JP2007003929A - Coating agent composition, electrophotographic photoreceptor, method for manufacturing the same and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptorusing a coating agent composition which enhances the mechanical strength and lubricity of an electrophotographic photoreceptor and can maintain these properties at a high level, over a prolonged period of time, and to provide a method for manufacturing the electrophotographic photoreceptor, and an image forming apparatus. <P>SOLUTION: The coating agent composition contains a phenol derivative having a methylol group, a charge transport compound having a functional group capable of reacting with the phenol derivative, and a compound represented by Formula (A), wherein at least one of A<SP>1</SP>-A<SP>8</SP>is a group having one selected from epoxy, carboxyl and hydroxyphenyl, and a and b each independently denotes an integer of 1-100. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a coating agent composition suitable as a material for an electrophotographic photosensitive member, an electrophotographic photosensitive member using the coating agent composition, a method for producing the same, and an image forming apparatus including the electrophotographic photosensitive member.

  A so-called xerographic image forming apparatus includes an electrophotographic photoreceptor (hereinafter, simply referred to as “photoreceptor”), a charging device, an exposure 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 improved in speed and life due to technological progress of each member and system. Accordingly, demands for high-speed compatibility and high reliability of each subsystem are higher than ever. In particular, there is a strong demand for high-speed compatibility and high reliability for a photoconductor used for image writing and a cleaning member for cleaning the photoconductor. In addition, the photosensitive member and the cleaning member receive more stress than the other members due to their mutual sliding. Therefore, the photoconductor is scratched or worn, which causes image defects.

  In order to suppress such scratches and wear, the electrophotographic photosensitive member uses a resin having high mechanical strength, and further extends its life. For example, in Patent Documents 1 and 2, the protective layer is configured using a charge transport material having a phenol resin and a hydroxyl group.

In Patent Documents 3 and 4, in a photoreceptor provided with a protective layer containing a phenolic resin, fluorine atom-containing resin particles, silicone particles, etc. are used for improving the electrical properties in order to improve the lubricity of the protective layer. Discloses a technique of adding conductive particles and a siloxane compound to the protective layer in order to improve coatability.
JP 2002-82469 A JP 2003-186234 A JP 2002-6527 A JP 2003-5408 A

  However, even the photoreceptors described in Patent Documents 1 to 4 have room for improvement in the following points in order to be put to practical use.

  For example, in the case of the photoconductors described in Patent Documents 1 and 2, the mechanical strength of the photoconductor is improved by using a crosslinkable resin. However, if a cleaning blade is used as a cleaning device of an image forming apparatus, the photoconductor Therefore, poor removal of discharge products adhering to the surface of the photoreceptor is likely to occur. For this reason, when these photoconductors are used, toner additives and the like aggregate on the blade edge, and the aggregates adhere to the surface of the electrophotographic photoconductor due to blade vibration (stick-slip phenomenon) accompanying the operation of the electrophotographic photoconductor. As a result, filming is likely to occur. This filming is a phenomenon that is noticeable in a color image forming apparatus that forms an image by superposing a plurality of color toner images.

  In the case of the photoreceptors described in Patent Documents 3 and 4, it is possible to improve the initial cleaning property by using a lubricant, but if the photoreceptor is used for a long period of time, the lubricant particles are detached from the surface layer. A dent is formed by falling off, and toner or an external additive is buried in the dent and filming occurs. Further, even when a siloxane compound is added to the protective layer, it is possible to improve the initial cleaning properties, but there is a problem that the intended effect cannot be obtained continuously.

  According to the study by the present inventors, it is considered that the problem when the lubricant or the siloxane compound is used is caused by the low affinity between the lubricant or the siloxane compound and other constituent materials. In particular, the effect of adding a siloxane compound cannot be obtained for a long period of time when the coating agent (coating liquid) containing the constituent material of the protective layer is cured by bleed-out of the siloxane compound in the vicinity of the surface of the protective layer obtained ( This is because the siloxane compound tends to be unevenly distributed in the vicinity of the interface on the lower layer side). Therefore, in order to suppress the occurrence of filming and obtain a stable image over a long period of time, it is important to improve the mechanical strength and lubricity of the surface layer and improve the affinity between the constituent materials. However, a coating agent that provides such a surface layer has not been developed yet.

  The present invention has been made in view of such circumstances, and is a coating composition useful as a material for a surface layer of an electrophotographic photosensitive member, which improves mechanical strength and lubricity in the cured product. In addition, an object of the present invention is to provide a coating composition capable of maintaining these properties at a high level for a long period of time. Another object of the present invention is to provide an electrophotographic photoreceptor using the coating composition, a method for producing the same, and an image forming apparatus including the electrophotographic photoreceptor.

  In order to solve the above problems, the present invention contains a phenol derivative having a methylol group, a charge transporting compound having a functional group capable of reacting with the phenol derivative, and a compound represented by the following general formula (A) A coating agent composition is provided.

［式（Ａ）中、Ａ^１〜Ａ^８はそれぞれ水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のエポキシ基置換アルキル基、炭素数１〜１０のエポキシ基置換アルコキシ基、炭素数１〜１５のフッ素置換アルキル、炭素数１〜１５のフッ素置換アルコキシ基、炭素数１〜１０のカルボキシル基置換アルキル基、炭素数１〜１０のカルボキシル基置換アルコキシ基、炭素数１〜１５のヒドロキシフェニル基置換アルキル基、又は炭素数１〜１５のアルコキシフェニル基置換アルキル基アルコキシ基を示し、Ａ^１〜Ａ^８のうち少なくとも一つはエポキシ基、カルボキシル基及びヒドロキシフェニル基から選択される一つを有する基であり、ａ及びｂはそれぞれ独立に１〜１００の整数を示す。］

[In Formula (A), A ^{1 to} A ⁸ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an epoxy group-substituted alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. -10 epoxy group-substituted alkoxy group, C1-C15 fluorine-substituted alkyl, C1-C15 fluorine-substituted alkoxy group, C1-C10 carboxyl group-substituted alkyl group, C1-C10 carboxyl group A substituted alkoxy group, a hydroxyphenyl group-substituted alkyl group having 1 to 15 carbon atoms, or an alkoxyphenyl group-substituted alkyl group alkoxy group having 1 to 15 carbon atoms, wherein at least one of A ^{1 to} A ⁸ is an epoxy group or a carboxyl group And a group having one selected from a hydroxyphenyl group, a and b each independently represent an integer of 1 to 100. ]

  The above-described phenol derivative, charge transporting compound and compound represented by the general formula (A) contained in the coating agent composition of the present invention have a sufficient affinity for each other. At the time of curing, chemical bonds can be formed in the cured film. Therefore, in the cured product of the coating composition of the present invention, mechanical strength, electrical characteristics mainly derived from the charge transporting compound, and lubricity mainly derived from the compound represented by the general formula (A) Can be achieved at a high level and with a good balance. Therefore, the electrical characteristics can be sufficiently maintained by using the functional layer made of the cured product of the coating agent composition of the present invention as the surface layer of the electrophotographic photosensitive member (the layer far from the conductive support of the photosensitive layer). On the other hand, it is possible to realize an electrophotographic photosensitive member capable of improving mechanical strength and lubricity and maintaining those characteristics at a high level over a long period of time.

  Although the compound represented by the general formula (A) is a so-called siloxane compound, the compound has sufficient affinity for other constituent materials as described above, and has good solubility in a solution state. Indicates. In addition, since the compound has one selected from an epoxy group, a carboxyl group, and a hydroxyphenyl group, the cured film obtained by curing the coating agent composition is uniformly and uniformly formed in the cured film by the formation of chemical bonds. It is held stably. Therefore, bleed-out that is a problem in the conventional photoconductor can be sufficiently suppressed, and a high level of lubricity improvement effect can be obtained over a long period of time.

  Further, the introduction of a group selected from an epoxy group, a carboxyl group and a hydroxyphenyl group in the compound represented by the general formula (A) is based on the knowledge of the present inventors that it is advantageous in terms of electrical characteristics of the cured film. Is. It is possible to form a chemical bond even by introducing an isocyanate group, an amino group, etc., but in this case, the cured film obtained has poor electrical characteristics and the electrophotographic photoreceptor has insufficient electrophotographic characteristics. Become.

In the present invention, the charge transporting compound preferably has a structure represented by any one of the following general formulas (I) to (V). By using the charge transporting compound having the structure represented by the general formulas (I) to (V), the mechanical strength and the electrical characteristics can be compatible at a higher level in the cured film of the coating agent composition. Become.
_{^{F [- (X 1) m}} -R 1 -Z 1 H] n ... (I)
[In Formula (I), F represents an n-valent organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, Sulfur atom, NH or COO, m represents 0 or 1, and n represents an integer of 1 to 4. ]
_{^{F [- (X 2) m1}} - (R 2) m2 - (Z 2) m3 G] n1 ... (II)
[In Formula (II), F represents an n1-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, Z ² represents an oxygen atom, S is a sulfur atom, NH or COO, G is an epoxy group, m1, m2 and m3 are each independently 0 or 1, and n1 is an integer of 1 to 4. ]
_{^{F [-D-Si (R 3}} ) (3-m4) Q m4] n2 ... (III)
[In Formula (III), F is an n2 valent organic group derived from a compound having a hole transporting ability, D is a divalent group having flexibility, and R ³ is a hydrogen atom, substituted or unsubstituted. Q represents a hydrolyzable group, m4 represents an integer of 1 to 3, and n2 represents an integer of 1 to 4. ]

［式（ＩＶ）中、Ｆは正孔輸送性を有するｎ３価の有機基を、Ｔ^１は２価の基を、Ｙは酸素原子又は硫黄原子を、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を、Ｒ^７は１価の有機基を、ｍ５は０又は１を、ｎ３は１〜４の整数を、それぞれ示す。但し、Ｒ^６とＲ^７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。］

[In Formula (IV), F represents an n3-valent organic group having hole transportability, T ¹ represents a divalent group, Y represents an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ represent independently a hydrogen atom or a monovalent organic group, the ^{R 7} is a monovalent organic group, m5 is 0 or 1, n3 is an integer of 1 to 4, respectively. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

［式（Ｖ）中、Ｆは正孔輸送性を有するｎ４価の有機基を、Ｔ２は２価の基を、Ｒ^８は１価の有機基を、ｍ６は０又は１を、ｎ４は１〜４の整数を、それぞれ示す。］
また、本発明においては、上記電荷輸送性化合物が下記一般式（ＶＩ）で表される構造を有することが好ましい。

[In Formula (V), at the n4 monovalent organic group F is having a hole transporting property, the T2 is a divalent radical, the ^{R 8} is a monovalent organic group, a is m6 0 or 1, n4 is 1 Integers of ~ 4 are shown respectively. ]
In the present invention, the charge transporting compound preferably has a structure represented by the following general formula (VI).

［式（ＶＩ）中、Ａｒ^１〜Ａｒ^４はそれぞれ独立に置換又は未置換のアリール基を示し、ｋは０又は１を示し、ｋが０のときＡｒ^５は置換又は未置換のアリール基を示し、ｋが１のときＡｒ^５は置換又は未置換のアリーレン基を示し、Ｂ^１、Ｂ^２、Ｂ^３、Ｂ^４及びＢ^５はそれぞれ下記一般式（ＶＩＩ）〜（ＸＩ）のいずれかで表される基を示し、ｃ、ｄ、ｅ、ｆ及びｇはそれぞれ０又は１を示し、ｃ、ｄ、ｅ、ｆ及びｇの和は１〜４の整数である。］
−（Ｘ^１）_ｍＲ^１−Ｚ^１Ｈ （ＶＩＩ）
［式（ＶＩＩ）中、Ｘ^１は酸素原子又は硫黄原子を示し、Ｒ^１はアルキレン基を示し、Ｚ^１は酸素原子、硫黄原子、ＮＨ基又はＣＯ_２基を示し、ｍは０又は１を示す。］
−（Ｘ^２）_ｍ１−（Ｒ^２）_ｍ２−（Ｚ^２）_ｍ３Ｇ （ＶＩＩＩ）
［式（ＶＩＩＩ）中、Ｘ^２は酸素原子又は硫黄原子を示し、Ｒ^２はアルキレン基を示し、Ｚ^２は酸素原子、硫黄原子、ＮＨ基又はＣＯ_２基を示し、Ｇはエポキシ基を示し、ｍ１、ｍ２及びｍ３はそれぞれ独立に０又は１を示す。］
−Ｄ−Ｓｉ（Ｒ^３）_{（３−ｍ４）}Ｑ_ｍ４ （ＩＸ）
[式（ＩＸ）中、Ｄは２価の基を示し、Ｒ^３は水素原子、アルキル基、又は置換若しくは未置換のアリール基を示し、Ｑは加水分解性基を示し、ｍ４は１〜３の整数を示す。]

[In Formula (VI), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, k represents 0 or 1, and when k is 0, Ar ⁵ represents a substituted or unsubstituted aryl group. And when k is 1, Ar ⁵ represents a substituted or unsubstituted arylene group, and B ¹ , B ² , B ³ , B ⁴ and B ⁵ are each represented by any of the following general formulas (VII) to (XI): The group represented is represented, c, d, e, f and g each represent 0 or 1, and the sum of c, d, e, f and g is an integer of 1 to 4. ]
_{^{- (X 1) m 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, an NH group or a CO ₂ group, and m represents 0 or 1 Show. ]
_{^{- (X 2) m1 - (}} R 2) m2 - (Z 2) m3 G (VIII)
[In Formula (VIII), X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, a sulfur atom, an NH group or a CO ₂ group, and G represents an epoxy group. , M1, m2 and m3 each independently represents 0 or 1. ]
-D-Si (R ³ ) _(3-m4) Q _m4 (IX)
[In Formula (IX), D represents a divalent group, R ³ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and m4 represents 1 to 3 Indicates an integer. ]

［式（Ｘ）中、Ｔ^１は２価の基を示し、Ｙは酸素原子又は硫黄原子を示し、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ^７は１価の有機基を示し、ｍ５は０又は１を示し、Ｒ^６とＲ^７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。］

[In formula (X), T ¹ represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 5 represents 0 or 1, and R ⁶ and R ⁷ may be bonded to each other to form a heterocycle having Y as a hetero atom. ]

［式（ＸＩ）中、Ｔ^２は２価の基を示し、Ｒ^８は１価の有機基を示し、ｍ６は０又は１を示す。］

[In formula (XI), T ² represents a divalent group, R ⁸ represents a monovalent organic group, and m6 represents 0 or 1. ]

  In addition, the coating agent composition of the present invention preferably further contains a solvent, and from the viewpoint of further reducing damage to the base during application of the coating agent composition, the proportion of the alcohol solvent in the total amount of the solvent is It is preferably 50% by volume or more. Furthermore, in this case, the coating agent composition of the present invention preferably further contains 5 to 20% by mass of an alcohol-soluble resin in addition to the phenol derivative having a methylol group. Thereby, the discharge gas resistance of a cured film obtained, mechanical strength, scratch resistance, particle dispersibility, adhesiveness, etc. can further be improved.

