  Moreover, the coating agent composition of the present invention can impart good antioxidant properties to the resulting cured product by containing the aromatic compound, and in particular, the charge due to the discharge product generated during charging. It is effective in suppressing deterioration of the transportable organic compound.

  In addition, in conventional photoreceptors, a charge trap site is formed in the functional layer because the catalyst used in the synthesis of the phenol resin and the curing catalyst used in the curing of the functional layer remain in the functional layer. In particular, there is a problem that the residual potential increases and causes image defects such as ghosts under low temperature and low humidity. On the other hand, the aromatic compound contained in the coating agent composition of the present invention has a higher reactivity than conventional phenolic resins, so that the amount used can be reduced without using a curing catalyst. It can reduce and can advance favorable hardening reaction. Therefore, the coating agent composition of the present invention is also effective in suppressing an increase in residual potential and image defects such as ghosts.

  Furthermore, since the coating agent composition of the present invention does not involve generation of formaldehyde during curing, it is excellent from the viewpoint of reducing environmental burden and safety.

［式（Ａ−１）中、Ａ^１はエチレン性不飽和結合を有する有機基を示し、Ａ^２は１価の基を示し、ｐ及びｑはそれぞれ１以上の整数を示し、ｒは０又は１以上の整数を示し、ｒが２以上のときｒ個のＲ^２は相互に結合して環を形成していてもよい。］ As said aromatic compound contained in the coating agent composition of this invention, the compound which has a structure represented, for example by the following general formula (A-1) is mentioned, A phenol derivative and a catechol derivative are used preferably especially.

[In Formula (A-1), A ¹ represents an organic group having an ethylenically unsaturated bond, A ² represents a monovalent group, p and q each represents an integer of 1 or more, and r represents 0 or Represents an integer of 1 or more, and when r is 2 or more, r R ^{2 s} may be bonded to each other to form a ring. ]

  The organic group having an ethylenically unsaturated bond is preferably an organic group having a plurality of ethylenically unsaturated bonds and having 10 or more carbon atoms.

  In addition, the coating agent composition of the present invention preferably contains a charge transporting organic compound, and the charge transporting organic compound has a crosslinked structure by a reaction with an aromatic compound and / or a reaction between the charge transporting organic compounds. It is preferable to have a reactive functional group capable of forming. As a result, a very dense cross-linked structure is formed in the cured product of the coating composition of the present invention, which improves the mechanical strength of the photoreceptor, further suppresses the increase in residual potential and suppresses image defects such as ghosts. It can be achieved at a higher level.

［式（ＩＩＩ）中、Ｆは正孔輸送能を有する化合物から誘導されるｎ５価の有機基を示し、Ｔは２価の基を示し、Ｙは酸素原子又は硫黄原子を示し、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ^６は１価の有機基を示し、ｍ1は０又は１を示し、ｎ５は１〜４の整数を示す。但し、Ｒ^５とＲ^６は互いに結合してＹをヘテロ原子とする複素環を形成してもよい。］

［式（ＩＶ）中、Ｆは正孔輸送能を有する化合物から誘導されるｎ６価の有機基を示し、Ｔは２価の基を示し、Ｒ^７は１価の有機基を示し、ｍ２は０又は１を示し、ｎ６は１〜４の整数を示す。］

［式（Ｖ）中、Ｆは正孔輸送能を有する化合物から誘導されるｎ７価の有機基を示し、Ｌはアルキレン基を示し、Ｒ⁸は１価の有機基を示し、ｎ７は１〜４の整数を示す。］ Preferable examples of the charge transporting organic compound having a reactive functional group include compounds having a structure represented by any one of the following general formulas (I) to (V).
F-[(X ¹ ) _n R ¹ -A] _m (I)
[In Formula (I), F represents an m-valent organic group derived from a compound having a hole transporting ability, R ¹ represents an alkylene group, and m represents an integer of 1 to 4. X ¹ represents an oxygen atom or a sulfur atom, and n represents 0 or 1. A represents a hydroxyl group, a carboxyl group, or a thiol group. ]
_{^{F - [(X 2) n1}} - (R 2) n2 - (Z 2) n3 G] n4 (II)
[In Formula (II), F represents an n4-valent organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, and Z ² represents An alkylene group, an oxygen atom, a sulfur atom, NH or COO, G represents an epoxy group, n1, n2 and n3 each independently represents 0 or 1, and n4 represents an integer of 1 to 4; ]

[In Formula (III), F represents an n5-valent organic group derived from a compound having a hole transporting ability, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁶ represents a monovalent organic group, m 1 represents 0 or 1, and n 5 represents an integer of 1 to 4. However, R ⁵ and R ⁶ may be bonded to each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (IV), F represents an n6 valent organic group derived from a compound having a hole transporting ability, T represents a divalent group, R ⁷ represents a monovalent organic group, and m2 represents 0 or 1 is shown, n6 shows the integer of 1-4. ]

[In formula (V), F represents an n7-valent organic group derived from a compound having a hole transporting ability, L represents an alkylene group, R ⁸ represents a monovalent organic group, and n7 represents 1 to 1 An integer of 4 is shown. ]

  The present invention also provides an electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer provided on the conductive substrate, wherein the photosensitive layer is disposed at a position furthest from the conductive substrate. It has the 1st functional layer containing the hardened | cured material of the coating agent composition of this invention, and the 2nd functional layer arrange | positioned adjacent to the 1st functional layer and containing a thermoplastic resin. An electrophotographic photosensitive member is provided.

  In the electrophotographic photosensitive member of the present invention, the first functional layer disposed at the position farthest from the conductive substrate of the photosensitive layer includes the cured product of the coating agent composition of the present invention. The mechanical strength of the first functional layer and the adhesion to the second functional layer containing the thermoplastic resin can be sufficiently improved. Therefore, according to the electrophotographic photosensitive member of the present invention, scratches and abrasion on the surface of the photosensitive member and peeling between layers can be suppressed, and good image quality can be stably obtained over a long period of time.

  The present invention also provides the electrophotographic photosensitive member of the present invention, a charging device for charging the electrophotographic photosensitive member, an image exposure device for forming an electrostatic latent image on the charged electrophotographic photosensitive member, An image forming apparatus comprising: a developing device for developing an electrostatic latent image with toner to form a toner image; and a transfer device for transferring the toner image from an electrophotographic photosensitive member to a transfer target. Providing equipment.

  The present invention also provides the electrophotographic photosensitive member of the present invention, a charging device for charging the electrophotographic photosensitive member, and the electrostatic latent image formed on the electrophotographic photosensitive member is developed with toner to form a toner image. And a developing device, and at least one selected from a cleaning device for removing toner remaining on the surface of the electrophotographic photosensitive member.

  According to the process cartridge and the image forming apparatus of the present invention, an electrophotographic process including charging, exposure, development, transfer, or further cleaning is performed using the electrophotographic photosensitive member of the present invention having excellent characteristics as described above. By doing so, good image quality can be stably obtained over a long period of time.

  As described above, according to the present invention, when used as a constituent material of an electrophotographic photosensitive member, a coating agent composition capable of achieving both improvement in mechanical strength and suppression of peeling is provided. Further, according to the present invention, there are provided an electrophotographic photosensitive member using the coating agent composition of the present invention as a constituent material, and an image forming apparatus and a process cartridge including the electrophotographic photosensitive member.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted.

(Coating agent composition)
The coating composition of the present invention comprises an aromatic compound having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an organic group having an ethylenically unsaturated bond bonded to the aromatic ring, and a charge transport property. It contains an organic compound and / or conductive inorganic particles.

  As an aromatic ring which the said aromatic compound has, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned, for example, Among these, a benzene ring is preferable.

  In addition, the number of hydroxyl groups bonded to the aromatic ring may be one or two or more, but preferably one or two. In addition, when two or more hydroxyl groups are bonded to the aromatic ring, the bonding position of each hydroxyl group is not particularly limited, but the compound has a structure in which at least two of the hydroxyl groups are bonded to carbon atoms adjacent to each other in the aromatic ring That is, a catechol derivative which is an o-substituted product is preferable.

  Moreover, in the organic group containing an ethylenically unsaturated bond, the number of ethylenically unsaturated bonds may be 1 or 2 or more, but preferably 2 or more, more preferably 2 to 4. Furthermore, the number of the organic group containing an ethylenically unsaturated bond per molecule of the aromatic compound may be one or more, but is preferably one. The number of carbon atoms of the organic group containing an ethylenically unsaturated bond is not particularly limited, but is preferably 10 or more, and more preferably 10-20. Moreover, the organic group containing an ethylenically unsaturated bond may be composed of only carbon atoms and hydrogen atoms, or may be composed of an ester bond, an ether bond, an amide bond, or the like.

［式（Ａ−１）中、Ａ^１はエチレン性不飽和結合を有する有機基を示し、Ａ^２は１価の基を示し、ｐ及びｑはそれぞれ１以上の整数を示し、ｒは０又は１以上の整数を示し、ｒが２以上のときｒ個のＲ^２は相互に結合して環を形成していてもよい。］ Preferable examples of the aromatic compound include compounds having a structure represented by the following general formula (A-1).

