JP2005092136A - Electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high sensitivity and high durability by using aromatic polycarbonate resin having specific diphenyl ether for an organic photoreceptor and/or an aromatic polycarbonate resin having charge transport. <P>SOLUTION: The electrophotographic photoreceptor is provided with a photosensitive layer containing as an effective component the polycarbonate resin having a repeating unit represented in general formula (1) on a conductive support. Here, in the general formula (1), A<SB>1</SB>denotes a substituted or non-substituted alkyl group, a substituted or non-substituted aryl group, and A<SB>2</SB>-A<SB>7</SB>is independently hydrogen atoms, halogen atoms, a substituted or non-substituted alkyl group of the number of carbons of 1-6. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photoreceptor containing a polycarbonate resin having a specific repeating unit useful as an electrophotographic photoreceptor material, and more specifically, a polycarbonate resin having a specific diphenyl ether structure and / or charge transport in a photosensitive layer. The present invention relates to a highly sensitive and highly durable photoreceptor for electrophotography containing an aromatic polycarbonate having the above.

  In recent years, organic photoreceptors (OPCs) are often used in copying machines and printers. As a typical configuration example of the organic photoreceptor, there is a laminated photoreceptor in which a charge generation layer (CGL) and a charge transport layer (CTL) are sequentially laminated on a conductive substrate. The charge transport layer is formed of a low molecular charge transport material (CTM) and a binder resin, and many aromatic polycarbonate resins have been proposed as the binder resin. However, the inclusion of a low-molecular charge transport material reduces the mechanical strength inherent in the binder resin, which causes wear, scratches, cracks, etc. of the photoreceptor and impairs the durability of the photoreceptor. It has become.

  In the past, vinyl polymers such as polyvinyl anthracene, polyvinyl pyrene, and poly-N-vinyl carbazole have been studied as charge transfer complex type photoconductors as photoconductive polymer materials, but they are satisfactory in terms of photosensitivity. It wasn't. On the other hand, in order to improve the drawbacks of the above-mentioned laminated type photoconductor, studies on a polymer material having a charge transporting ability have been made. For example, an acrylic resin having a triphenylamine structure (for example, see Non-Patent Document 1), a vinyl polymer having a hydrazone structure (for example, see Non-Patent Document 2), and a polycarbonate resin having a triarylamine structure (for example, Patent Documents 1 to 16), etc., but has not been put into practical use.

In addition, M.M. A. Abkowitz et al. Compared a low-dispersion type and a polymerized polycarbonate using a tetraarylbenzidine derivative as a model compound, but the polymer system has obtained a result that the drift mobility is an order of magnitude lower (for example, Non-Patent Document 3). Although the cause of this is not clear, it suggests that there are problems in electrical characteristics such as sensitivity and residual potential, although the mechanical strength is improved by polymerizing.
Although the cause of this is not clear, in the case of polymers having a charge transporting skeleton in the main chain, represented by tetraarylbenzidine derivatives, especially polycarbonate resins, electron withdrawing substituted with aryl groups on the tetraarylbenzidine skeleton It is presumed that electron localization occurs due to the electron donating effect of the neutral carbonyldioxy group and the tertiary amine, resulting in a molecular design that is disadvantageous for hole movement. This seems to be the cause of insufficient electrical properties such as sensitivity and residual potential due to the polymerization.
On the other hand, as a new attempt, Patent Document 17 discusses polyarylene vinylene.

US Pat. No. 4,801,517 US Pat. No. 4,806,443 US Pat. No. 4,806,444 US Pat. No. 4,937,165 US Pat. No. 4,959,288 US Pat. No. 5,030,532 US Pat. No. 5,034,296 US Pat. No. 5,080,989 Japanese Patent Laid-Open No. 64-9964 Japanese Patent Laid-Open No. 3-221522 JP-A-2-304456 JP-A-4-11627 Japanese Patent Laid-Open No. 4-175337 JP-A-4-18371 JP-A-4-31404 Japanese Patent Laid-Open No. 4-130665 Japanese Patent Laid-Open No. 10-310635 M. Stolka et al, J. Polym. Sci., Vol 21, 969 (1983) Japan Hard Copy '89 P. 67 Physical Review B46 6705 (1992)

  Accordingly, the present invention has been made in view of the above-described prior art, and uses an aromatic polycarbonate resin having a specific diphenyl ether structure and / or an aromatic polycarbonate resin having charge transport for use in an organic photoreceptor. Accordingly, an object of the present invention is to provide a highly sensitive and highly durable electrophotographic photoreceptor.

As a result of intensive studies, the present inventors have found that the above problems can be solved by providing an electrophotographic photoreceptor containing a polymer having a specific repeating unit, and have completed the present invention.
That is, the above-mentioned problem is characterized in that (1) “a photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (I) as an active ingredient is provided on a conductive support” of the present invention. An electrophotographic photoreceptor;

（式中、Ａ_１は置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表わし、Ａ_２〜Ａ_７は各々独立して水素原子、ハロゲン原子、炭素数１〜６の置換もしくは無置換のアルキル基を表わす。）」、（２）「導電性支持体上に、下記一般式（II）で示される繰り返し単位を有するポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

(In the formula, A ₁ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and A _{2 to} A ₇ each independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted group having 1 to 6 carbon atoms. Represents a substituted alkyl group.) ”, (2)“ A photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (II) as an active ingredient is provided on a conductive support. An electrophotographic photoreceptor;

（式中、Ａ_１は前記定義と同一である。）」、（３）「導電性支持体上に、主に上記一般式（Ｉ）或いは（II）と下記一般式（III）で表わされる構成単位からなり、一般式（Ｉ）或いは（II）で表わされる構成単位の組成比をｋ、一般式（III）で表わされる構成単位の組成比をｊとしたときに、組成比の割合が０＜ｋ／（ｋ＋ｊ）≦１であるポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

(Wherein A ₁ is the same as defined above) ”, (3)“ represented on the conductive support mainly by the general formula (I) or (II) and the following general formula (III). When the composition ratio of the structural unit represented by the general formula (I) or (II) is k and the composition ratio of the structural unit represented by the general formula (III) is j, the ratio of the composition ratio is An electrophotographic photosensitive member provided with a photosensitive layer containing, as an active ingredient, a polycarbonate resin in which 0 <k / (k + j) ≦ 1;

［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、またはこれらの２価基より選ばれた２価基を連結してできる２価基、または、

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

（ここで、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は独立して置換もしくは無置換のアルキル基、置換もしくは無置換の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は単結合、炭素原子数２〜１２の直鎖状のアルキレン基、炭素原子数３〜１２の分岐状のアルキレン基、炭素原子数３〜１２のポリオキシアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom, and a and b are each independently 0 to 0 4 is an integer of 4, c and d are each independently an integer of 0 to 3, Y is a single bond, a linear alkylene group having 2 to 12 carbon atoms, or a branched form having 3 to 12 carbon atoms. alkylene group, polyoxyalkylene group having 3 to 12 carbon atoms of, -O -, - S -, - SO -, - SO 2 -, - CO-,

から選ばれ、Ｚ^１、Ｚ^２は置換もしくは無置換の脂肪族の２価基または置換もしくは無置換のアリレン基を表わし、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２は各々独立して水素原子、ハロゲン原子、炭素数１〜５の置換もしくは無置換のアルキル基、炭素数１〜５の置換もしくは無置換のアルコキシ基、置換もしくは無置換のフェニル基を表わし、また、Ｒ^６とＲ^７は結合して炭素数５〜１２の炭素環または複素環を形成してもよく、また、Ｒ^６、Ｒ^７はＲ^２、Ｒ^３と共同で炭素環または複素環を形成してもよく、Ｒ^１３、Ｒ^１４は単結合または炭素数１〜４のアルキレン基又はポリオキシアルキレン基を表わし、Ｒ^１５、Ｒ^１６は各々独立して炭素数１〜５の置換もしくは無置換のアルキル基、置換もしくは無置換の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０〜４の整数を表わす。）を表わす。］」、（４）「導電性支持体上に、下記一般式（IV）で示される繰り返し単位を有するポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

Z ¹ and Z ^{2 each} represents a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group. , also may be ^{R 6} and ^{R 7} are bonded together to form a carbocyclic or heterocyclic ring having 5 to 12 carbon atoms, ^also R 6, ^{R 7} is or carbocyclic jointly with ^R 2, ^{R 3} complex A ring may be formed, and R ¹³ and R ^{14 each} represents a single bond, an alkylene group having 1 to 4 carbon atoms or a polyoxyalkylene group, and R ¹⁵ and R ¹⁶ are each independently substituted having 1 to 5 carbon atoms. Or an unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, e is an integer of 0 to 4, f is 0 to 20 integer, g represents an integer of 0-4. ). ], (4) "Electrophotographic photoreceptor characterized in that a photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (IV) as an active ingredient is provided on a conductive support. ;

（式中、Ａ_１〜Ａ_７およびＸは前定義と同一であり、ｎは繰り返し数で２〜５０００の整数を表わす。）」、（５）「導電性支持体上に、主に上記一般式（Ｉ）或いは（II）と下記一般式（Ｖ）で表わされる構成単位からなり、一般式（Ｉ）或いは（II）で表わされる構成単位の組成比をｋ、一般式（Ｖ）で表わされる構成単位の組成比をｊとしたときに、組成比の割合が０＜ｋ／（ｋ＋ｊ）≦１であるポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

(Wherein A _{1 to} A ₇ and X are the same as defined above, n represents an integer of 2 to 5000 in terms of the number of repetitions) ”, (5)“ on the conductive support, It is composed of structural units represented by the formula (I) or (II) and the following general formula (V), and the composition ratio of the structural units represented by the general formula (I) or (II) is represented by k and the general formula (V). And a photosensitive layer containing a polycarbonate resin having a composition ratio of 0 <k / (k + j) ≦ 1 as an active component, where j is the composition ratio of the structural unit to be produced. Photoconductor;

（式中、Ｂ_１は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表わし、Ａｒ_１は置換もしくは無置換のアリール基を表わし、Ａｒ_２，Ａｒ_３は置換もしくは無置換のアリレン基を表わす。）」、（６）「導電性支持体上に、下記一般式（VI）で示される繰り返し単位を有するポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

(In the formula, B ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, Ar ₁ represents a substituted or unsubstituted aryl group, and Ar ₂ and Ar ₃ represent substituted or unsubstituted. (Represents a substituted arylene group) ”, (6)“ A photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (VI) as an active ingredient is provided on a conductive support. An electrophotographic photoreceptor;