  The present invention also provides an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the support, wherein the photosensitive layer is provided on the side far from the conductive support. An electrophotographic photoreceptor comprising a functional layer made of a cured product of the coating agent composition is provided.

  According to the electrophotographic photoreceptor of the present invention, by providing a functional layer made of a cured product of the coating agent composition of the present invention on the side of the photosensitive layer far from the conductive support, the electrical characteristics can be sufficiently maintained. However, it is possible to improve the mechanical strength and lubricity and to maintain these characteristics at a high level over a long period of time.

  Moreover, it is preferable that the said functional layer with which the electrophotographic photoreceptor of this invention is equipped further contains 0.1-30 mass% of microparticles | fine-particles with a volume average particle diameter of 5-1,000 nm. As a result, surface properties such as contamination resistance adhesion and lubricity on the surface of the electrophotographic photosensitive member can be further improved.

  Moreover, it is preferable that the said functional layer with which the electrophotographic photoreceptor of this invention is equipped further contains 0.1-20 mass% of antioxidants. As described above, when 0.1 to 20% by mass of the antioxidant is contained in the functional layer, the antioxidant is uniformly dispersed and stably maintained, so that a high level of antioxidant characteristics is obtained. be able to.

  The present invention also relates to a method for producing an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the support, wherein the functional layer is provided on the side of the photosensitive layer remote from the conductive support. And preparing a target object to be an electrophotographic photosensitive member, and applying the coating composition of the present invention on the side of the target object far from the conductive support and curing to form a functional layer. A process for producing an electrophotographic photosensitive member, comprising the steps of:

  According to the method for producing an electrophotographic photosensitive member of the present invention, by having the above-described configuration, the mechanical strength and the lubricity are improved while maintaining the electrical characteristics sufficiently, and the characteristics are maintained at a high level for a long time. Thus, the electrophotographic photoreceptor of the present invention that can be effectively obtained.

  The present invention also provides an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the support, wherein the photosensitive layer is provided on the side far from the conductive support. An electrophotographic photosensitive member including a functional layer made of a cured product of a coating agent composition, a charging device for charging the electrophotographic photosensitive member, and an exposure device for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image A developing device that develops the electrostatic latent image with toner to form a toner image, a transfer device that transfers the toner image to a transfer medium, and a toner that remains on the electrophotographic photosensitive member after the toner image is transferred An image forming apparatus is provided.

  Since the image forming apparatus according to the present invention includes the electrophotographic photosensitive member according to the present invention, the surface of the photosensitive member may be damaged in the cleaning process, or filming may occur due to aggregates of toner external additives. Therefore, contaminants due to residual toner and discharge products can be reliably removed. Therefore, according to the image forming apparatus of the present invention, it is possible to realize both high speed, high performance, and long life, which were difficult to achieve with the conventional image forming apparatus.

  In the image forming apparatus of the present invention, a toner having an average shape factor of 100 to 150 can be preferably used. Note that, when a toner having an average shape factor in the range of 100 to 150 is used in a conventional image forming apparatus, the toner tends to slip through between the electrophotographic photosensitive member and the cleaning device. In the forming apparatus, even if a toner having an average shape factor of 100 to 150 is used, the toner can be sufficiently prevented from slipping through, so that a high level of image quality can be maintained for a long time. The average shape factor of the toner is more preferably from 100 to 140, and even more preferably from 100 to 130, from the viewpoint of high image quality.

  According to the present invention, it is a coating composition useful as a material for the surface layer of an electrophotographic photoreceptor, and in the resulting cured product, it improves mechanical strength and lubricity, and at the same time, has a high level of properties. A coating composition is provided that can be maintained. In addition, according to the present invention, an electrophotographic photoreceptor using the coating composition, a method for producing the same, and an image forming apparatus including the electrophotographic photoreceptor are provided.

  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 or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

(Coating agent composition)
Examples of the phenol derivative having a methylol group contained in the coating agent composition of the present invention include monomers of monomethylolphenols, dimethylolphenols or trimethylolphenols, mixtures thereof, those oligomerized, or those A mixture of monomers and oligomers can be mentioned. Such phenol derivatives having a methylol group include resorcin, bisphenol, etc., substituted phenols containing one hydroxyl group such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, and two hydroxyl groups such as catechol, resorcinol, hydroquinone, etc. It is obtained by reacting a compound having a phenol structure such as bisphenols such as substituted phenols, bisphenol A, and bisphenol Z with formaldehyde, paraformaldehyde, etc. in the presence of an acid catalyst or an alkali catalyst. What is marketed as can also be used. In the present specification, a relatively large molecule having about 2 to 20 repeating molecular structural units is referred to as an oligomer, and a molecule smaller than that is referred to as a monomer.

As the acid catalyst, sulfuric acid, paratoluenesulfonic acid, phosphoric acid and the like are used. Further, as the alkali catalyst, hydroxides or amine catalysts of alkali metals and alkaline earth metals such as NaOH, KOH, Ca (OH) ₂ and Ba (OH) ₂ are used.

  Examples of the amine catalyst include, but are not limited to, ammonia, hexamethylenetetramine, trimethylamine, triethylamine, and triethanolamine. When a basic catalyst is used, the carrier is remarkably trapped by the remaining catalyst, and the electrophotographic characteristics tend to be deteriorated. Therefore, it is preferable to inactivate or remove by neutralizing with an acid or contacting with an adsorbent such as silica gel or an ion exchange resin.

  Whether or not the cured product of the coating agent composition includes the above phenol derivative is indicated by the following general formula (B) by gas chromatography-mass spectrometry when the cured product is pyrolyzed. It can be easily determined depending on whether or not a phenol derivative is detected.

［式中、ｎは１〜３の整数を示す。］

[In formula, n shows the integer of 1-3. ]

  As a measurement condition for pyrolysis gas chromatography-mass spectrometry, a cured product of the coating agent composition was heated at 300 ° C. (or 600 ° C.) for 1 minute using a pyrolysis apparatus (manufactured by Frontier Laboratories: PY-2010D). Gas chromatography-mass spectrometer (manufactured by Hewlett Packard: HP6890 / HP5973), capillary column (manufactured by Hewlett Packard: HP-5MS: 5% -Diphenyl 95% -dimethylpolysiloxane copolymer, film thickness 0. 25 μm, inner diameter 0.25 mm, length 30 m), carrier gas (He: 1 ml / min.), 50 ° C. to 10 ° C./min. The column is heated up to 200 ° C. at a temperature rising rate of 5 ° C. and held at 200 ° C. for 5 minutes for measurement. The structure can be easily identified from the obtained spectrum using a spectrum database. In addition, when measuring about the surface layer of an electrophotographic photoconductor, a surface layer can be peeled from an electrophotographic photoconductor and said measurement can be performed.

  Although content of the said phenol derivative in the coating agent composition of this invention is arbitrary, Preferably it is 10-90 mass% on the basis of the composition whole quantity, More preferably, it is 15-85 mass%. When the content of the phenol derivative is less than 10% by mass, the charge transportability of the obtained cured product tends to be insufficient, and when it exceeds 90% by mass, the strength of the obtained cured product becomes insufficient. There is a tendency.

In addition, the charge transporting compound having a functional group capable of reacting with a phenol derivative contained in the coating agent composition of the present invention includes a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a carbonate group, a thiol group, and an amino group. A charge transporting compound having at least one selected from is preferably used. Specific examples of such charge transporting compounds include those represented by the following general formulas (I) to (V).
_{^{F [- (X 1) m}} -R 1 -Z 1 H] n ... (I)
[In Formula (I), F represents an n-valent organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, Sulfur atom, NH or COO, m represents 0 or 1, and n represents an integer of 1 to 4. ]
_{^{F [- (X 2) m1}} - (R 2) m2 - (Z 2) m3 G] n1 ... (II)
[In Formula (II), F represents an n1-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, Z ² represents an oxygen atom, S is a sulfur atom, NH or COO, G is an epoxy group, m1, m2 and m3 are each independently 0 or 1, and n1 is an integer of 1 to 4. ]
_{^{F [-D-Si (R 3}} ) (3-m4) Q m4] n2 ... (III)
[In Formula (III), F is an n2 valent organic group derived from a compound having a hole transporting ability, D is a divalent group having flexibility, and R ³ is a hydrogen atom, substituted or unsubstituted. Q represents a hydrolyzable group, m4 represents an integer of 1 to 3, and n2 represents an integer of 1 to 4. ]

［式（ＩＶ）中、Ｆは正孔輸送性を有するｎ３価の有機基を、Ｔは２価の基を、Ｙは酸素原子又は硫黄原子を、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を、Ｒ^７は１価の有機基を、ｍ５は０又は１を、ｎ３は１〜４の整数を、それぞれ示す。但し、Ｒ^６とＲ^７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。］

[In Formula (IV), F is an n3-valent organic group having a hole transporting property, T is a divalent group, Y is an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ are independent of each other. Represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m5 represents 0 or 1, and n3 represents an integer of 1 to 4. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

［式（Ｖ）中、Ｆは正孔輸送性を有するｎ４価の有機基を、Ｔは２価の基を、Ｒ^８は１価の有機基を、ｍ６は０又は１を、ｎ４は１〜４の整数を、それぞれ示す。］

[In the formula (V), F represents an n4 valent organic group having a hole transport property, T represents a divalent group, R ⁸ represents a monovalent organic group, m6 represents 0 or 1, and n4 represents 1 Integers of ~ 4 are shown respectively. ]

  Further, among the charge transport materials represented by the above formulas (I) to (V), a compound having a structure represented by the following general formula (VI) is more preferable.

［式（ＶＩ）中、Ａｒ^１〜Ａｒ^４はそれぞれ独立に置換又は未置換のアリール基を示し、ｋは０又は１を示し、ｋが０のときＡｒ^５は置換又は未置換のアリール基を示し、ｋが１のときＡｒ^５は置換又は未置換のアリーレン基を示し、Ｂ^１、Ｂ^２、Ｂ^３、Ｂ^４及びＢ^５はそれぞれ下記一般式（ＶＩＩ）〜（ＸＩ）のいずれかで表される基を示し、ｃ、ｄ、ｅ、ｆ及びｇはそれぞれ０又は１を示し、ｃ、ｄ、ｅ、ｆ及びｇの和は１〜４の整数である。］
−（Ｘ^１）_ｍＲ^１−Ｚ^１Ｈ （ＶＩＩ）
［式（ＶＩＩ）中、Ｘ^１は酸素原子又は硫黄原子を示し、Ｒ^１はアルキレン基を示し、Ｚ^１は酸素原子、硫黄原子、ＮＨ基又はＣＯ_２基を示し、ｍは０又は１を示す。］
−（Ｘ^２）_ｍ１−（Ｒ^２）_ｍ２−（Ｚ^２）_ｍ３Ｇ （ＶＩＩＩ）
［式（ＶＩＩＩ）中、Ｘ^２は酸素原子又は硫黄原子を示し、Ｒ^２はアルキレン基を示し、Ｚ^２は酸素原子、硫黄原子、ＮＨ基又はＣＯ_２基を示し、Ｇはエポキシ基を示し、ｍ１、ｍ２及びｍ３はそれぞれ独立に０又は１を示す。］
−Ｄ−Ｓｉ（Ｒ^３）_{（３−ｍ４）}Ｑ_ｍ４ （ＩＸ）
[式（ＩＸ）中、Ｄは２価の基を示し、Ｒ^３は水素原子、アルキル基、又は置換若しくは未置換のアリール基を示し、Ｑは加水分解性基を示し、ｍ４は１〜３の整数を示す。]

[In Formula (VI), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, k represents 0 or 1, and when k is 0, Ar ⁵ represents a substituted or unsubstituted aryl group. And when k is 1, Ar ⁵ represents a substituted or unsubstituted arylene group, and B ¹ , B ² , B ³ , B ⁴ and B ⁵ are each represented by any of the following general formulas (VII) to (XI): The group represented is represented, c, d, e, f and g each represent 0 or 1, and the sum of c, d, e, f and g is an integer of 1 to 4. ]
_{^{- (X 1) m 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, an NH group or a CO ₂ group, and m represents 0 or 1 Show. ]
_{^{- (X 2) m1 - (}} R 2) m2 - (Z 2) m3 G (VIII)
[In Formula (VIII), X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, a sulfur atom, an NH group or a CO ₂ group, and G represents an epoxy group. , M1, m2 and m3 each independently represents 0 or 1. ]
-D-Si (R ³ ) _(3-m4) Q _m4 (IX)
[In Formula (IX), D represents a divalent group, R ³ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and m4 represents 1 to 3 Indicates an integer. ]

［式（Ｘ）中、Ｔ^１は２価の基を示し、Ｙは酸素原子又は硫黄原子を示し、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ^７は１価の有機基を示し、ｍ５は０又は１を示し、Ｒ^６とＲ^７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。］

[In formula (X), T ¹ represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 5 represents 0 or 1, and R ⁶ and R ⁷ may be bonded to each other to form a heterocycle having Y as a hetero atom. ]

［式（ＸＩ）中、Ｔ^２は２価の基を示し、Ｒ^８は１価の有機基を示し、ｍ６は０又は１を示す。］

[In formula (XI), T ² represents a divalent group, R ⁸ represents a monovalent organic group, and m6 represents 0 or 1. ]

As the substituted or unsubstituted aryl group represented by Ar ^{1 to} Ar ⁴ in the general formula (VI), specifically, an aryl group represented by the following formulas (1) to (7) is preferable.

In the general formulas (1) to (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, or substituted with them. A phenyl group or an unsubstituted phenyl group, or an aralkyl group having 7 to 10 carbon atoms, wherein R ^{10 to} R ¹² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, carbon An alkoxy group having 1 to 4 carbon atoms, a phenyl or unsubstituted phenyl group substituted therewith, an aralkyl group having 7 to 10 carbon atoms or a halogen atom; Ar represents a substituted or unsubstituted arylene group; One of the structures represented by the general formulas (VII) to (XI) is shown, c and s each represent 0 or 1, and t represents an integer of 1 to 3.