[In Formula (A-1), A ¹ represents an organic group having an ethylenically unsaturated bond, A ² represents a monovalent group, p and q each represents an integer of 1 or more, and r represents 0 or Represents an integer of 1 or more, and when r is 2 or more, r R ^{2 s} may be bonded to each other to form a ring. ]

Among the compounds represented by the general formula (A), a compound in which the number of ethylenically unsaturated bonds in A ¹ is 2 or more and the number of carbon atoms in A ¹ is 10 or more is particularly preferable.

  In addition, as the aromatic compound, either a natural product or a synthetic product may be used. Examples of aromatic compounds derived from natural products include cardanol, which is a component of cashew nut shell liquid and a phenol derivative, and urushiol, laccol, and thiol, which are components of natural lacquer and are catechol derivatives. In the case of using an aromatic compound derived from a natural product such as cardanol, urushiol, laccol, or thiol, it is preferable to use after removing impurities such as rubber.

  Although content in particular of the said aromatic compound is not restrict | limited, 10-80 mass% is preferable on the basis of the total mass of the hardened | cured material of the coating agent composition of this invention, Furthermore, 20-60 mass% is more preferable.

  The coating agent composition of the present invention contains a charge transporting organic compound and / or conductive inorganic particles in addition to the aromatic compound. In the present invention, either a charge transporting organic compound or conductive inorganic particles may be used, or a charge transporting organic compound and conductive inorganic particles may be used in combination.

［式（ＩＩＩ）中、Ｆは正孔輸送能を有する化合物から誘導されるｎ５価の有機基を示し、Ｔは２価の基を示し、Ｙは酸素原子又は硫黄原子を示し、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ^６は１価の有機基を示し、ｍ1は０又は１を示し、ｎ５は１〜４の整数を示す。但し、Ｒ^５とＲ^６は互いに結合してＹをヘテロ原子とする複素環を形成してもよい。］

［式（ＩＶ）中、Ｆは正孔輸送能を有する化合物から誘導されるｎ６価の有機基を示し、Ｔは２価の基を示し、Ｒ^７は１価の有機基を示し、ｍ２は０又は１を示し、ｎ６は１〜４の整数を示す。］

［式（Ｖ）中、Ｆは正孔輸送能を有する化合物から誘導されるｎ７価の有機基を示し、Ｌは２価のアルキレン基を示し、Ｒ⁸は１価の有機基を示し、ｎ７は１〜４の整数を示す。］ The charge transporting organic compound used in the present invention preferably has a reactive functional group capable of forming a crosslinked structure by reaction with the aromatic compound and / or reaction between the charge transporting organic compounds. Preferable examples of such charge transporting organic compounds include compounds represented by the following general formulas (I) to (V).
F-[(X ¹ ) _n R ¹ -A] _m (I)
[In Formula (I), F represents an m-valent organic group derived from a compound having a hole transporting ability, R ¹ represents an alkylene group, and m represents an integer of 1 to 4. X ¹ represents an oxygen atom or a sulfur atom, and n represents 0 or 1. A represents a hydroxyl group, a carboxyl group, or a thiol group. ]
_{^{F - [(X 2) n1}} - (R 2) n2 - (Z 2) n3 G] n4 (II)
[In Formula (II), F represents an n4-valent organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, and Z ² represents An alkylene group, an oxygen atom, a sulfur atom, NH or COO, G represents an epoxy group, n1, n2 and n3 each independently represents 0 or 1, and n4 represents an integer of 1 to 4; ]

[In Formula (III), F represents an n5-valent organic group derived from a compound having a hole transporting ability, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁶ represents a monovalent organic group, m 1 represents 0 or 1, and n 5 represents an integer of 1 to 4. However, R ⁵ and R ⁶ may be bonded to each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (IV), F represents an n6 valent organic group derived from a compound having a hole transporting ability, T represents a divalent group, R ⁷ represents a monovalent organic group, and m2 represents 0 or 1 is shown, n6 shows the integer of 1-4. ]

[In Formula (V), F represents an n7-valent organic group derived from a compound having a hole transporting ability, L represents a divalent alkylene group, R ⁸ represents a monovalent organic group, and n7 Represents an integer of 1 to 4. ]

As the organic group F in the general formulas (I) to (V), an organic group having a structure represented by the following general formula (VI) is preferable.

［式（ＩＸ）中、Ｔは２価の基を、Ｙは酸素原子又は硫黄原子を、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子又は１価の有機基を、Ｒ^６は１価の有機基を、ｍ１は０又は１を、それぞれ示す。但し、Ｒ^５とＲ^６は互いに結合してＹをヘテロ原子とする複素環を形成してもよい。］

［式（Ｘ）中、Ｔは２価の基を、Ｒ^７は１価の有機基を、ｍ２は０又は１を、それぞれ示す。］

［式（ＸＩ）中、Ｌはアルキレン基を、Ｒ^８は１価の有機基を、それぞれ示す。］ In General Formula (VI), Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and Ar ^{1 to} Ar ⁵ 2 to 4 have a bond with a monovalent organic group represented by the following general formula (VII), (VIII), (IX), (X) or (XI) in the general formulas (I) to (V). Have.
_{^{- (X 1) n -R 1}} -Z 1 H (VII)
[In Formula (VII), X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, and n represents 0 or 1. ]
_{^{- (X 2) n1 - (}} R 2) n2 - (Z 2) n3 G (VIII)
[In the formula (VIII), X ² represents an oxygen atom or sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, sulfur atom, NH or COO, G represents an epoxy group, and n1, n2 and n3 represent Each independently represents 0 or 1. ]

[In Formula (IX), T is a divalent group, Y is an oxygen atom or a sulfur atom, R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group, and R ⁶ is 1 A valent organic group, m1 represents 0 or 1, respectively. However, R ⁵ and R ⁶ may be bonded to each other to form a heterocycle having Y as a heteroatom. ]

[In formula (X), T represents a divalent group, R ⁷ represents a monovalent organic group, and m2 represents 0 or 1. ]

[In Formula (XI), L represents an alkylene group, and R ⁸ represents a monovalent organic group. ]

In general formula (VI), the substituted or unsubstituted aryl groups represented by Ar ^{1 to} Ar ⁴ are specifically represented by general formulas (VI-1) to (VI-7) shown in Table 1 below. The aryl group is preferred. In general formulas (VI-1) to (VI-7), R ⁹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, R ^{10 to} R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a phenyl group that is substituted with them, an unsubstituted phenyl group, or an aralkyl group having 7 to 10 carbon atoms. An alkoxy group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted or unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom; The site | part shown by general formula (VII)-(XI) in V) is shown. M and s each independently represent 0 or 1, and t represents an integer of 1 to 3.

As Ar in the aryl group represented by the general formula (VI-7), an aryl group represented by the following formula (VI-8) or (VI-9) is preferable. In general formulas (VI-8) and (VI-9), R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom. -4 alkoxy group, a phenyl group substituted or unsubstituted phenyl group thereof, an aralkyl group having 7 to 10 carbon atoms or a halogen atom, X represents a general formula (VII) in general formulas (I) to (V). ) To (XI). Moreover, t shows the integer of 1-3.

Moreover, as Z in the aryl group represented by the above formula (VI-7), divalent groups represented by the following formulas (VI-10) to (VI-17) are preferable. In general formulas (VI-10) to (VI-17), R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom. -4 alkoxy group, a phenyl group substituted by them or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom. Q and r each independently represent an integer of 1 to 10, and t represents an integer of 1 to 3.

  In general formulas (VI-16) to (VI-17), W represents a divalent group represented by general formulas (VI-18) to (VI-26) in Table 4 below. In general formula (VI-25), u represents an integer of 0 to 3.

The specific structure of Ar ⁵ in the general formula (VI) is as follows. When k = 0, the structure of m = 1 in the specific structure of Ar ^{1 to} Ar ⁴ is Ar, and when k = 1, the structure of Ar 5 is Ar. ^The structure of m = 0 in the specific structure of ^{1 to} Ar ⁴ is given.

  Specific examples of the compound represented by the general formula (I) include compounds shown in Tables 5 to 10 below. In Tables 5 to 10 below, Me or a bond is described but a substituent is not described indicates a methyl group.

  Specific examples of the compound represented by the general formula (II) include compounds shown in Tables 11 to 24 below. In Tables 11 to 24 below, Me or a bond is described but a substituent is not described, and Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (III) include compounds shown in Tables 25 to 33 below. In Tables 25 to 33 below, Me or a bond is described but a substituent is not described, and a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (IV) include compounds shown in Tables 35 to 43 below. In Tables 35 to 43 below, Me or a bond is described but a substituent is not described indicates a methyl group.

  Specific examples of the compound represented by the general formula (V) include compounds shown in Tables 44 to 47 below. In Tables 44 to 47 below, Me or a bond is described but a substituent is not described indicates a methyl group, and Et indicates an ethyl group.

  Examples of the conductive particles used in the present invention include metals, metal oxides, and carbon black. Metals or metal oxides are preferable.

  Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel. Moreover, you may use what vapor-deposited these metals on the surface of the plastic particle.

  Examples of metal oxides include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. It is done. These can be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion.

  The average particle diameter of the conductive particles is preferably 0.3 μm or less and more preferably 0.1 μm or less from the viewpoint of the transparency of the cured product.

