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Publication numberCN1298123 A
Publication typeApplication
Application numberCN 00128352
Publication date6 Jun 2001
Filing date24 Nov 2000
Priority date24 Nov 1999
Also published asCN1229695C, DE10058212A1, DE10058212B4, US6423459
Publication number00128352.9, CN 00128352, CN 1298123 A, CN 1298123A, CN-A-1298123, CN00128352, CN00128352.9, CN1298123 A, CN1298123A
Inventors佐佐木辉夫, 原健一, 中村洋一, 铃木信二郎, 喜纳秀树
Applicant富士电机影像器材有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Electronic photoreceptor and its producing method
CN 1298123 A
Abstract  translated from Chinese
公开一种电子照相感光体,它包括导电基片和在该导电基片上至少含有酞菁化合物作为光敏材料的光敏层,其中,按1摩尔所述酞菁化合物计,所述光敏层包括100nmol—200mmol带邻苯二甲腈化合物作为配位体的金属酞菁化合物。 Discloses an electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer on the conductive substrate comprising at least a phthalocyanine compound as a photosensitive material, wherein, based on 1 mol of the phthalocyanine compound meter, said photosensitive layer comprises 100nmol- 200mmol phthalonitrile compound with a metal phthalocyanine compound ligands. 该感光体具有优良的电位保持率。 The photoreceptor has excellent potential holding rate. 还提供该感光体的制造方法,包括用涂料液涂覆形成光敏层的步骤,从而使得到的光敏层具有高的电位保持率。 Also provides a method of the photosensitive member, the photosensitive layer comprising the steps of coating a coating liquid is formed, so that the photosensitive layer obtained has a high potential holding rate.
Claims(11)  translated from Chinese
1. 1. 一种电子照相感光体,它包括:导电基片,和在该导电基片上含有至少一种酞菁化合物作为光敏材料的光敏层,其中,按1摩尔所述酞菁化合物计,所述光敏层包括100nmol-200mmol带邻苯二甲腈化合物作为配位体的金属酞菁化合物。 An electrophotographic photoreceptor comprising: a conductive substrate and a photosensitive layer on the conductive substrate comprises at least one phthalocyanine compound as a photosensitive material, wherein, based on 1 mol of the phthalocyanine compound meter, said photosensitive layer including 100nmol-200mmol phthalonitrile compound with a metal phthalocyanine compound adjacent ligands.
2. 2. 如权利要求1所述的电子照相感光体,其特征在于所述酞菁化合物是钛氧基酞菁。 The electrophotographic photoreceptor as claimed in claim 1, wherein said phthalocyanine compound is titanyl phthalocyanine.
3. 3. 如权利要求1所述的电子照相感光体,其特征在于所述酞菁化合物是无金属氧代酞菁。 The electrophotographic photoreceptor as claimed in claim 1, wherein said phthalocyanine compound is a metal-free phthalocyanine oxo.
4. 4. 如权利要求1所述的电子照相感光体,其特征在于所述酞菁化合物的中心元素是过渡金属。 The electrophotographic photoreceptor as claimed in claim 1, characterized in that the central element of the phthalocyanine compound is a transition metal.
5. 5. 如权利要求4所述的电子照相感光体,其特征在于所述过渡金属选自钛、钒、铬、锰、铁、钴、镍、铜、锆和铌。 The electrophotographic photoreceptor as claimed in claim 4, wherein said transition metal selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, and niobium.
6. 6. 如权利要求1所述的电子照相感光体,其特征在于所述酞菁化合物的中心元素选自铟、镓、铝、锗和锡。 The electrophotographic photoreceptor as claimed in claim 1, characterized in that the central element of the phthalocyanine compound selected from indium, gallium, aluminum, germanium and tin.
7. 7. 如权利要求1所述的电子照相感光体,其特征在于所述酞菁化合物由式(1)表示: An electrophotographic photosensitive member according to claim, characterized in that the phthalocyanine compound represented by the formula (1): 其中M代表氢原子、金属原子、金属氧化物、金属卤化物、金属氢氧化物、硅化合物或磷化合物;R1-R16各自为氢原子、卤原子、羟基、硝基、氰基、酯基、烷基、烯丙基、烷氧基、芳基或苯氧基。 Wherein M represents a hydrogen atom, a metal atom, a metal oxide, a metal halide, a metal hydroxide, a silicon compound or a phosphorus compound; R1-R16 are each a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an ester group, alkyl group, an allyl group, an alkoxy group, an aryl group or a phenoxy group.
8. 8. 如权利要求1-7中任何一项所述的电子照相感光体,其特征在于所述金属酞菁化合物是钛氧基氧代酞菁。 1-7 Any electrophotographic photosensitive member according to one of claims, characterized in that the metal phthalocyanine compound is titanyl phthalocyanine oxo.
9. 9. 如权利要求1-8中任何一项所述的电子照相感光体,其特征在于所述邻苯二甲腈化合物由式(2)表示: 1-8 Any electrophotographic photosensitive member according to one of claims, wherein said phthalonitrile compound represented by the formula (2): 其中R17-R20各自表示氢原子、卤原子、羟基、硝基、氰基、酯基、烷基、烯丙基、烷氧基、芳基或苯氧基。 Wherein R17-R20 each represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an ester group, an alkyl group, an allyl group, an alkoxy group, an aryl group or a phenoxy group.
10. 10. 如权利要求2所述的电子照相感光体,其特征在于所述光敏层中含有作为电荷产生剂的质量数为576的钛氧基氧代酞菁和质量数为704的带邻苯二甲腈化合物作为配位体的钛氧基氧代酞菁,在质谱中相对质量数为576的化合物的峰强度,质量数为704的化合物的峰强度为10-5%-20%。 The electrophotographic photoreceptor as claimed in claim 2, wherein said photosensitive layer contains a charge generating agent as a quality number for the oxo-titanyl phthalocyanine and a mass number of 576 to 704 with phthalonitrile oxo compounds as titanyl phthalocyanine ligand, in the mass spectrum of the peak intensity of the relative mass numbers of compounds 576, the peak intensity of the mass number of the compound 704 was 10-5% -20%.
11. 11. 一种电子照相感光体的制造方法,包括用含电荷产生剂的涂料液涂覆导电基片,形成光敏层的步骤,其中该涂料液含有酞菁化合物和带邻苯二甲腈化合物作为配位体的金属酞菁化合物,按1摩尔所述酞菁化合物计,所述金属酞菁化合物的含量为100nmol-200mmol。 A method of manufacturing an electrophotographic photosensitive member, comprising coating a conductive substrate a coating liquid containing a charge-generating agent, the step of forming a photosensitive layer, wherein the coating liquid containing a phthalocyanine compound and with phthalonitrile compound as a ligand metal phthalocyanine compound body, according to one mole of the compound meter, the content of the metal phthalocyanine compound of the phthalocyanine for 100nmol-200mmol.
Description  translated from Chinese
电子照相感光体及其制造方法 The electrophotographic photoreceptor and its manufacturing method

本发明涉及电子照相感光体(下面简称为感光体)及其制造方法,具体地说,本发明涉及由有机材料于导电基片上形成的光敏层中包括改进的光敏材料的感光体,从而显示出优良的电位保持率。 The present invention relates to an electrophotographic photosensitive member (hereinafter referred to as a photoreceptor) and its manufacturing method, and more particularly, the present invention relates to a photosensitive layer of an organic material formed on the conductive substrate in a photosensitive material comprising an improved photoreceptor, thus showing excellent potential holding rate. 这种电子照相用感光体适用于采用电子照相法的打印机、复印机或传真机。 This electrophotographic photosensitive member applicable to an electrophotographic method using a printer, copying machine or facsimile machine. 本发明还涉及这种感光体的制造方法。 The present invention also relates to a method for producing such a photosensitive member.

电子照相感光体一般需要具有在黑暗中保持表面电荷,受光后产生电荷并且受光后转移电荷的功能。 The electrophotographic photoreceptor is required to have generally maintained in the dark surface charge, charge is generated by light and rear light by the charge transfer function. 已知类型的感光体包括所谓的单层型感光体(它在单一层中具有所述功能)和所谓功能分离的叠层型感光体,叠层型感光体具有一层主要用于产生电荷的层和一层用于在黑暗中保持表面电荷而受光转移电荷的层。 Known type photosensitive member comprises a so-called monolayer type photoreceptor (which has the function in a single layer) and a so-called function separation lamination type photoreceptor, the laminate type photoreceptor having a charge-generating layer is mainly used for layer and a layer for holding the surface charge in the dark and the light of the charge transport layer is exposed.

这些类型的感光体用于用已知的电子照相方法(如Carlson法)形成影象。 These types of photoreceptor for forming an image by a known electrophotographic method (e.g., Carlson method). 用这种方法形成影象是通过在黑暗中利用电晕放电对感光体充电,在该感光体带电表面上形成静电潜影(如原文的字符或图画),用上色剂粉末显影如此形成的静电影象并将构成影象的该上色剂粉末转移并固定在载体(如纸)上而实现的。 In this way an image is formed by the use of corona discharge in the dark to charge the photoreceptor, forming an electrostatic latent image (e.g., original characters or pictures) on the charged surface of the photosensitive member, with the use of the developing toner powder thus formed The electrostatic image and the toner powder image is transferred and fixed to constitute the carrier (e.g. paper) achieved. 上色剂粉末转移后,使感光体消除静电,除去残留的上色剂粉末,用光照抹去残留的电荷就可重新使用该感光体。 After the transfer of toner powder, make photoreceptor eliminate static electricity, remove residual toner powder, with light to erase the residual charge can reuse the photoreceptor.

对于电子照相感光体的光敏材料,业已使用的有分散在树脂粘合剂中的无机光电导剂,如硒、硒合金、氧化锌和氧化镉,以及例如分散在树脂粘合剂中或者真空沉积的有机光电导剂,如聚N-乙烯基咔唑、聚乙烯基蒽、酞菁化合物或双偶氮化合物。 For light-sensitive material of the electrophotographic photosensitive member, there are dispersed in a resin binder of the inorganic photoconductive agent, such as selenium, selenium alloy, zinc oxide and cadmium oxide, and dispersed in a resin binder such as vacuum deposition or have been used organic photoconductive agents, such as poly N- vinylcarbazole, polyvinyl anthracene, a phthalocyanine compound or a bis azo compound.

在这些有机光敏材料中,已对酞菁化合物的合成方法进行了广泛的研究,包括研究在合成过程中作为副产品的衍生杂质。 Among these organic photosensitive materials, it has been a method of synthesizing the phthalocyanine compound conducted extensive studies, including as a by-product during the synthesis derived impurities. 日本未审查专利公开No.平3-35245公开了对合成钛氧基氧代酞菁过程中副产品氯化钛氧基酞菁的研究结果,确认过去的实施例中氯的含量为0.38-5重量%。 Japanese Unexamined Patent Publication No. Hei 3-35245 discloses a study of the synthesis of oxo-titanyl phthalocyanine chloride by-product during the titanyl phthalocyanine, confirming previous embodiments chlorine content is 0.38-5 wt. %. 该文献还公开了对不产生氯化酞菁副产品的钛氧基氧代酞菁合成方法的详细研究结果。 This document also discloses a titanyl phthalocyanine oxo synthesis method does not produce by-products of the chlorination of phthalocyanine detailed findings.

另外,如IMKeen和BWMalerbi在J.Inorg.Nucl.Chem.,Vol.27,p1311-1319(1965)所述,已知酞菁化合物分子结构,可以邻苯二甲腈化合物作为配位体。 Further, as IMKeen and BWMalerbi in J.Inorg.Nucl.Chem., Vol.27, p1311-1319 (1965) the known molecular structure of phthalocyanine compound, can be ortho-phthalonitrile compound as a ligand. 作为分子结构中邻苯二甲腈化合物作为配位体的金属酞菁化合物的例子,该文献公开了邻苯二甲腈(酞菁)氯合钌(Ⅲ)、邻苯二甲腈(酞菁)氯合锇(Ⅲ)、邻苯二甲腈(酞菁)二氧合锇(Ⅵ)和邻苯二甲腈(一氯酞菁)氯合铱(Ⅲ)。 As the molecular structure of the phthalonitrile compound as an example of the metal phthalocyanine compound ligand, which discloses a phthalonitrile (phthalocyanine) chlorine ruthenium (Ⅲ), phthalonitrile (phthalocyanine ) chlorine osmium (Ⅲ), phthalonitrile (phthalocyanine) two oxygenation osmium (Ⅵ) and phthalonitrile (a chlorine phthalocyanine) chlorine iridium (Ⅲ).

