JP5046614B2 - Electrophotographic photoreceptor, image forming method, image forming apparatus, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high abrasion resistance, high scratch resistance and good electric characteristics, particularly excellent in smoothness of a film owing to uniform curing of all over the whole layer in a crosslinked surface layer and having good cleaning characteristics, highly durable and actually expressing high image quality for a long period of time, and an image forming method, an image forming apparatus and a process cartridge for the image forming apparatus using the photoreceptor having long life and high performance. <P>SOLUTION: A polycarbonate containing two or more distilbene polycarbonate units and the electrophotographic photoreceptor having a layer comprising a polymerization reaction product of the polycarbonate containing two or more distilbene polycarbonate units with a polymerizable charge transfer material having carbon-carbon double bonds are provided. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention, electronic photoreceptor, image forming method, an image forming apparatus及beauty profile processes cartridge.

  In recent years, organic photoreceptors (OPC) have been widely used in copying machines, facsimile machines, laser printers, and composite machines in place of inorganic photoreceptors because of their good performance and various advantages. This is because, for example, (1) optical characteristics such as the light absorption wavelength range and the amount of absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, and (3) material selection range (4) Ease of manufacturing, (5) Low cost, (6) Non-toxicity, and the like.

  On the other hand, the diameter of the photoconductor has recently been reduced due to the downsizing of the image forming apparatus, and the high speed of the machine and the maintenance-free movement have been added to increase the durability of the photoconductor. From this point of view, organophotoreceptors are generally soft because the surface layer is mainly composed of low-molecular charge transport materials and inert polymers, and when used repeatedly in electrophotographic processes, they are mechanically driven by development and cleaning systems. There is a drawback that wear is likely to occur due to a typical load. In addition, due to the demand for higher image quality, the cleaning blade has to be increased in hardness and contact pressure with the aim of improving the cleaning properties as the particle size of the toner particles is reduced. This also promotes the wear of the photoreceptor. Is a factor. Such abrasion of the photoreceptor deteriorates electrical characteristics such as sensitivity deterioration and chargeability, and causes abnormal images such as image density reduction and background stains. Further, scratches where wear is locally generated cause streak-like stain images due to poor cleaning. Under the present circumstances, the wear and scratches are rate-determined and the life of the photoconductor has been replaced.

  Therefore, it is indispensable to reduce the above-mentioned wear amount in order to increase the durability of the organic photoreceptor, and this is the most pressing issue in this field.

As a technique for improving the abrasion resistance of the photosensitive layer, curing of 2,2′-diallylbisphenol A type polycarbonate resin is known (for example, see Patent Document 1). Further, a cured charge transport layer of 2,2′-diallyl bisphenol type polycarbonate resin and an acrylic group-substituted charge transport material has been proposed (see, for example, Patent Document 2), which is a reaction of an allyl group from a side chain. Therefore, the wear resistance such as hardness is not sufficient. Moreover, although the stilbene carbonate resin is disclosed (for example, refer to Patent Document 3), it has high crystallinity, high secondary structure of the molecular chain, and high toughness.
JP-A-4-291348 Japanese Patent No. 3081705 Japanese National Patent Publication No. 10-508064

The object of the present invention is high wear resistance, high scratch resistance, good electrical characteristics, and particularly excellent smoothness of the film by uniform curing over the entire cross-linked surface layer, and a clear cross-linked surface By forming a photosensitive layer, an electrophotographic photosensitive member having good cleaning characteristics, high durability, and high image quality over a long period of time is provided. an image forming method using high photoconductor is to provide an image forming apparatus及beauty profile processes cartridge.

  The above problems are solved by the present invention described below.

  (1) A polycarbonate containing a plurality of distilbene polycarbonate units represented by the following general formula (1).

一般式（１）
（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基を表わす。）
（２）下記一般式（２）で示されるジスチルベンカーボネートユニットとビスフェノール誘導体型カーボネートユニットとを複数含むポリカーボネート共重合体。

General formula (1)
(Wherein R ¹ and R ² represent hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms)
(2) A polycarbonate copolymer containing a plurality of distilbene carbonate units and bisphenol derivative-type carbonate units represented by the following general formula (2).

一般式（２）
（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基、Ｒ^３、Ｒ^４は水素、同一、又は異なる炭素数１〜４のアルキル基、炭素数５〜７のシクロアルキル基、炭素数６〜１２の置換若しくは無置換のアリール基を表わし、Ａは単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＳｉＯ（ＣＨ_３）_２−、−ＣＲ^５Ｒ^６−（Ｒ^５及びＲ^６はそれぞれ独立に水素原子、トリフオロメチル基、炭素数１〜６のアルキル基、又は炭素数６〜１２の置換若しくは無置換のアリール基である。）、炭素数５〜１１の１，１−シクロアルキリデン基を表わし、ａ，ｂはそれぞれ独立に０〜４の整数を表わし、ｈ，ｉは共重合ｍｏｌ％を表わし、ｈは５〜８０、ｉは２０〜９５を表わす。）
（３）下記一般式（１）で示されるジスチルベンポリカーボネートユニットを複数含むポリカーボネートと、炭素−炭素二重結合を有する重合性電荷輸送物質とからの重合反応生成物を含む層を有することを特徴とする電子写真感光体。

General formula (2)
(Wherein R ¹ and R ² are hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, R ³ and R ⁴ are hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, and 5 to 5 carbon atoms. 7 represents a cycloalkyl group having 7 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and A represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —SiO (CH ₃ ) ₂ —, —CR ⁵ R ⁶ — (R ⁵ and R ⁶ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or non-substituted group having 6 to 12 carbon atoms. A substituted aryl group), a 1,1-cycloalkylidene group having 5 to 11 carbon atoms, a and b each independently represent an integer of 0 to 4, and h and i each represents a copolymer mol%. H represents 5 to 80, and i represents 20 to 95.)
(3) It has a layer containing a polymerization reaction product from a polycarbonate containing a plurality of distilbene polycarbonate units represented by the following general formula (1) and a polymerizable charge transport material having a carbon-carbon double bond. An electrophotographic photoreceptor.

一般式（１）
（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基を表わす。）
（４）下記一般式（２）で示されるジスチルベンカーボネートユニットとビスフェノール誘導体型カーボネートユニットとを複数含むポリカーボネート共重合体と、前記炭素−炭素二重結合を有する電荷輸送物質とからの硬化させられた最上層を有することを特徴とする電子写真感光体。

General formula (1)
(Wherein R ¹ and R ² represent hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms)
(4) Cured from a polycarbonate copolymer including a plurality of distilbene carbonate units and bisphenol derivative-type carbonate units represented by the following general formula (2), and the charge transport material having the carbon-carbon double bond. An electrophotographic photosensitive member having an uppermost layer.

一般式（２）
（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基、Ｒ^３、Ｒ^４は水素、同一、又は異なる炭素数１〜４のアルキル基、炭素数５〜７のシクロアルキル基、炭素数６〜１２の置換若しくは無置換のアリール基を表わし、Ａは単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＳｉＯ（ＣＨ_３）_２−、−ＣＲ^５Ｒ^６−（Ｒ^５及びＲ^６はそれぞれ独立に水素原子、トリフオロメチル基、炭素数１〜６のアルキル基、又は炭素数６〜１２の置換若しくは無置換のアリール基である。）、炭素数５〜１１の１，１−シクロアルキリデン基を表わし、ａ，ｂはそれぞれ独立に０〜４の整数を表わし、ｈ，ｉは共重合ｍｏｌ％を表わし、ｈは５〜８０、ｉは２０〜９５を表わす。）
（５）前記炭素−炭素二重結合を有する電荷輸送物質が下記一般式（３）、一般式（４）で示されるものであることを特徴とする前記（３）又は（４）に記載の電子写真感光体。

General formula (2)
(Wherein R ¹ and R ² are hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, R ³ and R ⁴ are hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, and 5 to 5 carbon atoms. 7 represents a cycloalkyl group having 7 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and A represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —SiO (CH ₃ ) ₂ —, —CR ⁵ R ⁶ — (R ⁵ and R ⁶ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or non-substituted group having 6 to 12 carbon atoms. A substituted aryl group), a 1,1-cycloalkylidene group having 5 to 11 carbon atoms, a and b each independently represent an integer of 0 to 4, and h and i each represents a copolymer mol%. H represents 5 to 80, and i represents 20 to 95.)
(5) The charge transporting material having a carbon-carbon double bond is represented by the following general formula (3) or general formula (4), wherein (3) or (4) Electrophotographic photoreceptor.

一般式（３）

General formula (3)

一般式（４）
（式中、Ａｃｔは、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基から選択される炭素−炭素二重結合を表わし、Ｒ^７，Ｒ^８，Ｒ^９，Ｒ^１０，Ｒ^１１，Ｒ^１２は水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基を表わし、ｃ，ｄは１≦ｃ＋ｄ≦４を満たす整数、ｅ，ｆは１≦ｅ＋ｆ≦４を満たす整数である。）
（６）前記炭素−炭素二重結合を有する電荷輸送物質が下記一般式（５）で示されるものであることを特徴とする前記（３）又は（４）に記載の電子写真感光体。

General formula (4)
(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group, a methacryloyloxy group, and a vinyl group, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are hydrogen atoms. Represents an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, c and d are integers satisfying 1 ≦ c + d ≦ 4, and e and f are integers satisfying 1 ≦ e + f ≦ 4.
(6) The electrophotographic photoreceptor as described in (3) or (4) above, wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (5).

一般式（５）
（式中、Ａｃｔは炭素−炭素二重結合を表わし、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基を表わし、Ｒ^２０，Ｒ^２１は水素原子、炭素数１〜４のアルキル基を表わし、Ａｒ^１は置換、無置換のアリーレン基を表わし、ｇ，ｋ，ｏはそれぞれ独立に０〜２の整数を表わし、ｖは０又は１を表わす。）
（７）前記炭素−炭素二重結合を有する電荷輸送物質が下記一般式（６）で示されるものであることを特徴とする前記（３）又は（４）に記載の電子写真感光体。

General formula (5)
(In the formula, Act represents a carbon-carbon double bond, represents an acryloyloxy group, a methacryloyloxy group, and a vinyl group, R ²⁰ and R ²¹ represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Ar ¹ Represents a substituted or unsubstituted arylene group, g, k and o each independently represents an integer of 0 to 2, and v represents 0 or 1.)
(7) The electrophotographic photoreceptor as described in (3) or (4) above, wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (6).