  In the coating agent composition of the present invention, the content of the charge transporting organic compound and the conductive particles can be appropriately selected, but when the coating agent composition of the present invention is used as a constituent material of an electrophotographic photoreceptor, The total content of the charge transporting organic compound and the conductive particles is preferably 0.2 to 10 parts by mass with respect to 1 part by mass of the aromatic compound.

  The coating agent of the present invention can also contain an alcohol-soluble resin for the purposes of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear control, and pot life extension. . Here, the alcohol-soluble resin means a resin that dissolves 5 parts by mass or more with respect to 100 parts by mass of n-butanol at 25 ° C.

  Examples of alcohol-soluble resins include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal, acetoacetal, or the like (for example, SREC B manufactured by Sekisui Chemical Co., Ltd.). , K, etc.), polyamide resin, cellulose resin, polyvinylphenol resin and the like. In particular, polyvinyl acetal resin and polyvinyl phenol resin are preferable in terms of electrical characteristics.

  The average molecular weight of the resin soluble in alcohol is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. If the molecular weight of the resin is less than 2,000, the effect due to the addition of the resin tends to be insufficient, and if it exceeds 100,000, the solubility is reduced and the addition amount is limited, and further, a film formation defect is caused at the time of coating. There is a tendency.

  Moreover, it is preferable that content of resin soluble in alcohol is 1-40 mass% on the basis of the total mass of the film | membrane obtained by hardening the coating agent composition of this invention, and 1-30 mass%. It is more preferable that it is 5-20 mass%. If the addition amount of the resin is less than 1% by mass, the effect of the addition of the resin tends to be insufficient, and if it exceeds 40% by mass, image blurring under high temperature and high humidity tends to occur.

  In addition, the coating composition of the present invention can impart sufficient antioxidant properties to the cured product, but in order to more reliably suppress deterioration due to an oxidizing gas such as ozone generated in the charging device, You may further contain antioxidant.

  Antioxidants include organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants, hindered phenol antioxidants, or Although well-known antioxidants, such as a hindered amine antioxidant, are mentioned, a hindered phenolic antioxidant or a hindered amine antioxidant is preferable.

  Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N′-hexamethylene bis (3,5-di). -T-butyl-4-hydroxyhydrocinnamide, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-butyl-2- Dorokishi-5-methylbenzyl) -4-methylphenyl acrylate, 4,4'-butylidene bis (3-methyl -6-t-butylphenol) and the like.

  The content of the antioxidant is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total mass of the cured product of the coating agent composition of the present invention.

  The coating agent composition of the present invention may further contain various particles in order to improve the antifouling substance adhesion and lubricity on the surface of the electrophotographic photoreceptor. An example of the particles may include silicon-containing particles.

  The silicon-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles. The colloidal silica used as the silicon-containing particles is preferably a silica having an average particle diameter of 1 to 100 nm, more preferably 10 to 30 nm, dispersed in an acidic or alkaline aqueous dispersion or an organic solvent such as alcohol, ketone or ester. A commercially available product selected from those prepared can be used.

  The solid content of colloidal silica is not particularly limited, but is preferably 0 on the basis of the total mass of the cured product of the coating agent composition of the present invention in terms of film forming properties, electrical characteristics, and strength. 0.1 to 50% by mass, more preferably 0.1 to 30% by mass.

  Examples of the silicone particles include silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles. Commercially available products may be used. The silicone particles are usually spherical, and the average particle size is preferably 1 to 500 nm, more preferably 10 to 100 nm. Silicone particles are small particles that are chemically inert and excellent in dispersibility in resins, and since the content required to obtain more sufficient properties is low, the crosslinking reaction is not hindered. The surface properties of the photographic photoreceptor can be improved. In other words, it improves the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated in a strong cross-linked structure, and maintains good wear resistance and contamination resistance adhesion over a long period of time. Can do.

  The content of the silicone particles is preferably 0.1 to 30% by mass, more preferably 0.5 to 10% by mass, based on the total mass of the cured product of the coating agent composition of the present invention.

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and “8th Polymer Material Forum Lecture Proceedings p89”. Particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO ₂ —TiO ₂ , Examples thereof include semiconductive metal oxide particles such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO.

  For the same purpose, an oil such as silicone oil can be added. Silicone oils include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane; amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, mercapto-modified poly Reactive silicone oils such as siloxane and phenol-modified polysiloxane; cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; 1,3,5- Trimethyl-1.3.5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclo Cyclic methylphenylcyclosiloxanes such as trasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane; cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane Fluorine-containing cyclosiloxanes such as 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane; Hydrosilyl group-containing cyclosiloxanes such as methylhydrosiloxane mixture, pentamethylcyclopentasiloxane, and phenylhydrocyclosiloxane And vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane.

  Further, for the purpose of adjusting the film formability, flexibility, lubricity, and adhesiveness of the film, it may be used by mixing with other coupling agents and fluorine compounds. As such a compound, various silane coupling agents and commercially available silicone hard coat agents can be used.

  Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyl. Trimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxy Silane and dimethyldimethoxysilane can be used.

  Examples of commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow). Corning) can be used. In order to impart water repellency and the like, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (hepta) Fluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyl Fluorine-containing compounds such as triethoxysilane can also be used. The silane coupling agent can be used in any amount, but if the amount of the fluorine-containing compound is too large, there may be a problem in the film formability of the crosslinked film. Therefore, with respect to 1 part by mass of the compound not containing fluorine, It is desirable to make it 0.25 mass part or less.

  The coating agent composition of the present invention is prepared in the absence of a solvent or, if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether and dioxane. It can be carried out using a solvent such as water or water. Such solvents can be used singly or in combination of two or more, but preferably have a boiling point of 100 ° C. or lower. The amount of the solvent can be arbitrarily set, but if it is too small, the compounds represented by the above general formulas (I) to (V) are likely to be precipitated. Therefore, the compound 1 represented by the above general formulas (I) to (V) It is preferable to set it as 0.2-30 mass parts with respect to a mass part, and it is more preferable to set it as 1-20 mass parts.

  Moreover, when preparing the coating agent composition of the present invention, the above components may be simply mixed and dissolved, but it is room temperature to 100 ° C., preferably 30 ° C. to 80 ° C. for 10 minutes to 100 hours. The heating may be preferably performed for 1 hour to 50 hours. In this case, it is also preferable to irradiate ultrasonic waves. Thereby, a partial reaction probably proceeds, the uniformity of the coating liquid is increased, and a uniform film without coating film defects is easily obtained.

  The curing conditions of the coating agent composition of the present invention can be appropriately selected according to the components of the coating agent composition, but the coating agent composition contains a charge transporting organic compound having a reactive functional group. In this case, in order to sufficiently react the aromatic compound and the charge transporting organic compound, it is preferable to react and cure at a high temperature of 100 ° C. or higher.

  The coating composition of the present invention may be cured without a catalyst, but a catalyst may be used to accelerate the curing reaction. Examples of such a catalyst include laccase, peroxidase, iron-salen complex, cobalt naphthenate catalyst and the like, and these catalysts are effective in promoting the oxidative polymerization of the aromatic compound. Moreover, when the coating agent composition of the present invention contains a charge transporting organic compound having a reactive functional group, the curing reaction can be further accelerated by using an acid catalyst such as paratoluenesulfonic acid. The acid catalyst may be a compound blocked with a base.

  When urushiol is used as the aromatic compound, the coating agent composition of the present invention can be cured under low temperature and high humidity. In the case of curing at low temperature and high humidity, it is necessary to contain a curing polymerization catalyst such as laccase mentioned above. The curing temperature is preferably 20 ° C. to 60 ° C. and a humidity of 70% or more. When the humidity is less than 70%, the curing does not proceed, the required mechanical strength may not be obtained, and a long curing time of several tens of days may be required. It is preferable to promote the reaction.

(Electrophotographic photoreceptor)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photoreceptor of the present invention. The electrophotographic photosensitive member 1 shown in FIG. 1 is a so-called function-separated type photosensitive member in which a charge generation layer 5 and a charge transport layer 6 are separately provided in the photosensitive layer 3. Specifically, the photoreceptor 1 shown in FIG. 1 has a configuration in which an undercoat layer 4, a charge generation layer 5, a charge transport layer 6, and a protective layer 7 are laminated in this order on a conductive substrate 2. ing. And the protective layer 7 is comprised including the hardened | cured material of the coating agent composition of this invention, and is equivalent to a 1st functional layer. The charge transport layer 6 disposed adjacent to the protective layer 7 includes a thermoplastic resin and corresponds to a second functional layer.

  Next, each element constituting the electrophotographic photosensitive member 1 shown in FIG. 1 will be described.

  Examples of the conductive substrate 2 include a metal plate, a metal drum, a metal belt, or a conductive material using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Examples thereof include paper, a plastic film, a belt, and the like on which a conductive compound such as a polymer or indium oxide, or a metal or alloy such as aluminum, palladium, or gold is applied, deposited, or laminated.