但是除了上述IMKeen等的文献以外,其它文献均未提到过这类金属酞菁。 But in addition to the above literature IMKeen etc., were not mentioned in other documents such metal phthalocyanine. 具体地说,该文献例举的金属酞菁限于铂族元素,未公开过带有邻苯二甲腈化合物作为配位体的其它金属酞菁化合物。 Specifically, the document mentioned metal phthalocyanine limited PGE not disclosed other metal phthalocyanine compound ligand with phthalonitrile compound as the. 因此,从未研究过感光体中这类金属酞菁的用量与电位保持率之间的关系。 Therefore, never investigated the relationship between the photoreceptor in such an amount of metal phthalocyanine and the potential retention rate.

日本未审查专利申请No.平5-273775和平9-230615报道了钛氧基酞菁与二元醇反应形成钛配合物。 Japanese Unexamined Patent Application No. Hei 5-273775 9-230615 reported peace titanylphthalocyanine diol reacts with the formation of titanium complexes. 但是,这些文献的目的是要获得高灵敏度的感光体,而与获得高电位保持率无关。 However, the purpose of these documents is to obtain high sensitivity of the photoreceptor, regardless of the potential for high retention. 另外,这些文献未提到带有邻苯二甲腈化合物作为配位体的金属酞菁化合物。 In addition, these documents are not mentioned o-phthalonitrile compound having a metal phthalocyanine compound as a ligand.

如上所述,已知在感光体中使用酞菁化合物作为光敏材料,并且对该化合物的合成、纯化和副产品进行了许多研究工作。 As described above, it is known to use a phthalocyanine compound as a photosensitive material in the photosensitive member, and the synthesis, purification and byproduct compounds were much research effort. 但是,目前为止不知道不含氯的邻苯二甲腈化合物的聚合产物与电子照相感光体特性的关系。 However, so far do not know the relationship between the polymerization product properties of the electrophotographic photosensitive member of the non-chlorinated phthalonitrile compound. 尽管已经公开了酞菁化合物的各种合成方法,但是不知道合成酞菁化合物时的副产品的类型和含量与电子照相特性,尤其是电位保持率之间的关系。 Although various synthetic methods have been disclosed phthalocyanine compound, but do not know the type and content of electrophotographic characteristics of phthalocyanine compound synthesized byproduct, especially the relationship between the potential retention rate. 具体地说,带有邻苯二甲腈化合物作为配位体的金属酞菁的含量与电位保持率之间的关系从未得到过研究。 Specifically, with phthalonitrile compound as the content and the potential of the metal phthalocyanine ligands maintain relationships between the rate has never been studied.

因此,本发明的目的是通过了解这种关系,提供一种具有优良电子照相特性,尤其是电位保持率的电子照相感光体。 Accordingly, an object of the invention is achieved by understanding this relationship, to provide an excellent electrophotographic characteristics, especially the rate of the potential holding electrophotographic photoreceptor. 本发明另一个目的是提供一种电子照相感光体的制造方法,它包括涂覆涂料液形成光敏层的步骤,该涂覆步骤能形成具有优良电位保持率的光敏层。 Another object of the present invention is to provide a method of manufacturing an electrophotographic photosensitive member, comprising the step of coating the coating solution for formation of a photosensitive layer, the coating step to form a photosensitive layer having excellent potential retention rate.

本发明人经过对解决问题的方法进行大量研究以后,发现光敏层中当带有邻苯二甲腈化合物作为配位体的金属酞菁化合物(下面也称之为带配位体的金属酞菁)在含酞菁化合物的层中的含量在特定的范围内时,可明显提高感光体的电位保持率。 The inventors of the method to solve the problem after extensive research and found that the photosensitive layer when the phthalonitrile compound with a metal phthalocyanine compound as a ligand (hereinafter also referred to as a ligand with a metal phthalocyanine ) when the layer containing the phthalocyanine compound in an amount within a specific range, can significantly improve the potential holding rate photoreceptor. 本发明是在该发现的基础上完成的。 The present invention has been accomplished on the basis of this finding.

因此,本发明电子照相感光体包括导电基片和在该导电基片上至少含有酞菁化合物作为光敏材料的光敏层,其中,按1摩尔酞菁化合物计,所述含酞菁化合物的光敏层包括100nmol-200mmol带邻苯二甲腈化合物作为配位体的金属酞菁化合物。 Accordingly, the present invention is an electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer on the conductive substrate comprising at least a phthalocyanine compound as a photosensitive material, wherein 1 mole of phthalocyanine compounds according to the count, the photosensitive layer containing a phthalocyanine compound comprising 100nmol-200mmol with phthalonitrile compound as the metal phthalocyanine compound ligands.

另外,本发明人发现,在含酞菁化合物和带配位体的金属酞菁化合物(相对于前者,后者的含量在一定的范围内)的感光体的制造方法中,在涂覆步骤中使用这种含电荷产生剂的涂料液时,可明显提高感光体的电位保持率。 Further, the present inventors have found that, in the metal-containing phthalocyanine compound and a phthalocyanine compound with a ligand (with respect to the former, the latter in an amount within a certain range) the method of manufacturing a photosensitive body, in the coating step When using this coating liquid containing a charge-generating agent, can significantly improve the potential holding rate photoreceptor. 在该发现的基础上完成了本发明制造方法。 On the basis of this finding to complete the manufacturing process of the present invention.

因此,本发明感光体的制造方法包括用含电荷产生剂的涂料液涂覆导电基片形成光敏层的方法,其中所述涂料液包括酞菁化合物和带邻苯二甲腈化合物作为配位体的金属酞菁化合物,按1摩尔酞菁化合物计,金属酞菁的含量为100nmol-200mmol。 Accordingly, the manufacturing method of the present invention comprises a photoreceptor method of forming a conductive substrate coated with the coating liquid containing a charge-generating agent of the photosensitive layer, wherein the coating liquid comprises a phthalocyanine compound and with the phthalonitrile compound as a ligand metal phthalocyanine compounds, according to the content of one mole of a phthalocyanine compound meter, metal phthalocyanine is 100nmol-200mmol.

本发明感光体的光敏层可以是单层型或叠层型的,并且不限于某种类型。 The photosensitive layer of the photosensitive member of the present invention may be a single type or a laminate type, and is not limited to a certain type. 本发明制造方法中的涂覆方法可选自浸涂、喷涂和其它各种方法,并且不限于任何特定的方法。 The manufacturing method of the present invention a coating method selected from dipping, spraying and other various methods, and is not limited to any particular method.

下面将参照较好的实例和附图详细说明本发明。 Below with reference to preferred embodiments and the accompanying drawings illustrate the invention.

图1是本发明负电荷充电叠层型感光体一个例子的剖面图;图2是本发明带配位体金属酞菁化合物的钛氧基氧代酞菁的TOF-MS光谱的一个例子中,表示阳离子检测分析结果的谱图;图3是本发明带配位体金属酞菁化合物的钛氧基氧代酞菁的TOF-MS光谱的一个例子,表示质量数为704的带配位体的金属酞菁化合物分子离子的MS/MS分析结果谱图;图4是本发明带配位体金属酞菁化合物的钛氧基氧代酞菁的TOF-MS光谱的一个例子,表示阴离子检测分析结果的谱图;图5是本发明一个实例中带配位体金属酞菁化合物的钛氧基氧代酞菁的TOF-MS光谱的一个例子,表示阳离子检测分析结果的谱图。 Figure 1 of the present invention is a laminate type negatively chargeable photosensitive member cross-sectional view of an example; Fig. 2 is an example of titanyl phthalocyanine with oxo ligand metal phthalocyanine compound of the present invention is TOF-MS spectra, the represents a cation of the detection results of the spectrum analysis; Fig. 3 is an example of oxo-titanyl phthalocyanine of the present invention with a ligand of the metal phthalocyanine compound TOF-MS spectrum showing the mass number 704 with ligand metal phthalocyanine compound molecular ion MS / MS analysis of the spectrum; Figure 4 is an example of titanyl phthalocyanine oxo ligands present invention with a metal phthalocyanine compound TOF-MS spectrum, represents an anion detection results spectra; Fig. 5 is an example of the present invention is an example with a ligand-oxo-titanyl phthalocyanine metal phthalocyanine compound TOF-MS spectrum, showing the detection results of the cation spectra.

附图中标号1表示导电基片,标号2表示底涂层,标号3表示电荷产生层,标号4表示电荷转移层,标号5表示光敏层。 The drawings, reference numeral 1 denotes a conductive substrate, reference numeral 2 denotes the undercoat layer, reference numeral 3 denotes a charge generating layer, reference numeral 4 represents a charge transport layer, reference numeral 5 denotes a photosensitive layer.

电子照相感光体具有数种已知的类型,如负电荷充电叠层型感光体、正电荷充电叠层型感光体和正电荷充电单层型感光体。 An electrophotographic photoreceptor having several known types, such as laminate type negatively chargeable photosensitive member, a positively chargeable photosensitive member and laminate type positively charged single-layer type photoreceptor. 尽管下面以负电荷充电叠层型感光体作为例子进行详细描述,但是除了涉及金属酞菁化合物(其金属原子带有邻苯二甲腈配位体)的材料和方法以外,用于形成和制造本发明感光体的材料和方法可适当地选自任何已知的材料和方法。 Though an negatively chargeable laminate-type photoreceptor as an example described in detail, but in addition relates to a metal phthalocyanine compound (which is a metal atom with a phthalonitrile ligand) other than the materials and methods for forming and manufacturing Materials and Methods photoreceptor of the present invention may be selected from any known materials and methods as appropriate.

图1是负电荷充电叠层型感光体,它包括导电基片1,叠合在该基片上的底涂层2,和叠合在底涂层上的光敏层5。 Figure 1 is a laminate type negatively chargeable photosensitive member, comprising an electroconductive substrate 1, superimposed on the substrate an undercoat layer 2, and superposed on the undercoat layer of the photosensitive layer 5. 光敏层5包括电荷产生层3和叠合在该电荷产生层上的电荷转移层4。 5 comprises a photosensitive layer and a charge generating layer 3 laminated on the charge generation layer on the charge transport layer 4. 因此,该光敏层是由独立的电荷产生层3和电荷转移层4组成的功能独立型光敏层。 Therefore, the photosensitive layer is a layer 3 and a charge transport layer 4 function-separated type photosensitive layer consisting of a charge generated by independent.

在上述类型的感光体中底涂层2是非必要的。 In the bottom of the above type photoreceptor layer 2 is non-essential.

导电基片1用作感光体的电极,还用于支承其它各层。 An electroconductive substrate as an electrode of the photoreceptor, but also for supporting the other layers. 导电基片1可具有圆筒形、平面形或薄膜形的形状,并可由金属或合金(如铝、不锈钢或镍)或者经处理具有合适导电性的玻璃或树脂制成。 An electroconductive substrate 1 may have a cylindrical, planar or film like shape, and can be made of a metal or alloy (such as aluminum, stainless steel or nickel), or treated with a suitable electrically conductive glass or resin.

底涂层2可由醇溶性聚酰胺、可溶剂溶解的芳族聚酰胺或热固性聚氨酯树脂等制成。 The undercoat layer 2 may be alcohol-soluble polyamide, solvent-soluble aromatic polyamide or thermoset polyurethane resin or the like. 所述醇溶性聚酰胺较好是,如尼龙6、尼龙8、尼龙12、尼龙66、尼龙610或尼龙612等的共聚物,或者N-烷基改性的或N-烷氧基烷基改性的尼龙。 Preferably the alcohol-soluble polyamide copolymer such as nylon 6, nylon 8, nylon 12, nylon 66, nylon 610, or nylon 612, etc., or N- alkyl-modified or alkoxyalkyl modified N- of nylon. 上述化合物的具体例子有AMILAN CM8000(一种购自Toray Industries Inc.的6/66/610/12共聚尼龙)、ELBAMIDE 9061(一种购自Du Pont Japan Co.,Ltd的6/66/612共聚尼龙)和DAIAMIDE T-170(一种购自Daicel-Huels Co.,Ltd的主要含尼龙12的共聚尼龙)。 Specific examples of the above compounds are AMILAN CM8000 (A available from Toray Industries Inc. of 6/66/610/12 copolymer nylon), ELBAMIDE 9061 (a commercially available from Du Pont Japan Co., Ltd of 6/66/612 copolymer nylon) and DAIAMIDE T-170 (a commercially available from Daicel-Huels Co., Ltd mainly containing nylon copolymerized nylon 12). 底涂层2还可包括无机细粉末,如二氧化钛、二氧化锡、氧化铝、碳酸钙或二氧化硅。 The undercoat layer 2 may also include inorganic fine powders such as titanium dioxide, tin dioxide, aluminum oxide, calcium carbonate or silica.

