JP2009157104A - Coating agent composition, electrophotographic photoreceptor, image forming apparatus and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating agent composition which attains a longer lifetime as a coating liquid and forms an electrophotographic photoreceptor which is excellent in electric properties and less likely to cause wear due to repeated use, so that excellent durability is ensured. <P>SOLUTION: The coating agent composition used as a constituent material of an electrophotographic photoreceptor includes a compound represented by general formula (I) and a polyfunctional isocyanate compound which can form a cured film by crosslinking with the above compound, wherein F denotes an organic group derived from a compound having hole transporting property; R denotes a monovalent organic group; L denotes a divalent organic group; n denotes an integer of 1-4; and j denotes 0 or 1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  A so-called xerographic image forming apparatus includes an electrophotographic photosensitive member (hereinafter sometimes referred to as “photosensitive member”), a charging device, an 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. For this reason, the photoconductor is likely to be scratched or worn, which causes image defects.

In order to suppress such scratches and wear, a surface layer having high mechanical strength is used in the electrophotographic photosensitive member, and the life is further extended. For example, in Patent Document 1 below, the surface layer is formed using a polymer obtained by crosslinking an isocyanate, a polyol, and a charge transport material.
JP 2004-117766 A

  However, a constituent material that forms a surface layer that has high mechanical strength and is difficult to wear as described in Patent Document 1 has high reactivity, and the reaction between these constituent materials is likely to proceed in a coating liquid state. There is a problem that it is substantially unsuitable for production, for example, precipitates and gelation occur, the life of the coating liquid is shortened, and the use efficiency of the material is deteriorated, resulting in an increase in cost.

  As a means for suppressing the reaction in the coating liquid state, it is known to use a blocked isocyanate having a protective group. However, this protective group remains in the coating film after heat curing, and the electrical properties and mechanical strength are reduced. There was a problem of causing deterioration.

  In order to increase the mechanical strength of the surface layer, it is effective to use an isocyanate having 3 or more functional groups. However, as the number of functional groups increases, the number of isocyanate protecting groups required increases, and the above problem becomes more prominent. It becomes.

  The present invention has been made in view of such a situation, and can realize a long life as a coating liquid, is excellent in electrical characteristics, has little wear due to repeated use, and is excellent in durability. An object of the present invention is to provide a coating agent composition capable of forming an electrophotographic photoreceptor. Another object of the present invention is to provide an electrophotographic photosensitive member formed using the coating agent composition, and an image forming apparatus and a process cartridge including the electrophotographic photosensitive member.

［式（Ｉ）中、Ｆは正孔輸送性を有する化合物から誘導される有機基を示し、Ｒは１価の有機基を示し、Ｌは２価の有機基を示し、ｎは１以上４以下の整数を示し、ｊは０又は１を示す。］ In order to achieve the above object, the present invention provides a coating agent composition used as a constituent material of an electrophotographic photosensitive member, which is cured by crosslinking with a compound represented by the following general formula (I): A polyfunctional isocyanate compound capable of forming a film is provided, and a coating agent composition is provided.

[In Formula (I), F represents an organic group derived from a compound having a hole transporting property, R represents a monovalent organic group, L represents a divalent organic group, and n represents 1 or more and 4 The following integer is shown, j shows 0 or 1. ]

  According to such a coating agent composition, by having the above-described configuration, in the coating liquid state, it is possible to obtain a stable coating liquid by suppressing reaction between materials, and represented by the general formula (I) at the time of curing. The compound and the polyfunctional isocyanate compound are crosslinked to form a polymer, and a crosslinked cured film having excellent electrical properties, scratch resistance, and abrasion resistance can be formed. Here, the compound having the charge transporting property represented by the general formula (I) alone has low reactivity with the isocyanate compound, and the reaction with the isocyanate compound in a coating solution at room temperature can be suppressed. Therefore, even when a polyfunctional material having no protective group, which is advantageous from the viewpoint of electrical characteristics and abrasion resistance, is used as the isocyanate compound, the life of the coating liquid is not impaired. In addition, the compound represented by the general formula (I) can be reacted with an isocyanate compound in a heated state by using, for example, a thermal latent acid catalyst that exhibits activity during heat curing, and thus the electrical properties of the crosslinked film can be reduced. Properties and wear resistance can be improved. Therefore, by using such a coating agent composition as a constituent material of an electrophotographic photosensitive member, an electrophotographic photosensitive member having excellent electrical characteristics and less wear due to repeated use can be obtained.

［式（ＩＩ）中、Ｒ^１、Ｒ^２及びＲ^３は各々独立に、水素原子、ハロゲン原子又は１価の有機基を示す。］ In the coating agent composition of the present invention, in the general formula (I), R is preferably a group represented by the following general formula (II).

[In formula (II), R ¹ , R ² and R ³ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group. ]

  When R in the general formula (I) is a group represented by the general formula (II), the reactivity with the polyfunctional isocyanate compound in a coating solution at room temperature can be further reduced. The life of the liquid can be made longer.

  In the coating agent composition of the present invention, in the general formula (I), j is preferably 1 and L is an alkylene group. In the general formula (I), when L is present as an alkylene group, the electrical properties of the crosslinked film obtained by curing the coating composition can be improved, and the electrophotographic photosensitive material having more excellent electrical properties. You can get a body. Further, in the general formula (I), L is preferably a methylene group. Thereby, the crosslinking density of the crosslinked film formed by curing the coating agent composition is improved, and an electrophotographic photoreceptor having better wear resistance can be obtained.

［式（ＩＩＩ）中、Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４は各々独立に、置換もしくは未置換のアリール基を示し、Ａｒ^５は置換もしくは未置換のアリール基、又は、置換もしくは未置換のアリーレン基を示し、且つ、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４及びＡｒ^５のうち１乃至４個は、上記一般式（Ｉ）で表わされる化合物における下記一般式（ＩＶ）で示される部位と結合するための結合手を有し、ｋは０又は１を示す。］

［式（ＩＶ）中、Ｒは１価の有機基を示し、Ｌは２価の有機基を示し、ｊは０又は１を示す。］ In the coating agent composition of the present invention, in the general formula (I), the F is preferably a group represented by the following general formula (III).

[In formula (III), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted aryl group, or substituted or unsubstituted. ^{1 to 4 of} Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are represented by the following general formula (IV) in the compound represented by the above general formula (I) It has a bond for binding to the site, and k represents 0 or 1. ]

[In Formula (IV), R represents a monovalent organic group, L represents a divalent organic group, and j represents 0 or 1. ]

  When F in the general formula (I) is a group represented by the general formula (III), the electric characteristics and abrasion resistance of the electrophotographic photoreceptor formed using the coating agent composition are further improved. Can be improved.

［式（Ｖ）中、Ｙ^１、Ｙ^２及びＹ^３は各々独立に、ハロゲン原子、炭素数１以上１０以下のアルキル基、炭素数１以上１０以下のアルコキシル基、置換もしくは未置換のアリール基、炭素数７以上１０以下のアラルキル基、置換もしくは未置換のスチリル基、置換もしくは未置換のブタジエン基、又は、置換もしくは未置換のヒドラゾン基を示し、Ｒ^５、Ｒ^６及びＲ^７は各々独立に、炭素数１以上１８以下の１価の有機基を示し、Ｌ^５、Ｌ^６及びＬ^７は各々独立に、アルキレン基を示し、ｐ１、ｐ２及びｐ３は各々独立に、０以上２以下の整数を示し、ｑ１、ｑ２及びｑ３は、０又は１を示し、且つ、（ｑ１＋ｑ２＋ｑ３）≧１の条件を満たす。］ In the coating agent composition of the present invention, the compound represented by the general formula (I) is preferably a compound represented by the following general formula (V).

[In Formula (V), Y ¹ , Y ² and Y ³ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group. Represents an aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted styryl group, a substituted or unsubstituted butadiene group, or a substituted or unsubstituted hydrazone group, and R ⁵ , R ⁶ and R ⁷ are each independently Represents a monovalent organic group having 1 to 18 carbon atoms, L ⁵ , L ⁶ and L ⁷ each independently represents an alkylene group, and p 1, p 2 and p 3 each independently represents 0 to 2 An integer, q1, q2, and q3 represent 0 or 1, and satisfy the condition of (q1 + q2 + q3) ≧ 1. ]

  By using the compound represented by the general formula (V), it is possible to further improve the electrical characteristics and abrasion resistance of the electrophotographic photosensitive member formed using the coating agent composition.

  In the coating composition of the present invention, the isocyanate compound is preferably an isocyanate compound having 3 or more functional groups. As a result, a cured film having a high cross-linking density and having a three-dimensional cross-linking structure can be formed using the coating agent composition, and the abrasion resistance of the electrophotographic photosensitive member can be further improved.

  The present invention also includes a conductive support and a photosensitive layer formed on the conductive support, and the photosensitive layer is disposed on the side farthest from the conductive support. An electrophotographic photosensitive member having an outermost surface layer obtained by curing the coating agent composition is provided.

  According to such an electrophotographic photoreceptor, the outermost surface layer farthest from the conductive support is formed using the coating agent composition of the present invention, and the compound represented by the general formula (I) Since the polyfunctional isocyanate compound has a cross-linked structure, the electrical characteristics, scratch resistance and wear resistance can be improved. Such an electrophotographic photosensitive member is excellent in both electrical characteristics and wear resistance, and therefore, it is possible to obtain good image quality over a long period of time. In addition, since the reaction between the materials in the coating composition of the present invention is sufficiently suppressed in the coating liquid state, the electrophotographic photosensitive member having the outermost surface layer formed using the coating composition is stable with little variation. Characteristics can be obtained.

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

  The present invention further includes the electrophotographic photosensitive member of the present invention, a charging device for charging the electrophotographic photosensitive member, an exposure device for forming an electrostatic latent image on the charged electrophotographic photosensitive member, and the electrophotographic photosensitive member. At least one selected from the group consisting of a developing device for developing the formed electrostatic latent image with toner to form a toner image, and a cleaning device for removing the toner remaining on the surface of the electrophotographic photosensitive member. A process cartridge is provided.

  According to the image forming apparatus and the process cartridge of the present invention, since the electrophotographic photosensitive member of the present invention having excellent electrical characteristics and excellent wear resistance as described above is used, an image with good image quality over a long period of time. Can be formed stably.

  According to the present invention, it is possible to achieve a long life as a coating liquid, and it is possible to form an electrophotographic photosensitive member that has excellent electrical characteristics and little wear due to repeated use and excellent durability. A coating agent composition can be provided. In addition, the present invention can provide an electrophotographic photoreceptor excellent in electrical characteristics and abrasion resistance obtained by using the coating agent composition, and an image forming apparatus and a process cartridge including the electrophotographic photoreceptor. .

  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)
The coating agent composition of the present invention is a coating agent composition used as a constituent material of an electrophotographic photosensitive member, and forms a cured film by crosslinking with a compound represented by the following general formula (I): And a polyfunctional isocyanate compound that can be obtained.