  Further, in order to prevent interference fringes generated when laser light is irradiated, the surface of the conductive substrate 2 is preferably roughened, and the center line average roughness Ra in that case is 0.04 μm to 0.5 μm. Is preferred. As a roughening method, wet honing is performed by suspending an abrasive in water and spraying it on the support, or centerless grinding in which the support is pressed against a rotating grindstone and grinding is performed continuously, an anode Oxidation is preferred, and a layer in which conductive or semiconductive powder is dispersed in the resin layer without roughening the support surface itself is formed on the support surface and dispersed in the layer. A method of roughening with particles to be used is also preferably used. If Ra is smaller than 0.04 μm, it becomes close to a mirror surface, so that the effect of preventing interference cannot be obtained. If Ra is larger than 0.5 μm, the image quality becomes rough even if a film is formed, which is not suitable. When non-interfering light is used for the light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to the unevenness of the surface of the base material, which is suitable for longer life.

  The anodizing treatment is to form an oxide film on the aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the intact porous anodic oxide film is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores in the anodized film are sealed with pressurized water vapor or boiling water (a metal salt such as nickel may be added) by volume expansion due to a hydration reaction, and a sealing process is performed to change to a more stable hydrated oxide. .

  The film thickness of the anodized film is preferably 0.3 to 15 μm. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

  The treatment with an acidic treatment solution comprising phosphoric acid, chromic acid and hydrofluoric acid is carried out as follows. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 to 11% by mass, chromic acid is in the range of 3 to 5% by mass, and hydrofluoric acid is in the range of 0.5 to 2% by mass. The concentration of these acids as a whole is preferably in the range of 13.5 to 18% by mass. The processing temperature is 42 to 48 ° C., but by keeping the processing temperature high, a thicker film can be formed faster. About the film thickness of a film, 0.3-15 micrometers is preferable. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

  The boehmite treatment can be performed by immersing in pure water at 90 to 100 ° C. for 5 to 60 minutes or by contacting with heated steam at 90 to 120 ° C. for 5 to 60 minutes. About the film thickness of a film, 0.1-5 micrometers is preferable. This can be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate. Good.

  In addition, examples of the material used for the undercoat layer 4 include zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents, aluminum, and the like. In addition to organoaluminum compounds such as chelate compounds and aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxides Compound, aluminum titanium alkoxide compound, aluminum zirconium arco Sid compounds, and organometallic compounds such as. Among these, organic zirconium compounds, organic titanyl compounds, and organoaluminum compounds are preferably used because of their low residual potential and good electrophotographic characteristics.

  Also, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxycyclohexyltri It can be used by containing a silane coupling agent such as methoxysilane.

  Further, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, which are conventionally used for the undercoat layer Further, known binder resins such as phenol resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, and polyacrylic acid can also be used. These mixing ratios can be appropriately set as necessary.

  In the undercoat layer 4, an electron transport pigment can also be mixed / dispersed. Examples of the electron transport pigment include organic pigments such as perylene pigment, bisbenzimidazole perylene pigment, polycyclic quinone pigment, indigo pigment, and quinacridone pigment described in JP-A-47-30330, cyano group, nitro group, Examples thereof include organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitroso groups and halogen atoms, and inorganic pigments such as zinc oxide and titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments, zinc oxide, and titanium oxide are preferably used because of their high electron mobility. Further, the surface of these pigments may be surface-treated with the above-mentioned coupling agent or binder for the purpose of controlling dispersibility and charge transport property. If the amount of the electron transporting pigment is too large, the strength of the undercoat layer is lowered, and a coating film defect is generated, so that it is used at 95% by mass or less, preferably 90% by mass or less.

  Further, various inorganic particles and organic particles can be added to the undercoat layer 4 for the purpose of improving electrical characteristics and light scattering properties. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white and lithopone, inorganic pigments as extender pigments such as alumina, calcium carbonate and barium sulfate, polyethylene terephthalate resin particles, benzoguanamine resin particles, styrene resin Particles are effective. These particles may be used as they are, but can be used after the treatment with electrolytic alkaline water. The added fine powder has a particle size of 0.01 to 2 μm. The fine powder is added as necessary, but the addition amount is preferably 10 to 90% by mass, and 30 to 80% by mass with respect to the total mass of the solid content of the undercoat layer 4. More preferably.

  The undercoat layer 4 can be formed by applying a coating solution obtained by mixing / dispersing the above constituent materials in a predetermined solvent onto the conductive substrate 2 and drying it. As a mixing / dispersing method, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. As the solvent, any solvent can be used as long as it dissolves an organometallic compound or a resin and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene Ordinary organic solvents such as toluene can be used alone or in admixture of two or more. In addition, as a method for applying the coating solution for forming the undercoat layer 4, conventional methods such as a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used. Drying is performed at a temperature at which the solvent can be evaporated and a film can be formed. The thickness of the undercoat layer 4 is 0.01 to 30 μm, preferably 0.05 to 25 μm.

  Although the undercoat layer 4 is not necessarily provided, it is preferable to form the undercoat layer 4 because the substrate subjected to the acid solution treatment and the boehmite treatment tends to have insufficient defect concealing power.

  The charge generation layer 5 includes a charge generation material. Known charge generation materials include azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, organic pigments such as perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments, and inorganic pigments such as trigonal selenium and zinc oxide. In particular, when an exposure wavelength of 380 to 500 nm is used, metal and metal-free phthalocyanine pigments, trigonal selenium, dibromoanthanthrone and the like are preferable. Among them, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472 and special Dichlorotin phthalocyanine disclosed in Kaihei 5-140473 and titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 are particularly preferred. These charge generation materials may be used as they are, but can be used after being treated with electrolytic alkaline water.

  The charge generation layer 5 may contain a binder resin. The binder resin can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin. Insulating resins such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be mentioned, but are not limited thereto. These binder resins can be used alone or in admixture of two or more. The blending ratio (mass ratio) of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10.

  The charge generation layer 5 can be formed by applying a coating solution obtained by mixing / dispersing the above constituent materials in a predetermined solvent on the undercoat layer 4 and drying it. As a method for mixing / dispersing, a normal method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. At this time, a condition that the crystal type does not change by dispersion is required. . Further, at the time of mixing / dispersing, it is effective to make the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. Moreover, as a solvent to be used, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride Ordinary organic solvents such as chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more. In addition, as a coating method used when the charge generation layer is provided, usual methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used. The thickness of the charge generation layer 5 is generally 0.1 to 5 μm, preferably 0.2 to 2.0 μm.

  The charge transport layer 6 is formed containing a charge transport material and a binder resin, or is formed containing a polymer charge transport material.

  Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds Electron transporting compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include pore transporting compounds. These charge transport materials can be used alone or in combination of two or more, but are not limited thereto. These charge transport materials can be used alone or in combination of two or more. From the viewpoint of mobility, they are represented by the following general formula (XII-1), (XII-2) or (XII-3). Compounds are preferred.

Here, in the above formula (XII-1), R ¹⁷ is a hydrogen atom or a methyl group, k is 1 or 2, Ar ⁶ and Ar ⁷ are each independently a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —C ₆ H ₄ —CH═CH—CH═C (Ar) ₂ is represented, and the substituent is a halogen atom, carbon number 1 The substituted amino group substituted by the alkyl group of -5, a C1-C5 alkoxy group, or a C1-C3 alkyl group is shown. R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group.

Here, in the formula (XII-2), R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group substituted with an alkyl group having 1 to 2 carbon atoms, A substituted aryl group, —C ₆ H ₄ —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —C ₆ H ₄ —CH═CH—CH═C (Ar) ₂ , p, q, r, and s each independently represent an integer of 0-2. R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group.

Here, in the formula (XII-3), R ²⁷ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH. -CH = C (Ar) ₂ is shown. Ar represents a substituted or unsubstituted aryl group. R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each independently substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. A substituted amino group or a substituted or unsubstituted aryl group.

  Examples of the binder resin used for the charge transport layer 6 include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, and chloride. Vinylidene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly- N-vinyl carbazole, polysilane, and polymer charge transport materials such as polyester-based polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used alone or in admixture of two or more. In the present invention, a polycarbonate resin is more preferable from the viewpoints of electronic properties and strength, and it is desirable to increase the average molecular weight of the polycarbonate from the viewpoint of improving the adhesion between the charge transport layer 6 and the protective layer 7. Specifically, the viscosity average molecular weight of the polycarbonate is preferably 30000 or more, and more preferably 40000 or more. Further, the compounding ratio (mass ratio) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5, but from the viewpoint of improving the adhesiveness, it is preferable to increase the ratio of the binder resin. The blending ratio (mass ratio) is more preferably 1: 1 to 1: 5.

  Further, instead of using the low molecular charge transport material and the binder resin in combination, a high molecular charge transport material can be used alone. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, the polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material alone can be used as the charge transport layer, but it may be formed by mixing with the binder resin.

  The charge transport layer 6 can be formed by applying a coating liquid containing the above constituent materials onto the charge generation layer 5 and drying it. Solvents used in the coating solution for the charge transport layer 6 include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halongen such as methylene chloride, chloroform and ethylene chloride. Ordinary organic solvents such as cyclic aliphatic ethers such as fluorinated aliphatic hydrocarbons, tetrahydrofuran and ethyl ether. These can be used individually by 1 type or in mixture of 2 or more types. As a coating method of the coating solution for forming the charge transport layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method should be used. Can do. In order to maintain the adhesion between the charge transport layer 6 and the protective layer 7, it is desirable that the solvent is not left as much as possible after drying. Specifically, the residual solvent is sufficiently low to be 1% or less. It is preferred to evaporate the solvent at an elevated temperature. The film thickness of the charge transport layer 6 is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  As described above, the protective layer 7 includes a cured product of the coating agent composition of the present invention.