（式中、Ａ_１〜Ａ_７、Ａｒ_１，Ａｒ２，Ａｒ_３およびＢ_１は前定義と同一であり、ｎは繰り返し数で２〜５０００の整数を表わす。）」、（７）「導電性支持体上に、主に上記一般式（Ｉ）或いは（II）と下記一般式（VII）で表わされる構成単位からなり、一般式（Ｉ）或いは（II）で表わされる構成単位の組成比をk、一般式（VII）で表わされる構成単位の組成比をｊとしたときに、組成比の割合が０＜ｋ／（ｋ＋ｊ）≦１であるポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

(Wherein A _{1 to} A ₇ , Ar ₁ , Ar ₂ , Ar ₃ and B ₁ are the same as defined above, and n represents an integer of 2 to 5000 in terms of the number of repetitions) ”, (7)“ Conductivity On the support, mainly composed of the structural unit represented by the above general formula (I) or (II) and the following general formula (VII), the composition ratio of the structural unit represented by the general formula (I) or (II) is k, and a photosensitive layer containing, as an active ingredient, a polycarbonate resin having a composition ratio of 0 <k / (k + j) ≦ 1 when the composition ratio of the structural unit represented by the general formula (VII) is j. An electrophotographic photoreceptor characterized in that:

（式中、Ａｒ_２，Ａｒ_３は前記定義と同一であり、Ａｒ_４は置換もしくは無置換のアリレン基を表わす。Ｒ_１７，Ｒ_１８は同一または異なるアシル、基置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表わす。）」、（８）「導電性支持体上に、下記一般式（VIII）で示される繰り返し単位を有するポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

Wherein Ar ₂ and Ar ₃ are the same as defined above, Ar ₄ represents a substituted or unsubstituted arylene group. R ₁₇ and R ₁₈ are the same or different acyl, group-substituted or unsubstituted alkyl group, A substituted or unsubstituted aryl group is represented.) ”, (8)“ A photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (VIII) as an active ingredient was provided on a conductive support. An electrophotographic photoreceptor characterized by the above;

（式中、Ａ_１〜Ａ_７、Ａｒ_２、Ａｒ_３、Ａｒ_４、Ｒ_１７およびＲ_１８は前定義と同一であり、ｎは繰り返し数で２〜５０００の整数を表わす。）」、（９）「導電性支持体上に、主に上記一般式（Ｉ）或いは（II）と下記一般式（IX）で表わされる構成単位からなり、一般式（Ｉ）或いは（II）で表わされる構成単位の組成比をｋ、一般式（IX）で表わされる構成単位の組成比をｊとしたときに、組成比の割合が０＜ｋ／（ｋ＋ｊ）≦１であるポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

(In the formula, A _{1 to} A ₇ , Ar ₂ , Ar ₃ , Ar ₄ , R ₁₇ and R ₁₈ are the same as defined above, and n represents an integer of 2 to 5000 in terms of the number of repetitions) ”(9 ) "Constituent units consisting mainly of the above general formula (I) or (II) and the following general formula (IX) on the conductive support, represented by the general formula (I) or (II)" And a polycarbonate resin having a composition ratio of 0 <k / (k + j) ≦ 1 as an active ingredient, where k is the composition ratio and j is the composition ratio of the structural unit represented by the general formula (IX). An electrophotographic photosensitive member provided with a photosensitive layer;

（式中、Ｒ_１７，Ｒ_１８は前記定義と同一である。）」、（１０）「導電性支持体上に、下記一般式（Ｘ）で示される繰り返し単位を有するポリカーボネート樹脂を有効成分として含有した感光層を設けたことを特徴とする電子写真用感光体；

(In the formula, R ₁₇ and R ₁₈ are the same as defined above.) ”, (10)“ Polycarbonate resin having a repeating unit represented by the following general formula (X) on an electroconductive support as an active ingredient An electrophotographic photoreceptor comprising a photosensitive layer containing;

（式中、Ａ_１〜Ａ_７、Ｒ_１７およびＲ_１８は前定義と同一であり、ｎは繰り返し数で２〜５０００の整数を表わす。）」、（１１）「導電性支持体上に、電荷発生層及び電荷輸送層を有する電子写真用感光体において、電荷輸送層に前記第（１）項乃至第（１０）項の何れかに記載の繰り返し単位を有するポリカーボネート樹脂を有効成分として含有することを特徴とする電子写真用感光体」、（１２）「導電性支持体上に、少なくとも電荷発生物質と電荷輸送物質を含む電子写真用感光体において、電荷輸送物質として前記第（５）乃）項乃至第（１０）項の何れかに記載の繰り返し単位を有するポリカーボネート樹脂を有効成分として含有することを特徴とする電子写真用感光体」、（１３）「導電性支持体上に、少なくとも電荷発生物質と電荷輸送物質を含む電子写真用感光体において、その最表層に前記第（１）項乃至第（１０）項の何れかに記載の繰り返し単位を有するポリカーボネート樹脂を有効成分として含有することを特徴とする電子写真用感光体」、（１４）「感光層が単一層に形成される単層型電子写真感光体の感光層中に、前記第（１）項乃至第（１０）項の何れかに記載の繰り返し単位を有するポリカーボネート樹脂を有効成分として含有することを特徴とする電子写真用感光体」、（１５）「感光層が単一層に形成される単層型電子写真感光体の最表層に、前記第（１）項乃至第（１０）項の何れかに記載の繰り返し単位を有するポリカーボネート樹脂を有効成分として含有することを特徴とする電子写真用感光体」、（１６）「前記第（１）項乃至第（１０）項の何れかに記載の繰り返し単位を有するポリカーボネート樹脂が、ゲル浸透クロマトグラフィーにおいてその重量平均分子量（ポリスチレン換算）が７０００から１００００００であることを特徴とする前記第（１）項乃至第（１５）項の何れかに記載の電子写真用感光体」により達成される。

(Wherein A _{1 to} A ₇ , R ₁₇ and R ₁₈ are the same as defined above, n represents an integer of 2 to 5000 in terms of the number of repetitions) ”, (11)“ on the conductive support, In the electrophotographic photoreceptor having a charge generation layer and a charge transport layer, the charge transport layer contains a polycarbonate resin having a repeating unit according to any one of the items (1) to (10) as an active ingredient. (12) “In an electrophotographic photoreceptor comprising at least a charge generating substance and a charge transporting substance on a conductive support, the above-mentioned (5) No. 5 is used as a charge transporting substance. ) To (10) “a photosensitive member for electrophotography, comprising a polycarbonate resin having a repeating unit according to any one of items (10) to (10)” as an active ingredient. Charge generation In an electrophotographic photoreceptor containing a substance and a charge transporting substance, the outermost layer contains a polycarbonate resin having a repeating unit according to any one of (1) to (10) as an active ingredient. Characteristic electrophotographic photoreceptor ”, (14)“ In the photosensitive layer of the single-layer type electrophotographic photoreceptor in which the photosensitive layer is formed as a single layer, any one of the above items (1) to (10) ” An electrophotographic photoreceptor comprising a polycarbonate resin having a repeating unit as described above as an active ingredient, and (15) “a single-layer electrophotographic photoreceptor having a photosensitive layer formed as a single layer. An electrophotographic photoreceptor characterized in that the surface layer contains a polycarbonate resin having the repeating unit according to any one of the items (1) to (10) as an active ingredient ”, (16)“ The above ” The first (1) item Item (1) to Item (1), wherein the polycarbonate resin having the repeating unit according to any one of Items (10) has a weight average molecular weight (polystyrene conversion) of 7,000 to 1,000,000 in gel permeation chromatography. This is achieved by the electrophotographic photosensitive member according to any one of (15).

  The electrophotographic photoreceptor of the present invention contains, as an active ingredient, a polycarbonate resin having a structural unit having a specific diphenyl ether structure represented by the general formula (I) in the photosensitive layer. By using an aromatic polycarbonate resin having a specific diphenyl ether structure and / or an aromatic polycarbonate resin having a charge transport, high sensitivity and high durability can be obtained.

  The aromatic polycarbonate resin of the present invention is the general formula (I) to the general formula (IV) as a binder resin for an organic photoreceptor, or the general formula (V) to the general formula as a charge transporting polymer material. Polycarbonate resins containing at least the structural unit represented by the formula (X), and these aromatic polycarbonate resins are electrical properties, optical properties and mechanical properties required for the photosensitive layer of the electrophotographic photoreceptor. Are waiting for.

  That is, it is known that a polycarbonate resin using 4,4′-dihydroxydiphenyl ether as a raw material is a resin having excellent heat resistance, chemical resistance, and mechanical properties. However, this resin has poor solubility in a solvent, and it is difficult to obtain a highly polymerized compound by interfacial polymerization (similar to this production example). Even a polycarbonate resin using 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether improved as a raw material has a problem in solubility, although it is somewhat improved. Accordingly, these conventional polycarbonate resins using diphenyl ether as a raw material are mainly used as copolymerization seeds and exhibit excellent heat resistance, chemical resistance and mechanical properties. However, when a conventional polycarbonate resin having a structural unit having a diphenyl ether structure is used as an electrophotographic photoreceptor, there have been problems such as deterioration of the photoreceptor characteristics and generation of cracks. However, the polycarbonate resin having the diphenyl ether structure having a specific structure represented by the general formula (1) of the present invention as an active ingredient solves these problems, that is, electrophotographic characteristics and cracks, and thus a conventional polycarbonate resin. It has both heat resistance, chemical resistance and mechanical properties. This is because the conventional polycarbonate resin has a strong interaction between the diphenyl ether skeletons (crystallinity), so the solubility is poor, and the internal distortion is large when the photosensitive member is produced, and the distortion is not relaxed. (Because of its high crystallinity), it is a cause of deterioration of electrophotographic characteristics and generation of cracks. On the other hand, a diphenyl ether structure having a specific structure represented by the general formula (1) of the present invention is used as an active ingredient. It is inferred that the polycarbonate resin to be solved has solved these problems by imparting (controlling) flexibility as compared with a polycarbonate resin having a conventional diphenyl ether structure.

  As described above, the electrophotographic photoreceptor of the present invention is provided with a photoreceptor containing, as an active ingredient, a polycarbonate resin containing at least the structural unit represented by the general formula (I) in the photosensitive layer. These polycarbonate resins are novel substances and are produced by the following method.

Below, the manufacturing method of the aromatic polycarbonate resin of this invention is demonstrated.
The polycarbonate resin of the present invention can be produced by a method similar to the polymerization of bisphenol and a carbonic acid derivative known as a conventional method for producing a polycarbonate resin. That is, using at least one bisphenol compound represented by the following general formula (XI) or (XII),

（上記式中のＡ_１〜Ａ_７は前定義と同様である。）

(A _{1 to} A ₇ in the above formula are the same as defined above.)