一般式（６）
（式中、Ａｃｔは、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基から選択される炭素−炭素二重結合を表わし、Ｒ^２２，Ｒ^２３は水素原子、炭素数１〜４のアルキル基を表わし、炭素数１〜４のアルコキシ基を表わし、ｐ，ｑはそれぞれ独立に０〜２の整数を表わす。）
（８）前記炭素−炭素二重結合を有する電荷輸送物質が下記一般式（７）で示されるものであることを特徴とする前記（３）又は（４）に記載の電子写真感光体。

General formula (6)
(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group, a methacryloyloxy group and a vinyl group, R ²² and R ²³ represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Represents an alkoxy group having 1 to 4 carbon atoms, and p and q each independently represents an integer of 0 to 2.)
(8) The electrophotographic photoreceptor as described in (3) or (4) above, wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (7).

一般式（７）
（式中、Ａｃｔは、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基から選択された炭素−炭素二重結合を表わし、Ａｒ^２，Ａｒ^３は置換、無置換のアリール基を表わし、
Ｂは、

General formula (7)
(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group, a methacryloyloxy group, and a vinyl group, and Ar ² and Ar ³ represent a substituted or unsubstituted aryl group;
B is

を表わし、ここでＲ^２４，Ｒ^２５は水素原子、炭素数１〜５のアルキル基、置換、無置換のアリール基を表わし、ｒは１〜２の整数を表わす。）
（９）前記炭素−炭素二重結合を有する電荷輸送物質が下記一般式（８）で示されるものであることを特徴とする前記（３）又は（４）に記載の電子写真感光体。

Where R ²⁴ and R ²⁵ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, and r represents an integer of 1 to 2. )
(9) The electrophotographic photoreceptor as described in (3) or (4) above, wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (8).

一般式（８）
（式中、Ａｃｔは、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基から選択された炭素−炭素二重結合を表わし、Ａｒ^４は置換、無置換のアリール基を表わし、ｓ，ｕはそれぞれ独立に０〜２の整数を表わす。）
（１０）下記一般式（１）又は一般式（２）で示されるポリカーボネート共重合体、炭素−炭素二重結合を有する電荷輸送物質、及びアクリロイルオキシ基及び／又はメタクリロイルオキシ基を有するラジカル重合性モノマーの重合反応性生成物が感光層の最上層に含有されたことを特徴とする電子写真感光体。

General formula (8)
(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group, a methacryloyloxy group, and a vinyl group, Ar ⁴ represents a substituted or unsubstituted aryl group, and s and u represent each independently. Represents an integer of 0 to 2)
(10) Polycarbonate copolymer represented by the following general formula (1) or general formula (2), a charge transport material having a carbon-carbon double bond, and a radical polymerizability having an acryloyloxy group and / or a methacryloyloxy group. An electrophotographic photosensitive member comprising a monomer-reactive product contained in the uppermost layer of a photosensitive layer.

一般式（１）
（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基を表わす。）

General formula (1)
(Wherein R ¹ and R ² represent hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms)

一般式（２）
（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基、Ｒ^３、Ｒ^４は水素、同一、又は異なる炭素数１〜４のアルキル基、炭素数５〜７のシクロアルキル基、炭素数６〜１２の置換若しくは無置換のアリール基を表わし、Ａは単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＳｉＯ（ＣＨ_３）_２−、−ＣＲ^５Ｒ^６−（Ｒ^５及びＲ^６はそれぞれ独立に水素原子、トリフオロメチル基、炭素数１〜６のアルキル基、又は炭素数６〜１２の置換若しくは無置換のアリール基である。）、又は炭素数５〜１１の１，１−シクロアルキリデン基を表わし、ａ，ｂはそれぞれ独立に０〜４の整数を表わし、ｈ，ｉは共重合ｍｏｌ％を表わし、ｈは５〜８０、ｉは２０〜９５を表わす。）
（１１）前記炭素−炭素二重結合を有する電荷輸送物質は、上記一般式（３）乃至（８）の群から選択できることを特徴とする前記（１０）に記載の電子写真感光体。

General formula (2)
(Wherein R ¹ and R ² are hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, R ³ and R ⁴ are hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, and 5 to 5 carbon atoms. 7 represents a cycloalkyl group having 7 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and A represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —SiO (CH ₃ ) ₂ —, —CR ⁵ R ⁶ — (R ⁵ and R ⁶ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or non-substituted group having 6 to 12 carbon atoms. A substituted aryl group), or a 1,1-cycloalkylidene group having 5 to 11 carbon atoms, a and b each independently represent an integer of 0 to 4, h and i represent copolymer mol%. H represents 5 to 80, and i represents 20 to 95.)
(11) The electrophotographic photosensitive member according to (10), wherein the charge transport material having a carbon-carbon double bond can be selected from the group of the general formulas (3) to (8).

  (12) An electrophotographic photosensitive member according to any one of (3) to (11) is used as an electrophotographic photosensitive member, and at least the process of charging, image exposure, and development is performed on the electrophotographic photosensitive member. After that, an image forming method is characterized in that an image is formed by transferring and fixing a toner image onto an image holding member and cleaning the surface of the electrophotographic photosensitive member.

  (13) In an image forming apparatus including at least a charging unit, an image exposure unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member, the electrophotographic photosensitive member according to any one of (3) to (11) An image forming apparatus as described above.

  (14) An image is formed by integrally supporting the electrophotographic photosensitive member according to any one of (3) to (11) and at least one unit selected from a charging unit, a developing unit, and a cleaning unit. A process cartridge for an image forming apparatus, which is detachable from an apparatus main body.

The present invention Hardness increase can provide a highly durable photoreceptor by improving the wear resistance in the mechanical strength improved modulus.

  The present invention provides a curing reaction from a (resinous) polycarbonate compound having a plurality of distilbene skeleton units represented by the following general formula (1) and a polymerizable charge transporting material having a carbon-carbon double bond in the surface layer of the photosensitive layer. (Polymerization reaction) The present invention provides a high-sensitivity photosensitive member containing a product.

一般式（１）
（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基、ａ，ｂは１〜４の整数を表わす。）
［ジスチルベンユニットを有するポリカーボネート、前記一般式（２）で示される共重合体］
前記一般式（１）で示されるポリカーボネートは、以下のスキームで合成される。モノマーの合成はヒドロキベンズアルデヒドとジベンジルホスフォネートとのウィティヒ反応でジスチルベンを合成した。ポリカーボネート化はピリジン中で溶液重合法でトリホスゲンを作用させ、ポリカーボネートを合成した。

General formula (1)
(In the formula, R ¹ and R ² represent hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, and a and b each represents an integer of 1 to 4)
[Polycarbonate having distilbene unit, copolymer represented by the general formula (2)]
The polycarbonate represented by the general formula (1) is synthesized according to the following scheme. The monomer was synthesized by the Wittig reaction of hydroxybenzaldehyde and dibenzyl phosphonate. Polycarbonate was prepared by reacting triphosgene with a solution polymerization method in pyridine.

（式中Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基を表わす。）
本発明においては、ジスチルベンユニットを有するポリカーボネートとして、下記一般式（２）で示される共重合体も好ましく用いることができる。

(Wherein R ¹ and R ² represent hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms)
In the present invention, a copolymer represented by the following general formula (2) can also be preferably used as the polycarbonate having a distilbene unit.

一般式（２）
ジヒドロキシジスチルベンの単重合ポリマーは高い結晶性を示し、反応途中から析出してしまい、また溶媒に溶けなくなるが、他のビスフェノールとの共重合によって溶媒可溶にフィルム形成を行なう。共重合比率は全モル数で７０％以下、あるいは重量比率でも７０％以下が好ましい。

General formula (2)
A monopolymer of dihydroxydistilbene exhibits high crystallinity, precipitates during the reaction, and becomes insoluble in a solvent, but forms a film soluble in a solvent by copolymerization with other bisphenols. The copolymerization ratio is preferably 70% or less in terms of the total number of moles, or 70% or less in terms of weight ratio.

  Examples of the dihydric phenol used for obtaining the copolymer represented by the general formula (2) include those represented by the following general formula (9).