  The protective layer 7 can be formed by applying the coating agent composition of the present invention on the charge transport layer 6 and drying it. As a coating method, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a flow coating method can be used.

  Further, the drying temperature of the coating film to be the protective layer 7 can be appropriately selected. However, when the coating liquid for forming the protective layer 7 contains a charge transporting compound having a reactive functional group and a solvent, the curable resin and the charge are charged. In order to sufficiently react with the transporting compound and sufficiently evaporate the solvent, it is preferable to cure for a long time until the reaction sufficiently proceeds at a high temperature of 100 ° C. or higher, more preferably 120 ° C. or higher.

  The thickness of the protective layer 7 is generally 1 to 10 μm, preferably 2 to 8 μm.

  The electrophotographic photosensitive member of the present invention is not limited to the above embodiment. For example, in the above embodiment, the function-separated type photoconductor in which the charge generation layer 5 and the charge transport layer 6 are separately provided has been described. However, the electrophotographic photoconductor of the present invention has a charge generation material as shown in FIG. And a single-layer type photoreceptor having a layer (charge generation / charge transport layer) containing both the charge transport material and the charge transport material. The electrophotographic photosensitive member shown in FIG. 2 has a structure in which an undercoat layer 4, a charge generation / charge transport layer 8, and a protective layer 7 are laminated in this order on a conductive substrate 2. The charge transport layer 8 corresponds to the second functional layer, and the protective layer 7 corresponds to the first functional layer. In addition, when a stacked structure such as a charge generation layer, a charge transport layer, and a protective layer is used, it is possible to perform functional separation that each layer only has to satisfy each function, and from the viewpoint that higher functions can be realized, the electrophotography of the present invention. The photoreceptor is preferably a function separation type photoreceptor.

(Image forming device)
FIG. 3 is a schematic diagram showing a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 100 shown in FIG. 3 includes, in an image forming apparatus main body (not shown), a process cartridge 20 including the above-described electrophotographic photosensitive member 1 of the present invention, an exposure device 30, a transfer device 40, and an intermediate transfer. A body 50. In the image forming apparatus 100, the exposure device 30 is disposed at a position where the electrophotographic photosensitive member 1 can be exposed from the opening of the process cartridge 20, and the transfer device 40 is interposed between the electrophotographic photosensitive member via the intermediate transfer member 50. The intermediate transfer member 50 is disposed such that a part of the intermediate transfer member 50 can come into contact with the electrophotographic photosensitive member 1.

  The process cartridge 20 is obtained by integrating a charging device 21, a developing device 25, a cleaning device 27, and a fibrous member (toothbrush shape) 29 together with an electrophotographic photosensitive member 1 by a mounting rail in a case. The case is provided with an opening for exposure. Further, the fibrous member 29 is not necessarily provided.

  Here, the charging device 21 charges the electrophotographic photosensitive member 1 by a contact method. The developing device 25 develops the electrostatic latent image on the electrophotographic photosensitive member 1 to form a toner image.

Hereinafter, the toner used for the developing device 25 will be described. The toner preferably has an average shape factor (ML ² / A) of 100 to 150, and more preferably 100 to 140. Further, the toner preferably has a volume average particle diameter of 2 to 12 μm, more preferably 3 to 12 μm, and further preferably 3 to 9 μm. By using a toner satisfying such an average shape factor and volume average particle diameter, it is possible to obtain an image with high development, transferability and high image quality.

  The toner is not particularly limited by the production method as long as it satisfies the above average shape factor and volume average particle diameter. For example, the toner may include a binder resin, a colorant, a release agent, and the like. A kneading and pulverizing method in which a charge control agent is added, kneading, pulverizing, and classifying; a method in which the shape of particles obtained by the kneading and pulverizing method is changed by mechanical impact force or thermal energy; Emulsion polymerization of the body, and the resulting dispersion is mixed with a dispersion of a colorant, a release agent and, if necessary, a charge control agent, and then agglomerated and heat-fused to obtain toner particles. Suspension polymerization method in which a polymerizable monomer for obtaining a binder resin, a colorant, a release agent, and a charge control agent, if necessary, are suspended in an aqueous solvent and polymerized; A water-based solution of a resin, a colorant, a release agent, and a solution such as a charge control agent as necessary. Toner is used which is suspended in and produced by a dissolution suspension method in which granulated.

  Further, a known method such as a production method in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to give a core-shell structure can be used. The toner production method is preferably a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method in which an aqueous solvent is used from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly preferable.

  The toner base particles are composed of a binder resin, a colorant, and a release agent, and include silica and a charge control agent as necessary.

  Binder resins used for toner base particles include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Α-methylene aliphatics such as vinyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers and copolymers of monocarboxylic acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone Polyester resins by copolymerization of dicarboxylic acids and diols.

  Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. A polymer, polyethylene, polypropylene, a polyester resin, etc. can be mentioned. In addition, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can also be mentioned.

  In addition, as colorants, magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, Lamp Black, Rose Bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

  Typical examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer tropic wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  As the charge control agent, known ones can be used, and azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  The toner used in the developing device 25 can be manufactured by mixing the toner base particles and the external additive with a Henschel mixer or a V blender. In addition, when the toner base particles are produced by a wet method, external addition can also be performed by a wet method.

  Lubricating particles may be added to the toner used in the developing device 25. Lubricating particles include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids and fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, silicones having a softening point upon heating, oleic amides Aliphatic amides such as erucic acid amide, ricinoleic acid amide, stearic acid amide, etc., plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animals such as beeswax Minerals such as system waxes, montan waxes, ozokerites, ceresins, paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, etc., petroleum waxes, and modified products thereof can be used. These can be used individually by 1 type or in combination of 2 or more types. However, the volume average particle size is preferably in the range of 0.1 to 10 μm, and the particles having the above chemical structure may be pulverized to make the particle sizes uniform. The amount added to the toner is preferably in the range of 0.05 to 2.0 mass%, more preferably 0.1 to 1.5 mass%.

  To the toner used in the developing device 25, inorganic particles, organic particles, composite particles obtained by attaching inorganic particles to the organic particles, and the like can be added for the purpose of removing the adhered matter and deteriorated matter on the surface of the electrophotographic photoreceptor. .

  Inorganic particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used.

  In addition, the inorganic particles may be mixed with titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, γ- (2- Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxy Silane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane The treatment may be performed with a silane coupling agent such as run, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. In addition, those hydrophobized with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate and calcium stearate are also preferably used.

  Examples of the organic particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  The particle diameter is preferably a volume average particle diameter of 5 nm to 1000 nm, more preferably 5 nm to 800 nm, and still more preferably 5 nm to 700 nm. If the volume average particle diameter is less than the lower limit, the polishing ability tends to be lacking. On the other hand, if the volume average particle diameter exceeds the upper limit, the surface of the electrophotographic photosensitive member tends to be damaged. Moreover, it is preferable that the sum of the addition amount of the particle | grains mentioned above and lubricity particle | grains is 0.6 mass% or more.

  Other inorganic oxides added to the toner are small-diameter inorganic oxides with a primary particle size of 40 nm or less for powder flowability, charge control, etc. It is preferable to add a larger-diameter inorganic oxide. These inorganic oxide particles can be known ones, but it is preferable to use silica and titanium oxide in combination for precise charge control. Further, the surface treatment of the small-diameter inorganic particles increases the dispersibility and increases the effect of increasing the powder fluidity. Furthermore, it is also preferable to add carbonates such as calcium carbonate and magnesium carbonate and inorganic minerals such as hydrotalcite in order to remove the discharge purified product.

  In addition, the color toner for electrophotography is used by mixing with a carrier. As the carrier, iron powder, glass beads, ferrite powder, nickel powder, or those having a resin coating on the surface thereof are used. The mixing ratio with the carrier can be set as appropriate.

  The cleaning device 27 includes a fibrous member (roll shape) 27a and a cleaning blade (blade member) 27b.

Although the cleaning device 27 is provided with the fibrous member 27a and the cleaning blade 27b, the cleaning device 27 may be provided with either one. The fibrous member 27a may have a toothbrush shape in addition to the roll shape. Further, the fibrous member 27a may be fixed to the cleaning device main body, may be supported so as to be rotatable, and may be supported so as to be capable of oscillating in the photosensitive member axial direction. As the fibrous member 27a, polyester, nylon, acrylic, etc., cloth-like ones made of ultrafine fibers such as Toraysee (made by Toray Industries), resin fibers such as nylon, acrylic, polyolefin, polyester, etc. are used as a substrate or carpet. The brush-like thing etc. which were flocked to can be mentioned. Further, as the fibrous member 27a, a conductive powder or an ionic conductive agent is added to the above-described material to impart conductivity, or a conductive layer is formed inside or outside of each fiber. Can also be used. When conductivity is imparted, the resistance value is preferably 10 ² to 10 ⁹ Ω as a single fiber. The fiber thickness of the fibrous member 27a is preferably 30 d (denier) or less, more preferably 20 d or less, and the fiber density is preferably 20,000 fibers / inch ² or more, more preferably 30,000 fibers / inch. inch ² or more.