（上記式中のＡ_１は前定義と同様である。）

(A ₁ in the above formula is the same as defined above.)

  It is produced by a transesterification method with bisaryl carbonate, a solution with a carbonyl halide compound such as phosgene or an interfacial polymerization method, or a method using chloroformate such as bischloroformate derived from diol. 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. These known production methods are described, for example, in a polycarbonate resin handbook (editor: Seiichi Honma, published by Nikkan Kogyo Shimbun).

  Further, a dioxy compound represented by the following general formula (XIII) is used in combination with one or more bisphenol compounds represented by the general formula (XI) or (XII), and a copolymer having improved mechanical properties and the like: can do.

  In this case, one or more dioxy compounds represented by the general formula (XIII) may be used in combination. The ratio of the bisphenol compound represented by the general formula (XI) or (XII) and the dioxy compound represented by the general formula (XIII) can be selected from a wide range depending on the desired properties. Moreover, random copolymers, alternating copolymers, block copolymers, random alternating copolymers, random block copolymers and the like can be obtained by selecting an appropriate polymerization operation. For example, if the bisphenol compound represented by the general formula (XI) or (XII) and the dioxy compound represented by the general formula (XIII) are uniformly mixed from the beginning and the condensation reaction with phosgene is carried out, the general formula (I) or A random copolymer composed of the structural unit represented by (II) and the structural unit represented by the general formula (III) is obtained. A random block copolymer can be obtained by adding several kinds of dioxy compounds from the middle of the reaction. Further, when a condensation reaction between a bischloroformate derived from a dioxy compound represented by the general formula (XIII) and a bisphenol compound represented by the general formula (XI) or (XII) is carried out, it is represented by the general formula (IV). An alternating copolymer consisting of repeating units is obtained. In this case, the general formula (XI) or (XII) may be reversed by the condensation reaction of the bischloroformate derived from the bisphenol compound represented by the general formula (XI) or the dioxy compound represented by the general formula (XIII). An alternating copolymer consisting of repeating units represented by IV) is obtained. In the condensation reaction of these bischloroformates and diols, a random alternating copolymer can be obtained by using a plurality of bischloroformates and diols.

  Similarly, in combination with one or more bisphenol compounds represented by general formula (XI) or (XII), it has a charge transporting ability represented by the following general formula (XIV), general formula (XV), or general formula (XVI). A diol compound can be used to obtain a copolymer with improved mechanical properties and the like.

  In this case, one or more diol compounds represented by general formula (XIV), general formula (XV), and general formula (XVI) may be used in combination. The ratio of the bisphenol compound represented by general formula (XI) or (XII) to the diol compound represented by general formula (XIV), general formula (XV), or general formula (XVI) is selected from a wide range depending on the desired characteristics. can do. Moreover, random copolymers, alternating copolymers, block copolymers, random alternating copolymers, random block copolymers and the like can be obtained by selecting an appropriate polymerization operation. For example, the bisphenol compound represented by the general formula (XI) or (XII) and the diol compound represented by the general formula (XIV), the general formula (XV), or the general formula (XVI) are mixed uniformly from the beginning and mixed with phosgene. When the condensation reaction is performed, a random copolymer consisting of a structural unit represented by general formula (I) or (II) and a structural unit represented by general formula (V), general formula (VII), or general formula (IX) Coalescence is obtained. A random block copolymer can be obtained by adding several kinds of dioxy compounds from the middle of the reaction. Also, condensation of bischloroformate derived from a diol compound represented by general formula (XIV), general formula (XV) or general formula (XVI) with a bisphenol compound represented by general formula (XI) or (XII) By carrying out the reaction, an alternating copolymer composed of repeating units represented by the general formula (VI), general formula (VIII) or general formula (X) can be obtained. In this case, conversely, bischloroformate derived from a bisphenol compound represented by general formula (XI) or (XII) and a diol compound represented by general formula (XIV), general formula (XV) or general formula (XVI) Similarly, an alternating copolymer composed of repeating units represented by the general formula (VI), the general formula (VIII) or the general formula (X) can be obtained by the condensation reaction. In the condensation reaction of these bischloroformates and diols, a random alternating copolymer can be obtained by using a plurality of bischloroformates and diols.

In interfacial polymerization, the reaction is carried out in the presence of a carbonic acid derivative and a catalyst between two phases of an aqueous solution of a bisphenol compound or a diol compound that is substantially insoluble in water and an organic solvent that dissolves polycarbonate. At this time, a polycarbonate having a narrow molecular weight distribution can be obtained in a short time by emulsifying the reaction medium by high-speed stirring or addition of an emulsifying substance. The base used in the alkaline aqueous solution is an alkali metal or alkaline earth metal, and is usually a hydroxide such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, etc. Carbonates and the like. These bases may be used alone or in combination.
A preferred base is sodium hydroxide or potassium hydroxide. The water used is preferably distilled water or ion exchange water. Examples of the organic solvent include aliphatic halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane, and dichloropropane, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, or , A mixture of them. Moreover, the organic solvent which mixed aromatic hydrocarbons, such as toluene, xylene, and ethylbenzene, aliphatic hydrocarbons, such as hexane and a cyclohexane, etc. may be sufficient as them. The organic solvent is preferably an aliphatic halogenated hydrocarbon or an aromatic halogenated hydrocarbon, more preferably dichloromethane or chlorobenzene.

Polycarbonate-forming catalysts used in the production of polycarbonate include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, nitrogen-containing heterocyclic compounds and salts thereof, imino ethers and salts thereof, compounds having an amide group, etc. It is. Specific examples of the polycarbonate formation catalyst include trimethylamine, triethylamine, tri-n-propylamine, tri-n-hexylamine, N, N, N ′, N′-tetramethyl-1,4-tetramethylenediamine, 4-pyrroline. Dinopyridine, N, N'-dimethylpiperazine, N-ethylpiperidine, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium bromide, phenyltriethylammonium chloride, triethylphosphine, triphenylphosphine, diphenylbutylphosphine , Tetra (hydroxymethyl) phosphonium chloride, benzyltriethylphosphonium chloride, benzyltriphenylphosphonium chloride Id, 4-methylpyridine, 1-methylimidazole, 1,2-dimethylimidazole, 3-methylpyridazine, 4,6-dimethylpyrimidine, 1-cyclohexyl-3,5-dimethylpyrazole, 2,3,5,6- Tetramethylpyrazine and the like. These polycarbonate formation catalysts may be used alone or in combination. The polycarbonate-forming catalyst is preferably a tertiary amine, more preferably a tertiary amine having 3 to 30 carbon atoms, and particularly preferably triethylamine.
These catalysts can be added before and / or after adding carbonic acid derivatives such as phosgene and bischloroformate to the reaction system.

  As described above, it is desirable to use a terminal terminator as a molecular weight regulator in order to regulate the molecular weight in all polymerization operations, and therefore, a substituent based on the terminator is bonded to the terminal of the polycarbonate resin used in the present invention. Also good. The terminal terminator used is a monovalent aromatic hydroxy compound, a haloformate derivative of a monovalent aromatic hydroxy compound, a monovalent carboxylic acid, 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-bis (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 above monovalent aromatic hydroxy compound.

  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 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 molecular weight of the polycarbonate resin of the present invention is 1,000 to 500,000, more preferably 10,000 to 200,000 in terms of polystyrene-equivalent number average molecular weight.

  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-hydride) Loxyphenyl) cyclohexane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -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-chlorocarbonyloxyphthalic acid, trichlorate trimesic acid , Is cyanuric acid chloride or the like. These branching agents may be used alone or in combination.

Further, an antioxidant such as hydrosulfite may be added in order to prevent oxidation of the diol in the alkaline aqueous solution.
The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably kept at 10 or more.

  On the other hand, the solution polymerization can be obtained by dissolving a bisphenol compound or dioxy compound in a solvent, adding a deoxidizing agent, and adding bischloroformate, phosgene, or a phosgene multimer thereto. As the deoxidizer, tertiary amines such as trimethylamine, triethylamine, tripropylamine and pyridine are used. As the solvent used in the reaction, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene and chloroform, and cyclic ether solvents such as tetrahydrofuran and dioxane, and pyridine are preferable. Further, the same molecular weight regulator and branching agent as in the case of interfacial polymerization can be used. The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

  It is also produced by a transesterification method. In this case, a dioxy compound and bisaryl carbonate are mixed in the presence of an inert gas, and are usually reacted at 120 to 350 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the phenols produced are distilled out of the system at 1 mmHg or less. The reaction time is usually about 1 to 4 hours. Moreover, you may add a molecular weight regulator and antioxidant as needed. Examples of the bisaryl carbonate include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate.

The polycarbonate resin obtained as described above removes impurities such as the catalyst and antioxidant used during the polymerization, unreacted diol and terminal stopper, and inorganic salts generated during the polymerization. used. For these purification operations, a conventionally known method described in the previous polycarbonate resin handbook (editor: Seiichi Honma, published by Nikkan Kogyo Shimbun) can be used.
Moreover, additives, such as antioxidant, a light stabilizer, a heat stabilizer, a lubricant, and a plasticizer, can be added to the aromatic polycarbonate resin produced according to the above method, if necessary.

Next, the general formula (I) which is the main structural unit of the present invention will be described in more detail.
In the general formula (I), A ₁ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and A _{2 to} A ₇ each independently represent a hydrogen atom, a halogen atom, or a carbon number. 1 to 6 substituted or unsubstituted alkyl groups are represented.
Examples of the substituent used in A ₁ include the following as the substituted or unsubstituted alkyl group. A linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and these alkyl groups are further a fluorine atom, a cyano group, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a halogen atom, or a carbon atom having 1 to 1 carbon atoms. It may contain a phenyl group substituted with 6 linear, branched or cyclic alkyl groups. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-hexyl group, n-octyl group N-decyl group, n-dodecyl group, n-octadecyl group, trifluoromethyl group, 2-cyanoethyl group, methoxymethyl group, methoxyethyl group, benzyl group, 4-chlorobenzyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. The substituted or unsubstituted aryl group is an aryl group such as a phenyl group or a naphthyl group, and these aryl groups are further linear, branched or cyclic alkyl groups having 1 to 18 carbon atoms, fluorine atoms , A cyano group, or an alkoxy group having 1 to 18 carbon atoms. Specifically, phenyl group, naphthyl group, 4-methylphenyl group, 3-methylphenyl group, 4-butylphenyl group, 4-hexylphenyl group, 4-octylphenyl group, 4-fluorophenyl group, 4-cyano A phenyl group, 4-trifluoromethylphenyl group, etc. are mentioned.
Examples of the substituent used in A _{2 to} A ₇ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, the following can be mentioned as a C1-C6 substituted or unsubstituted alkyl group. A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and these alkyl groups are further a fluorine atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, or 1 to 1 carbon atom. It may contain a phenyl group substituted with 6 linear, branched or cyclic alkyl groups. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, trifluoromethyl group, 2-cyanoethyl group Methoxymethyl group, methoxyethyl group, benzyl group, 4-chlorobenzyl group, cyclopentyl group, cyclohexyl group and the like.
Furthermore, about general formula (I) which is a main structural unit of this invention, the manufacturing route of the bisphenol compound shown by the said general formula (XI) used as the raw material is shown in FIG.