一般式（９）
（Ｒ^３、Ｒ^４は水素、同一、又は異なる炭素数１〜４のアルキル基、炭素数５〜７のシクロアルキル基、炭素数６〜１２の置換若しくは無置換のアリール基を表わし、Ａは単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＳｉＯ（ＣＨ_３）_２−、−ＣＲ^５Ｒ^６−（Ｒ^５及びＲ^６はそれぞれ独立に水素原子、トリフオロメチル基、炭素数１〜６のアルキル基、又は炭素数６〜１２の置換若しくは無置換のアリール基である。）、炭素数５〜１１の１，１−シクロアルキリデン基を表わし、ｃ，ｄはそれぞれ独立に０〜４の整数を表わす。）
具体例としては、例えば、４，４’−ジヒドロキシビフェニル、３，３’−ジフルオロ−４，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシ−３，３’−ジメチルビフェニル、４，４’−ジヒドロキシ−２，２’−ジメチルビフェニル、４，４’−ジヒドロキシ−３，３’−ジシクロヘキシルビフェニル等の４，４’−ジヒドロキシビフェニル類；ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、１，２−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）プロパン（別名：ビスフェノールＡ）、２，２−ビス（３−メチル−４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）オクタン、４，４−ビス（４−ヒドロキシフェニル）ヘプタン、１，１−ビス（４−ヒドロキシフェニル）−１，１−ジフェニルメタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルメタン、１，１−ビス（４−ヒドロキシフェニル）シクロペンタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、２，２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン、２−（３−メチル−４−ヒドロキシフェニル）−２−（４−ヒドロキシフェニル）−１−フェニルエタン、ビス（３−メチル−４−ヒドロキシフェニル）メタン、１，１−ビス（３−メチル−４−ヒドロキシフェニル）シクロヘキサン、２，２−ビス（２−メチル−４−ヒドロキシフェニル）プロパン、１，１−ビス（２−ブチル−４−ヒドロキシ−５−メチルフェニル）ブタン、１，１−ビス（２−ｔｅｒｔ−ブチル−４−ヒドロキシ−３−メチルフェニル）エタン、１，１−ビス（２−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロパン、１，１−ビス（２−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）ブタン、１，１−ビス（２−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）イソブタン、１，１−ビス（２−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）ヘプタン、１，１−ビス（２−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）−１−フェニルメタン、１，１−ビス（４−ヒドロキシ−２−メチル−５−ｔｅｒｔ−ペンチルフェニル）ブタン、ビス（３−クロロ−４−ヒドロキシフェニル）メタン、ビス（３，５−ジブロモ−４−ヒドロキシフェニル）メタン、２，２−ビス（３−クロロ−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−フルオロ−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−ブロモ−４−ヒドロキシフェニル）プロパン、２，２−ビス（３，５−ジフルオロ−４−ヒドロキシフェニル）プロパン（別名：テトラフルオロビスフェノールＡ）、２，２−ビス（３，５−ジクロロ−４−ヒドロキシフェニル）プロパン（別名：テトラクロロビスフェノールＡ）、２，２−ビス（３，５−ジブロモ−４−ヒドロキシフェニル）プロパン（別名：テトラブロモビスフェノールＡ）、２，２−ビス（３−ブロモ−４−ヒドロキシ−５−クロロフェニル）プロパン、２，２−ビス（３，５−ジクロロ−４−ヒドロキシフェニル）ブタン、２，２−ビス（３，５−ジブロモ−４−ヒドロキシフェニル）ブタン、１−フェニル−１，１−ビス（３−フルオロ−４−ヒドロキシフェニル）エタン、１，１−ビス（３−シクロヘキシル−４−ヒドロキシフェニル）シクロヘキサン、２，２−ビス（３−ヒドロキシフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン、２，２−ビス（３−フェニル−４−ヒドロキシフェニル）プロパン、１，１−ビス（３−フェニル−４−ヒドロキシフェニル）シクロヘキサン等のビス（４−ヒドロキシフェニル）アルカン類；ビス（４−ヒドロキシフェニル）エーテル、ビス（３−フルオロ−４−ヒドロキシフェニル）エーテル等のビス（４−ヒドロキシフェニル）エーテル類；ビス（４−ヒドロキシフェニル）スルフィド、ビス（３−メチル−４−ヒドロキシフェニル）スルフィド等のビス（４−ヒドロキシフェニル）スルフィド類；ビス（４−ヒドロキシフェニル）スルホン、ビス（３−メチル−４−ヒドロキシフェニル）スルホン、ビス（３−フェニル−４−ヒドロキシフェニル）スルホン等のビス（４−ヒドロキシフェニル）スルホン類；４，４’−ジヒドロキシベンゾフェノン等が挙げられる。

General formula (9)
(R ³ and R ⁴ represent hydrogen, the same or different alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and A represents Single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —SiO (CH ₃ ) ₂ —, —CR ⁵ R ⁶ — (R ⁵ and R ⁶ are each independently hydrogen. An atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), and a 1,1-cycloalkylidene group having 5 to 11 carbon atoms. , C and d each independently represents an integer of 0 to 4.)
Specific examples include, for example, 4,4′-dihydroxybiphenyl, 3,3′-difluoro-4,4′-dihydroxybiphenyl, 4,4′-dihydroxy-3,3′-dimethylbiphenyl, 4,4′- 4,4′-dihydroxybiphenyls such as dihydroxy-2,2′-dimethylbiphenyl, 4,4′-dihydroxy-3,3′-dicyclohexylbiphenyl; bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (3-methyl-4) -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 4 , 4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1 -Bis (4-hydroxyphenyl) -1-phenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl) -4-hydroxyphenyl) propane, 2- (3-methyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) -1-phenylethane, bis (3-methyl-4-hydroxyphenyl) methane, 1, 1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (2-methyl-4-hydroxyphenyl) pro 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1,1- Bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2- tert-butyl-4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 1,1-bis (2-tert-butyl- 4-hydroxy-5-methylphenyl) -1-phenylmethane, 1,1-bis (4-hydroxy-2-methyl-5-tert-pentylphenyl) butane, bis ( -Chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3- Fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol) A), 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane (alias: tetrachlorobisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (alias) : Tetrabromobisphenol A), 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1-phenyl-1,1-bis (3 -Fluoro-4-hydroxyphenyl) ethane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3 Bis (4-hydroxyphenyl) alkanes such as hexafluoropropane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane; Bis (4-hydroxyphenyl) ether such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether Ethers; bis (4-hydroxyphenyl) sulfides such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone and bis (3-methyl) Bis (4-hydroxyphenyl) sulfones such as -4-hydroxyphenyl) sulfone and bis (3-phenyl-4-hydroxyphenyl) sulfone; 4,4′-dihydroxybenzophenone and the like.

  Among these, dihydric phenols preferably used are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1, 1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3- Phenylphenyl) propane, 4,4′-dihydroxybiphenyl and bis (4-hydroxyphenyl) sulfone, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used.

  These dihydric phenols of the general formula (9) are described in JP-A-4-291348.

[Polymerizable charge transport material (substance) having a carbon-carbon double bond]
The polymerizable charge transport material having a carbon-carbon double bond is a benzidine compound represented by the following general formula (3) or general formula (4). In the structural formula, Act represents acryloyloxy group, methacryloyloxy group, vinyl. R ⁷ , R ⁸ , R ³⁰ , R ³¹ , R ³² , and R ³³ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon number having 1 to 4 carbon atoms. Represents an alkoxy group, e and f are represented by 1 ≦ e + f ≦ 4, and l and m are represented by 1 ≦ l + m ≦ 4.

一般式（３）

General formula (3)

一般式（４）
アクリロイル基の導入は以下のルートで合成される。

General formula (4)
Introduction of an acryloyl group is synthesized by the following route.

ビニル基の導入は以下のルートで合成される。

The introduction of the vinyl group is synthesized by the following route.

以下に具体例を示すが、これらに限定されるものでない。

Although a specific example is shown below, it is not limited to these.

炭素−炭素二重結合を有する重合性電荷輸送材としては、下記一般式（５）で示されるアミノビフェニル化合物が挙げられる。

Examples of the polymerizable charge transport material having a carbon-carbon double bond include aminobiphenyl compounds represented by the following general formula (5).

一般式（５）
式中、Ａｃｔは炭素−炭素二重結合を表わし、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基を表わし、Ｒ^９，Ｒ^１０は水素原子、炭素数１〜４のアルキル基を表わし、Ａｒ^１は置換、無置換のアリーレン基を表わし、ｇ，ｋ、ｏはそれぞれ独立に０〜２の整数、好ましくは１≦ｇ＋ｋ＋ｏ≦４を満たす整数を表わし、ｖは０〜１の整数を表わす。

General formula (5)
In the formula, Act represents a carbon-carbon double bond, represents an acryloyloxy group, a methacryloyloxy group, and a vinyl group, R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and Ar ¹ represents A substituted or unsubstituted arylene group is represented, g, k, and o each independently represent an integer of 0 to 2, preferably 1 ≦ g + k + o ≦ 4, and v represents an integer of 0 to 1.

  Although a specific example is shown below, it is not limited to these. These are described in Japanese Patent No. 3081705 of Patent Document 2.

炭素−炭素二重結合を有する重合性電荷輸送材としては、下記一般式（６）で示されるフェニレンジアミン化合物が挙げられる。

Examples of the polymerizable charge transport material having a carbon-carbon double bond include a phenylenediamine compound represented by the following general formula (6).

一般式（６）
式中、Ａｃｔは炭素−炭素二重結合を表わし、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基を表わし、Ｒ^１１，Ｒ^１２は水素原子、炭素数１〜４のアルキル基を表わし、ｐ，ｑは、それぞれ独立に０〜２の整数、好ましくは１≦ｐ＋ｑ≦４を満たす整数を表わす。

General formula (6)
In the formula, Act represents a carbon-carbon double bond, represents an acryloyloxy group, a methacryloyloxy group, and a vinyl group, R ¹¹ and R ¹² represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, p, q Each independently represents an integer of 0 to 2, preferably 1 ≦ p + q ≦ 4.

  Although a specific example is shown below, it is not limited to these.

炭素−炭素二重結合を有する重合性電荷輸送材としては、下記一般式（７）で示される化合物が挙げられる。

Examples of the polymerizable charge transport material having a carbon-carbon double bond include compounds represented by the following general formula (7).

一般式（７）
式中、Ａｃｔは、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基から選択された炭素−炭素二重結合を表わし、Ａｒ^２，Ａｒ^３は置換、無置換のアリール基を表わし、Ｂは

General formula (7)
In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group, a methacryloyloxy group, and a vinyl group, Ar ² and Ar ³ represent a substituted or unsubstituted aryl group, and B represents

を表わし、ここでＲ^２４，Ｒ^２５は水素原子、炭素数１〜５のアルキル基、置換、無置換のアリール基を表わす。ｒは１〜２の整数を表わす。）
以下に具体例を示すが、これらに限定されるものではない。

Where R ²⁴ and R ²⁵ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group. r represents an integer of 1 to 2; )
Specific examples are shown below, but are not limited thereto.

炭素−炭素二重結合を有する重合性電荷輸送材としては、下記一般式（８）で示されるトリフェニルアミン化合物が挙げられる。

Examples of the polymerizable charge transport material having a carbon-carbon double bond include a triphenylamine compound represented by the following general formula (8).