  The cleaning device 27 is required to remove deposits (for example, discharge products) on the surface of the photoreceptor with a cleaning blade and a cleaning brush. In order to achieve this purpose over a long period of time and stabilize the function of the cleaning member, the cleaning member may be supplied with a lubricating substance (lubricating component) such as metal soap, higher alcohol, wax, silicone oil or the like. preferable.

  For example, when a roll-shaped member is used as the fibrous member 27a, it is preferable to supply a lubricating component to the surface of the electrophotographic photosensitive member by bringing it into contact with a lubricating substance such as metal soap or wax. A normal rubber blade is used as the cleaning blade 27b. As described above, when a rubber blade is used as the cleaning blade 27b, supplying a lubricating component to the surface of the electrophotographic photosensitive member is particularly effective in suppressing chipping and wear of the blade.

  The process cartridge 20 described above is detachable from the image forming apparatus main body, and constitutes the image forming apparatus together with the image forming apparatus main body.

  The exposure device 30 may be any device that exposes the charged electrophotographic photosensitive member 1 to form an electrostatic latent image. Further, it is preferable to use a multi-beam surface emitting laser as the light source of the exposure apparatus 30.

  The transfer device 40 may be any device that transfers the toner image on the electrophotographic photosensitive member 1 to a transfer medium (intermediate transfer member 50). For example, a roll-shaped one that is usually used is used.

  As the intermediate transfer member 50, a belt-like member (intermediate transfer belt) made of polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber or the like having semiconductivity is used. Further, as the form of the intermediate transfer member 50, a drum-like member can be used in addition to the belt-like member. Although there is a direct transfer type image forming apparatus that does not include the intermediate transfer body, the electrophotographic photosensitive member of the present invention is suitable for such an image forming apparatus. The reason is that in a direct transfer type image forming apparatus, paper dust, talc, and the like are generated from the print paper and are likely to adhere to the electrophotographic photosensitive member, and image quality defects due to the attached matter tend to occur. However, according to the electrophotographic photoreceptor of the present invention, it is easy to remove paper dust and talc because of its excellent cleaning properties, and a stable image can be obtained even with a direct transfer type image forming apparatus. it can.

  The transfer medium referred to in the present invention is not particularly limited as long as it is a medium to which a toner image formed on the electrophotographic photoreceptor 1 is transferred. For example, when transferring directly from the electrophotographic photosensitive member 1 to paper or the like, paper or the like is a transfer medium, and when the intermediate transfer member 50 is used, the intermediate transfer member is a transfer medium.

  FIG. 4 is a schematic view showing another embodiment of the image forming apparatus of the present invention. In the image forming apparatus 110 shown in FIG. 4, the electrophotographic photosensitive member 1 is fixed to the image forming apparatus main body, and the charging device 22, the developing device 25, and the cleaning device 27 are each formed into a cartridge, and the charging cartridge, the developing cartridge, It is provided independently as a cleaning cartridge. Note that the charging device 22 includes a charging device for charging by a corona discharge method, for example.

  In the image forming apparatus 110, the electrophotographic photosensitive member 1 and other apparatuses are separated, and the charging device 22, the developing device 25, and the cleaning device 27 are fixed to the image forming apparatus main body by screws, caulking, adhesion, or welding. It is possible to detach it by the operation by pulling out and pushing in without being done.

  Since the electrophotographic photosensitive member of the present invention is excellent in wear resistance, it may not be necessary to form a cartridge. Therefore, the charging device 22, the developing device 25, or the cleaning device 27 can be detached and attached by an operation by pulling out and pushing in without being fixed to the main body by screws, caulking, adhesion, or welding. The member cost per hit can be reduced. Further, two or more of these devices can be detachable as an integrated cartridge, thereby further reducing the member cost per print.

  The image forming apparatus 110 has the same configuration as that of the image forming apparatus 100 except that the charging device 22, the developing device 25, and the cleaning device 27 are each formed as a cartridge.

  FIG. 5 is a schematic view showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 120 is a tandem full-color image forming apparatus equipped with four process cartridges 20. In the image forming apparatus 120, four process cartridges 20 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member can be used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

  In the tandem-type image forming apparatus 120, the amount of wear of each electrophotographic photosensitive member varies depending on the use ratio of each color, and thus the electrical characteristics of each electrophotographic photosensitive member tend to vary. Along with this, the toner development characteristics gradually change from the initial state, and the hue of the print image changes, so that a stable image cannot be obtained. In particular, in order to reduce the size of the image forming apparatus, a small-diameter electrophotographic photosensitive member tends to be used, and this tendency becomes prominent when one having a diameter of 30 mmφ or less is used. Here, when the configuration of the electrophotographic photosensitive member of the present invention is adopted as the electrophotographic photosensitive member, the surface wear is sufficiently suppressed even when the diameter is 30 mmφ or less. Therefore, the electrophotographic photosensitive member of the present invention is particularly effective for a tandem type image forming apparatus.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.

[Production of electrophotographic photosensitive member]
Example 1
An 84 mmφ cylindrical aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness (10-point average roughness Rz in accordance with JIS-B0601) was set to Rz = 0.6 μm. As a cleaning process for the aluminum substrate, a degreasing process, an etching process for 1 minute with a 2% by mass sodium hydroxide solution, a neutralization process, and a pure water cleaning were sequentially performed. Next, as an anodizing treatment step, an anodized film (current density: 1.0 A / dm ² ) was formed on the surface of the aluminum substrate using a 10% by mass sulfuric acid solution. After washing with water, sealing was performed by dipping in a 1% by mass nickel acetate solution at 80 ° C. for 20 minutes. Furthermore, pure water washing | cleaning and the drying process were performed. In this way, an anodized film having a thickness of 7 μm was formed on the surface of the aluminum substrate.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 10 parts by mass of hydroxygallium phthalocyanine having a strong diffraction peak at 28.3 ° is mixed with 10 parts by mass of polyvinyl butyral (Esreck BM-S, Sekisui Chemical) and 1000 parts by mass of n-butyl acetate, and 1 with a paint shaker together with glass beads. The coating solution for forming the charge generation layer was obtained by time dispersion treatment. This coating solution was applied on the outer peripheral surface (anodized film) of the aluminum substrate by a dip coating method and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2.5 parts by mass of a benzidine compound represented by the following formula (B) and 3 parts by mass of a polymer compound having a structural unit represented by the following formula (B) (viscosity average molecular weight 39000) are added to 20 parts by mass of chlorobenzene. It was dissolved to obtain a coating solution for forming a charge transport layer. This coating solution was applied onto the charge generation layer by a dip coating method and heated at 115 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

Next, Zhugo lacquer (manufactured by Sekizaka Lacquerware Co., Ltd.) and an extraction solvent in which n-butanol and pure water were mixed at a mass ratio of 1: 1 were mixed so that the mass ratio was 10: 100. The urushiol component contained in the lacquer was extracted on the n-butanol side, and impurities were extracted on the water side to obtain a two-phase liquid. Of these, only the n-butanol extract was taken out, and the n-butanol in it was volatilized and removed. As a result, urushiol represented by the following formula (A-2) (R = C ₁₅ H ₃₁ , C ₁₅ H ₂₉ , C ₁₅ H ₂₇ , C ₁₅ H ₂₅ mixture) was obtained. 3 parts by mass of urushiol obtained, 3 parts by mass of compound (I-1) in Table 5, 0.01 part by mass of paratoluenesulfonic acid and 6 parts by mass of methanol were mixed to form a coating solution for forming a protective layer (hereinafter, "Coating agent composition (1)") was obtained. The obtained coating solution is applied on the charge transport layer by a ring-type dip coating method and dried at 160 ° C. for 60 minutes to form a protective layer having a thickness of 4 μm. Body (1) ").

(Example 2)
First, a 84 mmφ cylindrical aluminum substrate with a honing treatment was prepared as a conductive substrate.

  Next, 100 parts by mass of a zirconium compound (trade name: Orgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by mass of a silane compound (trade name: A1100, manufactured by Nihon Unicar), 400 parts by mass of isopropanol, and 200 parts by mass of butanol By mixing, a coating solution for forming an undercoat layer was obtained. The obtained coating solution was applied on the above aluminum substrate by a dip coating method and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.1 μm.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 10 parts by mass of hydroxygallium phthalocyanine having a strong diffraction peak at 28.3 °, 10 parts by mass of polyvinyl butyral (Esreck BM-S, Sekisui Chemical) and 1000 parts by mass of n-butyl acetate are mixed, and 1 with a paint shaker together with glass beads. The coating solution for forming the charge generation layer was obtained by time dispersion treatment. This coating solution was applied onto the undercoat layer by a dip coating method and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, a coating solution for forming a charge transport layer was prepared in the same manner as in Example 1. The obtained coating solution was applied onto the charge generation layer by a dip coating method, and heated at 115 ° C. for 40 minutes. A charge transport layer having a thickness of 29 μm was formed.

  Next, the coating agent composition (1) prepared in the same manner as in Example 1 was applied on the charge transport layer by a ring-type dip coating method and dried at 160 ° C. for 60 minutes to form a protective layer having a thickness of 4 μm. To obtain an intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor (2)”).

