JP2005115322A - Electrophotographic photoreceptor, image forming method using the same, image forming apparatus and process cartridge for image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which has high wear resistance and good electrical properties and realizes higher image quality for a long period, an image forming method using such long-life and high-performance photoreceptor, an image forming apparatus, and a process cartridge for the image forming apparatus. <P>SOLUTION: In the electrophotographic photoreceptor having at least a charge generating layer and a charge transport layer on a conductive support, the charge transport layer has at least two or more stacked layer structures and the surface layer is a crosslinked layer formed by curing at least a tri- or higher functional radical-polymerizable monomer not having a charge transport structure and a radical-polymerizable compound having the charge transport structure, and the charge transport layer in contact with the surface layer contains a polymeric charge transport material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member that has high durability and realizes high image quality over a long period of time by using a photosensitive layer having high wear resistance and good electrical characteristics. The present invention also relates to an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus using the long-life and high-performance photoconductor.

  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 systems 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 is required to increase its rubber hardness and contact pressure for the purpose of improving the cleaning property as the particle size of the toner particles is reduced. This also promotes the wear of the photoreceptor. It 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.
Techniques for improving the abrasion resistance of the photosensitive layer include (1) using a curable binder for the surface layer (for example, see Patent Document 1), and (2) using a polymeric charge transport material (for example, , Patent Document 2), (3) Those in which an inorganic filler is dispersed in the surface layer (for example, see Patent Document 3), and the like. Among these techniques, those using the curable binder (1) have poor compatibility with the charge transport material, and the residual potential increases due to impurities such as polymerization initiators and unreacted residues, resulting in a decrease in image density. Tends to occur. In addition, although the polymer charge transport material (2) can improve the abrasion resistance to some extent, the durability required for the organic photoreceptor is not fully satisfied. Not reached. The dispersion of the inorganic filler (3) exhibits higher wear resistance than a photoconductor in which a normal low molecular charge transport material is dispersed in an inert polymer, but traps present on the surface of the inorganic filler. As a result, the residual potential rises and the image density tends to decrease. In addition, when the unevenness of the inorganic filler and the binder resin on the surface of the photoconductor is large, defective cleaning may occur, which may cause toner filming and image flow. These techniques (1) to (3) do not sufficiently satisfy the overall durability including the electrical durability and mechanical durability required for the organic photoreceptor.

Furthermore, a photoreceptor containing a polyfunctional acrylate monomer cured product in order to improve the abrasion resistance and scratch resistance of (1) is also known (see Patent Document 4). However, in this photoreceptor, although there is a description that the polyfunctional acrylate monomer cured product is contained in the protective layer provided on the photosensitive layer, the protective layer may contain a charge transport material. However, when the surface layer contains a low-molecular charge transport material, there is a problem of compatibility with the cured product. In some cases, the molecular charge transport material is precipitated and the cloudiness phenomenon occurs, and the mechanical strength is also lowered.
Furthermore, since this photoconductor specifically reacts with a monomer in a state containing a polymer binder, curing does not proceed sufficiently, and there is a problem of compatibility between the cured product and the binder resin. There was a tendency for surface irregularities due to phase separation to cause poor cleaning.

  As a wear resistance technology for a photosensitive layer that replaces these, a charge transport layer formed by using a coating liquid comprising a monomer having a carbon-carbon double bond, a charge transport material having a carbon-carbon double bond, and a binder resin. It is known to provide (for example, refer to Patent Document 5), and the binder resin has a carbon-carbon double bond and is reactive to the charge transfer agent, and the double bond. And those that do not have reactivity. This photoconductor is remarkably compatible with wear resistance and good electrical properties, but when a non-reactive binder resin is used, the binder resin, the monomer and the charge transport agent are used. The compatibility with the cured product produced by this reaction was poor, and surface irregularities were generated during cross-linking from layer separation, and a tendency to cause poor cleaning was observed. Further, as described above, in this case, the binder resin prevents the curing of the monomer, and what is specifically described as the monomer used in the photoreceptor is a bifunctional one. The monomer has a small number of functional groups and a sufficient crosslinking density cannot be obtained, and these points have not yet been satisfactory in terms of wear resistance. Further, even when a reactive binder is used, due to the low number of functional groups contained in the monomer and the binder resin, it is difficult to achieve both the binding amount and the crosslinking density of the charge transport material, and the electrical characteristics and The abrasion resistance was not sufficient. As means for increasing the crosslinking density and improving the wear resistance, a method of decreasing the binder resin content or increasing the number of functional groups of the monomer having a carbon-carbon double bond can be considered. The film thickness of the charge transport layer varies depending on the system to be used (particularly charging potential), but is required to be at least 5 μm or more, and 10 μm or more is necessary in consideration of long-term use. Thus, when the charge transport layer thickness is 10 μm or more, when the content of the binder resin is decreased or the number of functional groups of the monomer having a carbon-carbon double bond is increased to form a film, The internal strain is increased, the internal stress is increased, and the charge transport layer is easily cracked.

As a means for improving wear resistance by increasing the crosslinking density, maintaining the charge transport layer thickness more than the necessary minimum, and suppressing the occurrence of cracks, it is conceivable to form the charge transport layer in a laminated configuration. . That is, a hole transporting compound having a chain polymerizable functional group is cross-linked on a charge transporting layer mainly composed of a low molecular charge transporting material and an inert polymer. By laminating the charge transport layer, it is possible to maintain a film thickness that is more than the necessary minimum (see, for example, Patent Document 6).
By adopting such a configuration, a charge transport layer with improved wear resistance can be formed initially. However, when used for a long period of time, there was a problem that the wear resistance gradually decreased. This is caused by the low molecular charge transport material constituting the charge transport material as the lower layer contained in the cross-linked film having the charge transport function. That is, when a crosslinkable charge transport layer is formed on a charge transport layer mainly composed of a low molecular charge transport material and an inert polymer, the lower molecular charge transport material is a crosslinkable charge transport layer coating solvent. It was found that it was dissolved in, and oozed out into the upper layer, thereby reducing the cross-linking density of the upper cross-linked film. For this reason, when the charge transport layer, which initially had good wear resistance, was used for a long period of time, there was a problem that the wear resistance gradually decreased as wear progressed.
Even in the conventional photoconductors having a cross-linked photosensitive layer in which a charge transporting structure is chemically bonded, it cannot be said that the present invention has sufficient comprehensive characteristics.

JP 56-48637 A JP-A 64-1728 JP-A-4-281461 Japanese Patent No. 3262488 Japanese Patent No. 3194392 JP 2000-66425 A

  An object of the present invention is to provide an electrophotographic photosensitive member that has high wear resistance, good electrical characteristics, and high image quality over a long period of time. To provide an image forming method, an image forming apparatus, and a process cartridge for an image forming apparatus using a photoconductor.

  As a result of intensive studies, the present inventors have found that in an electrophotographic photoreceptor having at least a charge generation layer and a charge transport layer on a conductive support, the charge transport layer has a laminated structure of at least two layers, and The surface layer is a cross-linked layer obtained by curing a tri- or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure, and the charge transport layer in contact with the surface layer is a polymer. It has been found that the object can be achieved by using a layer containing a charge transport material, and the present invention has been achieved.

  That is, the above-described problem is (1) “in an electrophotographic photoreceptor having at least a charge generation layer and a charge transport layer on a conductive support, and the charge transport layer has a laminate structure of at least two layers. A charge transport layer in which the surface layer is a crosslinked layer obtained by curing a radical polymerizable compound having a charge transport structure and a tri- or higher functional radical polymerizable monomer having at least a charge transport structure and in contact with the surface layer; An electrophotographic photosensitive member characterized by being a layer containing a polymer charge transporting substance ”, (2)“ the polymer charge transporting substance has a triarylamine structure in the main chain or branched chain; The electrophotographic photosensitive member according to item (1) above, (3) “The polymer charge transport material has a structure represented by the following general formula I: (1) Term or number 2) The electrophotographic photosensitive member according to claim;

〔但し、一般式Ｉ中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ独立して置換もしくは無置換のアルキル基又はハロゲン原子を表わし、Ｒ_４は水素原子又は置換もしくは無置換のアルキル基を表わし、Ｒ_５、Ｒ_６は置換もしくは無置換のアリール基を表わす。ｏ、ｐ、ｑはそれぞれ独立して０〜４の整数、ｋ，ｊは全構成単位の個数を１としたときの各構成単位の組成比を表わし、０．１≦ｋ≦１、０≦ｊ≦０．９、ｎは繰り返し単位数を表わし５〜５０００の整数である。Ｘは脂肪族炭化水素の２価基、環状脂肪族炭化水素の２価基、若しくは下記一般式（１）又は（２）で表わされる２価基を表わす。

[In the general formula I, R ₁ , R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group or a halogen atom, and R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group, R ₅ and R ₆ represent a substituted or unsubstituted aryl group. o, p and q are each independently an integer of 0 to 4, k and j are the composition ratios of the respective structural units when the number of all the structural units is 1, and 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9 and n represents the number of repeating units and is an integer of 5 to 5000. X represents a divalent group of an aliphatic hydrocarbon, a divalent group of a cyclic aliphatic hydrocarbon, or a divalent group represented by the following general formula (1) or (2).

（但し、一般式（１）中、Ｒ_１０１、Ｒ_１０２は各々独立して置換もしくは無置換のアルキル基、アリール基又はハロゲン原子を表わし、それぞれ同一でも異なっていてもよい。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、または−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表わす。）基を表わす。）

(In the general formula (1), R ₁₀₁ and R ₁₀₂ each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom, and may be the same or different. to 4 integer, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 -, - CO-, Or —CO—O—Z—O—CO— (wherein Z represents an aliphatic divalent group).

（但し、一般式（２）中、ａは１〜２０の整数、ｂは１〜２０００の整数、Ｒ_１０３、Ｒ_１０４は置換又は無置換のアルキル基又はアリール基を表わし、それぞれ同一でも異なってもよい。）〕」、（４）「前記高分子電荷輸送物質が、下記一般式IIで表わされる化学構造を有することを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(However, in General formula (2), a is an integer of 1-20, b is an integer of 1-2000, R < ₁₀₃ >, R < ₁₀₄ > represents a substituted or unsubstituted alkyl group or aryl group, and is the same or different, respectively. ]], (4) “The polymer charge transport material has a chemical structure represented by the following general formula II,” (1) or (2), Electrophotographic photoreceptor;

（但し、一般式II中、Ｒ_７、Ｒ_８は置換もしくは無置換のアリール基、Ａｒ_１、Ａｒ_２、Ａｒ_３は同一又は異なるアリーレン基を表わす。Ｘ，ｋ，ｊおよびｎは、一般式Ｉの場合と同じである。）」、（５）「前記高分子電荷輸送物質が、下記一般式IIIで表わされる化学構造を有することを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the general formula II, R ₇ and R ₈ are substituted or unsubstituted aryl groups, Ar ₁ , Ar ₂ and Ar ₃ are the same or different arylene groups. X, k, j and n are the general formulas) The same as in the case of I.) ”, (5)“ The polymer charge transporting substance has a chemical structure represented by the following general formula III, ”(1) or (2) The electrophotographic photosensitive member according to the item;

（但し、一般式III中、Ｒ_９、Ｒ_１０は置換もしくは無置換のアリール基、Ａｒ_４、Ａｒ_５、Ａｒ_６は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）、（６）「前記高分子電荷輸送物質が、下記一般式IVで表わされる化学構造を有することを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the general formula III, R ₉ and R ₁₀ represent substituted or unsubstituted aryl groups, Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n represent the general formula (6) “The polymer charge transporting material has a chemical structure represented by the following general formula IV: An electrophotographic photosensitive member according to claim 1;

（但し、一般式IV中、Ｒ_１１、Ｒ_１２は置換もしくは無置換のアリール基、Ａｒ_７、Ａｒ_８、Ａｒ_９は同一又は異なるアリーレン基、ｓは１〜５の整数を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）」、（７）「前記高分子電荷輸送物質が、下記一般式Ｖで表わされる化学構造を有することを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the general formula IV, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups, Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, and s represents an integer of 1 to 5. X, k , J and n are the same as those in formula I)), (7) “The polymer charge transport material has a chemical structure represented by the following formula V: The electrophotographic photosensitive member according to item 1) or (2);

（但し、一般式Ｖ中、Ｒ_１３、Ｒ_１４は置換もしくは無置換のアリール基、Ａｒ_１０、Ａｒ_１１、Ａｒ_１２は同一又は異なるアリーレン基、Ｘ_１、Ｘ_２は置換もしくは無置換のエチレン基、又は置換もしくは無置換のビニレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）」、（８）「前記高分子電荷輸送物質が、下記一般式VIで表わされる構造を有することを特徴とする前記第（１）項乃至第（７）項のいずれかに記載の電子写真感光体；

(In the general formula V, R ₁₃ and R ₁₄ are substituted or unsubstituted aryl groups, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups, and X ₁ and X ₂ are substituted or unsubstituted ethylene groups. Or a substituted or unsubstituted vinylene group, wherein X, k, j and n are the same as in the case of the general formula I.) ”, (8)“ The polymer charge transport material is represented by the following general formula VI The electrophotographic photosensitive member according to any one of (1) to (7) above, which has a structure represented by:

（但し、一般式VI中、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８は置換もしくは無置換のアリール基、Ａｒ_１３、Ａｒ_１４、Ａｒ_１５、Ａｒ_１６は同一又は異なるアリーレン基、Ｙ_１、Ｙ_２、Ｙ_３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表わし、同一であっても異なってもよい。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）」、（９）「前記高分子電荷輸送物質が、下記一般式VIIで表わされる化学構造を有することを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the general formula VI, R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ , Y ₃ represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, X, k, j and n are the same as in the case of general formula I.) ”, (9)“ The polymer charge transport material has a chemical structure represented by the following general formula VII: The electrophotographic photosensitive member according to item (1) or (2), wherein:

（但し、一般式VII中、Ｒ_１９、Ｒ_２０は水素原子、置換もしくは無置換のアリール基を表わし、Ｒ_１９とＲ_２０は環を形成していてもよい。Ａｒ_１７、Ａｒ_１８、Ａｒ_１９は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）」、（１０）「前記高分子電荷輸送物質として、下記一般式VIIIで表わされる化学構造を有することを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(However, in General Formula VII, R ₁₉ and R _{20 each} represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ , Ar ₁₉ Represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula I.), (10) “The polymer charge transport material is represented by the following general formula VIII. The electrophotographic photosensitive member according to item (1) or (2), which has a chemical structure;

（但し、一般式VIII中、Ｒ_２１は置換もしくは無置換のアリール基、Ａｒ_２０、Ａｒ_２１、Ａｒ_２２、Ａｒ_２３は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）」、（１１）「前記高分子電荷輸送物質が、下記一般式IXで表わされる構造を有することを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the general formula VIII, R ₂₁ represents a substituted or unsubstituted aryl group, Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , Ar ₂₃ represent the same or different arylene groups. X, k, j, and n represent the general formula The same as in the case of I.) ”, (11)“ The polymer charge transporting substance has a structure represented by the following general formula IX. ”(1) or (2) An electrophotographic photosensitive member according to claim 1;

（但し、一般式IX中、Ｒ_２２、Ｒ_２３、Ｒ_２４、Ｒ_２５は置換もしくは無置換のアリール基、Ａｒ_２４、Ａｒ_２５、Ａｒ_２６、Ａｒ_２７、Ａｒ_２８は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）」、（１２）「前記高分子電荷輸送物質として、下記一般式Ｘで表わされる構造を有することを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the general formula IX, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are substituted or unsubstituted aryl groups; Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ represent the same or different arylene groups. X, k, j and n are the same as those in the general formula I.), (12) “The polymer charge transport material has a structure represented by the following general formula X: The electrophotographic photosensitive member according to (1) or (2);

（但し、一般式Ｘ中、Ｒ_２６、Ｒ_２７は置換もしくは無置換のアリール基、Ａｒ_２９、Ａｒ_３０、Ａｒ_３１は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）」、（１３）「前記表面層が有機溶剤に対して溶解しないことを特徴とする前記第（１）項乃至第（１２）項のいずれかに記載の電子写真感光体」、（１４）「前記表面層に用いられている電荷輸送性構造を有しない３官能以上のラジカル重合性モノマーがアクリレートもしくはメタクリレートであることを特徴とする前記第（１）項乃至第（１３）項のいずれかに記載の電子写真感光体」、（１５）「前記表面層に用いられている電荷輸送性構造を有しない３官能以上のラジカル重合性モノマーの分子量に対する官能基割合（分子量／官能基）が２５０以下であることを特徴とする前記第（１）項乃至第（１４）項のいずれかに記載の電子写真感光体」、（１６）「前記表面層に用いられている電荷輸送性構造を有するラジカル重合性化合物がアクリレートもしくはメタクリレートであることを特徴とする前記第（１）項乃至第（１５）項のいずれかに記載の電子写真感光体」、（１７）「前記表面層に用いられている電荷輸送性構造を有するラジカル重合性化合物が、トリアリールアミン構造を有することを特徴とする前記第（１）項乃至第（１６）項のいずれかに記載の電子写真感光体」、（１８）「前記表面層に用いられている電荷輸送性構造を有するラジカル重合性化合物が、１官能であることを特徴とする前記第（１）項乃至第（１７）項のいずれかに記載の電子写真感光体」、（１９）「前記表面層に用いられる電荷輸送性構造を有するラジカル重合性化合物が、下記一般式XI又はXIIの一種以上であることを特徴とする前記第（１）項乃至第（１８）項のいずれかに記載の電子写真感光体；

(In the general formula X, R ₂₆ and R ₂₇ are substituted or unsubstituted aryl groups, Ar ₂₉ , Ar _{30 and} Ar ₃₁ are the same or different arylene groups. X, k, j and n are the general formulas. The same as in the case of I.) ”, (13)“ Electrons according to any one of items (1) to (12), wherein the surface layer does not dissolve in an organic solvent. Photosensitive member ”, (14)“ The trifunctional or higher functional radical-polymerizable monomer having no charge transporting structure used in the surface layer is an acrylate or a methacrylate ”, The electrophotographic photosensitive member according to any one of Items (13), (15) “Percentage of functional groups with respect to molecular weight of a tri- or higher functional radical polymerizable monomer having no charge transport structure used in the surface layer ( The molecular weight / functional group) is 250 or less. The electrophotographic photosensitive member according to any one of (1) to (14) above, (16) “used for the surface layer” The electrophotographic photosensitive member according to any one of (1) to (15), wherein the radically polymerizable compound having a charge transporting structure is an acrylate or a methacrylate ”, (17) “The radically polymerizable compound having a charge transporting structure used for the surface layer has a triarylamine structure,” according to any one of the above items (1) to (16), (1) to (17), wherein the radically polymerizable compound having a charge transporting structure used in the surface layer is monofunctional. In any of the paragraphs (19) The above (1), wherein the radical polymerizable compound having a charge transporting structure used for the surface layer is one or more of the following general formula XI or XII. The electrophotographic photosensitive member according to any one of Items 1 to 18;

（但し、一般式XIおよびXII中、Ｒ_２８は水素原子、ハロゲン原子、置換又は無置換のアルキル基、置換又は無置換のアラルキル基、置換又は無置換のアリール基、シアノ基、ニトロ基、アルコキシ基、−ＣＯＯＲ_２９（Ｒ_２９は水素原子、置換又は無置換のアルキル基、置換又は無置換のアラルキル基又は置換又は無置換のアリール基）、ハロゲン化カルボニル基若しくはＣＯＮＲ_３０Ｒ_３１（Ｒ_３０及びＲ_３１は水素原子、ハロゲン原子、置換又は無置換のアルキル基、置換又は無置換のアラルキル基又は置換又は無置換のアリール基を示し、互いに同一であっても異なっていてもよい）を表わし、Ａｒ_３２、Ａｒ_３３は置換もしくは無置換のアリーレン基を表わし、同一であっても異なってもよい。Ａｒ_３４、Ａｒ_３５は置換もしくは無置換のアリール基を表わし、同一であっても異なってもよい。Ｘ_１０は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表わす。Ｚは置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキレンエーテル基、アルキレンオキシカルボニル基を表わす。ｍ_１、ｎ_１は０〜３の整数を表わす。）」、（２０）「前記表面層に用いられる電荷輸送性構造を有するラジカル重合性化合物が、下記一般式XIIIの一種以上であることを特徴とする前記第（１）項乃至第（１９）項のいずれかに記載の電子写真感光体；

(In the general formulas XI and XII, R ₂₈ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a cyano group, a nitro group, an alkoxy group. A group, —COOR ₂₉ (R ₂₉ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group), a halogenated carbonyl group or CONR ₃₀ R ₃₁ (R ₃₀ and R ₃₁ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, which may be the same or different from each other). Ar _{32, Ar 33} represents a substituted or unsubstituted arylene group, which may be identical or different _.Ar 34, _{Ar 35} represents a substituted Properly represents the unsubstituted aryl group, good .X ₁₀ be the same or different single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether A group, an oxygen atom, a sulfur atom or a vinylene group, Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether group or an alkyleneoxycarbonyl group, m ₁ and n ₁ are integers of 0 to 3; ) ”, (20)“ The radical polymerizable compound having a charge transporting structure used in the surface layer is one or more of the following general formula XIII ”: (19) The electrophotographic photosensitive member according to any one of items

（但し、一般式XIII中、ｏ_１、ｐ_１、ｑ_１はそれぞれ０又は１の整数、Ｒａは水素原子又はメチル基を表わし、Ｒｂ、Ｒｃは水素原子以外の置換基で炭素数１〜６のアルキル基を表わし、複数の場合は異なっても良い。ｓ、ｔは０〜３の整数を表わす。Ｚａは単結合、メチレン基、エチレン基、

(In the general formula XIII, o ₁ , p ₁ and q ₁ are each an integer of 0 or 1, Ra represents a hydrogen atom or a methyl group, Rb and Rc are substituents other than a hydrogen atom and have 1 to 6 carbon atoms. A plurality of alkyl groups may be different, and s and t each represents an integer of 0 to 3. Za is a single bond, a methylene group, an ethylene group,

を表わす。）」、（２１）「前記表面層の硬化手段が加熱又は光エネルギー照射手段であることを特徴とする前記第（１）項乃至第（２０）項のいずれかに記載の電子写真感光体」によって解決される。
また、上記課題は、本発明の（２２）「前記第（１）項乃至第（２１）項のいずれかに記載の電子写真感光体を用いて、少なくとも帯電、画像露光、現像、転写を繰り返し行なうことを特徴とする画像形成方法」によって解決される。
また、上記課題は、本発明の（２３）「前記第（１）項乃至第（２１）項のいずれかに記載の電子写真感光体を有することを特徴とする画像形成装置」によって解決される。
また、上記課題は、本発明の（２４）「前記第（１）項乃至第（２１）項のいずれかに記載の電子写真感光体と、帯電手段、現像手段、転写手段、クリーニング手段および除電手段よりなる群から選ばれた少なくとも一つの手段を有するものであって、画像形成装置本体に着脱可能としたことを特徴とする画像形成装置用プロセスカートリッジ」によって解決される。

Represents. ) ", (21)" Electrophotographic photosensitive member according to any one of items (1) to (20), wherein the surface layer curing means is heating or light energy irradiation means " Solved by.
In addition, the above-described problem is that at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to any one of (22) and (1) to (21) of the present invention. The image forming method is characterized in that it is solved.
Further, the above problem is solved by (23) “an image forming apparatus comprising the electrophotographic photosensitive member according to any one of (1) to (21)” of the present invention. .
In addition, the above-mentioned problems are solved by (24) “the electrophotographic photosensitive member according to any one of (1) to (21)”, a charging unit, a developing unit, a transferring unit, a cleaning unit, and a static eliminating unit. An image forming apparatus process cartridge having at least one means selected from the group consisting of means and detachable from the main body of the image forming apparatus is solved.

  The photoreceptor of the present invention has a laminate structure in which the charge transport layer has at least two layers, and the charge transport layer comprises at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a charge transport layer. And a cross-linked surface layer obtained by curing a radically polymerizable compound having a crystalline structure, and the charge transport layer in contact with the surface layer is a layer containing a polymer charge transport material. And a highly durable and high-performance photoreceptor having good electrical characteristics. Therefore, it is possible to provide a high-performance and highly reliable image forming process, an image forming apparatus, and a process cartridge for an image forming apparatus that can provide a good image over a long period of time by using this photoconductor.

Hereinafter, the present invention will be described in detail.
The present invention relates to an electrophotographic photosensitive member having at least a charge generation layer and a charge transport layer on a conductive support, wherein the charge transport layer has a laminate structure of at least two layers, and the surface layer has at least a charge transport structure. A cross-linked layer obtained by curing a tri- or higher-functional radical polymerizable monomer having no charge and a radical polymerizable compound having a charge transport structure, and the charge transport layer in contact with the surface layer contains a polymer charge transport material By using the layer, an electrophotographic photosensitive member that has high wear resistance, is stable, and realizes high image quality over a long period of time can be achieved.
The reasons for this are as follows.

  The photoreceptor of the present invention has a photosensitive layer having a structure in which a charge generation layer and a charge transport layer are laminated. The charge transport layer has a laminated structure of at least two layers. The surface layer uses a tri- or higher-functional radical polymerizable monomer, which leads to the development of a three-dimensional network structure and a highly hard crosslinked surface layer with a very high degree of crosslinking, achieving high wear resistance. Is done. On the other hand, when only monofunctional and bifunctional radically polymerizable monomers are used, the cross-linking bond in the cross-linked surface layer becomes dilute, and a dramatic improvement in wear resistance cannot be achieved. When a polymer material is contained in the cross-linked surface layer, the development of the three-dimensional network structure is inhibited and the degree of cross-linking is lowered, so that sufficient wear resistance cannot be obtained as compared with the present invention. Furthermore, the compatibility between the polymer material and the cured product resulting from the reaction of the radically polymerizable composition (radically polymerizable monomer or radically polymerizable compound having a charge transporting structure) is poor, and local separation from phase separation occurs. Wears and appears as a scratch on the surface.

  Further, in the formation of the cross-linked surface layer of the present invention, in addition to the trifunctional radical polymerizable monomer, a radical polymerizable compound having a charge transporting structure is contained, which is the trifunctional or higher functional radical polymerizable monomer. It is incorporated into the cross-linking during curing. On the other hand, when a low molecular charge transport material having no functional group is contained in the cross-linked surface layer, precipitation of the low molecular charge transport material and white turbidity occur due to its low compatibility, and the cross-linked surface layer The mechanical strength also decreases.

Further, in the photoreceptor of the present invention, the charge transport layer in contact with the crosslinked surface layer is provided with a layer containing a polymer charge transport material, thereby maintaining the wear resistance of the photoreceptor for a long period of time.
On the other hand, when the charge transport layer in contact with the cross-linked surface layer is composed of a low molecular charge transport material and an inert polymer, the lower molecular charge transport material becomes a cross-linkable charge during film formation of the cross-linked surface layer. Dissolve in the transport layer coating solvent and ooze into the upper layer. As a result, a low molecular charge transport material having no functional group is contained in the cross-linked film, the cross-linking density is lowered, and accordingly, the mechanical strength is lowered and the wear resistance is lowered. The content of the low-molecular charge transport material in the cross-linked film increases as it approaches the lower layer. Initially, the cross-linked surface layer having high wear resistance gradually deteriorates in wear resistance (the amount of wear increases) after long-term use. On the other hand, in the case where the charge transport layer in contact with the crosslinked surface layer is a layer composed of a polymer charge transport material as in the present invention, the cross-linked film as described above is low. The crosslink density does not decrease due to the molecular charge transporting material oozing out, and a highly stable electrophotographic photosensitive member that maintains initial wear resistance even when used for a long time can be obtained.