［式（Ｉ）中、Ｆは正孔輸送性を有する化合物から誘導される有機基を示し、Ｒは１価の有機基を示し、Ｌは２価の有機基を示し、ｎは１以上４以下の整数を示し、ｊは０又は１を示す。］

[In Formula (I), F represents an organic group derived from a compound having a hole transporting property, R represents a monovalent organic group, L represents a divalent organic group, and n represents 1 or more and 4 The following integer is shown, j shows 0 or 1. ]

  Of the compounds represented by the above general formula (I), R is preferably represented by the following general formula (II) from the viewpoint of mainly improving the life of the coating agent composition. And a compound represented by the following general formula (Ia), which is a group represented by:

［式（ＩＩ）中、Ｒ^１、Ｒ^２及びＲ^３は各々独立に、水素原子、ハロゲン原子又は１価の有機基を示す。］

[In formula (II), R ¹ , R ² and R ³ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group. ]

［式（Ｉａ）中、Ｆ、Ｌ、Ｒ^１、Ｒ^２、Ｒ^３、ｎ及びｊはそれぞれ、式（Ｉ）又は（ＩＩ）中のＦ、Ｌ、Ｒ^１、Ｒ^２、Ｒ^３、ｎ及びｊと同義である。］

Wherein ^{(Ia), F, L,} R 1, R 2, R 3, respectively n and j, ^F in the formula (I) or ^{(II), L, R 1} , R 2, R 3, n And j. ]

Here, in the general formulas (Ia) and (II), R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, but preferably a monovalent organic group. . The monovalent organic group is preferably a monovalent organic group having 1 to 18 carbon atoms, and a monovalent hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom, or It is more desirable that it is a group represented by — (CH ₂ ) _a —O—R ⁴ , an alkyl group having 1 to 4 carbon atoms, or a group represented by — (CH ₂ ) _a —O—R ^4. More preferably, it is particularly preferably a methyl group. Further, from the viewpoint of solubility, film forming property, etc., as a combination of R ^{1 to} R ³ , R ¹ and R ² are hydrogen atoms, R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or , — (CH ₂ ) _a —O—R ⁴ is desirable. R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms and may form a ring, but is preferably an aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group. , A represents an integer of 1 to 12, and is preferably an integer of 1 to 4.

  In the general formulas (I) and (Ia), L represents a divalent organic group, but the divalent organic group may be an alkylene group having 1 to 18 carbon atoms that may be branched. Desirably, a methylene group is more desirable from the viewpoint of improving electrical characteristics.

  Moreover, as a preferable thing among the compounds represented by the said general formula (I), the said general formula (I) is mainly from a viewpoint of improving the electrical property and crosslinking density of the crosslinked film which harden | cure a coating agent composition. Examples thereof include compounds represented by the following general formula (Ib), wherein j is 1 and L is an alkylene group.

［式（Ｉｂ）中、Ｆ、Ｒ及びｎはそれぞれ、式（Ｉ）中のＦ、Ｒ及びｎと同義であり、Ｌ^１はアルキレン基を示す。］

[In Formula (Ib), F, R and n are the same as F, R and n in Formula (I), respectively, and L ¹ represents an alkylene group. ]

Here, from the viewpoint of further improving the electrical properties and crosslinking density of the crosslinked film obtained by curing the coating agent composition, L ¹ in the general formula (Ib) may have 1 to 18 carbon atoms which may be branched. An alkylene group is desirable, and a methylene group is more desirable from the viewpoint of improving electrical characteristics.

In the general formulas (I) and (Ib), R represents a monovalent organic group, preferably a monovalent organic group having 1 to 18 carbon atoms, which is substituted with a halogen atom. It is more preferably a monovalent hydrocarbon group having 1 to 18 carbon atoms or a group represented by — (CH ₂ ) _a —O—R ⁴ , an alkyl group having 1 to 4 carbon atoms, Alternatively, a group represented by — (CH ₂ ) _a —O—R ⁴ is more preferable, and a methyl group is particularly preferable. R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms and may form a ring, but is preferably an aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group. , A represents an integer of 1 to 12, and is preferably an integer of 1 to 4.

  Furthermore, from the viewpoint of achieving both improvement in the life of the coating agent composition and improvement in electrical characteristics and crosslinking density of the crosslinked film obtained by curing the coating agent composition, R in the general formula (Ib) is A group represented by the general formula (II) is also preferred.

In the general formulas (I), (Ia) and (Ib), when there are a plurality of R, R ¹ , R ² , R ³ , L, L ¹ or j, each may be the same or different. .

  Moreover, as a more preferable thing of the compound represented by the said general formula (I), the compound whose organic group F in general formula (I) is group shown by the following general formula (III) especially is mentioned.

［式（ＩＩＩ）中、Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４は各々独立に、置換もしくは未置換のアリール基を示し、Ａｒ^５は置換もしくは未置換のアリール基、又は、置換もしくは未置換のアリーレン基を示し、且つ、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４及びＡｒ^５のうち１乃至４個は、上記一般式（Ｉ）で表わされる化合物における下記一般式（ＩＶ）で示される部位と結合するための結合手を有し、ｋは０又は１を示す。］

[In formula (III), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted aryl group, or substituted or unsubstituted. ^{1 to 4 of} Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are represented by the following general formula (IV) in the compound represented by the above general formula (I) It has a bond for binding to the site, and k represents 0 or 1. ]

［式（ＩＶ）中、Ｒは１価の有機基を示し、Ｌは２価の有機基を示し、ｊは０又は１を示す。］

[In Formula (IV), R represents a monovalent organic group, L represents a divalent organic group, and j represents 0 or 1. ]

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

In the above formulas (1) to (7), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with them, or an unsubstituted phenyl group. Or an aralkyl group having 7 to 10 carbon atoms, wherein R ^{12 to} R ¹⁴ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, phenyl substituted with them A group or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, Ar represents a substituted or unsubstituted arylene group, and X represents a structure represented by the general formula (IV). , C and s each represent 0 or 1, and t represents an integer of 1 to 3.

  Moreover, as Ar in the aryl group represented by the above formula (7), an arylene group represented by the following formula (8) or (9) is preferable.

In the above formulas (8) and (9), R ¹⁵ and R ¹⁶ are each 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. Represents a phenyl group substituted or 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.

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

In the above formulas (10) to (17), R ¹⁷ and R ¹⁸ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents a phenyl group substituted by or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, W represents a divalent group, and q and r each represent 1 to 10 Represents an integer, and t represents an integer of 1 or more and 3 or less, respectively.

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

In addition, the specific structure of Ar ⁵ in the general formula (III) includes the structures exemplified as the specific structures of Ar ^{1 to} Ar ⁴ when k = 0, and the Ar ⁵ when k = 1. An arylene group in which one bond is added to the structure exemplified as the specific structure of ^{1 to} Ar ⁴ can be given.

  More specifically, as the compound represented by the general formula (I), the following compounds (I-1) to (I-5), the following compounds (Ia-1) to (Ia-41), and The following compounds (Ib-1) to (Ib-59) may be mentioned. In addition, the compound shown by the said general formula (I) is not limited at all by these. In the compounds shown in the following table, those having a bond but not having a substituent at the terminal indicate that the terminal is a methyl group, Me is a methyl group, Et is an ethyl group, and Pr is n-Propyl group is shown.

  These compounds represented by the general formula (I) may be used alone or in combination of two or more.

  The compound represented by the general formula (I) can be easily synthesized by, for example, a method in which a compound having a hydroxyalkyl group is reacted with an acid anhydride, an acid halide or the like and esterified. In that case, examples of the reagent to be used include acid anhydrides such as acetic anhydride, propionic anhydride and succinic anhydride, and acyl chloride compounds such as thionyl chloride and propionic acid chloride. These reagents may be used in an amount of 1 equivalent or more, preferably 2 equivalents or more based on the hydroxyalkyl group. In this case, it is desirable to use a basic substance such as trimethylamine, triethylamine, or pyridine as a catalyst, and these catalysts may be used in an amount of 1 equivalent or more, preferably 2 equivalents or more, based on the hydroxyalkyl group. Moreover, reaction is performed at the temperature in the range below 0 degreeC or more and the boiling point of a use solvent, for example.

  Moreover, although the said reaction may be performed under a non-solvent, you may carry out using a suitable solvent. Examples of the solvent used in the reaction include general solvents such as benzene, toluene and tetrahydrofuran, and a basic catalyst such as triethylamine and pyridine can also be used as the solvent. At that time, two or more solvents may be used in combination.

  When the compound represented by the general formula (I) is a compound represented by the general formula (Ib), the compound represented by the general formula (Ib) is represented by the following general formula (V). It is particularly preferred that the compound be

［式（Ｖ）中、Ｙ^１、Ｙ^２及びＹ^３は各々独立に、ハロゲン原子、炭素数１以上１０以下のアルキル基、炭素数１以上１０以下のアルコキシル基、置換もしくは未置換のアリール基、炭素数７以上１０以下のアラルキル基、置換もしくは未置換のスチリル基、置換もしくは未置換のブタジエン基、又は、置換もしくは未置換のヒドラゾン基を示し、Ｒ^５、Ｒ^６及びＲ^７は各々独立に、炭素数１以上１８以下の１価の有機基を示し、Ｌ^５、Ｌ^６及びＬ^７は各々独立に、アルキレン基を示し、ｐ１、ｐ２及びｐ３は各々独立に、０以上２以下の整数を示し、ｑ１、ｑ２及びｑ３は、０又は１を示し、且つ、（ｑ１＋ｑ２＋ｑ３）≧１の条件を満たす。］

[In Formula (V), Y ¹ , Y ² and Y ³ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group. Represents an aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted styryl group, a substituted or unsubstituted butadiene group, or a substituted or unsubstituted hydrazone group, and R ⁵ , R ⁶ and R ⁷ are each independently Represents a monovalent organic group having 1 to 18 carbon atoms, L ⁵ , L ⁶ and L ⁷ each independently represents an alkylene group, and p 1, p 2 and p 3 each independently represents 0 to 2 An integer, q1, q2, and q3 represent 0 or 1, and satisfy the condition of (q1 + q2 + q3) ≧ 1. ]

Here, in the general formula (V), R ⁵ , R ⁶ and R ⁷ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom, or — It is preferably a group represented by (CH ₂ ) _a —O—R ⁴ , and is an alkyl group having 1 to 4 carbon atoms or a group represented by — (CH ₂ ) _a —O—R ^4. Is more preferable, and a methyl group is particularly preferable. R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms and may form a ring, but is preferably an aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group. , A represents an integer of 1 to 12, and is preferably an integer of 1 to 4.

In the general formula (V), L ⁵ , L ⁶ and L ⁷ are each independently preferably an alkylene group having 1 to 18 carbon atoms which may be branched, and more preferably a methylene group. preferable.

Further, in the general formula (V), in Y ^1, Y ² and Y ³ are each independently, is an alkyl group having 1 to 10 carbon atoms and preferably, 1 to 4 alkyl group having a carbon number Is more preferable.

  Furthermore, in the general formula (V), q1, q2, and q3 preferably satisfy the condition of (q1 + q2 + q3) ≧ 2.

  The compound represented by the general formula (V) can be easily synthesized, for example, by a method in which a triphenylamine compound having a hydroxyalkyl group is reacted with a dialkyl sulfate or an alkyl iodide to etherify the hydroxyalkyl group. is there. In that case, as the reagent to be used, one arbitrarily selected from dimethyl sulfate, diethyl sulfate, methyl iodide, ethyl iodide and the like can be used, and it is 1 to 3 equivalents, preferably 1 with respect to the hydroxyalkyl group. Or 2 equivalents may be used. In addition, as a base catalyst, a catalyst arbitrarily selected from sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide, sodium hydride, sodium metal, etc. should be used. 1 to 3 equivalents, preferably 1 to 2 equivalents, may be used relative to the hydroxyalkyl group. The reaction can be carried out at a temperature in the range of 0 ° C. or higher and the boiling point of the solvent used.

  Examples of the solvent used in the reaction include benzene, toluene, methylene chloride, tetrahydrofuran, N, N′-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone. A single solvent selected from them or a mixed solvent of two or more kinds can be used. Depending on the reaction, a quaternary ammonium salt such as tetra-n-butylammonium iodide can be used as an interlayer transfer catalyst.

  In the coating agent composition of the present invention, the content of the compound represented by the general formula (I) is preferably 20% by mass or more and 80% by mass or less based on the total solid content of the coating agent composition, More preferably, it is 30 mass% or more and 70 mass% or less. When the content is less than 20% by mass, the electrical characteristics of the electrophotographic photosensitive member tend to be deteriorated, and when it exceeds 80% by mass, the wear resistance tends to decrease.

  The polyfunctional isocyanate compound contained in the coating agent composition of the present invention is not particularly limited as long as it can form a cured film by crosslinking with the compound represented by the general formula (I) during curing, Common isocyanate materials can be used. Specific examples include hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate, bis (isocyanate methyl) cyclohexane, trimethylhexamethylene diisocyanate, methylene dicyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, and the like, and And modified products of these monomer-type polyisocyanates (for example, biuret, isocyanurate, and trimethylolpropane adducts).