一般式（８）
式中、Ａｃｔは、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基から選択された炭素−炭素二重結合を表わしを表わし、Ａｒ^４は置換、無置換のアリール基を表わし、ｓ，ｕはそれぞれ独立に０〜２の整数、好ましくは１≦ｓ＋ｕ≦４を満たす整数を表わす。

General formula (8)
In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group, a methacryloyloxy group, and a vinyl group, Ar ⁴ represents a substituted or unsubstituted aryl group, and s and u are independent of each other. Represents an integer satisfying 0 to 2, preferably 1 ≦ s + u ≦ 4.

  Although a specific example is shown below, it is not limited to these.

一般式（３）〜（８）の炭素−炭素二重結合を有する電荷輸送物質と、一般式（１）で示されるユニットを有するポリカーボネート樹脂の配合比率は、炭素−炭素二重結合を有する電荷輸送物質１０重量に対しポリカーボネート樹脂６〜２０重量であり、好ましくは７〜１５重量である。

The compounding ratio of the charge transport material having a carbon-carbon double bond of the general formulas (3) to (8) and the polycarbonate resin having a unit represented by the general formula (1) is the charge having a carbon-carbon double bond. The polycarbonate resin is 6 to 20 weights, preferably 7 to 15 weights with respect to 10 weight of the transport material.

  Here, the alkyl group having 1 to 5 carbon atoms specifically includes methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i- A butyl group, n-pentyl group, etc. are mentioned.

  Examples of the aryl group include phenyl group, naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, and the like. Examples of the substituent include the aforementioned alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like.

  In the present invention, preferably, the resin has an acryloyloxy group and / or a methacryloyloxy group together with a polycarbonate resin having a unit represented by the general formula (1) or the general formula (2) and a charge transport material having a carbon-carbon double bond. A photosensitive layer is formed with a radical polymerizable monomer (or a cured product thereof).

  The acryloyloxy group and / or methacryloyloxy group compound is a bifunctional monomer, oligomer, and polymer such as diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meta ) Acrylate, 1,6-hexanediol di (meth) acrylate, etc .; trifunctional monomers, oligomers, polymers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, aliphatic tri (meth) acrylate Etc .; tetrafunctional monomer, oligomer, polymer such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, aliphatic Examples include tetra (meth) acrylates; 5-functional or higher monomers, oligomers, and polymers such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, as well as polyester skeleton, urethane skeleton, and phosphazene skeleton. (Meth) acrylate etc. which have this. In this invention, the said monomer can be used as a 1 type, or 2 or more types of mixture.

  These radically polymerizable monomers having an acryloyloxy group and / or a methacryloyloxy group are polycarbonate resins having a unit represented by the general formula (1) or the general formula (2), and charge transport materials having a carbon-carbon double bond. It is added in an amount of 2 to 50% by weight, preferably 10 to 30% by weight.

  Coating in which a polycarbonate resin having a repeating unit represented by the general formula (1) or the general formula (2) and a charge transport material having a carbon-carbon double bond, or an acryloyloxy group and / or a methacryloyloxy group compound are appropriately added. In order to radically polymerize the film, a thermal polymerization initiator or a photopolymerization initiator is contained and cured. The following are mentioned as a thermal-polymerization initiator and a photoinitiator.

  As the thermal polymerization initiator, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, bis-3,5 , 5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- (t-butyloxy) -hexane, 1,3 -Bis (t-butylperoxy-isopropyl) benzene, t-butylcumyl peroxide, di-tbutyl peroxide, 2,5-dimethyl-2,5- (di-t-butylperoxy) he Sun-3, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di (t-butylperoxy) butane, 4,4-di-t-butylperoxyvaleric acid n-butyl ester, 2,2-bis (4,4-t-butylperoxycyclohexyl) propane, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,5,5-trimethylhexaate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate Peroxides such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobissi Azo-based, such as Russia hexyl nitrile is used.

  Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Acetophenone-based or ketal-based photopolymerization initiators such as methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether Benzoin ether photopolymerization initiators such as benzoin isopropyl ether, benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, 1 Benzophenone photopolymerization initiators such as 2-benzoylbenzene, thioxanthones such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone As photopolymerization initiators and other photopolymerization initiators, ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl Phenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10 -Phenanthrene, an acridine type compound, a triazine type compound, an imidazole type compound is mentioned. Moreover, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4'-dimethylaminobenzophenone, and the like.

  These heat and photopolymerization initiators may be added to the formulation solution, respectively, and one or more thermal polymerization initiators, or one or more photopolymerization initiators may be mixed and used. The content of the polymerization initiator is 0.5 to 40 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the total content having radical polymerizability. The half-life of the thermal polymerization initiator is preferably 80 ° C. or higher, and if it is 50 ° C. or lower, the storage stability of the coating solution is deteriorated and the coating is cured.

  Furthermore, the coating liquid of the present invention can contain additives such as various plasticizers (for the purpose of stress relaxation and adhesion improvement), leveling agents, and low molecular charge transport materials having no radical reactivity as required. As these additives, known additives can be used, and as plasticizers, those used in general resins such as dibutyl phthalate and dioctyl phthalate can be used, and the amount used is the total solid content of the coating liquid. To 20% by weight or less, preferably 10% or less. As leveling agents, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the side chain can be used, and the amount used is based on the total solid content of the coating liquid. 3% by weight or less is appropriate.

  A polycarbonate resin having a unit represented by the general formula (1) or the general formula (2), a charge transport material having a carbon-carbon double bond, and an appropriately added acryloyloxy group and / or methacryloyloxy group compound radical polymerizability It is formed by applying and curing a coating solution containing a compound. When the radically polymerizable monomer is a liquid, such a coating liquid can be applied by dissolving other components in the liquid, but if necessary, it is diluted with a solvent and applied. Solvents used at this time include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane and propyl ether. And ethers such as dichloromethane, dichloroethane, trichloroethane, and chlorobenzene, aromatics such as benzene, toluene, and xylene, and cellosolves such as methyl cellosolve, ethyl cellosolve, and cellosolve acetate. These solvents may be used alone or in combination of two or more. The dilution ratio with the solvent varies depending on the solubility of the composition, the coating method, and the target film thickness, and is arbitrary. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.

In this invention, after apply | coating this coating liquid, an external energy is given and it hardens | cures and forms a crosslinked surface layer, As an external energy used at this time, there exist a heat | fever, light, and a radiation. The heat energy is applied by heating from the coating surface side or the support side using a gas such as air or nitrogen, steam, various heat media, infrared rays, or electromagnetic waves. The heating temperature is preferably 80 ° C. or more and 170 ° C. or less, and if it is less than 80 ° C., the reaction rate is slow and the reaction is not completely completed. At a temperature higher than 170 ° C., the reaction proceeds non-uniformly and a large strain is generated in the crosslinked surface layer. In order to advance the curing reaction uniformly, it is also effective to complete the reaction by heating at a relatively low temperature of less than 50 ° C. and then heating to 100 ° C. or more. As the energy of light, UV irradiation light sources such as high-pressure mercury lamps and metal halide lamps, which mainly have an emission wavelength in ultraviolet light, can be used. However, a visible light source can also be selected in accordance with the absorption wavelength of radical polymerizable substances and photopolymerization initiators. Is possible. Irradiation light amount is 50 mW / cm ² or more, preferably 1000 mW / cm ² or less, it takes time for the curing reaction is less than 50 mW / cm ^2. If it is higher than 1000 mW / cm ^2, the progress of the reaction becomes non-uniform and the cross-linked surface layer becomes very rough. Examples of radiation energy include those using electron beams. Among these energies, those using heat and light energy are useful because of easy reaction rate control and simple apparatus.

In the system to which the photocuring initiator and the thermosetting initiator of the present invention are added, either the light energy or the heat energy may be given first, and when the light energy such as a high-pressure mercury lamp is given, the projectile is heated to a high temperature. Becomes 80 ° C. or higher, and thermal polymerization curing proceeds,
Since the film thickness of the crosslinked surface layer of the present invention varies depending on the layer structure of the photoreceptor in which the crosslinked surface layer is used, it will be described later together with the layer structure.

Hereinafter, the present invention will be described according to the layer structure.
<About the layer structure of the electrophotographic photoreceptor>
The electrophotographic photosensitive member used in the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an electrophotographic photosensitive member of the present invention, in which a single layer structure in which a photosensitive layer (33) having a charge generating function and a charge transporting function is provided on a conductive support (31). This is a photoreceptor. FIG. 1A shows the case where the cross-linked surface layer is the entire photosensitive layer, and FIG. 1-B shows the case where the cross-linked surface layer is the surface portion of the photosensitive layer.

  FIG. 2 shows a photoreceptor having a laminated structure in which a charge generation layer (35) having a charge generation function and a charge transport layer (37) having a charge transport material function are laminated on a conductive support (31). is there. FIG. 2-A shows the case where the cross-linked surface layer is the entire charge transport layer, and FIG. 2-B shows the case where the cross-linked surface layer is the surface portion of the charge transport layer.

<About conductive support>
As the conductive support (31), a material having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, a metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation Metal oxide such as indium by vapor deposition or sputtering, film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. After conversion, a tube that has been subjected to surface treatment such as cutting, superfinishing, or polishing can be used. Further, an endless nickel belt and an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can be used as the conductive support (31).

  In addition, the conductive support dispersed in a suitable binder resin and coated on the support can also be used as the conductive support (31) of the present invention.

  Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. Can be mentioned. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Thermoplastic, thermosetting resin or photo-curing resin such as melamine resin, urethane resin, phenol resin, alkyd resin and the like can be mentioned. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support (31) of the present invention.

<About photosensitive layer>
Next, the photosensitive layer will be described. The photosensitive layer may have a laminated structure or a single layer structure.

  In the case of a laminated structure, the photosensitive layer is composed of a charge generation layer having a charge generation function and a charge transport layer having a charge transport function. In the case of a single layer structure, the photosensitive layer is a layer having a charge generation function and a charge transport function at the same time.

  Hereinafter, each of the photosensitive layer having a laminated structure and the photosensitive layer having a single layer structure will be described.

