JP2006016566A - Aromatic polycarbonate resin, method for producing the same, electrophotographic photoreceptor, method and apparatus for image formation and process cartridge for image formation apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new aromatic polycarbonate resin suitable as a molding material having excellent abrasion resistance, durable sliding properties and low friction properties of surface, to provide a method for producing the same, to obtain an electrophotographic photoreceptor using the aromatic polycarbonate resin, having excellent low surface energy, extremely durable low friction properties of surface, high and stable abrasion resistance, excellent electric properties, especially suitable for a polymerized toner and actualizing high picture qualities for a long period of time and to provide a method, an apparatus and a process cartridge for image formation using the same. <P>SOLUTION: The aromatic polycarbonate resin is obtained by subjecting a hydroxy group-containing acrylic modified organopolysiloxane, a diol compound represented by general formula (a) [X is an aliphatic bifunctional group, an alicyclic bifunctional group, an aromatic bifunctional group or a bifunctional group obtained by connecting them or a group represented by general formula (1-1) or formula (1-2)] and a carbonate derivative to condensation polymerization. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a novel polycarbonate resin useful for various uses having an acrylic-modified polyorganosiloxane structure and a method for producing the same.
In addition, the present invention uses the novel polycarbonate resin, has a durable surface having excellent durability with low surface friction, high wear resistance, and good electrical characteristics, and has high durability. The present invention relates to an electrophotographic photoreceptor that achieves high image quality over a long period of time.
The present invention further relates to an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus using the above-mentioned long-life, high-performance electrophotographic photosensitive member.

  As an aromatic polycarbonate resin, a polycarbonate resin obtained by reacting phosgene or diphenyl carbonate with 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) is known as a typical one. Yes. Such polycarbonate resin from bisphenol A has excellent properties in terms of transparency, heat resistance, dimensional accuracy, mechanical strength, and the like, and is used in many fields.

The purpose of improving surface low friction to improve surface scratch resistance, abrasion resistance, slidability, etc., which are disadvantages of polycarbonate resin, or for the purpose of improving fluidity, and further at the time of injection molding Various attempts have been made to introduce a polysiloxane structure into a polycarbonate for the purpose of improving releasability from the mold surface. For example, Patent Documents 1 and 2 disclose synthesis of a block copolymer by reaction of a polyorganosiloxane having a terminal terminated with a halogen and dihydroxy polycarbonate, and Patent Documents 3, 4, and 5 disclose a terminal terminated with a halogen. Synthesis of a block copolymer that phosgenates a reaction product of a polyorganosiloxane having bisphenol and bisphenol is disclosed. Patent Document 6 discloses the synthesis of a block copolymer using a cyclic polycarbonate oligomer. Discloses the synthesis of a block copolymer by the reaction of oligomeric carbonate bischlorofomate and oligomeric bisphenol A-terminated diorganosiloxane, and Patent Document 8 uses polydimethylsiloxane having a specific phenolic terminal. Block copolymers are disclosed and patent documents Polycarbonate resin having a polysiloxane side chain is disclosed in 9.
However, although the conventional technique has an initial surface modification effect by introducing a small amount of polysiloxane, the long-term durability thereof is insufficient. On the other hand, when trying to increase the polysiloxane composition, many methods are not used. There was a problem that unreacted polysiloxane remained.

  In addition, interfacial polymerization is widely used industrially as a method for producing aromatic polycarbonate resins, but it is necessary to completely remove electrolyte substances such as salts and alkalis as impurities from the polymer solution. Implementation requires considerable skill. Patent Documents 10, 11, 12 and the like have proposed a solution polymerization method using chloroformate, but lacks a variety of reactions because the synthesis of chloroformate is required. Further, this method has a problem that it is difficult to obtain a high molecular weight polymer. In addition, since the acrylic-modified polyorganosiloxane having a hydroxyl group, which is one of the polymerization raw materials of the present invention, is precipitated in an alkaline aqueous solution for interfacial polymerization, the desired polymer cannot be obtained.

On the other hand, in recent years, organic photoreceptors (OPC) have been widely used in copying machines, facsimiles, laser printers, and their combined 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 production, (5) Low cost, (6) Non-toxicity, and the like.
A typical example of an organic photoreceptor is a laminated photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated on a conductive substrate, and the charge transport layer is formed of a low molecular charge transport material and a binder resin. It is well known.

  In recent years, there has been a demand for a photoreceptor having good low surface energy sustainability as image quality is improved. Many photoconductors using various aromatic polycarbonate resins have been proposed in order to improve the low energy property of the surface. For example, one using a polysiloxane block copolymer as a binder (see Patent Documents 13 and 14), one using a low molecular weight polysiloxane terminal compound (see Patent Document 15), one using a fluorine atom-containing polycarbonate ( Patent Documents 16, 17, and 18) and those using a polysiloxane compound as a binder (see Patent Document 19) have been proposed, but none of them have sufficient effects or have adverse effects on electrical characteristics and printing durability. Including problems such as

Further, a method using a polysiloxane-terminated polycarbonate (see Patent Document 20) has also been proposed, but low surface energy durability could not be realized because the polysiloxane content is low.
Many methods have also been proposed in which various particulate lubricants are added to the binder of the surface layer. For example, a method of containing a fluororesin powder in a binder (see Patent Document 21), a method of containing silicone fine particles in a surface layer (see Patent Documents 22 and 23), and the like have been proposed. However, although the photoreceptors obtained by these methods have an initial low surface friction property, their long-term durability is insufficient.
Furthermore, a method (see Patent Document 24) in which an acrylic-modified polyorganosiloxane having compatibility with the binder resin is contained in the surface layer has been proposed, and has effects such as surface energy reduction, cleaning properties, and image blur suppression. However, there remain the disadvantages of using a special dispersion method and that the dispersed acrylic-modified polyorganosiloxane is easily removed from the binder resin.

JP 48-66697 A JP-A-52-71600 JP 50-29695 A JP 50-29696 A JP 50-69182 A Japanese Patent Laid-Open No. 62-25129 JP-A-2-219820 JP-A-3-79626 JP-A-5-155999 JP-A-8-261983 Japanese Patent Laid-Open No. 9-151248 Japanese Patent Laid-Open No. 9-272735 Japanese Patent Application Laid-Open No. 61-132594 JP-A-2-240655 JP 7-261440 A JP-A-5-306335 JP-A-6-32884 Japanese Patent Laid-Open No. 6-282094 JP 2000-281792 A JP 2000-171989 Japanese Patent Laid-Open No. 02-144550 Japanese Patent Laid-Open No. 07-128772 Japanese Patent Laid-Open No. 10-254160 Japanese Patent Application No. 2003-202686 Specification

The present invention has been made in view of the above-described prior art, and that the object can be achieved by using an acrylic-modified polyorganosiloxane having a hydroxyl group and a diol compound as raw materials and performing condensation polymerization with a carbonic acid derivative. It discovered and came to make this invention.
That is, an object of the present invention is to provide a novel aromatic polycarbonate resin suitable for a molding material having excellent wear resistance, continuous slidability, and low surface friction.
Another object of the present invention is to avoid the disadvantages in the interfacial polymerization method by a solution polymerization method that can be produced using a simple apparatus in a uniform liquid phase at around room temperature, and easily has a high molecular weight. It is providing the manufacturing method of said novel aromatic polycarbonate resin from which the polymer of this is obtained.
Still another object of the present invention is to use the above-mentioned novel aromatic polycarbonate resin, which is excellent in low surface energy, has a remarkable continuous low surface friction, is highly wear resistant and stable, and has electrical characteristics. It is an object to provide an electrophotographic photosensitive member that is good, particularly suitable for polymerized toner (or spherical toner), and that achieves high image quality over a long period of time.
Still another object of the present invention is to provide an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus using the electrophotographic photosensitive member.

  The above-mentioned problem is (1) “aromatic polycarbonate resin obtained by condensation polymerization of an acrylic-modified polyorganosiloxane having a hydroxyl group, a diol compound represented by the following general formula (a) and a carbonic acid derivative;

[式中、Ｘは脂肪族の２価基、環状脂肪族の２価基、芳香族の２価基、又はこれらを連結してできる２価基、又は、

[Wherein, X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or

（ここで、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は独立してアルキル基、アリール基またはハロゲン原子であり、ａ及びｂは各々独立して０〜４の整数であり、ｃ及びｄは各々独立して０〜３の整数であり、Ｙ^１は単結合、炭素原子数２〜１２の直鎖状のアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−,−ＣＯ−，−ＣＯＯ−、または下記式

(Where R ¹ , R ² , R ³ , R ⁴ are each independently an alkyl group, an aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, and c and d are Each independently represents an integer of 0 to 3, and Y ¹ represents a single bond, a linear alkylene group having 2 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —, —. CO-, -COO-, or the following formula

から選ばれ、Ｚ^１、Ｚ^２は脂肪族の２価基又はアリレン基を表し、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１は各々独立して水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、アリール基を表し、また、Ｒ^５とＲ^６は結合して炭素数６〜１２の炭素環または複素環を形成してもよく、また、Ｒ^５、Ｒ^６はＲ^１、Ｒ^２と共同で炭素環または複素環を形成してもよく、Ｒ^１２、Ｒ^１３は単結合または炭素数１〜４のアルキレン基を表し、Ｒ^１４、Ｒ^１５は各々独立して炭素数１〜５のアルキル基、アリール基を表し、ｅは０〜４の整数、ｆは０〜２０の整数、ｇは０〜２０００の整数を表す。）を表す。]」、
（２）「前記水酸基を有するアクリル変性ポリオルガノシロキサンがシリコーン主鎖にアクリル単量体をグラフト化させた化合物であることを特徴とする前記第（１）項に記載の芳香族ポリカーボネート樹脂」、
（３）「前記アクリル変性ポリオルガノシロキサンの水酸基がフェノール性水酸基であることを特徴とする前記第（１）項または第（２）項に記載の芳香族ポリカーボネート樹脂」、
（４）「前記アクリル変性ポリオルガノシロキサンの水酸基が、下記構造式で表わされるヒドロキシフェネチル−メタクリレート化合物から由来するものであることを特徴とする前記第（１）項乃至第（３）項の何れかに記載の芳香族ポリカーボネート樹脂；