受光产生电荷的电荷产生层3是将有机光电导性物质的颗粒真空沉积在底涂层2上,或者将由有机光电导性物质的粒子分散在树脂粘合剂中形成的涂料液涂覆底涂层2而制得的。 Charges of light-generated charge-generating layer 3 is a particulate organic photoconductive substance vacuum deposited on the undercoat layer 2, or by particles of an organic photoconductive substance dispersed in a resin binder coating liquid is coated to form the undercoat Layer 2 and prepared. 重要的是电荷产生层3能高效地将产生的电荷注入电荷转移层4并且能高效地产生电荷。 Important that the charge generating layer 3 can be efficiently generated by the charge injection and charge transport layer 4 can efficiently generate charges. 也就是说,要求电荷产生层3能产生电荷而很少依赖电场,并即使在弱电场中也能很好地使电荷注入。 That is, the requirement to produce a charge generation layer 3 and a charge less dependent on the electric field, and even in a weak electric field can be a good charge injection.

尽管要求本发明电荷产生剂至少含有一种酞菁化合物,但是还可并用例如选自偶氮化合物、醌化合物、靛蓝化合物、花青化合物、squarilium化合物和azurenium化合物的其它颜料或染料。 Although the present invention requires a charge generating agent comprises at least one phthalocyanine compound, but also with, for example selected from azo compounds, quinone compounds, indigo compounds, cyanine compound, squarilium compound and other pigments or dyes azurenium compound.

按1摩尔酞菁化合物计,本发明感光体中电荷产生层3包括100nmol-200mmol带邻苯二甲腈化合物作为配位体的金属酞菁化合物。 1 mol of a phthalocyanine compound according to the count, the photoreceptor of the present invention comprises a charge generating layer 3 100nmol-200mmol with phthalonitrile compound as a ligand of the metal phthalocyanine compound. 当光敏层所含的带配位体的金属酞菁化合物相对于酞菁化合物的量在该具体的范围内时,可明显提高电位保持率。 When the metal phthalocyanine compound contained in the photosensitive layer with a ligand with respect to the amount of the phthalocyanine compound is within the specific range, can significantly improve the potential holding rate. 尽管其作用机理未完全了解,但是这可能是下列原因造成的。 Although the mechanism is not fully understood, but it may be due to the following reasons.

低于100nmol的少量带配位体的金属酞菁会使酞菁化合物太纯,使晶体生长太快,或者破坏了分散性能,这两种因素均会导致电位保持率下降。 Metal phthalocyanines cause a phthalocyanine compound below 100nmol ligand with too small amount of pure, crystal growth is too fast, or destroy the dispersion performance, these two factors will result in a potential holding rate. 另一方面,超过200mmol的较高含量会使酞菁化合物晶体结构的无序性太高,或者带邻苯二甲腈化合物配位体的金属酞菁本身会产生不利的作用,导致电位保持率下降。 On the other hand, a higher content than would 200mmol phthalocyanine compound crystal structure disorder is too high, or the phthalonitrile compound with a ligand of the metal phthalocyanine per se would have a negative effect, resulting in the potential retention rate decline.

适用于本发明的酞菁化合物的合成可采用已知的方法,例如,CCLenzoff等在VCH Publishers,Inc 1989年出版的“酞菁”或者FHMoser等在CRCPress1983年出版的“酞菁”中所述的方法。 Synthesis of phthalocyanine compound of the present invention may be applied to known methods, e.g., CCLenzoff et etc. VCH Publishers, Inc 1989 published "phthalocyanine" or FHMoser published in CRCPress1983 year "phthalocyanine" as described in Methods.

本发明酞菁化合物较好是钛氧基氧代酞菁或无金属酞菁。 Phthalocyanine compounds of the present invention preferably is oxo-titanyl phthalocyanine or metal-free phthalocyanine. 酞菁的中心金属元素可选自过渡金属,尤其是钛、钒、铬、锰、铁、钴、镍、铜、锆和铌。 Phthalocyanine center metal element selected from transition metals, particularly titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, and niobium. 酞菁的中心金属元素还可选自铟、镓、铝、锗和锡。 Phthalocyanine center metal element may also be selected from indium, gallium, aluminum, germanium and tin. 如通式(1)所示酞菁化合物可以是具有各种官能团的酞菁化合物: General formula (1) phthalocyanine compounds may have a variety of functional groups of the phthalocyanine compound: 其中M代表氢原子、金属原子、金属氧化物、金属卤化物、金属氢氧化物、硅化合物或磷化合物;R1-R16各自为氢原子、卤原子、羟基、硝基、氰基、酯基、烷基、烯丙基、烷氧基、芳基或苯氧基。 Wherein M represents a hydrogen atom, a metal atom, a metal oxide, a metal halide, a metal hydroxide, a silicon compound or a phosphorus compound; R1-R16 are each a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an ester group, alkyl group, an allyl group, an alkoxy group, an aryl group or a phenoxy group.

带邻苯二甲腈化合物作为配位体的金属酞菁化合物可选自各种化合物,包括如J.Inorg.Nucl.Chem,Vol.27,p1311-1319(1965)所述的一邻苯二甲腈(酞菁)氯合钌(Ⅲ)、一邻苯二甲腈(酞菁)氯合锇(Ⅲ)、一邻苯二甲腈(酞菁)二氧合锇(Ⅵ)和一邻苯二甲腈(一氯酞菁)氯合铱(Ⅲ)。 Ortho-phthalonitrile compound as a ligand with a metal phthalocyanine compound selected from a variety of compounds, including a phthalyl e.g. J.Inorg.Nucl.Chem, Vol.27, p1311-1319 (1965), wherein A nitrile (phthalocyanine) chlorine ruthenium (Ⅲ), a phthalonitrile (phthalocyanine) chlorine osmium (Ⅲ), a phthalonitrile (phthalocyanine) two oxygenation osmium (Ⅵ) and a neighbor phthalonitrile (a chlorine phthalocyanine) chlorine iridium (Ⅲ). 较好的是,金属酞菁化合物是钛氧基氧代酞菁化合物,作为配位体的邻苯二甲腈化合物可如通式(2)所示具有取代基: Preferably, the metal phthalocyanine compound is titanyl phthalocyanine-oxo compound, as phthalonitrile compound ligand can be the general formula (2) having a substituent group: 其中R17-R20各种表示氢原子、卤原子、羟基、硝基、氰基、酯基、烷基、烯丙基、烷氧基、芳基或苯氧基。 Wherein R17-R20 represents a variety of hydrogen atom, halogen atom, a hydroxyl group, a nitro group, a cyano group, an ester group, an alkyl group, an allyl group, an alkoxy group, an aryl group or a phenoxy group.

下面描述本发明人发现的带邻苯二甲腈化合物作为配位体的金属酞菁化合物的组合物体系。 The following description with phthalonitrile compounds of the present invention have found that the system as a composition of metal phthalocyanine compounds ligands.

起初,在合成钛氧基氧代酞菁过程中发现一种副产品。 Initially, the discovery of a by-product in the synthesis of titanyl phthalocyanine oxo process. 该副产品的分子结构中一个相应于邻苯二甲腈化合物的结构额外地作为钛氧基氧代酞菁化合物的金属配位结合。 The molecular structure of the by-products in a corresponding ortho structures additionally phthalonitrile compound as the metal complex oxo titanyl phthalocyanine compound in combination. 该副产品的化学式为(C8H4N2)5OTi,分子量为704.5,下面将其称为钛氧基氧代五聚物。 The by-products of the formula (C8H4N2) 5OTi, a molecular weight of 704.5, the following referred to as titanyl oxo pentamer. 本发明人成功地大量制得该副产品并分离之。 The present inventors have successfully prepared a large number of by-products and the separation of.

为了了解该钛氧基氧代五聚物的结构,本发明人使用激光切断电离飞行时间质谱法(简称TOF-MS)对含钛氧基氧代五聚物副产品的钛氧基氧代酞菁试样进行分析。 In order to understand the structure of the oxo-titanyl pentamer, the present inventors used a laser ionization time of flight mass spectrometry cutting (referred to as TOF-MS) on a titanium-containing titanyl oxo group pentamer byproducts oxo phthalocyanine sample was analyzed. 图2-4是含钛氧基氧代五聚物的钛氧基氧代酞菁的TOF-MS谱图的例子。 Figure 2-4 is a titanium-containing group oxo pentamer oxo-titanyl phthalocyanine TOF-MS spectra of an example. 图2是阳离子检测分析结果,表明除了质量数为576的钛氧基氧代酞菁分子的离子外,还测得质量数为704的钛氧基氧代五聚物分子的离子。 Figure 2 is a cationic detection results, showed in addition to the mass number 576 oxo-titanyl phthalocyanine molecule ion, but also the measured mass of the oxo-titanyl 704 pentamer molecule ions.

随后,将注意力集中在质量数为704的钛氧基氧代五聚物分子的该离子上,对该离子进行阳离子检测MS-MS分析。 Subsequently, the focus on the mass number of titanyl oxo pentamer molecules 704 such ions, the ions are cations detecting MS-MS analysis. 结果如图3所示。 The results shown in Fig. 3. 结果表明由质量数为704的五聚物离子产生质量数为576的片断离子,并且钛氧基氧代五聚物分子的离子结构中分子量为128的邻苯二甲腈位于酞菁环的外面。 The results showed that the mass number 704 out of the ion generating pentamer 576 mass fragment ions, and ion structure titanyl oxo pentamer molecules of a molecular weight of 128 phthalonitrile located phthalocyanine ring .

图4是同样的试样的阴离子探测结果。 Figure 4 is the result of a sample of the same anion detection. 结果高灵敏度地测得钛氧基氧代酞菁的质量数为576的分子离子。 Several quality results measured with high sensitivity titanyl phthalocyanine oxo 576 molecular ion. 对于钛氧基氧代五聚物,不仅未测得该分子的离子,而且未测得反映钛氧基氧代五聚物结构的任何其它离子。 For titanyl oxo pentamer, not only measured the molecular ion, and did not reflect any other measured ion titanyl oxo pentamer structure.

上面的分析表明,对于钛氧基氧代五聚物的结构,难以产生能直接反映钛氧基氧代五聚物分子结构的其它离子,附加的邻苯二甲腈是作为配位体连接在钛氧基氧代酞菁上的。 The above analysis shows that the structure titanyl oxo pentamer, it is difficult to produce directly reflect other ions titanyl oxo pentamer molecular structure, additional phthalonitrile is attached as a ligand oxo-titanyl phthalocyanine on.

在本发明酞菁化合物是钛氧基氧代酞菁时,质量数为704的带邻苯二甲腈化合物作为配位体的钛氧基氧代酞菁化合物的质谱峰强度较好占质量数为576的钛氧基氧代酞菁的峰强度的10-5%-20%。 MS peak intensity oxo-titanyl phthalocyanine compound in the phthalocyanine compound of the present invention is titanyl phthalocyanine oxo, the mass number 704 with phthalonitrile compound as a ligand is preferably accounted mass 10-5% -20% of the peak intensity of the oxo-titanyl phthalocyanine of 576.

通过升华可控制用于本发明的带邻苯二甲腈作为配位体的金属酞菁化合物的含量。 By sublimation can be controlled with a phthalonitrile used in the present invention as the content of the metal phthalocyanine compound ligand. 可将合成中的金属酞菁副产品作为用作本发明感光体的金属酞菁。 Can be synthesized in the metal phthalocyanine byproduct used as the photoreceptor of the present invention the metal phthalocyanine.

电荷产生层3的膜厚度决定于电荷产生剂的吸光系数,较好控制在不超过5微米,最好不超过1微米。 The charge generation layer 3 depends on the film thickness of the optical absorption coefficient of the charge generating agent is preferably controlled to not more than 5 microns, preferably not more than 1 micron.

电荷产生层3含有电荷产生剂作为主要组分并可加入电荷转移剂和其它物质。 The charge generation layer 3 containing a charge-generating agent as a main component can be added to the charge transfer agent and other substances. 用于电荷产生层3的树脂粘合剂可选自聚碳酸酯、聚酯、聚酰胺、聚氨酯、环氧树脂、聚乙烯醇缩丁醛、苯氧化合物、硅氧烷、甲基丙烯酸酯的聚合物、共聚物以及这些物质的卤化物和氰乙基化合物等的适当组合。 A resin binder for the charge generating layer 3 is selected from polycarbonates, polyesters, polyamides, polyurethanes, epoxy resins, polyvinyl butyral, phenoxy compounds, silicone, methacrylate appropriate combination of polymers, copolymers, and these halides and cyanoethyl compounds substance. 按100重量份树脂粘合剂计,用于电荷产生层的电荷产生剂的用量较好为10-5000重量份,更好为50-1000重量份。 The amount of resin binder per 100 parts by weight meter, for a charge generating layer, a charge generating agent is preferably 10-5000 parts by weight, preferably 50-1000 parts by weight.