<Photosensitive layer comprising a charge generation layer and a charge transport layer>
(Charge generation layer)
The charge generation layer (35) is a layer mainly composed of a charge generation material having a charge generation function, and a binder resin can be used in combination as necessary. As the charge generation material, inorganic materials and organic materials can be used.

  Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used.

  On the other hand, a known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo pigments having a bis-stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, indigo Id based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  The binder resin used as necessary for the charge generation layer (35) is polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-. Examples thereof include vinyl carbazole and polyacrylamide. These binder resins can be used alone or as a mixture of two or more. In addition to the binder resin described above as a binder resin for the charge generation layer, a polymer charge transport material having a charge transport function, such as an arylamine skeleton, benzidine skeleton, hydrazone skeleton, carbazole skeleton, stilbene skeleton, pyrazoline skeleton, etc. Polymer materials such as polycarbonate, polyester, polyurethane, polyether, polysiloxane, and acrylic resin, polymer materials having a polysilane skeleton, and the like can be used.

  Specific examples of the former include JP-A-01-001728, JP-A-01-009964, JP-A-01-013061, JP-A-01-019049, JP-A-01-241559, Japanese Unexamined Patent Publication Nos. 04-011627, 04-175337, 04-183719, 04-2225014, 04-230767, 04-320420, 05 -232727, JP-A 05-310904, JP-A 06-234836, JP-A 06-234837, JP-A 06-234838, JP-A 06-234839, JP-A 06-234840. No. 1, JP-A 06-234841, JP-A 06-239049, Japanese Unexamined Patent Publication Nos. 06-236050, 06-236051, 06-295077, 07-0756374, 08-176293, 08-208820, 08 No. -21640, JP 08-253568, JP 08-269183, JP 09-062019, JP 09-043883, JP 09-71642, JP 09-87376. No. 1, JP-A 09-104746, JP 09-110974, JP 09-110976, JP 09-157378, JP 09-221544, JP 09-227669. JP 09-235367 A, JP 09-241369 A Charge transporting polymer materials described in JP 09-268226 A, JP 09-272735 A, JP 09-302084 A, JP 09-302085 A, JP 09-328539 A, etc. Can be mentioned.

  Specific examples of the latter include polysilylene polymers described in, for example, JP-A No. 63-285552, JP-A No. 05-19497, JP-A No. 05-70595, JP-A No. 10-73944, and the like. Illustrated.

  The charge generation layer (35) may contain a low molecular charge transport material.

  Low molecular charge transport materials that can be used in combination with the charge generation layer (35) include hole transport materials and electron transport materials.

  Examples of the electron transporting material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and diphenoquinone derivatives. These electron transport materials can be used alone or as a mixture of two or more.

  Examples of the hole transporting material include the electron donating materials shown below and are used favorably. As hole transport materials, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triaryls Other known materials such as methane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like can be given. These hole transport materials can be used alone or as a mixture of two or more.

  Methods for forming the charge generation layer (35) include a vacuum thin film preparation method and a casting method from a solution dispersion system.

  As the former method, a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-described inorganic materials and organic materials can be satisfactorily formed.

  In addition, in order to provide a charge generation layer by the casting method described later, if necessary, the inorganic or organic charge generation material together with a binder resin, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclohexane. Can be formed by dispersing with a ball mill, attritor, sand mill, bead mill, etc. using a solvent such as pentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, etc. . Moreover, leveling agents, such as a dimethyl silicone oil and a methylphenyl silicone oil, can be added as needed. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.

  The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.

(About charge transport layer)
The charge transport layer (37) is a layer having a charge transport function, and includes a polycarbonate resin having a unit represented by the general formula (1) or the general formula (2) of the present invention, and a charge transport material having a carbon-carbon double bond. The crosslinked surface layer is useful as a charge transport layer. When the cross-linked surface layer is the entire charge transport layer (37), a coating liquid is applied onto the charge generation layer (35) as described in the above-mentioned cross-linked surface layer preparation method, and after drying, if necessary, external The curing reaction is initiated by energy, and a crosslinked surface layer is formed. At this time, the film thickness of the crosslinked surface layer is 10 to 30 μm, preferably 10 to 25 μm. If it is thinner than 10 μm, a sufficient charging potential cannot be maintained, and if it is thicker than 30 μm, peeling from the lower layer tends to occur due to volume shrinkage during curing.

  When the cross-linked surface layer is formed on the surface portion of the charge transport layer (37) and the charge transport layer (37) has a laminated structure, the lower layer portion of the charge transport layer has a charge transport material having a charge transport function and a binder. The resin is dissolved or dispersed in an appropriate solvent, and this is formed by coating and drying on the charge generation layer (35), and the resin is represented by the above general formula (1) or general formula (2) of the present invention. A coating liquid containing a polycarbonate resin having a unit and a charge transport material having a carbon-carbon double bond is applied and cross-linked and cured by external energy.

  As the charge transport material, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer (35) can be used. As described above, the use of the polymer charge transport material can reduce the solubility of the lower layer when the surface layer is applied, and is particularly useful.

  As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin And thermoplastic or thermosetting resins such as phenol resins and alkyd resins.

  The amount of the charge transport material is 20 to 300 weights, preferably 40 to 150 weights per 100 weight of the binder resin. However, when a polymer charge transport material is used, it can be used alone or in combination with a binder resin.

  As the solvent used for coating the lower layer portion of the charge transport layer, the same solvent as that for the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. The lower layer portion of the charge transport layer can be formed by a coating method similar to that for the charge generation layer (35).

  If necessary, a plasticizer and a leveling agent can be added.

  As a plasticizer that can be used in combination with the lower layer portion of the charge transport layer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is 100 parts by weight of the binder resin. On the other hand, about 0 to 30 parts by weight is appropriate.

  As a leveling agent that can be used in combination with the lower layer portion of the charge transport layer, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain are used. About 0 to 1 part by weight is appropriate for 100 parts by weight of the binder resin.

  The thickness of the lower layer portion of the charge transport layer is appropriately about 5 to 40 μm, preferably about 10 to 30 μm.

  When the cross-linked surface layer is the surface portion of the charge transport layer (37), as described in the above cross-linked surface layer preparation method, the general formula (1) or general formula of the present invention is formed on the lower layer portion of the charge transport layer. Apply a coating solution containing a polycarbonate resin having the unit shown in (2) and a charge transport material having a carbon-carbon double bond, and if necessary, start a curing reaction by external energy such as heat or light after drying. To form a crosslinked surface layer. At this time, the film thickness of the crosslinked surface layer is 1 to 20 μm, preferably 2 to 10 μm. If the thickness is less than 1 μm, the durability varies due to uneven film thickness. If the thickness is more than 20 μm, the entire thickness of the charge transport layer is increased, and the reproducibility of the image is reduced due to the diffusion of charges.

<Single photosensitive layer>
The photosensitive layer having a single layer structure is a layer having a charge generation function and a charge transport function at the same time, and the crosslinked surface layer having the charge transport structure of the present invention contains a charge generation material having a charge generation function, thereby providing a single layer structure. It is useful as a photosensitive layer. As described in the method for casting the charge generation layer, the charge generation material has a polycarbonate resin having a unit represented by the general formula (1) or the general formula (2) of the present invention, and a carbon-carbon double bond. After being dispersed together with the coating liquid containing the charge transporting material, coated on the conductive support (31), and dried if necessary, a curing reaction is initiated by light and heat energy to form a crosslinked surface layer. In addition, you may add the liquid in which the charge generation material was previously disperse | distributed with the solvent to this coating material for bridge | crosslinking surface layers. At this time, the film thickness of the crosslinked surface layer is 10 to 30 μm, preferably 10 to 25 μm. If the thickness is less than 10 μm, a sufficient charging potential cannot be maintained. If the thickness is more than 30 μm, peeling from the conductive substrate or the undercoat layer tends to occur due to volume shrinkage during curing.

  Further, when the crosslinked surface layer is a surface portion of a photosensitive layer having a single layer structure, the lower layer portion of the photosensitive layer is composed of a charge generating material having a charge generating function, a charge transporting material having a charge transport function, and a binder resin in an appropriate solvent. It can be formed by dissolving or dispersing in, coating and drying. Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. As the charge generation material dispersion method, the charge generation material, the charge transport material, the plasticizer, and the leveling agent may be the same as those already described in the charge generation layer (35) and the charge transport layer (37). As the binder resin, in addition to the binder resin previously mentioned in the section of the charge transport layer (37), the binder resin mentioned in the charge generation layer (35) may be mixed and used. In addition, the above-described polymer charge transport materials can also be used, which is useful in that contamination of the lower photosensitive layer composition into the crosslinked surface layer can be reduced. The thickness of the lower layer portion of the photosensitive layer is suitably about 5 to 30 μm, preferably about 10 to 25 μm.

  When the crosslinked surface layer is a surface portion of a photosensitive layer having a single layer structure, the polycarbonate having the unit represented by the general formula (1) or the general formula (2) of the present invention on the lower layer portion of the photosensitive layer as described above A coating liquid containing a resin, a charge transport material having a carbon-carbon double bond and a charge generation material is applied, and if necessary, dried and then cured by external energy of heat and light to form a crosslinked surface layer. At this time, the film thickness of the crosslinked surface layer is 1 to 20 μm, preferably 2 to 10 μm. When the thickness is less than 1 μm, the durability varies due to the film thickness unevenness.

  The charge generation material contained in the photosensitive layer having a single layer structure is preferably 1 to 30% by weight based on the total amount of the photosensitive layer, and the binder resin contained in the lower layer portion of the photosensitive layer is 20 to 80% by weight of the total amount. The transport material is preferably used in an amount of 10 to 70 parts by weight.

<About the intermediate layer>
In the photoreceptor of the present invention, when the crosslinked surface layer becomes the surface portion of the photosensitive layer, an intermediate layer can be provided between the crosslinked surface layer and the lower photosensitive layer. This intermediate layer prevents inhibition of the curing reaction and unevenness of the crosslinked surface layer caused by mixing of the lower photosensitive layer composition in the crosslinked surface layer containing the radical polymerizable composition. It is also possible to improve the adhesion between the lower photosensitive layer and the surface cross-linked layer.