Next, the constituent material of the charge transport layer in contact with the crosslinked surface layer of the present invention will be described.
As the polymer charge transporting material used in the present invention, those having a triarylamine structure in the main chain or branched chain are effectively used. Furthermore, polymer charge transport materials represented by the following general formulas I to X are effectively used.
Examples of the polymer charge transport materials represented by the general formulas I to X are shown below.

〔但し、一般式Ｉ中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ独立して置換もしくは無置換のアルキル基又はハロゲン原子を表わし、Ｒ_４は水素原子又は置換もしくは無置換のアルキル基を表わし、Ｒ_５、Ｒ_６は置換もしくは無置換のアリール基を表わす。ｏ、ｐ、ｑはそれぞれ独立して０〜４の整数、ｋ，ｊは全構成単位の個数を１としたときの各構成単位の組成比を表わし、０．１≦ｋ≦１、０≦ｊ≦０．９、ｎは繰り返し単位数を表わし５〜５０００の整数である。Ｘは脂肪族炭化水素の２価基、環状脂肪族炭化水素の２価基、若しくは下記一般式（１）又は（２）で表わされる２価基を表わす。

[In the general formula I, R ₁ , R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group or a halogen atom, and R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group, R ₅ and R ₆ represent a substituted or unsubstituted aryl group. o, p and q are each independently an integer of 0 to 4, k and j are the composition ratios of the respective structural units when the number of all the structural units is 1, and 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9 and n represents the number of repeating units and is an integer of 5 to 5000. X represents a divalent group of an aliphatic hydrocarbon, a divalent group of a cyclic aliphatic hydrocarbon, or a divalent group represented by the following general formula (1) or (2).

（但し、一般式（１）中、Ｒ_１０１、Ｒ_１０２は各々独立して置換もしくは無置換のアルキル基、アリール基又はハロゲン原子を表わし、それぞれ同一でも異なっていてもよい。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、または−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表わす。）基を表わす。）

(In the general formula (1), R ₁₀₁ and R ₁₀₂ each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom, and may be the same or different. to 4 integer, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 -, - CO-, Or —CO—O—Z—O—CO— (wherein Z represents an aliphatic divalent group).

（但し、一般式（２）中、ａは１〜２０の整数、ｂは１〜２０００の整数、Ｒ_１０３、Ｒ_１０４は置換又は無置換のアルキル基又はアリール基を表わし、それぞれ同一でも異なってもよい。）〕

(However, in General formula (2), a is an integer of 1-20, b is an integer of 1-2000, R < ₁₀₃ >, R < ₁₀₄ > represents a substituted or unsubstituted alkyl group or aryl group, and is the same or different, respectively. It is good.)]

Description of Substituents of General Formula I (1) As described above, R ₁ , R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group or a halogen atom. Specific examples thereof are as follows: Can be the same or different.
a. Preferred examples of the alkyl group include C _{1 to} C _12, particularly C _{1 to} C ₈ , more preferably C _{1 to} C ₄ linear or branched alkyl groups, and these alkyl groups are further fluorine atoms. , a hydroxyl group, a cyano _group, an alkoxy group of C 1 -C _4, a phenyl group, or a halogen _atom, optionally substituted by a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C ₄ Also good. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
b. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
(2) R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and specific examples of the alkyl group are the same as those for R ₁ , R ₂ and R ₃ described above (see (1) a.) Is mentioned.
(3) R ₅ and R _{6 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, Examples of the 5H-dibenzo [a, d] cycloheptenylidenephenyl group and the non-condensed polycyclic group include a biphenylyl group and a terphenylyl group.
b. Heterocyclic group. For example, a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, a carbazolyl group, and the like can be given.
(4) The above aryl group has the following a. ~ G. You may have as a substituent the group shown.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Examples of the alkyl group include the same groups as those described above for R ₁ , R ₂ and R ₃ (see (1) a.).
c. An alkoxy group (—OR ₁₀₅ ; wherein R ₁₀₅ is the same as the alkyl group in (4) b. Above); Specifically, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2- Examples include cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. The aryl group may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group, or a halogen atom as a substituent.
Specifically, for example, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group, etc. Can be mentioned.
e. Substituted mercapto group or aryl mercapto group. Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f. An alkyl-substituted amino group; As the alkyl group of the alkyl-substituted amino group, the above (4) b. The thing similar to what was shown by these is mentioned, Specifically, a dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N- dibenzylamino group etc. are mentioned.
g. An acyl group. Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
(5) X is a main chain obtained by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (A) using a phosgene method, a transesterification method or the like. Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (A) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

(However, in the formula, R _{1 to} R ₆ and X are the same as those in the general formula I.)
Specific examples of the diol compound of the general formula (B) include the following.
a. Aliphatic diol.
For example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1, Aliphatic diols such as 3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene ether glycol, or And cycloaliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and cyclohexane-1,4-dimethanol.
b. Aromatic diol.
For example, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2 , 2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4- Hydroxyphenyl) cyclopentane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) ) Butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibu Lomo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxy Diphenyl sulfide, 4,4′-dihydroxydiphenyl oxide, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) ) Xanthene, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate) 1,3-bis (4-hydroxyphenyl) -tetramethyldi Shiroki Emissions, phenol-modified silicone oils.
A specific synthesis method of the general formula I is exemplified in JP-A-9-151248.

（但し、一般式II中、Ｒ_７、Ｒ_８は置換もしくは無置換のアリール基、Ａｒ_１、Ａｒ_２、Ａｒ_３は同一又は異なるアリーレン基を表わす。Ｘ，ｋ，ｊおよびｎは、一般式Ｉの場合と同じである。）

(In the general formula II, R ₇ and R ₈ are substituted or unsubstituted aryl groups, Ar ₁ , Ar ₂ and Ar ₃ are the same or different arylene groups. X, k, j and n are the general formulas) Same as I.)

Description of Substituents of General Formula II (1) R ₇ and R ₈ represent substituted or unsubstituted aryl groups. Specific examples thereof include the following a. ~ C. And may be the same or different.
a. Aromatic hydrocarbon group.
For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, Examples of the 5H-dibenzo [a, d] cycloheptenylidenephenyl group and the non-condensed polycyclic group include a biphenylyl group and a terphenylyl group.
b.

（上記式中、Ｒ_１０６は、下記（３）ａ．〜ｇ．に示す置換基と同様であり、Ｗは−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−及び以下（イ）〜（ニ）の２価基を表わす。
（イ）

(In the above formula, R ₁₀₆ is the same as the substituents shown in the following (3) a. To g., And W represents —O—, —S—, —SO—, —SO ₂ —, —CO—, and The divalent groups (a) to (d) below are represented.
(I)

（式中、ｃは１〜１２の整数を表わす。）
（ロ）

(Wherein c represents an integer of 1 to 12)
(B)

（式中、ｄは１〜３の整数を表わす。）
(ハ)

(In the formula, d represents an integer of 1 to 3.)
(C)

（式中、Ｒ_１０７は、下記（３）ａ．〜ｇ．に示す置換基と同様であり、ｅは１〜３の整数を表わす。）
（ニ）

(Wherein R ₁₀₇ is the same as the substituents shown in the following (3) a. To g., E represents an integer of 1 to 3)
(D)

（式中、Ｒ_１０８は、下記（３）ａ．〜ｇ．に示す置換基と同様であり、ｆは１〜３の整数を表わす。））
ｃ．複素環基。
例えば、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
（２）Ａｒ_１、Ａｒ_２およびＡｒ_３で示されるアリーレン基としては一般式中II中Ｒ_７およびＲ_８について示されたアリール基の２価基が挙げられ、同一であっても異なってもよい。
（３）上述のアリール基及びアリーレン基は以下ａ．〜ｇ．に示す基を置換基として有してもよい。
なお、これら置換基は上記一般式中のＲ_１０６、Ｒ_１０７、Ｒ_１０８の具体例でもある。
ａ．ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
ｂ．アルキル基。好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_１８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、又はハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有しても良い。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
ｃ．アルコキシ基（−ＯＲ_１０９）。Ｒ_１０９は上記（３）ｂ．で示されたアルキル基と同様である。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
ｄ．アリールオキシ基。アリールオキシ基のアリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有しても良い。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
ｅ．置換メルカプト基またはアリールメルカプト基。具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
ｆ．

(Wherein R ₁₀₈ is the same as the substituents shown in the following (3) a. To g., F represents an integer of 1 to 3))
c. Heterocyclic group.
For example, a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, a carbazolyl group, and the like can be given.
(2) The arylene group represented by Ar ₁ , Ar ₂ and Ar ₃ includes the divalent group of the aryl group represented by R ₇ and R ₈ in II in the general formula. Good.
(3) The above aryl group and arylene group are represented by the following a. ~ G. You may have as a substituent the group shown.
These substituents are also specific examples of R ₁₀₆ , R ₁₀₇ , and R _{108 in} the above general formula.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₁₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further fluorine atom, hydroxyl group, cyano group, C 1 ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C _4. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
c. An alkoxy group (—OR ₁₀₉ ); R ₁₀₉ is the above (3) b. It is the same as the alkyl group shown by. Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
e. Substituted mercapto group or aryl mercapto group. Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f.

（式中、Ｒ_１１０及びＲ_１１１は各々独立に上記（３）ｂ．で示したアルキル基、またはアリール基を表わし、アリール基としては例えばフェニル基、ビフェニル基、またはナフチル基が挙げられ、これらはＣ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有しても良い。またアリール基上の炭素原子と共同で環を形成しても良い。
具体的には、ジエチルアミノ基、Ｎ−メチル−Ｎ−フェニルアミノ基、Ｎ，Ｎ−ジフェニルアミノ基、Ｎ，Ｎ−ジ（ｐ−トリル）アミノ基、ジベンジルアミノ基、ピペリジノ基、モルホリノ基、ユロリジル基等が挙げられる。
ｇ．メチレンジオキシ基、またはメチレンジチオ基等のアルキレンジオキシ基またはアルキレンジチオ基等。
（４）Ｘは下記一般式（Ｃ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、又はブロック共重合体となる。また、Ｘは下記一般式（Ｃ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。

(In the formula, R ₁₁₀ and R ₁₁₁ each independently represents the alkyl group or aryl group shown in (3) b.), And examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. alkoxy groups C ₁ ~C _4, C ₁ ~C may contain ₄ alkyl group or a halogen atom as a substituent. also it may form a ring in cooperation with carbon atoms on the aryl groups.
Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group, Examples include a yurolidyl group.
g. An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group;
(4) X is a main chain formed by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (C) using a phosgene method, a transesterification method or the like. Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (C) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_７、Ｒ_８、Ａｒ_１、Ａｒ_２、Ａｒ_３及びＸは、上記一般式IIと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式IIの具体的な合成方法としては、特開平９−２７２７３５号公報に例示されている。

(However, in the formula, R ₇ , R ₈ , Ar ₁ , Ar ₂ , Ar ₃ and X are the same as those in the general formula II.)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
A specific synthesis method of the general formula II is exemplified in JP-A-9-272735.

（但し、一般式III中、Ｒ_９、Ｒ_１０は置換もしくは無置換のアリール基、Ａｒ_４、Ａｒ_５、Ａｒ_６は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。

(In the general formula III, R ₉ and R ₁₀ are substituted or unsubstituted aryl groups, Ar ₄ , Ar ₅ and Ar ₆ are the same or different arylene groups. X, k, j and n are the general formulas. Same as I.

Description of Substituents of General Formula III (1) R ₉ and R _{10 each} represents a substituted or unsubstituted aryl group. Specific examples thereof include the following a. Or b. And may be the same or different.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, Examples of the 5H-dibenzo [a, d] cycloheptenylidenephenyl group and the non-condensed polycyclic group include a biphenylyl group and a terphenylyl group.
b. Heterocyclic group. For example, a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, a carbazolyl group, and the like can be given.
(2) The arylene group represented by Ar _4, Ar ₅ , and Ar ₆ includes the divalent group of the aryl group represented by R ₉ and R ₁₀ , and may be the same or different.
(3) The aryl group and arylene group are represented by the following a. ~ G. The group shown may have as a substituent.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C _4. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
c. An alkoxy group (—OR ₁₁₂ ); R ₁₁₂ is (3) b. It is the same as the alkyl group represented by Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
e. Substituted mercapto group or aryl mercapto group. Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f. An alkyl-substituted amino group; The alkyl group of the alkyl-substituted amino group is (3) b. This is the same as the alkyl group shown in. Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
g. An acyl group. Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
(4) X is a main chain obtained by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (D) using a phosgene method, a transesterification method or the like. Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (D) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_９、Ｒ_１０、Ａｒ_４、Ａｒ_５、Ａｒ_６及びＸは、上記一般式IIIと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式IIIの具体的な合成方法としては、特開平９−２３５３６７号公報に例示されている。

(However, in the formula, R ₉ , R ₁₀ , Ar ₄ , Ar ₅ , Ar ₆ and X are the same as those in the general formula III.)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
A specific synthesis method of the general formula III is exemplified in JP-A-9-235367.

（但し、一般式IV中、Ｒ_１１、Ｒ_１２は置換もしくは無置換のアリール基、Ａｒ_７、Ａｒ_８、Ａｒ_９は同一又は異なるアリーレン基、ｓは１〜５の整数を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）

(In the general formula IV, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups, Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, and s represents an integer of 1 to 5. X, k , J and n are the same as in general formula I.)