电荷转移层4是一层涂层膜,它是由电荷转移剂溶解在树脂粘合剂中的材料制成的。 Charge transfer layer 4 is a layer of the coating film, it is a charge transfer agent material is dissolved in a resin binder made. 电荷转移剂可例如选自腙化合物、苯乙烯基化合物、胺化合物及其衍生物,它们可单独使用或适当地组合使用。 Charge transfer agents may be for example selected from hydrazone compounds, styryl compounds, amine compounds and derivatives thereof, which may be used alone or in appropriate combination. 在黑暗中电荷转移层4作为绝缘层用于保留感光体的电荷,并在受光后用于转移来自电荷产生层的电荷。 In the dark, the charge transport layer 4 as an insulating layer for charge retention of the photoreceptor, and, after the light used to transfer charge from the charge generating layer. 用于电荷转移层的粘合剂树脂可例如选自聚碳酸酯、聚酯、聚苯乙烯和甲基丙烯酸酯等聚合物、聚合物混合物和共聚物。 The binder resin for the charge transport layer may be, for example a polymer selected from polycarbonate, polyester, polystyrene, and methyl acrylate, a mixture of polymers and copolymers. 与电荷转移剂的相容性以及机械、化学和电气稳定性和粘性对树脂粘合剂的选择是重要的。 And compatibility and mechanical, chemical and electrical stability and charge-transfer agent for the viscous resin binder choice is important. 按100重量份树脂粘合剂计,电荷转移剂的用量较好为20-500重量份,更好为30-300重量份。 Based on 100 parts by weight of the resin binder used in an amount of charge transfer agent is preferably 20-500 parts by weight, more preferably 30-300 parts by weight.

电荷转移层4的膜厚较好控制在3-50微米,更好控制在15-40微米以保持实际有效的表面电位。 Film thickness of the charge transport layer 4 is preferably controlled to 3-50 microns, more preferably 15-40 microns in order to maintain control of the actual effective surface potential.

下面参照实施例说明本发明,但是本发明不限于这些实施例。 The following reference examples illustrate the present invention, but the present invention is not limited to these embodiments.

实施例1制造底涂层将70重量份购自Toray Industries,Inc.的聚酰胺树脂AMILAN CM8000和930重量份甲醇(和光纯药工业(株)制)混合在一起制得用于底涂层的涂料液。 1 producing the primer layer 70 parts by weight available from Toray Industries, Inc. AMILAN CM8000 polyamide resin and 930 parts by weight of methanol in Example (Wako Pure Chemical Industries, (Ltd.)) were mixed together to prepare for the undercoat layer a coating liquid. 用浸涂法将该涂料液涂覆在铝基片上,干燥后形成0.5微米厚的底涂层。 The coating liquid by dip coated on an aluminum substrate, dried to form a 0.5 micron-thick undercoating layer.

合成钛氧基氧代酞菁将800g邻苯二甲腈(东京化成工业(株)制)和1.8升喹啉(东京化成工业(株)制)加入反应容器中并搅拌之。 Synthesis of titanyl phthalocyanine to 800g oxo phthalonitrile (Tokyo Kasei Kogyo (K.K.)) and 1.8 l quinoline (Tokyo Kasei Kogyo (K.K.)) was added to the reaction vessel and stirred. 接着在氮气氛中滴加297g四氯化钛(KishidaChemical Co.,Ltd)并搅拌之,接着在2小时内加热至180℃并在该温度下搅拌15小时。 Followed by dropwise addition of 297g of titanium tetrachloride (KishidaChemical Co., Ltd) under a nitrogen atmosphere and stirred, followed by heating to 180 ℃ over 2 hours and stirred at this temperature for 15 hours.

使反应液冷却至130℃,过滤,用3升N-甲基-2-吡咯烷酮(关东化学(株)制)洗涤之。 The reaction mixture was cooled to 130 ℃, filtered, washed with 3 liters N- methyl-2-pyrrolidone (Kanto Chemical (Co., Ltd.)) was washed of. 在1.8升N-甲基-2-吡咯烷酮中在氮气氛中将形成的湿滤饼在160℃加热搅拌1小时。 Wet cake was 1.8 liters N- methyl-2-pyrrolidone in a nitrogen atmosphere was heated at 160 ℃ stirred for 1 hour. 冷却形成的混合物并过滤。 The mixture was cooled and filtered formed. 随后用3升N-甲基-2-吡咯烷酮、2升丙酮(关东化学(株)制)、2升甲醇(关东化学(株)制)和4升温纯水依次洗涤,得到湿滤饼。 Then with 3 liters of N- methyl-2-pyrrolidone, 2 liters of acetone (Kanto Chemical Co. (Ltd.)), 2 liters of methanol (manufactured by Kanto Chemical (Co., Ltd.)) and washed successively 4 heated water to obtain a wet cake.

将如此形成的钛氧基氧代酞菁湿滤饼在用360ml 36%盐酸(关东化学(株)制)和4升水制得的稀盐酸中在80℃加热搅拌1小时,使之冷却并过滤,用4升温水洗涤,并干燥。 The oxo-titanyl phthalocyanine wet cake thus formed with 360ml 36% hydrochloric acid (Kanto Chemical Co. (Ltd.)), and 4 liters of water to obtain a dilute hydrochloric acid was heated with stirring at 80 ℃ 1 hour allowed to cool and filtered. , washed with 4 water heating, and dried. 得到的产物真空升华3次进行纯化并干燥。 The product obtained was purified by vacuum sublimation three times and dried.

随后,边冷却和搅拌边在-5℃将200g如此制得的干产物加至4kg 96%硫酸(关东化学(株)制)中,使得液体温度保持在-5℃或更低。 Subsequently, while cooling and stirring at -5 ℃ 200g of the dry product so obtained was added to 4kg 96% sulfuric acid (Kanto Chemical Co. (Ltd.)), and such that the liquid temperature was maintained at -5 ℃ or lower. 在-5℃进一步搅拌并冷却1小时。 Further stirred for 1 hour and cooled at -5 ℃. 将形成的硫酸溶液加至35升水和5kg冰的混合物中,使温度保持在10℃或更低,将其冷却并搅拌1小时。 Sulfuric acid solution was added to 35 liters of water and 5kg ice mixture formed, maintaining the temperature at 10 ℃ or less, it was cooled and stirred for 1 hour. 过滤并用10升温水洗涤。 Filtered and washed with 10 heating water.

将如此得到的产物与由10升水和770ml 36%盐酸组成的稀盐酸相混合,并在80℃将其加热搅拌1小时。 The product thus obtained with dilute hydrochloric acid by 10 liters of water and 770ml 36% hydrochloric acid and the composition is mixed and heated with stirring at 80 ℃ its one hour. 冷却、过滤并用10升温水洗涤,干燥后得到钛氧基氧代酞菁,经升华纯化后得到纯的钛氧基氧代酞菁。 Cooled, filtered and washed with 10 heating water, and dried to give oxo-titanyl phthalocyanine, after purification by sublimation to give pure oxo-titanyl phthalocyanine.

合成带配位体的金属酞菁化合物重复与上面钛氧基氧代酞菁合成方法相同的步骤,但是在干燥氮气氛中实施的步骤改成在空气中进行,同时向反应容器中持续吹入外界空气。 Synthesis was repeated with ligand and metal phthalocyanine compounds above-oxo-titanyl phthalocyanine synthesis same method steps, but the steps implemented in a dry nitrogen atmosphere was changed in air, while continuously blown into the reaction vessel outside air.

本方法制得带有附加邻苯二甲腈与钛氧基氧代酞菁金属原子相连的结构的带配位体的金属酞菁与钛氧基氧代酞菁的混合物。 The mixture was prepared as metal phthalocyanine and oxo-titanyl phthalocyanine with additional ligands phthalonitrile and oxo-titanyl phthalocyanine metal atom attached to a structure with. 图5是带配位体的金属酞菁化合物混合钛氧基氧代酞菁的TOF-MS阳离子检测结果的谱图。 Figure 5 is a metal phthalocyanine compound mixed with a ligand-oxo-titanyl phthalocyanine TOF-MS spectrum of the cation test results.

在TOF-MS阳离子检测分析中测得钛氧基氧代酞菁和带配位体的金属酞菁的峰强度比为1∶1。 Cation in TOF-MS analysis detected peak intensity measured titanyl phthalocyanine and oxo ligands with metal phthalocyanine ratio of 1. 用升华法对混合物进行纯化,得到纯的带配位体的金属酞菁化合物。 Mixture by sublimation to obtain pure metal phthalocyanine compound with a ligand. 带配位体的金属酞菁的产率按邻苯二甲腈计为10-15%。 Yield ligands with metal phthalocyanine by phthalonitrile counted as 10-15%.

制造电荷产生层将100nmol如此制得的带配位体的金属酞菁化合物加至1mol钛氧基氧代酞菁中。 Producing a charge generation layer with metal phthalocyanine compound thus obtained with 100nmol ligand to oxo 1mol titanyl phthalocyanine. 将该混合物与0.5升水和1.5升邻二氯苯(Kanto Chemical Co.,Ltd制)一起加至带6.6kg直径为8mm的氧化锆球的球磨机中研磨24小时。 The mixture was mixed with 0.5 liters of water and 1.5 liters of o-dichlorobenzene (Kanto Chemical Co., Ltd) was added together with 6.6kg to 8mm diameter zirconia balls of ball mill for 24 hours. 用1.5升丙酮和1.5升甲醇取出,过滤,用水1.5升洗涤,干燥。 With 1.5 liters of acetone and 1.5 liters of methanol removed by filtration, washed with water 1.5 liters, dried.

将10重量份该含带配位体的金属酞菁化合物的钛氧基氧代酞菁与10重量份聚氯乙烯树脂(MR-110,Nippon Zeon Co.,Ltd制)、686重量份二氯甲烷和294重量份1,2-二氯乙烷相混合,超声波分散后制得用于电荷产生层的涂料液。 The parts of titanyl containing 10 parts by weight of the ligand with the metal phthalocyanine compound and the phthalocyanine-oxo-10 weight polyvinyl chloride resin (MR-110, Nippon Zeon Co., Ltd, Ltd.), 686 parts by weight of dichloro methane and 294 parts by weight of 1,2-dichloroethane were mixed, after ultrasonic dispersion to prepare a coating liquid for a charge generating layer. 用浸涂法将该涂料液涂覆在上述底涂层上,干燥后形成厚0.2微米的电荷产生层。 Charge by dip coating liquid was coated on the above undercoat layer, and dried to form a thickness of 0.2 m generating layer.

制造电荷转移层将100重量份4-(二苯基氨基)苯甲醛苯基(2-噻吩基甲基)腙(Fuji ElectricCo.,Ltd制)、100重量份聚碳酸酯树脂(PANLITE K-1300,购自Teijin ChemicalCo.,Ltd)、800重量份二氯甲烷、1重量份硅烷偶联剂(KP-340,购自Shin'etsuChemical Co.,Ltd)和4重量份苯基亚膦酸二(2,4-二叔丁基苯基)酯(FujiElectric Co.,Ltd制)混合在一起制得用于电荷转移层的涂料液。 Manufacture of charge-transfer layer 100 parts by weight of 4- (diphenylamino) benzaldehyde phenyl (2-thienylmethyl) hydrazone (Fuji ElectricCo., Ltd, Ltd.), 100 parts by weight of a polycarbonate resin (PANLITE K-1300 available from Teijin ChemicalCo., Ltd), 800 parts by weight of methylene chloride, 1 part by weight of a silane coupling agent (KP-340, available from Shin'etsuChemical Co., Ltd) and 4 parts by weight of phenyl phosphonic acid ( 2,4-di-t-butylphenyl) phosphite (FujiElectric Co., Ltd) were mixed together to prepare a coating liquid for a charge transport layer. 用浸涂法将该涂料液涂覆在上述带有电荷产生层的基片上,干燥后形成厚度为20微米的电荷转移层。 The coating liquid by dip coated on the above substrate with a charge generating layer, and dried to form a charge transport layer having a thickness of 20 microns. 从而制得感光体。 Thereby preparing a photosensitive member.

实施例2用与实施例1相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 2 Using the same method as in Example 1 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compounds with ligand was changed to 10 micromolar.

实施例3用与实施例1相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成1mmol。 Example 3 The same method as in Example 1 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compound with a ligand into 1mmol.

实施例4用与实施例1相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成100mmol。 Example 4 The same method as in Example 1 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compound with a ligand into 100mmol.

