JPH0549231B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor used in an electrophotographic process. Conventional technology Conventionally, amorphous selenium,
Those using inorganic photosensitive materials such as selenium alloys and organic photosensitive materials such as polyvinylcarbazole are widely known. In addition, in recent years, electrophotographic photoreceptors using various organic photosensitive materials have been researched, and in particular, laminated electrophotographic photoreceptors having a charge generation layer and a charge transport layer have superior electrical properties compared to conventional photoreceptors. It has been reported that. Known charge generating materials used in these electrophotographic photoreceptors include bisazo compounds, trisazo compounds, phthalocyanines, pyrylium compounds, and squarium compounds. Among these, phthalocyanines, trisazo compounds, and squarium compounds are known. is known to have sensitivity from the visible region to the near-infrared region. Problems to be Solved by the Invention However, phthalocyanines have spectral sensitivity biased toward long wavelengths and poor red reproducibility, and trisazo compounds do not have excellent electrical properties and sufficient sensitivity. Furthermore, the squarium compound disclosed in Japanese Patent Application Laid-Open No. 49-105536 does not achieve both high sensitivity and low dark decay. Furthermore, the squarium compound disclosed in Japanese Patent Application Laid-Open No. 58-214162 does not have sufficient sensitivity. Furthermore, even if a charge generating agent with a high ability to generate optical carriers is used, if the selection of the charge transporting agent is inappropriate, the injection efficiency of the optical carriers generated in the charge generating layer may be poor, and the Sensitivity may be lowered due to insufficient carrier movement, so the selection had to be made carefully. The present invention aims to eliminate the above-mentioned drawbacks. Therefore, an object of the present invention is to efficiently generate optical carriers even when irradiated with long wavelength light, and to efficiently inject optical carriers into a charge transport layer.
Another object of the present invention is to provide a highly sensitive electrophotographic photoreceptor in which light carriers move quickly. Another object of the present invention is to provide an electrophotographic photoreceptor that has sensitivity in the range from visible light to long wavelength region and has high photoresponsiveness when irradiated with long wavelength light. Means for Solving the Problems As a result of intensive research, the present inventors have determined that in a laminated electrophotographic photoreceptor, the charge generation layer has the following general formula (). (In the formula, R ₁ , R ₂ , R ₄ and R ₅ each represent an alkyl group, R ₃ and R ₆ each represent a hydrogen atom,
Indicates a hydroxyl group, methyl group, trifluoromethyl group, or halogen atom. However, the base