Z ¹ and Z ² represent an aliphatic divalent group or an arylene group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, Represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group, and R ⁵ and R ⁶ are bonded to form a carbocyclic or heterocyclic ring having 6 to 12 carbon atoms. R ⁵ and R ⁶ may form a carbocyclic or heterocyclic ring together with R ¹ and R ^2, and R ¹² and R ¹³ are a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁴ and R ¹⁵ each independently represents an alkyl group having 1 to 5 carbon atoms or an aryl group, e is an integer of 0 to 4, f is an integer of 0 to 20, and g is an integer of 0 to 2000. Represents. ). ] "
(2) "The aromatic polycarbonate resin according to item (1), wherein the acrylic-modified polyorganosiloxane having a hydroxyl group is a compound obtained by grafting an acrylic monomer to a silicone main chain",
(3) "Aromatic polycarbonate resin according to item (1) or (2), wherein the hydroxyl group of the acrylic-modified polyorganosiloxane is a phenolic hydroxyl group",
(4) "Any of the above items (1) to (3), wherein the hydroxyl group of the acrylic-modified polyorganosiloxane is derived from a hydroxyphenethyl-methacrylate compound represented by the following structural formula: An aromatic polycarbonate resin according to claim 1;

」、
（５）「前記アクリル変性ポリオルガノシロキサンが粒状を呈することを特徴とする前記第（１）項乃至第（４）項の何れかに記載の芳香族ポリカーボネート樹脂」により達成される。
また、上記課題は、本発明の（６）「前記第（１）項に記載の水酸基を有するアクリル変性ポリオルガノシロキサンと一般式（ａ）で表わされるジオール化合物とハロゲン化カルボニル系化合物との縮合重合を溶液重合で行なうことを特徴とする前記第（１）項に記載の芳香族ポリカーボネート樹脂の製造方法」、
（７）「前記溶液重合において、脱酸剤として脱水ピリジンを用い、かつその反応溶媒中の割合が５〜１００体積％であることを特徴とする前記第（６）項に記載の芳香族ポリカーボネート樹脂の製造方法」により達成される。
また、上記課題は、本発明の（８）「前記第（１）項乃至第（５）項の何れかに記載の芳香族ポリカーボネート樹脂を有効成分として含有する感光層を設けたことを特徴とする電子写真感光体」により達成される。
また、上記課題は、本発明の（９）「前記第（８）項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」により達成される。
また、上記課題は、本発明の（１０）「前記第（８）項に記載の電子写真感光体を具備することを特徴とする画像形成装置」により達成される。
また、上記課題は、本発明の（１１）「前記第（８）項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」により達成される。

"
(5) "Aromatic polycarbonate resin according to any one of (1) to (4) above, wherein the acrylic-modified polyorganosiloxane is granular."
In addition, the above-mentioned problem is the condensation of (6) “acrylic-modified polyorganosiloxane having a hydroxyl group described in the above item (1), a diol compound represented by the general formula (a) and a carbonyl halide compound”. The method for producing an aromatic polycarbonate resin according to item (1), wherein the polymerization is performed by solution polymerization ",
(7) “Aromatic polycarbonate according to item (6), wherein dehydrated pyridine is used as a deoxidizing agent in the solution polymerization, and the proportion in the reaction solvent is 5 to 100% by volume. This is achieved by the “resin production method”.
In addition, the above-described problem is characterized in that a photosensitive layer containing the aromatic polycarbonate resin according to any one of (8) “(1) to (5) of the present invention as an active ingredient is provided. This is achieved by the “electrophotographic photoreceptor”.
Further, the above object is to provide an image forming method characterized in that at least charging, image exposure, development and transfer are repeated using the electrophotographic photosensitive member according to (9) “(8) of the present invention”. Is achieved.
Further, the above object is achieved by (10) “an image forming apparatus comprising the electrophotographic photosensitive member according to item (8)” of the present invention.
Further, the above-mentioned problem is at least selected from the group consisting of the electrophotographic photosensitive member according to (11) “(8) of the present invention, and a charging unit, a developing unit, a transfer unit, a cleaning unit, and a discharging unit. This is achieved by an image forming apparatus process cartridge having one means and being detachable from the main body of the image forming apparatus.

That is, in the above (1), in the case of a polycarbonate resin terminated with polysiloxane as described in the prior art, it is produced by interfacial condensation polymerization of a polycarbonate oligomer and a polysiloxane oligomer, so that a sufficient molecular weight is reached. It is common knowledge that a large amount of polysiloxane cannot be added, and when the film is formed, since a small amount of polysiloxane is easily segregated on the surface, it is not required to maintain a low surface friction. Therefore, by adding an acrylic-modified polyorganosiloxane having a hydroxyl group to the polymerization stage of the polycarbonate resin and connecting the acrylic-modified polyorganosiloxane and the polycarbonate resin with an ester bond, both high wear resistance and low surface energy sustainability can be achieved. As a result, when the polymerization was examined using a new acrylic-modified polyorganosiloxane compound having a hydroxyl group and a diol compound as raw materials, the obtained new aromatic polycarbonate resin was compatible with both low energy and wear resistance.
In addition, according to the above (2), the acrylic-modified polyorganosiloxane in the aromatic polycarbonate resin of the present invention exhibits slipperiness and low surface energy at the siloxane structure, and the grafted acrylic polymer part. Therefore, the binder can be copolymerized in a sufficient amount because it is compatible with the aromatic polycarbonate resin which is a binder. Such copolymerization of acrylic-modified polyorganosiloxane improved the durability of the low surface energy of the aromatic polycarbonate resin.
Moreover, since it is said (3) and (4), it is easy to advance reaction, many acrylic modified polyorganosiloxane compounds can be copolymerized, and it can implement | achieve that surface energy is lower.
In the above item (5), the acrylic-modified polyorganosiloxane compound expresses slipperiness and low surface energy at the organosiloxane portion and expresses compatibility at the acrylic polymerization portion as described above. However, in order to increase the slipperiness of the aromatic polycarbonate resin, it is more advantageous to compare a film in which the siloxane portion is partially dispersed at a high concentration than a uniform film at a low concentration at the same concentration. is there. Examples of the method include adjusting the composition ratio and controlling the compatibility, or further performing a dispersion treatment to copolymerize the acrylic-modified polyorganosiloxane in a granular form. In such a polycarbonate resin, continuous low friction is achieved.
Furthermore, according to the above (6) and (7), the solution polymerization is easier to disperse in the solvent than the interfacial polymerization, so that the polymerization proceeds more smoothly and the addition amount can be increased. It becomes.

In said (8), the polycarbonate resin in any one of said (1)-(5) is contained in a photosensitive layer. As described above, in the case of a polycarbonate resin terminated with polysiloxane as described in the prior art, it is produced by interfacial condensation polymerization of a polycarbonate oligomer and a polysiloxane oligomer, so that a sufficient molecular weight is reached. It is common sense that a large amount cannot be added, and since the polysiloxane present in a small amount tends to segregate on the surface when forming a film, the durability of the surface low friction is not required. On the other hand, in the method of adding acrylic-modified polyorganosiloxane to the polycarbonate resin of the binder, if the acrylic-modified polyorganosiloxane that is dispersed with compatibility and does not have a bond with the binder is subjected to physical hazards such as wear, it will fall off. Therefore, it is difficult to achieve both wear resistance and low friction properties of the photoreceptor. Further, since the acrylic-modified polyorganosiloxane is well dispersed in the binder, the use of special dispersion means is disadvantageous for the production process. Therefore, by adding an acrylic-modified polyorganosiloxane compound having a hydroxyl group to the polymerization stage of the polycarbonate and linking the acrylic-modified polyorganosiloxane and the polycarbonate with an ester bond, it is possible to achieve both high wear resistance and low surface energy sustainability. By incorporating the novel aromatic polycarbonate resin described in (1) into the photoreceptor, both low energy and wear resistance can be achieved. Another feature is that it is easy to use because it does not require a dispersion step.
In addition, the acrylic modified polyorganosiloxane in the novel aromatic polycarbonate described in the above (2) exhibits slipperiness and low surface energy at the siloxane structure, and a binder at the grafted acrylic polymer. Therefore, it is possible to copolymerize a sufficient amount in the binder, and there are few side effects on the electrophotographic characteristics of the photoreceptor. Such copolymerization of acrylic-modified polyorganosiloxane improves the durability of the low surface energy of the photoreceptor and has an effect on low surface friction.
In addition, the novel aromatic polycarbonate resins described in (3) and (4) are easy to proceed, can copolymerize a large amount of an acrylic-modified polyorganosiloxane compound, and have a lower surface energy. A body surface layer can be realized.
In addition, in the novel aromatic polycarbonate resin described in the above item (5), the acrylic-modified polyorganosiloxane compound exhibits slipping property and low surface energy property in the organosiloxane portion as described above, and has compatibility in the acrylic polymerization portion. In order to improve the slipperiness of the photoreceptor, a film in which the siloxane portion is partially dispersed at a high concentration is compared with a uniform film at the same concentration compared to a uniform film at a low concentration. As an advantage, since the acrylic-modified polyorganosiloxane compound is copolymerized in a granular form, such a polycarbonate resin can be used as a film to sensitize even a system with a small amount of addition of the acrylic-modified polyorganosiloxane compound. Good slipperiness and cleanability of the body are achieved.