  The first step is a process for obtaining a diacyloxydiphenyl ether compound (XVIII) by acylating the dihydroxydiphenyl ether compound (XVII) with an acid anhydride or acid chloride, and is a known method (for example, New Experimental Chemistry Course 14 (II ) 1012). That is, it is acylated by using an acid anhydride or acid chloride in an amount of 2 times or more molar amount with respect to the dihydroxydiphenyl ether compound (XVII). In the case of an acid anhydride, an acid such as sulfuric acid, p-toluenesulfonic acid or zinc chloride, or a base such as pyridine or 4-dimethylaminopyridine is used as a reaction catalyst. In the case of acid chloride, a base such as pyridine or 4-dimethylaminopyridine is used as a reaction catalyst.

  The second step is a process in which diacyloxydiphenyl ether compound (XVIII) is subjected to Fries transfer in the presence of an acid catalyst to obtain dihydroxydiacyl compound (XIX), which is a known method (for example, New Experimental Chemistry Course 14 (II) 776, or Org. React., 1,343 (1942)). That is, it reacts with the diacyloxydiphenyl ether compound (XVIII) by adding an acid catalyst such as aluminum chloride or zinc chloride at twice the molar amount all at once and heating to 70 ° C. or higher. For the reaction, no solvent is used, or 1,2-dichloroethane, chlorobenzene, 1,1,2,2-tetrachloroethane, nitrobenzene or the like is used. This Fries transition is selectively transferred to the ortho position of the OH group (particularly because the para position is substituted).

In the third step, the bisphenol compound (XI) can be obtained by reducing the carbonyl group of the dihydroxydiacyl compound (XIX). As a method for reducing the carbonyl group, a known method can be used.
i) Reduction with hydrazine <Wolff-Kishner reduction>
(For example, New Experimental Chemistry Course 15 (II) 224) uses a high-boiling glycol as a solvent, dihydroxydiacyl compound (XIX), and caustic alkali such as hydrated hydrazine, sodium hydroxide, or potassium hydroxide. The bisphenol compound (XI) can be obtained by a heating reaction in the presence. Usually, the reaction temperature is 150 ° C to 200 ° C.
ii) Reduction with metal hydride complex (for example, New Experimental Chemistry Course 15 (II) 179) uses various metal hydride complex compounds for reduction of carbonyl group, among which sodium borohydride is excellent, The dihydroxydiacyl compound (XIX) can be obtained by refluxing in an aqueous sodium borohydride solution to obtain the bisphenol compound (XI).
iii) Reduction with zinc amalgam <Clemmensen reduction>
(For example, New Experimental Chemistry Course 15 (II) 64) can obtain the bisphenol compound (XI) by heating the dihydroxydiacyl compound (IV) using zinc amalgam and hydrochloric acid. For the reaction, no solvent, ethanol, dioxane, acetic acid, toluene or the like is used, and the reaction temperature is usually from 70 ° C to 130 ° C.
iv) Reduction with hydrosilane (For example, New Experimental Chemistry Course 15 (II) 118) Dihydroxydiacyl compound (XIX) can be obtained by treating with trialkylsilane in trifluoroacetic acid to obtain bisphenol compound (XI).
As the trialkylsilane, trimethylsilane, triethylsilane, polymethylhydrosiloxane and the like are used, and the reaction is performed at room temperature and in a high yield.
Although bisphenol compound (XI) can be obtained under acidic and mild conditions, iv) reduction with hydrosilane can be suitably used.

  For the general formula (III), which is another main structural unit, a conventionally known structural unit of a polycarbonate resin can be used as it is. For example, basic units described in a polycarbonate resin handbook (editor; Seiichi Honma, published by Nikkan Kogyo Shimbun) can be used. Among such conventionally known structural units, the general formula (II) will be described in detail by giving an example of the general formula (XIII) as a raw material for the general formula (II).

  Specific examples of the dioxy compound when X in the general formula (XIII) is an aliphatic divalent group or a cycloaliphatic divalent group include 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-hexanediol, 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-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, 2,2-bis (4-hydroxy (Cyclohexyl) propane, xylylenediol, 1,4-bis (2-hydroxyethyl) benzene, 1,4-bis (3-hydroxypropyl) benzene, 14,14-bis (4-hydroxybutyl) benzene, 1,4- Examples thereof include bis (5-hydroxypentyl) benzene and 1,4-bis (6-hydroxyhexyl) benzene.

  Specific examples of preferable dioxy compounds when X is an aromatic divalent group include bis (4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) methane, and 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-hydroxyphenyl) Propane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 1,1-bis (4-hydroxy) Loxyphenyl) -2-methylpropane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane 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) cyclopenta 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'-dihydroxyphenyl 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'-dihydro Cispiro (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-dihydroxybenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxy S Thiine, 9,10-dimethyl-2,7-dihydroxyphenazine, 3,6-dihydroxybenzofuran, 3,6-dihydroxybenzothiophene, 4,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 2,7-dihydroxy Pyrene, hydroquinone, resorcin, 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 reaction of 2 mol of diol with 1 mol of isophthaloyl chloride or 1 mol of terephthaloyl chloride.

Next, the structural unit represented by the general formula (V), which is the main structural unit of the aromatic polycarbonate resin of the present invention, will be described in more detail (same as described in JP-A-9-272735).
In the present invention, “aryl” represents a group including a heterocyclic group. In the general formula (V), B ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Examples of the substituted or unsubstituted alkyl group for B ₁ include the following. A linear or branched alkyl group having 1 to 5 carbon atoms, and these alkyl groups are further a fluorine atom, a cyano group, a phenyl group, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. It may contain a substituted phenyl group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-cyanoethyl group Benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group and the like.
Examples of the substituted or unsubstituted aryl group for B ₁ include the following. Phenyl group, naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [A, d] cycloheptenylidenephenyl group, thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group, pyridinyl group, pyrrolidyl group, oxazolyl group, etc., and these are substituted or unsubstituted as described above It has an alkyl group, an alkoxy group having the above-mentioned substituted or unsubstituted alkyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and an amino group represented by the following general formula as a substituent. Also good.

（式中、Ｒ_１９、Ｒ_２０はＢ_１で定義される置換もしくは無置換のアルキル基、Ｂ_１で定義される置換もしくは無置換のアリール基を表わすと共にＲ_１９とＲ_２０が共同で環を形成したり、アリール基上の炭素原子と共同で環を形成してもよい。このような具体例としてピペリジノ基、モルホリノ基、ユロリジル基等が挙げられる。）

_(Wherein, R _{19, R 20} is a substituted or unsubstituted alkyl group as defined by _{B 1, R 19} and _{R 20} together represent a substituted or unsubstituted aryl group as defined _{B 1} is a ring joint And may form a ring together with the carbon atom on the aryl group, such as piperidino group, morpholino group, urolidyl group, etc.)

In the general formula (V), Ar ₁ represents a substituted or unsubstituted aryl group. Examples of the substituted or unsubstituted aryl group represented by Ar ₁ include a group represented by the following general formula (XX), and pyrrole, pyrazole, imidazole, triazole, dioxazole, indole, isoindole, benzimidazole, benzotriazole, and benzisoxene. Examples thereof include monovalent groups derived from heterocyclic groups having an amine structure such as sazine, carbazole, and phenoxazine. These may have a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group defined by R ₁ , and a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom as a substituent.

（式中、Ｒ_１７、Ｒ_１８はアシル基、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表わす。Ａｒ_４はアリレン基を表わす。ｈは１〜３の整数を表わす。）

(Wherein R ₁₇ and R ₁₈ represent an acyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ₄ represents an arylene group. H represents an integer of 1 to 3)

In the general formula (XX), examples of the acyl group of R ₁₇ and R ₁₈ include an acetyl group, a propionyl group, and a benzoyl group. Examples of the substituted or unsubstituted alkyl group for R ₁₇ and R ₁₈ include the same as the substituted or unsubstituted alkyl group defined for B ₁ . Examples of the substituted or unsubstituted aryl group represented by R ₁₇ and R ₁₈ include groups represented by the following general formula (XXI) in addition to the substituted or unsubstituted aryl group defined by B ₁ .

［式中、Ｂ_２は−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−及び以下の２価基から選ばれる。

[Wherein, B ₂ is selected from —O—, —S—, —SO—, —SO ₂ —, —CO—, and the following divalent groups.

(Wherein, R ₂₁ is a hydrogen atom, a substituted or unsubstituted alkyl group defined in B _1, an alkoxy group, a halogen atom, defined substituted or unsubstituted aryl group B _1, an amino group, a nitro group represents a cyano group, R ₂₂ is a hydrogen atom, a substituted or unsubstituted alkyl group defined in B _1, represents the defined substituted or unsubstituted aryl group B _1, i is an integer from 1 to 12 , J represents an integer of 1 to 3)]

Specific examples of the alkoxy group of R ₂₁ include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, 2-hydroxy Examples include ethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like. Examples of the halogen atom for R ₂₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The amino group of R ₂₁ represents an amino group defined as a substituent of the substituted or unsubstituted aryl group of R ₁ . In the general formula (XX), examples of the arylene group of Ar ₄ include a divalent group derived from a substituted or unsubstituted aryl group defined by B ₁ .

In the general formula (V), Ar ₂ and Ar ₃ represent a substituted or unsubstituted arylene group. Examples of the arylene group of Ar ₂ and Ar ₃ include a divalent group derived from a substituted or unsubstituted aryl group defined by B ₁ .
The structural unit of the general formula (V) has been described above, but the same symbols have the same definition in other general formulas.

  The diols represented by the general formulas (XIV), (XV), and (XVI) that are raw material monomers of the novel aromatic polycarbonate resin of the present invention will be described. These compounds, for example, the diol represented by the general formula (XIV) are composed of a phosphonic acid ester represented by the following general formula (XIV) and a carbonyl compound represented by the general formula (XV) as shown in the following synthesis route. A stilbene compound represented by the following general formula (XVI) can be obtained, and then produced by cleavage of an ether group or an ester group.