  Moreover, in order to raise the mechanical strength of the cured film obtained, it is preferable to use an isocyanate compound having 3 or more functional groups.

  Further, a blocked isocyanate compound of a type in which these monomer type polyisocyanate and modified isocyanate are blocked with a protecting group capable of regenerating isocyanate by heating can also be used.

  Protecting groups for isocyanates include alcohols, phenols and cresols that are phenols, lactams, amines, ε-caprolactams that are amides, methyl ethyl ketoxime and acetoxime that are oximes, and β-diketones. Examples include diethyl malonate and ethyl acetoacetate.

  In addition, since the compound represented by the general formula (I) is inhibited from reacting with an isocyanate compound in a coating solution at room temperature, the isocyanate compound has a viewpoint of electrical characteristics and wear resistance of the resulting cured film. It is preferable to use an isocyanate compound having a polyfunctional structure which does not have a protective group, which is advantageous.

  The isocyanate material mentioned above can be used individually by 1 type or in mixture of 2 or more types. In addition, when using 2 or more types of isocyanate compounds, it is preferable that at least 1 type uses the isocyanate compound which does not have a protective group.

  In the coating agent composition of the present invention, the content of the isocyanate compound is preferably 20% by mass or more and 80% by mass or less, and preferably 30% by mass or more and 70% by mass or less based on the total solid content of the coating agent composition. It is more preferable that When the content is less than 20% by mass, the wear resistance of the electrophotographic photosensitive member tends to be reduced, and when it exceeds 80% by mass, the electrical characteristics tend to deteriorate.

  Moreover, the coating agent composition of the present invention may contain conductive particles in order to lower the residual potential of the cured film. Examples of the conductive particles include metals, metal oxides, and carbon black. Among these, metals or metal oxides are more preferable. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, or those obtained by depositing these metals on the surface of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. It is done. These can be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion. From the viewpoint of transparency of the cured film, the average particle size of the conductive particles is preferably 0.3 μm or less, and particularly preferably 0.1 μm or less.

  In the coating agent composition of the present invention, the content of the conductive particles is not particularly limited, but may be 0.1% by mass or more and 30% by mass or less based on the total solid content of the coating agent composition. Preferably, it is 0.5 mass% or more and 20 mass% or less. If this content is less than 0.1% by mass, the effect of lowering the residual potential of the electrophotographic photosensitive member tends to be lost, and if it exceeds 30% by mass, the image quality characteristics tend to deteriorate.

  Furthermore, the coating agent composition of the present invention may contain various fine particles in order to control the contamination resistance adhesion, lubricity, hardness and the like of the cured film. The fine particles may be used alone or in combination of two or more. Examples of the fine particles include silicon-containing fine particles. Silicon-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. Colloidal silica used as silicon-containing fine particles is a dispersion in which particles having an average particle diameter of 1 nm or more and 100 nm or less, preferably 10 nm or more and 30 nm or less, are dispersed in acidic or alkaline water or an organic solvent such as alcohol, ketone or ester. Those selected from liquids and commercially available can be used.

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

  Silicone fine particles used as silicon-containing fine particles are spherical and have an average particle diameter of 1 nm to 500 nm, preferably 10 nm to 100 nm, selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. You can use what you have. 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. That is, it can improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and maintain good wear resistance and adherence to contaminants over a long period of time. it can.

  In the coating agent composition of the present invention, the content of the silicone fine particles is not particularly limited, but is preferably 0.1% by mass or more and 30% by mass or less based on the total solid content of the coating agent composition. More preferably, the content is 0.5% by mass or more and 10% by mass or less.

Other fine particles include fluorine fine particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, and vinylidene fluoride, and “The 8th Polymer Materials Forum Lecture Proceedings, p89”. Fine particles made of a resin obtained by copolymerizing the above fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , semiconductive metal oxides such as MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO can be given. For the same purpose, 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 coating solution, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  Moreover, the coating agent composition of this invention can further 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.

Antioxidants include hindered phenols, hindered amines, thioethers, or antioxidants having a phosphite partial structure, which can be substituted with a material that forms a crosslinked film, such as a substituent such as an alkoxysilyl group. It may be modified with These antioxidants are effective in improving the potential stability and image quality when the environment changes, and among them, hindered phenols and hindered amine antioxidants are preferable.

  Examples of hindered phenol-based antioxidants include “Sumilizer BHT-R”, “Sumilizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW”, “Sumizer BP-76”. ”,“ Sumilizer BP-101 ”,“ Sumilizer GA-80 ”,“ Sumilizer GM ”,“ Sumilizer GS ”(manufactured by Sumitomo Chemical Co., Ltd.),“ IRGANOX1010 ”,“ IRGANOX1035 ”,“ IRGANOX1076 ”,“ IRGANOX1098 ” “IRGANOX1135”, “IRGANOX1141”, “IRGANOX1222”, “IRGANOX1330”, “IRGANOX1425WL”, “ “RGANOX1520L”, “IRGANOX245”, “IRGANOX259”, “IRGANOX3114”, “IRGANOX3790”, “IRGANOX5057”, “IRGANOX565” (above, manufactured by Ciba Specialty Chemicals), “Adekastab AO-20”, “Adekastab AO-30” "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", "ADK STAB AO-330" (above, manufactured by Asahi Denka) Is mentioned. Examples of the hindered amine antioxidant include “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744” (manufactured by Sankyo Lifetech Co., Ltd.), “Tinuvin 144”, “Tinuvin” "622LD" (manufactured by Ciba Specialty Chemicals Co., Ltd.), "Mark LA57", "Mark LA67", "Mark LA62", "Mark LA68", "Mark LA63" (manufactured above by ADEKA), "Smilizer TPS" ( As mentioned above, Sumitomo Chemical Co., Ltd. Examples of the thioether-based antioxidant include “Smilizer TP-D” (manufactured by Sumitomo Chemical Co., Ltd.), and examples of the phosphite-based antioxidant include “Mark 2112”, “Mark PEP • 8 ”,“ Mark PEP · 24G ”,“ Mark PEP · 36 ”,“ Mark 329K ”,“ Mark HP · 10 ”(manufactured by ADEKA).

  In the coating agent composition of the present invention, the content of the antioxidant is not particularly limited, but is 0.1% by mass or more and 30% by mass or less based on the total solid content of the coating agent composition. Preferably, it is 0.1 mass% or more and 20 mass% or less. If this content is less than 0.1% by mass, the desired effect tends to be difficult to obtain, and if it exceeds 30% by mass, characteristic deterioration such as deterioration of electrical characteristics tends to occur.

  In addition, the coating agent composition of the present invention 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 An insulating resin such as a resin, an acrylic resin, a polyacrylamide resin, a polyvinyl pyridine resin, a cellulose resin, a urethane resin, an epoxy resin, casein, a polyvinyl alcohol resin, or a polyvinyl pyrrolidone resin may be contained. In this case, the insulating resin can be added at a desired ratio, thereby making it possible to improve the adhesion between the obtained cured film and other layers constituting the electrophotographic photosensitive member. In addition, coating film defects caused by heat shrinkage and repelling can be suppressed.

  The coating agent composition of the present invention can form a cured film by heating and curing. During the curing treatment, a catalyst is added to the coating agent composition. Catalysts include acid compounds such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, phosphoric acid, sulfonic acid, and trifluoroacetic acid; amine compounds such as diethylamine, triethylamine, and pentamethyldiethylenetriamine; dibutyltin diacetate, dibutyltin dilaurate, stannous octoate Organic tin compounds such as tetra-n-butyl titanate and tetraisopropyl titanate; iron salts, manganese salts, cobalt salts, zinc salts and zirconium salts of organic carboxylic acids.

  In addition, it is preferable to use a blocking catalyst such as a sulfonic acid compound or a phosphoric acid compound containing an amine compound as a blocking agent from the viewpoint of suppressing the reaction in the coating liquid state. Examples of the blocking catalyst include NACURE 2500, 5225, X49-110, 3525, 4167 (manufactured by King Industries).

  The amount of these curing catalysts used is not particularly limited, but is preferably 0.1 parts by mass or more and 20 parts by mass or less, based on a total of 100 parts by mass of the solid content contained in the coating agent composition, The amount is particularly preferably 10 parts by mass or less.

  In addition, the coating agent composition may contain, if necessary, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, propanol, butanol and methyl cellosolve and derivatives thereof; ketones such as acetone, methyl ethyl ketone and cyclohexanone; Various solvents can be used in addition to ethers such as tetrahydrofuran, diethyl ether and dioxane; esters such as ethyl acetate and butyl acetate. In order to apply a dip coating method generally used for production of an electrophotographic photosensitive member, an alcohol solvent, a ketone solvent, or a mixed solvent thereof is preferable. Moreover, the boiling point of the solvent used is preferably 50 ° C. or higher and 150 ° C. or lower, and these can be arbitrarily mixed and used.

  In addition, since an alcohol solvent, a ketone solvent, or those mixed solvents are preferable as a solvent, it is preferable that the charge transport material represented by the said general formula (I) is soluble in those solvents.

  The amount of the solvent can be set arbitrarily, but if it is too small, the constituent materials are likely to precipitate, so that the total amount of solids contained in the coating agent composition is 0.5 parts by mass or more and 30 parts by mass. The content is preferably 1 to 20 parts by mass and more preferably 1 part by mass or less.

  Examples of coating methods for forming a cured film using the coating composition include blade coating, wire bar coating, spray coating, dip coating, bead coating, air knife coating, and curtain coating. Conventional methods can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. In addition, when performing the multiple application | coating several times, a heat processing may be performed every time of application | coating, and after multiple application | coating may be carried out.

  The reaction temperature and reaction time for curing the coating agent composition of the present invention are not particularly limited, but the reaction temperature is preferably 60 ° C. or higher from the viewpoint of mechanical strength and chemical stability of the resulting cured film. Preferably it is 80 degreeC or more and 200 degrees C or less, Reaction time becomes like this. Preferably it is 10 minutes or more and 5 hours or less.

(Electrophotographic photoreceptor)
The electrophotographic photosensitive member of the present invention includes a conductive support and a photosensitive layer formed on the conductive support, and the photosensitive layer is disposed on the side farthest from the conductive support. It has an outermost surface layer formed by curing the coating agent composition of the present invention.

  The photosensitive layer provided in the electrophotographic photosensitive member of the present invention is a single layer type photosensitive layer containing a charge generation material and a charge transport material in the same layer, or a layer containing a charge generation material (charge generation layer). And a functional separation type photosensitive layer in which a layer containing a charge transport material (charge transport layer) is separately provided. In the case of the function-separated type photosensitive layer, any of the stacking order of the charge generation layer and the charge transport layer may be the upper layer. In the case of the function-separated photosensitive layer, higher functions can be realized because the functions can be separated such that each layer only has to satisfy each function.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photosensitive member of the present invention. As shown in FIG. 1, the electrophotographic photosensitive member 1 includes a conductive support 2 and a photosensitive layer 3. The photosensitive layer 3 has a structure in which an undercoat layer 4, a charge generation layer 5, and a charge transport layer 6 are laminated in this order on a conductive support 2. In the electrophotographic photoreceptor 1 shown in FIG. 1, the charge transport layer 6 is the outermost surface layer made of a cured product of the coating agent composition of the present invention, and the compound represented by the above general formula (I) and the above polyfunctional isocyanate compound And a layer containing a crosslinked polymer.

  2 to 5 are schematic sectional views showing other preferred embodiments of the electrophotographic photosensitive member of the present invention. The electrophotographic photosensitive member shown in FIGS. 2 to 3 includes the photosensitive layer 3 in which the functions are separated into the charge generation layer 5 and the charge transport layer 6 as in the electrophotographic photosensitive member shown in FIG. 4 to 5 show that the charge generation material and the charge transport material are contained in the same layer (single-layer type photosensitive layer 8).