In the above (9), by using the electrophotographic photosensitive member described in the above (8), at least charging, image exposure, development, and transfer can be repeated to form an image.
In the above (10) and (11), the electrophotographic photosensitive member described in the above (8) is provided in an image forming apparatus or a process cartridge for an image forming apparatus, thereby repeatedly performing excellent image formation. be able to.

  The novel aromatic polycarbonate resin of the present invention contains acrylic modified polyorganosiloxane as an active ingredient. This acrylic-modified polyorganosiloxane is used in combination with a diol compound and copolymerized with a carbonic acid derivative, and since it is linked to the polycarbonate resin by chemical bonding, it has an excellent low friction and excellent wear resistance. The present invention can provide the aromatic polycarbonate resin and a method for producing the aromatic polycarbonate resin. The aromatic polycarbonate resin of the present invention has excellent fluidity, slidability, low surface friction, releasability, etc., which are disadvantages of conventional polycarbonate resins, by having an acrylic modified polyorganosiloxane, and various injection moldings. It is not only suitable for use in various machine parts, automobile parts, general merchandise, etc. as engineering plastics such as films and sheets, but also as binder resin for organic electrophotographic photoreceptors used in copying machines. It is useful as various binders.

The electrophotographic photoreceptor of the present invention comprises an aromatic polycarbonate resin having the acrylic modified polyorganosiloxane of the present invention in the photosensitive layer. Since this acrylic-modified polyorganosiloxane is used in combination with a diol compound and copolymerized with a carbonic acid derivative, and linked to a polycarbonate resin through a chemical bond, according to the present invention, it has high wear resistance and good electrical properties, Furthermore, it is possible to provide an electrophotographic photosensitive member that can maintain low surface energy for a long period of time and has high durability and high performance.
Further, according to the present invention, it is possible to provide a high-performance and highly reliable image forming method, 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.
In the present invention, by using a polyorganosiloxane having a hydroxyl group and a diol compound together and copolymerizing with a carbonic acid derivative, the obtained aromatic polycarbonate resin is excellent in continuous low friction, high wear resistance, and stable. It is.

The reasons for this are as follows.
In the aromatic polycarbonate resin of the present invention, polyorganosiloxane having a hydroxyl group and a diol compound are used together and copolymerized with a carbonic acid derivative, and linked by an ester bond. In addition, the dispersibility and the durability of low friction are greatly improved, and the surface smoothness is remarkably improved and both wear resistance and low surface energy are realized.
Further, the acrylic-modified polyorganosiloxane is preferably stable and has a lower surface energy, because the siloxane chain is a main chain and the acrylic chain is graft-copolymerized as a side chain to improve compatibility. It is a new aromatic polycarbonate.

  Further, in the present invention, by using an aromatic polycarbonate resin obtained by copolymerizing the polyorganosiloxane compound having a hydroxyl group and a diol compound, the surface is excellent in low surface friction, has high wear resistance, is stable, In addition, an electrophotographic photoreceptor that achieves high image quality over a long period of time is achieved.

The reasons for this are as follows.
Since the photosensitive layer of the photoreceptor of the present invention contains an aromatic polycarbonate resin obtained by copolymerizing a polyorganosiloxane compound having a hydroxyl group and a diol compound, discharge products, toner external additives, paper powder, etc. It is needless to say that the foreign matter is easily removed from the surface of the photoconductor because the surface energy of the photoconductor is reduced and the releasability is improved. Furthermore, since the polyorganosiloxane compound has a hydroxyl group that can be condensation-polymerized with the diol compound, by connecting with an ester bond, the resulting polycarbonate resin film has significantly reduced cohesiveness of the polyorganosiloxane and dispersibility. The durability of the low friction is greatly improved, the surface smoothness of the photoreceptor is remarkably improved, the polyorganosiloxane drops off due to wear, and both wear resistance and low surface energy are realized. On the other hand, since the method in which the acrylic-modified polyorganosiloxane is directly added to the polycarbonate is agglomerated, a smooth and strong surface layer cannot be realized.

Further, the acrylic-modified polyorganosiloxane is preferably stable and has a lower surface energy, because the siloxane chain is a main chain and the acrylic chain is graft-copolymerized as a side chain to improve compatibility. A polycarbonate resin for the surface layer can be provided.
As a result, the electrophotographic photosensitive member using such a polycarbonate resin has an effect that foreign matter such as a discharge product, a toner external additive, paper powder, and the like adhering to the surface of the photosensitive member is difficult to adhere or is easily removed. In addition, the stability of the effect has been greatly enhanced, not only suppressing image blur, but also improving transfer efficiency, improving cleanability, suppressing abnormal images due to filming and foreign matter adhesion, and wear resistance. Has been achieved, and has many effects for high durability and high image quality.

Next, the constituent material of the present invention will be described.
Hereinafter, the acrylic-modified polyorganosiloxane having a hydroxyl group used in the present invention will be described in detail.
The acrylic-modified polyorganosiloxane is preferably the following general formula (1)

〔式中のＲ^１６、Ｒ^１７、Ｒ^１８はそれぞれ同一又は異なる炭素数１〜２０の炭化水素基又はハロゲン化炭化水素基、Ｙ^２はラジカル反応性基又はＳＨ基もしくはその両方を有する有機基、Ｚ^３、Ｚ^４はそれぞれ同一又は異なる水素原子、低級アルキル基又は下記式

[In the formula, R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different, respectively, a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, Y ² is an organic group having a radical reactive group, an SH group or both. , Z ³ , and Z ⁴ are the same or different hydrogen atoms, lower alkyl groups, or the following formulae

（式中のＲ^１９、Ｒ^２０はそれぞれ同一又は異なる炭素数１〜２０の炭化水素基又はハロゲン化炭化水素基、Ｒ^２１は炭素数１〜２０の炭化水素基もしくはハロゲン化炭化水素基、あるいはラジカル反応性基又はＳＨ基もしくはその両方を有する有機基である）で表わされるトリオルガノシリル基、ｕは１０，０００以下の正の整数、ｖは１以上の整数である。〕
で表わされるポリオルガノシロキサンに、好ましくは下記一般式（２）

(In the formula, R ¹⁹ and R ²⁰ are the same or different, respectively, a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, R ²¹ is a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, or A triorganosilyl group represented by a radical-reactive group or an SH group or an organic group having both, u is a positive integer of 10,000 or less, and v is an integer of 1 or more. ]
Preferably, polyorganosiloxane represented by the following general formula (2)

（式中のＲ^２２は水素原子又はメチル基、Ｒ^２３はアルキル基、アルコキシ置換アルキル基、シクロアルキル基又はアリール基である。）
で表わされる（メタ）アクリル酸エステル及び所望に応じて用いられる共重合可能な単量体を、乳化重合法によりグラフト重合させることにより製造される。
前記一般式（２）で表わされる（メタ）アクリル酸エステル等のグラフト重合用単量体として、少なくともその１部に水酸基を有するものを用いることが好ましく、これによりアクリル変性ポリオルガノシロキサンに水酸基を導入することができる。

(In the formula, R ²² is a hydrogen atom or a methyl group, and R ²³ is an alkyl group, an alkoxy-substituted alkyl group, a cycloalkyl group, or an aryl group.)
(Meth) acrylic acid ester represented by the formula (1) and a copolymerizable monomer used as desired are produced by graft polymerization using an emulsion polymerization method.
As the graft polymerization monomer such as (meth) acrylic acid ester represented by the general formula (2), it is preferable to use a monomer having a hydroxyl group in at least one part thereof, whereby a hydroxyl group is added to the acrylic-modified polyorganosiloxane. Can be introduced.

In the polyorganosiloxane represented by the general formula (1), R ¹⁶ , R ¹⁷ and R ¹⁸ are alkyl groups such as methyl group, ethyl group, propyl group and butyl group, phenyl group, tolyl group and xylyl group, respectively. , Halogenated groups having 1 to 20 carbon atoms in which at least one of the hydrocarbon groups having 1 to 20 carbon atoms such as an aryl group such as a naphthyl group or the hydrogen atoms bonded to the carbon atoms of these hydrocarbon groups is substituted with a halogen atom It is a hydrocarbon group, Comprising: R <^16> , R <^17> and R < ¹⁸ > may be the same respectively, and may mutually differ. Y ² is an organic group having a radical reactive group such as vinyl group, allyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, or SH group and / or both. . Z ³ and Z ⁴ are a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a triorganosilyl group represented by the above formula, and R ¹⁹ and R ²⁰ in this triorganosilyl group are Each having the same or different hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, R ²¹ is a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, radical reactive group, SH group or its An organic group having both. Examples of the organic group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group and a radical reactive group or an SH group or both in the triorganosilyl group include those exemplified above. Z ³ and Z ⁴ may be the same or different from each other. Further, u is a positive integer of 10,000 or less, preferably an integer in the range of 500 to 8,000, and v is an integer of 1 or more, preferably an integer in the range of 1 to 500.

  The polyorganosiloxane represented by the general formula (1) is a cyclic polyorganosiloxane, a liquid polydimethylsiloxane in which both molecular chain ends are blocked with hydroxyl groups, a liquid polydimethylsiloxane in which both molecular chain ends are blocked with alkoxy groups, Polydimethylsiloxane with both ends of the molecular chain blocked with trimethylsilyl groups, silanes for introducing radical reactive groups and / or SH groups, or hydrolyzed products of silanes, etc., if desired The trifunctional trialkoxysilane in an amount that does not impair the object of the present invention and its hydrolysis product can be used for the reaction.