［ここで、Ｒ_２３、Ｒ_２４は前記Ｂ_１と同じ定義の置換もしくは無置換のアルキル基、前記Ｒ_１７、Ｒ_１８と同じ定義のアシル基を表わす。Ｒ_２５は、低級アルキル基を表わし、具体例としては炭素数１〜５の直鎖または分岐鎖のアルキル基であり、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、ｎ−ペンチル基等が挙げられる。Ｒ_１、Ａｒ_１、Ａｒ_２、Ａｒ_３は前記定義と同一である。］
また、前記一般式（XV）、（XVI）で表わされるジオールも対応するホスホン酸エステルと、対応するカルボニル化合物とから一般式（XIV）で表わされるジオールの場合と同様な方法で製造することができる。

[Wherein R ₂₃ and R ₂₄ represent a substituted or unsubstituted alkyl group having the same definition as in B ₁ and an acyl group having the same definition as in R ₁₇ and R ₁₈ . R ₂₅ represents a lower alkyl group, and specific examples thereof are linear or branched alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, t -Butyl group, s-butyl group, n-butyl group, i-butyl group, n-pentyl group and the like can be mentioned. R ₁ , Ar ₁ , Ar ₂ , Ar ₃ are the same as defined above. ]
The diols represented by the general formulas (XV) and (XVI) can also be produced from the corresponding phosphonate ester and the corresponding carbonyl compound in the same manner as in the case of the diol represented by the general formula (XIV). it can.

  In the copolymer polycarbonate resin of the structural unit represented by the general formula (V) and the structural unit represented by the general formula (I) or (II), the proportion of the structural unit represented by the general formula (V) is arbitrary. However, since the content of the structural unit of the general formula (V) corresponds to the charge transport property of the polycarbonate resin, it is preferably 5 mol% or more, more preferably, in all the structural units. It is desirable to contain 20 mol% or more.

  The preferred molecular weight of the polycarbonate resin represented by the above general formula is 7,000 to 1,000,000, more preferably 10,000 to 500,000 in terms of polystyrene-reduced number average molecular weight. When the molecular weight is too small, the film formability such as the generation of cracks is deteriorated and the practicality becomes poor. On the other hand, when the molecular weight is too large, the solubility in a general organic solvent is deteriorated, the viscosity of the solution becomes high and the coating becomes difficult, which is also a practical problem.

  The polycarbonate resin of the present invention exhibits good solubility in various common organic solvents such as dichloromethane, tetrahydrofuran, chloroform, toluene, dichlorobenzene and xylene. Therefore, a solution having an appropriate concentration can be prepared with an appropriate solvent capable of dissolving the polycarbonate resin of the present invention, and various photoconductors can be prepared by a known coating method using the solution.

The polycarbonate resin used in the electrophotographic photoreceptor of the present invention has been described above. An embodiment in which the polycarbonate resin is contained in the photosensitive layer will be described below.
First, cross-sectional views of the photoreceptor of the present invention are shown in FIGS.
In the photoreceptor of the present invention, one or more of the polycarbonate resins as described above are used as the photosensitive layer (2) <(2 ′), (2 ″), (2 ′ ″), (2 ′ ″). '), (2''''')>, but it is used as shown in FIG. 1, FIG. 2, FIG. 3, FIG. 4, FIG. be able to.

  The photoreceptor in FIG. 1 has a photosensitive layer (2) made of a sensitizing dye and a charge transporting polycarbonate resin, and optionally a binder (binder resin), on a conductive support (1). The charge transporting polycarbonate resin here acts as a photoconductive substance, and the generation and movement of charge carriers necessary for light attenuation are performed via the charge transporting polycarbonate resin. However, since the charge transporting polycarbonate resin has almost no absorption in the visible region of light, for the purpose of forming an image with visible light, a sensitizing dye having absorption in the visible region is added for sensitization. There is a need to.

  The photoreceptor in FIG. 2 is a photosensitive material in which a charge generating material (3) is dispersed on a conductive support (1) in a charge transport medium (4) formed by using a charge transporting polycarbonate resin alone or in combination with a binder. A layer (2 ′) is provided. The charge transporting polycarbonate resin used here alone or in combination with a binder forms a charge transport medium, while the charge generating material (3) (charge generating material such as an inorganic or organic pigment) generates a charge carrier. To do. In this case, the charge transport medium (4) is mainly responsible for receiving and transporting charge carriers generated by the charge generating material (3). In this photoreceptor, the basic condition is that the absorption wavelength region of the charge generating material and the charge transporting polycarbonate resin do not overlap each other mainly in the visible region. This is because it is necessary to transmit light to the surface of the charge generation material in order to efficiently generate charge carriers in the charge generation material (3). The charge transporting polycarbonate resin used in the present invention is combined with a charge generating substance (3) that absorbs light in the visible region to the near infrared region and generates a charge carrier in general with little absorption at a wavelength of 600 nm or more. In that case, it is particularly effective to act as a charge transport material. The charge transport medium (4) may contain a low molecular charge transport material.

The photoconductor in FIG. 3 includes a charge generation layer (5) mainly comprising a charge generation material (3) on a conductive support (1), and a charge transport layer containing a charge transport polycarbonate resin having a charge transport capability. A photosensitive layer (2 ″) comprising a laminate with (4) is provided. In this photoreceptor, light that has passed through the charge transport layer (4) reaches the charge generation layer (5), where charge carriers are generated, while the charge transport layer (4) injects charge carriers. The charge carriers required for light attenuation are generated by the charge generating material (3), and the charge carriers are transported by the charge transport layer (4). Such a mechanism is the same as that described in the photoconductor shown in FIG.
The charge transport layer (4) is formed by the charge transport polycarbonate resin used in the present invention alone or in combination with a binder. In order to increase the charge generation efficiency, the charge generation layer (5) may contain the charge transporting polycarbonate resin used in the present invention. For the same purpose, a low molecular charge transport material may be used in combination in the photosensitive layer (2 ″). The same applies to photosensitive layers (2 ′ ″) to (2 ′ ″ ″) described later.

  The photoreceptor in FIG. 4 has a protective layer (6) provided on a charge transport layer (4). In the case of this configuration, a protective layer is formed on the charge transport layer (4) in combination with a charge transport polycarbonate resin or a binder. As a matter of course, formation on a low molecular dispersion type charge transport layer, which has been widely used in the past, is effective. A protective layer may be similarly provided on the photosensitive layer (2 ′) shown in FIG.

The photoconductor in FIG. 5 is obtained by reversing the stacking order of the charge generation layer (5) in FIG. 3 and the charge transport layer (4) containing a charge transporting polycarbonate resin. The mechanism can be the same as described above. In this case, considering the mechanical strength, a protective layer (6) can be provided on the charge generation layer (5) as shown in FIG.
Actually, in order to produce the photoreceptor of the present invention, the photoreceptor shown in FIG. 1 is dissolved in combination with a charge transporting polycarbonate resin or a binder, and further a sensitizing dye is added thereto. And a photosensitive layer (2) may be formed by applying the solution onto the conductive support (1) and drying it.

  The thickness of the photosensitive layer is 3 to 50 μm, preferably 5 to 40 μm. The amount of the charge transporting polycarbonate resin in the photosensitive layer (2) is 30 to 100% by weight, and the amount of the sensitizing dye in the photosensitive layer (2) is 0.1 to 5% by weight, preferably 0.8. 5 to 3% by weight. Examples of sensitizing dyes include triarylmethane dyes such as brilliant green, Victoria blue B, methyl violet, crystal violet, and acid violet 6B, rhodamine B, rhodamine 6G, rhodamine G extra, eosin S, erythrocin, rose bengal, and fluorescein. Xanthene dyes, thiazine dyes such as methylene blue, and cyanine dyes such as cyanine.

  In order to produce the photoreceptor shown in FIG. 2, fine particles of the charge generating material (3) are dispersed in a solution in which a charge transporting polycarbonate resin or a binder is used in combination, and this is dispersed into a conductive support (1 The photosensitive layer (2 ') may be formed by applying the composition on the substrate and drying it.

  The thickness of the photosensitive layer (2 ′) is 3 to 50 μm, preferably 5 to 40 μm. The amount of the charge transporting polycarbonate resin in the photosensitive layer (2 ′) is 40 to 100% by weight, and the amount of the charge generating material (3) in the photosensitive layer (2 ′) is 0.1 to 50% by weight. , Preferably 1 to 20% by weight. Examples of the charge generating substance (3) include inorganic materials such as selenium, selenium-tellurium, cadmium sulfide, cadmium sulfide-selenium, and α-silicon, and examples of organic materials include C.I. Pigment Blue 25 (Color Index CI21180) and C.I. Pigment Red. 41 (CI21200), CI Acid Red 52 (CI45100), CI Basic Red 3 (CI45210), an azo pigment having a carbazole skeleton (described in JP-A-53-95033), an azo pigment having a distyrylbenzene skeleton (special feature) No. 53-133445), an azo pigment having a triphenylamine skeleton (described in JP-A-53-132347), an azo pigment having a dibenzothiophene skeleton (described in JP-A-54-21728). ) An azo pigment having a sadiazole skeleton (described in JP-A No. 54-12742), an azo pigment having a fluorenone skeleton (described in JP-A No. 54-22834), an azo pigment having a bis-stilbene skeleton (Japanese Patent Laid-Open No. No. 17733), azo pigments having a distyryl oxadiazole skeleton (described in JP-A No. 54-2129), azo pigments having a distyrylcarbazole skeleton (described in JP-A No. 54-14967) ) Azo pigments, for example, phthalocyanine pigments such as C.I. Pigment Blue 16 (CI74100), indigo pigments such as C.I. Indense Scarlet R (Bayer) And perylene pigments. These charge generation materials may be used alone or in combination of two or more.

  Further, among the above charge generating materials, a highly sensitive and highly durable photoconductor can be obtained particularly by a combination with a phthalocyanine pigment. The phthalocyanine pigment is a compound having a phthalocyanine skeleton represented by the following general formula (N), and M (center metal) includes metal and nonmetal (hydrogen) elements.

  Here, M mentioned is H, Li, Be, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, Pa, U, Np, Am, etc., or oxide, chloride, fluoride It consists of two or more elements such as hydroxide and bromide. The central metal is not limited to these elements. The charge generation material having a phthalocyanine skeleton in the present invention may have at least a basic skeleton of the general formula (N), a substance having a multimeric structure such as a dimer or trimer, and a higher order high-order substance. It may have a molecular structure. In addition, the basic skeleton may have various substituents.