实施例5用与实施例1相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成200mmol。 Example 5 using the same method as in Example 1 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compound with a ligand into 200mmol.

实施例6用与实施例1相同的方法制得感光体,但是在加入实施例1的带配位体的金属酞菁化合物后,用96%硫酸(关东化学(株)制)对形成的混合物进行酸糊粘合处理,接着用水洗涤,然后干燥。 6 using the same as in Example 1 was prepared photoreceptor embodiment, but after the addition of the metal phthalocyanine compound with a ligand of Example 1, using 96% sulfuric acid (Kanto Chemical Co. (Ltd.)) to the resulting mixture acid paste adhesive treatment, then washed with water, and then dried.

实施例7用与实施例6相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 7 using the same method as in Example 6 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compounds with ligand was changed to 10 micromolar.

实施例8用与实施例6相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成1mmol。 Example 8 using the same method as in Example 6 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compound with a ligand into 1mmol.

实施例9用与实施例6相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成100mmol。 Example 9 Example 6 was prepared the same manner as the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compound with a ligand into 100mmol.

实施例10用与实施例6相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成200mmol。 Example 10 using the same method as in Example 6 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of oxo-titanyl phthalocyanine compound with a ligand into 200mmol.

比较例1用与实施例1相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成50nmol。 1 using the same method as in Example 1 to obtain a photosensitive member, it will be added to 1 mole of the metal phthalocyanine compounds oxo-titanyl phthalocyanine compound with an amount of ligand Comparative Example changed 50nmol.

比较例2用与实施例1相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 2 using the same method as in Example 1 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compound with a ligand into 300mmol.

比较例3用与实施例6相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 3 using the same method as in Example 6 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of oxo-titanyl phthalocyanine compound with a ligand into 50nmol.

比较例4用与实施例6相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的带配位体的金属酞菁化合物的量改成300mmol。 4 using the same method as in Example 6 was prepared photosensitive member, it will be added to 1 mole of the metal phthalocyanine compounds oxo-titanyl phthalocyanine compound with an amount of ligand Comparative Example changed 300mmol.

用Kawaguchi Electric Works Co.,Ltd制造的EPA-8200型静电记录纸试验仪分别测定实施例1-10和比较例1-4的感光体的电气特性。 EPA-8200 type electrostatic recording paper test apparatus with Kawaguchi Electric Works Co., Ltd manufactured were measured electrical properties of the photoreceptor in Example 1-10 and Comparative Examples 1-4. 在黑暗中将感光体电晕充电至表面电位为-600V,并在黑暗中静置5秒钟。 In the corona charging the photoreceptor in the dark to a surface potential of -600V, and allowed to stand for 5 seconds in the dark. 测定其间的电位保持率。 Potential retention rate during the measurement. 结果列于表1。 The results are shown in Table 1.

表1<tables id="table1" num="001"> <table>试样电位保持率实施例198.1实施例297.9实施例398.2实施例497.6实施例597.6实施例698.3实施例798.0实施例898.2实施例998.1实施例1097.7比较例191.5比较例290.4比较例391.3比较例490.2</table> </tables>由表1可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 1 <tables id = "table1" num = "001"> <table> sample potential retention EXAMPLE EXAMPLE 297.9 198.1 597.6 EXAMPLES EXAMPLE EXAMPLE 497.6 698.3 398.2 implementation EXAMPLE EXAMPLE 798.0 998.1 898.2 EXAMPLE Example Comparative Example 191.5 1097.7 290.4 Comparative Example Comparative Example Comparative Example 391.3 490.2 </ table> </ tables> Table 1 shows that all samples have a high embodiment of a high potential retention, as compared to Comparative Example all The samples have a lower potential holding rate.

实施例11用与实施例1相同的方法制得感光体,但是用常用方法合成的无金属酞菁代替钛氧基氧代酞菁。 11 using the same method as in Example 1 was obtained in Example photoreceptor, but with a conventional method for the synthesis of metal-free phthalocyanine instead of the oxo-titanyl phthalocyanine.

实施例12用与实施例11相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 12 In the same manner as in Example 11 to prepare a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mole of metal-free phthalocyanine compound with a ligand was changed to 10 micromolar.

实施例13用与实施例11相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成1mmol。 Example 13 In the same manner as in Example 11 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mole of metal-free phthalocyanine compound with a ligand into 1mmol.

实施例14用与实施例11相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成100mmol。 Example 14 The same manner as in Example 11 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of metal-free phthalocyanine compound with a ligand into 100mmol.

实施例15用与实施例11相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成200mmol。 Example 15 and the same manner as in Example 11 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of metal-free phthalocyanine compound with a ligand into 200mmol.

实施例16用与实施例11相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸(关东化学(株)制)对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 16 By a similar to Example 11 was prepared photosensitive member, but after the addition of the metal phthalocyanine compound ligand band, with 96% sulfuric acid (Kanto Chemical Co. (Ltd.)) The resulting mixture was an acid paste viscosity knot treatment, then washed with water, and then dried.

实施例17用与实施例16相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 17 and the same manner as in Example 16 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of metal-free phthalocyanine compound with a ligand was changed to 10 micromolar.

实施例18用与实施例16相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成1mmol。 Example 18 using the same method as in Example 16 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mole of metal-free phthalocyanine compound with a ligand into 1mmol.

实施例19用与实施例16相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成100mmol。 Example 19 The method of Example 16 was obtained in the same photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mole of metal-free phthalocyanine compound with a ligand into 100mmol.

实施例20用与实施例16相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成200mmol。 Example 16 was prepared in the same manner Photoconductor Example 20 was carried out, but the added amount of the metal phthalocyanine compound to 1 mole of metal-free phthalocyanine compound with a ligand into 200mmol.

比较例5用与实施例11相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 5 using the same method as in Example 11 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mole of metal-free phthalocyanine compound with a ligand into 50nmol.

比较例6用与实施例11相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 6 using the same method as in Example 11 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mole of metal-free phthalocyanine compound with a ligand into 300mmol.

比较例7用与实施例16相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 7 was carried out in the same manner as in Example 16 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mole of metal-free phthalocyanine compound with a ligand into 50nmol.

比较例8用与实施例16相同的方法制得感光体,但是将加入1摩尔无金属酞菁化合物中的带配位体的金属酞菁化合物的量改成300mmol。 8 using the same method as in Example 16 to obtain a photosensitive member, it will be added to 1 mol of the metal phthalocyanine compound metal-free phthalocyanine compound with an amount of ligand Comparative Example changed 300mmol.

用与上述实施例和比较例相同的方法测定实施例11-20和比较例5-8的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example 11-20 and Comparative Examples 5-8 of the electrical characteristics of the photoreceptor, the potential obtained retention (%). 结果列于表2。 The results are shown in Table 2.

表2 Table 2

由表2可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 2 shows that all samples have a high embodiment of a high potential retention, as compared to a sample of all the comparative examples have a lower potential holding rate.

实施例21用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁钒代替钛氧基氧代酞菁。 Example 21 In the same manner as in Example 1 to obtain a photosensitive member, but synthesized by conventional method instead of titanyl phthalocyanine oxo vanadium phthalocyanine.

实施例22用与实施例21相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 22 using the same method as in Example 21 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of vanadium phthalocyanine with ligand was changed to 10 micromolar.

实施例23用与实施例21相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成1mmol。 Example 23 In the same manner as in Example 21 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 1mmol.

实施例24用与实施例21相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成100mmol。 Example 24 In the same manner as in Example 21 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 100mmol.

实施例25用与实施例21相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成200mmol。 Example 25 using the same method as in Example 21 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 200mmol.

实施例26用与实施例21相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸(关东化学(株)制)对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 26 Example in the same manner 21 obtained photosensitive member, but after the addition of the metal phthalocyanine compound ligand band, with 96% sulfuric acid (Kanto Chemical Co. (Ltd.)) of the mixture was subjected to acid pasting viscosity knot treatment, then washed with water, and then dried.

实施例27用与实施例26相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 27 using the same method as in Example 26 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of vanadium phthalocyanine ligand was changed with 10 micromolar.

实施例28用与实施例26相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成1mmol。 Example 28 using the same method as in Example 26 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 1mmol.

实施例29用与实施例26相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成100mmol。 Example 29 using the same method as in Example 26 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 100mmol.

实施例30用与实施例26相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成200mmol。 Example 30 using the same method as in Example 26 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 200mmol.

比较例9用与实施例21相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 9 using the same method as in Example 21 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 50nmol.

比较例10用与实施例21相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 10 using the same method as in Example 21 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 300mmol.

比较例11用与实施例26相同的方法制得感光体,但是将加入1摩尔酞菁钒化合物中的带配位体的金属酞菁化合物的量改成50nmol。 11 using the same method as in Example 26 to obtain a photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound phthalocyanine vanadium compounds with a ligand in an amount changed to Comparative Example 50nmol.

比较例12用与实施例26相同的方法制得感光体,但是将加入1摩尔酞菁钒中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 12 using the same method as in Example 26 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine of vanadium with a ligand into 300mmol.

用与上述实施例和比较例相同的方法测定实施例21-30和比较例9-12的感光体的电气特性,得出电位保持率。 As in the above Examples and Comparative Examples was measured in the same manner embodiment of the electrical characteristics of the photoreceptor in Example 21-30 and Comparative Examples 9-12, obtained potential holding rate. 结果列于表3。 The results are shown in Table 3.

表3<tables id="table3" num="003"> <table>试样电位保持率(%)实施例2195.2实施例2295.1实施例2395.3实施例2495.0实施例2595.1实施例2695.2实施例2794.9实施例2895.2实施例2995.0实施例3095.1比较例987.9比较例1088.6比较例1188.2比较例1288.4</table> </tables>由表3可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 3 <tables id = "table3" num = "003"> <table> sample potential holding ratio (%) Example Example Example 2395.3 2195.2 Example embodiments 2595.1 2295.1 2495.0 Example Example Example 2695.2 2895.2 2794.9 Example 2995.0 3095.1 Example Comparative Example Comparative Example Example 987.9 1188.2 1088.6 Comparative Example Comparative Example 1288.4 </ table> </ tables> Table 3 shows that all samples have a high embodiment of a high potential retention, as compared to All samples of Comparative Examples have a low potential holding rate.

实施例31用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁铌代替钛氧基氧代酞菁。 Example 31 using the same method as in Example 1 to obtain a photosensitive member, but synthesized by conventional method instead of titanyl phthalocyanine niobium oxo phthalocyanine.

实施例32用与实施例31相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 32 using the same method as in Example 31 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand was changed to 10 micromolar.

实施例33用与实施例31相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成1mmol。 Example 33 using the same method as in Example 31 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand into 1mmol.

实施例34用与实施例31相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成100mmol。 Example 34 using the same method as in Example 31 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand into 100mmol.

实施例35用与实施例31相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成200mmol。 Example 35 using the same method as in Example 31 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand into 200mmol.

实施例36用与实施例31相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 36 using the same method as in Example 31 to obtain photoreceptor embodiment, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例37用与实施例36相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 37 and using the same manner as in Example 36 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand was changed to 10 micromolar.

实施例38用与实施例36相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成1mmol。 Example 38 and using the same manner as in Example 36 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand into 1mmol.

实施例39用与实施例36相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成100mmol。 Example 39 and using the same manner as in Example 36 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand into 100mmol.

实施例40用与实施例36相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成200mmol。 Example 40 using the same method as in Example 36 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand into 200mmol.

比较例13用与实施例31相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成50nmol。 13 using the same method as in Example 31 was prepared photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound phthalocyanine niobium with a ligand in an amount changed to Comparative Example 50nmol.

比较例14用与实施例31相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成300mmol。 14 using the same method as in Example 31 was prepared photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound phthalocyanine niobium with a ligand in an amount changed to Comparative Example 300mmol.

比较例15用与实施例36相同的方法制得感光体,但是将加入1摩尔酞菁铌化合物中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 15 was carried out in the same manner as in Example 36 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the niobium phthalocyanine compound with a ligand into 50nmol.

比较例16用与实施例36相同的方法制得感光体,但是将加入1摩尔酞菁铌中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 16 using the same method as in Example 36 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the phthalocyanine niobium with ligand into 300mmol.

用与上述实施例和比较例相同的方法测定实施例31-40和比较例13-16的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example photoreceptor 31-40 Examples 13-16 and Comparative embodiment of electrical characteristics, obtained potential retention (%). 结果列于表4。 The results are shown in Table 4.