Description of Substituents of General Formula IV (1) R ₁₁ and R _{12 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following a. Or b. And may be the same or different.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, Examples of the 5H-dibenzo [a, d] cycloheptenylidenephenyl group and the non-condensed polycyclic group include a biphenylyl group and a terphenylyl group.
b. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
(2) The arylene group represented by Ar ₇ , Ar ₈ , and Ar ₉ includes the divalent group of the aryl group shown for R ₁₁ and R ₁₂ , and may be the same or different.
(3) The above aryl group and arylene group are represented by the following a. ~ G. You may have as a substituent the group shown.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C _4. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxy Examples include ethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. .
c. An alkoxy group (—OR ₁₁₃ ); R ₁₁₃ is the same as (3) b. It is the same as the alkyl group shown by. Specifically, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2- Examples include cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specifically, for example, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group, etc. Can be mentioned.
e. Substituted mercapto group or aryl mercapto group. Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f. An alkyl-substituted amino group; The alkyl group of the alkyl-substituted amino group is (3) b. It is the same as that shown in. Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
g. An acyl group. Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
(4) X is a main chain formed by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when the diol compound having a triarylamino group of the following general formula (E) is polymerized using a phosgene method, a transesterification method or the like. Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (E) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_１１、Ｒ_１２、Ａｒ_７、Ａｒ_８、Ａｒ_９及びＸは、上記一般式IVと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式IVの具体的な合成方法としては、特開平９−８７３７６号公報に例示されている。

(However, in the formula, R ₁₁ , R ₁₂ , Ar ₇ , Ar ₈ , Ar ₉ and X are the same as those in the general formula IV.)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
A specific synthesis method of the general formula IV is exemplified in JP-A-9-87376.

（但し、一般式Ｖ中、Ｒ_１３、Ｒ_１４は置換もしくは無置換のアリール基、Ａｒ_１０、Ａｒ_１１、Ａｒ_１２は同一又は異なるアリーレン基、Ｘ_１、Ｘ_２は置換もしくは無置換のエチレン基、又は置換もしくは無置換のビニレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）

(In the general formula V, R ₁₃ and R ₁₄ are substituted or unsubstituted aryl groups, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups, and X ₁ and X ₂ are substituted or unsubstituted ethylene groups. Or a substituted or unsubstituted vinylene group, wherein X, k, j and n are the same as those in formula I.)

Description of Substituents of General Formula V (1) R ₁₃ and R _{14 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. Good.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, Examples of the 5H-dibenzo [a, d] cycloheptenylidenephenyl group and the non-condensed polycyclic group include a biphenylyl group and a terphenylyl group.
b. Heterocyclic group. For example, a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, a carbazolyl group, and the like can be given.
(2) The arylene group represented by Ar ₁₀ , Ar ₁₁ and Ar ₁₂ includes the divalent group of the aryl group shown for R ₁₃ and R ₁₄ , and may be the same or different.
(3) The above aryl group and arylene group may have the following groups as substituents.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C _4. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxy Examples include ethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. .
c. An alkoxy group (—OR ₁₁₄ ); R ₁₁₄ is (3) b. It is the same as the alkyl group represented by Specifically, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2- Examples include cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
e. Substituted mercapto group or aryl mercapto group. Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f. An alkyl-substituted amino group; Alkyl-substituted amino group The alkyl group is the above (3) b. It is the same as the alkyl group represented by Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
g. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
(4) X ₁ and X _{2 each} represents a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. Examples of the substituent include a cyano group, a halogen atom, a nitro group, and the above R ₁₃ and R ₁₄ . Or an alkyl group represented by the above (2) b.
(5) X is a main chain obtained by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (F) using a phosgene method, transesterification method, Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (F) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_１３、Ｒ_１４、Ａｒ_１０、Ａｒ_１１、Ａｒ_１２及びＸは、上記一般式Ｖと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式Ｖの具体的な合成方法としては、特開平９−７１６４２号公報、特開平９−２０４７４６号公報に例示されている。

(However, in formula, R < ₁₃ >, R < ₁₄ >, Ar < ₁₀ >, Ar < ₁₁ >, Ar < ₁₂ > and X are the same as the said general formula V.)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
Specific synthesis methods of the general formula V are exemplified in JP-A-9-71642 and JP-A-9-204746.

（但し、一般式VI中、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８は置換もしくは無置換のアリール基、Ａｒ_１３、Ａｒ_１４、Ａｒ_１５、Ａｒ_１６は同一又は異なるアリーレン基、Ｙ_１、Ｙ_２、Ｙ_３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表わし、同一であっても異なってもよい。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）

(In the general formula VI, R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ , Y ₃ represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, X, k, j and n are the same as in general formula I.)

Description of Substituents of General Formula VI (1) R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent substituted or unsubstituted aryl groups. Specific examples thereof include the following a. Or b. And may be the same or different.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H -Dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic group include biphenylyl group and terphenylyl group.
b. Heterocyclic group. For example, thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group and the like can be mentioned.
(2) Examples of the arylene group represented by Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ include the divalent groups of the aryl groups described above for R ₁₅ , R ₁₆ , R ₁₇ and R _18. It may or may not be.
(3) The above aryl group and arylene group are represented by the following a. ~ G. You may have as a substituent the group shown.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C _4. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
c. An alkoxy group (—OR ₁₁₅ ); R ₁₁₅ is (3) b. It is the same as the alkyl group shown by. Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(4) Y ₁ , Y ₂ and Y ₃ are a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group. , Which may be the same or different.
As the alkylene group, the above (2) b. Represents a divalent group derived from an alkyl group represented by Specifically, for example, methylene group, ethylene group, 1,3-propylene group, 1,4-butylene group, 2-methyl-1,3-propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group, methoxy Examples thereof include an ethylene group, a phenylmethylene group, a 4-methylphenylmethylene group, a 2,2-propylene group, a 2,2-butylene group, and a diphenylmethylene group.
Examples of the cycloalkylene group include a 1,1-cyclopentylene group, a 1,1-cyclohexylene group, a 1,1-cyclooctylene group, and the like.
Examples of the alkylene ether group include a dimethylene ether group, a diethylene ether group, an ethylene methylene ether group, a bis (triethylene) ether group, and a polytetramethylene ether group.
(5) X is a main chain obtained by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (G) using a phosgene method, a transesterification method or the like. Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (G) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８、Ａｒ_１３、Ａｒ_１４、Ａｒ_１５、Ａｒ_１６、Ｙ_１、Ｙ_２、Ｙ_３及びＸは、上記一般式VIと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式VIの具体的な合成方法としては、特開平９−１１０９７６号公報に例示されている。

(However, in the formula, R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , Ar ₁₆ , Y ₁ , Y ₂ , Y ₃ and X are the same as those in the above general formula VI. .)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
A specific synthesis method of the general formula VI is exemplified in JP-A-9-110976.

（但し、一般式VII中、Ｒ_１９、Ｒ_２０は水素原子、置換もしくは無置換のアリール基を表わし、Ｒ_１９とＲ_２０は環を形成していてもよい。Ａｒ_１７、Ａｒ_１８、Ａｒ_１９は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）

(However, in General Formula VII, R ₁₉ and R _{20 each} represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ , Ar ₁₉ Represent the same or different arylene groups, and X, k, j and n are the same as those in formula I.)

Description of Substituents of General Formula VII (1) R ₁₉ and R _{20 each} represents a substituted or unsubstituted aryl group. Specific examples thereof include the following a. ~ C. And may be the same or different.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, Examples of the 5H-dibenzo [a, d] cycloheptenylidenephenyl group and the non-condensed polycyclic group include a biphenylyl group and a terphenylyl group.
b. Heterocyclic group. For example, thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group and the like can be mentioned.
c. When R ₁₉ and R ₂₀ form a ring, examples include 9-fluorenylidene, 5H-dibenzo [a, d] cyclohebutenylidene, and the like.
(2) The arylene group represented by Ar ₁₇ , Ar ₁₈ and Ar ₁₉ includes the divalent group of the aryl group shown for R ₁₉ and R ₂₀ and may be the same or different.
(3) The above aryl group and arylene group are represented by the following a. ~ G. You may have as a substituent the group shown.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C _4. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
c. An alkoxy group (—OR ₁₁₆ ); R ₁₁₆ is (3) b. It is the same as the alkyl group shown by. Specifically, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2- Examples include cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
e. Substituted mercapto group or aryl mercapto group. Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f. An alkyl-substituted amino group; The alkyl group of the alkyl-substituted amino group is (3) b. It is the same as that shown in. Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
g. An acyl group. Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
(4) X is a main chain formed by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (H) using a phosgene method, a transesterification method or the like. Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (H) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_１９、Ｒ_２０、Ａｒ_１７、Ａｒ_１８、Ａｒ_１９及びＸは、上記一般式VIIと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式VIIの具体的な合成方法としては、特開平９−１１０９７６号公報に例示されている。

(In the formula, R ₁₉ , R ₂₀ , Ar ₁₇ , Ar ₁₈ , Ar ₁₉ and X are the same as those in the general formula VII.)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
A specific synthesis method of the general formula VII is exemplified in JP-A-9-110976.

（但し、一般式VIII中、Ｒ_２１は置換もしくは無置換のアリール基、Ａｒ_２０、Ａｒ_２１、Ａｒ_２２、Ａｒ_２３は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）

(In the general formula VIII, R ₂₁ represents a substituted or unsubstituted aryl group, Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , Ar ₂₃ represent the same or different arylene groups. X, k, j, and n represent the general formula Same as I.)

Description of Substituents of General Formula VIII (1) R ₂₁ represents a substituted or unsubstituted aryl group. Specific examples thereof include the following a. ~ G. And may be the same or different.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, Examples of the 5H-dibenzo [a, d] cycloheptenylidenephenyl group and the non-condensed polycyclic group include a biphenylyl group and a terphenylyl group.
b. Heterocyclic group. For example, a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, a carbazolyl group, and the like can be given.
(2) The arylene group represented by Ar ₂₀ , Ar ₂₁ , Ar ₂₂ and Ar ₂₃ includes the divalent group of the aryl group shown for R ₂₁ , which may be the same or different.
(3) The above aryl group and arylene group may have the following groups as substituents.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C _4. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxy Examples include ethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. .
c. An alkoxy group (—OR ₁₁₇ ); R ₁₁₇ is (3) b. It is the same as the alkyl group shown by. Specifically, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2- Examples include cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
e. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f. An alkyl-substituted amino group; The alkyl group of the alkyl-substituted amino group is (3) b. It is the same as the alkyl group represented by Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
g. An acyl group. Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
(4) X is a main chain formed by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when the diol compound having a triarylamino group of the following general formula (J) is polymerized using a phosgene method, a transesterification method or the like. Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (J) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_２１、Ａｒ_２０、Ａｒ_２１、Ａｒ_２２、Ａｒ_２３及びＸは、上記一般式VIIIと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式VIIIの具体的な合成方法としては、特開平９−２６８２２６号公報に例示されている。

(However, in the formula, R ₂₁ , Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and X are the same as those in the general formula VIII.)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
A specific synthesis method of the general formula VIII is exemplified in JP-A-9-268226.

（但し、一般式IX中、Ｒ_２２、Ｒ_２３、Ｒ_２４、Ｒ_２５は置換もしくは無置換のアリール基、Ａｒ_２４、Ａｒ_２５、Ａｒ_２６、Ａｒ_２７、Ａｒ_２８は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）

(In the general formula IX, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are substituted or unsubstituted aryl groups, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ represent the same or different arylene groups. X, k, j and n are the same as in general formula I.)

Description of Substituents of General Formula IX (1) R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ represent substituted or unsubstituted aryl groups. Specific examples thereof include the following a. ~ G. And may be the same or different.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, Examples of the 5H-dibenzo [a, d] cycloheptenylidenephenyl group and the non-condensed polycyclic group include a biphenylyl group and a terphenylyl group.
b. Heterocyclic group. For example, a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, a carbazolyl group, and the like can be given.
(2) The arylene group represented by Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ includes the divalent group of the aryl group described above for R ₂₂ , R ₂₃ , R ₂₄ and R _25. , May be the same or different.
(3) The above-mentioned aryl group and arylene group have the following a. ~ G. You may have as a substituent the group shown.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C _4. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2- Hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. It is done.
c. An alkoxy group (—OR ₁₁₈ ); R ₁₁₈ is (3) b. It is the same as the alkyl group represented by Specifically, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2- Examples include cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specifically, for example, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group, etc. Can be mentioned.
e. Substituted mercapto group or aryl mercapto group. Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f. An alkyl-substituted amino group; The alkyl group of the alkyl-substituted amino group is (3) b. It is the same as the alkyl group represented by Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
g. An acyl group. Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
(4) When X is a diol compound having a triarylamino group represented by the following general formula (L) and polymerized using a phosgene method, a transesterification method, etc., the main chain is obtained by using the diol compound represented by the following general formula (B) together Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (L) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_２２、Ｒ_２３、Ｒ_２４、Ｒ_２５、Ａｒ_２４、Ａｒ_２５、Ａｒ_２６、Ａｒ_２７、Ａｒ_２８及びＸは、上記一般式IXと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式IXの具体的な合成方法としては、特開平９−２２７６６９号公報に例示されている。

(However, in the formula, R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar ₂₈ and X are the same as those in the general formula IX.)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
A specific synthesis method of the general formula IX is exemplified in JP-A-9-227669.

（但し、一般式Ｘ中、Ｒ_２６、Ｒ_２７は置換もしくは無置換のアリール基、Ａｒ_２９、Ａｒ_３０、Ａｒ_３１は同一又は異なるアリーレン基を表わす。Ｘ、ｋ、ｊおよびｎは、一般式Ｉの場合と同じである。）

(In the general formula X, R ₂₆ and R ₂₇ are substituted or unsubstituted aryl groups, Ar ₂₉ , Ar _{30 and} Ar ₃₁ are the same or different arylene groups. X, k, j and n are the general formulas. Same as I.)

Description of Substituents of General Formula X (1) R ₂₆ and R _{27 each} represents a substituted or unsubstituted aryl group. Specific examples thereof include the following a. Or b. And may be the same or different.
a. Aromatic hydrocarbon group. For example, phenyl group, condensed polycyclic group such as naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H -Dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic group include biphenylyl group and terphenylyl group.
b. Heterocyclic group. For example, a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, a carbazolyl group, and the like can be given.
(2) The arylene group represented by Ar ₂₉ , Ar ₃₀ and Ar ₃₁ includes the divalent group of the aryl group shown for R ₂₆ and R ₂₇ and may be the same or different.
(3) The above aryl group and arylene group are represented by the following a. ~ G. You may have as a substituent the group shown.
a. Halogen atom, trifluoromethyl group, cyano group, nitro group.
b. An alkyl group; Preferably, it is a C ₁ -C _12, especially C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen _atom, may contain a phenyl group substituted with an alkyl group or C1~C4 alkoxy group C 1 -C _4. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxy Examples include ethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. .
c. An alkoxy group _{(-OR 119). R119} is (3) b. It is the same as the alkyl group represented by Specifically, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2- Examples include cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
d. An aryloxy group; Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
e. Substituted mercapto group or aryl mercapto group. Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
f. An alkyl-substituted amino group; The alkyl group of the alkyl-substituted amino group is (3) b. It is the same as the alkyl group shown by. Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
g. An acyl group. Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
(4) X is a main chain obtained by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (M) using a phosgene method, a transesterification method or the like. Introduced in. In this case, the manufactured polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (M) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.