  Next, different examples of the method for producing the polyorganosiloxane represented by the general formula (1) will be described. First, the first method uses, for example, a cyclic low-molecular siloxane such as the aforementioned octamethylcyclotetrasiloxane, a dialkoxysilane compound having a radical reactive group and / or an SH group, or a hydrolyzate thereof as raw materials. This is a method for obtaining a high molecular weight polyorganosiloxane by polymerizing in the presence of a strongly alkaline or strongly acidic catalyst. The high molecular weight polyorganosiloxane thus obtained is emulsified and dispersed in an aqueous medium in the presence of a suitable emulsifier in order to be used for the emulsion graft copolymerization in the next step.

  Next, the second method uses, for example, the low-molecular polyorganosiloxane as a raw material, a dialkoxysilane having a radical reactive group and / or an SH group, or a hydrolyzate thereof, and a sulfonic acid-based interface. In this method, emulsion polymerization is carried out in an aqueous medium in the presence of an activator or a sulfate ester surfactant. In this emulsion polymerization, the same raw materials are used, and after emulsifying and dispersing in an aqueous medium with a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, an appropriate amount of potassium hydroxide or sodium hydroxide is obtained. It can also be polymerized by adding a strong alkaline compound such as.

  When the polyorganosiloxane represented by the general formula (1) thus obtained has a low molecular weight, the molded article obtained from the composition is imparted with durable slidability and wear resistance. Since the effect becomes inferior, it is preferable that the molecular weight is as large as possible. For this reason, in the first method, it is necessary to leave the polyorganosiloxane of high molecular weight in the polymerization and to emulsify and disperse it, and in the second method, the aging treatment performed after the emulsion polymerization. In this case, since the molecular weight of the polyorganosiloxane increases if the temperature is lowered, the aging temperature is advantageously 30 ° C. or less, preferably 15 ° C. or less.

  In the present invention, the (meth) acrylic acid ester represented by the general formula (2) to be graft-polymerized to the polyorganosiloxane represented by the general formula (1) includes, for example, methyl (meth) acrylate, ethyl (meth) Acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) Alkyl (meth) acrylates such as acrylate, stearyl (meth) acrylate, alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate Relate, phenyl (meth) acrylate and benzyl (meth) acrylate. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  In addition, as desired, copolymerizable monomers used with these (meth) acrylic acid esters include polyfunctional monomers, various functional group-containing unsaturated monomers, and ethylenically unsaturated monomers. Examples include a polymer. Examples of the monomer include 1,3,5,7-tetramethyl-3,5,7-trivinylcyclotetrasiloxypropyl methacrylate, tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate. Polyfunctional monomers with multiple unsaturated groups such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, glycidyl (meth) acrylate, glycidyl allyl ether, etc. Oxirane group-containing unsaturated monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyphenyl (meth) acrylate, hydroxyphenethyl (me ) Hydroxyl group-containing unsaturated monomers such as acrylate, carboxyl group-containing ethylenically unsaturated monomers such as (meth) acrylic acid, maleic anhydride, crotonic acid and itaconic acid, ethylene oxide and propylene of (meth) acrylic acid Polyalkylene oxide group-containing unsaturated monomers such as oxide adducts, polyhydric alcohols such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and (meth) acrylic acid And ethylenically unsaturated amides such as (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxymethyl (meth) acrylamide And alkyl group or alkoxyalkylated ethylenically unsaturated amide, amino group such as N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, and imide group-containing unsaturation such as acryloyloxyethyl hexahydrophthalimide And monomers. These may be used alone or in combination of two or more. In particular, the addition of a hydroxyl group-containing unsaturated monomer allows condensation polymerization with a diol compound to obtain a polycarbonate resin having an acrylic-modified polyorganosiloxane. These polyfunctional monomers have an effect of imparting elasticity, durability, heat resistance and the like to the surface layer by participating in crosslinking between polymers in the acrylic-modified polyorganosiloxane.

  On the other hand, examples of the ethylenically unsaturated monomer include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, and vinyl versatate. These monomers may be used singly or in combination of two or more, or in combination of one or more of these monomers and one or more of the above functional monomers. May be.

The amount of the copolymerizable monomer used as desired is 0 based on the total weight of the (meth) acrylic acid ester represented by the general formula (2) and the copolymerizable monomer. It is preferable to select in the range of 1% by weight to 30% by weight. If this amount exceeds 30% by weight, the miscibility between the resulting acrylic-modified polyorganosiloxane and the polycarbonate resin is lowered, and if it is less than 0.1% by weight, elasticity, durability, heat resistance and the like cannot be imparted.
In addition, the monomer for graft copolymerization of the component represented by the general formula (2) preferably has a glass transition temperature of the polymerized product in order to impart excellent slidability and wear resistance to the molded film. Is preferably 20 ° C. or higher, more preferably 30 ° C. or higher.

The acrylic-modified polyorganosiloxane in the present invention comprises a polyorganosiloxane represented by the general formula (1) and a monomer represented by the general formula (2) in a weight ratio of 5:95 to 95: 5. It is obtained by graft copolymerization using an emulsion polymerization method in a proportion. If the proportion of the polyorganosiloxane represented by the general formula (1) is less than the above range, the resulting acrylic-modified polyorganosiloxane cannot sufficiently exhibit the effects of the polyorganosiloxane itself, and the acrylic polymer Adhesive feeling, which is a drawback of the above, will occur, and if it exceeds the above range, the acryl-modified polyorganosiloxane will be less miscible with the polycarbonate resin and will tend to bleed on the surface of the molded article, slidability, wear resistance There is a tendency that the property and the like tend to decrease with time.
In the emulsion graft copolymerization of the component of the general formula (1) and the component of the general formula (2), an aqueous emulsion of polyorganosiloxane is used as the component of the general formula (1), and a normal radical initiator is used. Can be carried out by a known emulsion polymerization method.
The acrylic-modified polyorganosiloxane can be obtained by adding a salting-out agent to the emulsion obtained by the emulsion polymerization method, performing precipitation, washing with water, and drying, or by spray drying such as a spray dryer. It can be obtained as particles having an average particle size of about 10 μm to 500 μm. In the present invention, the particles are further refined by dissolution and / or dispersion, and are preferably used after being dispersed in the form of particles having an average particle diameter of about 0.01 μm to 5 μm, more preferably 0.05 μm to 0.5 μm.

  In addition, in the acrylic-modified polyorganosiloxane used in the present invention, residual impurities such as an emulsifier and a flocculant used in polymerization may be impaired in an electrophotographic photoreceptor having an electrical property problem. It is preferable to use after purification. Examples of the purification method include a method of stirring and washing with an acid, an aqueous alkali solution, water and alcohol, and a solid-liquid extraction method such as Soxhlet extraction.

  The content of the acrylic-modified polyorganosiloxane is 1 to 20% by weight, preferably 5 to 10% by weight, corresponding to the polycarbonate resin. If the amount is less than 1% by weight, the effect of improving the surface slipperiness is insufficient, and if it exceeds 20% by weight, the transparency is adversely affected.

  As the structural unit represented by the general formula (a), a structural unit of a conventionally known polycarbonate resin can be used as it is. For example, basic units described in a polycarbonate resin handbook (editor: Seiichi Honma, issue: Nikkan Kogyo Shimbun) can be used. Among such conventionally known structural units, preferred examples include the structural unit represented by the general formula (a). The diol compound represented by the general formula (a) will be described in detail below.

  Typical examples of the diol when X in the general formula (a) is an aliphatic divalent group or a cycloaliphatic divalent group are ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene ether Glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,5-hexane Diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, neopentyl glycol 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propyl Pandiol, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, 2,2-bis (4-hydroxycyclohexyl) Propane, xylylenediol, 1,4-bis (2-hydroxyethyl) benzene, 1,4-bis (3-hydroxypropyl) benzene, 1,4-bis (4-hydroxybutyl) benzene, 1, 4-bis (5-hydroxypentyl) benzene, 1,4-bis (6-hydroxyhexyl) benzene and the like.

Furthermore, as when X is divalent aromatic may be mentioned divalent groups derived from aryl groups exemplified in R ¹⁶ to R ^18. X represents a divalent group shown below.

（ここで、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は独立してアルキル基、アリール基またはハロゲン原子であり、ａ及びｂは各々独立して０〜４の整数であり、ｃ及びｄは各々独立して０〜３の整数であり、Ｙ^１は単結合、炭素原子数２〜１２の直鎖状のアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＯ−、または下記式

(Where R ¹ , R ² , R ³ , R ⁴ are each independently an alkyl group, an aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, and c and d are Each independently represents an integer of 0 to 3, and Y ¹ represents a single bond, a linear alkylene group having 2 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —, — CO-, -COO-, or the following formula

から選ばれ、Ｚ^１、Ｚ^２は脂肪族の２価基又はアリレン基を表わし、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１は各々独立して水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、アリール基を表わし、また、Ｒ^５とＲ^６は結合して炭素数６〜１２の炭素環または複素環を形成してもよく、また、Ｒ^５、Ｒ^６はＲ^１、Ｒ^２と共同で炭素環または複素環を形成してもよく、Ｒ^１２、Ｒ^1３は単結合または炭素数１〜４のアルキレン基を表わし、Ｒ^１４、Ｒ^１５は各々独立して炭素数１〜５のアルキル基、アリール基を表わし、ｅは０〜４の整数、ｆは０〜２０の整数、ｇは０〜２０００の整数を表す。）

Z ¹ and Z ² represent an aliphatic divalent group or an arylene group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, Represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group, and R ⁵ and R ⁶ are bonded to form a carbocyclic or heterocyclic ring having 6 to 12 carbon atoms. R ⁵ and R ⁶ may form a carbocyclic or heterocyclic ring together with R ¹ and R ^2, and R ¹² and R ¹³ are a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁴ and R ¹⁵ each independently represents an alkyl group having 1 to 5 carbon atoms or an aryl group, e is an integer of 0 to 4, f is an integer of 0 to 20, and g is an integer of 0 to 2000. Represents. )