  Ar in the aryl group represented by the general formula (7) is preferably an arylene group represented by the following general formula (8) or (9).

In the general formulas (8) and (9), R ¹³ and R ¹⁴ are each substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. A substituted phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, and t represents an integer of 1 to 3.

  Further, as Z ′ in the aryl group represented by the general formula (7), divalent groups represented by the following formulas (10) to (17) are preferable.

In the general formulas (10) to (17), R ¹⁵ and R ¹⁶ are each substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. A substituted phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, W represents a divalent group, q and r each represent an integer of 1 to 10, t represents an integer of 1 to 3, respectively.

  In the above formulas (16) to (17), W represents a divalent group represented by the following general formulas (18) to (26). In general formula (25), u represents an integer of 0 to 3.

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

  Specific examples of the compound represented by the general formula (I) include the following compounds (I-1) to (I-37). In addition, in the following table | surface, although the bond is described, the thing in which the substituent is not described shows a methyl group.

  Specific examples of the compound represented by the general formula (II) include the following compounds (II-1) to (II-47). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

Specific examples of the compound represented by the general formula (III) include the following compounds (III-1) to (III-61). The following compounds (III-1) to (III-61) are a combination of Ar ^{1 to} Ar ⁵ and k of the compound represented by the general formula (VI) as shown in the following table, and an alkoxysilyl group. (S) is the specific one shown in the table below.

  Specific examples of the compound represented by the general formula (IV) include the following compounds (IV-1) to (IV-40). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (V) include the following compounds (V-1) to (V-13). In the following table, Me or a bond is described but a substituent is not described indicates a methyl group.

  Among the compounds represented by the general formulas (I) to (V), when the compound represented by the general formula (V) is used, a decarboxylation reaction occurs during curing, and the base in the phenol resin is neutralized. Therefore, the thing excellent in an electrical property is obtained.

  Although content of the said charge transportable compound in the coating agent composition of this invention is arbitrary, Preferably it is 10-90 mass% on the basis of the composition whole quantity, More preferably, it is 15-85 mass%. When the content of the charge transporting compound is less than 10% by mass, the charge transporting property of the obtained cured product tends to be insufficient, and when it exceeds 90% by mass, the mechanical strength of the obtained cured product is poor. It tends to be sufficient.

  Moreover, the coating agent composition of the present invention contains a compound represented by the following general formula (A) in addition to the above-described phenol derivative having a methylol group and a charge transporting compound.

［上記一般式（Ａ）中、Ａ^１〜Ａ^８はそれぞれ水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のエポキシ基置換アルキル基、炭素数１〜１０のエポキシ基置換アルコキシ基、炭素数１〜１５のフッ素置換アルキル、炭素数１〜１５のフッ素置換アルコキシ基、炭素数１〜１０のカルボキシル基置換アルキル基、炭素数１〜１０のカルボキシル基置換アルコキシ基、炭素数１〜１５のヒドロキシフェニル基置換アルキル基、又は炭素数１〜１５のアルコキシフェニル基置換アルキル基アルコキシ基を示し、Ａ^１〜Ａ^８のうち少なくとも一つはエポキシ基、カルボキシル基及びヒドロキシフェニル基から選択される一つを有する基である。］

[In the general formula ^(A), A 1 ~A ⁸ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an epoxy group-substituted alkyl group having 1 to 10 carbon atoms, carbon An epoxy group-substituted alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 15 carbon atoms, a fluorine-substituted alkoxy group having 1 to 15 carbon atoms, a carboxyl group-substituted alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms A carboxyl group-substituted alkoxy group, a hydroxyphenyl group-substituted alkyl group having 1 to 15 carbon atoms, or an alkoxyphenyl group-substituted alkyl group alkoxy group having 1 to 15 carbon atoms, wherein at least one of A ^{1 to} A ⁸ is an epoxy group , A group having one selected from a carboxyl group and a hydroxyphenyl group. ]

  Moreover, in said general formula (A), a and b show the integer of 1-100 each independently. From the viewpoint of film formability, the sum of a and b is preferably 10 or more, and more preferably 15 or more. From the viewpoint of solubility, the sum of a and b is preferably 200 or less, and more preferably 150 or less.

  Preferable examples of the compound represented by the general formula (A) include compounds (A-1) to (A-24) shown in Table 50 and Table 51 below.

  The content of the compound represented by the general formula (A) in the coating agent composition of the present invention is arbitrary, but the total amount of the phenol derivative having a methylol group and the charge transporting compound having a reactive functional group is 100 mass. Preferably it is 0.01-5 mass parts with respect to a part, More preferably, it is 0.1-3 mass part. When the content of the compound represented by the general formula (A) is less than 0.01 parts by mass, the film formability and the lubricity of the obtained cured product tend to be insufficient, and when the content exceeds 5 parts by mass. The resulting cured product tends to have insufficient adhesion to the ground and mechanical strength.

  As will be described later, the coating composition of the present invention has the above-described phenol derivative, charge transporting compound and general one depending on the properties required when the cured product is applied to the functional layer of the electrophotographic photoreceptor. You may further contain components other than the compound shown by Formula (A).

  The coating agent composition of the present invention may be prepared without a solvent, but if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, diethyl ether and dioxane It can carry out using solvents, such as ethers. 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 the amount is too small, the compounds represented by the general formulas (I) to (V) are likely to be precipitated. Therefore, relative to 1 part by mass of the compounds represented by the general formulas (I) to (V) The amount is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass. Further, from the viewpoint of preventing dissolution of the base, the proportion of the alcohol solvent in the total amount of the solvent is preferably 50% by volume or more.

  In addition, when a coating composition is obtained by reacting the above components, it may be simply mixed and dissolved, but it is room temperature to 100 ° C., preferably 30 ° C. to 80 ° C., 10 minutes to 100 hours, preferably 1 You may heat for time-50 hours. In this case, it is also preferable to apply an ultrasonic wave. Thereby, since partial reaction advances and the uniformity of a coating agent composition increases, it becomes easy to obtain the uniform film | membrane without a coating-film defect in the case of hardening.

(Electrophotographic photoreceptor and manufacturing method thereof)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photosensitive member according to the present invention. The electrophotographic photoreceptor 1 shown in FIG. 1 includes a conductive support 11 and a photosensitive layer 12, and the photosensitive layer 12 is an undercoat layer 13, a charge generation layer 14, a charge in order from the side close to the conductive support 11. The transport layer 15 and the protective layer 16 are stacked. The surface layer in the electrophotographic photoreceptor 1 shown in FIG. 1 is a protective layer 16, and this protective layer 16 is composed of a cured product of the coating agent composition of the present invention.

  Hereinafter, each element of the electrophotographic photoreceptor 1 shown in FIG. 1 will be described.

  Examples of the conductive support 11 include a metal plate, a metal drum, and a metal belt formed using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Etc. Examples of the conductive support 11 include a paper, a plastic film, a belt, and the like on which a conductive polymer, a conductive compound such as indium oxide, or a metal or alloy such as aluminum, palladium, or gold is applied, evaporated, or laminated.

  When the photosensitive member 1 is used in a laser printer, the laser oscillation wavelength is preferably 350 nm to 850 nm, and the shorter wavelength is preferable because the resolution is excellent. The surface of the conductive support 11 is preferably roughened to a center line average roughness Ra of 0.04 μm to 0.5 μm in order to prevent interference fringes generated when laser light is irradiated. If Ra is less than 0.04 μm, it tends to be close to a mirror surface, so that the effect of preventing interference tends not to be obtained. On the other hand, if Ra exceeds 0.5 μm, the image quality tends to be rough even if a film is formed. . Further, 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 conductive support 11, which is suitable for longer life.

  As a roughening method, a wet honing process in which an abrasive is suspended in water and sprayed on a support, a centerless grinding process in which a support is pressed against a rotating grindstone, and grinding is continuously performed, an anode Examples thereof include an oxidation treatment or a method of forming a layer containing organic or inorganic semiconductive fine particles.

  Anodizing treatment is to form an oxide film on an 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 porous anodic oxide film as it is after the treatment is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the anodic oxide film is treated with pressurized steam or boiling water (a metal salt such as nickel may be added), blocked by volume expansion due to micropore hydration reaction, and converted into a more stable hydrated oxide. It is preferable to perform a hole treatment.

  The thickness of the anodized film is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against implantation is poor and the effect tends to be insufficient. On the other hand, if it exceeds 15 μm, the residual potential tends to increase due to repeated use.

  Further, the conductive support 11 may be subjected to treatment with an acidic treatment liquid or boehmite treatment. The treatment with the acidic treatment liquid is carried out as follows using an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid. 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 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. The film thickness is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against implantation is poor and the effect tends to be insufficient. On the other hand, if it exceeds 15 μm, the residual potential tends to increase due to repeated use.

  The boehmite treatment can be performed by immersing the conductive support 11 in pure water at 90 to 100 ° C. for 5 to 60 minutes, or by contacting it with heated steam at 90 to 120 ° C. for 5 to 60 minutes. The film thickness is preferably 0.1 to 5 μm. This may be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate, etc. Good.

  In the case of forming a layer containing organic or inorganic semiconductive fine particles, organic or inorganic semiconductive fine particles include perylene pigments, bisbenzimidazole perylene pigments, polycyclic rings described in JP-A-47-30330. Organic pigments such as quinone pigments, indigo pigments, quinacridone pigments, organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as cyano group, nitro group, nitroso group, halogen atom, zinc oxide, oxidation Examples include inorganic pigments such as titanium and aluminum oxide. Among these pigments, zinc oxide and titanium oxide are preferable because they have high charge transport ability and are effective for thickening.

  The surface of these pigments may be surface treated with an organic titanium compound such as a titanate coupling agent, an aluminum chelate compound, an aluminum coupling agent or the like for the purpose of improving dispersibility or adjusting the energy level. In particular, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxy It is preferable to treat with a silane coupling agent such as cyclohexyltrimethoxysilane.

  When there are too many organic or inorganic semiconductive fine particles, the strength of the layer is lowered and a coating film defect is caused. Therefore, it is preferably used at 95% by mass or less, more preferably 90% by mass or less.

  As a method for mixing / dispersing the organic or inorganic semiconductive fine particles, a method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent, but as an organic solvent, a fixed metal compound or resin is dissolved, and no gelation or aggregation occurs when organic / inorganic semiconductive fine particles are mixed / dispersed. Anything is acceptable.

  Examples of the organic solvent include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. Ordinary organic solvents such as chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more.

  The undercoat layer 13 includes an organometallic compound and a binder resin. As organometallic compounds, zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organotitanium compounds such as titanate coupling agents, aluminum chelate compounds, aluminum coupling agents In addition to organoaluminum compounds such as 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 alkoxide compounds, aluminum titanium alkoxide compounds, And aluminum zirconium alkoxide compounds. . As the organometallic compound, an organic zirconium compound, an organic titanyl compound, and an organoaluminum compound are particularly preferably used since they have low residual potential and good electrophotographic characteristics.

  As binder resin, 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, phenol resin , Vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, polyacrylic acid, and other known binder resins can be used. These mixing ratios can be appropriately set as necessary.

  The undercoat layer 13 includes vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxy. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, Silane coupling agents such as β-3,4-epoxycyclohexyltrimethoxysilane can also be included.

  In the undercoat layer 13, an electron transporting 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 coupling agent, binder resin or the like 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 caused. Therefore, the amount is preferably 95% by mass or less, more preferably 90% by mass or less.

  The undercoat layer 13 is configured using a coating solution for forming an undercoat layer containing the above constituent materials.

  As a method for mixing / dispersing the coating solution for forming the undercoat layer, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent. The organic solvent dissolves a periodical metal compound and a binder resin, and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. I just need it.

  Examples of the organic solvent include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. Ordinary organic solvents such as chloroform, chlorobenzene and toluene. These can be used individually by 1 type or in mixture of 2 or more types.

  As the coating method used when the undercoat layer 13 is provided, 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.

  After coating, the coating film is dried to obtain an undercoat layer. Usually, the drying is performed at a temperature at which the solvent can be evaporated and a film can be formed. In particular, the conductive support 11 subjected to the acidic solution treatment and the boehmite treatment is preferably formed with the undercoat layer 13 because its defect concealing power tends to be insufficient.

  The thickness of the undercoat layer 13 is preferably 0.1 to 30 μm, more preferably 0.2 to 25 μm.

  The charge generation layer 14 includes a charge generation material or a charge generation material and a binder resin.

  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. All known ones can be used. As the charge generation material, an inorganic pigment is preferable when a light source with an exposure wavelength of 380 nm to 500 nm is used, and a metal and a metal-free phthalocyanine pigment are preferable when a light source with an exposure wavelength of 700 nm to 800 nm is used. 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 or titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 is particularly preferable.

  As the charge generation material, Bragg angles (2θ ± 0.2 °) with respect to CuKα characteristic X-rays of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25 Hydroxygallium phthalocyanine having diffraction peaks at .1 ° and 28.3 °, titanyl phthalocyanine having a strong diffraction peak at 27.2 ° with a Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray, CuKα characteristic X Also preferred are chlorogallium phthalocyanines with strong diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° of the Bragg angle to the line (2θ ± 0.2 °).

  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-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene and polysilane. Preferred binder resins include polyvinyl butyral resins, polyarylate resins (for example, polycondensates of bisphenols and aromatic divalent carboxylic acids such as polycondensates of bisphenol A and phthalic acid), polycarbonate resins, polyester resins, Insulating resins such as phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin It can be mentioned, but is not limited to these. These binder resins can be used individually by 1 type or in mixture of 2 or more types.

  The charge generation layer 14 is formed by vapor deposition using the charge generation material or using a charge generation layer forming coating solution containing the charge generation material and a binder resin.

  In the charge generation layer forming coating solution, the mixing ratio (mass ratio) of the charge generation material and the binder resin is preferably 10: 1 to 1:10. Further, as a method for dispersing them, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. According to these dispersion methods, it is possible to prevent a change in the crystal form of the charge generation material due to the dispersion.

  Further, in this dispersion, it is effective that the particles have a particle size of preferably 0.5 μm or less, more preferably 0.3 μm or less, and still more preferably 0.15 μm or less.

  Moreover, as a solvent used for these dispersions, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, Examples include ordinary organic solvents such as tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. These can be used individually by 1 type or in mixture of 2 or more types.