(Example 3)
Cashew nut oil was vacuum distilled, and an extraction solvent prepared by mixing n-butanol and pure water at a mass ratio of 1: 1 was mixed at a mass ratio of 10: 100, and the cardanol component contained in the cashew nut oil was n- Two-phase liquid was obtained by extracting to the butanol side and extracting impurities to the water side. Of these, only the n-butanol extract was taken out, and the n-butanol in it was volatilized and removed. Thereby, cardanol represented by the following formula (A-3) (R = C ₁₅ H ₃₁ , C ₁₅ H ₂₉ , C ₁₅ H ₂₇ , C ₁₅ H ₂₅ mixture) was obtained. Next, 3 parts by mass of the obtained cardanol, 3 parts by mass of the compound (I-1) in Table 5, 0.01 part by mass of paratoluenesulfonic acid and 6 parts by mass of methanol were mixed, and a coating solution for forming a protective layer ( Hereinafter, “coating agent composition (2)”) was prepared.

  Next, in the same manner as in Example 1 except that the protective layer was formed using the coating agent composition (2) instead of the coating agent composition (1), an electrophotographic photosensitive member (hereinafter referred to as “photosensitive member” 3) ") was produced.

Example 4
An electrophotographic photoreceptor (hereinafter referred to as “photoreceptor (4)”) was prepared in the same manner as in Example 2 except that the protective layer was formed using the coating composition (2) instead of the coating composition (1). Produced).

(Example 5)
An immobilized lipase (manufactured by Novozym 435 Novo Nordisk), a compound represented by the following formula (A-4) and a compound represented by the following formula (A-5) in a THF solvent were stirred at a temperature of 40 ° C. for 4 hours. Esterification was performed, and the reaction solution was filtered and purified to obtain a compound represented by the following formula (A-6). Next, 3 parts by mass of the compound represented by the following formula (A-6), 3 parts by mass of the compound (I-1) in Table 5, 0.01 part by mass of paratoluenesulfonic acid, and 6 parts by mass of methanol were mixed. A coating liquid for forming a protective layer (hereinafter referred to as “coating agent composition (3)”) was obtained.

  Next, in the same manner as in Example 1 except that the protective layer was formed using the coating agent composition (3) instead of the coating agent composition (1), an electrophotographic photosensitive member (hereinafter referred to as “photosensitive member”). 5) ").

(Example 6)
An electrophotographic photosensitive member (hereinafter referred to as “photosensitive member (6)”) was prepared in the same manner as in Example 2 except that the protective layer was formed using the coating agent composition (3) instead of the coating agent composition (1). Was made.

(Comparative Example 1)
3 parts by mass of the compound (I-1) in Table 5, 3 parts by mass of a resol type phenolic resin (PL-4852, manufactured by Gunei Chemical), 0.01 parts by mass of paratoluenesulfonic acid and 6 parts by mass of methanol were mixed. A coating liquid for forming a protective layer (hereinafter referred to as “coating agent composition (4)”) was obtained.

  Next, in the same manner as in Example 1 except that the protective layer was formed using the coating agent composition (4) instead of the coating agent composition (1), an electrophotographic photosensitive member (hereinafter referred to as “photosensitive member (hereinafter referred to as“ photosensitive member ”)). 7) ").

(Comparative Example 2)
The electrophotographic photosensitive member (hereinafter referred to as “photosensitive member (8)”) was prepared in the same manner as in Example 1 except that the protective layer was formed using the coating agent composition (4) instead of the coating agent composition (1). .) Was produced.

(Comparative Example 3)
In Table 5, 3 parts by mass of compound (I-1), 3 parts by mass of o-cresol, 0.01 part by mass of paratoluenesulfonic acid and 6 parts by mass of methanol were mixed to form a coating solution for forming a protective layer (hereinafter referred to as “coating Agent composition (5) ").

  Next, in the same manner as in Example 1 except that the protective layer was formed using the coating agent composition (5) instead of the coating agent composition (1), an electrophotographic photosensitive member (hereinafter referred to as “photosensitive member” 9) ").

(Comparative Example 4)
The electrophotographic photosensitive member (hereinafter referred to as “photosensitive member (10)”) was prepared in the same manner as in Example 1 except that the protective layer was formed using the coating agent composition (5) instead of the coating agent composition (1). .) Was produced.

[Measurement of residual potential]
Using the photoreceptors (1) to (10), the residual potential was measured as follows. First, in a low temperature and low humidity (10 ° C., 15% RH) environment, each electrophotographic photosensitive member was charged to −700 V with a scorotron charger having a grid applied voltage of −700 V. Next, each electrophotographic photosensitive member 1 second after charging was discharged by irradiating it with 10 mJ / m ² of light using a semiconductor laser of 780 nm. Further, 3 seconds after discharging, each electrophotographic photosensitive member is irradiated with 50 mJ / m ² of red LED light to eliminate static electricity, and the surface potential of each electrophotographic photosensitive member at this time is measured to measure the residual potential Rp ( V). The results obtained are shown in Table 48.

[Developer preparation]
A developer was prepared as follows. Each physical property value was measured by the following method.
(Toner, composite particle size distribution)
Using a multisizer (manufactured by Nikka Machine Co., Ltd.), measurement was performed with an aperture diameter of 100 μm.
(Toner, composite particle average shape factor ML ² / A)
It means a value calculated by the following formula. In the case of a true sphere, ML ² / A = 100.
ML ² / A = (maximum length) ² × π × 100 / (area × 4)
As a specific method for obtaining the average shape factor, a toner image is taken from an optical microscope into an image analyzer (LUZEXIII, manufactured by Nireco), and an equivalent circle diameter is measured for any 100 toners, and the maximum length and From the area, the value of ML ² / A in the above formula was obtained for each particle, and the average value was taken as the average shape factor ML ² / A.

(Manufacture of toner mother particles)
A mixture obtained by mixing 370 parts by mass of styrene, 30 parts by mass of n-butyl acrylate, 8 parts by mass of acrylic acid, 24 parts by mass of dodecanethiol, and 4 parts by mass of carbon tetrabromide, and a nonionic surfactant (Nonipol 400: Sanyo Kasei) (Product) 6 mass parts and anionic surfactant (Neogen SC: Daiichi Kogyo Seiyaku Co., Ltd. product) 10 mass parts were emulsion-polymerized in the flask with ion-exchange water 550 mass parts, While slowly mixing for 10 minutes, 50 parts by mass of ion-exchanged water in which 4 parts by mass of ammonium persulfate was dissolved was added. After carrying out nitrogen substitution, the inside of the flask was stirred and heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin particle dispersion 1 was obtained in which resin particles having an average particle diameter of 150 nm, Tg = 58 ° C., and weight average molecular weight Mw = 11500 were dispersed. The solid content concentration of this dispersion was 40% by mass.

(Preparation of colorant dispersion (1))
60 parts by mass of carbon black (Mogal L: Cabot), 6 parts by mass of nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and 240 parts by mass of ion-exchanged water were mixed, and a homogenizer (Ultra Turrax T50: The mixture was stirred for 10 minutes using IKA, and then dispersed with an optimizer to prepare a colorant dispersion (1) in which colorant (carbon black) particles having an average particle size of 250 nm were dispersed. .

(Preparation of colorant dispersion (2))
60 parts by mass of Cyan pigment (B15: 3), 5 parts by mass of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and 240 parts by mass of ion-exchanged water were mixed together, and a homogenizer (Ultra Turrax T50: IKA) was mixed. The colorant dispersion (2) was prepared by dispersing the colorant (Cyan pigment) particles having an average particle diameter of 250 nm by dispersing with an optimizer.

(Preparation of colorant dispersion (3))
60 parts by weight of Magenta pigment (R122), 5 parts by weight of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and 240 parts by weight of ion-exchanged water were mixed together, and a homogenizer (Ultra Turrax T50: manufactured by IKA). Then, a colorant dispersion (3) in which colorant (Magenta pigment) particles having an average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer for 10 minutes.

(Preparation of colorant dispersion (4))
90 parts by weight of Yellow pigment (Y180), 5 parts by weight of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and 240 parts by weight of ion-exchanged water were mixed together, and a homogenizer (Ultra Turrax T50: manufactured by IKA). Then, a colorant dispersion (4) in which colorant (Yellow pigment) particles having an average particle size of 250 nm were dispersed was prepared by dispersing with an optimizer for 10 minutes.

(Preparation of release agent dispersion (1))
100 parts by weight of paraffin wax (HNP0190: manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.), 5 parts by weight of a cationic surfactant (Sanisol B50: manufactured by Kao Corporation) and 240 parts by weight of ion-exchanged water are mixed. After dispersing for 10 minutes in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), the dispersion was performed with a pressure discharge type homogenizer, and release agent particles having an average particle diameter of 550 nm were dispersed. A release agent dispersion (1) was prepared.

(Preparation of toner mother particles K1)
Resin particle dispersion (1) 234 parts by mass, colorant dispersion (1) 30 parts by mass, release agent dispersion (1) 40 parts by mass, polyaluminum hydroxide (manufactured by Asada Chemical Co., Ltd., Paho2S) 0.5 part by mass And 600 parts by mass of ion-exchanged water were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then stirred in the oil bath for heating. Heated to 40 ° C. After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were produced. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and D50 was 5.3 μm. Thereafter, 26 parts by weight of the resin particle dispersion (1) was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles was added with 1N sodium hydroxide to adjust the pH of the system to 7.0, and then the stainless steel flask was sealed and heated to 80 ° C. while continuing to stir using a magnetic seal. And held for 4 hours. After cooling, the toner base particles were separated by filtration, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K1. The toner base particle K1 had a D50 of 5.9 μm and an average shape factor ML ² / A of 132.