Among these, alkyl groups, exemplified alkyl groups any aryl group in R ¹⁶ to R ^18, may be the same as the aryl group. The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Further, when Z ¹ and Z ² are aliphatic divalent groups, a divalent group obtained by removing a hydroxy group from a diol when X is an aliphatic divalent group or a cyclic aliphatic divalent group is Can be mentioned. ^Further, as the case Z 1, ^{Z 2} is an arylene group may include a divalent group derived from an aryl group exemplified in ^R 16 ^{to R 18.}

Representative specific examples r of preferred diols in which X is an aromatic divalent group include bis (4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) methane, bis (3 -Methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4- Hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis (4-hydroxyphenyl) -1,1-dimethylpropane, 2,2-bis (4-hydroxy) Phenyl) propane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 1,1-bis (4-hydroxy) Droxyphenyl) -2-methylpropane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) Pentan, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2 , 2-bis (4-hydroxyphenyl) nonane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis ( 3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-te t-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2, 2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) Propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclopentene 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy) Phenyl) cycloheptane, 2,2-bis (4-hydroxyphenyl) norbornane, 2,2-bis (4-hydroxyphenyl) adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 ' -Dimethyldiphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide, 4,4 '-Dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfone, 3,3 '-Diphenyl-4,4'-dihydroxydiphenylsulfone, 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) ketone, bis (3-methyl-4-hydroxyphenyl) ketone 3,3,3 ', 3'-tetramethyl-6,6'-dihydride Xyspiro (bis) indane, 3,3 ', 4,4'-tetrahydro-4,4,4', 4'-tetramethyl-2,2'-spirobi (2H-1-benzopyran) -7,7 ' -Diol, trans-2,3-bis (4-hydroxyphenyl) -2-butene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, 1,6 -Bis (4-hydroxyphenyl) -1,6-hexanedione, α, α, α ', α'-tetramethyl-α, α'-bis (4-hydroxyphenyl) -p-xylene, α, α, α ′, α′-tetramethyl-α, α′-bis (4-hydroxyphenyl) -m-xylene, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxy Fe Xanthine, 9,10-dimethyl-2,7-dihydroxyphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, 4,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 2,7-dihydroxy Pyrene, hydroquinone, resorcin, 4-hydroxyphenyl-4-hydroxybenzoate, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate), 1 , 3-bis (4-hydroxyphenyl) tetramethyldisiloxane, phenol-modified silicone oil, and the like. Also useful are aromatic diol compounds containing an ester bond produced by the reaction of 2 moles of diol with 1 mole of isophthaloyl chloride or terephthaloyl chloride.
The content of the diol component (structure part excluding hydrogen at the terminal OH) is preferably 70% by weight to 99% by weight, and more preferably 80% by weight to 95% by weight with respect to the polycarbonate resin. If it is less than 70% by weight, the mechanical strength is insufficient, and if it exceeds 99% by weight, the amount of acrylic-modified polyorganosiloxane added is extremely reduced, and the effect of low surface energy is small.

As a method for producing an aromatic polycarbonate resin, an interfacial polymerization method is widely used industrially, but it is preferable to completely remove electrolyte substances such as salts and alkali as impurities from the polymer solution. A considerable amount of technology is required for the implementation, and more advanced technology is particularly required to obtain a high-purity product required as a polymer material for an electrophotographic photoreceptor. In addition, since the acrylic-modified polyorganosiloxane having a hydroxyl group, which is one of the polymerization raw materials of the present invention, is precipitated in an alkaline aqueous solution for interfacial polymerization, the desired polymer cannot be obtained.
One of the major features of the present invention is that a high molecular weight polymer can be easily obtained by the production method of the present invention. That is, the present invention is an aromatic that is preferable for an electrophotographic photosensitive member that can avoid the problems in the interfacial polymerization method by a solution polymerization method that can be produced using a simple apparatus in a uniform liquid phase at around room temperature. A method for producing a polycarbonate resin can be provided.

  In the solution polymerization of the production method of the present invention, for example, an acrylic-modified polyorganosiloxane having a hydroxyl group and a diol compound are dissolved in a solvent, a deoxidizing agent is added, and a carbonyl halide compound which is one type of carbonic acid derivative is added thereto. It is obtained by adding. As the halogenated carbonyl compound, trichloromethyl chloroformate, which is a dimer of phosgene, and bis (trichloromethyl) carbonate, which is a trimer of phosgene, are also useful instead of phosgene, and halogens derived from halogens other than chlorine. Also useful are carbonyl chloride compounds such as carbonyl bromide, carbonyl iodide, carbonyl fluoride. As other carbonic acid derivatives, carbonic acid diesters (for example, dialkyl carbonates, diaryl carbonates, etc.), dioxy compound biscarbonates (for example, dioxy compound bisalkyl carbonates, dioxy compound biscycloalkyl carbonates, etc.) can also be used. it can. This production method is described in, for example, a polycarbonate resin handbook (editor: Seiichi Honma, published by Nikkan Kogyo Shimbun). As the deoxidizer, tertiary amines such as trimethylamine, triethylamine and tripropylamine and pyridine are used. Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene, and chloroform, and cyclic ether solvents such as tetrahydrofuran and dioxane, and hydrocarbon solvents such as toluene and xylene. And pyridine are preferred.

  In the present invention, when pyridine is used as a deoxidizer, pyridine forms an adduct with phosgene, which is more reactive with bisphenol than phosgene itself. If the phosgene-pyridine adduct is present in excess relative to bisphenol, both ends of the polymer will form a chloroformate-pyridine adduct. In such a case, the molecular weight will be equal to the equivalent amount of bisphenol. Strictly doubled. Strictly speaking, bisphenol, phosgene and pyridine stoichiometric amounts must be used to produce a high molecular weight polycarbonate resin, but usually phosgene is slightly in excess of the theoretical amount and pyridine is more than the theoretical amount for phosgene. Slightly excessive use is most preferable because it provides a good yield. The molecular weight of the produced polycarbonate resin is mainly governed by the reaction temperature, the amount of pyridine, the amount of phosgene, the addition rate of phosgene, the amount of addition of the molecular weight regulator and the like. In the solution polymerization of the present invention, dehydrated pyridine is used as a deoxidizer, and the proportion in the reaction solvent is 5 to 100% by volume, preferably 30 to 50% by volume. In the solution method, the presence of water decomposes the phosgene-pyridine adduct or the chloroformate-pyridine adduct at the molecular end, so it must be carried out in a completely dehydrated non-aqueous system.

  In order to adjust the molecular weight in the above polymerization operation, it is desirable to use a terminal terminator as the molecular weight regulator, and therefore a substituent based on the terminator may be bonded to the terminal of the polycarbonate resin used in the present invention. . The terminal terminator used is a monovalent aromatic hydroxy compound, a haloformate derivative of a monovalent aromatic hydroxy compound, a monovalent carboxylic acid or a salt thereof, a halide derivative of a monovalent carboxylic acid, or the like. Monovalent aromatic hydroxy compounds include, for example, phenol, p-cresol, o-ethylphenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-cumylphenol, p-cyclohexylphenol, p -Octylphenol, p-nonylphenol, 2,4-xylenol, p-methoxyphenol, p-hexyloxyphenol, p-decyloxyphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, p-bromophenol, Pentabromophenol, pentachlorophenol, p-phenylphenol, p-isopropenylphenol, 2,4-di (1'-methyl-1'-phenylethyl) phenol, β-naphthol, α-naphthol, p- (2 ′, 4 ', 4'-trimethylchromanyl) phenol, phenols such as 2- (4'-methoxyphenyl) -2- (4 "-hydroxyphenyl) propane, or alkali metal salts and alkaline earth metal salts thereof. The haloformate derivative of the monovalent aromatic hydroxy compound is the haloformate derivative of the monovalent aromatic hydroxy compound described above.

Examples of monovalent carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid, 3-methylbutyric acid, 3,3-dimethylbutyric acid, 4- Fatty acids such as methyl valeric acid, 3,3-dimethyl valeric acid, 4-methyl caproic acid, 3,5-dimethyl caproic acid, phenoxyacetic acid or the like, alkali metal salts and alkaline earth metal salts thereof, benzoic acid, p- Benzoic acids such as methylbenzoic acid, p-tert-butylbenzoic acid, p-butoxybenzoic acid, p-octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid, p-chlorobenzoic acid or their alkalis Metal salts and alkaline earth metal salts. Examples of the monovalent carboxylic acid halide derivative include the above-described monovalent carboxylic acid halide derivatives. These terminal blocking agents may be used alone or in combination. The end-capping agent is preferably a monovalent aromatic hydroxy compound, and more preferably phenol, p-tert-butylphenol or p-cumylphenol. The preferred viscosity average molecular weight of the polycarbonate resin of the present invention is 1,000 to 200,000, more preferably 10,000 to 100,000. The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.
As described above, a molecular weight regulator can be added as necessary to obtain a desired molecular weight.
In this case, the amount of the molecular weight regulator added is preferably 0.1% by weight to 10% by weight, more preferably 0.1% by weight to 5% by weight with respect to the polycarbonate resin. If it is less than 0.1% by weight, the molecular weight may be abnormally high. If it exceeds 10% by weight, a sufficient molecular weight cannot be obtained.