  In addition, as a coating method used when the charge generation layer 14 is provided, a normal method 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, a curtain coating method, or the like is used. Can be used.

  The film thickness of the charge generation layer 14 is preferably 0.1 to 5 μm, more preferably 0.2 to 2.0 μm.

  The charge transport layer 15 includes a charge transport material and a binder resin, or includes a polymer charge transport material.

  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 transport 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 singly or in combination of two or more, but are not limited thereto.

  Moreover, as a charge transport material, the compound shown by the following general formula (a-1), (a-2) or (a-3) from a mobility viewpoint is preferable.

In the above formula (a-1), R ³⁴ represents a hydrogen atom or a methyl group, and k10 represents 1 or 2. Ar ⁶ and Ar ⁷ represent a substituted or unsubstituted aryl group, and the substituent is 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 3 carbon atoms. A substituted amino group substituted with an alkyl group can be mentioned.

Here, in said formula (a-2), R ^<35> and R ^<35 '> respectively independently represent a hydrogen atom, a halogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, R ^<36> , R ³⁶ ′, R ³⁷ and R ³⁷ ′ 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 or unsubstituted aryl group, —C (R ³⁸ ) ═C (R ³⁹ ) (R ⁴⁰ ), or —CH═CH—CH═C (Ar) ₂ , R ³⁸ , R ³⁹ and R ⁴⁰ are Each independently represents 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. m7 and m8 each independently represents an integer of 0-2.

Here, in the formula (a-3), R ⁴¹ 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. It shows a -CH = C _{(Ar) 2.} Ar represents a substituted or unsubstituted aryl group. R ⁴² , R ⁴² ′, R ⁴³ , and R ⁴³ ′ are each independently 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 having 1 to 2 carbon atoms. An amino group substituted with a group, or a substituted or unsubstituted aryl group is shown.

  As the binder resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-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-vinylcarbazole, polysilane, Polymer charge transport materials such as polyester 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 individually by 1 type or in mixture of 2 or more types. The blending ratio (mass ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  A polymer charge transport material can also be used alone. As the polymer charge transport material, known materials having charge transport properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, 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 15 is configured using a charge transport layer forming coating solution containing the above-described constituent materials. Solvents used in the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride. Examples include ordinary organic solvents such as aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether, and linear ethers. These can be used individually by 1 type or in mixture of 2 or more types. Moreover, a well-known method can be used as a dispersion | distribution method of said each constituent material.

  Coating methods for coating the charge transport layer forming coating solution on the charge generation layer 14 include blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain A usual method such as a coating method can be used.

  The film thickness of the charge transport layer 15 is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  The protective layer 16 is a functional layer made of a cured product of the coating agent composition of the present invention.

  In the present invention, the following components can be used to further enhance the function of the protective layer 16.

For example, a compound represented by the following general formula (XII) can be added to the protective layer 16 in order to control various physical properties such as strength and film resistance of the protective layer 16.
Si (R ⁵⁰ ) _(4-c) Q _c (XII)
[In the above formula (XII), R ⁵⁰ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and c represents an integer of 1 to 4. ]

  Specific examples of the compound represented by the general formula (XII) include the following silane coupling agents. Examples of silane coupling agents include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl L) Triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H , 1H, 2H, 2H-perfluorodecyltriethoxysilane, trifunctional alkoxysilanes such as 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (c = 3); dimethyldimethoxysilane, diphenyldimethoxysilane, methyl And bifunctional alkoxysilanes such as phenyldimethoxysilane (c = 2); monofunctional alkoxysilanes such as trimethylmethoxysilane (c = 1), and the like. Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and monofunctional and bifunctional alkoxysilanes are preferable for improving the flexibility and film formability.

  The silane coupling agent can be used in any amount, but when a fluorine-containing compound is used, the content of the fluorine-containing compound is preferably 0.25 times or less by mass with respect to the compound not containing fluorine. When this content is exceeded, a problem may occur in the film formability of the crosslinked film.

  In addition, a silicon-based hard coat agent produced mainly from these coupling agents can also be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Etc.) can be used.

In order to increase the strength of the protective layer 16, it is also preferable to use a compound having two or more silicon atoms as shown in the following general formula (XIII).
B- (Si (R ⁵¹ ) _(3-d) Q _d ) ₂ (XIII)
[In the above formula (XIII), B represents a divalent organic group, R ⁵¹ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and d represents an integer of 1 to 3. Indicates. ]

  More specific examples of the compound represented by the general formula (XIII) include the following compounds (XIII-1) to (XIII-16).

  Further, a resin soluble in an alcohol solvent or a ketone solvent may be added for controlling the film characteristics and extending the liquid life. Examples of such 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 has been modified with formal, acetoacetal, or the like (for example, ESREC B, K manufactured by Sekisui Chemical Co., Ltd.). Etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable from the viewpoint of improving electrical characteristics.

  Various resins can be added for the purposes of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. In the present embodiment, it is preferable to further add a resin that dissolves in alcohol. Examples of resins soluble in alcohol solvents include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral has been modified with formal or acetoacetal (for example, manufactured by Sekisui Chemical Co., Ltd.) ESREC B, K, etc.), polyamide resin, cellulose resin and the like. In particular, polyvinyl acetal resin is preferable from the viewpoint of improving electrical characteristics.

  The molecular weight of the resin is preferably 2000-100000, more preferably 5000-50000. If the molecular weight is less than 2000, the desired effect tends not to be obtained. If the molecular weight is more than 100000, the solubility tends to be low and the addition amount is limited, or the film formation tends to be poor during coating. The addition amount is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and most preferably 5 to 20% by mass. When the addition amount is less than 1% by mass, it is difficult to obtain a desired effect. When the addition amount is more than 40% by mass, there is a risk of image blurring at high temperature and high humidity. Moreover, although said resin may be used independently, you may mix and use them.

  In order to extend the pot life and control the film properties, it is preferable to contain a cyclic compound having a repeating structural unit represented by the following general formula (XIV) or a derivative thereof.

［上記式（ＸＩＶ）中、Ａ^１及びＡ^２は、それぞれ独立に一価の有機基を示す。］

[In the above formula (XIV), A ¹ and A ² each independently represent a monovalent organic group. ]

  Examples of the cyclic compound having a repeating structural unit represented by the general formula (XIV) include commercially available cyclic siloxanes. Specifically, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5- Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7 , 9-pentaphenylcyclopentasiloxane and other cyclic methylphenylcyclosiloxanes, hexaphenylcyclotrisiloxane and other cyclic phenylcyclosiloxanes, and 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine Atom-containing cyclosiloxanes, methylhydrosiloxa Mixture, pentamethylcyclopentasiloxane, mention may be made of phenyl hydrosilyl group-containing cyclosiloxanes of hydrocyclosiloxane like, cyclic siloxanes and vinyl group-containing cyclosiloxanes such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or in combination of two or more.

  Further, various fine particles can be added to the protective layer 16 in order to control the contamination resistance adhesion, lubricity, hardness and the like of the surface of the electrophotographic photosensitive member.

  Examples of the fine particles include silicon atom-containing fine particles or fluorine atom-containing resin particles. The silicon atom-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon atom-containing fine particles preferably has a volume average particle diameter of 1 to 100 nm, more preferably 10 to 30 nm, in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone or ester. It is selected from those dispersed in, and commercially available products can be used. The solid content of the colloidal silica in the protective layer 16 is not particularly limited, but preferably 0.1 to 0.1 on the basis of the total solid content of the protective layer 16 in terms of film formability, electrical characteristics, and strength. It is used in the range of 50% by mass, more preferably in the range of 0.1-30% by mass.

  The silicone fine particles used as the silicon atom-containing fine particles are spherical and preferably have a volume average particle size of 1 to 500 nm, more preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles. A commercially available product can be used.

  Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. In other words, in a state in which it is uniformly incorporated into a strong cross-linked structure, it improves the lubricity and water repellency of the surface of the electrophotographic photosensitive member, and maintains good wear resistance and contamination resistance adhesion over a long period of time. Can do. The content of the silicone fine particles in the protective layer 16 is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.5 to 10% by mass, based on the total solid content of the protective layer 16. .

  Fluorine atom-containing resin particles include fluorine-based fine particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings p89. And fine particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group.

Other fine particles include ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—. Examples thereof include semiconductive metal oxides such as TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. The volume average particle diameter of these fine particles can be controlled by the material composition, production method, etc., but if they are too small, the dispersion state tends to become unstable, and if they are too large, the smoothness of the surface of the photoreceptor is lowered. Therefore, those having a thickness of 1 to 1500 nm, more preferably 5 to 1000 nm are used.

  For the same purpose, an oil such as silicone oil can be added. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes. These may be added in advance to the protective layer-forming coating solution, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  Moreover, the protective layer 16 can also contain additives, such as a plasticizer, a surface modifier, antioxidant, and a photodegradation inhibitor. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons.

  It is particularly preferable to add an antioxidant to the protective layer 16 for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated in the charging device. When the mechanical strength of the surface of the photoconductor is increased and the photoconductor has a long life, the photoconductor is in contact with the oxidizing gas for a long time, and therefore, stronger oxidation resistance is required than before. Antioxidants are preferably hindered phenols or hindered amines, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. , Etc., may be used. The addition amount of the antioxidant in the protective layer 16 is preferably 20% by mass or less, and more preferably 10% by mass or less.

  Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N′-hexamethylenebis (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-tert-butylphenol), 2,5-di-tert-amylhydroquinone, 2-tert-butyl-6- (3-butyl) -2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), and the like.

  Further, commercially available hindered phenol-based antioxidants include, for example, “Sumilizer BHT-R”, “Sumilizer MDP-S”, “Sumilizer BBM-S”, “Sumizer WX-R”. , “Sumizer NW”, “Sumizer BP-76”, “Sumizer BP-101”, “Sumizer GA-80”, “Sumizer GM”, “Sumizer GS” and above, manufactured by Sumitomo Chemical Co., Ltd., “IRGANOX1010”, “IRGANOX”, “35” “IRGANOX1076”, “IRGANOX1098”, “IRGANOX1135”, “IRGANOX1141”, “IRGANOX1222”, “IRGANOX1330”, “IR “ANOX1425WL”, “IRGANOX1520L”, “IRGANOX245”, “IRGANOX259”, “IRGANOX3114”, “IRGANOX3790”, “IRGANOX5057”, “IRGANOX565” or more, manufactured by Ciba Specialty Chemicals, “Adekastab AO-20” ”,“ ADK STAB AO-40 ”,“ ADK STAB AO-50 ”,“ ADK STAB AO-60 ”,“ ADK STAB AO-70 ”,“ ADK STAB AO-80 ”,“ ADK STAB AO-330 ”or more, manufactured by Asahi Denka, Hindert As the amine system, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744” or more manufactured by Sankyo Lifetech Co., Ltd., “Tinubin 144”, “Chi Nubin 622LD "or more, manufactured by Ciba Specialty Chemicals," Mark LA57 "," Mark LA67 "," Mark LA62 "," Mark LA68 "," Mark LA63 "," Smilizer TPS ", “D” or more, manufactured by Sumitomo Chemical Co., Ltd., and the phosphite system includes “Mark 2112”, “Mark PEP · 8”, “Mark PEP · 24G”, “Mark PEP · 36”, “Mark 329K”, “Mark HP · 10” Asahi Denka Co., Ltd. is mentioned above. Furthermore, these may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

  The protective layer 16 includes 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 An insulating resin such as a resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, or polyvinyl pyrrolidone resin may be contained. In this case, the insulating resin can be added at a desired ratio, thereby suppressing adhesion with the charge transport layer 15, coating film defects due to heat shrinkage, and repellency.

  The protective layer 16 is formed using the coating agent composition of the present invention to which the above components are added as necessary as a coating solution for forming a protective layer. In addition, the preparation method of the coating liquid for protective layer formation is the same as the preparation method of a coating agent composition except using the said component.

  When the coating liquid for forming the protective layer is applied onto the charge transport layer 15, the coating methods are blade coating method, Meyer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating. Ordinary methods such as a method can be used. And after application | coating, the protective layer 16 forms by drying a coating film.

  In addition, in the case of application | coating, when a required film thickness cannot be obtained by one application | coating, a required film thickness can be obtained by apply | coating several times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

  The reaction temperature and reaction time for curing the curable component in the coating liquid for forming the protective layer are not particularly limited, but the reaction temperature is preferably 60 ° C. from the viewpoint of mechanical strength and chemical stability of the obtained resin. As mentioned above, More preferably, it is 80-200 degreeC, and reaction time becomes like this. Preferably it is 10 minutes-5 hours. In addition, maintaining the organic layer obtained by curing the coating liquid in a high humidity state is effective in stabilizing the characteristics of the organic layer. Furthermore, the protective layer 16 obtained can be hydrophobized by subjecting it to a surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like depending on the application.

  The thickness of the protective layer 16 is preferably 0.5 to 15 μm, more preferably 1 to 10 μm, and further preferably 1 to 5 μm.

  The electrophotographic photosensitive member of the present invention is not limited to the above embodiment. For example, in the electrophotographic photoreceptor of the present invention, the undercoat layer 13 is not necessarily provided.

  The electrophotographic photoreceptor shown in FIG. 1 includes a protective layer 16 made of a cured product of the coating agent composition of the present invention, but the cured product of the coating agent composition of the present invention has excellent mechanical strength. In addition, since it has sufficient photoelectric characteristics, it can be used as it is as a charge transport layer of a laminated photoreceptor. An example of such an electrophotographic photoreceptor is shown in FIG. The electrophotographic photosensitive member 1 shown in FIG. 2 has a structure in which an undercoat layer 13, a charge generation layer 14, and a charge transport layer 15 are sequentially laminated on a conductive support 11, and the charge transport layer 15 of the present invention. It is the surface layer comprised with the hardened | cured material of the coating agent composition. The undercoat layer 13 and the charge generation layer 14 on the conductive support 11 are the same as those of the electrophotographic photosensitive member shown in FIG. 1 (hereinafter the same).

  Further, the order of stacking the charge generation layer 14 and the charge transport layer 15 may be reversed from the case of the above embodiment. An example of such an electrophotographic photoreceptor is shown in FIG. The electrophotographic photoreceptor shown in FIG. 3 has a structure in which an undercoat layer 13, a charge transport layer 14, a charge generation layer 15 and a protective layer 16 are sequentially laminated on a conductive support 11. Is a surface layer made of a cured product of the coating agent composition of the present invention.