（但し、式中、Ｒ_２６、Ｒ_２７、Ａｒ_２９、Ａｒ_３０、Ａｒ_３１及びＸは、上記一般式Ｘと同様である。）
一般式（Ｂ）のジオール化合物は一般式Ｉと同じものが挙げられる。
一般式Ｘの具体的な合成方法としては、特開平９−３０２０８４号公報に例示されている。

(However, in the formula, R ₂₆ , R ₂₇ , Ar ₂₉ , Ar ₃₀ , Ar ₃₁ and X are the same as those in the general formula X.)
Examples of the diol compound of the general formula (B) are the same as those of the general formula I.
A specific synthesis method of the general formula X is exemplified in JP-A-9-302084.

Next, the constituent material of the crosslinked surface layer coating solution of the present invention will be described.
The trifunctional or higher functional radical polymerizable monomer having no charge transporting property used in the present invention is a hole transporting structure such as triarylamine, hydrazone, pyrazoline, carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group. And a monomer having no electron transport structure such as an electron-withdrawing aromatic ring having a nitro group and having three or more radical polymerizable functional groups. The radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and is capable of radical polymerization. Examples of these radical polymerizable functional groups include 1-substituted ethylene functional groups and 1,1-substituted ethylene functional groups shown below.

(1) Examples of the 1-substituted ethylene functional group include functional groups represented by the following formulas.

（ただし、式中、Ｘ_２０は、置換又は無置換のフェニレン基、ナフチレン基等のアリーレン基、置換又は無置換のアルケニレン基、−ＣＯ−基、−ＣＯＯ−基、−ＣＯＮ（Ｒ_３６）−基（Ｒ_３６は、水素、メチル基、エチル基等のアルキル基、ベンジル基、ナフチルメチル基、フェネチル基等のアラルキル基、フェニル基、ナフチル基等のアリール基を表わす。）、または−Ｓ−基を表わす。）
これらの置換基を具体的に例示すると、ビニル基、スチリル基、２−メチル−１，３−ブタジエニル基、ビニルカルボニル基、アクリロイルオキシ基、アクリロイルアミド基、ビニルチオエーテル基等が挙げられる。

(In the formula, X ₂₀ represents an arylene group such as a substituted or unsubstituted phenylene group or a naphthylene group, a substituted or unsubstituted alkenylene group, a —CO— group, a —COO— group, —CON (R ₃₆ ) — A group (R ₃₆ represents hydrogen, an alkyl group such as a methyl group or an ethyl group, an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group, an aryl group such as a phenyl group or a naphthyl group), or —S—. Represents a group.)
Specific examples of these substituents include a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyloxy group, an acryloylamide group, and a vinyl thioether group.

(2) Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following formulas.

（ただし、式中、Ｙ_４は、置換又は無置換のアルキル基、置換又は無置換のアラルキル基、置換又は無置換のフェニル基、ナフチル基等のアリール基、ハロゲン原子、シアノ基、ニトロ基、メトキシ基あるいはエトキシ基等のアルコキシ基、−ＣＯＯＲ_３７基（Ｒ_３７は、水素原子、置換又は無置換のメチル基、エチル基等のアルキル基、置換又は無置換のベンジル、フェネチル基等のアラルキル基、置換又は無置換のフェニル基、ナフチル基等のアリール基、または−ＣＯＮＲ_３８Ｒ_３９（Ｒ_３８およびＲ_３９は、水素原子、置換又は無置換のメチル基、エチル基等のアルキル基、置換又は無置換のベンジル基、ナフチルメチル基、あるいはフェネチル基等のアラルキル基、または置換又は無置換のフェニル基、ナフチル基等のアリール基を表わし、互いに同一または異なっていてもよい。）、また、Ｘ_２１は上記式のＸ_２０と同一の置換基及び単結合、アルキレン基を表わす。ただし、Ｙ_４，Ｘ_２１の少なくとも何れか一方がオキシカルボニル基、シアノ基、アルケニレン基、及び芳香族環である。）
これらの置換基を具体的に例示すると、α−塩化アクリロイルオキシ基、メタクリロイルオキシ基、α−シアノエチレン基、α−シアノアクリロイルオキシ基、α−シアノフェニレン基、メタクリロイルアミノ基等が挙げられる。
なお、これらＸ_２０、Ｘ_２１、Ｙ_４についての置換基にさらに置換される置換基としては、例えばハロゲン原子、ニトロ基、シアノ基、メチル基、エチル基等のアルキル基、メトキシ基、エトキシ基等のアルコキシ基、フェノキシ基等のアリールオキシ基、フェニル基、ナフチル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基等が挙げられる。
これらのラジカル重合性官能基の中では、特にアクリロイルオキシ基、メタクリロイルオキシ基が有用であり、３個以上のアクリロイルオキシ基を有する化合物は、例えば水酸基がその分子中に３個以上ある化合物とアクリル酸（塩）、アクリル酸ハライド、アクリル酸エステルを用い、エステル反応あるいはエステル交換反応させることにより得ることができる。また、３個以上のメタクリロイルオキシ基を有する化合物も同様にして得ることができる。また、ラジカル重合性官能基を３個以上有する単量体中のラジカル重合性官能基は、同一でも異なっても良い。

(In the formula, Y ₄ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, an aryl group such as a naphthyl group, a halogen atom, a cyano group, a nitro group, Alkoxy group such as methoxy group or ethoxy group, -COOR ₃₇ group (R ₃₇ is hydrogen atom, substituted or unsubstituted methyl group, alkyl group such as ethyl group, aralkyl group such as substituted or unsubstituted benzyl, phenethyl group, etc. , An aryl group such as a substituted or unsubstituted phenyl group or a naphthyl group, or —CONR ₃₈ R ₃₉ (R ₃₈ and R ₃₉ are a hydrogen atom, an alkyl group such as a substituted or unsubstituted methyl group or an ethyl group, a substituted or Aralkyl groups such as an unsubstituted benzyl group, naphthylmethyl group, or phenethyl group, or an aryl group such as a substituted or unsubstituted phenyl group or naphthyl group Represents a group, which may be the same or different from each other.) Further, X ₂₁ represents X ₂₀ and identical substituents and a single bond, an alkylene group of the above formula. However, at least one of Y _4, X ₂₁ One of them is an oxycarbonyl group, a cyano group, an alkenylene group, and an aromatic ring.)
Specific examples of these substituents include an α-acryloyloxy chloride group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α-cyanophenylene group, and a methacryloylamino group.
In addition, examples of the substituent further substituted with the substituent for X ₂₀ , X ₂₁ , and Y ₄ include, for example, an alkyl group such as a halogen atom, a nitro group, a cyano group, a methyl group, and an ethyl group, a methoxy group, and an ethoxy group. And aryloxy groups such as phenoxy group, aryl groups such as phenyl group and naphthyl group, and aralkyl groups such as benzyl group and phenethyl group.
Among these radical polymerizable functional groups, acryloyloxy group and methacryloyloxy group are particularly useful, and a compound having three or more acryloyloxy groups is, for example, a compound having three or more hydroxyl groups in the molecule and an acrylic group. It can be obtained by using an acid (salt), an acrylic acid halide, or an acrylic ester to cause an ester reaction or a transesterification reaction. A compound having three or more methacryloyloxy groups can be obtained in the same manner. Further, the radical polymerizable functional groups in the monomer having three or more radical polymerizable functional groups may be the same or different.

Specific examples of the trifunctional or higher functional radical polymerizable monomer having no charge transporting structure include the following, but are not limited to these compounds.
That is, examples of the radical polymerizable monomer used in the present invention include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, HPA-modified trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, and PO-modified. Trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate , PO-modified glycerol triacrylate, Lith (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl Modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, EO modified phosphoric acid triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, etc. These may be used alone or in combination of two or more.

  The trifunctional or higher functional radical polymerizable monomer having no charge transport structure used in the present invention is a ratio of molecular weight to the number of functional groups in the monomer in order to form a dense crosslink in the cross-linked surface layer. (Molecular weight / functional group number) is preferably 250 or less. Further, when this ratio is larger than 250, the crosslinked surface layer is soft and wear resistance is somewhat lowered. Therefore, among the monomers exemplified above, monomers having a modifying group such as HPA, EO, and PO are extremely long. It is not preferable to use one having a modifying group alone. Moreover, the component ratio of the trifunctional or higher functional radical polymerizable monomer having no charge transporting structure used for the crosslinked surface layer is 20 to 80% by weight, preferably 30 to 70% by weight, based on the total amount of the crosslinked surface layer. When the monomer component is less than 20% by weight, the three-dimensional cross-linking density of the cross-linked surface layer is small, and a drastic improvement in wear resistance is not achieved as compared with the case of using a conventional thermoplastic binder resin. On the other hand, if it is 80% by weight or more, the content of the charge transporting compound is lowered, and the electrical characteristics are deteriorated. Since the required wear resistance and electrical characteristics differ depending on the process used, it cannot be said unconditionally, but considering the balance of both characteristics, the range of 30 to 70% by weight is most preferable.

  The radical polymerizable compound having a charge transporting structure used in the present invention includes a hole transporting structure such as triarylamine, hydrazone, pyrazoline, carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group and nitro group. It refers to a compound having an electron transport structure such as an electron-withdrawing aromatic ring and having a radical polymerizable functional group. Examples of the radical polymerizable functional group include those shown in the above radical polymerizable monomer, and acryloyloxy group and methacryloyloxy group are particularly useful.

  In addition, as the radical polymerizable compound having a charge transporting structure, a polyfunctional compound having two or more functional groups can be used, but a monofunctional compound is preferable in terms of film quality and electrostatic characteristics. This is because when a bifunctional or higher functional charge transport compound is used, it is fixed in the crosslinked structure by a plurality of bonds. However, since the charge transport structure is very bulky, distortion occurs in the cured resin, resulting in a crosslinked surface layer. The internal stress increases, and it becomes easy to cause cracks and scratches due to carrier adhesion and the like. When the film thickness is 5 μm or less, there is no particular problem, but when a film exceeding 5 μm is formed, the internal stress of the crosslinked surface layer becomes very high, and cracks are likely to occur immediately after crosslinking.

  Also, in terms of electrostatic properties, when a bifunctional or higher functional charge transporting compound is used, it is fixed in the crosslinked structure by a plurality of bonds, so that the intermediate structure (cation radical) during charge transport is stable. It cannot be maintained, and the sensitivity is lowered due to charge trapping, and the residual potential is easily increased. Such deterioration of the electrical characteristics appears as an image such as a decrease in image density and thinning of characters. For this reason, the radical polymerizable compound having a charge transporting structure uses a radical polymerizable compound having a monofunctional charge transporting structure and is fixed in a pendant shape between crosslinks, thereby causing cracks and scratches. And stabilization of electrostatic characteristics can be achieved.

  As the charge transporting structure, a triarylamine structure is highly effective. Moreover, what has one functional group is preferable, and when the compound shown by the structure of the following general formula XI or XII is used, electrical characteristics, such as a sensitivity and a residual potential, are maintained favorably.

（但し、一般式XIおよびXII中、Ｒ_２８は水素原子、ハロゲン原子、置換又は無置換のアルキル基、置換又は無置換のアラルキル基、置換又は無置換のアリール基、シアノ基、ニトロ基、アルコキシ基、−ＣＯＯＲ_２９（Ｒ_２９は水素原子、置換又は無置換のアルキル基、置換又は無置換のアラルキル基又は置換又は無置換のアリール基）、ハロゲン化カルボニル基若しくはＣＯＮＲ_３０Ｒ_３１（Ｒ_３０及びＲ_３１は水素原子、ハロゲン原子、置換又は無置換のアルキル基、置換又は無置換のアラルキル基又は置換又は無置換のアリール基を示し、互いに同一であっても異なっていてもよい）を表わし、Ａｒ_３２、Ａｒ_３３は置換もしくは無置換のアリーレン基を表わし、同一であっても異なってもよい。Ａｒ_３４、Ａｒ_３５は置換もしくは無置換のアリール基を表わし、同一であっても異なってもよい。Ｘ_１０は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表わす。Ｚは置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキレンエーテル基、アルキレンオキシカルボニル基を表わす。ｍ_１、ｎ_１は０〜３の整数を表わす。）

(In the general formulas XI and XII, R ₂₈ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a cyano group, a nitro group, an alkoxy group. A group, —COOR ₂₉ (R ₂₉ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group), a halogenated carbonyl group or CONR ₃₀ R ₃₁ (R ₃₀ and R ₃₁ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, which may be the same or different from each other). Ar _{32, Ar 33} represents a substituted or unsubstituted arylene group, which may be identical or different _.Ar 34, _{Ar 35} represents a substituted Properly represents the unsubstituted aryl group, good .X ₁₀ be the same or different single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether A group, an oxygen atom, a sulfur atom or a vinylene group, Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether group or an alkyleneoxycarbonyl group, m ₁ and n ₁ are integers of 0 to 3; Represents.)