  Also, a small amount of a branching agent can be added during the polymerization in order to improve the mechanical properties. The branching agent used is a compound having three or more (same or different) reactive groups selected from an aromatic hydroxy group, a haloformate group, a carboxylic acid group, a carboxylic acid halide group, or an active halogen atom. is there. Specific examples of the branching agent include phloroglucinol, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4,6-tris. (4'-hydroxyphenyl) heptane, 1,3,5-tris (4'-hydroxyphenyl) benzene, 1,1,1-tris (4'-hydroxyphenyl) ethane, 1,1,2-tris (4 '-Hydroxyphenyl) propane, α, α, α'-tris (4'-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 2,4-bis [α-methyl-α- (4'-hydroxyphenyl) ) Ethyl] phenol, 2- (4′-hydroxyphenyl) -2- (2 ″, 4 ″ -dihydroxyphenyl) propane, tris (4-hydroxyphenyl) phosphine, 1,1,4,4- Tetrakis (4′-hydroxyphenyl) cyclohexane, 2,2-bis [4 ′, 4′-bis (4 ″ -hydroxyphenyl) cyclohexyl] propane, α, α, α ′, α′-tetrakis (4′-hydroxy) Phenyl) -1,4-diethylbenzene, 2,2,5,5-tetrakis (4'-hydroxyphenyl) hexane, 1,1,2,3-tetrakis (4'-hydroxyphenyl) propane, 1,4-bis (4 ′, 4 ″ -dihydroxytriphenylmethyl) benzene, 3,3 ′, 5,5′-tetrahydroxydiphenyl ether, 3,5-dihydroxybenzoic acid, 3,5-bis (chlorocarbonyloxy) benzoic acid, 4 -Hydroxyisophthalic acid, 4-chlorocarbonyloxyisophthalic acid, 5-hydroxyphthalic acid, 5-chlorocarbonylo Shifutaru acid, trimesic acid trichloride, a cyanuric acid chloride or the like. These branching agents may be used alone or in combination.

  The polycarbonate resin obtained as described above is used after pyridine removal, washing with water and reprecipitation. In addition, additives such as an antioxidant, a light stabilizer, a heat stabilizer, and a plasticizer can be added to the aromatic polycarbonate resin produced according to the above method, if necessary.

  As described above, the polycarbonate resin having the acrylic-modified polyorganosiloxane that is suitably used for the photosensitive layer of the electrophotographic photoreceptor of the present invention has been described. Embodiments in which this is contained in the photosensitive layer will be described below. .

<About the layer structure of the electrophotographic photoreceptor>
The electrophotographic photosensitive member of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view of the electrophotographic photosensitive member of the present invention, which is a single-layered photosensitive member in which a photosensitive layer having a charge generating function and a charge transporting function is provided on a conductive support.
FIG. 2 shows a photoreceptor having a laminated structure in which a charge generation layer having a charge generation function and a charge transport layer having a charge transport material function are laminated on a conductive support.

<About conductive support>
Examples of the conductive support include those having a volume resistance of 1 × 10 ¹⁰ Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, indium oxide Evaporation or sputtering of metal oxides such as film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. Thereafter, a tube subjected to surface treatment such as cutting, superfinishing, or 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-vinylcarbazole, 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.

  Further, 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, polytetrafluoroethylene-based fluororesin on a suitable cylindrical substrate. Those provided with a conductive layer can be used favorably as the conductive support of the present invention.

<About photosensitive layer>
Next, the photosensitive layer will be described. The photosensitive layer may have a laminated structure or a single layer structure.
In the case of a laminated structure, the photosensitive layer is composed of a charge generation layer having a charge generation function and a charge transport layer having a charge transport function. In the case of a single layer structure, the photosensitive layer is a layer having a charge generation function and a charge transport function at the same time.

Hereinafter, each of the photosensitive layer having a laminated structure and the photosensitive layer having a single layer structure will be described.
<Photosensitive layer having a laminated structure>
(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 carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo pigments having a bis-stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, 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, Japanese Unexamined Patent Publication Nos. 04-011627, 04-175337, 04-183719, 04-2225014, 04-230767, 04-320420, 05 -232727, JP-A 05-310904, JP-A 06-234836, JP-A 06-234837, JP-A 06-234838, JP-A 06-234839, JP-A 06-234840. No. 1, JP-A 06-234841, JP-A 06-239049, Japanese Unexamined Patent Publication Nos. 06-236050, 06-236051, 06-295077, 07-0756374, 08-176293, 08-208820, 08 No. -21640, JP 08-253568, JP 08-269183, JP 09-062019, JP 09-043883, JP 09-71642, JP 09-87376. No. 1, JP-A 09-104746, JP 09-110974, JP 09-110976, JP 09-157378, JP 09-221544, JP 09-227669. JP 09-235367 A, JP 09-241369 A Charge transporting polymer materials described in JP 09-268226 A, JP 09-272735 A, JP 09-302084 A, JP 09-302085 A, JP 09-328539 A, etc. Can be mentioned.
Specific examples of the latter include polysilylene polymers described in, for example, JP-A No. 63-285552, JP-A No. 05-19497, JP-A No. 05-70595, JP-A No. 10-73944, and the like. Illustrated.

The charge generation layer 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.

Representative 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 the charge transport material having the charge transport structure and the aromatic polycarbonate resin having the acrylic modified polyorganosiloxane structure of the present invention are dissolved or dispersed in a suitable solvent, and this is charged. It is formed by applying and drying on the generation layer. At this time, the film thickness of the charge transport layer is suitably about 10 to 40 μm, preferably 10 to 25 μm.
As the charge transport material, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer can be used.
The amount of the charge transport material is preferably 20 to 300 parts by weight, more preferably 40 to 150 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin having an acrylic modified polyorganosiloxane structure.
As the solvent used for the coating of the charge transport layer, the same solvent as the charge generation layer can be used, but a solvent that dissolves the charge transport material and the aromatic polycarbonate resin having an acrylic modified polyorganosiloxane structure is suitable. Yes. These solvents may be used alone or in combination of two or more. The charge transport layer can be formed by the same coating method as that for the charge generation layer.

If necessary, a plasticizer and a leveling agent can be added.
As the plasticizer that can be used in combination with the charge transport layer, those used as general resin plasticizers such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is 0 to 100 parts by weight of the aromatic polycarbonate. About 30 parts by weight is appropriate.
Examples of leveling agents that can be used in the charge transport layer include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount used is an aromatic polycarbonate. About 0 to 1 part by weight is appropriate for 100 parts by weight.

<Single photosensitive layer>
The photosensitive layer having a single layer structure is a layer having both a charge generation function and a charge transport function, and the aromatic polycarbonate resin having an acrylic modified polyorganosiloxane structure of the present invention is usefully used as a binder resin. This photosensitive layer can be formed by dissolving or dispersing a charge generating material having a charge generating function, a charge transporting material having a charge transport function, and a binder resin in an appropriate solvent, and applying and drying the solution. The film thickness of the photosensitive layer is preferably 10 to 40 μm, more preferably 10 to 25 μm.
Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. As the charge generation material dispersion method, the charge generation material, the charge transport material, the plasticizer, and the leveling agent may be the same as those already described in the charge generation layer and the charge transport layer.
The charge generating material contained in the photosensitive layer having a single layer structure is preferably 1 to 30% by weight based on the total amount of the photosensitive layer, and the aromatic polycarbonate resin having an acrylic-modified polyorganosiloxane structure is 20 to 80% by weight of the total amount. The transport material is preferably used in an amount of 10 to 70 parts by weight.

<About the 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, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.
These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, in the undercoat layer of the present invention, Al ₂ O ₃ is provided by anodization, organic substances such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

<Addition of antioxidant to each layer>
In the present invention, in order to improve environmental resistance, an antioxidant is added to each of the charge generation layer, the charge transport layer, and the undercoat layer, particularly for the purpose of preventing a decrease in sensitivity and an increase in residual potential. can do.
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- [meth -3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyl Rick acid] cricol ester, tocopherols and the like.

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

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

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

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

These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
The addition amount of the antioxidant in the present invention is suitably 0.01 to 10% by weight with respect to 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 an aromatic polycarbonate resin having an acrylic-modified polyorganosiloxane structure as a binder resin. For example, at least the photoconductor is charged, exposed to an image, and developed. An image forming method and an image forming apparatus including a process of transferring a toner image onto an image holding member (transfer paper), fixing, and cleaning the surface of the photosensitive member after passing through the process.
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, the image exposure unit (5) is used to form an electrostatic latent image on the uniformly charged photoreceptor (1). As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

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

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

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

Next, a fur brush (14) and a cleaning blade (15) are used to clean the toner remaining on the photoreceptor after transfer. Further, a pre-cleaning charger (13) may be used in order to perform cleaning more efficiently. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination.
Next, a neutralizing unit is used for the purpose of removing the latent image on the photoreceptor as required. As the charge removal means, a charge removal lamp (2) and a charge removal charger are used, and the exposure light source and the charging means can be used respectively.

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

The present invention is an image forming method and an image forming apparatus using the electrophotographic photoreceptor according to the present invention for such image forming means.
The image forming means may be fixedly incorporated in a copying apparatus, facsimile, or printer, but may be incorporated in these apparatuses in the form of a process cartridge and detachable. An example of the process cartridge is shown in FIG.
The process cartridge for the image forming apparatus includes a photoreceptor (101), and in addition, a charging unit (102), a developing unit (104), a transfer unit (106), a cleaning unit (107), and a discharging unit (not shown). ), And an apparatus (part) that can be attached to and detached from the image forming apparatus main body.

  Referring to the image forming process by the apparatus illustrated in FIG. 4, the photosensitive member (101) is rotated on the surface of the photosensitive member (101) by charging by the charging means (102) and exposure by the exposure means (103) while rotating in the clockwise direction. An electrostatic latent image corresponding to the exposure image is formed, and this 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), Printed out. Next, the surface of the photoconductor after the image transfer is cleaned by a cleaning unit (107), and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

The present invention provides a process cartridge for an image forming apparatus in which a photosensitive member using an aromatic polycarbonate resin having an acrylic modified polyorganosiloxane structure as a binder resin and at least one of charging, developing, transferring, cleaning, and static eliminating means are integrated. To do.
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.