  The photosensitive layer provided in the electrophotographic photosensitive member of the present invention may be a single-layer type photosensitive layer containing both a charge generating material and a charge transport material. Examples of electrophotographic photoreceptors having a single layer type photosensitive layer are shown in FIGS.

  The electrophotographic photosensitive member 1 shown in FIG. 4 has a structure in which an undercoat layer 13 and a single layer type photosensitive layer 17 are sequentially laminated on a conductive support 11, and the single layer type photosensitive layer 17 is a surface layer. is there. This single-layer type photosensitive layer 17 is a coating solution in which a charge generating material and, if necessary, a binder resin other than a phenol resin, a charge transporting material, and other additives are blended with the coating composition of the present invention. Can be used. The charge generation material is the same as that used for the charge generation layer in the function-separated type photosensitive layer. As the binder resin other than the phenol resin, polyvinyl butyral resin, polyvinyl formal resin, and a part of butyral are formal or acetate. Polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins modified with acetal or the like (for example, Sleksui B or K manufactured by Sekisui Chemical Co., Ltd.), polyamide resins, cellulose resins, or the like can be used. The content of the charge generating material in the single-layer type photosensitive layer is preferably 10 to 85% by mass, more preferably 20 to 50% by mass, based on the total solid content in the single-layer type photosensitive layer. A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by mass based on the total solid content in the single-layer type photosensitive layer. Moreover, the solvent and coating method used for coating can be the same as those for the above layers. The film thickness of the single-layer type photosensitive layer 17 is preferably about 5 to 50 μm, and more preferably 10 to 40 μm.

  The electrophotographic photoreceptor 1 shown in FIG. 5 has a structure in which an undercoat layer 13, a single-layer type photosensitive layer 17, and a protective layer 16 are sequentially laminated on a conductive support 11. It is a surface layer which consists of hardened | cured material of the coating agent composition of this invention.

(Image forming device)
FIG. 6 is a schematic configuration diagram showing the image forming apparatus according to the first embodiment of the present invention. In the image forming apparatus 100 shown in FIG. 6, the electrophotographic photosensitive member 1 is supported by a support 9, and can rotate around the support 9 in the direction of the arrow at a predetermined rotation speed. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 7 are arranged in this order along the rotation direction of the electrophotographic photosensitive member 1. In the image forming apparatus 100, charging, exposure, development, and transfer are sequentially performed during the rotation of the electrophotographic photosensitive member 1, and an image is formed on the transfer target P. The transfer medium P after the transfer process is transported to the image fixing device 6 and used for the image fixing process. Here, the electrophotographic photosensitive member 1 is the electrophotographic photosensitive member of the present invention, and includes a functional layer (for example, the protective layer 16 described above) made of a cured product of the coating agent composition of the present invention as a surface layer.

  Hereinafter, each element other than the electrophotographic photoreceptor 1 will be described in detail.

  The charging device 2 is a contact charging type charging device including a charging roll. When charging is performed by the contact charging method, the stress on the electrophotographic photosensitive member 1 is increased, but the image forming apparatus 100 shown in FIG. Since an electrophotographic photosensitive member provided with the layer 16 is used, excellent durability that has been difficult to achieve in the past can be obtained. Instead of the contact charging type charging device, a conventionally known non-contact type charging device using corotron or scorotron can also be used.

  As the exposure device 3, an optical system device that can expose a light source such as a semiconductor laser, an LED (light emitting diode), a liquid crystal shutter, or the like on the surface of the electrophotographic photosensitive member 1 in a desired image manner can be used. Among these, when an exposure apparatus capable of exposing non-interference light is used, interference fringes between the support (substrate) of the electrophotographic photosensitive member 1 and the photosensitive layer can be prevented. In the present embodiment, it is preferable to use a multi-beam exposure apparatus that scans a plurality of light beams on the electrophotographic photosensitive member as the exposure apparatus 3. According to such an image forming apparatus, speeding up can be realized more effectively. The multi-beam type image forming apparatus is effective for speeding up the image forming process, but it is necessary to suppress the rotation unevenness of the photoreceptor in order to stably obtain a good image quality. According to this embodiment, since it is easy to suppress rotation unevenness, it is possible to stably obtain a good image quality over a long period of time even when the speed is increased by the exposure unit.

  As the developing device 4, a conventionally known developing device using a regular or reversal developer such as a one-component system or a two-component system can be used. Further, the shape of the toner to be used is not particularly limited, and for example, an amorphous toner by a pulverization method or a spherical toner by a chemical polymerization method is preferably used.

  Further, in the image forming apparatus of the present invention, the toner remaining on the electrophotographic photosensitive member 1 can be sufficiently removed even when toner having an average shape factor of 100 to 150 is used. Therefore, by using such a toner, a high-quality image can be obtained without impairing the cleaning characteristics. Further, the volume average particle diameter of the toner used in the exemplary embodiment is preferably 1 to 12 μm, and more preferably 3 to 9 μm.

A toner having an average shape factor (ML ² / A) of 100 to 150 is, for example, a kneading and pulverizing method in which a binder resin, a colorant, a release agent, and a charge control agent, if necessary, are kneaded, pulverized, and classified; A method of changing the shape of particles obtained by the method by mechanical impact force or heat energy; emulsion polymerization of a polymerizable monomer of a binder resin, a formed dispersion, a colorant, and a release agent , If necessary, a dispersion of a charge control agent or the like is mixed, agglomerated and heat-fused to obtain toner particles; an emulsion polymerization aggregation method; a polymerizable monomer and a colorant for separating the binder resin; Suspension polymerization method in which a mold agent, if necessary, a solution such as a charge control agent is suspended in an aqueous solvent for polymerization; a binder resin and a colorant, a release agent, and if necessary, a solution such as a charge control agent It can be obtained by a dissolution suspension method in which it is suspended in an aqueous solvent and granulated. In addition, toner obtained by 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. As the toner production method, from the viewpoint of shape control and particle size distribution control, suspension polymerization method, emulsion polymerization aggregation method, and dissolution suspension method in which an aqueous solvent is used are preferable, and emulsion polymerization aggregation method is particularly preferable.

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

  Binder resins used in the toner include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate. , Α-methylene aliphatic monocarboxylic such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Examples of homopolymers and copolymers of acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl butyl ether, and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene. -Maleic anhydride copolymer, polyethylene, polypropylene, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like. A crystalline low melting point (melting point of 100 ° C. or lower) resin, particularly a polyester resin can also be used.

  In addition, toner colorants include 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, and malachite green oxa. Rate, 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.

  In addition, a charge control agent may be added to the toner as necessary. Known charge control agents can be used, but 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 used in the present invention may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  The toner used in the present invention can be produced by mixing the toner particles and the external additive with a Henschel mixer or a V blender. In addition, when the toner particles are produced by a wet method, external addition can be performed by a wet method.

  The lubricating particles added to the toner used in the present invention include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids, fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene, and polybutene, and softening by heating. Aliphatic amides such as pointed silicones, oleic amides, erucic acid amides, ricinoleic acid amides, stearic acid amides, carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil etc. Minerals such as plant waxes, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc., petroleum waxes, and modifications thereof can be used. Use alone Either, or it may be used in combination. However, the volume average particle size may be in the range of 0.1 to 10 μm, and the particles having the above chemical structure may be pulverized to have the same particle size. The amount of the active particles added to the toner is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.5% by mass.

  In addition, inorganic particles such as aluminum oxide, cerium oxide, and barium sulfate can be added to the toner for the purpose of more reliably removing deposits and deteriorated materials on the surface of the electrophotographic photosensitive member 1, and cerium oxide is particularly preferable. preferable. The volume average particle diameter of these inorganic particles is preferably 0.1 to 3.0 μm, more preferably 0.5 to 2.0 μm. When inorganic particles are added, the amount added to the toner is preferably larger than that of the lubricant particles, and the sum of the amount added with the lubricant particles is preferably 0.6% by mass or more.

  By making the addition amounts of the inorganic particles and the lubricating particles within the above-mentioned preferable ranges, it is possible to more surely satisfy both the cleaning characteristics for the discharge product and the cleaning characteristics for the toner having an average shape factor of 100 to 150.

  The toner uses a small-diameter inorganic oxide with a primary particle size of 40 nm or less for the purpose of powder flowability, charge control, etc., and a larger-diameter inorganic oxide for adhesion reduction and charge control. It is preferable to add. These inorganic oxide fine particles may 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 fine particles increases the dispersibility and increases the effect of increasing the powder fluidity.

  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.

  Examples of the transfer device 5 include a contact transfer charger using a belt, a roller, a film, a rubber blade, and the like, a scorotron transfer charger using a corona discharge, a corotron transfer charger, and the like.

  An example of the image fixing device 6 includes an image fixing member such as a roller.

  Although a cleaning blade made of urethane rubber may be used as the cleaning device 7, from the viewpoint of extending the life of the image forming apparatus, it is preferable to use a cleaning apparatus having a brush member as shown in FIG. it can. Hereinafter, the cleaning device 7 will be described in detail with reference to FIG.

  The cleaning device 7 shown in FIG. 7 is of a cartridge type and includes two cleaning units. That is, in FIG. 7, a housing 700 includes a first cleaning unit including a roll brush member 701a, a recovery roll member 702a, and a scraper 703a, and a first cleaning unit including a roll brush member 701b, a recovery roll member 702b, and a scraper 703b. Two cleaning units are accommodated. The side close to the electrophotographic photosensitive member 1 of the housing 700 is open, and the outer peripheral surfaces (surfaces formed by the brush tips) of the roll-shaped brush members 701 a and 701 are respectively the outer peripheral surfaces of the electrophotographic photosensitive member 1 at the opening. Abut.

  The roll-shaped brush member 701a (or 701b) is formed in a roll shape by arranging a plurality of fibers on the outer peripheral surface of the shaft 705a (or 705b) from the center to the outer peripheral surface. The shafts 705a and 705b are arranged in parallel to the tangent line to the electrophotographic photosensitive member 1, and the roll-like brush members 701a and 701b are rotatable around the shafts 705a and 705b. The distance between each of the shafts 705a and 705b and the electrophotographic photosensitive member 1 is such that the amount of biting into the electrophotographic photosensitive member 1 at the brush tip of the roll-shaped brush members 701a and 701b is a predetermined value (preferably 0.5 to 2). 0.0 mm, more preferably 0.9 to 1.8 mm).

Examples of the fibers of the roll-shaped brush members 701a and 701b include resin fibers such as nylon, acrylic, polyolefin, and polyester. Beltron (manufactured by Kanebo), SA-7 (manufactured by Toray Industries, Inc.), UU nylon (manufactured by Unitika) Commercial products such as these can be used. The thickness of these fibers is preferably 30 denier or less, more preferably 20 denier or less, and still more preferably 1 to 10 denier. The fiber density is preferably 20,000 fibers / inch ² or more, more preferably 60,000 fibers / inch ² or more.

  The recovery roll members 702a and 702b are obtained by curing a thermosetting resin and molding it into a roll shape and arranging it on the outer periphery of the shafts 705a and 705b. The outer peripheral surface of the collection roll 702a (or 702b) is in contact with the brush tip of the brush member 701a (or 701b). The shaft 705a (or 705b) is disposed in parallel to the shaft 704a (or 704b), and the recovery roll member 702a (or 702b) can rotate about the shaft 705a (or 705b) as a rotation axis.

  Examples of the thermosetting resin used for the collection roll members 702a and 702b include phenol resin, urea resin, melamine resin, unsaturated polyester, epoxy resin, and polyimide resin. Among them, the phenol resin is preferable because it has advantages such as high dimensional accuracy, easy molding, excellent surface smoothness of the molded body, and low cost.

The bending elastic modulus of the collection roll members 702a and 702b is preferably 700 kPa or more. When the flexural modulus is less than 700 kPa, the collection roll member is bent, and it is difficult to maintain the contact position and the amount of biting with the brush member or the blade member at a predetermined value. In addition, if a material having a flexural modulus of less than 700 kPa is used to increase the thickness of the recovery roll member to maintain rigidity, molding shrinkage increases, resulting in insufficient dimensional accuracy, and further increases the mass. Costs increase due to problems such as an increase in molding time and the need for subsequent processes. The flexural modulus here is a value measured in accordance with the provisions of JIS K7203 “Bending test method of hard plastic”, and is loaded at a constant speed at the center of a predetermined test piece supported at two points. Measures the deflection of the test piece produced by adding, and is calculated by the following formula.
Ef = (L / 4bh) · (F / Y)
[Where Ef is the elastic modulus (kgf / mm ² ) {N / mm ² }, L is the distance between support points (mm), b is the width (mm) of the test piece, and h is the height of the test piece. (Mm), F is the load (kgf) {N} at an arbitrarily selected point in the first linear portion of the load-deflection curve, and Y is a value measured according to the deflection (mm) at the load F. , Respectively. ]

  Further, since the collection roll members 702a and 702b are in contact with the roll brush members 701a and 701b and the blade members 703a and 703b, respectively, the outer peripheral surfaces of the collection roll members 702a and 702b can be worn by the operation. In the present invention, when the amount of wear is measured in accordance with JIS K6902 on the outer peripheral surface of the recovery roll member, the amount of wear is preferably 20 mg or less. Thereby, the contact pressure and biting amount of the brush member and the blade member can be set to a large value, and even in that case, stable cleaning can be performed over a long period of time. If the amount of wear exceeds 20 mg, the life of the collecting roll member becomes insufficient and frequent replacement is required.

  Further, the Rockwell hardness (M scale) of the collection roll members 702a and 702b is preferably 100 or more. When the Rockwell hardness is 100 or more, molding with high dimensional accuracy is possible, and the roll member is extremely strong against scraping. Here, the Rockwell hardness is a value measured according to JIS K7202.

  The scrapers 703a and 703b are made of a thin metal plate, and are arranged so that an edge portion at one end thereof is in contact with the outer peripheral surface of the recovery roll members 702a and 702b. The other ends of the scrapers 703a and 703b are each fixed to the housing 700, but the fixing method thereof is not particularly limited, and may be fixed by using a mounting bracket 706 like the scraper 703a, or the housing like the scraper 703b. You may fix to 700 directly.

  The material of the scrapers 703a and 703b is preferably stainless steel or phosphor bronze from the viewpoint of high durability and low cost. The thickness of the scrapers 703a and 703b is preferably 0.02 to 2 mm, more preferably 0.05 to 1 mm. A blade member may be used instead of the scraper.