Specific examples of the substituent in general formulas XI and XII are shown below.
In the general formulas XI and XII, in the substituent of R ₂₈ , as the alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, etc., as aryl group, phenyl group, naphthyl group, etc. as aralkyl group Benzyl group, phenethyl group, naphthylmethyl group, alkoxy groups include methoxy group, ethoxy group, propoxy group, etc., and these include halogen atom, nitro group, cyano group, methyl group, ethyl group, etc. An alkyl group, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, an aryl group such as a phenyl group and a naphthyl group, an aralkyl group such as a benzyl group and a phenethyl group, and the like.
Of the substituents for R ₂₈ , particularly preferred are a hydrogen atom and a methyl group.
Substituted or unsubstituted Ar ₃₄ and Ar ₃₅ are aryl groups, and examples of the aryl group include condensed polycyclic hydrocarbon groups, non-condensed cyclic hydrocarbon groups, and heterocyclic groups.
The condensed polycyclic hydrocarbon group preferably has 18 or less carbon atoms forming a ring, for example, a pentanyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group. , S-indacenyl group, fluorenyl group, acenaphthylenyl group, preadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylyl group, pyrenyl group , A chrycenyl group, a naphthacenyl group, and the like.

  Examples of the non-fused cyclic hydrocarbon group include monovalent groups of monocyclic hydrocarbon compounds such as benzene, diphenyl ether, polyethylene diphenyl ether, diphenyl thioether and diphenyl sulfone, or biphenyl, polyphenyl, diphenylalkane, diphenylalkene, diphenylalkyne, Monovalent groups of non-condensed polycyclic hydrocarbon compounds such as triphenylmethane, distyrylbenzene, 1,1-diphenylcycloalkane, polyphenylalkane, and polyphenylalkene, or ring assemblies such as 9,9-diphenylfluorene And monovalent groups of hydrocarbon compounds.

Examples of the heterocyclic group include monovalent groups such as carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.
The aryl group represented by Ar ₃₄ or Ar ₃₄ may have a substituent as shown below, for example.
(1) Halogen atom, cyano group, nitro group and the like.
(2) An alkyl group. _Preferably, C 1 _{-C 12} especially _C 1 -C _8, more preferably a straight or branched alkyl group of _C 1 -C _4, in the alkyl group a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group which may have a phenyl group or a halogen _atom, C 1 -C ₄ alkyl or _C 1 -C ₄ phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-butyl group, i-propyl group, t-butyl group, s-butyl group, n-propyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-ethoxyethyl Group, 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-phenylbenzyl group and the like.
(3) An alkoxy group (—OR ₃₂ ), and R ₃₂ is the same as the alkyl group shown in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, benzyloxy group And a trifluoromethoxy group.
(4) Aryloxy group. Examples of the aryl group of the aryloxy group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.
(5) Alkyl mercapto group or aryl mercapto group, and specific examples include methylthio group, ethylthio group, phenylthio group, p-methylphenylthio group and the like.
(6)

（式中、Ｒ_３３及びＲ_３４は各々独立に水素原子、前記（２）で示したアルキル基、またはアリール基を表わす。アリール基としては、例えばフェニル基、ビフェニル基又はナフチル基が挙げられ、これらはＣ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。Ｒ_３３及びＲ_３４は共同で環を形成してもよい）
具体的には、アミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−フェニルアミノ基、Ｎ，Ｎ−ジフェニルアミノ基、Ｎ，Ｎ−ジ（トリール）アミノ基、ジベンジルアミノ基、ピペリジノ基、モルホリノ基、ピロリジノ基等が挙げられる。
（７）メチレンジオキシ基、又はメチレンジチオ基等のアルキレンジオキシ基又はアルキレンジチオ基等。
（８）置換又は無置換のスチリル基、置換又は無置換のβ−フェニルスチリル基、ジフェニルアミノフェニル基、ジトリルアミノフェニル基等。

(In the formula, R ₃₃ and R ₃₄ each independently represent a hydrogen atom, the alkyl group shown in the above (2), or an aryl group. Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. these may form a ring _C 1 -C ₄ alkoxy _groups, C 1 alkyl group or a halogen atom -C ₄ jointly good _{.R 33} and _{R 34} may contain as a substituent)
Specifically, amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (tolyl) amino group, dibenzylamino group, piperidino group, morpholino group And pyrrolidino group.
(7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.
(8) A substituted or unsubstituted styryl group, a substituted or unsubstituted β-phenylstyryl group, a diphenylaminophenyl group, a ditolylaminophenyl group, and the like.

Examples of the arylene group represented by Ar ₃₂ and Ar ₃₃ include a divalent group derived from the aryl group represented by Ar ₃₄ and Ar ₃₅ .
X ₁₀ represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group.
Examples of the substituted or unsubstituted alkylene group include C _{1 to} C ₁₂ , preferably C _{1 to} C ₈ , and more preferably C _{1 to} C ₄ linear or branched alkylene groups. a fluorine atom, a hydroxyl group, organic cyano _group, an alkoxy group of C 1 -C _4, a phenyl group or a halogen _atom, a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C ₄ You may do it. Specifically, methylene group, ethylene group, n-butylene group, i-propylene group, t-butylene group, s-butylene group, n-propylene group, trifluoromethylene group, 2-hydroxyethylene group, 2-ethoxyethylene Group, 2-cyanoethylene group, 2-methoxyethylene group, benzylidene group, phenylethylene group, 4-chlorophenylethylene group, 4-methylphenylethylene group, 4-biphenylethylene group and the like.
Examples of the substituted or unsubstituted cycloalkylene group include a C _{5 to} C ₇ cyclic alkylene group, and these cyclic alkylene groups include a fluorine atom, a hydroxyl group, a C _{1 to} C ₄ alkyl group, and C as a substituent. _It may have a _{1 to} C ₄ alkoxy group. Specific examples include a cyclohexylidene group, a cyclohexylene group, and a 3,3-dimethylcyclohexylidene group.
Examples of the substituted or unsubstituted alkylene ether group include a —CH ₂ CH ₂ O— group, a CH ₂ CH ₂ CH ₂ —O— group, a — (OCH ₂ CH ₂ ) _h —O— group, and — (OCH ₂ CH ₂ CH _{2) i} -O- group.
However, h and i in the above formula each represent an integer of 1 to 4.
The alkylene group of the alkylene ether group may have a substituent such as a hydroxyl group, a methyl group, or an ethyl group.
The vinylene group is

または、

Or

で表わされ、
Ｒ_３５は水素、アルキル基（前記（２）で定義されるアルキル基と同じ）、アリール基（前記Ａｒ_３４、Ａｒ_３５で表わされるアリール基と同じ）、ａは１または２、ｂは１〜３を表わす。

Represented by
R ₃₅ is hydrogen, an alkyl group (same as the alkyl group defined in (2) above), an aryl group (same as the aryl group represented by Ar ₃₄ or Ar ₃₅ above), a is 1 or 2, and b is 1 to 2 3 is represented.

Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether group, or an alkyleneoxycarbonyl group.
Examples of the substituted or unsubstituted alkylene group include the same alkylene groups as those described above for X ₁ .
The substituted or unsubstituted alkylene ether groups include alkylene ether groups of the X _1.
Examples of the alkyleneoxycarbonyl group include a caprolactone-modified group.

  Further, the radical polymerizable compound having a monofunctional charge transport structure of the present invention is more preferably a compound having the structure of the following general formula XIII.

（但し、一般式XIII中、ｏ_１、ｐ_１、ｑ_１はそれぞれ０又は１の整数、Ｒａは水素原子又はメチル基を表わし、Ｒｂ、Ｒｃは水素原子以外の置換基で炭素数１〜６のアルキル基を表わし、複数の場合は異なっても良い。ｓ、ｔは０〜３の整数を表わす。Ｚａは単結合、メチレン基、エチレン基、

(In the general formula XIII, o ₁ , p ₁ and q ₁ are each an integer of 0 or 1, Ra represents a hydrogen atom or a methyl group, Rb and Rc are substituents other than a hydrogen atom and have 1 to 6 carbon atoms. A plurality of alkyl groups may be different, and s and t each represents an integer of 0 to 3. Za is a single bond, a methylene group, an ethylene group,

を表わす。）
上記一般式XIIIで表わされる化合物としては、Ｒｂ、Ｒｃの置換基として、特にメチル基、エチル基である化合物が好ましい。

Represents. )
As the compound represented by the general formula XIII, compounds having a methyl group or an ethyl group as substituents for Rb and Rc are particularly preferable.

  The crosslinked surface layer formed by the present invention is free from cracks and has excellent electrical characteristics. The reason is that the radically polymerizable compound having a monofunctional charge transport structure of the above general formulas XI and XII, particularly XIII, used in the present invention is polymerized because the carbon-carbon double bond is opened on both sides. In a polymer that does not become a terminal structure, is incorporated in a chain polymer, and is crosslinked by polymerization with a radically polymerizable monomer having three or more functions, it exists in the main chain of the polymer, and the main chain- Present in the cross-linked chain between the main chains (this cross-linked chain includes an inter-molecular cross-linked chain between one polymer and another polymer, a site with a main chain folded in one polymer, and a main chain. There are intramolecular cross-linked chains that are cross-linked with other sites derived from the polymerized monomer at positions away from this in the chain), but they are also present in the cross-linked chain even if they are present in the main chain Even if the triarylamine structure suspended from the chain moiety is a nitrogen atom It has at least three aryl groups arranged in the radial direction and is bulky, but is not directly bonded to the chain part, but is suspended from the chain part via a carbonyl group, etc. Since these triarylamine structures can be arranged adjacent to each other in the polymer, there is little structural distortion in the molecule, and the surface of the electrophotographic photosensitive member is also fixed. In the case of a layer, it is presumed that an intramolecular structure that is relatively free from interruption of the charge transport pathway can be adopted.

  Specific examples of the radically polymerizable compound having a monofunctional charge transporting structure of the present invention are shown below, but are not limited to the compounds having these structures.

  Specific examples of the radical polymerizable compound having a bifunctional charge transporting structure of the present invention are shown below, but are not limited to the compounds having these structures.

  Specific examples of the radical polymerizable compound having a trifunctional charge transporting structure of the present invention are shown below, but are not limited to the compounds having these structures.

  The radical polymerizable compound having a charge transport structure used in the present invention is important for imparting the charge transport performance of the crosslinked surface layer, and this component is preferably 20 to 80% by weight, preferably based on the total amount of the crosslinked surface layer. Is 30 to 70% by weight. When this component is less than 20% by weight, the charge transport performance of the crosslinked surface layer cannot be maintained sufficiently, and deterioration of electrical characteristics such as a decrease in sensitivity and an increase in residual potential appears with repeated use. On the other hand, if it exceeds 80% by weight, the content of the trifunctional monomer having no charge transport structure is lowered, and the crosslink density is lowered, so that high wear resistance is not exhibited. The required electrical characteristics and wear resistance differ depending on the process to be used, so it cannot be said unconditionally, but considering the balance of both characteristics, the range of 30 to 70% by weight is most preferable.

  The surface layer of the present invention is obtained by curing at least a trifunctional or higher-functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. Monofunctional and bifunctional radically polymerizable monomers and radically polymerizable oligomers can be used in combination for the purpose of adjustment, stress relaxation of the cross-linked surface layer, lower surface energy, and reduction of friction coefficient. Known radical polymerizable monomers and oligomers can be used.

  Examples of the monofunctional radical monomer include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, and cyclohexyl acrylate. , Isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, and the like.

  Examples of the bifunctional radical polymerizable monomer include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1, Examples include 6-hexanediol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, and neopentyl glycol diacrylate.

  Examples of the functional monomer include those substituted with a fluorine atom such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluoroisononylethyl acrylate, No. 60503, JP-B-6-45770, siloxane repeating units: 20-70 acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane propyl, acryloyl polydimethylsiloxane butyl, diacryloyl polydimethylsiloxane Examples include vinyl monomers having a polysiloxane group such as diethyl, acrylates and methacrylates.

  Examples of the radical polymerizable oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate oligomers. However, when a large amount of monofunctional and bifunctional radically polymerizable monomers and radically polymerizable oligomers are contained, the three-dimensional cross-linking density of the cross-linked surface layer is substantially reduced, resulting in a decrease in wear resistance. For this reason, the content of these monomers and oligomers is limited to 50 parts by weight or less, preferably 30 parts by weight or less, with respect to 100 parts by weight of the tri- or higher functional radical polymerizable monomer.

  In addition, the surface layer of the present invention is obtained by curing at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. In order to make the process proceed efficiently, a polymerization initiator may be used in the crosslinked surface layer.

  Examples of the thermal polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di ( Peroxybenzoyl) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, peroxide initiators such as lauroyl peroxide, azobisisobutylnitrile, azobiscyclohexanecarbonitrile Azo initiators such as methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, 4,4′-azobis-4-cyanovaleric acid.

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, Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene, thioxanthones such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Examples of photopolymerization initiators and other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoic acid. 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 thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylaminobenzophenone, and the like.
These polymerization initiators may be used alone or in combination of two or more. 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.

  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.

  The crosslinked surface layer of the present invention is formed by applying and curing a coating liquid containing at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. . 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, 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 the present invention, after applying such a coating solution, energy is applied from the outside and cured to form a crosslinked surface layer. The external energy used at this time includes heat, light, and 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 100 ° C. or higher and 170 ° C. or lower. If the heating temperature is lower than 100 ° 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 100 ° 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, but a visible light source can also be selected according to the absorption wavelength of radically 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 the ease of reaction rate control and the simplicity of the apparatus.

  The cured surface layer is preferably insoluble in organic solvents. Those that are not sufficiently cured are films that are soluble in organic solvents and have low mechanical durability.

  In the composition contained in the crosslinked surface layer coating solution, it is possible to contain a binder resin as long as the smoothness, electrical characteristics, or durability of the photoreceptor surface is not impaired. However, when a polymer material such as a binder resin is included in the coating liquid, it is in phase with the polymer formed by the curing reaction of the radical polymerizable composition (radical polymerizable monomer and radical polymerizable compound having a charge transporting structure). Phase separation occurs due to poor solubility, and the surface of the crosslinked surface layer becomes uneven. Therefore, it is preferable not to use a binder resin.

  In the cross-linked surface layer of the present invention, it is necessary to contain a bulky charge transporting structure in order to maintain electrical characteristics and to increase the cross-linking density in order to increase the strength. In such curing after application of the crosslinked surface layer, if very high energy is applied from the outside and the reaction proceeds rapidly, curing proceeds unevenly and the unevenness of the crosslinked film surface becomes severe. For this reason, the thing using the heat | fever which can control reaction rate according to heating conditions, light irradiation intensity | strength, and the amount of polymerization initiators, or the external energy of light is preferable.