[Formula] and group,

[Formula] means different things. ) Contains a squarium compound represented by
And, the charge transport layer has the following general formula () (In the formula, R ₇ represents an alkyl group or an alkoxy group, and R ₈ and R ₉ each represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a substituted amino group.) The above object could be achieved by incorporating a benzidine compound. That is, when the above-mentioned squarium-based compound and the above-mentioned benzidine-based compound are used in combination, an electrophotographic photoreceptor with extremely high photoresponsiveness upon irradiation with long wavelength light can be obtained. The structure of the electrophotographic photoreceptor of the present invention will be explained with reference to the drawings. As shown in FIGS. 1 and 2, a squarium compound represented by the general formula ( A photosensitive layer 4 is provided, which is a laminate of a charge generation layer 2 containing a charge-generating layer 2 and a charge transport layer 3 containing a benzidine-based compound represented by the general formula (2). The stacking order of the charge generation layer 2 and the charge transport layer 3 is arbitrary. In the present invention, a protective layer may be provided on the photosensitive layer 4, or an intermediate layer may be provided between the photosensitive layer 4 and the conductive support 1. Next, each layer constituting the electrophotographic photoreceptor of the present invention will be explained. The charge generation layer contains a squarium-based compound represented by the above general formula (), and for example, the following compounds are used. These squarium-based compounds are squarium phosphate chloride and the general expression () (or ()) (In the formula, R ₁ to _{R 6} have the same meanings as described above.) After reacting the aniline derivative represented by the following by Friedel-Crafts type reaction and hydrolyzing the obtained cyclobutenedione derivative, It can be obtained by reacting with an aniline derivative represented by the general formula () (or ()). The charge generation layer may be formed of a squarium-based compound alone, but it can also be formed using a squarium compound in combination with a binder resin. In the latter case, the proportion of squarium compound to binder resin is from 10% to 90% by weight, preferably from 30% to 70% by weight. When using a binder resin, examples of the binder resin include polystyrene, silicone resin, polycarbonate, acrylic resin, methacrylic resin, polyester, vinyl polymer,
For example, polyvinyl butyral, celluloses, cellulose esters, cellulose ethers, alkyd resins, etc. can be used. The thickness of the charge generation layer is 0.05 to 3μ, preferably 0.1
~1μ. The charge generation layer is formed by a well-known method. That is, when a charge generation layer is formed using a squarerium compound alone without using a binder resin, solvent coating and vacuum evaporation methods can be used. Furthermore, when a binder resin is used in combination, the squarium-based compound is crushed and then dispersed in the binder resin. As the grinding method, known methods such as SPEX MILL,
Ball mills, RED DEVIL (product name), etc. can be used. The binder resin in which the squarium compound is dispersed is used as a charge transport layer ⊥ or a conductive support ⊥
is applied to. Coating methods include a dipping method, a spray method, a bar coater method, and an applicator method, and a good charge generation layer can be formed by any of these methods. On the other hand, the charge transport layer contains a benzidine compound represented by the above general formula (), and usable benzidine compounds include the following. In addition, in the formula, Me is a methyl group, Et is an ethyl group,
Pr represents a propyl group, and Bu represents a butyl group. Since these compounds do not have film-forming properties by themselves, they are used in combination with a binder resin that has good film-forming properties. Binder resins that can be used include:
Examples include general-purpose resins such as acrylic resin, methacrylic resin, polystyrene, polyester, polyarylate, polysulfone, and polycarbonate. The charge transport layer is formed by dissolving the benzidine compound represented by the general formula () and a binder resin in a solvent that dissolves both, and coating the solution. The blending ratio of the former and the latter is 5:1 to 1:5, preferably 3:1 to 1:3. The thickness of the charge transport layer is about 5 to 50 microns. Further, as the conductive support, metal, paper treated with conductivity, a polymer film having a conductive layer, glass, etc. can be used. In the present invention, the optional protective layer may include a metal oxide dispersed in a resin;
Examples include resins in which an electron-accepting compound is added. Examples of the intermediate layer include metal oxides such as aluminum oxide, acrylic resins, phenolic resins, polyester resins, polyurethanes, and the like. In the electrophotographic photoreceptor of the present invention, whether or not the charge injection and transport functions are performed appropriately can be determined by measuring the amount of exposure required until the surface potential decreases to 1/5 after initial charging. . this is,
This is because the above characteristics mainly depend on charge injection efficiency and transport efficiency. Even when a charge transport layer containing a benzidine compound represented by the above general formula () is used, if a squarium compound represented by the above general formula (2) is not used in the charge generation layer, a highly photoresponsive layer can be obtained. A photoreceptor cannot be obtained. This seems to be due to the charge generation function of the charge generation agent and the poor charge injection properties. Thus, in the present invention, the selection of the above two compounds is extremely important in terms of charge injection properties. Examples Next, the present invention will be explained by examples. Example 1 1 part by weight of polyvinyl butyral resin (trade name: BLX manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 40 parts by weight of cyclohexanone, and 1 part by weight of Exemplified Compound No. 4 was mixed therein as a charge generating material, The mixture was then well dispersed using a paint shaker, and the resulting dispersion was applied onto an aluminum sheet using an applicator and dried to form a charge generating layer. The film thickness after drying was 0.2 μm. On this charge generation layer, 1 part by weight of Exemplified Compound No. 5, which is a charge transport material, and polycarbonate resin (trade name: Lexan 145, manufactured by GE, molecular weight 35,000 ~
40,000) and 15 parts by weight of dichloromethane was applied using an applicator and dried to form a charge transport layer. The film thickness was 20 μm. The photoreceptor obtained as described above was subjected to the following characteristic evaluation using an electrostatic copying paper tester (SP-428 manufactured by Kawaguchi Electric Seisakusho). First, apply a corona discharge of -6KV to make it negatively charged, then leave it in a dark place for 2 seconds, measure the surface potential Vpo (Volt) at that time, and then use a tungsten lamp to increase the illuminance of the surface to 5 lux. Irradiate the light in this way,
The time required for the surface potential to become 1/5 of Vpo was determined, and the exposure amount E1/5 (lux·sec) was calculated. As a result, Vpo=-890V and E1/5=2.9lux·sec. Moreover, the sensitivity to long wavelength light was measured as follows. After the photoreceptor was charged by corona discharge in a dark place, spectroscopy was performed at 800 nm using a monochromator.
Irradiated with 1MW/ ^cm2 monochromatic light, the surface potential was reduced to 1/5
The amount of exposure was determined by measuring the time it took for the light to change. The result was 14.5erg/ ^cm2 . Examples 2 to 10 Electrophotographic photoreceptors were prepared and evaluated in the same manner as in Example 1, except that the combinations of charge-generating materials and charge-transporting materials were changed as shown in Table 1. The results are shown in Table 1.

[Table] Comparative Example 1 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the charge transport material was changed to the following compound. Comparative Example 2 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the charge transport material was changed to the following compound. Comparative Example 3 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the charge transport material was changed to the following compound. Comparative Example 4 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the charge generating material was changed to the following compound. Comparative Example 5 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the charge transport material was changed to the following compound. The results of Comparative Examples 1 to 5 are shown in Table 2.

[Table] Effects of the Invention As is clear from the comparison of Tables 1 and 2 above, the electrophotographic photoreceptor of the present invention is composed of a squarium compound represented by the general formula () and the general formula (2). By using a combination with a benzidine compound represented by the formula (), it has sensitivity in the range from visible light to long wavelength region, and
Shows high photoresponse when irradiated with long wavelength light. The electrophotographic photoreceptor of the present invention can be widely used not only in electrophotographic copying machines but also in semiconductor laser printers and the like.

[Brief explanation of the drawing]

1 and 2 are schematic diagrams of the electrophotographic photoreceptor of the present invention, respectively. DESCRIPTION OF SYMBOLS 1... Conductive support, 2... Charge generation layer, 3...
...Charge transport layer, 4...Photosensitive layer.

Claims (1)

[Scope of Claims] 1. In a laminated electrophotographic photoreceptor comprising a charge generation layer and a charge transport layer provided on a conductive support, the charge generation layer has the following general formula (). (In the formula, R ₁ , R ₂ , R ₄ and R ₅ each represent an alkyl group, R ₃ and R ₆ each represent a hydrogen atom,
Indicates a hydroxyl group, methyl group, trifluoromethyl group, or halogen atom. However, the group [formula] and the group [formula] have different meanings. ) Contains a squarium compound represented by
And, the charge transport layer has the following general formula () (In the formula, R ₇ represents an alkyl group or an alkoxy group, and R ₈ and R ₉ each represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a substituted amino group.) An electrophotographic photoreceptor comprising a benzidine compound.