  In the cleaning device 7 having the above configuration, first, toner (residual toner) remaining on the electrophotographic photosensitive member 1 after the transfer process is removed by the roll-shaped brush members 701a and 701b. Next, the residual toner is transferred to the contact position with the collection roll members 702a and 702b by the rotation of the roll brush members 701a and 701b and collected. As a result, the brush tips of the roll-shaped brush members 701 a and 701 b are regenerated and repeatedly used for cleaning the electrophotographic photoreceptor 1. The residual toner adhering to the collection roll members 702a and 702b is transferred to a contact position with the scrapers 703a and 703b by the rotation of the collection roll members 702a and 702b, and is removed by the scrapers 703a and 703b. Thereby, the surface of the collection | recovery roll members 702a and 702b is also reproduced | regenerated and it is repeatedly used for reproduction | regeneration of the brush front-end | tip of a roll-shaped brush member.

  Here, in order to electrostatically attract and move fine powders such as toner and paper powder efficiently, there is no potential difference between the roll brush member 701a (or 701b) and the recovery roll member 702a (or 702b). A mechanism for applying a certain cleaning bias is preferable. More specifically, by applying a predetermined voltage to the roll-shaped brush member 701a (or 701b), the residual toner on the electrophotographic photosensitive member 1 is removed from the roll-shaped brush member 701a (or 701b) by the electrostatic attraction force. Can be attached to. And the residual which adhered to brush member 701a (or 701b) by applying the voltage whose absolute value is larger than the applied voltage to brush member 701a (or 701b) and the same polarity is applied to recovery roll member 702a (or 702b) The toner can be attached to the collecting roll member 702a (or 702b). The potential difference (absolute value) between the roll brush member and the collection roll member is preferably 100 V or higher, more preferably 200 V or higher, and further preferably 650 V.

When a voltage is applied to the roll-shaped brush members 701a and 701b, as a method of imparting conductivity to the fibers of the brush members, a method of blending conductive powder or an ionic conductive material into the fibers, conductive inside or outside of the fibers Examples include a method of forming a layer. In addition, the resistance value of the fiber provided with conductivity is preferably 10 ² to 10 ⁹ Ω · cm for a single fiber.

  Examples of a method for adjusting the electrical resistance of the collection roll members 702a and 702b include a method of filling an inorganic filler and / or an organic filler. When the collection roll member is filled with an inorganic filler or an organic filler, there is an advantage that the rigidity of the collection roll member is increased. Inorganic fillers include metal powders such as tin, iron, copper, and aluminum, metal fibers, glass fibers, magnetic powders, metal oxides such as zinc oxide, tin oxide, and titanium oxide, and metal sulfides such as copper sulfide and zinc sulfide. So-called hard ferrites such as strontium, barium and rare earth, magnetite, ferrites such as copper, zinc, nickel and manganese, or those whose surfaces are subjected to conductive treatment as necessary, copper, iron, manganese, nickel, zinc and cobalt Selected from oxides, hydroxides, carbonates or metal compounds containing different metal elements such as barium, aluminum, tin, lithium, magnesium, silicon, phosphorus, etc. Examples include solid solutions, so-called complex metal oxides, and the like. Examples of the organic filler include carbon black, carbon powder, graphite, polyaniline and the like.

The resistance value when a voltage of 500 V is applied to the collection roll members 702a and 702b is preferably 1 × 10 ⁵ to 1 × 10 ¹⁰ Ω · cm, more preferably 1 × 10 ⁶ to 1 × 10 ⁸ Ω · cm. When the resistance value is less than 1 × 10 ⁵ Ω · cm, charge injection into the collecting roll member occurs, and the polarity of the fine powder such as toner and paper powder scraped off by the brush member is reversed. It becomes difficult to adsorb. On the other hand, if the electrical resistance of the collection roll member exceeds 1 × 10 ¹⁰ Ω · cm, a phenomenon in which charges are accumulated in the collection roll member (charge-up) is likely to occur. In this case, too, a fine powder such as toner or paper dust Becomes difficult to be electrically adsorbed.

  The cleaning device shown in FIG. 7 includes two cleaning units including a roll-shaped brush member, a recovery roll member, and a scraper. However, in the present invention, the number of such cleaning units is not particularly limited. You may use the cleaning apparatus provided with one cleaning unit. However, a device having a plurality of cleaning units such as the cleaning device 7 shown in FIG. 7 has the following advantages.

  That is, the polarity of the toner (residual toner) remaining on the electrophotographic photoreceptor 1 after the transfer process is likely to vary due to the influence of the transfer electric field. That is, most of the residual toner exists with the positive electrode (original charged polarity) as it is, but a part of the residual toner may be reversed to the opposite polarity. In such a case, the cleaning unit composed of the roll brush member 701a, the recovery roll member 702a, and the scraper 703a and the cleaning unit composed of the roll brush member 701b, the recovery roll member 702b, and the scraper 703b are charged with different polarities. By using one for the remaining toner of the positive electrode and the other for the remaining toner inverted to the opposite polarity, both the remaining toner of the positive electrode and the remaining toner of the opposite polarity can be efficiently removed. More specifically, first, in the second cleaning unit, a cleaning bias having a polarity different from that of the toner is applied to the brush member 701b and the collecting roll 702b to electrostatically adsorb the positive toner occupying most of the remaining toner. Move. Next, in the first cleaning unit, it is effective to electrostatically attract and move the toner reversed to the opposite polarity by applying a cleaning bias having the same polarity as the toner to the brush member 701a and the collecting roll 702a. .

  Next, a tandem color image forming apparatus will be described as another example of the image forming apparatus of the present invention.

  FIG. 8 is a side view schematically showing an image forming apparatus according to the second embodiment of the present invention. As shown in FIG. 8, the image forming apparatus 40 according to this embodiment is a so-called tandem color image forming apparatus, and includes four image forming units 41 (41a to 41d).

  As shown in FIG. 8, the image forming unit 41 includes, in addition to the electrophotographic photosensitive member 1, a charging device 42 that charges the surface of the electrophotographic photosensitive member 1, and the electrophotographic photosensitive member 1 that is charged by the charging device 42. An exposure device 43 for exposing, a developing device 44 for developing the electrostatic latent image formed by the exposure device 43 with toner, and a toner image developed on the electrophotographic photosensitive member 1 by the developing device 44 to be transferred such as paper The image forming apparatus includes a transfer device 45 that transfers onto P, and a cleaning device 46 that cleans the surface of the photoconductor after the image is transferred to the transfer target P by the transfer device 45. Here, the electrophotographic photosensitive member 1 and the cleaning devices 46a to 46d in the image forming units 41a to 41d have the same configurations as the electrophotographic photosensitive member 1 and the cleaning device 7 of the image forming apparatus shown in FIG.

  The image forming units 41a to 41d are for forming images of different colors, and toners of different colors are used in the developing devices 44 of the image forming units 41a to 41d.

  In addition, the image forming apparatus 40 includes a belt conveying device 47 that is disposed in a portion facing the image forming unit 41 and conveys the recording material P, and a recording material supply device 60 that supplies the recording material P to the belt conveying device 47. It has. The belt conveyance device 47 has an endless conveyance belt 48, and the conveyance belt 48 is stretched over, for example, six stretching rolls 49 to 54 and four transfer devices 45. Then, when the conveying belt 48 is circulated and conveyed, and the recording material P is supplied to the belt conveying device 47 by the recording material supply device 60, the recording material P is adsorbed and held by the adsorbing roll 55, and each of the image forming units 41a to 41d. It is sequentially moved to the transcription site. The recording material P that has passed through the four image forming units 41 a to 41 d is stored in the storage tray 57 after the transferred color toner image is fixed by the fixing device 56. Reference numeral 58 denotes a tension roll that applies a predetermined tension to the conveyor belt 48, and reference numeral 59 denotes a belt cleaner that cleans the surface of the conveyor belt 48.

  As described above, in the second embodiment, in the image forming units 41a to 41d, the electrophotographic photosensitive member 1 provided with the surface layer 16 and the cleaning devices 46a to 46d having roll-shaped brush members are used. By setting the product of the surface roughness after rotating the photoconductor 200,000 times (Rz: μm) and the wear rate per 1,000 rotations (We: nm) to about Rz × We ≦ 1. The residual toner is reliably removed without causing damage to the surface of the electrophotographic photosensitive member 1, filming due to aggregates of the external additive of the toner, slipping of the toner, and the like. Therefore, even in a color image forming apparatus, it is possible to realize high speed, high performance, and long life.

  The present invention is not limited to the above embodiment. For example, the image forming apparatus of the present invention may further include a static eliminating device such as an erase light irradiation device. As a result, when the electrophotographic photosensitive member is repeatedly used, the phenomenon that the residual potential of the electrophotographic photosensitive member is brought into the next cycle is prevented, so that the image quality can be further improved. Further, not only the belt system but also an image forming apparatus having any configuration such as an apparatus using an intermediate transfer member can be used effectively.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

[Production of electrophotographic photosensitive member]
(Photoreceptor-1)
A drawing tube (diameter: 84 mm, length: 357 mm) made of JIS A3003 alloy was prepared and polished with a centerless polishing apparatus to a surface roughness _Rz of 0.6 μm. Next, a degreasing treatment, an etching treatment with a 2% by mass sodium hydroxide solution for 1 minute, a neutralization treatment, and a pure water cleaning were sequentially performed on the outer peripheral surface of the drawing tube. Next, as an anodizing treatment step, an anodized film (current density: 1.0 A / dm ² ) was formed on the cylinder surface with 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. Further, pure water cleaning and drying treatment were performed. In this way, a 7 μm anodic oxide film was formed on the outer peripheral surface of the extraction tube to obtain a conductive support.

  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 °, 28 .1 part by weight of hydroxygallium phthalocyanine having a strong diffraction peak at 3 ° is mixed with 1 part by weight of polyvinyl butyral (Esreck BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 80 parts by weight of n-butyl acetate, and a glass shaker and a paint shaker A charge generation layer coating solution was prepared by dispersing for 1 hour. The obtained coating solution was dip-coated on a conductive support on which an anodized film was formed, 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 (27) and 3 parts by mass of a polymer compound having a repeating unit represented by the following formula (28) (viscosity average molecular weight: 69,000) were added to chlorobenzene. A coating solution for a charge transport layer was prepared by dissolving in 25 parts. The obtained coating solution was applied onto the charge generation layer by a dip coating method, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, 4 parts by mass of compound (I-2) in Table 5, 0.5 part of compound (A-3) in Table 50, 3 parts by mass of curable resin (Resitop PL-2211, manufactured by Gunei Chemical Co., Ltd.) , 0.3 parts by weight of colloidal silica, 0.5 parts of polyvinylphenol resin (manufactured by Aldrich), 5 parts by weight of isopropyl alcohol, 5 parts by weight of methyl isobutyl ketone, and 3,5-di-t-butyl-4-hydroxytoluene ( BHT) 0.4 parts by mass was added to prepare a coating solution for a protective layer. This coating solution is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 150 ° C. for 1 hour to form a protective layer having a thickness of about 4 μm. An electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-1”) was obtained.

(Photoreceptor-2)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as Photoreceptor-1, except that Compound (I-19) in Table 9 was used instead of Compound (I-2) in Table 5, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-2”).

(Photoreceptor-3)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as in Photoreceptor-1, except that Compound (I-25) in Table 10 was used instead of Compound (I-2) in Table 5, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-3”).

(Photoreceptor-4)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as for Photoreceptor-1, except that Compound (II-5) in Table 15 was used instead of Compound (I-2) in Table 5, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-4”).

(Photoreceptor-5)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as in Photoreceptor-1, except that Compound (II-14) in Table 17 was used instead of Compound (I-2) in Table 5, and an electrophotographic photoconductor (Hereinafter referred to as “photoreceptor-5”).

(Photoreceptor-6)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as in Photoreceptor-1 except that Compound (IV-3) in Table 36 was used instead of Compound (I-2) in Table 5, and an electrophotographic photoconductor (Hereinafter referred to as “photoreceptor-6”).

(Photoreceptor-7)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as Photoreceptor-1 except that Compound (IV-25) in Table 42 was used instead of Compound (I-2) in Table 5, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-7”).

(Photoreceptor-8)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as in Photoreceptor-1, except that Compound (V-4) in Table 46 was used instead of Compound (I-2) in Table 5, and an electrophotographic photoconductor (Hereinafter referred to as “photoreceptor-8”).

(Photoreceptor-9)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as in Photoreceptor-1, except that Compound (V-11) in Table 48 was used instead of Compound (I-2) in Table 5, and an electrophotographic photoconductor (Hereinafter referred to as “photoreceptor-9”).

(Photoreceptor-10)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as Photoreceptor-1 except that Compound (A-5) in Table 50 was used instead of Compound (A-3) in Table 50, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-10”).

(Photoreceptor-11)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as Photoreceptor-1 except that Compound (A-6) in Table 50 was used instead of Compound (A-3) in Table 50, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-11”).

(Photoreceptor-12)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as for Photoreceptor-1 except that Compound (A-8) in Table 50 was used instead of Compound (A-3) in Table 50, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-12”).

(Photoreceptor-13)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as Photoreceptor-1 except that Compound (A-11) in Table 50 was used instead of Compound (A-3) in Table 50, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-13”).

(Photoreceptor-14)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as for Photoreceptor-1 except that Compound (A-12) in Table 50 was used instead of Compound (A-3) in Table 50, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-14”).

(Photoreceptor-15)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as in Photoreceptor-1 except that Compound (A-15) in Table 51 was used instead of Compound (A-3) in Table 50, and an electrophotographic photoreceptor was obtained. (Hereinafter referred to as “photoreceptor-15”).

(Photoreceptor-16)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer is formed in the same manner as in the photoreceptor 1 except that the compound (A-20) in Table 51 is used instead of the compound (A-3) in Table 50, and an electrophotographic photoreceptor is obtained. (Hereinafter referred to as “photoreceptor-16”).

(Photoreceptor-17)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer is formed in the same manner as in the photoreceptor 1 except that the compound (A-22) in Table 51 is used instead of the compound (A-3) in Table 50, and an electrophotographic photoreceptor is obtained. (Hereinafter referred to as “photoreceptor-17”).

(Photoreceptor-18)
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, a protective layer was formed in the same manner as in Photoreceptor-1 except that Compound (A-24) in Table 51 was used instead of Compound (A-3) in Table 50, and an electrophotographic photoconductor (Hereinafter referred to as “photoreceptor-18”).