  In the case of using the crosslinked surface layer forming material of the present invention, examples of the coating method include, for example, an acrylate monomer having three acryloyloxy groups and a triarylamine compound having one acryloyloxy group as a coating solution. When these are used, their use ratio is 7: 3 to 3: 7, and 3-20% by weight of a polymerization initiator is added to the total amount of these acrylate compounds, and a solvent is added to prepare a coating solution. To do. For example, in the case where the charge transport layer which is the lower layer of the cross-linked surface layer uses a triarylamine donor as the charge transport material and polycarbonate as the binder resin, and the cross-linked surface layer is formed by spray coating, the above coating solution As the solvent, tetrahydrofuran, 2-butanone, ethyl acetate and the like are preferable, and the use ratio thereof is 3 to 10 times the total amount of the acrylate compound.

Next, for example, the prepared coating solution is applied by spraying or the like on a photoreceptor in which an undercoat layer, a charge generation layer, and the charge transport layer are sequentially laminated on a support such as an aluminum cylinder. Thereafter, it is dried at a relatively low temperature for a short time (25 to 80 ° C., 1 to 10 minutes) and cured by UV irradiation or heating.
For UV irradiation, uses a metal halide lamp, illuminance 50 mW / cm ² or more, preferably 1000 mW / cm ² or less, for example, the case of irradiation with UV light of 700 mW / cm ^2, for example upon curing, by rotating the drum All the surfaces may be uniformly irradiated for about 20 seconds. At this time, the drum temperature is controlled so as not to exceed 50 ° C.
In the case of thermosetting, the heating temperature is preferably 100 to 170 ° C. For example, when a blowing oven is used as a heating means and the heating temperature is set to 150 ° C, the heating time is 20 minutes to 3 hours.
After completion of curing, the photosensitive member of the present invention is obtained by heating at 100 to 150 ° C. for 10 to 30 minutes to reduce the residual solvent.

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. On a conductive support, a charge generation layer having a charge generation function, a charge transport layer containing a polymer charge transport material, and a charge transport function FIG. 2 is a view showing an electrophotographic photosensitive member having a structure in which a crosslinked surface layer having a layer is laminated.
FIG. 2 shows an undercoat layer provided on the conductive support in the present invention, a charge generation layer having a charge generation function, a charge transport layer containing a polymer charge transport material, and a crosslinked surface layer having a charge transport function FIG.

<About conductive support>
Examples of the conductive support include those having a volume resistance of 10 ¹⁰ Ω · cm or less, such as metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, and platinum, tin oxide, and indium oxide. After metal oxide is deposited or sputtered, film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. Pipes that have been subjected to surface treatment such as cutting, super-finishing, and polishing can be used. Further, endless nickel belts and endless stainless steel belts disclosed in JP-A-52-36016 can also be used as the conductive support.
In addition, those obtained by dispersing and coating conductive powder in an appropriate binder resin on the support can also be used as the conductive support 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-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. 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 of the present invention.

<About photosensitive layer>
Next, the photosensitive layer will be described.
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.
(Charge generation layer)
The charge generation layer 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 a carbazole skeleton, azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having fluorenone skeleton, azo pigments having oxadiazole skeleton, azo pigments having bis-stilbene skeleton, azo pigments having distyryl oxadiazole skeleton, azo pigments having distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Goido based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  As a binder resin used as necessary for the charge generation layer, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, Examples include 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, No. 04-011627, No. 04-175337, No. 04-183719, No. 04-2225014, No. 04-230767, No. 04-320420, No. 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. JP-A 09-104746, JP-A 09-110974, JP-A 09-110976, JP-A 09-157378, JP-A 09-221544, JP-A 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 63-285552, JP-A 05-19497, JP-A 05-70595, JP-A 10-73944, and the like. Illustrated.

The charge generation layer may contain a low molecular charge transport material.
Low molecular charge transport materials that can be used in the charge generation layer 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 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 is a layer having a charge transport function, and a charge transport layer containing at least the polymer charge transport material of the present invention and a crosslinked surface layer having a charge transport structure are laminated.
The charge transport layer having a polymer charge transport material can be formed by dissolving or dispersing a polymer charge transport material in a suitable solvent, and applying and drying this on the charge generation layer. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.

As the polymer charge transport material, in addition to the polymer compounds of the above general formulas I to X, the following can also be used.
(A) Polymer having a carbazole ring in the main chain and / or side chain For example, poly-N-vinylcarbazole, JP 50-82056 A, JP 54-9632 A, JP Examples thereof include compounds described in JP-A Nos. 54-11737 and 4-183719.
(B) Polymer having a hydrazone structure in the main chain and / or side chain Examples thereof include compounds described in JP-A-57-78402 and JP-A-3-50555.
(C) Polysilylene polymer For example, the compounds described in JP-A-63-285552, JP-A-5-19497, and JP-A-5-70595 are exemplified.
(D) Polymer having tertiary amine structure in main chain and / or side chain For example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-13061, JP-A-1 -19049, JP-A-1-1728, JP-A-1-105260, JP-A-2-167335, JP-A-5-66598, JP-A-5-40350, and the like. Illustrated.
(E) Other polymers Examples include, for example, formaldehyde condensation polymers of nitropyrene, compounds described in JP-A Nos. 51-73888 and 56-150749, and the like.
The polymer having an electron donating group used in the present invention is not limited to the above-mentioned polymer, but also a copolymer of a known monomer, a block polymer, a graft polymer, a star polymer, It is also possible to use a cross-linked polymer having an electron donating group as disclosed in JP-A-3-109406.
However, although these known materials can be used in the present invention, the polymer charge transport materials of the above general formulas I to X are particularly preferably used for achieving the object of the present invention.
The thickness of the charge transport layer is suitably about 5 to 40 μm, preferably about 10 to 30 μm.

In the present invention, a plasticizer may be added to the charge transport layer.
As the plasticizer, 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 suitably about 0 to 30 parts by weight with respect to 100 parts by weight. .
In the present invention, an antioxidant may be added to the charge transport layer.

  As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the chain are used, and the amount used is 100 parts by weight of binder resin. 0 to 1 part by weight is suitable.

The crosslinked surface layer is formed on the polymer charge transport layer by the radical polymerizable composition of the present invention (a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure; the same applies hereinafter). ), A curing reaction is started by external energy after applying and drying as necessary.
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.

<About the undercoat layer>
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support 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, it may be a resin having a 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. In addition, a fine powder pigment of a metal oxide which can be 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, oxidation is performed on each layer such as a crosslinked surface layer, a charge generation layer, a charge transport layer, and an undercoat layer. An inhibitor can be added.

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 ] Glycol esters, tocopherols, etc.

(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 cross-linked surface layer. For example, at least after the photoconductor is subjected to charging, image exposure, and development processes, image holding is performed. 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. A charging charger (3) is used as a means for charging the photoconductor on average. 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 system 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.
Next, in order to form an electrostatic latent image on the uniformly charged photoreceptor (1), exposure is performed by the image exposure unit (5). 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, in order to visualize the electrostatic latent image formed on the photoreceptor (1), the electrostatic latent image is developed by the developing unit (6). 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, the toner image visualized on the photosensitive member is transferred onto the transfer member (9) by the transfer charger (10). 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, the transfer body (9) is separated from the photoreceptor (1) using the separation charger (11) and the separation claw (12). 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, the toner remaining on the photoreceptor after the transfer is cleaned and removed using a fur brush (14) and a cleaning blade (15). In this case, a pre-cleaning charger (13) may be used for more efficient cleaning. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination.
Next, neutralizing means is applied for the purpose of removing the latent image on the photoconductor 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 is 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 the cross-linked surface layer and at least one of charging, developing, transferring, cleaning, and charge eliminating 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.

<Synthesis Example of Compound having Charge Transporting Structure>
The compound having a charge transporting structure in the present invention is synthesized, for example, by the method described in Japanese Patent No. 3164426. An example of this is shown below.
(1) Synthesis of hydroxy group-substituted triarylamine compound (the following structural formula B) 113.85 g (0.3 mol) of a methoxy group-substituted triarylamine compound (the following structural formula A) and 138 g (0.92 mol) of sodium iodide To this, 240 ml of sulfolane was added and heated to 60 ° C. in a nitrogen stream. In this solution, 99 g (0.91 mol) of trimethylchlorosilane was added dropwise over 1 hour and stirred at a temperature of about 60 ° C. for 4 and a half hours to complete the reaction. About 1.5 L of toluene was added to the reaction solution, cooled to room temperature, and washed repeatedly with water and an aqueous sodium carbonate solution. Thereafter, the solvent was removed from the toluene solution and purified by column chromatography (adsorption medium: silica gel, developing solvent: toluene: ethyl acetate = 20: 1). Cyclohexane was added to the obtained pale yellow oil to precipitate crystals. In this way, 88.1 g (yield = 80.4%) of white crystals of the following structural formula B was obtained.
Melting point: 64.0-66.0 ° C

(2) Triarylamino group-substituted acrylate compound (Exemplary Compound No. 54 in Table 1)
82.9 g (0.227 mol) of the hydroxy group-substituted triarylamine compound (Structural Formula B) obtained in (1) above was dissolved in 400 ml of tetrahydrofuran, and an aqueous sodium hydroxide solution (NaOH: 12.4 g, Water: 100 ml) was added dropwise. The solution was cooled to 5 ° C., and 25.2 g (0.272 mol) of acrylic acid chloride was added dropwise over 40 minutes. Then, it stirred at 5 degreeC for 3 hours, and reaction was complete | finished. The reaction solution was poured into water and extracted with toluene. This extract was repeatedly washed with an aqueous sodium bicarbonate solution and water. Thereafter, the solvent was removed from the toluene solution and purified by column chromatography (adsorption medium: silica gel, developing solvent: toluene). N-Hexane was added to the obtained colorless oil to precipitate crystals. In this way, Exemplified Compound No. As a result, 80.73 g (yield = 84.8%) of 54 white crystals were obtained.
Melting point: 117.5-119.0 ° C

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. Note that “parts” used in the examples all represent parts by weight.
Example 1
An undercoat layer was formed on an Al support (outer diameter 30 mmφ) by dipping so that the film thickness after drying was 3.5 μm.
・ Coating liquid for undercoat layer 6 parts alkyd resin (Beckosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.)
Titanium oxide 40 parts (CR-EL: Ishihara Sangyo)
50 parts of methyl ethyl ketone On this undercoat layer, a charge generation layer coating solution containing a bisazo pigment having the following structure was dip coated and dried by heating to form a 0.2 μm thick charge generation layer.
-Coating solution for charge generation layer 2.5 parts of bisazo pigment with the following structure

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
この電荷発生層上に下記構造の高分子電荷輸送物質を含む電荷輸送層用塗工液を用いて、浸積塗工し、加熱乾燥させ、膜厚２２μｍの電荷輸送層とした。
・電荷輸送層用塗工液
下記構造の高分子電荷輸送物質 ２０部

Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 part Cyclohexanone 200 parts Methyl ethyl ketone 80 parts On this charge generation layer, dip coating is performed using a coating liquid for a charge transport layer containing a polymer charge transport material having the following structure. And dried by heating to obtain a charge transport layer having a thickness of 22 μm.
・ Coating liquid for charge transport layer 20 parts of polymer charge transport material with the following structure

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で５０１００、重量平均分子量で１１５０００であった。）
テトラヒドロフラン ８０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）
高分子電荷輸送層上に下記構成の架橋表面層塗工液を用いて、スプレー塗工し、メタルハライドランプ、照射強度：７００ｍＷ／ｃｍ２、照射時間：２０秒の条件で光照射を行ない、更に１３０℃で３０分乾燥を加え４．２μｍの架橋表面層を設け、本発明の電子写真感光体を得た。
・架橋表面層塗工液
電荷輸送性構造を有さない３官能以上のラジカル重合性モノマー ９部
トリメチロールプロパントリアクリレート
（ＫＡＹＡＲＡＤ ＴＭＰＴＡ、日本化薬製）
分子量：３８２、官能基数：３官能、分子量／官能基数＝９９
電荷輸送性構造を有するラジカル重合性化合物 ９部
（例示化合物Ｎｏ．３６４）
光重合開始剤 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 １００部

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 50100, and the weight average molecular weight was 115000.)
Tetrahydrofuran 80 parts Tetrahydrofuran solution of 1% silicone oil 0.2 parts (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)
Spray coating is performed on the polymer charge transport layer using a crosslinked surface layer coating liquid having the following constitution, and light irradiation is performed under the conditions of a metal halide lamp, irradiation intensity: 700 mW / cm 2, irradiation time: 20 seconds, and further 130 Drying was carried out at 30 ° C. for 30 minutes to provide a 4.2 μm cross-linked surface layer to obtain the electrophotographic photosensitive member of the present invention.
・ Crosslinked surface layer coating liquid Trifunctional or higher radical polymerizable monomer having no charge transporting structure 9 parts Trimethylolpropane triacrylate (KAYARAD TMPTA, Nippon Kayaku)
Molecular weight: 382, number of functional groups: trifunctional, molecular weight / number of functional groups = 99
9 parts of radically polymerizable compound having a charge transporting structure (Exemplary Compound No. 364)
Photoinitiator 2 parts 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran 100 parts

Example 2
As the radical polymerizable compound having the charge transporting structure of Example 1, Exemplified Compound No. 1 was used. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 182 was used. The film thickness of the crosslinked surface layer at this time was 4.4 μm.

Example 3
As the radical polymerizable compound having the charge transporting structure of Example 1, the exemplified compound NO. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 54 was used. The film thickness of the crosslinked surface layer at this time was 4.5 μm.

Example 4
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で６１０００、重量平均分子量で１３２０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 61000, and the weight average molecular weight was 132000.)

Example 5
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で５２０００、重量平均分子量で１１５０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 52,000, and the weight average molecular weight was 115000.)