  The electrophotographic photoreceptor 1 shown in FIG. 2 has a structure in which an undercoat layer 4, a charge generation layer 5, a charge transport layer 6 and a protective layer 7 are sequentially laminated on a conductive support 2. The electrophotographic photoreceptor 1 shown in FIG. 3 has a structure in which an undercoat layer 4, a charge transport layer 6, a charge generation layer 5, and a protective layer 7 are sequentially laminated on a conductive support 2. In the electrophotographic photoreceptor 1 shown in FIGS. 2 and 3, the protective layer 7 is the outermost surface layer made of a cured product of the coating agent composition of the present invention, and the compound represented by the above general formula (I) and the above polyfunctional It is a layer containing a crosslinked polymer with an isocyanate compound.

  The electrophotographic photoreceptor 1 shown in FIG. 4 has a structure in which an undercoat layer 4 and a single-layer type photosensitive layer 8 are sequentially laminated on a conductive support 2. In the electrophotographic photoreceptor 1 shown in FIG. 4, the single-layer type photosensitive layer 8 is the outermost surface layer made of a cured product of the coating agent composition of the present invention, and the compound represented by the above general formula (I) and the above-mentioned many It is a layer containing a cross-linked polymer with a functional isocyanate compound.

  The electrophotographic photoreceptor 1 shown in FIG. 5 has a structure in which an undercoat layer 4, a single-layer type photosensitive layer 8, and a protective layer 7 are sequentially laminated on a conductive support 2. In the electrophotographic photoreceptor 1 shown in FIG. 5, the protective layer 7 is the outermost surface layer made of a cured product of the coating agent composition of the present invention, and the compound represented by the above general formula (I) and the above polyfunctional isocyanate compound And a layer containing a crosslinked polymer.

  In the electrophotographic photosensitive member shown in FIGS. 1 to 5, the undercoat layer 4 is not necessarily provided.

  Hereinafter, each element will be described based on the electrophotographic photosensitive member 1 shown in FIG.

  Examples of the conductive support 2 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. Further, as the conductive support 2, paper, plastic film, belt or the like coated, vapor-deposited or laminated with a conductive polymer, a conductive compound such as indium oxide, or a metal or alloy such as aluminum, palladium, or gold can be used.

  The surface of the conductive support 2 is preferably roughened to a centerline average roughness Ra of 0.04 μm or more and 0.5 μm or less in order to prevent interference fringes generated when laser light is irradiated. If Ra on the surface of the conductive support 2 is less than 0.04 μm, the effect of preventing interference tends to be insufficient because it is close to a mirror surface. On the other hand, if Ra exceeds 0.5 μm, the image quality tends to be insufficient even if a film is formed. When non-interfering light is used as a light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to irregularities on the surface of the conductive support 2, which is suitable for longer life.

  Surface roughening methods include wet honing by suspending the abrasive in water and spraying it on the support, or centerless grinding and anodic oxidation in which the support is pressed against a rotating grindstone and continuously ground. Treatment etc. are preferred.

  As a roughening method, without roughening the surface of the conductive support 2, a conductive or semiconductive powder is dispersed in the resin, and a layer is formed on the surface of the support. A method of roughening with fine particles dispersed therein is also preferably used.

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

  The thickness of the anodized film is preferably 0.3 μm or more and 15 μm or less. If it is less than 0.3 μm, the barrier property against injection tends to be poor and the effect tends to be insufficient. On the other hand, when it exceeds 15 μm, there is a tendency that the residual potential increases due to repeated use.

  Further, the conductive support 2 may be subjected to treatment with an acidic aqueous solution or boehmite treatment. The treatment with an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid is carried out as follows. First, an acidic treatment liquid is prepared. 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% by mass to 11% by mass, chromic acid is in the range of 3% by mass to 5% by mass, and hydrofluoric acid is 0.00%. The concentration of these acids is preferably in the range of 13.5% by mass or more and 18% by mass or less. The treatment temperature is preferably 42 ° C. or more and 48 ° C. or less. However, by keeping the treatment temperature high, a thicker film can be formed faster. The film thickness is preferably from 0.3 μm to 15 μm. If it is less than 0.3 μm, the barrier property against injection tends to be poor and the effect tends to be insufficient. On the other hand, when it exceeds 15 μm, there is a tendency that the residual potential increases due to repeated use.

  The boehmite treatment can be performed by immersing in pure water at 90 ° C. or more and 100 ° C. or less for 5 minutes or more and 60 minutes or less, or by contacting with heated steam at 90 ° C. or more and 120 ° C. or less for 5 minutes or more and 60 minutes or less. . The film thickness is preferably 0.1 μm or more and 5 μm or less. 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.

  The undercoat layer 4 is formed on the conductive support 2. The undercoat layer 4 includes an organometallic compound and / or a binder resin.

  As organometallic compounds, zirconium chelate compounds, zirconium alkoxide compounds, organozirconium 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 because of low residual potential and good electrophotographic characteristics.

  As the binder resin, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol resin, Examples include known vinyl chloride-vinyl acetate copolymers, epoxy resins, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, polyacrylic acid, and the like. When these are used in combination of two or more, the mixing ratio can be appropriately set as necessary.

  The undercoat layer 4 includes vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β- A silane coupling agent such as 3,4-epoxycyclohexyltrimethoxysilane may be contained.

  In the undercoat layer 4, an electron transporting pigment can also be mixed / dispersed from the viewpoints of lowering the residual potential and environmental stability. 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, polycyclic quinone pigments, zinc oxide or titanium oxide are preferably used because of their high electron mobility.

  In addition, the surface of these pigments may be surface-treated with the above coupling agent or binder resin for the purpose of controlling dispersibility and charge transporting property.

  If the amount of the electron transporting pigment is too large, the strength of the undercoat layer 4 is reduced and causes coating film defects. Therefore, the amount is preferably 95% by mass or less, more preferably 90% by mass based on the total solid content of the undercoat layer 4. % Used.

  In addition, it is preferable to add various kinds of fine powders of organic compounds or fine powders of inorganic compounds to the undercoat layer 4 for the purpose of improving electrical characteristics and light scattering properties. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white, lithopone, and inorganic pigments such as alumina, calcium carbonate, barium sulfate, polytetrafluoroethylene resin particles, benzoguanamine resin particles, Styrene resin particles and the like are effective.

  The particle diameter of the added fine powder is preferably 0.01 μm or more and 2 μm or less. The fine powder is added as necessary, but the addition amount is preferably 10% by mass or more and 90% by mass or less, and 30% by mass or more and 80% by mass or less based on the total solid content of the undercoat layer 4. It is more preferable that

  The undercoat layer 4 is formed using an undercoat layer forming coating solution containing the above-described constituent materials. The organic solvent used in the coating solution for forming the undercoat layer is one that dissolves an organometallic compound or a binder resin and does not cause gelation or aggregation when an electron transporting pigment is mixed and / or dispersed. If it is.

  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. , Chloroform, chlorobenzene, toluene and the like. These can be used individually by 1 type or in mixture of 2 or more types.

  As a method for mixing and / or dispersing each constituent material, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, a vibrating ball mill, a colloid mill, a paint shaker, an ultrasonic wave, or the like is applied. Mixing and / or dispersion is performed in an organic solvent.

  As a coating method for forming the undercoat layer 4, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. be able to.

  The drying is usually performed at a temperature at which the solvent can be evaporated and a film can be formed. In particular, the conductive support 2 subjected to the acidic solution treatment and the boehmite treatment is preferably formed with the undercoat layer 4 because the defect concealing power of the substrate tends to be insufficient.

  The thickness of the undercoat layer 4 is preferably 0.01 μm or more and 30 μm or less, more preferably 0.05 μm or more and 30 μm or less, further preferably 0.1 μm or more and 30 μm or less, and particularly preferably 0.2 μm or more and 25 μm or less.

  The charge generation layer 5 includes a charge generation material and, if necessary, 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. A well-known thing can be used. As the charge generation material, metal and metal-free phthalocyanine pigments, trigonal selenium, dibromoanthanthrone and the like are particularly preferable when a light source having an exposure wavelength of 380 nm to 500 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 and titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 are particularly preferred.

  The binder resin can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane.

  The binder resin is preferably 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, Insulating resins such as acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, and polyvinyl pyrrolidone resin can be mentioned, but are not limited thereto. These binder resins can be used individually by 1 type or in mixture of 2 or more types.

  The charge generation layer 5 is formed by vapor deposition of a charge generation material, or using a charge generation layer forming coating solution containing a charge generation material and a binder resin. When the charge generation layer 5 is formed using a charge generation layer forming coating solution, the blending ratio (mass ratio) of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10.

  As a method for dispersing each of the constituent materials in the charge generation layer forming coating solution, a normal method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be used. At this time, a condition that the crystal form of the pigment is not changed by the dispersion is required. Further, at the time of 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.

  Solvents used for dispersion 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.

  When forming the charge generation layer 5 using the coating solution for forming the charge generation layer, the coating methods are blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating. Ordinary methods such as a method and a curtain coating method can be used.

  The film thickness of the charge generation layer 5 is preferably 0.1 μm or more and 5 μm or less, more preferably 0.2 μm or more and 2.0 μm or less.

  The charge transport layer 6 includes a charge transport material and a binder resin, or 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, but are not limited to, hole transporting compounds. These charge transport materials can be used singly or in combination of two or more.

  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 methyl group, and k10 represents an integer of 0 or more and 2 or less. Ar ⁶ and Ar ⁷ are each independently a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ³⁸ ) ═C (R ³⁹ ) (R ⁴⁰ ), or —C ₆ H ₄ —CH. ═CH—CH═C (Ar ′) ₂ 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 And a substituted amino group substituted with a group. R ³⁸ , R ³⁹ and R ⁴⁰ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar ′ represents a substituted or unsubstituted aryl group.

In the formula (a-2), R ³⁵ and R ³⁵ ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, R ³⁶ , R ³⁶ ′, R ³⁷ and R ³⁷ ′ are each independently substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. An amino group, 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 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar ′ represents a substituted or unsubstituted aryl group. M4 and m5 each independently represent an integer of 0 or more and 2 or less.

In the above 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—. CH = C (Ar ′) ₂ is shown. 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 1 to 2 carbon atoms. The amino group substituted by the following alkyl groups, or a substituted or unsubstituted aryl group is shown.

  Examples of the binder resin used for the charge transport layer 6 include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, and 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, and the like. These binder resins can be used individually by 1 type or in mixture of 2 or more types. The blending ratio (mass ratio) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, the polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable.

  Although the polymer charge transport material alone can be used as a constituent material of the charge transport layer 6, it may be mixed with the binder resin to form a film.

  The charge transport layer 6 is formed using a charge transport layer forming coating solution containing the above-described constituent materials.

  Examples of the solvent for 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 halogenated fats such as methylene chloride, chloroform and ethylene chloride. Examples thereof include ordinary organic solvents such as aromatic 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.

  As a coating method of the coating solution for forming the charge transport layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method should be used. Can do.

  The film thickness of the charge transport layer 6 is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 30 μm or less.

  In the electrophotographic photosensitive member of this embodiment, the protective layer 7 is the outermost surface layer disposed on the side farthest from the conductive support 2. The protective layer 7 is a layer obtained by curing the above-described coating agent composition of the present invention, and contains at least a polymer in which the compound represented by the general formula (I) and the polyfunctional isocyanate compound are crosslinked. It has the composition to do.

  When the protective layer 7 is formed, the coating composition of the present invention is applied onto the charge transport layer 6 by using a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air coating method. Usual methods such as a knife coating method and a curtain coating method can be used.

  In addition, the reaction temperature and reaction time for curing the coating agent composition applied on the charge transport layer 6 can be appropriately selected, but from the viewpoint of mechanical strength and chemical stability of the resulting cured film, The reaction temperature is preferably 60 ° C. or higher, more preferably 80 ° C. or higher and 200 ° C. or lower, and the reaction time is preferably 10 minutes or longer and 5 hours or shorter.

  The thickness of the protective layer 7 is preferably 0.5 μm to 15 μm, more preferably 1 μm to 10 μm, and particularly preferably 1 μm to 5 μm. In addition, when a required film thickness is not 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.