  In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a generally used coating method is employed as described above. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.

<About the undercoat layer>
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support (31) and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.

These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, in the undercoat layer of the present invention, Al ₂ O ₃ is provided by anodization, organic substances such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

<Addition of antioxidant to each layer>
In the present invention, in order to improve environmental resistance, in order to prevent a decrease in sensitivity and an increase in residual potential, a surface cross-linked layer, a photosensitive layer, a charge generation layer, a charge transport layer, an undercoat layer, an intermediate layer An antioxidant can be added to each layer such as a layer.

The following are mentioned as antioxidant which can be used for this invention.
(Phenolic compounds)
2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4, 4'-thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4 -Hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene- -(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid ] Cryol ester, tocopherols and the like.

(Paraphenylenediamines)
N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N'- Di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.

(Hydroquinones)
2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- (2-octadecenyl) ) -5-methylhydroquinone and the like.

(Organic sulfur compounds)
Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.

(Organic phosphorus compounds)
Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.

  These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.

  The addition amount of the antioxidant in the present invention is 0.01 to 10% by weight based on the total weight of the layer to be added.

<Image Forming Method and Apparatus>
Next, the image forming method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.

  The image forming method and the image forming apparatus of the present invention use a photoconductor having a smooth charge transporting surface cross-linked layer. For example, at least after the photoconductor is charged, exposed to an image, and developed, the image is held. An image forming method and an image forming apparatus including a process of transferring a toner image onto a body (transfer paper), fixing, and cleaning of the surface of a photoreceptor.

  In some cases, an image forming method or the like in which an electrostatic latent image is directly transferred to a transfer member and developed does not necessarily have the above-described process arranged on a photosensitive member.

  FIG. 3 is a schematic diagram illustrating an example of an image forming apparatus. In the image forming apparatus of this example, a charging charger (3), an eraser (4), an image exposure unit (5), a developing unit (6), a transfer unit, which are examples of charging means, are provided around the photoreceptor (1). A separation charger (11) formed integrally with a front charger (7) and a transfer charger (10) for transferring a toner image to a transfer paper (9) conveyed by a registration roller (8) from a transfer paper tray (not shown). A separation claw (12), a pre-cleaning charger (13), a cleaning fur brush (14), a cleaning blade (15), and a static elimination lamp (2) are arranged. As a means for charging the photoconductor (1) on average, a charging charger (3) is used. As the charging means, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and a known method can be used.

  In particular, the configuration of the present invention is effective when a charging unit such as a contact charging method or a non-contact proximity arrangement charging method is used in which the photosensitive composition is decomposed by proximity discharge from the charging unit. The contact charging method referred to here is a charging method in which a charging roller, a charging brush, a charging blade, or the like is in direct contact with the photosensitive member. On the other hand, the proximity charging method is, for example, a type in which the charging roller is arranged in a non-contact state so as to have a gap of 200 μm or less between the surface of the photoreceptor and the charging means. If this gap is too large, the charging tends to become unstable, and if it is too small, the surface of the charging member may be contaminated when toner remaining on the photoreceptor exists. is there. Accordingly, the gap is suitably 10 to 200 μm, preferably 10 to 100 μm.

  Next, the image exposure unit (5) is used to form an electrostatic latent image on the uniformly charged photoreceptor (1). As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

  Next, the developing unit (6) is used to visualize the electrostatic latent image formed on the photoreceptor (1). Development methods include a one-component development method using a dry toner, a two-component development method, and a wet development method using a wet toner. When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.

  Next, a transfer charger (10) is used to transfer the toner image visualized on the photoconductor onto the transfer body (9). In addition, a pre-transfer charger (7) may be used for better transfer. As these transfer means, a transfer charger, an electrostatic transfer method using a bias roller, a mechanical transfer method such as an adhesive transfer method and a pressure transfer method, and a magnetic transfer method can be used. As the electrostatic transfer method, the charging means can be used.

  Next, a separation charger (11) and a separation claw (12) are used as means for separating the transfer body (9) from the photoreceptor (1). As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger (11), the charging means can be used.

  Next, a fur brush (14) and a cleaning blade (15) are used to clean the toner remaining on the photoreceptor after transfer. Further, a pre-cleaning charger (13) may be used in order to perform cleaning more efficiently. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination.

  Next, a neutralizing unit is used for the purpose of removing the latent image on the photoreceptor as required. As the charge removal means, a charge removal lamp (2) and a charge removal charger are used, and the exposure light source and the charging means can be used respectively.

  In addition, known processes can be used for reading, feeding, fixing, paper discharge and the like that are not close to the photoconductor.

  The present invention is an image forming method and an image forming apparatus using the electrophotographic photoreceptor according to the present invention for such image forming means.

  The image forming means may be fixedly incorporated in a copying apparatus, facsimile, or printer, but may be incorporated in these apparatuses in the form of a process cartridge and detachable. An example of the process cartridge is shown in FIG.

  The process cartridge for the image forming apparatus includes a photoreceptor (101), and in addition, a charging unit (102), a developing unit (104), a transfer unit (106), a cleaning unit (107), and a discharging unit (not shown). ), And an apparatus (part) that can be attached to and detached from the image forming apparatus main body.

  Referring to the image forming process by the apparatus illustrated in FIG. 4, the surface of the photoreceptor (101) is exposed by charging by the charging means (102) and exposure by the exposure means (103) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed, and the electrostatic latent image is developed with toner by the developing means (104). The toner development is transferred to the transfer body (105) by the transfer means (106), and printed. Be out. Next, the surface of the photoconductor after the image transfer is cleaned by a cleaning unit (107), and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  The present invention provides a process cartridge for an image forming apparatus in which a photosensitive member having a smooth charge transporting surface cross-linked layer and at least one of charging, developing, transferring, cleaning, and neutralizing means are integrated.

  As is apparent from the above description, the electrophotographic photosensitive member of the present invention is not only used in electrophotographic copying machines, but also in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. Can also be used widely.

Example 1
Synthesis of 1,4-bis (3-hydroxystyryl) benzene 3-hydroxybenzaldehyde 25 g (0.2047 mol), 1,4-xylylene-bis (phosphonic acid diethyl ester) 34.8 g (0.092 mol), DMF Take 300 ml into a four-diameter flask and dissolve with stirring at room temperature. To this, potassium tertiary butyl oxide was added in a temperature range not exceeding 40 ° C. over 1 hour and 30 minutes, and then reacted for 5 hours. The reaction product was poured into 400 ml of water, and the precipitate was acidified with acetic acid. The filtrate was washed with 500 ml of water three times, dried, filtered hot with ethanol: ethyl acetate = 300: 100 vol and recrystallized. Yellow 20.9 g m. p. : 279-281 ° C LCMS m / z 314
I. R. : Fig. 5
Synthesis of Polycarbonate 2.22 g (7.06 mmol) of the above distyryl body, 1.62 g (7.1 mmol) of bisphenol A, and 100 ml of dehydrated pyridine were placed in a four-diameter flask, cooled to 5 ° C. in an ice-water bath, cooled, The water bath was removed, and a solution of 2.63 g (8.86 mmol) of triphosgene in 30 ml of methylene chloride was added dropwise over 20 minutes with vigorous stirring. A yellow product precipitated and became an emulsion, exothermed to 26 ° C., and reacted for 2 hours. 200 ml of methylene chloride was added, and the organic layer was separated. The organic layer was not transparent, washed 3 times with 150 ml of 7% hydrochloric acid aqueous solution, washed twice with 2% aqueous hydrochloric acid, and washed 5 times with 150 ml of ion-exchanged water. The organic layer became transparent. The organic layer was poured into 1.5 L of methanol and precipitated to obtain 3 g of polycarbonate.
GPC polystyrene conversion molecular weight was Mn: 4400, Mw: 10500. The polycarbonate copolymer thus prepared is referred to as Synthesis Example 1.
I. R. : Fig. 6
Similarly, Examples 2 and 3 were copolymerized using the monomers shown in Table 1 below. The polycarbonate copolymers prepared in Examples 2 and 3 are referred to as Synthesis Examples 2 and 3, respectively.

＜実施例４＞
φ３０ｍｍのアルミニウムシリンダー上に、下記組成の下引き層用塗工液、電荷発生層用塗工液、電荷輸送層用塗工液を順次、塗布、乾燥することにより、３．５μｍの下引き層、０．２μｍの電荷発生層、２２μｍの電荷輸送層を形成した。メタルハライドランプ：１６０Ｗ／ｃｍ、照射距離：１２０ｍｍ、照射強度：５００ｍＷ／ｃｍ^２、照射時間：３０秒の条件で光照射を行ない、その後１５０℃で３０分間乾燥し本発明の電子写真感光体を得た。
〔下引き層用塗工液〕
アルキッド樹脂 ６部
（ベッコゾール１３０７−６０−ＥＬ、大日本インキ化学工業製）
メラミン樹脂 ４部
（スーパーベッカミン Ｇ−８２１−６０、大日本インキ化学工業製）
酸化チタン ４０部
メチルエチルケトン ５０部
〔電荷発生層用塗工液〕
下記構造式（Ｉ）のビスアゾ顔料 ２．５部
ポリビニルブチラール（ＸＹＨＬ、ＵＣＣ製） ０．５部
シクロヘキサノン ２００部
メチルエチルケトン ８０部

<Example 4>
By coating and drying an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution in the following order on a φ30 mm aluminum cylinder in sequence, an undercoat layer of 3.5 μm A 0.2 μm charge generation layer and a 22 μm charge transport layer were formed. Metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , irradiation time: irradiation for 30 seconds, and then drying at 150 ° C. for 30 minutes to obtain the electrophotographic photoreceptor of the present invention. It was.
[Coating liquid for undercoat layer]
Alkyd resin 6 parts (Beckosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.)
Titanium oxide 40 parts Methyl ethyl ketone 50 parts [Coating liquid for charge generation layer]
Bisazo pigment of the following structural formula (I) 2.5 parts Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 part Cyclohexanone 200 parts Methyl ethyl ketone 80 parts

構造式I
〔電荷輸送層用塗工液〕
合成例１のポリカーボネート共重合体 ２部
炭素−炭素二重結合を有する電荷輸送物質Ｎｏ．１ ２部
トリメチロールプロパントリアクリレート（ＴＭＰＴＡ） ０．５部
光重合開始剤 ０．２部
１−ヒドロキシ−シクロヘキシル−フェニル−ケトン
（イルガキュア１８４、チバ・スペシャルティ・ケミカルズ製）
テトラヒドロフラン（ＴＨＦ） １６部
１％シリコーンオイル（ＫＦ５０ 信越化学社製）ＴＨＦ溶液 ０．１部
＜実施例５〜８＞
実施例４と同様にして表２の電荷輸送層用塗工液のポリカーボネート樹脂と電荷輸送物質に変えて本発明の感光体を作成した。

Structural formula I
[Coating liquid for charge transport layer]
Polycarbonate copolymer of Synthesis Example 1 2 parts Charge transport material No. 1 having a carbon-carbon double bond 1 2 parts Trimethylolpropane triacrylate (TMPTA) 0.5 part Photopolymerization initiator 0.2 part 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran (THF) 16 parts 1% silicone oil (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) THF solution 0.1 part <Examples 5 to 8>
A photoconductor of the present invention was prepared in the same manner as in Example 4 except that the polycarbonate resin and charge transport material of the charge transport layer coating solution shown in Table 2 were used.