Example 6
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で５８０００、重量平均分子量で１２２０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 58000, and the weight average molecular weight was 122,000.)

Example 7
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で６２０００、重量平均分子量で１３５０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 62000, and the weight average molecular weight was 135000.)

Example 8
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で７２０００、重量平均分子量で１４１０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 72000, and the weight average molecular weight was 141000.)

Example 9
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で６２０００、重量平均分子量で１３５０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 62000, and the weight average molecular weight was 135000.)

Example 10
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で５６０００、重量平均分子量で１２６０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 56000, and the weight average molecular weight was 126000.)

Example 11
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で６１０００、重量平均分子量で１３２０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 61000, and the weight average molecular weight was 132000.)

Example 12
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the polymer charge transport material in the polymer charge transport layer coating solution of Example 1 having the following structure was used.

（構造式中の構成単位の添字は全構成単位の個数を１としたときの各構成単位の組成比を表わしている。この樹脂の分子量をゲルパーミッションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は、数平均分子量で５５０００、重量平均分子量で１２１０００であった。）

(The subscript of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all structural units is 1. The molecular weight of this resin was measured by gel permeation chromatography. The number average molecular weight was 55000, and the weight average molecular weight was 121000.)

Example 13
Electrophotography as in Example 3 except that the tri- or higher functional radical polymerizable monomer having no charge transporting structure contained in the crosslinked surface layer coating solution of Example 3 was changed to the following monomer. A photoreceptor was prepared.
Trifunctional or higher radical polymerizable monomer having no charge transporting structure Caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.)
Molecular weight: 1263, number of functional groups: 6 functions, molecular weight / number of functional groups = 211

Example 14
Electrophotographic photosensitivity in the same manner as in Example 3, except that the trifunctional or higher-functional radical polymerizable monomer having no charge transporting structure contained in the crosslinked surface layer coating solution of Example 3 was changed to the following monomer. The body was made.
Trifunctional or higher functional radical polymerizable monomer having no charge transporting structure Caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-120, manufactured by Nippon Kayaku)
Molecular weight: 1947, number of functional groups: 6 functions, molecular weight / number of functional groups = 325

Example 15
The radically polymerizable compound having a charge transporting structure contained in the crosslinked surface layer coating solution of Example 3 is exemplified by Compound No. 1. An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the number was changed to 131.

Example 16
The radically polymerizable compound having a charge transporting structure contained in the crosslinked surface layer coating solution of Example 3 is exemplified by Compound No. 1. Change to 97 and 9 parts, change the photopolymerization initiator to the following thermal polymerization initiator, apply it on the charge transport layer in the same manner, heat at 70 ° C for 30 minutes using a blow-type oven, and further heat at 150 ° C for 1 hour. A photoconductor of the present invention was obtained by providing a 4.2 μm cross-linked surface layer.
Thermal polymerization initiator 2 parts 2,2-bis (4,4-di-t-butylperoxycyclohexyl)
Propane (Parkadox 12-EB20, manufactured by Kayaku Akzo)

Example 17
The radical polymerizable compound having a charge transporting structure contained in the coating solution for a crosslinked surface layer of Example 16 is exemplified by Compound No. 1. An electrophotographic photosensitive member was produced in the same manner as in Example 16 except that it was changed to 142.

Comparative Example 1
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge transport tank coating solution was a coating solution having the following constitution.
[Coating liquid for charge transport layer]
Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals)
7 parts of low molecular charge transport material of the following structural formula

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）

Tetrahydrofuran 100 parts 1% silicone oil tetrahydrofuran solution 0.2 parts (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

Comparative Example 2
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the charge transport layer coating solution was the same as in Comparative Example 1.

Comparative Example 3
The coating liquid for the crosslinked surface layer of Example 1 does not contain a tri- or higher functional radical polymerizable monomer having no charge transporting structure, and the amount of the radical polymerizable compound having a charge transporting structure is changed to 18 parts. Except for the above, an electrophotographic photosensitive member was produced in the same manner as in Example 1.

Comparative Example 4
The crosslinking surface layer coating solution of Example 1 does not contain a radical polymerizable compound having a charge transporting structure, and the amount of the trifunctional or higher functional radical polymerizable monomer having no charge transporting structure is changed to 18 parts. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that.

Comparative Example 5
The same procedure as in Example 1 was conducted except that the low molecular charge transport material shown in Comparative Example 1 was used instead of the radical polymerizable compound having a charge transport structure in the crosslinked surface layer coating solution of Example 1. An electrophotographic photoreceptor was prepared.

Comparative Example 6
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the coating liquid for the crosslinked surface layer was a coating liquid having the following constitution.
Trifunctional or higher-functional radical polymerizable monomer having no charge transporting structure 8 parts Trimethylolpropane triacrylate (KAYARAD TMPTA, manufactured by Nippon Kayaku Co., Ltd.)
Molecular weight: 296, number of functional groups: trifunctional, molecular weight / number of functional groups = 99
8 parts of radically polymerizable compound having a charge transporting structure (Exemplary Compound No. 54)
Bisphenol Z polycarbonate 2 parts (Panlite TS-2050, manufactured by Teijin Chemicals)
Photoinitiator 2 parts 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran 100 parts

Comparative Example 7
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the cross-linked surface layer of Example 1 was not provided and the thickness of the charge transport layer was 25 μm.

Comparative Example 8
An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 1 except that the cross-linked surface layer of Comparative Example 1 was not provided and the charge transport layer thickness was 26 μm.

(Real machine paper test)
The electrophotographic photosensitive member produced as described above was subjected to a 100,000-sheet actual paper feeding test (A4, NBS Ricoh MyPaper) using a Ricoh imagio MF2200 remodeling machine (655 nm semiconductor laser as an image exposure light source). Then, wear characteristics, in-machine potential, and image evaluation were performed. The results are shown in Table 6, Table 7, and Table 8, respectively.

地汚れ：○→良好、×→発生
スジ画像：○→良好、△→局部的に発生、×→画像全面に発生
画像濃度：○→良好、×→画像濃度低下

Ground stain: ○ → Good, × → Generated streak image: ○ → Good, △ → Locally generated, × → Generated over the entire image Image density: ○ → Good, × → Image density decreased

In Comparative Examples 1 and 2, the wear rate increased as the film thickness decreased, and the wear resistance was not good.
In Comparative Example 3, a number of cracks occurred immediately after the crosslinked surface layer was formed, and a streak-like image was generated on the entire surface.
In Comparative Example 4, the exposed area potential was larger than the initial stage, and the image density decreased.
In Comparative Examples 5, 6, 7, and 8, the amount of wear was very large.
Therefore, the charge transport layer of the present invention has a laminate structure of at least two layers, and the surface layer has at least a trifunctional or higher radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. A long-life and high performance capable of maintaining a good image for a long time by assuming that the charge transport layer in contact with the surface layer is a layer containing a polymer charge transport material. It has been found that a photoconductor can be provided. In addition, it has been found that the image forming process, the image forming apparatus, and the process cartridge for the image forming apparatus using the photoconductor of the present invention have high performance and high reliability.

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.

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 101 Photosensitive drum 102 Charging device 103 Exposure 104 Developing device 105 Transfer body 106 Transfer device 107 Cleaning blade

Claims (24)

In an electrophotographic photoreceptor having at least a charge generation layer and a charge transport layer on a conductive support, the charge transport layer has a laminate structure of at least two layers, and the surface layer does not have at least a charge transport structure. It is a cross-linked layer obtained by curing a radical polymerizable monomer having a functionality or higher and a radical polymerizable compound having a charge transport structure, and the charge transport layer in contact with the surface layer is a layer containing a polymer charge transport material. An electrophotographic photosensitive member characterized by the above. 2. The electrophotographic photosensitive member according to claim 1, wherein the polymer charge transport material has a triarylamine structure in a main chain or a branched chain. 3. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transport material has a structure represented by the following general formula I.

[In the general formula I, R ₁ , R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group or a halogen atom, and R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group, R ₅ and R ₆ represent a substituted or unsubstituted aryl group. o, p and q are each independently an integer of 0 to 4, k and j are the composition ratios of the respective structural units when the number of all the structural units is 1, and 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9 and n represents the number of repeating units and is an integer of 5 to 5000. X represents a divalent group of an aliphatic hydrocarbon, a divalent group of a cyclic aliphatic hydrocarbon, or a divalent group represented by the following general formula (1) or (2).

(In the general formula (1), R ₁₀₁ and R ₁₀₂ each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom, and may be the same or different. to 4 integer, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 -, - CO-, Or —CO—O—Z—O—CO— (wherein Z represents an aliphatic divalent group).

(However, in General formula (2), a is an integer of 1-20, b is an integer of 1-2000, R < ₁₀₃ >, R < ₁₀₄ > represents a substituted or unsubstituted alkyl group or aryl group, and is the same or different, respectively. It is good.)] 3. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transport material has a chemical structure represented by the following general formula II.

(In the general formula II, R ₇ and R ₈ are substituted or unsubstituted aryl groups, Ar ₁ , Ar ₂ and Ar ₃ are the same or different arylene groups. X, k, j and n are the general formulas) Same as I.) 3. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transport material has a chemical structure represented by the following general formula III.

(In the general formula III, R ₉ and R ₁₀ are substituted or unsubstituted aryl groups, Ar ₄ , Ar ₅ and Ar ₆ are the same or different arylene groups. X, k, j and n are the general formulas. Same as I. 3. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transport material has a chemical structure represented by the following general formula IV.

(In the general formula IV, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups, Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, and s represents an integer of 1 to 5. X, k , J and n are the same as in general formula I.) 3. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transport material has a chemical structure represented by the following general formula V.

(In the general formula V, R ₁₃ and R ₁₄ are substituted or unsubstituted aryl groups, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups, and X ₁ and X ₂ are substituted or unsubstituted ethylene groups. Or a substituted or unsubstituted vinylene group, wherein X, k, j and n are the same as those in formula I.) 8. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transport material has a structure represented by the following general formula VI.

(In the general formula VI, R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ , Y ₃ represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, X, k, j and n are the same as in general formula I.) The electrophotographic photosensitive member according to claim 1, wherein the polymer charge transport material has a chemical structure represented by the following general formula VII.

(However, in General Formula VII, R ₁₉ and R _{20 each} represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ , Ar ₁₉ Represent the same or different arylene groups, and X, k, j and n are the same as those in formula I.) The electrophotographic photosensitive member according to claim 1, wherein the polymer charge transport material has a chemical structure represented by the following general formula VIII.

(In the general formula VIII, R ₂₁ represents a substituted or unsubstituted aryl group, Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , Ar ₂₃ represent the same or different arylene groups. X, k, j, and n represent the general formula Same as I.) 3. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transport material has a structure represented by the following general formula IX.

(In the general formula IX, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are substituted or unsubstituted aryl groups, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ represent the same or different arylene groups. X, k, j and n are the same as in general formula I.) The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transport material has a structure represented by the following general formula X.

(In the general formula X, R ₂₆ and R ₂₇ are substituted or unsubstituted aryl groups, Ar ₂₉ , Ar _{30 and} Ar ₃₁ are the same or different arylene groups. X, k, j and n are the general formulas. Same as I.) The electrophotographic photosensitive member according to claim 1, wherein the surface layer does not dissolve in an organic solvent. The electrophotographic photosensitive member according to any one of claims 1 to 13, wherein the trifunctional or higher-functional radical polymerizable monomer having no charge transporting structure used in the surface layer is an acrylate or a methacrylate. The functional group ratio (molecular weight / functional group) with respect to the molecular weight of a trifunctional or higher functional radical polymerizable monomer having no charge transporting structure used in the surface layer is 250 or less. The electrophotographic photosensitive member according to any one of the above. 16. The electrophotographic photosensitive member according to claim 1, wherein the radical polymerizable compound having a charge transporting structure used in the surface layer is an acrylate or a methacrylate. 17. The electrophotographic photosensitive member according to claim 1, wherein the radical polymerizable compound having a charge transporting structure used in the surface layer has a triarylamine structure. The electrophotographic photosensitive member according to claim 1, wherein the radical polymerizable compound having a charge transporting structure used in the surface layer is monofunctional. 19. The electrophotographic photosensitive member according to claim 1, wherein the radical polymerizable compound having a charge transporting structure used for the surface layer is one or more of the following general formula XI or XII.

(In the general formulas XI and XII, R ₂₈ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a cyano group, a nitro group, an alkoxy group. A group, —COOR ₂₉ (R ₂₉ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group), a halogenated carbonyl group or CONR ₃₀ R ₃₁ (R ₃₀ and R ₃₁ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, which may be the same or different from each other). Ar _{32, Ar 33} represents a substituted or unsubstituted arylene group, which may be identical or different _.Ar 34, _{Ar 35} represents a substituted Properly represents the unsubstituted aryl group, good .X ₁₀ be the same or different single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether A group, an oxygen atom, a sulfur atom or a vinylene group, Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether group or an alkyleneoxycarbonyl group, m ₁ and n ₁ are integers of 0 to 3; Represents.) 20. The electrophotographic photosensitive member according to claim 1, wherein the radical polymerizable compound having a charge transporting structure used for the surface layer is one or more of the following general formula XIII.

(In the general formula XIII, o ₁ , p ₁ and q ₁ are each an integer of 0 or 1, Ra represents a hydrogen atom or a methyl group, Rb and Rc are substituents other than a hydrogen atom and have 1 to 6 carbon atoms. A plurality of alkyl groups may be different, and s and t each represents an integer of 0 to 3. Za is a single bond, a methylene group, an ethylene group,

Represents. ) 21. The electrophotographic photosensitive member according to claim 1, wherein the curing means for the surface layer is a heating or light energy irradiation means. 22. An image forming method, wherein at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to any one of claims 1 to 21. An image forming apparatus comprising the electrophotographic photosensitive member according to claim 1. An electrophotographic photosensitive member according to any one of claims 1 to 21, and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, a cleaning means, and a static elimination means, A process cartridge for an image forming apparatus, wherein the process cartridge is detachable from the forming apparatus main body.

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