Of these various phthalocyanines, oxotitanium phthalocyanine having TiO as a central metal and metal-free phthalocyanine having H are particularly preferable in terms of photoreceptor characteristics.
These phthalocyanines are also known to have various crystal systems. For example, in the case of oxotitanium phthalocyanine, α, β, γ, m, y type, etc., in the case of copper phthalocyanine, α, β, γ, etc. It has a polycrystal system of Even in a phthalocyanine having the same central metal, various properties change as the crystal system changes. Among them, it has been reported that the characteristics of the photoreceptor also change with such a crystal system change (Journal of Electrophotographic Society, Vol. 29, No. 4, (1990)). For this reason, each phthalocyanine has an optimum crystal system in terms of the characteristics of the photoreceptor, and in particular for oxotitanium phthalocyanine, a y-type crystal system is desirable.

  In addition, these charge generation materials may be a mixture of two or more charge generation materials having a phthalocyanine skeleton. Further, it may be mixed with other charge generation materials. In this case, examples of the charge transport material to be mixed include inorganic materials and organic materials.

Further, in order to produce the photoreceptor shown in FIG. 3, a charge generating substance is vacuum-deposited on the conductive support (1), or fine particles (3) of the charge generating substance are dissolved in a binder if necessary. The dispersion liquid dispersed in a suitable solvent is applied and dried, and if necessary, the surface is finished and the film thickness is adjusted by a method such as buffing to form the charge generation layer (5), and the charge transport The charge transport layer (4) may be formed by applying a solution dissolved in combination with a conductive polycarbonate resin or a binder and drying.
Here, the charge generation material used for forming the charge generation layer (5) is the same as described for the photosensitive layer (2 ′).
The thickness of the charge generation layer (5) is 5 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer (4) is 3 to 50 μm, preferably 5 to 40 μm. When the charge generation layer (5) is of a type in which fine particles (3) of the charge generation layer material are dispersed in a binder, the ratio of the charge generation material particles (3) to the charge generation layer (5) Is about 10 to 100% by weight, preferably about 50 to 100% by weight. The amount of the charge transporting polycarbonate resin in the charge transport layer (4) is 40 to 100% by weight.

As described above, the photosensitive layer (2 ″) in FIG. 3 may contain a low molecular charge transport material. Examples of the charge transport material used here include the following.
Oxazole derivatives, oxadiazole derivatives (described in JP-A-52-139065, JP-A-52-139066), imidazole derivatives, triphenylamine derivatives (described in JP-A-3-285960), benzidine derivatives (Described in JP-B-58-32372), α-phenylstilbene derivatives (described in JP-A-57-73075), hydrazone derivatives (JP-A-55-154955, JP-A-55-156554) , JP 55-52063 A, JP 56-81850 A, etc.), triphenylmethane derivatives (described in JP-B 51-10983), anthracene derivatives (JP 51-94829 A). And styryl derivatives (Japanese Patent Laid-Open Nos. 56-29245 and 58-1980). No. 3 described in Japanese), described in JP-carbazole derivatives (JP-58-58552), pyrene derivatives (described in JP-A-2-94812).

  To prepare the photoreceptor shown in FIG. 4, a solution in which the polycarbonate resin of the present invention is dissolved alone or in combination with a binder or a charge transport material as required is applied onto the photoreceptor shown in FIG. And dried to provide a protective layer (6). The thickness of the protective layer is preferably 0.15 to 10 μm. The amount of the polymer of the present invention in the protective layer (6) is 40 to 100% by weight.

To prepare the photoreceptor shown in FIG. 5, a solution prepared by dissolving the polycarbonate resin of the present invention together with a binder or a charge transporting material as necessary is applied onto a conductive support (1) and dried. After forming the charge transport layer (4), a dispersion liquid in which a fine particle of the charge generation layer material is dispersed in a solvent in which a binder is dissolved if necessary is applied and dried on the charge transport layer by a method such as spray coating. Thus, the charge generation layer (5) may be formed. The amount ratio of the charge generation layer or the charge transport layer is the same as that described in FIG.
By forming the above-mentioned protective layer (6) on the charge generation layer (5) of the photoreceptor thus obtained, the photoreceptor shown in FIG. 6 can be produced.

In any of these photoreceptors, a metal plate or a metal foil such as aluminum, a plastic film vapor-deposited with a metal such as aluminum, or paper subjected to a conductive treatment is used for the conductive support (1). It is done.
In addition, as the binder, a condensation resin such as polyamide, polyurethane, polyester, epoxy resin, polyketone, or polycarbonate, or a vinyl polymer such as polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, or polyacrylamide is used. Any insulating and adhesive resin can be used. A plasticizer is added to the binder as necessary. Examples of such a plasticizer include halogenated paraffin, dimethylnaphthalene, and dibutyl phthalate. If necessary, additives such as an antioxidant, a light stabilizer, a heat stabilizer, and a lubricant can be added.

Furthermore, the photoreceptor obtained as described above can be provided with an adhesive layer or a barrier layer between the conductive support and the photosensitive layer, if necessary. Materials used for these layers include polyamide, nitrocellulose, aluminum oxide, titanium oxide, and the like, and the film thickness is preferably 1 μm or less.
In order to perform copying using the photoreceptor of the present invention, the photosensitive surface is charged and exposed, then developed and transferred to paper or the like as necessary.
The photoreceptor of the present invention has high sensitivity and is excellent in durability.

Hereinafter, the present invention will be described by way of examples.
First, a production example of a polymer in the present invention is shown.
(Synthesis Example 1)
<Production of 4,4′-diacetoxydiphenyl ether (compound of general formula (XVIII) where A ₁ = CH ₃ , A ₂ = A ₃ = A ₄ = A ₅ = A ₆ = A ₇ = H)>
To 80.88 g (0.4 mol) of 4,4′-diphenyl ether and 102.09 g (1 mol) of acetic anhydride, 1 drop of 95% sulfuric acid was added with stirring at room temperature, and the mixture was stirred at room temperature for 2 hours. In addition to ice / water, the precipitated crystals were collected by filtration, washed with water, dried, and recrystallized and purified from ethanol to obtain 109.24 g (95.4%) of the desired product.
Melting point: 112.5-113.5 ° C
Elemental analysis value (%) Measured value / calculated value
C: 66.98 / 67.13
H: 4.98 / 4.93

(Synthesis Example 2)
<Production of 4,4′-dihydroxy-3,3′-diatyl diphenyl ether (in formula (XIX), A ₁ = CH ₃ , A ₂ = A ₃ = A ₄ = A ₅ = A ₆ = A ₇ = H Compound)>
In a 150 ml 1,1,2,2-tetrachloroethane solution of 28.63 g (0.1 mol) of 4,4′-diacetoxydiphenyl ether obtained in Synthesis Example 1 48 g (0.36 mol) of aluminum chloride (anhydrous) ) Is added at once, and the reaction mixture is heated and stirred at 120 ° C. for 1 hour. After cooling, the reaction mixture is added to ice / water, hydrochloric acid is added, and the mixture is extracted with dichloromethane. The phase was washed with water and dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was recrystallized and purified from n-butanol to obtain 22.45 g (78.4%) of the desired product.
Melting point: 185.0-185.5 ° C
Elemental analysis value (%) Measured value / calculated value
C: 67.02 / 67.13
H: 4.91 / 4.93

(Synthesis Example 3)
<Production of 4,4′-dihydroxy-3,3′-diethyldiphenyl ether (in formula (XI), A ₁ = CH ₃ , A ₂ = A ₃ = A ₄ = A ₅ = A ₆ = A ₇ = H Compound)>
29.07 g of triethylsilane was added to a solution of 171 g of trifluoroacetic acid in 14.31 g (0.05 mol) of 4,4′-dihydroxy-3,3′-diatyl diphenyl ether obtained in Synthesis Example 2 under stirring at room temperature. 0.25 mol) is added dropwise over 1 hour and reacted under the same conditions for 4 hours. Next, the reaction product is allowed to cool, then the reaction product is added to ice / water, extracted with dichloromethane, the dichloromethane phase is washed with water and dried over anhydrous magnesium sulfate, the solvent is distilled off, and the residue is subjected to silica gel column chromatography. The treatment was carried out using a mixed solvent of toluene / ethyl acetate (9/1), and further recrystallized and purified with toluene to obtain 10.95 g (84.8%) of 4,4′-dihydroxy-3,3′-diethyldiphenyl ether. Obtained.
Melting point: 85.5-86.5 ° C
Elemental analysis value (%) Measured value / calculated value
C: 74.42 / 74.40
H: 7.03 / 7.02

(Synthesis Example 4)
3.64 g of 4,4′-dihydroxy-3,3′-diethyldiphenyl ether prepared in Synthesis Example 3, 64 mg of 4-tert-butylphenol, 2.82 g of sodium hydroxide and 66 mg of sodium hydrosulfite in 28 ml of water under a nitrogen atmosphere The solution dissolved in was added and dissolved. After stirring for 1 hour, a solution prepared by dissolving 1.68 g of bis (trichloromethyl) carbonate in 22 ml of methylene chloride was added and stirred vigorously at 18 ° C. for 15 minutes. Thereafter, a catalytic amount of triethylamine was added and stirred at room temperature for 1 hour. Dilute the contents with methylene chloride, separate the organic layer, wash twice with ion-exchanged water, then wash with 2% aqueous hydrochloric acid, and until the conductivity of the washing solution is the same as the value of ion-exchanged water Washed with ion exchange water. This organic layer was dropped into a large amount of methanol, and the obtained polymer was dried under reduced pressure at 80 ° C. to obtain 2.64 of an aromatic polycarbonate resin (No. 1) represented by the following formula.

元素分析値（％）実測値／計算値
Ｃ：７７．７７／７１．８２，Ｈ：５．６４／５．６７
ゲルパーミエーションクロマトグラフィーによるポリスチレン換算分子量
数平均分子量＝４２，０００ 重量平均分子量＝１４５，３００

Elemental analysis value (%) Measured value / calculated value
C: 77.77 / 71.82, H: 5.64 / 5.67
Polystyrene conversion molecular weight by gel permeation chromatography
Number average molecular weight = 42,000 Weight average molecular weight = 145,300

(Synthesis Example 5)
4.4 g of 4,4′-dihydroxy-3,3′-diethyldiphenyl ether prepared in Synthesis Example 3, 1.34 g of 1,1-bis (4-hydroxyphenyl) cyclohexane, 63 mg of 4-tert-butylphenol under nitrogen atmosphere Then, a solution prepared by dissolving 2.78 g of sodium hydroxide and 66 mg of sodium hydrosulfite in 27 ml of water was added and dissolved. After stirring for 1 hour, a solution prepared by dissolving 1.65 g of bis (trichloromethyl) carbonate in 22 ml of methylene chloride was added and stirred vigorously at 18 ° C. for 15 minutes. Thereafter, a catalytic amount of triethylamine was added and stirred at room temperature for 1 hour. Dilute the contents with methylene chloride, separate the organic layer, wash twice with ion-exchanged water, then wash with 2% aqueous hydrochloric acid, and until the conductivity of the washing solution is the same as the value of ion-exchanged water Washed with ion exchange water. The organic layer was dropped into a large amount of methanol, and the obtained polymer was dried under reduced pressure at 80 ° C. to obtain 3.44 of an aromatic polycarbonate resin (No. 2) represented by the following formula.