  Hereinafter, the present invention will be described by way of examples.

<Production example>
Although the manufacture example of the acrylic modified polyorganosiloxane which has a hydroxyl group is demonstrated concretely, this invention is not restrict | limited to the following manufacture example. In addition, the part and% in an example show a weight part and weight%, respectively.

<Preparation of organopolysiloxane>
After mixing 1,500 parts of octamethylcyclotetrasiloxane, 8.8 parts of vinyldimethoxymethylsilane, and 1,500 parts of ion-exchanged water, 15 parts of sodium lauryl sulfate and 10 parts of dodecylbenzenesulfonic acid are added thereto. After stirring and emulsifying with a homomixer, the emulsion was passed twice through a homogenizer at a pressure of 3,000 bar to form a stable emulsion. Next, this was charged into a flask, heated at 70 ° C. for 12 hours, cooled to 25 ° C. and aged for 24 hours. Then, the pH of the emulsion was adjusted to 7 using sodium carbonate, and nitrogen gas was blown in for 4 hours. The volatile siloxane was distilled off by steam distillation, and then ion-exchanged water was added to adjust the non-volatile content to 45% to obtain a polysiloxane emulsion.

<Manufacture of copolymer emulsion>
Into a 2 L three-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet, 778 parts of the emulsion obtained above (350 parts of siloxane) and 322 parts of ion-exchanged water were charged under a nitrogen gas stream. After adjusting the inside of the vessel to 30 ° C., 1.0 part of t-butyl hydroperoxide, 0.5 part of L-ascorbic acid and 0.002 part of ferrous sulfate heptahydrate are added, and then the inside temperature is increased. While maintaining at 30 ° C., 112.4 parts of methyl methacrylate, 7.5 parts of tris (2-acryloyloxyethyl) isocyanurate, 30 parts of 3- (N-benzotriazole) -4-hydroxyphenethyl-methacrylate for 5 hours It was dripped over. After completion of the dropwise addition, stirring was further continued for 3 hours to complete the reaction. The resulting copolymer emulsion had a solid content concentration of 39.6%.
Next, 1000 parts of this emulsion was placed in a flask equipped with a stirrer and heated to 80 ° C., and a solution in which 70 parts of sodium sulfate was dissolved in 280 parts of ion-exchanged water was added to precipitate acrylic modified polyorganosiloxane, which was filtered and washed with water. Was repeated and dried at 80 ° C. to obtain an acrylic-modified polyorganosiloxane.

(Example 1)
0.26 g of acrylic modified polyorganosiloxane obtained in the production example in a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel, 1,1-bis (4-hydroxyphenyl) cyclohexane as diol 4.56 g, 35 ml of dehydrated pyridine and 5 ml of dehydrated toluene were added and dissolved by stirring under a nitrogen gas stream. A solution prepared by dissolving 2.0 g of bis (trichloromethane) carbonate, which is a phosgene trimer, in 10 ml of dehydrated toluene was added dropwise over 20 minutes while keeping the internal temperature at 20 ° C. in a water bath. The reaction was carried out for 1.5 hours. After the stirring was stopped, the reaction solution was washed with 5% aqueous hydrochloric acid solution and then with ion exchange water. The obtained solution was dropped into 1.5 liters of methanol to precipitate a white polycarbonate resin, which was dried to obtain 4.1 g of a polycarbonate resin (resin No. 1) having an acrylic modified polyorganosiloxane structure. The viscosity average molecular weight using dichloromethane as a solvent was 54,000. The infrared absorption spectrum (cast film on NaCl plate) is shown in FIG.

(Example 2)
0.26 g of acrylic modified polyorganosiloxane obtained in the production example in a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel, 1,1-bis (4-hydroxyphenyl) cyclohexane as diol 4.56 g, dehydrated pyridine 15 ml and dehydrated dichloromethane 25 ml were added and dissolved by stirring under a nitrogen gas stream. A solution prepared by dissolving 2.0 g of bis (trichloromethane) carbonate, which is a phosgene trimer, in 10 ml of dehydrated dichloromethane was added dropwise over 20 minutes while maintaining the internal temperature at 20 ° C. in a water bath. The reaction was carried out for 1 hour. After the stirring was stopped, the reaction solution was washed with 5% aqueous hydrochloric acid solution and then with ion exchange water. The obtained solution was dropped into 1.5 liters of methanol to precipitate a yellow polycarbonate resin and dried to obtain 4.1 g of a polycarbonate resin (resin No. 2) having an acrylic-modified polyorganosiloxane structure. . The viscosity average molecular weight using dichloromethane as a solvent was 73,000. The infrared absorption spectrum (cast film on NaCl plate) is shown in FIG.

(Example 3)
Acrylic-modified polyorganosiloxane 0.56 g obtained in Production Example in a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel, 1,1-bis (4-hydroxyphenyl) cyclohexane as diol 4.56 g, dehydrated pyridine 15 ml and dehydrated dichloromethane 25 ml were added and dissolved by stirring under a nitrogen gas stream. A solution prepared by dissolving 2.0 g of bis (trichloromethane) carbonate, which is a phosgene trimer, in 10 ml of dehydrated dichloromethane was added dropwise over 20 minutes while maintaining the internal temperature at 20 ° C. in a water bath. The reaction was carried out for 1 hour. After the stirring was stopped, the reaction solution was washed with 5% aqueous hydrochloric acid solution and then with ion exchange water. The obtained solution was dropped into 1.5 liters of methanol to precipitate a yellow polycarbonate resin and dried to obtain 4.1 g of a polycarbonate resin (resin No. 3) having an acrylic modified polyorganosiloxane. The viscosity average molecular weight using dichloromethane as a solvent was 44,000. The infrared absorption spectrum (cast film on NaCl plate) is shown in FIG.

(Comparative Example 1)
Polymerization was carried out by the interfacial polymerization method described in JP-A-9-272735. That is, 0.26 g of the acrylic-modified polyorganosiloxane obtained in the production example, 4.56 g of 1,1-bis (4-hydroxyphenyl) cyclohexane as a diol, and 15 mg of 4-tert-butylphenol as a molecular weight regulator are stirred and reacted. In a container, a solution prepared by dissolving 2.62 g of sodium hydroxide and 66 mg of sodium hydrosulfite in 34.0 ml of water was added and dispersed by stirring under a nitrogen stream. Thereafter, the solution is cooled to 20 ° C., and a solution of 1.44 g of phosgene trimer bis (trichloromethyl) carbonate dissolved in 28 ml of dichloromethane is added with vigorous stirring and stirred for 15 minutes to form a uniform emulsion. There wasn't. Thereafter, one drop of triethylamine was added as a catalyst and stirred vigorously at room temperature. However, the reaction solution did not thicken and the desired polycarbonate could not be obtained. This is presumed to be because the acrylic-modified polyorganosiloxane is not sufficiently dissolved.

(Example 4)
A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a methanol / butanol mixed solvent was applied onto an aluminum plate with a doctor blade, and air dried to provide a 0.3 μm peeling prevention layer.
Next, the resin No. 1 obtained in Example 1 was used. 1 polycarbonate resin was dissolved in dichloromethane, and this solution was applied onto the peeling prevention layer with a doctor blade, air dried, and then dried at 120 ° C. for 20 minutes to prepare a polycarbonate film having a thickness of 20 μm.
A Taber abrasion test was conducted using the obtained polycarbonate film as a sample. In accordance with the industrial standard JIS K 7204 (1995), using a CS-10 wear wheel with a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.), 1500 cycles of wear test with no load (wear wheel's own weight). The amount of wear after the spotting is shown in Table 5. Using the photoreceptor after the Taber abrasion test as a sample, the pure water contact angle of the worn surface was measured with AUTOMATIC CONTACT ANGLE METER (KYOWA INTERFACE SCIENCE Co. LTD). Using the same sample, the static friction coefficient between the stainless steel ball and the wear surface was measured with a fully automatic friction and wear analyzer (Kyowa Interface Science Co., Ltd.). The results are shown in Table 5.

(Example 5)
In Example 4, resin no. A polycarbonate film was formed in the same manner as in Example 4 except that the polycarbonate resin in Example 1 was changed to that in Example 2 (resin No. 2), and the Taber abrasion test, the pure water contact angle, and the static friction coefficient were measured. . The results are shown in Table 5.

(Example 6)
In Example 4, resin no. A polycarbonate film was formed in the same manner as in Example 4 except that the polycarbonate resin in Example 1 was changed to the polycarbonate resin in Example 3 (resin No. 3), and the Taber abrasion test, the pure water contact angle and the static friction coefficient were measured. . The results are shown in Table 5.

(Comparative Example 2)
In Example 4, resin no. An electrophotographic photoreceptor was produced in the same manner as in Example 4 except that the polycarbonate resin 1 was replaced with a polycarbonate resin (Panlite TS2050, manufactured by Teijin Chemicals Ltd.). A polycarbonate film was formed in the same manner as in Example 4, and a Taber abrasion test, a pure water contact angle, and a static friction coefficient were measured. The results are shown in Table 5.

これらの結果から明らかなように、本発明の芳香族ポリカーボネート樹脂は比較例に比べ撥水性と低摩擦性を有していることがわかる。

As is clear from these results, it can be seen that the aromatic polycarbonate resin of the present invention has water repellency and low friction compared to the comparative example.

(Example 7)
The polycarbonate resin membrane sections of Examples 4 to 6 were stained with ruthenic acid vapor, and the morphology was observed with a transmission electron microscope (H-9000NAR).
As a result, it can be seen that all the films have a so-called microphase separation structure in which the acrylic-modified polyorganosiloxane is uniformly distributed in the matrix phase of the polycarbonate resin.