(Preparation of toner base particles C1)
Toner base particles C1 were obtained in the same manner as toner base particles K1, except that the colorant dispersion (2) was used instead of the colorant dispersion (1). D50 of the toner mother particles C1 was 5.8 μm, and the average shape factor ML ² / A was 131.

(Preparation of toner mother particles M1)
Toner base particles M1 were obtained in the same manner as toner base particles K1, except that the colorant dispersion (3) was used instead of the colorant dispersion (1). D50 of the toner mother particles M1 was 5.5 μm, and the average shape factor ML ² / A was 135.

(Preparation of toner mother particles Y1)
Toner base particles Y1 were obtained in the same manner as toner base particles K1, except that the colorant dispersion liquid (4) was used instead of the colorant dispersion liquid (1). D50 of the toner base particle Y1 was 5.9 μm, and the average shape factor ML ² / A was 130.

(Preparation of carrier)
First, 14 parts by mass of toluene, 2 parts by mass of a styrene / methacrylate copolymer (component ratio: 90/10) and 0.2 parts by mass of carbon black (R330: manufactured by Cabot) were mixed and stirred with a stirrer for 10 minutes. A dispersion was obtained. Next, the dispersion and 100 parts by mass of ferrite particles (average particle size: 50 μm) are put in a vacuum degassing kneader, stirred at 60 ° C. for 30 minutes, and then degassed by heating under reduced pressure, A carrier was obtained by drying. This carrier had a volume resistivity of 10 ¹¹ Ωcm when an applied electric field of 1000 V / cm was applied.

(Preparation of developer (1))
100 parts by mass of each of the toner base particles K1, C1, M1, Y1 is 1 part by mass of rutile type titanium oxide (volume average particle diameter 20 nm, treated with n-decyltrimethoxysilane), silica (volume average particle diameter). 40 nm, silicone oil treatment, gas phase oxidation method 2 parts by mass, cerium oxide (average particle size 0.7 μm) 1 part by mass, and higher fatty acid alcohol (higher fatty acid alcohol with molecular weight 700, zinc stearate and calcium carbonate (average) (Particle size 0.1 μm) was mixed at a mass ratio of 5: 1: 1 and pulverized with a jet mill to obtain a volume average particle size of 8.0 μm, 0.3 parts by mass using a 5 L Henschel mixer and a peripheral speed of 30 m The mixture was then blended for 15 minutes at / s, and then coarse particles were removed using a sieve having an opening of 45 μm to obtain toner (1), and then toner (1) 5 100 parts by mass of the carrier obtained above was added to a part by weight and stirred for 20 minutes at 40 rpm using a V-blender, and then sieved with a sieve having an opening of 212 μm to obtain developer (1). It was.

[Production of image forming apparatus]
(Examples 7-12, Comparative Examples 5-8)
In Examples 7 to 12 and Comparative Examples 5 to 8, image forming apparatuses were produced using the photoreceptors (1) to (10) and the developer (1), respectively. The exposure apparatus used was a threshold beam surface emitting laser having an oscillation wavelength of 780 nm. The other elements were the same as those of Fuji Xerox printer DocuCenter Color 500.

[Evaluation of image flow, peeling and wear]
Using each image forming apparatus of Examples 7 to 12 and Comparative Examples 5 to 8, 10,000 sheets in each environment of high temperature and high humidity (28 ° C., 85% RH) and low temperature and low humidity (10 ° C., 20% RH) After printing, the image quality after standing for one day (24 hours) in the printer was visually evaluated. The results obtained are shown in Table 49. In Table 49, “A” means “good” and “B” means that the image flow is clearly generated.

  Further, the presence or absence of peeling was visually observed for each electrophotographic photosensitive member after the printing test. The results obtained are shown in Table 49. In Table 49, “A” means good and “B” means that peeling occurred.

  Moreover, about each electrophotographic photoreceptor after the said print test, the film thickness of the part which has not peeled was measured, and the abrasion rate per 1000 cycles was calculated | required from this measured value and the film thickness before use. The results obtained are shown in Table 49.

  Further, for each electrophotographic photosensitive member after the printing test, the presence or absence of deposits on the surface of the photosensitive member was visually observed. The results obtained are shown in Table 49. In Table 49, “A” means that no deposit was found, and “B” means that a deposit was found.

  In addition, in order to cope with the adhesion between the charge transport layer and the protective layer and the evaluation of peeling in the print test, 100 1 mm square grids were put on the surface of each electrophotographic photosensitive member, and Sumitomo 3M Co., Ltd. ) Manufactured adhesive tape (transparent light packaging OPP tape, product number 605) was applied, and the number of peeled grids was measured. The results obtained are shown in Table 49.

[Ghost evaluation]
Using the image forming apparatuses of Examples 7 to 12 and Comparative Examples 5 to 8, the x chart shown in FIG. 6A was printed under the environment of low temperature and low humidity (10 ° C., 20% RH), and the output image was visually observed. Observed and evaluated. The obtained results are shown in Table 49. In Table 49, “A” was good as shown in FIG. 6A, and “B” was slightly ghosted as shown in FIG. 6B. “C” means that a ghost has clearly occurred as shown in FIG.

1 is a schematic cross-sectional view showing a preferred embodiment of an electrophotographic photoreceptor of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. 1 is a schematic diagram showing a preferred embodiment of an image forming apparatus of the present invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. (A)-(c) is explanatory drawing which shows the reference | standard of ghost evaluation, respectively.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photosensitive member, 2 ... Conductive support body, 3 ... Photosensitive layer, 4 ... Undercoat layer, 5 ... Charge generation layer, 6 ... Charge transport layer, 7 ... Protective layer, 8 ... Single layer type photosensitive layer, 20 Process cartridge, 100, 110, 120, 130 Image forming apparatus.

Claims (8)

An aromatic compound having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an organic group containing an ethylenically unsaturated bond bonded to the aromatic ring;
A coating composition comprising a charge transporting organic compound and / or conductive inorganic particles.   The coating composition according to claim 1, wherein the aromatic compound is a phenol derivative or a catechol derivative.   The coating agent composition according to claim 1 or 2, wherein the organic group is an organic group having a plurality of ethylenically unsaturated bonds and having 10 or more carbon atoms.   The coating agent composition contains a charge transporting organic compound, and the charge transporting organic compound is a reactive functional group capable of forming a crosslinked structure by reaction with the aromatic compound and / or reaction between the charge transporting organic compounds. It has group, The coating agent composition as described in any one of Claims 1-3 characterized by the above-mentioned. The coating agent composition contains a charge transporting organic compound, and the charge transporting organic compound has a structure represented by any one of the following general formulas (I) to (V): Item 5. The coating agent composition according to any one of Items 1 to 4.
F-[(X ¹ ) _n R ¹ -A] _m (I)
[In Formula (I), F represents an m-valent organic group derived from a compound having a hole transporting ability, R ¹ represents an alkylene group, and m represents an integer of 1 to 4. X ¹ represents an oxygen atom or a sulfur atom, and n represents 0 or 1. A represents a hydroxyl group, a carboxyl group, or a thiol group. ]
_{^{F - [(X 2) n1}} - (R 2) n2 - (Z 2) n3 G] n4 (II)
[In Formula (II), F represents an n4-valent organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, and Z ² represents An alkylene group, an oxygen atom, a sulfur atom, NH or COO, G represents an epoxy group, n1, n2 and n3 each independently represents 0 or 1, and n4 represents an integer of 1 to 4; ]

[In Formula (III), F represents an n5-valent organic group derived from a compound having a hole transporting ability, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁶ represents a monovalent organic group, m 1 represents 0 or 1, and n 5 represents an integer of 1 to 4. However, R ⁵ and R ⁶ may be bonded to each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (IV), F represents an n6 valent organic group derived from a compound having a hole transporting ability, T represents a divalent group, R ⁷ represents a monovalent organic group, and m2 represents 0 or 1 is shown, n6 shows the integer of 1-4. ]

[In formula (V), F represents an n7-valent organic group derived from a compound having a hole transporting ability, L represents an alkylene group, R ⁸ represents a monovalent organic group, and n7 represents 1 to 1 An integer of 4 is shown. ] An electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer provided on the conductive substrate,
The photosensitive layer is
A first functional layer disposed at a position farthest from the conductive substrate and containing a cured product of the coating agent composition according to claim 1,
An electrophotographic photosensitive member comprising a second functional layer disposed adjacent to the first functional layer and containing a thermoplastic resin. An electrophotographic photoreceptor according to claim 6;
A charging device for charging the electrophotographic photoreceptor;
An image exposure apparatus for forming an electrostatic latent image on the charged electrophotographic photosensitive member;
A developing device for developing the electrostatic latent image with toner to form a toner image;
A transfer device for transferring the toner image from the electrophotographic photosensitive member to a transfer target;
An image forming apparatus comprising: An electrophotographic photoreceptor according to claim 6;
A charging device for charging the electrophotographic photosensitive member, a developing device for developing an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image, and an electrophotographic photosensitive member A process cartridge comprising: at least one selected from a cleaning device for removing toner remaining on the surface.

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