表4<tables id="table4" num="004"> <table>试样电位保持率实施例3195.2实施例3294.8实施例3395.2实施例3495.0实施例3595.1实施例3695.3实施例3794.9实施例3895.0实施例3995.3实施例4095.2比较例1389.2比较例1488.4比较例1588.2比较例1687.4</table> </tables>由表4可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 4 <tables id = "table4" num = "004"> <table> sample retention potential implementation embodiment 3195.2 3695.3 3895.0 EXAMPLE EXAMPLES EXAMPLE 3794.9 3995.3 3294.8 embodiment example embodiment 3495.0 3395.2 3595.1 EXAMPLE implementation Example Comparative Example 1389.2 4095.2 1488.4 Comparative Example Comparative Example Comparative Example 1588.2 1687.4 </ table> </ tables> Table 4 shows that all samples have a high embodiment of a high potential retention, as compared to Comparative Example all The samples have a lower potential holding rate.

实施例41用与实施例11相同的方法制得感光体,但是用常用方法合成的酞菁铟代替实施例1的无金属酞菁。 41 using the same method as in Example 11 was prepared photosensitive member, but synthesized by conventional methods used in Example indium phthalocyanine metal-free phthalocyanine of Example 1.

实施例42用与实施例41相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 42 using the same method as in Example 41 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand was changed with 10 micromolar.

实施例43用与实施例41相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成1mmol。 Example 43 using the same method as in Example 41 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand into belt 1mmol.

实施例44用与实施例41相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成100mmol。 Example 44 using the same method as in Example 41 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand into belt 100mmol.

实施例45用与实施例41相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成200mmol。 Example 45 In the same manner as in Example 41 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand into belt 200mmol.

实施例46用与实施例41相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 46 using the same method as in Example 41 was prepared photosensitive member, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例47用与实施例46相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 47 using the same method as in Example 46 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand was changed with 10 micromolar.

实施例48用与实施例46相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成1mmol。 Example 48 using the same method as in Example 46 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand into belt 1mmol.

实施例49用与实施例46相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成100mmol。 Example 49 using the same method as in Example 46 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand into belt 100mmol.

实施例50用与实施例46相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成200mmol。 Example 50 using the same method as in Example 46 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand into belt 200mmol.

比较例17用与实施例41相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成50nmol。 Amount of Comparative Example 17 was carried out in the same manner as in Example 41 was prepared photosensitive member, it will be added to 1 mole of indium phthalocyanine ligand with a metal phthalocyanine compound into 50nmol.

比较例18用与实施例41相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成300mmol。 18 using the same method as in Example 41 to obtain a photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound of indium phthalocyanine ligand with an amount of Comparative Example changed 300mmol.

比较例19用与实施例46相同的方法制得感光体,但是将加入1摩尔酞菁铟化合物中的带配位体的金属酞菁化合物的量改成50nmol。 Amount of Comparative Example 19 was carried out in the same manner as in Example 46 was prepared photosensitive member, it will be added to 1 mole of phthalocyanine indium compound with a ligand of the metal phthalocyanine compound into 50nmol.

比较例20用与实施例46相同的方法制得感光体,但是将加入1摩尔酞菁铟中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 20 In the same manner as in Example 46 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the indium phthalocyanine ligand into belt 300mmol.

用与上述实施例和比较例相同的方法测定实施例41-50和比较例17-20的感光体的电气特性,得出电位保持率。 As in the above Examples and Comparative Examples was measured in the same manner embodiment of the electrical characteristics of the photoreceptor in Example 41-50 and Comparative Examples 17-20, the draw potential holding rate. 结果列于表5。 The results are shown in Table 5.

表5 Table 5

由表5可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Be seen from Table 5 that all samples have a high embodiment of a high potential retention, as compared to a sample of all the comparative examples have a lower potential holding rate.

实施例51用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁镓代替钛氧基氧代酞菁。 Example 51 using the same method as in Example 1 to obtain a photosensitive member, but synthesized by conventional method instead of titanyl phthalocyanine oxo gallium phthalocyanine.

实施例52用与实施例51相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 52 using the same method as in Example 51 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of gallium phthalocyanine ligand was changed with 10 micromolar.

实施例53用与实施例51相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成1mmol。 Example 53 In the same manner as in Example 51 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 1mmol.

实施例54用与实施例51相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成100mmol。 Example 54 using the same method as in Example 51 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 100mmol.

实施例55用与实施例51相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成200mmol。 Example 55 In the same manner as in Example 51 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 200mmol.

实施例56用与实施例51相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 56 In the same manner as in Example 51 was prepared photosensitive member, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例57用与实施例56相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 57 In the same manner as in Example 56 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of gallium phthalocyanine ligand was changed with 10 micromolar.

实施例58用与实施例56相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成1mmol。 Example 58 In the same manner as in Example 56 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 1mmol.

实施例59用与实施例56相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成100mmol。 Example 59 In the same manner as in Example 56 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 100mmol.

实施例60用与实施例56相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成200mmol。 Example 60 using the same method as in Example 56 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 200mmol.

比较例21用与实施例51相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 21 In the same manner as in Example 51 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 50nmol.

比较例22用与实施例51相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 22 using the same method as in Example 51 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 300mmol.

比较例23用与实施例56相同的方法制得感光体,但是将加入1摩尔酞菁镓化合物中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 23 In the same manner as in Example 56 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine compounds with ligand into 50nmol.

比较例24用与实施例56相同的方法制得感光体,但是将加入1摩尔酞菁镓中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 24 In the same manner as in Example 56 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of gallium phthalocyanine ligand with changed 300mmol.

用与上述实施例和比较例相同的方法测定实施例51-60和比较例21-24的感光体的电气特性,得出电位保持率。 As in the above Examples and Comparative Examples was measured in the same manner embodiment photoreceptor electrical properties Example 51-60 and Comparative Examples 21-24, the draw potential holding rate. 结果列于表6。 The results are shown in Table 6.

表6<tables id="table6" num="006"> <table>试样电位保持率(%)实施例5195.5实施例5295.3实施例5395.0实施例5495.3实施例5595.1实施例5695.4实施例5794.9实施例5895.2实施例5995.3实施例6095.1比较例2189.4比较例2288.7比较例2389.8比较例2489.0</table> </tables>由表6可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 6 <tables id = "table6" num = "006"> <table> sample potential holding ratio (%) Example Example 5295.3 5195.5 5395.0 Example Example Example 5595.1 5495.3 5695.4 Example Example Example 5,895.2 5,794.9 5995.3 6095.1 Example Comparative Example Example Comparative Example 2288.7 2189.4 2389.8 Comparative Example Comparative Example 2489.0 </ table> </ tables> be seen from Table 6 that samples are all embodiments having a high potential holding rate is good, in contrast to All samples of Comparative Examples have a low potential holding rate.

实施例61用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁锆代替钛氧基氧代酞菁。 Example 61 In the same manner as in Example 1 was prepared photosensitive member, but synthesized by conventional method instead of titanyl phthalocyanine oxo zirconium phthalocyanine.

实施例62用与实施例61相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 62 In the same manner as in Example 61 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with ligand was changed to 10 micromolar.

实施例63用与实施例61相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成1mmol。 Example 63 using the same method as in Example 61 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with a ligand into 1mmol.

实施例64用与实施例61相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成100mmol。 Example 64 using the same method as in Example 61 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with a ligand into 100mmol.

实施例65用与实施例61相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成200mmol。 Example 65 using the same method as in Example 61 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with a ligand into 200mmol.

实施例66用与实施例61相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 66 using the same method as in Example 61 was prepared photosensitive member, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例67用与实施例66相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成10微摩尔。 67 using the same method as in Example 66 to obtain photoreceptor embodiment, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with ligand was changed to 10 micromolar.

实施例68用与实施例66相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成1mmol。 Example 68 using the same method as in Example 66 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with a ligand into 1mmol.

实施例69用与实施例66相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成100mmol。 Example 69 using the same method as in Example 66 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with a ligand into 100mmol.

实施例70用与实施例66相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成200mmol。 Amount of Example 70 was carried out in the same manner as in Example 66 to obtain a photosensitive member, it will be added to 1 mole of zirconium phthalocyanine with a ligand of the metal phthalocyanine compound into 200mmol.

比较例25用与实施例61相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 25 using the same method as in Example 61 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with a ligand into 50nmol.

比较例26用与实施例61相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 26 with the amount described in the same manner as in Example 61 was prepared photosensitive member, it will be added to 1 mole of zirconium phthalocyanine with a ligand of the metal phthalocyanine compound into 300mmol.

比较例27用与实施例66相同的方法制得感光体,但是将加入1摩尔酞菁锆化合物中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 27 In the same manner as in Example 66 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine compound with a ligand into 50nmol.

比较例28用与实施例66相同的方法制得感光体,但是将加入1摩尔酞菁锆中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 28 In the same manner as in Example 66 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the zirconium phthalocyanine with a ligand into 300mmol.

用与上述实施例和比较例相同的方法测定实施例61-70和比较例25-28的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example 61-70 and Comparative Examples 25-28 of the electrical characteristics of the photoreceptor, the potential obtained retention (%). 结果列于表7。 The results are shown in Table 7.

表7<tables id="table7" num="007"> <table>试样电位保持率(%)实施例6195.1实施例6295.5实施例6395.3实施例6495.5实施例6595.2实施例6695.6实施例6795.1实施例6895.4实施例6995.3实施例7095.1比较例2588.8比较例2689.0比较例2789.2比较例2888.7</table> </tables>由表7可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 7 <tables id = "table7" num = "007"> <table> sample potential holding ratio (%) Example Example 6495.5 6795.1 6695.6 Example Example Example Example 6595.2 6895.4 Example embodiments 6195.1 6395.3 6295.5 Example embodiments 6995.3 7095.1 Example Comparative Example Example Comparative Example 2689.0 2588.8 2789.2 Comparative Example Comparative Example 2888.7 </ table> </ tables> be seen from Table 7, samples are all embodiments having a high potential holding rate is good, in contrast to All samples of Comparative Examples have a low potential holding rate.

实施例71用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁锗代替钛氧基氧代酞菁。 Example 71 was carried out in the same manner as in Example 1 was prepared photoreceptor embodiment, but synthesized by conventional method instead of titanyl phthalocyanine oxo germanium phthalocyanine.

实施例72用与实施例71相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 72 using the same method as in Example 71 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with ligand was changed to 10 micromolar.

实施例73用与实施例71相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成1mmol。 Example 73 using the same method as in Example 71 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 1mmol.

实施例74用与实施例71相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成100mmol。 Example 74 using the same method as in Example 71 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 100mmol.

实施例75用与实施例71相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成200mmol。 Example 75 In the same manner as in Example 71 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 200mmol.

实施例76用与实施例71相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 76 using the same method as in Example 71 was prepared photosensitive member, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例77用与实施例76相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 77 using the same method as in Example 76 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with ligand was changed to 10 micromolar.

实施例78用与实施例76相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成1mmol。 Example 78 using the same method as in Example 76 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 1mmol.

实施例79用与实施例76相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成100mmol。 Example 79 using the same method as in Example 76 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 100mmol.

实施例80用与实施例76相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成200mmol。 Example 80 using the same method as in Example 76 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 200mmol.

比较例29用与实施例71相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 29 In the same manner as in Example 71 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 50nmol.

比较例30用与实施例71相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 30 using the same method as in Example 71 to obtain a photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 300mmol.

比较例31用与实施例76相同的方法制得感光体,但是将加入1摩尔酞菁锗化合物中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 31 using the same method as in Example 76 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine compound of germanium with a ligand into 50nmol.

比较例32用与实施例76相同的方法制得感光体,但是将加入1摩尔酞菁锗中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 32 In the same manner as in Example 76 was prepared photosensitive member, but the added amount of the metal phthalocyanine compound to 1 mol of the phthalocyanine germanium with a ligand into 300mmol.

用与上述实施例和比较例相同的方法测定实施例71-80和比较例29-32的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example photoreceptor 71-80 Examples 29-32 and Comparative embodiment of electrical characteristics, obtained potential retention (%). 结果列于表8。 The results are shown in Table 8.

表8<tables id="table8" num="008"> <table>试样电位保持率(%)实施例7195.4实施例7295.1实施例7395.3实施例7495.0实施例7595.1实施例7695.2实施例7794.9实施例7895.0实施例7995.2实施例8095.2比较例2988.3比较例3087.7比较例3188.2比较例3288.0</table> </tables>由表8可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 8 <tables id = "table8" num = "008"> <table> sample potential holding ratio (%) Example Example 7195.4 7295.1 7794.9 7695.2 Example Example Example Example Example 7395.3 7595.1 7495.0 Example embodiment embodiment 7895.0 Comparative Example Example 8095.2 7995.2 2988.3 3087.7 Comparative Example Comparative Example Comparative Example Example 3188.2 3288.0 </ table> </ tables> be seen from Table 8, samples are all embodiments having a high potential holding rate is good, in contrast to All samples of Comparative Examples have a low potential holding rate.