(Example 8)
A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a methanol / butanol mixed solvent was applied onto an aluminum plate with a doctor blade, and air dried to provide a 0.3 μm intermediate layer. On this, a bisazo compound represented by the following formula as a charge generating material is pulverized by a ball mill in a mixed solvent of cyclohexanone and 2-butanone, and the resulting dispersion is applied with a doctor blade, and then air-dried to 0.5 μm. A charge generation layer was formed.

  Next, the resin No. 1 obtained in Example 1 was used. 1 polycarbonate resin and a charge transport material represented by the following formula are dissolved in dichloromethane, this solution is applied onto the charge generation layer with a doctor blade, air-dried, and then dried at 120 ° C. for 20 minutes to a thickness of 20 μm. A charge transport layer was formed to prepare a photoreceptor.

The photoreceptor thus prepared was charged by performing a -6 KV corona discharge for 20 seconds in the dark using a commercially available electrostatic copying paper testing apparatus [SP428 type manufactured by Kawaguchi Electric Co., Ltd.] The surface potential Vm (V) was measured, and after being left in the dark for 20 seconds, the surface potential V0 (V) was measured. Next, a tungsten lamp light is irradiated so that the illuminance on the surface of the photosensitive member becomes 5.3 lux, and the time (second) until V0 becomes 1/2 is obtained, and the exposure amount E1 / 2 (lux · sec) Was calculated. The results are shown below.
Vm = -1730 V
V0 = -1570 V
E1 / 2 = 0.67 lux · sec

Example 9
In Example 8, resin no. 1 polycarbonate resin. An electrophotographic photosensitive member was produced in the same manner as in Example 8 except that the polycarbonate resin 2 was used.
The electrical characteristics were evaluated in the same manner as in Example 8. The results are shown below.
Vm = -1710 V
V0 = -1546 V
E1 / 2 = 0.63 lux · sec

(Example 10)
In Example 8, resin no. 1 polycarbonate resin. An electrophotographic photoreceptor was produced in the same manner as in Example 8 except that the polycarbonate resin 3 was used.
The electrical characteristics were evaluated in the same manner as in Example 8. The results are shown below.
Vm = -1746 V
V0 = −1601 V
E1 / 2 = 0.69 lux ・ sec

  Further, after charging the photoconductors prepared in Examples 8 to 10 using a commercially available electrophotographic copying machine, light irradiation is performed through the original drawing to form an electrostatic latent image, and a dry developer is used. When the resulting image (toner image) was electrostatically transferred and fixed on plain paper, a clear transferred image was obtained. Similarly, a clear transfer image was obtained when a wet developer was used as the developer.

(Example 11)
A Taber abrasion test was conducted using the photoreceptor obtained in Example 8 as a sample. In accordance with the industrial standard JIS K 7204 (1995), using a CS-10 wear wheel with a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.), performing a wear test of 1,500 revolutions without load (the weight of the wear wheel) Table 6 shows the amount of wear after 1,500 revolutions. Using the photoreceptor after the Taber abrasion test as a sample, the pure water contact angle of the worn surface was measured with AUTOMATIC CONTACT ANGLE METER (KYOWA INTERFACE SCIENCE Co. LTD). Using the same sample, the static friction coefficient between the stainless steel ball and the wear surface was measured with a fully automatic friction and wear analyzer (Kyowa Interface Science Co., Ltd.). The results are shown in Table 6.

Example 12
The photoreceptor used in Example 9 was subjected to the same Taber abrasion test, pure water contact angle and static friction coefficient as in Example 11. The results are shown in Table 6.

(Example 13)
The photoreceptor used in Example 10 was subjected to the Taber abrasion test, pure water contact angle and static friction coefficient measurement in the same manner as in Example 11. The results are shown in Table 6.

(Comparative Example 3)
In Example 8, resin no. An electrophotographic photoreceptor was produced in the same manner as in Example 8, except that the polycarbonate resin 1 was replaced with a polycarbonate resin represented by the following structural formula (Panlite TS2050, manufactured by Teijin Chemicals Ltd.). The Taber abrasion test, pure water contact angle, and static friction coefficient were measured in the same manner as in Example 11. The results are shown in Table 6.

(Comparative Example 4)
In Example 8, resin no. 1 polycarbonate resin of the same usage ratio, an acrylic-modified polyorganosiloxane (Charine R-170S) whose main chain is polyorganosiloxane and whose side chain is acrylic (acrylic / polyorganosiloxane weight ratio 3/7) An electrophotographic photoreceptor was produced in the same manner as in Example 8, except that the mixture was changed to a polycarbonate resin (Panlite TS2050, manufactured by Teijin Chemicals Ltd.). The Taber abrasion test, pure water contact angle, and static friction coefficient were measured in the same manner as in Example 11. The results are shown in Table 6.

これらの結果から明らかなように、本発明の芳香族ポリカーボネート樹脂を含有する感光体は比較例に比べ撥水性と低摩擦性を有していることがわかる。

As is apparent from these results, it can be seen that the photoreceptor containing the aromatic polycarbonate resin of the present invention has water repellency and low friction compared to the comparative example.

(Example 14)
The charge transport layer sections of the photoreceptors of Examples 11 to 13 were stained with ruthenic acid vapor, and the morphology was observed with a transmission electron microscope (H-9000NAR).
As a result, it can be seen that any charge transport layer exhibits a so-called microphase separation structure in which the acrylic-modified polyorganosiloxane dispersed phase is uniformly distributed in the matrix phase of the polycarbonate resin.

(Comparative Example 5)
The charge transport layer section of the photoreceptor of Comparative Example 4 was stained with ruthenic acid vapor, and the morphology was observed with a transmission electron microscope (H-9000NAR).
It can be seen that huge acrylic-modified polyorganosiloxane aggregates of several micrometers are present in the matrix phase of the polycarbonate.

1 is a cross-sectional view of an electrophotographic photosensitive member having a single layer structure in which a photosensitive layer is provided on a conductive support according to the present invention. FIG. 2 is a cross-sectional view of an electrophotographic photoreceptor having a laminated structure in which a charge generation layer having a charge generation function and a charge transport layer having a charge transport material function are laminated on a conductive support according to the present invention. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. FIG. 2 is a schematic diagram illustrating an example of a process cartridge for an image forming apparatus according to the present invention. It is an infrared absorption spectrum figure of aromatic polycarbonate resin (No. 1) obtained in Example 1 (cast film on a NaCl board). It is an infrared absorption spectrum figure of aromatic polycarbonate resin (No. 2) obtained in Example 2 (cast film | membrane on a NaCl board). It is an infrared absorption spectrum figure of aromatic polycarbonate resin (No. 3) obtained in Example 3 (cast film on a NaCl board).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger charger 4 Eraser 5 Image exposure part 6 Development unit 7 Charger before transfer 8 Registration roller 9 Transfer body 10 Transfer charger 11 Separation charger 12 Separation nail 13 Charger before cleaning 14 Fur brush 15 Cleaning blade 101 Photoconductor 102 Charging means 103 Exposure means 104 Development means 105 Transfer body 106 Transfer means 107 Cleaning means

Claims (11)

An aromatic polycarbonate resin obtained by condensation polymerization of an acrylic-modified polyorganosiloxane having a hydroxyl group, a diol compound represented by the following general formula (a) and a carbonic acid derivative.

[Wherein, X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or

(Where R ¹ , R ² , R ³ , R ⁴ are each independently an alkyl group, an aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, and c and d are Each independently represents an integer of 0 to 3, and Y ¹ represents a single bond, a linear alkylene group having 2 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —, —. CO-, -COO-, or the following formula

Z ¹ and Z ² represent an aliphatic divalent group or an arylene group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, Represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group, and R ⁵ and R ⁶ are bonded to form a carbocyclic or heterocyclic ring having 6 to 12 carbon atoms. R ⁵ and R ⁶ may form a carbocyclic or heterocyclic ring together with R ¹ and R ^2, and R ¹² and R ¹³ are a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁴ and R ¹⁵ each independently represents an alkyl group having 1 to 5 carbon atoms or an aryl group, e is an integer of 0 to 4, f is an integer of 0 to 20, and g is an integer of 0 to 2000. Represents. ). ] The aromatic polycarbonate resin according to claim 1, wherein the acrylic-modified polyorganosiloxane having a hydroxyl group is a compound obtained by grafting an acrylic monomer to a silicone main chain. The aromatic polycarbonate resin according to claim 1 or 2, wherein the hydroxyl group of the acrylic-modified polyorganosiloxane is a phenolic hydroxyl group. The aromatic polycarbonate resin according to any one of claims 1 to 3, wherein the hydroxyl group of the acrylic-modified polyorganosiloxane is derived from a hydroxyphenethyl-methacrylate compound represented by the following structural formula.

The aromatic polycarbonate resin according to any one of claims 1 to 4, wherein the acrylic-modified polyorganosiloxane is granular. The condensation polymerization of the acrylic-modified polyorganosiloxane having a hydroxyl group according to claim 1, the diol compound represented by the general formula (a) and a carbonyl halide compound is performed by solution polymerization. Process for producing an aromatic polycarbonate resin. The method for producing an aromatic polycarbonate resin according to claim 6, wherein dehydrated pyridine is used as a deoxidizing agent in the solution polymerization, and the ratio in the reaction solvent is 5 to 100% by volume. An electrophotographic photosensitive member comprising a photosensitive layer containing the aromatic polycarbonate resin according to claim 1 as an active ingredient. 9. An image forming method, wherein at least charging, image exposure, development and transfer are repeated using the electrophotographic photosensitive member according to claim 8. An image forming apparatus comprising the electrophotographic photosensitive member according to claim 8. 9. The electrophotographic photosensitive member according to claim 8 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 charge eliminating means, and is attached to and detached from the image forming apparatus main body. A process cartridge for an image forming apparatus, characterized by being made possible.

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