＜比較例１＞
実施例４と同様に下引き層、電荷発生層を設けた上に下記電荷輸送層２２μｍを設けた。
〔電荷輸送層用塗工液〕
ビスフェノールＺポリカーボネート １０部
（パンライトＴＳ−２０５０、帝人化成製）
下記構造式（II）の低分子電荷輸送物質（Ｄ−１） ７部
テトラヒドロフラン １００部
１％シリコーンオイルのテトラヒドロフラン溶液 ０．２部
（ＫＦ５０−１００ＣＳ、信越化学工業製）

<Comparative Example 1>
In the same manner as in Example 4, the undercoat layer and the charge generation layer were provided, and the following charge transport layer 22 μm was provided.
[Coating liquid for charge transport layer]
Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals)
Low molecular charge transport material (D-1) having the following structural formula (II) 7 parts Tetrahydrofuran 100 parts 1% silicone oil tetrahydrofuran solution 0.2 part (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

構造式II
＜比較例２＞
実施例４と同様に下引き層、電荷発生層を設けた上に下記電荷輸送層２２μｍを設けた。
〔電荷輸送層用塗工液〕
合成例１のポリカーボネート共重合体 ２部
下記構造式（II）の低分子電荷輸送物質（Ｄ−１） １．４部
テトラヒドロフラン １４部
１％シリコーンオイルのテトラヒドロフラン溶液 ０．１部
（ＫＦ５０−１００ＣＳ、信越化学工業製）

Structural formula II
<Comparative example 2>
In the same manner as in Example 4, the undercoat layer and the charge generation layer were provided, and the following charge transport layer 22 μm was provided.
[Coating liquid for charge transport layer]
Polycarbonate copolymer of Synthesis Example 1 2 parts Low molecular charge transport material (D-1) having the following structural formula (II) 1.4 parts Tetrahydrofuran 14 parts Tetrahydrofuran solution of 1% silicone oil 0.1 part (KF50-100CS, (Shin-Etsu Chemical)

構造式II
＜評価＞
硬度計測にはフィシャー・インストルメンツ社製、微小硬度計 Ｈ−１００を用いて、ビッカース圧子９．８ｍＮの力で３０秒で押し込み、５秒保持し、９．８ｍＮの力で３０秒間で抜き、マルテンス硬度、変形回復率を求めた。結果を以下に示す。

Structural formula II
<Evaluation>
For hardness measurement, a microhardness meter H-100 manufactured by Fischer Instruments Co., Ltd., was pressed in 30 seconds with a force of Vickers indenter of 9.8 mN, held for 5 seconds, and extracted with a force of 9.8 mN in 30 seconds. Martens hardness and deformation recovery rate were determined. The results are shown below.

実施例４〜８、比較例１、２の電子写真感光体について、Ａ４サイズ１万枚の通紙試験を実施した。まず、前記感光体を電子写真装置用プロセスカートリッジに装着し、画像露光光源として６５５ｎｍの半導体レーザーを用いたリコー製ｉｍａｇｉｏ Ｎｅｏ ２７０改造機にて初期暗部電位を−７００Ｖに設定した。その後通紙試験を開始し、１万枚複写後の膜厚減少量の測定を行なった。結果を以下に示す。なお、初期から画像不良が著しい感光体は通紙試験を中止した。

The electrophotographic photosensitive members of Examples 4 to 8 and Comparative Examples 1 and 2 were subjected to a paper passing test of 10,000 sheets of A4 size. First, the photosensitive member was mounted on a process cartridge for an electrophotographic apparatus, and the initial dark portion potential was set to −700 V with a Ricoh imagio Neo 270 remodeling machine using a 655 nm semiconductor laser as an image exposure light source. Thereafter, a paper passing test was started, and the amount of film thickness reduction after copying 10,000 sheets was measured. The results are shown below. In addition, the sheet passing test was stopped for the photoconductor having a remarkable image defect from the beginning.

  The film thickness was measured with an eddy current film thickness meter Fischerscope MMS manufactured by Fischer Instruments.

以上のように本発明の感光体は機械的強度が高く、耐摩耗性が高いものであり、高耐久性が高い。

As described above, the photoreceptor of the present invention has high mechanical strength, high wear resistance, and high durability.

<Example 9>
By coating and drying an intermediate layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution of the following composition in sequence on a φ100 mm aluminum cylinder, a 3.5 μm intermediate layer, 0.2 μm And a charge transport layer of 20 μm were formed. Further, a crosslinked surface layer coating solution was applied thereon by a spray method, photocured with a photocuring apparatus, and then dried at 150 ° C. for 30 minutes to provide a 7 μm cured charge transporting layer.
[Coating liquid for intermediate layer]
The following composition was dispersed and adjusted with a ball mill for 24 hours.

Alkyd resin 6 parts (Beccosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink and Chemicals)
Titanium oxide (CREL Ishihara Sangyo Co., Ltd.) 40 parts Methyl ethyl ketone 200 parts [Coating liquid for charge generation layer]
The following composition was dispersed and adjusted with a ball mill for 24 hours.

Oxotitanium phthalocyanine pigment 2 parts Polyvinyl butyral (UCC: XYHL) 0.2 part Tetrahydrofuran 50 parts [Coating liquid for charge transport layer]
The following composition was dissolved and adjusted.

Polystyrene (MW1C, manufactured by Toyo Styrene Co., Ltd.) 12 parts Low molecular charge transport material of the following structural formula (V) 12 parts

構造式V
ＴＨＦ ９０部
１％シリコーンオイル（ＫＦ５０信越シリコーン社製）ジクロルメタン溶液
１部
〔架橋表面層用塗工液〕
合成例２のポリカーボネート共重合体 １部
Ｎｏ．２０の化合物 １部
ペンタエリスリトールテトラアクリレート
（ＳＲ−２９５、日本化薬製） ０．５部
ジトリメチロールプロパンテトラアクリレート
（ＳＲ−３５５、日本化薬製） ０．２５部
光重合開始剤 ０．２部
１−ヒドロキシ−シクロヘキシル−フェニル−ケトン
（イルガキュア１８４、チバ・スペシャルティ・ケミカルズ製）
テトラヒドロフラン ３０部
シクロヘキサノン １０部
＜実施例１０＞
実施例９と同様にして下引き層、電荷発生層、電荷輸送層を設けた上に下記表面架橋層を実施例９と同様に設けた。
〔架橋表面層用塗工液〕
合成例１のポリカーボネート共重合体 １部
Ｎｏ．２４の化合物 １部
ペンタエリスリトールテトラアクリレート
（ＳＲ−２９５、日本化薬製） ０．５部
ジトリメチロールプロパンテトラアクリレート
（ＳＲ−３５５、日本化薬製） ０．２５部
光重合開始剤 ０．２部
１−ヒドロキシ−シクロヘキシル−フェニル−ケトン
（イルガキュア１８４、チバ・スペシャルティ・ケミカルズ製）
テトラヒドロフラン ３０部
シクロヘキサノン １０部
＜比較例３＞
実施例９と同様に中間層、電荷発生層を設けた上に電荷輸送層バインダー樹脂をＺポリカ樹脂（ＴＳ２０５０ 帝人化成社製）に変え、膜厚を２７μｍを順次、塗布乾燥することにより感光体を作成した。

Structural formula V
90 parts of THF 1% silicone oil (KF50 manufactured by Shin-Etsu Silicone) dichloromethane solution
1 part [Coating liquid for cross-linked surface layer]
1 part of the polycarbonate copolymer of Synthesis Example 2 20 compounds 1 part Pentaerythritol tetraacrylate (SR-295, manufactured by Nippon Kayaku) 0.5 part Ditrimethylolpropane tetraacrylate (SR-355, manufactured by Nippon Kayaku) 0.25 part Photopolymerization initiator 0.2 part 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran 30 parts Cyclohexanone 10 parts <Example 10>
In the same manner as in Example 9, an undercoat layer, a charge generation layer, and a charge transport layer were provided, and the following surface cross-linked layer was provided in the same manner as in Example 9.
[Coating liquid for cross-linked surface layer]
1 part of the polycarbonate copolymer of Synthesis Example 1 24 compounds 1 part Pentaerythritol tetraacrylate (SR-295, manufactured by Nippon Kayaku) 0.5 part Ditrimethylolpropane tetraacrylate (SR-355, manufactured by Nippon Kayaku) 0.25 part Photopolymerization initiator 0.2 part 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran 30 parts Cyclohexanone 10 parts <Comparative Example 3>
In the same manner as in Example 9, an intermediate layer and a charge generation layer were provided, and the charge transport layer binder resin was changed to Z polycarbonate resin (TS2050, manufactured by Teijin Kasei Co., Ltd.). It was created.