  In addition, each layer constituting the photosensitive layer 3 includes an antioxidant, a light stabilizer, and a heat stabilizer for the purpose of preventing deterioration of the photoreceptor due to ozone, an oxidizing gas, or light and heat generated in the image forming apparatus. Additives such as agents can be added.

  Examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine.

  Each layer constituting the photosensitive layer 3 may contain at least one electron accepting substance for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like.

Examples of the electron acceptor include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, Examples include chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, and phthalic acid. Of these, fluorenone-based, quinone-based, and benzene derivatives having an electron-withdrawing substituent such as Cl, CN, NO ₂ are particularly preferable.

  In the present embodiment, the outermost surface layer obtained by curing the coating agent composition of the present invention is the protective layer 7, but the electrophotographic photoreceptor may not have the protective layer 7, and The outermost surface layer obtained by curing the coating agent composition may be the charge transport layer 6 as in the electrophotographic photoreceptor shown in FIG. In this case, since the cured film of the coating agent composition of the present invention has excellent mechanical strength and sufficient charge transportability, the cured film can be used as it is as a charge transport layer. Alternatively, the charge transporting material, the binder resin, the polymer charge transporting material and the like exemplified in the description of the charge transport layer 6 are contained in the coating agent composition of the present invention to form a coating solution, and the coating solution is used to charge A transport layer may be formed.

  4 and 5, when the electrophotographic photosensitive member includes a single-layer type photosensitive layer 8, the single-layer type photosensitive layer 8 contains a charge generation material and, if necessary, a binder resin. It is formed. The charge generation material is the same as that used for the charge generation layer in the function separation type photosensitive layer, and the binder resin is a binder resin used for the charge generation layer and the charge transport layer in the function separation type photosensitive layer. Similar ones can be used. The content of the charge generating material in the single-layer type photosensitive layer 8 is preferably 10% by mass or more and 85% by mass or less, more preferably 20% by mass or more and 50% by mass based on the total solid content in the single-layer type photosensitive layer 8. It is as follows. In addition, a charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer 8 for the purpose of improving photoelectric characteristics. As the charge transport material, the same materials as those used for the charge transport layer in the function separation type photosensitive layer can be used. The addition amount of the charge transport material is preferably 5% by mass or more and 50% by mass or less based on the total solid content in the single-layer type photosensitive layer 8. 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 is preferably about 5 μm to 50 μm, and more preferably 10 μm to 40 μm.

  In the electrophotographic photoreceptor 1 shown in FIG. 4, the single-layer type photosensitive layer 8 is an outermost surface layer formed by curing the coating agent composition of the present invention. In this case, the single-layer type photosensitive layer 8 uses a coating solution in which a charge generation material, a charge transport material as necessary, and a binder resin as necessary are contained in the coating composition of the present invention. It is formed.

(Image forming apparatus and process cartridge)
FIG. 6 is a schematic diagram showing a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 100 shown in FIG. 6 includes a process cartridge 20 including an electrophotographic photosensitive member 1, an exposure device 30, a transfer device 40, and an intermediate transfer member 50 in an image forming apparatus main body (not shown). . In the image forming apparatus 100, the exposure device 30 is disposed at a position where the electrophotographic photosensitive member 1 can be exposed from the opening of the process cartridge 20, and the transfer device 40 is interposed between the electrophotographic photosensitive member via the intermediate transfer member 50. The intermediate transfer member 50 is disposed such that a part of the intermediate transfer member 50 can come into contact with the electrophotographic photosensitive member 1.

  The process cartridge 20 is obtained by integrating a charging device 21, a developing device 25, a cleaning device 27, and a fibrous member (toothbrush shape) 29 together with an electrophotographic photosensitive member 1 by a mounting rail in a case. The case is provided with an opening for exposure.

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

Hereinafter, the toner used for the developing device 25 will be described. The toner preferably has an average shape factor (ML ² / A) of 100 or more and 150 or less, and more preferably 100 or more and 140 or less. Further, the toner preferably has an average particle size of 2 μm or more and 12 μm or less, more preferably 3 μm or more and 12 μm or less, and further preferably 3 μm or more and 9 μm or less. By using a toner satisfying such an average shape factor and average particle diameter, a high-quality image having high developability and transferability can be obtained.

  The toner is not particularly limited by the production method as long as it satisfies the above average shape factor and average particle diameter. For example, the toner may be a binder resin, a colorant and a release agent, and charged as necessary. A kneading and pulverizing method in which a control agent is added to knead, pulverizing, and classifying; a method of changing the shape of particles obtained by the kneading and pulverizing method with mechanical impact force or thermal energy; a polymerizable monomer for a binder resin Emulsion polymerization and agglomeration, and a dispersion of the formed dispersion and a dispersion of a colorant, a release agent, and a charge control agent as necessary are agglomerated and heat-fused to obtain toner particles. A suspension polymerization method in which a polymerizable monomer for obtaining a binder resin, a colorant, a release agent, and a charge control agent, if necessary, are suspended in an aqueous solvent and polymerized; the binder resin And a solution such as a colorant, a release agent, and a charge control agent as necessary in an aqueous solvent. Nigosa was toners produced by dissolution suspension method in which granulated are employed.

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

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

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

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

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

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

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

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

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

  To the toner used in the developing device 25, inorganic fine particles, organic fine particles, composite fine particles obtained by attaching inorganic fine particles to the organic fine particles, and the like can be added for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photosensitive member. .

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

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

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

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

  Other inorganic oxides added to the toner are small-diameter inorganic oxides with a primary particle size of 40 nm or less for powder flowability, charge control, etc. It is preferable to add a larger-diameter inorganic oxide. These inorganic oxide 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 powder flowability. Furthermore, it is also preferable to add carbonates such as calcium carbonate and magnesium carbonate and inorganic minerals such as hydrotalcite in order to remove the discharge purified product.

  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 surface coated with resin coating are used. The mixing ratio with the carrier can be set as appropriate.

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

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

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

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

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

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

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

  As the intermediate transfer member 50, a belt-like member (intermediate transfer belt) made of polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber or the like having semiconductivity is used. Further, as the form of the intermediate transfer member 50, a drum-like member can be used in addition to the belt-like member.

  When using the electrophotographic photoreceptor of the present invention, paper dust, talc, etc. are generated from the print paper, which easily adheres to the electrophotographic photoreceptor, and the electrophotographic photoreceptor of the present invention is resistant. It is difficult to remove paper dust, talc and the like because of its high wear resistance. Therefore, it is preferable to use the intermediate transfer member 50 in order to prevent adhesion of paper dust and talc and obtain a stable image.

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

  FIG. 7 is a schematic view showing another embodiment of the image forming apparatus of the present invention. In the image forming apparatus 110 shown in FIG. 7, the electrophotographic photosensitive member 1 is fixed to the main body of the image forming apparatus, and the charging device 22, the developing device 25, and the cleaning device 27 are each formed into a cartridge. It is provided independently as a cleaning cartridge. Note that the charging device 22 includes a charging device for charging by a corona discharge method.

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

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

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

  FIG. 8 is a schematic diagram showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 120 is a tandem full-color image forming apparatus equipped with four process cartridges 20. In the image forming apparatus 120, four process cartridges 20 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member can be used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

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

  FIG. 9 is a schematic view showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 130 shown in FIG. 9 is a so-called four-cycle image forming apparatus that forms toner images of a plurality of colors with one electrophotographic photosensitive member. The image forming apparatus 130 includes a photosensitive drum 1 that is rotated by a driving device (not shown) at a predetermined rotational speed in the direction of arrow A in the figure, and above the photosensitive drum 1 is a photosensitive member. A charging device 22 for charging the outer peripheral surface of the drum 1 is provided.

  Further, an exposure device 30 having a surface emitting laser array as an exposure light source is disposed above the charging device 22. The exposure device 30 modulates a plurality of laser beams emitted from a light source in accordance with an image to be formed and deflects the laser beams in the main scanning direction so that the axis of the photosensitive drum 1 is on the outer peripheral surface of the photosensitive drum 1. Scan in parallel. Thereby, an electrostatic latent image is formed on the outer peripheral surface of the charged photosensitive drum 1.

  A developing device 25 is disposed on the side of the photosensitive drum 1. The developing device 25 includes a roller-shaped container that is rotatably arranged. Four containers are formed inside the container, and developing units 25Y, 25M, 25C, and 25K are provided in each container. The developing devices 25Y, 25M, 25C, and 25K each include a developing roller 26, and store Y, M, C, and K color toners therein.

  The full-color image is formed by the image forming apparatus 130 while the photosensitive drum 1 is rotated four times. That is, while the photosensitive drum 1 rotates four times, the charging device 22 charges the outer peripheral surface of the photosensitive drum 1, and the exposure device 20 includes Y, M, C, and K image data representing a color image to be formed. Scanning the outer peripheral surface of the photosensitive drum 1 with the laser beam modulated according to any one of the above is repeated while switching the image data used for modulation of the laser beam every time the photosensitive drum 1 rotates. Further, the developing device 25 operates the developing device corresponding to the outer peripheral surface in a state where any of the developing rollers 26 of the developing devices 25Y, 25M, 25C, and 25K corresponds to the outer peripheral surface of the photosensitive drum 1. The photosensitive drum 1 is the one that develops the electrostatic latent image formed on the outer peripheral surface of the photosensitive drum 1 to a specific color and forms a toner image of the specific color on the outer peripheral surface of the photosensitive drum 1. Each time it rotates, the process is repeated while rotating the container so that the developing unit used for developing the electrostatic latent image is switched. As a result, every time the photosensitive drum 1 rotates, the Y, M, C, and K toner images are sequentially formed on the outer peripheral surface of the photosensitive drum 1 so as to overlap each other. When the drum 1 rotates four times, a full-color toner image is formed on the outer peripheral surface of the photosensitive drum 1.

  An endless intermediate transfer belt 50 is disposed substantially below the photosensitive drum 1. The intermediate transfer belt 50 is wound around rollers 51, 53, and 55, and is disposed so that the outer peripheral surface is in contact with the outer peripheral surface of the photosensitive drum 1. The rollers 51, 53, and 55 are rotated by a driving force of a motor (not shown) and rotate the intermediate transfer belt 50 in the direction of arrow B in FIG.

  A transfer device (transfer device) 40 is disposed on the opposite side of the photosensitive drum 1 across the intermediate transfer belt 50, and the toner image formed on the outer peripheral surface of the photosensitive drum 1 is intermediate transferred by the transfer device 40. The image is transferred onto the image forming surface of the belt 50.

  A lubricant supply device 29 and a cleaning device 27 are disposed on the outer peripheral surface of the photosensitive drum 1 on the opposite side of the developing device 25 with the photosensitive drum 1 interposed therebetween. When the toner image formed on the outer peripheral surface of the photoconductive drum 12 is transferred to the intermediate transfer belt 50, the lubricant is supplied to the outer peripheral surface of the photoconductive drum 1 by the lubricant supply device 29. The area carrying the transferred toner image is cleaned by the cleaning device 27.

  A tray 60 is disposed below the intermediate transfer belt 50, and a large number of sheets P as recording materials are accommodated in the tray 60 in a stacked state. A take-out roller 61 is disposed obliquely above and to the left of the tray 60, and a roller pair 63 and a roller 65 are arranged in this order on the downstream side in the take-out direction of the paper P by the take-out roller 61. The uppermost recording sheet in the stacked state is taken out from the tray 60 by the take-out roller 61 rotating, and is conveyed by the roller pair 63 and the roller 65.

  A transfer device 42 is disposed on the opposite side of the roller 55 with the intermediate transfer belt 50 interposed therebetween. The paper P conveyed by the roller pair 63 and the roller 65 is sent between the intermediate transfer belt 50 and the transfer device 42, and the toner image formed on the image forming surface of the intermediate transfer belt 50 is transferred by the transfer device 42. . A fixing device 44 having a pair of fixing rollers is arranged on the downstream side of the transfer device 42 in the conveyance direction of the paper P. The paper P on which the toner image is transferred is transferred by the fixing device 44. After being fused and fixed, the sheet is discharged out of the image forming apparatus 130 and placed on a discharge tray (not shown).