(Photoconductor-19 to 27)
Compounds (A-5), (A-6), (A-8), (A-11), (A-12), (A-15), (A-20) in photoreceptors-10 to 18, Photoconductors 19 to 27 were produced in the same manner as the photoconductors 10 to 18 except that (A-22) and (A-24) were not used.

(Photoreceptor-28)
Similarly to Photoreceptor-1, a charge transport layer was formed and Photoreceptor-28 was obtained without providing a protective layer.

[Production of cleaning device]
The following cleaning units were used as the first and second cleaning units, respectively, and cleaning devices-1 to 3 (both of which were process cartridges) shown in FIG. 7 were produced. A cleaning blade was used as the cleaning device-4.

(Cleaning device-1)
<First cleaning unit>
Roll brush member:
Brush material: conductive nylon, fiber thickness: 2 denier (about 17 μm), electrical resistance: 1 × 10 ⁵ Ω, hair length: 4 mm, fiber density: 50,000 / inch ² , biting into the photoreceptor Amount: about 1.5 mm, peripheral speed: 50 mm / s, rotation direction: reverse rotation with respect to the rotation direction of the photoconductor, brush application bias: +200 V
Collection roll member:
Material: phenol resin in which conductive carbon is dispersed, electric resistance: 1 × 10 ⁶ Ω, flexural modulus (JIS K7203): 100 MPa, wear amount (JIS K6902): 2 mg, Rockwell hardness (JIS K7202, M scale): 120, amount of biting into the brush member: 1.5 mm, peripheral speed: 70 mm / s, applied bias: +600 V
scraper:
Material: SUS304, thickness: 80 μm, amount of biting into the recovery roll member: 1.3 mm, free length (free length): 8.0 mm.

<Second cleaning unit>
Roll brush member:
Brush material: conductive nylon, fiber thickness: 2 denier (about 17 μm), electric resistance: 1 × 10 ⁵ Ω, hair length: 4 mm, fiber density: 50,000 / inch ² , biting into the photoreceptor Amount: about 1.5 mm, peripheral speed: 60 mm / s, rotation direction: reverse rotation with respect to rotation direction of photoconductor, brush application bias: -400 V
Collection roll member:
Material: phenol resin in which conductive carbon is dispersed, electric resistance: 1 × 10 ⁶ Ω, flexural modulus (JIS K7203): 100 MPa, wear amount (JIS K6902): 2 mg, Rockwell hardness (JIS K7202, M scale): 120, amount of biting into the brush member: 1.5 mm, peripheral speed: 70 mm / s, applied bias: −800 V
scraper:
Material: SUS304, thickness: 80 μm, amount of biting into the recovery roll member: 1.3 mm, free length (free length): 8.0 mm.

(Cleaning device-2)
<First cleaning unit>
Roll brush member:
Brush material: conductive nylon, fiber thickness: 5 denier (about 43 μm), electric resistance: 1 × 10 ⁵ Ω, hair length: 4 mm, fiber density: 150,000 / inch ² , biting into the photoreceptor Amount: about 1.5 mm, peripheral speed: 50 mm / s, rotation direction: reverse rotation with respect to the rotation direction of the photoconductor, brush application bias: +200 V
Collection roll member:
Material: phenol resin in which conductive carbon is dispersed, electric resistance: 1 × 10 ⁶ Ω, flexural modulus (JIS K7203): 100 MPa, wear amount (JIS K6902): 2 mg, Rockwell hardness (JIS K7202, M scale): 120, amount of biting into the brush member: 1.5 mm, peripheral speed: 70 mm / s, applied bias: +600 V
scraper:
Material: SUS304, thickness: 80 μm, amount of biting into the recovery roll member: 1.3 mm, free length (free length): 8.0 mm.

<Second cleaning unit>
Roll brush member:
Brush material: conductive nylon, fiber thickness: 2 denier (about 17 μm), electrical resistance: 1 × 10 ⁵ Ω, hair length: 4 mm, fiber density: 150,000 / inch ² , biting into the photoreceptor Amount: about 1.5 mm, peripheral speed: 60 mm / s, rotation direction: reverse rotation with respect to the rotation direction of the photoconductor, brush application bias: −400 V
Collection roll member:
Material: phenol resin in which conductive carbon is dispersed, electric resistance: 1 × 10 ⁶ Ω, flexural modulus (JIS K7203): 100 MPa, wear amount (JIS K6902): 2 mg, Rockwell hardness (JIS K7202, M scale): 120, amount of biting into the brush: 1.5 mm, peripheral speed: 70 mm / s, applied bias: -800 V
scraper:
Material: SUS304, thickness: 80 μm, amount of biting into the recovery roll member: 1.3 mm, free length (free length): 8.0 mm.

(Cleaning device-3)
<First cleaning unit>
Roll brush member:
Brush material: conductive nylon, fiber thickness: 10 denier (approx. 85 μm), electrical resistance: 1 × 10 ⁵ Ω, hair length: 4 mm, fiber density: 150,000 / inch ² , biting into the photoreceptor Amount: about 1.5 mm, peripheral speed: 10 mm / s, rotation direction: reverse rotation with respect to the rotation direction of the photoconductor, brush application bias: +200 V
Collection roll member:
Material: phenol resin in which conductive carbon is dispersed, electrical resistance: 1 × 10 ⁸ Ω, flexural modulus (JIS K7203): 100 MPa, wear amount (JIS K6902): 2 mg, Rockwell hardness (JIS K7202, M scale): 120, amount of biting into the brush member: 1.5 mm, peripheral speed: 70 mm / s, applied bias: +600 V
scraper:
Material: SUS304, thickness: 80 μm, amount of biting into the recovery roll member: 1.3 mm, free length (free length): 8.0 mm.

<Second cleaning unit>
Roll brush member:
Brush material: conductive nylon, fiber thickness: 5 denier (approximately 43 μm), electrical resistance: 1 × 10 ⁵ Ω, hair length: 4 mm, fiber density: 150,000 / inch ² , biting into the photoreceptor Amount: about 1.5 mm, peripheral speed: 10 mm / s, rotation direction: reverse rotation with respect to the rotation direction of the photoconductor, brush application bias: −400 V
Collection roll member:
Material: phenol resin in which conductive carbon is dispersed, electrical resistance: 1 × 10 ⁸ Ω, flexural modulus (JIS K7203): 100 MPa, wear amount (JIS K6902): 2 mg, Rockwell hardness (JIS K7202, M scale): 120, amount of biting into the brush: 1.5 mm, peripheral speed: 70 mm / s, applied bias: -800 V
scraper:
Material: SUS304, thickness: 80 μm, amount of biting into the recovery roll member: 1.3 mm, free length (free length): 8.0 mm.

(Cleaning device-4)
Blade material: Urethane rubber, Thickness: 2 mm, Amount of biting into the photoconductor: 1.0 mm, Free length (free length): 10 mm, Arrangement direction: Doctor direction with respect to the photoconductor.

[Production of developer]
In the following description, 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.

Average shape factor ML ² / A of toner and composite particles:
The toner or composite particles were observed with an optical microscope, and the image was taken into an image analyzer (LUZEX III, manufactured by Nireco) to measure the equivalent circle diameter. Next, from the maximum length and area of the toner particles or composite particles, the shape factor value is obtained for each of 1000 particles according to the following formula (29), and the average value of 1000 particles is obtained to obtain the average shape factor ML ² / L was determined.
(Shape factor) = (maximum length) ² × π × 100 / [4 × (area)] (29)

(Developer-1)
{Manufacture of toner base particles}
<Preparation of resin fine particle dispersion>
370 g of styrene, 30 g of n-butyl acrylate, 8 g of acrylic acid, 24 g of dodecanethiol and 4 g of carbon tetrabromide, and 6 g of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) And 10 g of anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and a solution in 550 g of ion-exchanged water are mixed to start emulsion polymerization in the flask, while slowly mixing for 10 minutes. 50 g of ion exchange water in which 4 g of ammonium persulfate was dissolved was added. After carrying out nitrogen substitution in the flask, the mixed solution was heated with an oil bath until the temperature of the mixed solution reached 70 ° C. while stirring, and emulsion polymerization was continued for 5 hours. As a result, a resin fine particle dispersion in which resin fine particles having a volume average particle size of 150 nm, a glass transition temperature (T _g ) of 58 ° C., and a mass average molecular weight (M _w ) of 11,500 was obtained. The solid content concentration of this dispersion was 40% by mass.

<Preparation of Colorant Dispersion-1>
Carbon black (Mogal L, manufactured by Cabot) 60 g, nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) 6 g, and ion-exchanged water 2400 g were mixed, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used. And stirred for 10 minutes. Then, the dispersion process was carried out with the optimizer, and the colorant dispersion liquid-1 in which the colorant (carbon black) particles having a volume average particle diameter of 250 nm were dispersed was prepared.

<Preparation of Colorant Dispersion-2>
360 g of cyan pigment (B15, manufactured by Dainichi Seika), 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) and 2400 g of ion-exchanged water are mixed together, and a homogenizer (Ultra Turrax T50, manufactured by IKA) is mixed. And stirred for 10 minutes. Thereafter, a colorant dispersion-2 in which colorant (cyan pigment) particles having a volume average particle diameter of 250 nm were dispersed by dispersing with an optimizer was prepared.

<Preparation of Colorant Dispersion-3>
60 g of magenta pigment (R122, manufactured by Dainichi Seika), 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) and 240 g of ion-exchanged water are mixed together, and a homogenizer (Ultra Turrax T50, manufactured by IKA) is mixed. And stirred for 10 minutes. Thereafter, a dispersion treatment with an optimizer was performed to prepare a colorant dispersion-3 in which colorant (magenta pigment) particles having a volume average particle diameter of 250 nm were dispersed.

<Preparation of colored dispersion-4>
90 g of yellow pigment (Y180), 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 240 g of ion-exchanged water are mixed and stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA). did. Thereafter, a dispersion treatment was performed using an optimizer to prepare a colorant dispersion liquid-4 in which colorant (yellow pigment) particles having a volume average particle diameter of 250 nm were dispersed.

<Preparation of release agent dispersion>
100 g of paraffin wax (HNP0190, manufactured by Nippon Seiwa Co., Ltd., melting point: 85 ° C.), 5 g of a cationic surfactant (Sanisol B50: manufactured by Kao Corporation) and 240 g of ion-exchanged water are mixed and made of round stainless steel The mixture was dispersed in the flask for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA). Thereafter, a dispersion treatment was performed using a pressure discharge type homogenizer to prepare a release agent dispersion liquid in which release agent particles having a volume average particle diameter of 550 nm were dispersed.

<Preparation of toner mother particles K1>
234 parts by mass of the resin fine particle dispersion, 30 parts by mass of the colorant dispersion-1, 40 parts by mass of the release agent dispersion, and 0.5 parts by mass of polyaluminum hydroxide (Paho2S, manufactured by Asada Chemical Co., Ltd.) Then, 600 parts by mass of ion-exchanged water was charged into each of the round stainless steel flasks, and mixed and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the mixed solution was heated with stirring in an oil bath for heating and maintained at 40 ° C. for 30 minutes. At this time, it was confirmed that aggregated particles having a volume average particle diameter of 4.5 μm were produced in the mixed solution. Furthermore, when the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, the volume average particle size was 5.3 μm. After adding 26 parts by mass of the resin fine particle dispersion to the dispersion containing the aggregate particles, the mixture was held at 50 ° C. for 30 minutes using a heating oil bath. After adding 1N sodium hydroxide to the dispersion containing the aggregated particles to adjust the pH of the dispersion to 7.0, the flask is sealed and heated with continued stirring using a magnetic seal at 85 ° C. Held for 4 hours. After the dispersion was cooled, the toner base particles produced in the dispersion were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K1. Toner base particles K1 had a volume average particle size of 5.9 μm and an average shape factor ML ² / L of 125.

<Preparation of toner base particles C1>
Toner base particle C1 was prepared in the same manner as toner base particle K1, except that colored particle dispersion-2 was used instead of colored particle dispersion-1. The resulting toner base particles C1 had a volume average particle size of 5.8 μm and an average shape factor ML ² / A of 124.

<Preparation of toner mother particles M1>
Toner base particles M1 were prepared in the same manner as toner base particles K1, except that Colored Particle Dispersion-3 was used instead of Colored Particle Dispersion-1. The resulting toner base particles M1 had a volume average particle size of 5.5 μm and an average shape factor ML ² / A of 127.

<Preparation of toner mother particles Y1>
Toner base particles Y1 were prepared in the same manner as toner base particles K1, except that Colored Particle Dispersion-4 was used instead of Colored Particle Dispersion-1. The resulting toner base particles Y1 had a volume average particle size of 5.9 μm and an average shape factor ML ² / A of 123.

<Manufacture of carriers>
14 parts by mass of toluene, 2 parts by mass of a styrene-methacrylate copolymer (component ratio: 90/10) and 0.2 part of carbon black (R330: manufactured by Cabot Corporation) were mixed and dispersed by stirring with a stirrer for 10 minutes. A coating solution was prepared. Next, 100 parts by mass of the coating liquid and ferrite particles (volume average particle size: 50 μm) are put in a vacuum degassing type kneader and stirred at 60 ° C. for 30 minutes, and then degassed by further reducing pressure while heating. A carrier was obtained by drying. This carrier had a volume resistivity of 10 ¹¹ Ω · cm when an applied electric field of 1000 V / cm was applied.

<Preparation of Toner-1 and Developer-1>
100 parts by mass of each of the toner base particles K1, C1, M1, and Y1, 1 part by mass of rutile type titanium oxide (particle size: 20 nm, treated with n-decyltrimethoxysilane), silica (particle size: 40 nm, gas 2.0 parts by mass prepared by a phase oxidation method and treated with silicone oil), 1 part by mass of cerium oxide (volume average particle size: 0.7 μm), higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700 is pulverized with a jet mill. Then, 0.3 parts by mass was blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s for 15 minutes. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain toner-1 (four colors of black, cyan, magenta, and yellow). Further, 100 parts by mass of carrier and 5 parts by mass of toner-1 were stirred for 20 minutes at 40 rpm using a V-blender, and sieved with a sieve having an opening of 212 μm, thereby developing-1 (black, cyan, Magenta and yellow).