  The photoreceptors of Examples 6 and 7 and Comparative Example 3 were mounted on the apparatus shown in FIG. 3 and Imagio Neo1050Pro manufactured by Ricoh Co., Ltd., and 1,000,000 sheets were tested.

本来比較例は架橋表面層がないものではあるが、使用した電荷輸送層バインダー樹脂がポリスチレン表層であると機械的強度がなく耐久試験には適さないため強靱なＺポリカ樹脂とした。

The comparative example originally has no cross-linked surface layer, but if the charge transport layer binder resin used is a polystyrene surface layer, it has mechanical strength and is not suitable for a durability test, so it was made a tough Z-polyca resin.

<Example 11>
(Dispersion 1)
A 15 cm ball mill pot was charged with the following charge generation material and solvent, and ball milled for 48 hours using 10φ zirconia media, and then 500 parts of cyclohexanone was added to adjust the mill base.

    22 parts of charge generating substance of the following structural formula

シクロヘキサノン ４００部
（塗工液１）
テトラヒドロフラン（ＴＨＦ） ６６部
合成例２のポリカーボネート共重合体 ８部
Ｎｏ．２４化合物 ４部
ポリエチレングリコール ０．２部
（イオネットＭＣ１４００ 三洋化成社）
シリコーンオイル（ＫＦ５０ 信越化学社製） ０．０１部
分散液１を１２部、塗工液１を２０部、混合攪拌して塗工液２を調整した。

400 parts of cyclohexanone (Coating fluid 1)
Tetrahydrofuran (THF) 66 parts Polycarbonate copolymer of Synthesis Example 2 8 parts 24 compounds 4 parts Polyethylene glycol 0.2 parts (Ionette MC1400 Sanyo Kasei)
Silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.01 part 12 parts of dispersion 1 and 20 parts of coating liquid 1 were mixed and stirred to prepare coating liquid 2.

A solution of 10 parts of polyamide resin (CM8000 manufactured by Toray Industries, Inc.), 220 parts of methanol, and 100 parts of n-butanol is dip-coated at 5 mm / sec on a φ30 mm aluminum cylinder, dried at 100 ° C. for 10 minutes, and below 0.3 μm. A pull layer was provided. The coating solution 2 was coated thereon to provide a 20 μm single layer photoreceptor. This was irradiated with light under the conditions of a metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , irradiation time: 60 seconds, and then dried at 150 ° C. for 30 minutes, and the electrophotographic photoreceptor of the present invention. Got.

<Comparative example 4>
(Coating fluid 3)
Tetrahydrofuran (THF) 66 parts Polycarbonate resin (C1400, manufactured by Teijin Chemicals Ltd.) 8 parts Low molecular charge transport material (D-1) of the following structural formula (II) 4 parts

構造式II
ポリエチレングリコール
（イオネットＭＣ１４００、三洋化成社） ０．２部
シリコーンオイル（ＫＦ５０ 信越化学社製） ０．０１部
分散液１を１２部、塗工液３を２０部、混合攪拌して塗工液４を調整した。

Structural formula II
Polyethylene glycol (Ionette MC1400, Sanyo Chemical Co., Ltd.) 0.2 part Silicone oil (KF50, Shin-Etsu Chemical Co., Ltd.) 0.01 part Dispersion 1 is 12 parts, coating liquid 3 is 20 parts, and the mixture is stirred and applied to coating liquid 4 Adjusted.

  A solution of 10 parts of polyamide resin (CM8000 manufactured by Toray Industries, Inc.), 220 parts of methanol, and 100 parts of n-butanol is dip coated on a φ30 mm aluminum cylinder and dried at 100 ° C. for 10 minutes to provide an undercoat layer of 0.3 μm. It was. A coating liquid 4 was applied thereon to prepare a 20 μm comparative photoconductor.

  Example 11 and Comparative Example 4 were mounted on a process cartridge for an electrophotographic apparatus, a 655 nm semiconductor laser was used as an image exposure light source, and an initial dark portion was obtained with a modified Ricoh imagio Neo 270 machine having a positive charge polarity. The potential was set to 700V. Thereafter, a paper passing test was started and a 1000 sheet copying test was conducted.

  Example 11 was a clear image, but the photoreceptor of Comparative Example 4 was confirmed to generate white lines and black lines. This is considered to be due to the difference in surface hardness, and it is considered that the photoconductor of the example was cross-linked to improve the scratch resistance with increasing hardness and to obtain a clear image.

  The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to such specific embodiments, and various modifications can be made within the scope of the gist of the present invention described in the claims.・ Change is possible.

1 is an example of a cross-sectional view of an electrophotographic photosensitive member of the present invention. It is another example of sectional drawing of the electrophotographic photosensitive member of this invention. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. FIG. 2 is a schematic diagram illustrating an example of a process cartridge for an image forming apparatus according to the present invention. It is a graph which shows the infrared spectrum of the distyryl monomer of this invention. It is a graph which shows the infrared spectrum of the distyryl polycarbonate of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Pre-transfer charger 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation claw 13 Pre-cleaning charger 14 Fur brush 15 Cleaning blade 31 Conductivity Support 33 Photosensitive layer 35 Charge generation layer 37 Charge transport layer 39 Protective layer 101 Photosensitive drum 102 Charging device 103 Exposure device 104 Development device 105 Transfer body 106 Transfer device 107 Cleaning blade

Claims (12)

General formula

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
In polycarbonate having a di stilbene polycarbonate units represented, carbon - electrophotographic photoreceptor composition comprising a polymerizable charge transport material quality carbon double bonds and having a layer is cured.   General formula

(Wherein R ¹ And R ² Are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )
A composition comprising a polycarbonate having a distilbene polycarbonate unit represented by the following formula, a polymerizable charge transporting substance having a carbon-carbon double bond, and a radically polymerizable monomer having an acryloyloxy group and / or a methacryloyloxy group is cured. An electrophotographic photosensitive member, comprising: General formula

(Wherein, ^{R 1} and ^{R 2} are independently a hydrogen atom or a carbon number from 1 to 4 alkyl groups, ^{R 3} and ^{R 4} each independently represent a hydrogen atom or a carbon number from 1 to 4 An alkyl group, a cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and A is a single bond, —O—, —CO—, —S—, _{-SO -, - SO 2 -,} - SiO (CH 3) 2 -, the formula
-CR ⁵ R ⁶ -
(Wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. )
A 1,5-cycloalkylidene group having 5 to 11 carbon atoms, a and b are each independently an integer of 0 to 4, h and i are mol%, h is 5 to 80, and i is 20 to 95. )
In a polycarbonate copolymer having a di-stilbene carbonate units and bisphenol-derivative carbonate units shown, carbon-containing - to have a layer including a composition of a polymerizable charge transport material having a carbon-carbon double bond is cured An electrophotographic photoreceptor characterized by the above .   General formula

(Wherein R ¹ And R ² Are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; ³ And R ⁴ Are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and A is Single bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -SiO (CH ₃ ) ₂ -, General formula
  -CR ⁵ R ⁶ −
(Wherein R ⁵ And R ⁶ Are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. )
A 1,5-cycloalkylidene group having 5 to 11 carbon atoms, a and b are each independently an integer of 0 to 4, h and i are mol%, h is 5 to 80, and i is 20 to 95. )
A polycarbonate copolymer having a distilbene carbonate unit and a bisphenol derivative-type carbonate unit represented by formula (1), a polymerizable charge transport material having a carbon-carbon double bond, and a radical polymerizability having an acryloyloxy group and / or a methacryloyloxy group. An electrophotographic photosensitive member comprising a layer in which a composition containing a monomer is cured. The polymerizable charge transport material has the general formula

(In the formula, Act is an acryloyloxy group, a methacryloyloxy group or a vinyl group, and R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. Wherein c and d are of the formula
1 ≦ c + d ≦ 4
It is an integer that satisfies )
Or a compound represented by the general formula

(In the formula, Act is an acryloyloxy group, a methacryloyloxy group or a vinyl group, and R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or An alkoxy group having 1 to 4 carbon atoms, and e and f have the formula
1 ≦ e + f ≦ 4
It is an integer that satisfies )
The electrophotographic photosensitive member according to any one of claims 1 to 4, characterized in that in a compound represented. The polymerizable charge transport material has the general formula

(In the formula, Act is an acryloyloxy group, a methacryloyloxy group, or a vinyl group, R ²⁰ and R ²¹ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar ¹ is A substituted or unsubstituted arylene group, g, k and o are each independently an integer of 0 to 2, and v is 0 or 1.
The electrophotographic photosensitive member according to any one of claims 1 to 4, characterized in that in a compound represented. The polymerizable charge transport material has the general formula

(In the formula, Act is an acryloyloxy group, a methacryloyloxy group, or a vinyl group, and R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. And p and q are each independently an integer of 0 to 2.)
The electrophotographic photosensitive member according to any one of claims 1 to 4, characterized in that in a compound represented. The polymerizable charge transport material has the general formula

(In the formula, Act is an acryloyloxy group, a methacryloyloxy group or a vinyl group, Ar ² and Ar ³ are substituted or unsubstituted aryl groups, and B is a general formula

(Wherein R ²⁴ and R ²⁵ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group.)
And r is an integer of 1 to 2. )
The electrophotographic photosensitive member according to any one of claims 1 to 4, characterized in that in a compound represented. The polymerizable charge transport material has the general formula

(In the formula, Act is an acryloyloxy group, a methacryloyloxy group or a vinyl group, Ar ⁴ is a substituted or unsubstituted aryl group, and s and u are each independently an integer of 0 to 2. .)
The electrophotographic photosensitive member according to any one of claims 1 to 4, characterized in that in a compound represented. 請 Motomeko using electronic photosensitive member according to any one of 1 to 9, an image forming method and forming an image. 請 Motomeko image forming apparatus characterized by having an electrophotographic photosensitive member according to any one of 1 to 9. The electrophotographic photosensitive member according to any one of claims 1 to 9 ,
Features and to pulp b Seth cartridge that is detachable to the main body of the image forming apparatus.

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