  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.

[Preparation of Photoreceptor a]
100 parts by mass of zinc oxide (trade name: MZ-150, manufactured by Teika Co., Ltd., volume average particle size: 70 nm, specific surface area value: 15 m ² / g) is stirred and mixed with 500 parts by mass of tetrahydrofuran, and a silane coupling agent (trade name) : KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.3 parts by mass was added and stirred for 2 hours. Thereafter, tetrahydrofuran was distilled off under reduced pressure and baked at 120 ° C. for 3 hours to obtain a silane coupling agent surface-treated zinc oxide.

  110 parts by mass of the obtained surface-treated zinc oxide was stirred and mixed with 500 parts by mass of tetrahydrofuran, a solution in which 0.6 part by mass of alizarin was dissolved in 50 parts by mass of tetrahydrofuran was added, and the mixture was stirred at 50 ° C. for 5 hours. Then, the zinc oxide to which alizarin was imparted by filtration under reduced pressure was filtered off, and further dried at 60 ° C. under reduced pressure to obtain alizarin imparted zinc oxide.

  60 parts by mass of this alizarin-provided zinc oxide, 13.5 parts by mass of blocked isocyanate (trade name: Sumidur 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) as a curing agent, and butyral resin (trade name: ESREC BM-1, Sekisui) 15 parts by mass of Chemical) were mixed with 85 parts by mass of methyl ethyl ketone. 38 parts by mass of this mixed liquid and 25 parts by mass of methyl ethyl ketone were mixed, and dispersion was performed for 2 hours with a sand mill using 1 mmφ glass beads to obtain a dispersion. To the obtained dispersion, 0.005 parts by mass of dioctyltin dilaurate as a catalyst and 40 parts by mass of silicone resin particles (trade name: Tospearl 145, manufactured by GE Toshiba Silicone) are added, and a coating liquid for forming an undercoat layer is added. Obtained. This coating solution was applied on an aluminum substrate having a diameter of 30 mm, a length of 340 mm, and a wall thickness of 1 mm by a dip coating method, followed by drying and curing at 170 ° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

  Next, the Bragg angles (2θ ± 0.2 °) of the X-ray diffraction spectrum using the Cukα characteristic X-ray as the charge generation material are at least 7.3 °, 16.0 °, 24.9 °, 28.0. 15 parts by mass of hydroxygallium phthalocyanine having a diffraction peak at the position of °, 10 parts by mass of vinyl chloride / vinyl acetate copolymer resin (trade name: VMCH, manufactured by Nihon Unicar) as binder resin, 200 parts by mass of n-butyl acetate The mixture of parts was dispersed for 4 hours in a sand mill using glass beads having a diameter of 1 mmφ. To the obtained dispersion, 175 parts by mass of n-butyl acetate and 180 parts by mass of methyl ethyl ketone were added and stirred to obtain a coating solution for forming a charge generation layer. This coating solution was dip-coated on the undercoat layer and dried at room temperature to form a charge generation layer having a thickness of 0.2 μm.

  Next, 2.5 parts by mass of a benzidine compound represented by the following formula (VI-1) and 3 parts by mass of a polymer compound (viscosity average molecular weight 39,000) having a structural unit represented by the following formula (VI-2) Then, 20 parts by mass of chlorobenzene was mixed and dissolved to obtain a coating solution for forming a charge transport layer.

  This coating solution was applied onto the charge generation layer by dip coating, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 15 μm. In this way, the photoreceptor in which the undercoat layer, the charge generation layer, and the charge transport layer were formed on the aluminum base material was referred to as “photoreceptor a”.

[Preparation of Photoreceptor b]
First, a 84 mmφ cylindrical aluminum base material subjected to a honing treatment was prepared. Next, 100 parts by mass of a zirconium compound (trade name: Orgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by mass of a silane compound (trade name: A1100, manufactured by Nihon Unicar), 400 parts by mass of isopropanol, and 200 parts by mass of butanol Were mixed to obtain a coating solution for forming the undercoat layer. This coating solution was applied by dip coating on the aluminum base material and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.1 μm.

  Next, a charge generation layer was formed on the undercoat layer in the same manner as the photoreceptor a.

  Next, 2 parts by mass of a charge transport material represented by the following formula (VI-3), 3 parts by mass of a polymer compound (viscosity average molecular weight 50,000) having a structural unit represented by the above formula (VI-2), and Then, 20 parts by mass of chlorobenzene was mixed to obtain a coating solution for forming a charge transport layer.

  The obtained coating solution for forming a charge transport layer 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. In this way, the photoconductor in which the undercoat layer, the charge generation layer, and the charge transport layer were formed on the honing-treated aluminum base material was referred to as “photoconductor b”.

[Example 1]
10 parts by mass of the compound (Ia-7), 10 parts by mass of a burette-modified polyisocyanate compound represented by the following formula (VII-1), 1 part by mass of NACURE 2500 (trade name, manufactured by King Industries), 25 parts by mass of isopropanol And it was dissolved in 10 parts by mass of methyl ethyl ketone to prepare a coating agent composition as a coating solution for forming a protective layer. This coating agent composition was applied onto the photoreceptor a by a spray coating method and dried at 150 ° C. for 60 minutes to form a protective layer having a thickness of 3 μm. The obtained photoreceptor is referred to as “PR-1”.

  Further, when the coating composition was stored in a sealed state at room temperature (20 ° C.), no precipitation and viscosity increase occurred after two months, and no problem in producing a photoreceptor was generated.

[Example 2]
In the same manner as in Example 1 except that 1 part by mass of hindered phenol and hindered amine composite antioxidant (trade name: Sanol LS2626, manufactured by Sankyo Lifetech Co., Ltd.) was further added to the coating composition of Example 1. A coating agent composition as a coating solution for forming a protective layer was prepared, and a protective layer having a thickness of 3 μm was formed on the photoreceptor a in the same manner as in Example 1. The obtained photoreceptor is referred to as “PR-2”. Further, when the coating composition was stored in a sealed state at room temperature (20 ° C.), no precipitation and viscosity increase occurred after two months, and no problem in producing a photoreceptor was generated.

[Example 3]
A coating agent composition as a coating solution for forming a protective layer was prepared in the same manner as in Example 2 except that 10 parts by mass of the compound (Ia-7) was replaced with 10 parts by mass of the compound (Ia-29). Using this, a protective layer having a thickness of 3 μm was formed on the photoreceptor a in the same manner as in Example 1. The obtained photoreceptor is referred to as “PR-3”. Further, when the coating composition was stored in a sealed state at room temperature (20 ° C.), no precipitation and viscosity increase occurred after two months, and no problem in producing a photoreceptor was generated.

[Example 4]
A coating agent composition as a coating solution for forming a protective layer was prepared in the same manner as in Example 2 except that 10 parts by mass of the compound (Ia-7) was replaced with 10 parts by mass of the compound (Ia-31). Using this, a protective layer having a thickness of 3 μm was formed on the photoreceptor a in the same manner as in Example 1. The obtained photoreceptor is referred to as “PR-4”. Further, when the coating composition was stored in a sealed state at room temperature (20 ° C.), no precipitation and viscosity increase occurred after two months, and no problem in producing a photoreceptor was generated.

[Examples 5 to 8]
A protective layer having a thickness of 3 μm was formed on the photoconductor b in the same manner as in Examples 1 to 4, except that the photoconductor b was used instead of the photoconductor a. The obtained photoreceptors were designated as “PR-5”, “PR-6”, “PR-7”, and “PR-8”, respectively.

[Comparative Example 1]
In the coating agent composition of Example 2, protection was carried out in the same manner as in Example 2 except that 10 parts by mass of the following compound (VIII-1) was used instead of 10 parts by mass of the compound (Ia-7) as the charge transport material. A coating agent composition as a layer forming coating solution was prepared, and a protective layer having a thickness of 3 μm was formed on the photoreceptor a in the same manner as in Example 1. The obtained photoreceptor is referred to as “RPR-1”. Further, when the coating agent composition was stored in a sealed state at room temperature (20 ° C.), precipitation occurred in 5 days, making it impossible to produce a photoreceptor.

[Comparative Example 2]
The same as Comparative Example 1 except that 10 mass parts of the burette-modified polyisocyanate compound represented by the above formula (VII-1) was replaced with 10 mass parts of a block type polyisocyanate (trade name: Sumidur BL3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.). Then, a coating agent composition as a coating solution for forming a protective layer was prepared, and a protective layer having a thickness of 3 μm was formed on the photoconductor a in the same manner as in Example 1. The obtained photoreceptor is referred to as “RPR-2”. Further, when the coating composition was stored in a sealed state at room temperature (20 ° C.), no precipitation and viscosity increase occurred after two months, and no problem in producing a photoreceptor was generated.

[Comparative Example 3]
10 masses of a burette-modified polyisocyanate compound represented by the above formula (VII-1) was added to a resol type phenol resin (trade name: Phenolite J-325, manufactured by Dainippon Ink & Chemicals, Inc., solid content: 70 mass%). A coating agent composition as a coating solution for forming a protective layer was prepared in the same manner as in Comparative Example 1 except that the amount was changed to parts by mass, and this was used to form a coating having a thickness of 3 μm on the photoreceptor a in the same manner as in Example 1. A protective layer was formed. The obtained photoreceptor is referred to as “RPR-3”. Further, when the coating composition was stored in a sealed state at room temperature (20 ° C.), no precipitation and viscosity increase occurred after two months, and no problem in producing a photoreceptor was generated.
[Comparative Examples 4 to 5]
A protective layer having a thickness of 3 μm was formed on the photoreceptor b in the same manner as in Comparative Examples 1 and 2, except that the photoreceptor b was used instead of the photoreceptor a. The obtained photoreceptors were designated as “RPR-4” and “RPR-5”, respectively.

[Preparation of Photoreceptor c]
First, a 30 mmφ cylindrical aluminum substrate was prepared. This aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was set to Rz = 0.6 μm. In order to clean the aluminum substrate subjected to the centerless polishing treatment, a degreasing treatment, an etching treatment with a 2% by mass sodium hydroxide solution for 1 minute, a neutralization treatment and a pure water washing were performed in this order. Next, an anodic oxide film (current density 1.0 A / dm ² ) was formed on the surface of the aluminum base material with a 10% by mass sulfuric acid solution. After washing with water, sealing treatment was performed by dipping in a 1 mass% nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this way, an aluminum substrate having a 7 μm anodic oxide film formed on the surface was obtained.

  Next, 1 mass of chlorogallium phthalocyanine having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum of 7.4 °, 16.6 °, 25.5 ° and 28.3 °. Part, polyvinyl butyral (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by mass of n-butyl acetate are mixed and treated with a glass shaker for 1 hour to disperse to generate charges. A layer forming coating solution was obtained. This coating solution was dip-coated on the aluminum base material after the formation of the anodic oxide film, 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 above formula (VI-1) and 3 parts by mass of a polymer compound having a structural unit represented by the above formula (VI-2) (viscosity average molecular weight 39,000) Then, 20 parts by mass of chlorobenzene was mixed and dissolved to obtain a coating solution for forming a charge transport layer. This coating solution was applied on 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. In this way, the photoreceptor in which the charge generation layer and the charge transport layer were formed on the aluminum base material on which the anodized film was formed was designated as “photoreceptor c”.