元素分析値（％）実測値／計算値
Ｃ：７３．８５／７３．９１
Ｈ：５．８３／５．８５
ゲルパーミエーションクロマトグラフィーによるポリスチレン換算分子量
数平均分子量＝３３，６００ 重量平均分子量＝９８，０００
赤外吸収スペクトルを図８に示した。
ＣＯ伸縮振動（カーボネート結合） ｃｍ^−１

Elemental analysis value (%) Measured value / calculated value
C: 73.85 / 73.91
H: 5.83 / 5.85
Polystyrene conversion molecular weight by gel permeation chromatography
Number average molecular weight = 33,600 Weight average molecular weight = 98,000
The infrared absorption spectrum is shown in FIG.
CO stretching vibration (carbonate bond) cm ^-1

(Synthesis Example 6)
4,4′-dihydroxy-3,3′-diethyldiphenyl ether prepared in Synthesis Example 3 2.30 g, 1,2-bis (4-hydroxy-3-methylphenyl) propane 1.33 g, 4-tert-butylphenol 64 mg In a nitrogen atmosphere, a solution prepared by dissolving 2.82 g of sodium hydroxide and 66 mg of sodium hydrosulfite in 27 ml of water was added and dissolved. After stirring for 1 hour, a solution prepared by dissolving 1.67 g of bis (trichloromethyl) carbonate in 22 ml of methylene chloride was added, and the mixture was vigorously stirred at 18 ° C. for 15 minutes. Thereafter, a catalytic amount of triethylamine was added and stirred at room temperature for 1 hour. Dilute the contents with methylene chloride, separate the organic layer, wash twice with ion-exchanged water, then wash with 2% aqueous hydrochloric acid, and until the conductivity of the washing solution is the same as the value of ion-exchanged water Washed with ion exchange water. This organic layer was dropped into a large amount of methanol, and the obtained polymer was dried under reduced pressure at 80 ° C. to obtain 3.44 g of an aromatic polycarbonate resin (No. 3) represented by the following formula.

元素分析値（％）実測値／計算値
Ｃ：７３．５９／７３．５６
Ｈ：５．９０／５．９５
ゲルパーミエーションクロマトグラフィーによるポリスチレン換算分子量
数平均分子量＝３１，６００ 重量平均分子量＝９３，９００

Elemental analysis value (%) Measured value / calculated value
C: 73.59 / 73.56
H: 5.90 / 5.95
Polystyrene conversion molecular weight by gel permeation chromatography
Number average molecular weight = 31,600 Weight average molecular weight = 93,900

(Synthesis Example 7)
2.15 g of N- {4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl} -N, N-bis (4-tolyl) amine as a diol having a charge transporting ability, and 4,4′- A solution prepared by dissolving 2.11 g of sodium hydroxide and 66 mg of sodium hydrosulfite in 27 ml of water in 1.57 g of dihydroxy-3,3′-diethyldiphenyl ether and 79 mg of 4-tert-butylphenol was dissolved in 27 ml of water. After stirring for 1 hour, a solution in which 1.25 g of bis (trichloromethyl) carbonate was dissolved in 22 ml of methylene chloride was added and stirred vigorously at 18 ° C. for 15 minutes. Thereafter, a catalytic amount of triethylamine was added and stirred at room temperature for 1 hour. Dilute the contents with methylene chloride, separate the organic layer, wash twice with ion-exchanged water, then wash with 2% aqueous hydrochloric acid, and until the conductivity of the washing solution is the same as the value of ion-exchanged water Washed with ion exchange water. This organic layer was dropped into a large amount of methanol, and the obtained polymer was dried under reduced pressure at 80 ° C. to obtain 3.51 g of an aromatic polycarbonate resin (No. 4) represented by the following formula.

元素分析値（％）実測値／計算値
Ｃ：７７．９７／７７．８７
Ｈ：５．４０／５．４８
Ｎ：１．５９／１．５６
ゲルパーミエーションクロマトグラフィーによるポリスチレン換算分子量
数平均分子量：２１９００，重量平均分子量：９８６００

Elemental analysis value (%) Measured value / calculated value
C: 77.97 / 77.87
H: 5.40 / 5.48
N: 1.59 / 1.56
Polystyrene conversion molecular weight by gel permeation chromatography
Number average molecular weight: 21900, weight average molecular weight: 98600

(Example 1)
A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a methanol / butanol mixed solvent was applied on an aluminum plate support with a doctor blade, and dried at 100 ° C. for 5 minutes to provide a 0.5 μm intermediate layer. . On this, a bisazo compound represented by the following formula (P-1) 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 air-dried. A 0.5 μm charge generation layer was formed.

  Next, 1 part of the charge transport material represented by the following structural formula (D-1) and 1 part of the polycarbonate resin (No. 1) obtained in Synthesis Example 4 are dissolved in 8 parts of tetrahydrofuran, and this solution is used to generate the charge. The film was coated with a doctor blade on the layer, naturally dried, dried at 80 ° C. for 5 minutes and at 120 ° C. for 20 minutes to form a charge transport layer having a thickness of 20 μm. 1 was produced.

(Example 2)
In Example 1, except that the polycarbonate resin (No. 1) obtained in Synthesis Example 4 is replaced with the polycarbonate resin (No. 2) obtained in Synthesis Example 5, the photoreceptor No. 2 was created.

(Example 3)
In Example 1, except that the polycarbonate resin (No. 1) obtained in Synthesis Example 4 is replaced with the polycarbonate resin (No. 3) obtained in Synthesis Example 6, the photoreceptor No. 3 was created.

Example 4
After preparing the same intermediate layer and charge generation layer as in Example 1, 1 part of the polycarbonate resin (No. 4) having charge transport ability obtained in Synthesis Example 7 was dissolved in 4 parts of tetrahydrofuran, The charge generation layer was coated with a doctor blade, naturally dried, and dried at 80 ° C. for 5 minutes and at 120 ° C. for 20 minutes to form a charge transport layer having a thickness of 20 μm. 4 was produced.

(Comparative Example 1)
In Example 1, except that the polycarbonate resin (No. 1) obtained in Synthesis Example 4 was replaced with Polycarbonate Z (PC-Z, manufactured by Teijin Chemicals), Photoconductor No. 1 was prepared in the same manner as in Example 1. 5 was created.

(Example 5)
In Example 1, as a charge generation layer, 3 parts of an X-type metal-free phthalocyanine as a charge generation substance and 2 parts of polyvinyl butyral resin (BM-S: manufactured by Sekisui Chemical Co., Ltd.) were pulverized with a ball mill in 328 parts of tetrahydrofuran solvent to obtain The resulting dispersion was applied with a doctor blade and naturally dried to form a 0.5 μm charge generation layer. 6 was created.

(Example 6)
In Example 2, as a charge generation layer, 3 parts of an X-type metal-free phthalocyanine as a charge generation material and 2 parts of polyvinyl butyral resin (BM-S: manufactured by Sekisui Chemical Co., Ltd.) were pulverized with a ball mill in 328 parts of a tetrahydrofuran solvent. The resulting dispersion was applied with a doctor blade and naturally dried to form a charge generation layer having a thickness of 0.5 μm. 7 was created.

(Example 7)
In Example 3, as a charge generation layer, 3 parts of an X-type metal-free phthalocyanine as a charge generation material and 2 parts of polyvinyl butyral resin (BM-S: manufactured by Sekisui Chemical Co., Ltd.) were pulverized by ball milling in 328 parts of a tetrahydrofuran solvent. The resulting dispersion was applied with a doctor blade and naturally dried to form a charge generation layer having a thickness of 0.5 μm. 8 was created.

(Example 8)
In Example 4, as a charge generation layer, 3 parts of X-type metal-free phthalocyanine as a charge generation substance and 2 parts of polyvinyl butyral resin (BM-S: manufactured by Sekisui Chemical Co., Ltd.) were pulverized in a ball solvent in 328 parts of tetrahydrofuran solvent to obtain The resulting dispersion was applied with a doctor blade and air-dried to form a 0.5 μm charge generation layer. 9 was created.

(Comparative Example 2)
In Example 6, except that the polycarbonate resin (No. 2) obtained in Synthesis Example 5 used was replaced with polycarbonate Z (PC-Z, manufactured by Teijin Chemicals), the photoreceptor No. 10 was created.

The electrostatic characteristics of the laminated electrophotographic photoreceptors produced in the above examples and comparative examples were measured in accordance with the photoreceptor No. 1-No. No. 10 Using a commercially available electrostatic copying paper test apparatus [EPA-8200 manufactured by Kawaguchi Denki Seisakusho Co., Ltd.], charged with -6 KV corona discharge for 20 seconds in the dark, and then left in the dark for another 20 seconds. Then, the surface potential V ₀ (V) was measured. Next, a tungsten lamp light is irradiated so that the illuminance on the surface of the photosensitive member becomes 4.5 lux, and a time (second) until V ₀ becomes 1/2 is obtained, and an exposure amount E1 / 2 (lux · sec) is obtained. ) Was calculated. The results are shown in Table 1.

Example 9
A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a methanol / butanol mixed solvent was applied on an aluminum plate support with a doctor blade, and dried at 100 ° C. for 5 minutes to provide a 0.5 μm intermediate layer. . Next, 1 part of X-type metal-free phthalocyanine was ball milled and dispersed together with a solution comprising 1 part of the polycarbonate resin (No. 1) obtained in Synthesis Example 4 and 38 parts of tetrahydrofuran, and then 2% by weight of pigment composition, PC- Z composition is 50% by weight, low molecular charge transfer material represented by the above structural formula (D-1) is 30% by weight, acceptor compound represented by the following structural formula (E-1) is 18% by weight, silicone oil (KF50: (Shin-Etsu Chemical Co., Ltd.) A low molecular charge transporting substance, an acceptor compound, tetrahydrofuran, and silicone oil were added so as to be 0.001% by weight to prepare a photoreceptor coating solution having a solid content of 20% by weight. The thus prepared photoreceptor coating solution is applied onto the intermediate layer with a doctor blade, dried at 80 ° C. for 5 minutes and 120 ° C. for 20 minutes, and has a photosensitive layer having a thickness of 20 μm. Photoconductor, Photoconductor No. 11 was created.

