JPH01257967A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body good in chargeability, rapid in potential decay due to exposure to light, high in sensitivity, and further, small in dependence of potential decay on an electric field by combining an electric charge generating layer containing a phthalocyanine pigment with a charge transfer layer containing a benzidine derivative. CONSTITUTION:The charge generating layer contains one of the phthalocyanine pigments represented by formula I and the charge transfer layer contains one of the benzidine derivatives represented by formula II. In formulae I and II, X is a divalent or higher valent metal atom. capable of combining with 2 H, oxygen, or halogen atom. or atoms.; R1 is H, alkyl, or alkoxy; and each of R2 and R3 is H, alkyl, or the like when R1 is H, and each is H, methyl, or the like when R1 is alkyl or alkoxy, thus permitting the obtained electrophotographic sensitive body to be freed of trailing of potential and almost freed of residual potential.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an electrophotographic photoreceptor having a layer structure in which a charge generation layer and a charge transport layer are functionally separated.

Conventional technology Conventional electrophotographic photoreceptors include those with a single-layer photoconductive layer and those with a multilayer photoconductive layer, but in recent years, in particular, organic photoconductive materials have been bonded with resin etc. as a photoconductive layer, and a charge transport layer has been developed. Various proposals have been made regarding an organic electrophotographic photoreceptor having a layer structure in which a charge generation layer and a charge generation layer are functionally separated, and various charge generation materials and charge transport materials have also been proposed. For example, known charge generating materials include polycyclic quinone pigments, perylene pigments, indigo pigments, bisbenzimidazole pigments, quinacridone pigments, phthalocyanine pigments, monoazo pigments, bisazo pigments, trisazo or polyazo additives, and charge transporting materials. Materials include amine compounds, hydrazone compounds, pyrazoline compounds, oxazole compounds, oxadiazole compounds, stilbene compounds,
Carbazole compounds and the like are known. Various proposals have also been made to use these charge-generating materials and charge-transporting materials in combination. (For combinations with phthalocyanine pigments, for example, JP-A Nos. 57-54942, 60-59355, 61-203461, 62
-47054@, 62-67094, etc.) Problems to be Solved by the Invention By the way, in a laminated electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are functionally separated, satisfactory electrophotographic characteristics can be achieved. In order to obtain this, the following conditions must be met: 1. Charges are efficiently generated in response to the light absorbed by the charge generating material, and 2. The generated charges are efficiently injected into the charge transport material and transported. Needed. That is, 1
Even if condition 1 is satisfied, if condition 2 is not satisfied, satisfactory photoresponsiveness cannot be obtained.

In addition, when the electrophotographic photoreceptor is one in which a charge generation layer and a charge transport layer are laminated in this order, and light irradiation is performed from the charge transport layer side, the following conditions must be met in order to obtain high sensitivity:
It is necessary that the charge transport layer be sufficiently transparent to the light that activates the charge generation layer.

In order to create an electrophotographic photoreceptor using a charge-generating material and a charge-transporting material, the above-mentioned conditions must be met, including sensitivity, acceptance potential, potential retention, potential stability, residual potential, and spectroscopy. Electrophotographic properties such as properties, strength, durability,
A material must be selected that satisfies all aspects, including usage characteristics such as stain resistance, and manufacturing stability and quality stability when manufactured by coating. However, it is extremely difficult to select a combination of materials that satisfies all of these points, and the above conditions have not been met for previously proposed combinations of charge-generating materials and charge-transporting materials. I haven't been able to find anything that satisfies me. .

The present invention was made in view of the above circumstances, and it is possible to create an excellent electrophotographic photoreceptor by finding a combination of materials that satisfies all of the requirements for an electrophotographic photoreceptor. The purpose is to provide

Means for Solving the Problems and Effect A phthalocyanine pigment represented by the following (representing a divalent or higher valence metal in which atoms may be bonded) is used as the charge transport material of the charge transport layer: represents an alkyl group or an alkoxy group, and when R1 represents a hydrogen atom, R2 and R3 each represent a hydrogen atom, a furkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a substituted amino group, and R1 represents an alkyl group. or, in the case of an alkoxy group, a hydrogen atom, a methyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a substituted amine group, respectively).

That is, the electrophotographic photoreceptor of the present invention is one in which a photosensitive layer consisting of a charge generation layer and a charge transport layer is provided on a conductive substrate, and the charge generation layer is necessarily represented by the above-mentioned symbol (I). containing a bisazo pigment, and the charge transport layer is the above-mentioned
It is characterized by containing a benzidine compound represented by:

The present invention will be explained in detail below.