[Production of Photosensitive Member d]
First, a 84 mmφ cylindrical aluminum base material subjected to a honing treatment was prepared. Next, 100 parts by mass of a zirconium compound (trade name: Orgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by mass of a silane compound (trade name: A1100, manufactured by Nihon Unicar), 400 parts by mass of isopropanol, and 200 parts by mass of butanol Were mixed to obtain a coating solution for forming the undercoat layer. This coating solution was applied by dip coating on the aluminum base material and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.1 μm.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 1 part by mass of hydroxygallium phthalocyanine having a strong diffraction peak at 28.3 °, 1 part by mass of polyvinyl butyral (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.), and 100 parts by mass of n-butyl acetate are further mixed. The glass beads were dispersed for 1 hour in a paint shaker to obtain a coating solution for forming a charge generation layer. This coating solution was dip-coated on the undercoat layer 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 parts by mass of the charge transport material represented by the above formula (VI-3), 3 parts by mass of a polymer compound having a structural unit represented by the above formula (VI-2) (viscosity average molecular weight 50,000), and Then, 20 parts by mass of chlorobenzene was mixed to obtain a coating solution for forming a charge transport layer. The obtained charge transport layer forming 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. In this way, the photoreceptor in which the undercoat layer, the charge generation layer, and the charge transport layer were formed on the honing-treated aluminum substrate was designated as “photoreceptor d”.

[Example 9]
10 parts by mass of the compound (Ib-10), 10 parts by mass of a burette-modified polyisocyanate compound represented by the formula (VII-1), 1 part by mass of NACURE 2500 (trade name, manufactured by Enomoto Kasei Co., Ltd.), 25 parts by mass of isopropanol And it was dissolved in 10 parts by mass of methyl ethyl ketone to prepare a coating agent composition as a coating solution for forming a protective layer. This coating agent composition was applied onto the photoreceptor c by spray coating and dried at 150 ° C. for 60 minutes to form a protective layer having a thickness of 3 μm. The obtained photoreceptor is referred to as “PR-9”. In addition, when the coating composition was stored tightly at room temperature (20 ° C.), after two months, a slight increase in viscosity that did not occur after one month had occurred, but precipitation did not occur and the photosensitive member was produced. Did not cause any problems.

[Example 10]
In the same manner as in Example 1 except that 1 part by mass of hindered phenol and hindered amine composite antioxidant (trade name: Sanol LS2626, manufactured by Sankyo Lifetech Co., Ltd.) was further added to the coating agent composition of Example 9. A coating agent composition as a coating solution for forming a protective layer was prepared, and a protective layer having a thickness of 3 μm was formed on the photoreceptor c in the same manner as in Example 9 using this coating agent composition. The obtained photoreceptor is referred to as “PR-10”. In addition, when the coating composition was stored tightly at room temperature (20 ° C.), after two months, a slight increase in viscosity that did not occur after one month had occurred, but precipitation did not occur and the photosensitive member was produced. Did not cause any problems.

[Example 11]
A coating agent composition as a coating solution for forming a protective layer was prepared in the same manner as in Example 10 except that 10 parts by mass of the compound (Ib-10) was replaced by 10 parts by mass of the compound (Ib-13). Using this, a protective layer having a thickness of 3 μm was formed on the photoreceptor c in the same manner as in Example 9. The obtained photoreceptor is referred to as “PR-11”. In addition, when the coating composition was stored tightly at room temperature (20 ° C.), after two months, a slight increase in viscosity that did not occur after one month had occurred, but precipitation did not occur and the photosensitive member was produced. Did not cause any problems.

[Example 12]
A coating agent composition as a coating solution for forming a protective layer was prepared in the same manner as in Example 10 except that 10 parts by mass of the compound (Ib-10) was replaced with 10 parts by mass of the compound (Ib-12). Using this, a protective layer having a thickness of 3 μm was formed on the photoreceptor c in the same manner as in Example 9. The obtained photoreceptor is referred to as “PR-12”. In addition, when the coating composition was stored tightly at room temperature (20 ° C.), after two months, a slight increase in viscosity that did not occur after one month had occurred, but precipitation did not occur and the photosensitive member was produced. Did not cause any problems.

[Examples 13 to 16]
A protective layer having a thickness of 3 μm was formed on the photoreceptor d in the same manner as in Examples 9 to 12 except that the photoreceptor d was used instead of the photoreceptor c. The obtained photoreceptors were designated as “PR-13”, “PR-14”, “PR-15”, and “PR-16”, respectively.

[Comparative Example 6]
In the coating agent composition of Example 10, protection was carried out in the same manner as in Example 10 except that 10 parts by mass of the compound (VIII-1) was used instead of 10 parts by mass of the compound (Ib-10) as the charge transport material. A coating agent composition as a layer-forming coating solution was prepared, and a protective layer having a thickness of 3 μm was formed on the photoreceptor c in the same manner as in Example 9 using the coating agent composition. The obtained photoreceptor is referred to as “RPR-6”. Further, when the coating agent composition was stored in a sealed state at room temperature (20 ° C.), precipitation occurred in 5 days, making it impossible to produce a photoreceptor.

[Comparative Example 7]
The same as Comparative Example 5 except that 10 mass parts of the burette-modified polyisocyanate compound represented by the above formula (VII-1) was replaced with 10 mass parts of block-type polyisocyanate (trade name: Sumidur BL3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.). Then, a coating agent composition as a coating solution for forming a protective layer was prepared, and a protective layer having a thickness of 3 μm was formed on the photoreceptor c in the same manner as in Example 9 using the coating composition. The obtained photoreceptor is referred to as “RPR-7”. In addition, when the coating composition was stored tightly at room temperature (20 ° C.), after two months, a slight increase in viscosity that did not occur after one month had occurred, but precipitation did not occur and the photosensitive member was produced. Did not cause any problems.

[Comparative Example 8]
10 masses of the burette-modified polyisocyanate compound represented by the above formula (VII-1) is added to 7 mass parts of a resol type phenol resin (Phenolite J-325, manufactured by Dainippon Ink & Chemicals, Inc., solid content 70 mass%). A coating agent composition as a coating solution for forming a protective layer was prepared in the same manner as in Comparative Example 5 except that the protective layer was replaced. Using this, a protective layer having a thickness of 3 μm was formed on the photoreceptor c in the same manner as in Example 9. Formed. The obtained photoreceptor is referred to as “RPR-8”. In addition, when the coating composition was stored in a sealed state at room temperature (20 ° C.), after two months, a slight increase in viscosity that did not occur after one month had occurred. The above problem did not occur.
[Comparative Examples 9 to 10]
A protective layer having a thickness of 3 μm was formed on the photoreceptor d in the same manner as in Comparative Examples 6 to 7 except that the photoreceptor d was used instead of the photoreceptor c. The obtained photoreceptors were designated as “RPR-9” and “RPR-10”, respectively.

[Production of developer]
The developer was produced by first producing a toner and a carrier. In the following description regarding the developer, each physical property value was measured by the following method. That is, the particle size distribution of the toner and composite particles was measured using a multisizer (manufactured by Nikka Kisha Co., Ltd.) with an aperture diameter of 100 μm. Further, the average shape factor ML ² / A of the toner and the composite particles is expressed by the following formula:
ML ² / A = (maximum length) ² × π × 100 / (area × 4)
In the case of a true sphere, ML ² / A = 100. The average shape factor is determined by taking a toner image from an optical microscope into an image analyzer (trade name: LUZEX (III), manufactured by Nireco), measuring the equivalent circle diameter, and calculating the maximum length and area for each particle. The ML ² / A value of the above formula was determined, and the average of 1000 particles was defined as the average shape factor ML ² / A.

<Developer 1>
(Manufacture of toner)
In producing the toner, first, a resin fine particle dispersion, a colorant dispersion, and a release agent dispersion were produced, and toner base particles were produced using them. Next, a toner was manufactured using the toner base particles.

(Resin fine particle dispersion)
370 parts by mass of styrene, 30 parts by mass of n-butyl acrylate, 8 parts by mass of acrylic acid, 24 parts by mass of dodecanethiol, and 4 parts by mass of carbon tetrabromide were mixed and dissolved. The solution was mixed with 6 parts by weight of a nonionic surfactant (trade name: Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.), an anionic surfactant (trade name: Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10 50 parts by mass of ion-exchanged water in which 4 parts by mass of ammonium persulfate was dissolved was added to the flask in which the mass part and 550 parts by mass of ion-exchanged water were mixed and emulsion polymerized, and slowly mixed for 10 minutes. After carrying out nitrogen substitution, the inside of the flask was stirred with an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin fine particle dispersion in which resin particles having an average particle size of 150 nm, a Tg of 58 ° C., and a mass average molecular weight (Mw) of 11500 is obtained. The solid content concentration of this dispersion was 40% by mass.

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

(Colorant dispersion (2))
60 parts by mass of Cyan pigment (B15: 3), 5 parts by mass of a nonionic surfactant (trade name: Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.), and 240 parts by mass of ion-exchanged water were mixed. The solution was stirred for 10 minutes using a homogenizer (trade name: Ultra Tarrax T50, manufactured by IKA), and then dispersed with an optimizer. Then, a colorant dispersion liquid (2) in which colorant (Cyan pigment) particles having an average particle diameter of 250 nm were dispersed was obtained.

(Colorant dispersion (3))
60 parts by mass of Magenta pigment (R122), 5 parts by mass of a nonionic surfactant (trade name: Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.), and 240 parts by mass of ion-exchanged water were mixed. The solution was stirred for 10 minutes using a homogenizer (trade name: Ultra Tarrax T50, manufactured by IKA), and then dispersed with an optimizer to give colorant (Magenta pigment) particles having an average particle size of 250 nm. A colorant dispersion (3) in which was dispersed was obtained.

(Colored dispersion (4))
90 parts by weight of a yellow pigment (Y180), 5 parts by weight of a nonionic surfactant (trade name: Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.), and 240 parts by weight of ion-exchanged water were mixed. The solution was stirred for 10 minutes using a homogenizer (trade name: Ultra Tarrax T50, manufactured by IKA), and then dispersed with an optimizer. And the colorant dispersion liquid (4) in which the colorant (Yellow pigment) particle | grains whose average particle diameter is 250 nm was disperse | distributed was obtained.

(Release agent dispersion)
100 parts by weight of paraffin wax (trade name: HNP0190, manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.), 5 parts by weight of a cationic surfactant (trade name: Sanizol B50, manufactured by Kao Corporation), and 240 parts by weight of ion-exchanged water Mixed. The solution was dispersed for 10 minutes in a round stainless steel flask using a homogenizer (trade name: Ultra Turrax T50, manufactured by IKA), and then dispersed with a pressure discharge type homogenizer. And the mold release agent dispersion liquid in which the mold release agent particle whose average particle diameter is 550 nm was disperse | distributed was obtained.

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

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

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

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

  Each of the toner base particles K1, C1, M1, Y1 is 100 parts by mass, rutile-type titanium oxide (particle diameter 20 nm, n-decyltrimethoxysilane treatment) 1 part by mass, silica (particle diameter 40 nm, silicone oil treatment, 2.0 parts by mass of gas phase oxidation method), 1 part by mass of cerium oxide (average particle size 0.7 μm), higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700), zinc stearate, and calcium carbonate ( And an average particle size of 0.1 μm) is mixed at a mass ratio of 5: 1: 1 and pulverized by a jet mill to obtain an average particle size of 8.0 μm. Was blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain toner 1.

(Career)
Ferrite particles (average particle size: 50 μm) 100 parts by mass, toluene 14 parts by mass, styrene / methacrylate copolymer (component ratio: 90/10) 2 parts by mass, carbon black (trade name: R330, manufactured by Cabot Corporation) Two parts by mass were prepared. First, the above components excluding ferrite particles were mixed and stirred with a stirrer for 10 minutes to prepare a dispersed coating solution. Next, this coating solution and ferrite particles were put in a vacuum degassing type kneader and stirred at 60 ° C. for 30 minutes. Thereafter, the carrier was obtained by depressurizing and degassing while further heating and drying. This carrier had a volume resistivity of 10 ¹¹ Ωcm when an applied electric field of 1000 V / cm.

  Further, 100 parts by weight of the carrier and 5 parts by weight of the toner 1 were mixed, further stirred with a V-blender at 40 rpm × 20 minutes, and sieved with a sieve having an opening of 212 μm to obtain developer 1.