实施例81用与实施例1相同的方法制得感光体,但是用常用方法合成的1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-十六氟-29H,31H-酞菁铁(Ⅱ)(下面简称为酞菁氟铁)代替钛氧基氧代酞菁。 81 using the same method as in Example 1 was Photoconductor Example, but using conventional synthetic methods 1,2,3,4,8,9,10,11,15,16,17,18,22,23, 24,25 sixteen fluorine -29H, 31H- iron phthalocyanine (Ⅱ) (hereinafter referred to as fluorine iron phthalocyanine) instead of oxo-titanyl phthalocyanine.

实施例82用与实施例81相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成10微摩尔。 82 in Example 81 was prepared in the same manner photoreceptor embodiment, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with ligand was changed to 10 micromolar.

实施例83用与实施例81相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成1mmol。 Amount of Example 83 using the same method as in Example 81 to obtain a photosensitive member, it will be added to 1 mole of fluorine-iron phthalocyanine ligand with a metal phthalocyanine compound into 1mmol.

实施例84用与实施例81相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成100mmol。 Example 84 using the same method as in Example 81 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with a ligand into 100mmol.

实施例85用与实施例81相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成200mmol。 Example 85 using the same method as in Example 81 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with a ligand into 200mmol.

实施例86用与实施例81相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 86 In the same manner as in Example 81 was prepared photoreceptor embodiment, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例87用与实施例86相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 87 using the same method as in Example 86 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with ligand was changed to 10 micromolar.

实施例88用与实施例86相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成1mmol。 Amount of Example 88 using the same method as in Example 86 to obtain a photosensitive member, it will be added to 1 mole of fluorine-iron phthalocyanine ligand with a metal phthalocyanine compound into 1mmol.

实施例89用与实施例86相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成100mmol。 Example 89 In the same manner as in Example 86 was prepared photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with a ligand into 100mmol.

实施例90用与实施例86相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成200mmol。 Example 90 using the same method as in Example 86 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with a ligand into 200mmol.

比较例33用与实施例81相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 33 using the same method as in Example 81 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with a ligand into 50nmol.

比较例34用与实施例81相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 34 using the same method as in Example 81 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with a ligand into 300mmol.

比较例35用与实施例86相同的方法制得感光体,但是将加入1摩尔酞菁氟铁化合物中的带配位体的金属酞菁化合物的量改成50nmol。 35 using the same method as in Example 86 to obtain a photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound fluorine iron phthalocyanine compound with an amount of ligand Comparative Example changed 50nmol.

比较例36用与实施例86相同的方法制得感光体,但是将加入1摩尔酞菁氟铁中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 36 using the same method as in Example 86 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine fluoride with a ligand into 300mmol.

用与上述实施例和比较例相同的方法测定实施例81-90和比较例33-36的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example photoreceptor 81-90 Examples 33-36 and Comparative embodiment of electrical characteristics, obtained potential retention (%). 结果列于表9。 The results are shown in Table 9.

表9 Table 9

由表9可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Seen from Table 9 samples were all embodiments having a high potential holding rate of good, in contrast to the comparative example sample all have low potential holding rate.

实施例91用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁锡代替钛氧基氧代酞菁。 Example 91 using the same method as in Example 1 to obtain a photosensitive member, but synthesized by conventional method instead of titanyl phthalocyanine, tin phthalocyanine oxo.

实施例92用与实施例91相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 92 using the same method as in Example 91 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the tin phthalocyanine ligand into belt 10 micromolar.

实施例93用与实施例91相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成1mmol。 The amount of metal phthalocyanine compound of Example 93 using the same method as in Example 91 to obtain a photosensitive member, it will be added to 1 mole of phthalocyanine and tin with a ligand into 1mmol.

实施例94用与实施例91相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成100mmol。 Example 94 using the same method as in Example 91 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the tin phthalocyanine ligand into belt 100mmol.

实施例95用与实施例91相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成200mmol。 Example 95 using the same method as in Example 91 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the tin phthalocyanine ligand into belt 200mmol.

实施例96用与实施例91相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 96 using the same method as in Example 91 was prepared photosensitive member, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例97用与实施例96相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 97 using the same method as in Example 96 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the tin phthalocyanine ligand into belt 10 micromolar.

实施例98用与实施例96相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成1mmol。 The amount of metal phthalocyanine compound of Example 98 using the same method as in Example 96 to obtain a photosensitive member, it will be added to 1 mole of phthalocyanine and tin with a ligand into 1mmol.

实施例99用与实施例96相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成100mmol。 Amount used in Example 99 the same manner as in Example 96 was prepared photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound of tin phthalocyanine with ligand was changed to 100mmol.

实施例100用与实施例96相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成200mmol。 Example 100 using the same method as in Example 96 to obtain photoreceptor embodiment, but the added amount of the metal phthalocyanine compound to 1 mol of the tin phthalocyanine ligand into belt 200mmol.

比较例37用与实施例91相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 37 using the same method as in Example 91 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the tin phthalocyanine ligand into belt 50nmol.

比较例38用与实施例91相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成300mmol。 The amount of metal phthalocyanine compound of Comparative Example 38 using the same method as in Example 91 to obtain a photosensitive member, it will be added to 1 mole of phthalocyanine and tin with a ligand into 300mmol.

比较例39用与实施例96相同的方法制得感光体,但是将加入1摩尔酞菁锡化合物中的带配位体的金属酞菁化合物的量改成50nmol。 39 using the same method as in Example 96 to obtain a photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound of tin phthalocyanine compound with an amount of ligand Comparative Example changed 50nmol.

比较例40用与实施例96相同的方法制得感光体,但是将加入1摩尔酞菁锡中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 40 using the same method as in Example 96 to obtain a photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the tin phthalocyanine ligand into belt 300mmol.

用与上述实施例和比较例相同的方法测定实施例91-100和比较例37-40的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example photoreceptor 91-100 and Comparative Examples 37-40 of the embodiment of the electrical characteristics, obtained potential retention (%). 结果列于表10。 The results are shown in Table 10.

表10<tables id="table10" num="010"> <table>试样电位保持率(%)实施例9195.0实施例9294.8实施例9394.7实施例9494.9实施例9594.6实施例9694.8实施例9794.9实施例9895.0实施例9994.8实施例10094.6比较例3787.9比较例3887.1比较例3988.0比较例4087.4</table> </tables>由表10可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 10 <tables id = "table10" num = "010"> <table> sample potential holding ratio (%) Example Example 9294.8 9895.0 9794.9 Example Example Example 9594.6 9494.9 9394.7 Example Example Example 9195.0 9694.8 embodiment 9,994.8 10,094.6 Comparative Example Example Comparative Example Example 3787.9 3988.0 3887.1 Comparative Example Comparative Example 4087.4 </ table> </ tables> Table 10 Example visible all samples have a high potential of good retention, in contrast to All samples of Comparative Examples have a low potential holding rate.

实施例101用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁锰代替钛氧基氧代酞菁。 Example 101 using the same method as in Example 1 to obtain a photosensitive member, but synthesized by conventional method instead of titanyl phthalocyanine manganese phthalocyanine oxo.

实施例102用与实施例101相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 102 using the same method as in Example 101 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the manganese phthalocyanine ligand was changed with 10 micromolar.

实施例103用与实施例101相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成1mmol。 Example 103 using the same method as in Example 101 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the manganese phthalocyanine ligand into belt 1mmol.

实施例104用与实施例101相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成100mmol。 Example 104 using the same method as in Example 101 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the manganese phthalocyanine ligand into belt 100mmol.

实施例105用与实施例101相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成200mmol。 Example 105 using the same method as in Example 101 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the manganese phthalocyanine ligand into belt 200mmol.

实施例106用与实施例101相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 106 in Example 101 was obtained in the same manner photoreceptor embodiment, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例107用与实施例106相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 107 using the same method as in Example 106 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the manganese phthalocyanine ligand was changed with 10 micromolar.

实施例108用与实施例106相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成1mmol。 Amount of Example 108 was carried out in the same manner as in Example 106 to prepare the photosensitive member, it will be added to 1 mol of the manganese phthalocyanine ligand with a metal phthalocyanine compound into 1mmol.

实施例109用与实施例106相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成100mmol。 Example 109 using the same method as in Example 106 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the manganese phthalocyanine ligand into belt 100mmol.

实施例110用与实施例106相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成200mmol。 Example 110 using the same method as in Example 106 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the manganese phthalocyanine ligand into belt 200mmol.

比较例41用与实施例101相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成50nmol。 41 using the same method as in Example 101 to prepare the photosensitive member, it will be added to 1 mol of the metal phthalocyanine compound and manganese phthalocyanine ligand with an amount of Comparative Example changed 50nmol.

比较例42用与实施例101相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 42 using the same method as in Example 101 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the manganese phthalocyanine ligand into belt 300mmol.

比较例43用与实施例106相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成50nmol。 43 using the same method as in Example 106 to prepare the photosensitive member, it will be added to 1 mol of the metal phthalocyanine compound and manganese phthalocyanine ligand with an amount of Comparative Example changed 50nmol.

比较例44用与实施例106相同的方法制得感光体,但是将加入1摩尔酞菁锰中的带配位体的金属酞菁化合物的量改成300mmol。 44 using the same method as in Example 106 to prepare the photosensitive member, it will be added to 1 mol of the metal phthalocyanine compound and manganese phthalocyanine ligand with an amount of Comparative Example changed 300mmol.

用与上述实施例和比较例相同的方法测定实施例101-110和比较例41-44的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example photoreceptor 101-110 and Comparative Examples 41-44 of the embodiment of the electrical characteristics, obtained potential retention (%). 结果列于表11。 The results are shown in Table 11.

表11<tables id="table11" num="011"> <table>试样电位保持率(%)实施例10195.5实施例10295.7实施例10395.2实施例10495.5实施例10595.4实施例10695.6实施例10795.5实施例10895.0实施例10995.3实施例11095.1比较例4187.6比较例4286.9比较例4387.1比较例4487.3</table> </tables>由表11可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Example Example 10,595.4 10,695.6 Table 11 <tables id = "table11" num = "011"> <table> sample potential holding ratio (%) Example Example 10395.2 10295.7 10195.5 Example Example Example 10495.5 10895.0 10795.5 Example Example Example 11095.1 4286.9 10995.3 4387.1 Comparative Example Comparative Example Comparative Example Comparative Example 4187.6 4487.3 </ table> </ tables> be seen from Table 11 samples are all embodiments having a high potential holding rate is good, in contrast to All samples of Comparative Examples have a low potential holding rate.

实施例111用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁铝代替钛氧基氧代酞菁。 111 using the same method as in Example 1 to obtain a photosensitive member, but synthesized by conventional method instead of titanyl phthalocyanine oxo aluminum phthalocyanine embodiment.

实施例112用与实施例111相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 112 using the same method as in Example 111 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with the ligand was changed to 10 micromolar.

实施例113用与实施例111相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成1mmol。 Example 113 using the same method as in Example 111 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with a ligand into 1mmol.

实施例114用与实施例111相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成100mmol。 Example 114 using the same method as in Example 111 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with a ligand into 100mmol.

实施例115用与实施例111相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成200mmol。 Example 115 using the same method as in Example 111 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with a ligand into 200mmol.

实施例116用与实施例111相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 116 using the same method as in Example 111 to prepare the photosensitive member, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例117用与实施例116相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 117 using the same method as in Example 116 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with the ligand was changed to 10 micromolar.

实施例118用与实施例116相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成1mmol。 Example 118 using the same method as in Example 116 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with a ligand into 1mmol.

实施例119用与实施例116相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成100mmol。 Example 119 using the same method as in Example 116 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with a ligand into 100mmol.

实施例120用与实施例116相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成200mmol。 Example 120 using the same method as in Example 116 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with a ligand into 200mmol.

比较例45用与实施例111相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成50nmol。 45 using the same method as in Example 111 to prepare the photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound with aluminum phthalocyanine ligand of the amount in Comparative Example changed 50nmol.

比较例46用与实施例111相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成300mmol。 46 using the same method as in Example 111 to prepare the photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound with aluminum phthalocyanine ligand of the amount in Comparative Example changed 300mmol.

比较例47用与实施例116相同的方法制得感光体,但是将加入1摩尔酞菁铝化合物中的带配位体的金属酞菁化合物的量改成50nmol。 47 using the same method as in Example 116 to prepare the photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound of aluminum phthalocyanine compound with an amount of ligand Comparative Example changed 50nmol.