(Developer-2)
<Preparation of toner mother particles K2>
234 parts by mass of resin fine particle dispersion (prepared at the time of preparing composite fine particles), 30 parts by mass of colorant dispersion-1, 40 parts by mass of release agent dispersion, polyaluminum hydroxide (Paho2S, manufactured by Asada Chemical Co., Ltd.) ) And 600 parts by mass of ion-exchanged water were each placed in a round stainless steel flask, and mixed and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the mixed solution was heated while being stirred in a heating oil bath and maintained at 40 ° C. for 30 minutes, and then it was confirmed that aggregated particles having a volume average particle size of 4.5 μm were formed. Furthermore, when the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, the volume average particle size was 5.3 μm. Thereafter, 26 parts by mass of a resin fine particle dispersion was added to the dispersion containing the aggregated particles, and then heated with an oil bath for heating and held at 50 ° C. for 30 minutes. After adding 1N sodium hydroxide to the dispersion containing the aggregated particles to adjust the pH of the system to 5.0, the flask is sealed and heated with continuous stirring using a magnetic seal at 95 ° C. Hold for 5 hours. After the dispersion was cooled, the toner base particles produced in the dispersion were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K2. The volume average particle size of the toner base particles K2 is 5.8 μm, and the average shape factor ML ² / A is 103.

<Preparation of toner mother particle C2>
Toner base particles C2 were prepared in the same manner as toner base particles K2, except that Colored Particle Dispersion-2 was used instead of Colored Particle Dispersion-1. The resulting toner base particles C2 had a volume average particle size of 5.7 μm and an average shape factor ML ² / L of 104.

<Preparation of toner mother particles M2>
Toner base particles M2 were prepared in the same manner as toner base particles K2, except that Colored Particle Dispersion-3 was used instead of Colored Particle Dispersion-1. The resulting toner base particles M2 had a volume average particle size of 5.6 μm and an average shape factor ML ² / A of 106.

<Preparation of toner mother particle Y2>
Toner base particles Y2 were prepared in the same manner as toner base particles K2, except that Colored Particle Dispersion-4 was used instead of Colored Particle Dispersion-1. The resulting toner base particles Y2 had a volume average particle size of 5.8 μm and an average shape factor ML ² / A of 103.

<Preparation of Toner-2 and Developer-2>
Toner-1 except that toner base particles K2, C2, M2, and Y2 were used, respectively, and aluminum oxide (volume average particle size: 0.1 μm) was used instead of cerium oxide (volume average particle size: 0.7 μm). In addition, toner-2 and developer-2 (four colors of black, cyan, magenta, and yellow, respectively) were prepared in the same manner as developer-1.

(Developer-3)
<Preparation of toner mother particles K3>
100 parts by mass of polyester resin (linear polyester obtained from terephthalic acid-bisphenol A ethylene oxide adduct-cyclohexanedimethanol, T _g : 62 ° C., M _n : 12,000, M _w : 32,000), carbon black 4 parts by mass (Mogal L, manufactured by Cabot) and 5 parts by mass of carnauba wax were kneaded with an extruder and pulverized with a jet mill. The obtained pulverized product was classified with a wind classifier to obtain toner mother particles K3. The resulting toner base particles K3 had a volume average particle size of 5.9 μm and an average shape factor ML ² / A of 145.

<Preparation of toner base particles C3>
Toner base particles C3 were prepared in the same manner as toner base particles K3 except that a cyan colorant (CI Pigment Blue 15: 3) was used instead of carbon black. The resulting toner base particles C3 had a volume average particle size of 5.6 μm and an average shape factor ML ² / A of 141.

<Preparation of toner mother particles M3>
Toner base particles M3 were prepared in the same manner as toner base particles K3 except that magenta colorant (R122) was used instead of carbon black. The resulting toner base particles M3 had a volume average particle size of 5.9 μm and an average shape factor ML ² / A of 149.

<Preparation of toner mother particles Y3>
Toner base particles Y3 were prepared in the same manner as toner base particles K3 except that a yellow colorant (Y180) was used instead of carbon black. The resulting toner base particles Y3 had a volume average particle size of 5.8 μm and an average shape factor ML ² / A of 144.

<Preparation of Toner-3 and Developer-3>
Toner-3 and developer-3 (four colors of black, cyan, magenta, and yellow, respectively) in the same manner as toner-2 and developer-2 except that toner base particles K3, C3, M3, and Y3 were used, respectively. Was prepared.

[Examples 1-30, Comparative Examples 1-10]
In Examples 1 to 30 and Comparative Examples 1 to 10, the electrophotographic photosensitive member, the cleaning device, and the developer are the combinations shown in Table 53 and Table 54, respectively, and the tandem method having the configuration shown in FIG. Color image forming apparatus (process speed 220 mm / sec) was prepared. The elements other than the electrophotographic photosensitive member, the cleaning device, and the developer were the same as those of Docu Color 4040 manufactured by Fuji Xerox.

  Next, an image formation test was performed on each of the image forming apparatuses of Examples 1 to 30 and Comparative Examples 1 to 10. Specifically, 100,000 sheets of images were formed in an environment of high temperature and high humidity (30 ° C., 80% RH), and then 100,000 sheets of images were formed in an environment of low temperature and low humidity (10 ° C., 20% RH). Went. Further, the surface roughness (ten-point average surface roughness: Rz (μm)) of the electrophotographic photosensitive member surface at a time corresponding to 2,000,000 cycles was measured.

  After the above image formation test, the electrophotographic photoreceptor wear rate (amount of wear per 1,000 cycles), surface roughness, presence or absence of deposits on the photoreceptor surface, and toner cleaning properties in a low-temperature and low-humidity environment (cleaning) The charging device contamination and image quality deterioration due to defects), transferability and image quality were evaluated. Moreover, about each Example and the comparative example, the product (RzxWe) of surface roughness Rz and wear rate We was calculated | required. The obtained results are shown in Table 53 and Table 54.

  Regarding the surface roughness (10-point average surface roughness: Rz (μm)), a surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd. is used, and the cutoff (standard length) is 0 according to the provisions of JIS B0601 (1994). Measured at .8 mm and a measurement length of 4 mm.

In addition, the presence or absence of deposits on the surface of the photoreceptor is visually observed, and the following criteria:
A: No adhesion B: Partial adhesion (about 30% or less of the whole) C: Evaluation based on adhesion.

In addition, the cleaning property is visually observed, and the following criteria:
A: Good B: Partially (about 10% or less of the whole) with image quality defects such as streaks C: Evaluation based on image quality defects in a wide area.

により求めた転写効率を指標として、以下の基準：
Ａ：転写効率９０％以上
Ｂ：転写効率８５〜９０％
Ｃ：転写効率８５％未満
に基づいて評価したものである。 In addition, the transferability is measured by measuring the mass of the toner remaining on the surface of the photoreceptor after the transfer step and attaching the toner to the adhesive tape.

The following criteria:
A: Transfer efficiency of 90% or more B: Transfer efficiency of 85 to 90%
C: The evaluation is based on a transfer efficiency of less than 85%.

  Further, the image quality was visually observed, and A was shown when it was good, and details were shown when image quality defects were observed.

［比較例１１］
先ず、感光体−１と同様にして電荷輸送層までを形成した。次に、表５０中の化合物（Ａ−３）０．５質量部の代わりに下記式（３０）で示される化合物０．５質量部を用いたこと以外は感光体−１と同様にして保護層を形成し、電子写真感光体（以下、「感光体−２９」という）を得た。

次に、感光体−１の代わりに感光体−２９を用いた以外は実施例１と同様にして、画像形成装置を作製し、同様の評価を試みたが、電気特性が劣悪であり、安定した画像を得ることができなかった。

[Comparative Example 11]
First, up to the charge transport layer was formed in the same manner as the photoreceptor-1. Next, protection was carried out in the same manner as in Photosensitive member-1, except that 0.5 part by mass of the compound represented by the following formula (30) was used instead of 0.5 part by mass of the compound (A-3) in Table 50. The layer was formed to obtain an electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-29”).

Next, an image forming apparatus was produced in the same manner as in Example 1 except that Photoreceptor-29 was used instead of Photoreceptor-1, and the same evaluation was attempted. However, the electrical characteristics were poor and stable. Image could not be obtained.

1 is a schematic cross-sectional view showing a preferred embodiment of an electrophotographic photoreceptor of the present invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. 1 is a schematic configuration diagram illustrating a preferred embodiment of an image forming apparatus of the present invention. It is a schematic block diagram which shows an example of the cleaning apparatus used by this invention. It is a schematic block diagram which shows other embodiment of the image forming apparatus of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photoreceptor, 11 ... Conductive support, 12 ... Photosensitive layer, 13 ... Undercoat layer, 14 ... Charge generation layer, 15 ... Charge transport layer, 16 ... Protective layer, 17 ... Charge generation / charge transport layer 2, 42 ... charging device, 3, 43 ... exposure device, 4, 44 ... developing device, 5, 45 ... transfer device, 6 ... image fixing device, 7, 46 ... cleaning device, 700 ... housing, 701a, 701b ... Rolled brush members, 702a, 702b ... recovery roll members, 703a, 703b ... scrapers, 704a, 704b, 705a, 705b ... shafts, 706 ... mounting brackets, 40 ... image forming apparatuses, 47 ... belt conveying apparatuses, 48 ... conveying belts 49 ... tension roll, 55 ... suction roll, 56 ... fixing roll, 57 ... storage tray, 58 ... tension roll, 59 ... belt cleaner, 60 ... recording material supply Apparatus.

Claims (7)

A phenol derivative having a methylol group;
A charge transporting compound having a functional group capable of reacting with the phenol derivative;
A coating agent composition comprising a compound represented by the following general formula (A):

[In Formula (A), A ^{1 to} A ⁸ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an epoxy group-substituted alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. -10 epoxy group-substituted alkoxy group, C1-C15 fluorine-substituted alkyl, C1-C15 fluorine-substituted alkoxy group, C1-C10 carboxyl group-substituted alkyl group, C1-C10 carboxyl group A substituted alkoxy group, a hydroxyphenyl group-substituted alkyl group having 1 to 15 carbon atoms, or an alkoxyphenyl group-substituted alkyl group alkoxy group having 1 to 15 carbon atoms, wherein at least one of A ^{1 to} A ⁸ is an epoxy group or a carboxyl group And a group having one selected from a hydroxyphenyl group, a and b each independently represent an integer of 1 to 100. ] The coating composition according to claim 1, wherein the charge transporting compound has a structure represented by any one of the following general formulas (I) to (V).
_{^{F [- (X 1) m}} -R 1 -Z 1 H] n ... (I)
[In Formula (I), F represents an n-valent organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, Sulfur atom, NH or COO, m represents 0 or 1, and n represents an integer of 1 to 4. ]
_{^{F [- (X 2) m1}} - (R 2) m2 - (Z 2) m3 G] n1 ... (II)
[In Formula (II), F represents an n1-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, Z ² represents an oxygen atom, S is a sulfur atom, NH or COO, G is an epoxy group, m1, m2 and m3 are each independently 0 or 1, and n1 is an integer of 1 to 4. ]
_{^{F [-D-Si (R 3}} ) (3-m4) Q m4] n2 ... (III)
[In Formula (III), F is an n2 valent organic group derived from a compound having a hole transporting ability, D is a divalent group having flexibility, and R ³ is a hydrogen atom, substituted or unsubstituted. Q represents a hydrolyzable group, m4 represents an integer of 1 to 3, and n2 represents an integer of 1 to 4. ]

[In Formula (IV), F represents an n3-valent organic group having hole transportability, T ¹ represents a divalent group, Y represents an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ represent independently a hydrogen atom or a monovalent organic group, the ^{R 7} is a monovalent organic group, m5 is 0 or 1, n3 is an integer of 1 to 4, respectively. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (V), at the n4 monovalent organic group F is having a hole transporting property, the T2 is a divalent radical, the ^{R 8} is a monovalent organic group, a is m6 0 or 1, n4 is 1 Integers of ~ 4 are shown respectively. ] The coating composition according to claim 1 or 2, wherein the charge transporting compound has a structure represented by the following general formula (VI).

[In Formula (VI), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, k represents 0 or 1, and when k is 0, Ar ⁵ represents a substituted or unsubstituted aryl group. And when k is 1, Ar ⁵ represents a substituted or unsubstituted arylene group, and B ¹ , B ² , B ³ , B ⁴ and B ⁵ are each represented by any of the following general formulas (VII) to (XI): The group represented is represented, c, d, e, f and g each represent 0 or 1, and the sum of c, d, e, f and g is an integer of 1 to 4. ]
_{^{- (X 1) m 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, an NH group or a CO ₂ group, and m represents 0 or 1 Show. ]
_{^{- (X 2) m1 - (}} R 2) m2 - (Z 2) m3 G (VIII)
[In Formula (VIII), X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, a sulfur atom, an NH group or a CO ₂ group, and G represents an epoxy group. , M1, m2 and m3 each independently represents 0 or 1. ]
-D-Si (R ³ ) _(3-m4) Q _m4 (IX)
[In Formula (IX), D represents a divalent group, R ³ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and m4 represents 1 to 3 Indicates an integer. ]

[In formula (X), T ¹ represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 5 represents 0 or 1, and R ⁶ and R ⁷ may be bonded to each other to form a heterocycle having Y as a hetero atom. ]

[In formula (XI), T ² represents a divalent group, R ⁸ represents a monovalent organic group, and m6 represents 0 or 1. ]   The coating agent composition according to any one of claims 1 to 3, further comprising a solvent, wherein the proportion of the alcohol-based solvent in the total amount of the solvent is 50% by volume or more. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the support,
The said photosensitive layer contains the functional layer which consists of the hardened | cured material of the coating agent composition as described in any one of Claims 1-4 provided in the side far from the said electroconductive support body. Electrophotographic photoreceptor. A method for producing an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the support,
Preparing a target object to be an electrophotographic photosensitive member provided with a functional layer on the side of the photosensitive layer remote from the conductive support;
Applying the coating agent composition according to any one of claims 1 to 4 to a side far from the conductive support of the object to be treated, and curing the composition to form a functional layer. A method for producing an electrophotographic photosensitive member. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the support, wherein the photosensitive layer is provided on a side far from the conductive support. An electrophotographic photosensitive member comprising a functional layer comprising a cured product of the coating agent composition according to any one of
A charging device for charging the electrophotographic photosensitive member;
An exposure apparatus that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image; and
A developing device for developing the electrostatic latent image with toner to form a toner image;
A transfer device for transferring the toner image to a transfer medium;
An image forming apparatus comprising: a cleaning device that removes toner remaining on the electrophotographic photosensitive member after transfer of the toner image.

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