<Developer 2>
(Toner mother particle K2)
234 parts by mass of resin fine particle dispersion, 30 parts by mass of colorant dispersion (1), 40 parts by mass of release agent dispersion, 0.5 parts by mass of polyaluminum hydroxide (trade name: Paho2S, manufactured by Asada Chemical Co., Ltd.) 600 parts by mass of ion-exchanged water was mixed. This solution was mixed and dispersed in a round stainless steel flask using a homogenizer (trade name: Ultra Turrax T50, manufactured by IKA). Then, it heated to 40 degreeC, stirring the inside of a flask in the oil bath for heating. After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were formed. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and D50 was 5.3 μm. Thereafter, 26 parts by mass of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. After adding 1N sodium hydroxide to the dispersion containing the aggregate particles and adjusting the pH of the system to 5.0, the stainless steel flask is sealed, and stirring is continued using a magnetic seal up to 95 ° C. Heated and held for 4 hours. After cooling, the toner base particles were filtered off, washed four times with ion exchange water, and then freeze-dried to obtain toner base particles K2. The toner base particle K2 has a D50 of 5.8 μm and an average shape factor ML ² / A of 109.

(Toner mother particle C2)
Toner base particles C2 were obtained in the same manner as toner base particles K2, except that the colored particle dispersion (2) was used instead of the colored particle dispersion (1). The toner base particles C2 had a D50 of 5.7 μm and an average shape factor ML ² / A of 110.

(Toner mother particle M2)
Toner mother particles M2 were obtained in the same manner as toner mother particles K2, except that colored particle dispersion (3) was used instead of colored particle dispersion (1). The toner mother particles M2 had a D50 of 5.6 μm and an average shape factor ML ² / A of 114.

(Toner mother particle Y2)
Toner base particles Y2 were obtained in the same manner as toner base particles K2, except that the colored particle dispersion liquid (4) was used instead of the colored particle dispersion liquid (1). The toner base particle Y2 has a D50 of 5.8 μm and an average shape factor ML ² / A of 108.

  K2, C2, M2, and Y2 are used as toner base particles, aluminum oxide (average particle size 0.1 μm) is used instead of cerium oxide (average particle size 0.7 μm), and magnesium carbonate (average particle size is used instead of calcium carbonate). A toner 2 was obtained in the same manner as the toner 1 except that 0.1 μm) was used, and a developer 2 was obtained in the same manner as the developer 1 using the toner 2.

<Developer 3>
(Toner mother particles K3)
100 parts by mass of polyester resin (terephthalic acid-bisphenol A ethylene oxide adduct-linear polyester obtained from cyclohexanedimethanol, Tg 62 ° C., Mn 12000, Mw 32000), 4 parts by mass of carbon black, and 5 parts by mass of carnauba wax are mixed. The mixture was kneaded with an extruder and pulverized with a jet mill. Thereafter, the toner was classified by a wind classifier to obtain toner base particles K3 having an average particle diameter of 5.9 μm and a shape factor (ML ² / A) of 145.

(Toner mother particle C3)
The average particle size is 5.6 μm and the shape factor (ML ² / A) is 141 in the same manner as the toner base particles K3 except that a cyan colorant (CI Pigment Blue 15: 3) is used instead of carbon black. Toner base particles C3 were obtained.

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

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

  A toner 3 was obtained in the same manner as the toner 1 except that K3, C3, M3, and Y3 were used as toner base particles, and a developer 3 was obtained in the same manner as the developer 1 using the toner 3.

[Examples 17 to 28 and Comparative Examples 11 to 19]
Table 24 shows photoreceptors PR-1 to PR-4 obtained in Examples 1 to 4, photoreceptors RPR-1 to RPR-3 obtained in Comparative Examples 1 to 3, and developers 1 to 3. As shown, the image forming apparatuses of Examples 17 to 28 and Comparative Examples 11 to 19 were manufactured by being combined and mounted on a printer (DocuCenter Color 400CP, manufactured by Fuji Xerox Co., Ltd.).

[Image formation test]
An image formation test was performed using the image forming apparatuses of Examples 17 to 20 and Comparative Examples 9 to 10. That is, first, an image forming test for 10,000 sheets is performed in an environment of low temperature and low humidity (10 ° C., 20% RH), and then, 10,000 sheets in an environment of high temperature and high humidity (28 ° C., 75% RH). An image formation test was conducted. Thereafter, the wear rate and image quality of the photoreceptor were evaluated.

  Regarding the wear rate, the amount of wear of the photoconductor after printing 20,000 sheets was measured and calculated as the wear rate per 1000 sheets of image formation. Regarding the image quality, the print image quality after 20,000 prints was visually observed, and A: Good, B: Slightly decreased image density, C1: Remarkably low image density, C2: Generation of streak-like defects Judgment was made and evaluated.

The photoreceptor after the image formation test was charged to −700 V at normal temperature and normal humidity (20 ° C., 50% RH), exposed to 4.9 mJ / m ² flash at 780 nm, and then surface potential (VL) after 50 msec. Was monitored. The results are shown in Table 24.

[Examples 29 to 40 and Comparative Examples 20 to 28]
Table 25 shows photoreceptors PR-5 to PR-8 obtained in Examples 5 to 8, photoreceptors RPR-3 to RPR-5 obtained in Comparative Examples 3 to 5, and developers 1 to 3. As shown, the exposure apparatus is mounted on a printer (DocuCenter Color 500, manufactured by Fuji Xerox Co., Ltd.) modified to a multi-beam surface emitting laser with an oscillation wavelength of 780 nm, and image formation of Examples 29 to 40 and Comparative Examples 20 to 28 is performed. A device was made.

[Image formation test]
Using the image forming apparatuses of Examples 29 to 40 and Comparative Examples 20 to 28, image forming tests were performed in the same manner as described above. That is, first, an image forming test for 10,000 sheets is performed in an environment of low temperature and low humidity (10 ° C., 20% RH), and then, 10,000 sheets in an environment of high temperature and high humidity (28 ° C., 75% RH). An image formation test was conducted. Thereafter, the wear rate, image quality and VL of the photoreceptor were evaluated in the same manner as described above. The results are shown in Table 25.

  As is apparent from the results shown in Table 24 and Table 25 above, it was confirmed that the coating agent composition of the present invention and the electrophotographic photosensitive member using the composition were excellent in manufacturability, and could realize high image quality and long life. It was. In addition, the image forming apparatus and the process cartridge of the present invention using such an electrophotographic photosensitive member can realize high image quality and long life without causing image quality defects even during long-term use.

[Examples 41 to 52 and Comparative Examples 29 to 37]
Table 26 shows photoreceptors PR-9 to PR-12 obtained in Examples 9 to 12, photoreceptors RPR-6 to RPR-8 obtained in Comparative Examples 6 to 8, and developers 1 to 3. As shown, the image forming apparatuses of Examples 25 to 36 and Comparative Examples 29 to 37 were manufactured by combining and mounting on a printer (DocuCenter Color 400CP, manufactured by Fuji Xerox Co., Ltd.).

[Image formation test]
Using the image forming apparatuses of Examples 41 to 52 and Comparative Examples 29 to 37, image forming tests were performed in the same manner as described above. That is, first, an image forming test for 10,000 sheets is performed in an environment of low temperature and low humidity (10 ° C., 20% RH), and then, 10,000 sheets in an environment of high temperature and high humidity (28 ° C., 75% RH). An image formation test was conducted. Thereafter, the wear rate, image quality and VL of the photoreceptor were evaluated in the same manner as described above. The results are shown in Table 26.

[Examples 53 to 64 and Comparative Examples 38 to 46]
Table 27 shows photoreceptors PR-13 to PR-16 obtained in Examples 13 to 16, photoreceptors RPR-8 to RPR-10 obtained in Comparative Examples 8 to 10, and developers 1 to 3. In combination, as shown, the exposure apparatus is mounted on a printer (DocuCenter Color 500, manufactured by Fuji Xerox Co., Ltd.) modified to a multi-beam surface emitting laser with an oscillation wavelength of 780 nm, and image formation of Examples 53 to 64 and Comparative Examples 38 to 46 is performed. A device was made.

[Image formation test]
Using the image forming apparatuses of Examples 53 to 64 and Comparative Examples 38 to 46, image forming tests were performed in the same manner as described above. That is, first, an image forming test for 10,000 sheets is performed in an environment of low temperature and low humidity (10 ° C., 20% RH), and then, 10,000 sheets in an environment of high temperature and high humidity (28 ° C., 75% RH). An image formation test was conducted. Thereafter, the wear rate, image quality and VL of the photoreceptor were evaluated in the same manner as described above. The results are shown in Table 27.

  As is apparent from the results shown in Table 26 and Table 27 above, it was confirmed that the coating agent composition of the present invention and the electrophotographic photosensitive member using the composition are excellent in manufacturability, and can realize high image quality and long life. It was. In addition, the image forming apparatus and the process cartridge of the present invention using such an electrophotographic photosensitive member can realize high image quality and long life without causing image quality defects even during long-term use.

1 is a schematic cross-sectional view showing a preferred embodiment of an electrophotographic photoreceptor of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. 1 is a schematic diagram showing a preferred embodiment of an image forming apparatus of the present invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention.

Explanation of symbols

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

Claims (10)

A coating agent composition used as a constituent material of an electrophotographic photoreceptor,
A coating agent composition comprising: a compound represented by the following general formula (I); and a polyfunctional isocyanate compound that can be crosslinked with the compound to form a cured film.

[In Formula (I), F represents an organic group derived from a compound having a hole transporting property, R represents a monovalent organic group, L represents a divalent organic group, and n represents 1 or more and 4 The following integer is shown, j shows 0 or 1. ] 2. The coating agent composition according to claim 1, wherein in the general formula (I), the R is a group represented by the following general formula (II).

[In formula (II), R ¹ , R ² and R ³ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group. ]   The coating agent composition according to claim 1 or 2, wherein in the general formula (I), j is 1 and L is an alkylene group.   The coating agent composition according to claim 3, wherein in the general formula (I), the L is a methylene group. The coating agent composition according to any one of claims 1 to 4, wherein in the general formula (I), the F is a group represented by the following general formula (III).

[In formula (III), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted aryl group, or substituted or unsubstituted. ^{1 to 4 of} Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are represented by the following general formula (IV) in the compound represented by the above general formula (I) It has a bond for binding to the site, and k represents 0 or 1. ]

[In Formula (IV), R represents a monovalent organic group, L represents a divalent organic group, and j represents 0 or 1. ] The coating agent composition according to any one of claims 1 to 5, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (V).

[In Formula (V), Y ¹ , Y ² and Y ³ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group. Represents an aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted styryl group, a substituted or unsubstituted butadiene group, or a substituted or unsubstituted hydrazone group, and R ⁵ , R ⁶ and R ⁷ are each independently Represents a monovalent organic group having 1 to 18 carbon atoms, L ⁵ , L ⁶ and L ⁷ each independently represents an alkylene group, and p 1, p 2 and p 3 each independently represents 0 to 2 An integer, q1, q2, and q3 represent 0 or 1, and satisfy the condition of (q1 + q2 + q3) ≧ 1. ]   The coating composition according to any one of claims 1 to 6, wherein the isocyanate compound is an isocyanate compound having 3 or more functional groups. A conductive support, and a photosensitive layer formed on the conductive support,
The said photosensitive layer has the outermost surface layer formed by hardening | curing the coating agent composition as described in any one of Claims 1 thru | or 7 arrange | positioned in the side farthest from the said electroconductive support body, It is characterized by the above-mentioned. An electrophotographic photoreceptor. The electrophotographic photosensitive member according to claim 8,
A charging device for charging the electrophotographic photoreceptor;
An exposure device that forms an electrostatic latent image on the charged electrophotographic photosensitive member;
A developing device for developing the electrostatic latent image with toner to form a toner image;
A transfer device for transferring the toner image from the electrophotographic photosensitive member to a transfer target;
An image forming apparatus comprising: The electrophotographic photosensitive member according to claim 8,
A charging device for charging the electrophotographic photosensitive member, an exposure device for forming an electrostatic latent image on the charged electrophotographic photosensitive member, and a toner image obtained by developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner. And at least one selected from the group consisting of a developing device for forming a toner and a cleaning device for removing toner remaining on the surface of the electrophotographic photosensitive member,
A process cartridge comprising:

Images