(Example 10)
In Example 9, Photoreceptor No. 1 was the same as Example 1 except that the polycarbonate resin (No. 1) obtained in Synthesis Example 4 was replaced with the polycarbonate resin (No. 2) obtained in Synthesis Example 5. 12 was created.

(Example 11)
In Example 9, Photoreceptor No. 1 was changed in the same manner as in Example 1 except that the polycarbonate resin (No. 1) obtained in Synthesis Example 4 was replaced with the polycarbonate resin (No. 3) obtained in Synthesis Example 6. 13 was created.

(Example 12)
On the same intermediate layer as in Example 9, 1 part of an X-type metal-free phthalocyanine was added together with a solution consisting of 1 part of the polycarbonate resin (No. 4) having charge transport ability obtained in Synthesis Example 7 and 38 parts of tetrahydrofuran. After ball milling dispersion, the pigment composition was 2% by weight, the polycarbonate resin (No. 4) having charge transporting ability was 60% by weight, the acceptor compound represented by the structural formula (E-1) was 18% by weight, silicone oil (KF50) (Manufactured by Shin-Etsu Chemical Co., Ltd.) A polycarbonate resin (No. 4) having a charge transporting ability so as to be 0.001% by weight, an acceptor compound, tetrahydrofuran and silicone oil are added, and a photoreceptor coating solution having a solid content of 20% by weight Adjusted. The thus prepared photoreceptor coating solution is applied onto the intermediate layer with a doctor blade, dried at 80 ° C. for 5 minutes and 120 ° C. for 20 minutes, and has a photosensitive layer having a thickness of 20 μm. Photoconductor, Photoconductor No. 14 was created.

(Comparative Example 3)
In Example 11, Photoreceptor No. 3 was used in the same manner as in Example 1 except that the polycarbonate resin (No. 3) obtained in Synthesis Example 6 was replaced with polycarbonate Z (PC-Z, manufactured by Teijin Chemicals). 15 was created.

<Evaluation 1>
Single layer type electrophotographic photosensitive member No. 1 prepared in the above examples and comparative examples. 11-No. The surface potential V ₀ after electrostatic charge of 15 using an electrostatic copying paper test apparatus EPA-8200 (manufactured by Kawaguchi Denki Seisakusho), first charged for 20 seconds at an applied voltage +6 KV and then left in a dark place for 20 seconds. (V) is measured, and then a monochromatic light of 780 nm is irradiated so that the illuminance on the surface of the photoreceptor becomes 2.5 μW / cm ² , and the half-exposure amount Em required for the surface potential of the photoreceptor from 800 V to 400 V _1/2 (μJ / cm ² ) was measured as the sensitivity of the LD light source region (near infrared region). The results are shown in Table 2.

<Evaluation 2>
The single layer type electrophotographic photosensitive member of Example 11 (Photoreceptor No. 13), Example 12 (Photoreceptor No. 14), and Comparative Example 3 (Photoreceptor No. 15) is used as a drum with a linear velocity of 260 mm / s. Wearing, plus charging, exposure, and light quench were repeated 5000 times, and the initial and 5000 times charging potential Vd (V) and post-exposure potential Vl (V) were measured.
The results are shown in Table 3.

FIG. 2 is a cross-sectional view showing an example of a layer configuration of an electrophotographic photoreceptor according to the present invention. It is sectional drawing which shows the other example of a layer structure of the electrophotographic photoreceptor concerning this invention. It is sectional drawing which shows the other example of a layer structure of the electrophotographic photoreceptor concerning this invention. It is sectional drawing which shows the other example of a layer structure of the electrophotographic photoreceptor concerning this invention. It is sectional drawing which shows the other example of a layer structure of the electrophotographic photoreceptor concerning this invention. It is sectional drawing which shows the other example of a layer structure of the electrophotographic photoreceptor concerning this invention. It is the figure which showed the manufacturing path | route of the bisphenol compound used by this invention. It is a figure which shows the infrared absorption spectrum used in the synthesis example 5 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Photosensitive layer 2 'Photosensitive layer 2''Photosensitive layer 2''' Photosensitive layer 2 '''' Photosensitive layer 2 '''''Photosensitive layer 3 Charge generating substance 4 Charge transport layer or charge transport medium 5 Charge generation layer 6 Protective layer

Claims (16)

An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (I) as an active ingredient.

(In the formula, A ₁ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and A _{2 to} A ₇ each independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted group having 1 to 6 carbon atoms. Represents a substituted alkyl group.) An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (II) as an active ingredient.

(Wherein A ₁ is the same as defined above.) The composition of the structural unit represented by the general formula (I) or (II) is mainly composed of the structural unit represented by the above general formula (I) or (II) and the following general formula (III) on the conductive support. A photosensitive layer containing, as an active ingredient, a polycarbonate resin in which the ratio of the composition ratio is 0 <k / (k + j) ≦ 1, where k is the ratio and j is the composition ratio of the structural unit represented by the general formula (III). An electrophotographic photoconductor characterized by comprising:

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

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom, and a and b are each independently 0 to 0 4 is an integer of 4, c and d are each independently an integer of 0 to 3, Y is a single bond, a linear alkylene group having 2 to 12 carbon atoms, or a branched form having 3 to 12 carbon atoms. alkylene group, polyoxyalkylene group having 3 to 12 carbon atoms of, -O -, - S -, - SO -, - SO 2 -, - CO-,

Z ¹ and Z ^{2 each} represents a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group. , also may be ^{R 6} and ^{R 7} are bonded together to form a carbocyclic or heterocyclic ring having 5 to 12 carbon atoms, ^also R 6, ^{R 7} is or carbocyclic jointly with ^R 2, ^{R 3} complex A ring may be formed, and R ¹³ and R ^{14 each} represents a single bond, an alkylene group having 1 to 4 carbon atoms or a polyoxyalkylene group, and R ¹⁵ and R ¹⁶ are each independently substituted having 1 to 5 carbon atoms. Or an unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, e is an integer of 0 to 4, f is 0 to 20 integer, g represents an integer of 0-4. ). ] An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (IV) as an active ingredient.

(In the formula, A _{1 to} A ₇ and X are the same as defined above, and n represents an integer of 2 to 5000 as the number of repetitions.) The composition of the structural unit represented by the general formula (I) or (II) is mainly composed of the structural unit represented by the above general formula (I) or (II) and the following general formula (V) on the conductive support. A photosensitive layer containing, as an active ingredient, a polycarbonate resin in which the ratio of the composition ratio is 0 <k / (k + j) ≦ 1, where k is the ratio and j is the composition ratio of the structural unit represented by the general formula (V). An electrophotographic photoconductor characterized by comprising:

(In the formula, B ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, Ar ₁ represents a substituted or unsubstituted aryl group, and Ar ₂ and Ar ₃ represent substituted or unsubstituted. Represents a substituted arylene group.) An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (VI) as an active ingredient.

(In the formula, A _{1 to} A ₇ , Ar ₁ , Ar ₂ , Ar ₃ and B ₁ are the same as defined above, and n represents an integer of 2 to 5000 as the number of repetitions.) The composition of the structural unit represented by the general formula (I) or (II) is mainly composed of the structural unit represented by the general formula (I) or (II) and the following general formula (VII) on the conductive support. A photosensitive layer containing, as an active ingredient, a polycarbonate resin in which the ratio of the composition ratio is 0 <k / (k + j) ≦ 1, where k is the ratio and j is the composition ratio of the structural unit represented by the general formula (VII) An electrophotographic photoconductor characterized by comprising:

(In the formula, Ar ₂ and Ar ₃ are the same as defined above, Ar ₄ represents a substituted or unsubstituted arylene group. R ₁₇ and R ₁₈ are the same or different acyl, group-substituted or unsubstituted alkyl group, Represents a substituted or unsubstituted aryl group.) An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (VIII) as an active ingredient.

(In the formula, A _{1 to} A ₇ , Ar ₂ , Ar ₃ , Ar ₄ , R ₁₇ and R ₁₈ are the same as defined above, and n represents an integer of 2 to 5000 as the number of repetitions.) The composition of the structural unit represented by the general formula (I) or (II) is mainly composed of the structural unit represented by the general formula (I) or (II) and the following general formula (IX) on the conductive support. A photosensitive layer containing, as an active ingredient, a polycarbonate resin in which the ratio of the composition ratio is 0 <k / (k + j) ≦ 1, where k is the ratio and j is the composition ratio of the structural unit represented by the general formula (IX). An electrophotographic photoconductor characterized by comprising:

(Wherein R ₁₇ and R ₁₈ are the same as defined above.) An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing a polycarbonate resin having a repeating unit represented by the following general formula (X) as an active ingredient.

(In the formula, A _{1 to} A ₇ , R ₁₇ and R ₁₈ are the same as defined above, and n represents an integer of 2 to 5000 as the number of repetitions.) In the electrophotographic photoreceptor having a charge generation layer and a charge transport layer on a conductive support, the charge transport layer contains a polycarbonate resin having a repeating unit according to any one of claims 1 to 10 as an active ingredient. An electrophotographic photoreceptor characterized by the above. 11. An electrophotographic photoreceptor containing at least a charge generating material and a charge transport material on a conductive support, comprising as an active ingredient a polycarbonate resin having a repeating unit according to claim 5 as a charge transport material. An electrophotographic photoreceptor characterized in that: An electrophotographic photoreceptor containing at least a charge generating material and a charge transport material on a conductive support, the polycarbonate resin having a repeating unit according to any one of claims 1 to 10 as an active ingredient on the outermost layer An electrophotographic photoreceptor characterized in that: The polycarbonate layer having a repeating unit according to any one of claims 1 to 10 is contained as an active ingredient in a photosensitive layer of a single layer type electrophotographic photoreceptor in which the photosensitive layer is formed as a single layer. Electrophotographic photoreceptor. An electron comprising a polycarbonate resin having a repeating unit according to any one of claims 1 to 10 as an active ingredient in an outermost layer of a single-layer type electrophotographic photoreceptor having a single photosensitive layer. Photoconductor for photography. The polycarbonate resin having a repeating unit according to any one of claims 1 to 10 has a weight average molecular weight (polystyrene conversion) of 7,000 to 1,000,000 in gel permeation chromatography. The electrophotographic photoreceptor according to claim 1.

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