比较例48用与实施例116相同的方法制得感光体,但是将加入1摩尔酞菁铝中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 48 using the same method as in Example 116 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of the aluminum phthalocyanine with a ligand into 300mmol.

用与上述实施例和比较例相同的方法测定实施例111-120和比较例45-48的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example photoreceptor 111-120 and Comparative Examples 45-48 of the embodiment of the electrical characteristics, obtained potential retention (%). 结果列于表12。 The results are shown in Table 12.

表12 Table 12

由表12可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Be seen from Table 12 samples were all embodiments having a high potential holding rate of good, in contrast to the comparative example sample all have low potential holding rate.

实施例121用与实施例1相同的方法制得感光体,但是用常用方法合成的酞菁铁代替钛氧基氧代酞菁。 Example 121 using the same method as in Example 1 to obtain a photosensitive member, but synthesized by conventional method instead of titanyl phthalocyanine oxo iron phthalocyanine.

实施例122用与实施例121相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 122 and using the same manner as in Example 121 to obtain the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand was changed with 10 micromolar.

实施例123用与实施例121相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成1mmol。 Example 123 using the same method as in Example 121 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand into belt 1mmol.

实施例124用与实施例121相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成100mmol。 Example 124 using the same method as in Example 121 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand into belt 100mmol.

实施例125用与实施例121相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成200mmol。 Example 125 and using the same manner as in Example 121 to obtain the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand into belt 200mmol.

实施例126用与实施例121相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 126 and Example 121 using the same method as in Example was prepared photosensitive member, but after the addition of the metal phthalocyanine compound with a ligand, with a mixture of 96% sulfuric acid formed in the paste adhesion treatment, and then washed with water, then dry.

实施例127用与实施例126相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 127 using the same method as in Example 126 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand was changed with 10 micromolar.

实施例128用与实施例126相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成1mmol。 Amount of Example 128 was carried out in the same manner as in Example 126 to prepare the photosensitive member, it will be added to 1 mole of iron phthalocyanine ligand with a metal phthalocyanine compound into 1mmol.

实施例129用与实施例126相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成100mmol。 Example 129 using the same method as in Example 126 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand into belt 100mmol.

实施例130用与实施例126相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成200mmol。 Example 130 using the same method as in Example 126 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand into belt 200mmol.

比较例49用与实施例121相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成50nmol。 49 using the same method as in Example 121 to prepare the photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound with iron phthalocyanine in an amount of ligand Comparative Example changed 50nmol.

比较例50用与实施例121相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 50 using the same method as in Example 121 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand into belt 300mmol.

比较例51用与实施例126相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 51 using the same method as in Example 126 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand into belt 50nmol.

比较例52用与实施例126相同的方法制得感光体,但是将加入1摩尔酞菁铁中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 52 using the same method as in Example 126 to prepare the photosensitive member, but the amount of the metal phthalocyanine compound is added to 1 mol of iron phthalocyanine ligand into belt 300mmol.

用与上述实施例和比较例相同的方法测定实施例121-130和比较例49-52的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example photoreceptor 121-130 and Comparative Examples 49-52 of the embodiment of the electrical characteristics, obtained potential retention (%). 结果列于表13。 The results are shown in Table 13.

表13 Table 13

由表13可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 13 Example visible all samples have a high potential of good retention, in contrast to the comparative example sample all have low potential holding rate.

实施例131用与实施例1相同的方法制得感光体,但是用常用方法(特开平3-94264号公报揭示)合成的钛氧基四氯酞菁代替钛氧基氧代酞菁。 Example 131 using the same method as in Example 1 was photoreceptor embodiment, but instead of using the conventional method oxo-titanyl phthalocyanine (Laid-Open Publication No. 3-94264 discloses) Synthesis of titanyl phthalocyanine tetrachloride.

实施例132用与实施例131相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 132 using the same method as in Example 131 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand was changed to 10 micromolar.

实施例133用与实施例131相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成1mmol。 Example 133 using the same method as in Example 131 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand into 1mmol.

实施例134用与实施例131相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成100mmol。 Example 134 using the same method as in Example 131 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand into 100mmol.

实施例135用与实施例131相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成200mmol。 Example 135 using the same method as in Example 131 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand into 200mmol.

实施例136用与实施例131相同的方法制得感光体,但是在加入带配位体的金属酞菁化合物后,用96%硫酸(关东化学制)对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 136 using the same method as in Example 131 to prepare the photosensitive member, but after the addition of the metal phthalocyanine compound with a ligand, with a 96% sulfuric acid (Kanto Chemical Co., Ltd.) The resulting mixture is subjected to acid treatment paste adhesive, then washed with water, and then dried.

实施例137用与实施例136相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成10微摩尔。 Example 137 using the same method as in Example 136 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand was changed to 10 micromolar.

实施例138用与实施例136相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成1mmol。 Example 138 using the same method as in Example 136 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand into 1mmol.

实施例139用与实施例136相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成100mmol。 Example 139 using the same method as in Example 136 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand into 100mmol.

实施例140用与实施例136相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成200mmol。 Example 140 using the same method as in Example 136 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand into 200mmol.

比较例53用与实施例131相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成50nmol。 Comparative Example 53 In the same manner as in Example 131 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand into 50nmol.

比较例54用与实施例131相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成300mmol。 Comparative Example 54 using the same method as in Example 131 to prepare the photosensitive member, but the added amount of the metal phthalocyanine compound 1 mole of titanyl phthalocyanine with tetrachlorophthalic ligand into 300mmol.

比较例55用与实施例136相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成50nmol。 55 using the same method as in Example 136 to prepare the photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound titanyl phthalocyanine tetrachloride with the ligand in an amount changed to Comparative Example 50nmol.

比较例56用与实施例136相同的方法制得感光体,但是将加入1摩尔钛氧基四氯酞菁中的带配位体的金属酞菁化合物的量改成300mmol。 56 using the same method as in Example 136 to prepare the photosensitive member, it will be added to 1 mole of the metal phthalocyanine compound titanyl phthalocyanine tetrachloride with the ligand in an amount changed to Comparative Example 300mmol.

用与上述实施例和比较例相同的方法测定实施例131-140和比较例53-56的感光体的电气特性,得出电位保持率。 As in the above Examples and Comparative Examples was measured in the same manner embodiment ELECTRICAL CHARACTERISTICS photoreceptor 131-140 and Comparative Examples 53-56, the draw potential holding rate. 结果列于表14。 The results are shown in Table 14.

表14 Table 14

由表14可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Seen from Table 14 samples were all embodiments having a high potential holding rate of good, in contrast to the comparative example sample all have low potential holding rate.

实施例141用与实施例1相同的方法制得感光体,但是用文献J.Inorg.Nucl.Chem,1965,Vol.27,p1311-1319所述方法合成的邻苯二甲腈(-氯酞菁)氯合铱(Ⅲ)(下面简称为铱五聚物)代替带配位体的金属酞菁化合物。 Phthalonitrile (Example 141 using the same method as in Example 1 to obtain a photosensitive member, but the synthesis of the literature J.Inorg.Nucl.Chem, 1965 Vol.27, p1311-1319 the method of - chloro phthalocyanine Jing) chlorine iridium (Ⅲ) (hereinafter referred to as iridium pentamer) instead of metal phthalocyanine compounds with ligands.

实施例142用与实施例141相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成10微摩尔。 Example 142 and using the same manner as in Example 141 to obtain the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer was changed to 10 micromolar.

实施例143用与实施例141相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成1mmol。 Example 143 using the same method as in Example 141 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 1mmol.

实施例144用与实施例141相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成100mmol。 Example 144 using the same method as in Example 141 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 100mmol.

实施例145用与实施例141相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成200mmol。 Example 145 and using the same manner as in Example 141 to obtain the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 200mmol.

实施例146用与实施例141相同的方法制得感光体,但是在加入铱五聚物后,用96%硫酸对形成的混合物进行酸糊粘结处理,接着用水洗涤,然后干燥。 Example 146 using the same method as in Example 141 to prepare the photosensitive member, but after the addition of iridium pentamer, with 96% sulfuric acid to the mixture was subjected to acid pasting adhesion treatment, and then washed with water, and then dried.

实施例147用与实施例146相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成10微摩尔。 Example 147 using the same method as in Example 146 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer was changed to 10 micromolar.

实施例148用与实施例146相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成1mmol。 Example 148 using the same method as in Example 146 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 1mmol.

实施例149用与实施例146相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成100mmol。 Example 149 using the same method as in Example 146 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 100mmol.

实施例150用与实施例146相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成200mmol。 150 using the same method as in Example 146 was prepared photoreceptor embodiment, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 200mmol.

比较例57用与实施例141相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成50nmol。 Comparative Example 57 In the same manner as in Example 141 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 50nmol.

比较例58用与实施例141相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成300mmol。 Comparative Example 58 In the same manner as in Example 141 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 300mmol.

比较例59用与实施例146相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁化合物中的铱五聚物的量改成50nmol。 Comparative Example 59 In the same manner as in Example 146 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine compound in an amount of iridium pentamer into 50nmol.

比较例60用与实施例146相同的方法制得感光体,但是将加入1摩尔钛氧基氧代酞菁中的铱五聚物的量改成300mmol。 Comparative Example 60 using the same method as in Example 146 to prepare the photosensitive member, it will be added to 1 mole of oxo-titanyl phthalocyanine in an amount of iridium pentamer into 300mmol.

用与上述实施例和比较例相同的方法测定实施例141-150和比较例57-60的感光体的电气特性,得出电位保持率(%)。 As in the above Examples and Comparative Examples was measured in the same manner in Example photoreceptor 141-150 and Comparative Examples 57-60 of the embodiment of the electrical characteristics, obtained potential retention (%). 结果列于表15。 The results are shown in Table 15.

表15<tables id="table15" num="015"> <table>试样电位保持率(%)实施例14197.5实施例14297.7实施例14397.6实施例14497.4实施例14597.3实施例14697.9实施例14797.4实施例14897.5实施例14997.6实施例15097.4比较例5790.1比较例5889.4比较例5990.7比较例6089.8</table> </tables>由表15可见所有实施例试样均具有高的良好的电位保持率,而相比之下所有比较例的试样均具有较低的电位保持率。 Table 15 <tables id = "table15" num = "015"> <table> sample potential holding ratio (%) Example Example 14397.6 14297.7 14197.5 Example Example Example Example 14697.9 14497.4 Example 14797.4 14897.5 14597.3 Example embodiments Example 14,997.6 15,097.4 Comparative Example Example Comparative Example 5889.4 5790.1 5990.7 Comparative Example Comparative Example 6089.8 </ table> </ tables> Table 15 Example visible all samples have a high potential of good retention, in contrast to All samples of Comparative Examples have a low potential holding rate.

本发明感光体包括含有至少一种酞菁化合物作为光敏材料的光敏层,其中该光敏层含有带相当于邻苯二甲腈化合物的结构作为配位体的分子结构的金属酞菁化合物。 The present invention comprises a photosensitive body comprising at least one phthalocyanine compound as a photosensitive material, the photosensitive layer, wherein the photosensitive layer contains the structure of phthalonitrile compound with the metal phthalocyanine compound corresponds to the molecular structure of ligand. 在本发明感光体中,按1摩尔酞菁化合物计,光敏层中带配位体的金属酞菁的含量为100nmol-200mmol,使电子照相感光体具有优良的电位保持率。 In the photoconductor of the present invention, 1 mol of a phthalocyanine compound according to the count, the content of the photosensitive layer of the metal phthalocyanine ligand band 100nmol-200mmol, the electrophotographic photosensitive member having excellent potential holding rate.

本发明还提供一种感光体的制造方法,包括用含电荷产生剂的涂料液涂覆导电基片形成感光层的步骤,其中该涂料液还含有带相当于邻苯二甲腈化合物的结构作为配位体分子结构的金属酞菁化合物。 The present invention also provides a process for producing a photoreceptor, comprising the steps of forming a conductive substrate coated with a coating liquid containing a charge-generating agent of the photosensitive layer, wherein the coating liquid further contains phthalonitrile compound with the structure as an equivalent of o metal-ligand molecular structure of phthalocyanine compounds. 在本发明方法中,按1摩尔酞菁化合物计,用于光敏层的涂料液中带配位体的金属酞菁的含量为100nmol-200mmol,使电子照相感光体具有优良的电位保持率。 In the method of the present invention, 1 mole of phthalocyanine compounds according to the count, for the content of the metal phthalocyanine in the photosensitive layer coating liquid with a ligand for 100nmol-200mmol, the electrophotographic photosensitive member having excellent potential holding rate.

Classifications
International ClassificationC09B47/067, G03G5/06, G03G5/05, G03G5/00
Cooperative ClassificationG03G5/0696
European ClassificationG03G5/06H6
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