In the present invention, the phthalocyanine pigment to be contained in the charge generation layer is represented by the above-mentioned -Isen (I>), and specifically, compounds in which X in -Isen (I>) represents the following are included.

■-I X=2 hydrogen atoms (metal-free phthalocyanine) I-2X=Cu (copper phthalocyanine) I-3X=Mg Needed -8 X=GaBr 1-9 X=GaI I-10X=AICI nee ii x=v.

I −12X=TiO In the present invention, the particle size of these phthalocyanine pigments is
It is preferable that it is less than 21IJrI.

As a binder resin for dispersing phthalocyanine pigments,
Well-known materials such as polycarbonate, polystyrene,
Polyester, polyvinyl butyral, methacrylic acid ester polymer or copolymer, vinyl acetate polymer or copolymer, cellulose ester or ether, polybutadiene, polyurethane, epoxy resin, etc. are used.

On the other hand, as the charge transport material in the charge transport layer, benzidine compounds represented by the above-mentioned (n) are used, and specific examples of these benzidine compounds include:
The following can be mentioned.

Since these compounds do not have film-forming properties by themselves, they are used in combination with resins that have good film-forming properties. Examples of resins that can be used include polycarbonate, polyacrylate, polyester, polyarylate, polystyrene,
Styrene-acrylonitrile copolymer, polysulfone,
Examples include polymethacrylic ester, styrene-methacrylic ester copolymer, and the like. Among these, polycarbonate is preferred.

To explain in more detail the method for producing the electrophotographic photoreceptor of the present invention, first, the charge generation layer is formed by dispersing a phthalocyanine pigment in a binder resin solution and coating the solution. Dispersion means include ball mill, roll mill,
Commonly used tools such as sand mills and attritors can be used. The blending ratio of the phthalocyanine pigment and the binder resin is 40:1 to 1:4, preferably 20:1 to 1:4.
It is 2.

If the ratio of the phthalocyanine pigment is too high, the stability of the coating solution will decrease, and if it is too low, the sensitivity will decrease, so it is desirable to keep it within the above range. Further, as the solvent for the binder resin, any solvent can be used as long as it is soluble, but it is desirable to select a solvent that has good pigment dispersibility.

Further, a plurality of solvents may be used in combination.

The charge transport layer is formed by dissolving a benzidine compound represented by (II) and a film-forming resin in a solvent that dissolves both, and applying the solution.

The blending ratio of the former and the latter is 5:1 to 1:5, preferably 3:1 to 1:3. If the former ratio is too high, the mechanical strength of the charge transport layer will decrease, and if it is too low, the sensitivity will decrease, so it is desirable to keep it within the above range.

In the electrophotographic photoreceptor of the present invention, the layer structure of the photosensitive layer formed on the conductive substrate may include a charge transport layer provided on the charge generation layer, or a charge transport layer provided on the charge transport layer. A generation layer may also be provided. The thickness of the charge generation layer is 0.05 to 5%, and the thickness of the charge transport layer is 5 to 50%.
Further, in the electrophotographic photoreceptor of the present invention, it is preferable to provide a charge injection blocking layer between the photosensitive layer and the conductive substrate.

Example Next, the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 1 part by weight of polyvinyl butyral resin (trade name: BLX, manufactured by Tsukusui Kagaku Co., Ltd.) was dissolved in 40 parts by weight of cyclohexanone, and 3 parts by weight of Exemplary Compound I-1 was added therein as a charge generating material. 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 mm.

Next, on this charge generation layer, 31 parts by weight of exemplary compound n-3 which is a charge transport material, polycarbonate resin (trade name Nilexane 145, manufactured by GE Corporation, molecular weight = 35.000 to 4
A homogeneous solution consisting of 0,000>1 part by weight and 15 parts by weight of dichloromethane was applied using an applicator and dried to form a charge transport layer. The film thickness after drying was 20 mm.

The electrophotographic photoreceptor sheet thus prepared was tested using an electrostatic copying paper tester (5P-428, manufactured by Kawaguchi Electric Seisakusho ■).
The characteristics were evaluated as follows.

First, a model that was negatively charged by applying corona discharge of -6KV, 2
The surface potential Vpo (volt
), then using a tungsten lamp, irradiate light so that the illuminance of the surface becomes 5 lux, find the time until the surface potential reaches 175 of Vpo, and calculate the exposure amount E.
115 (IUX-sec) was calculated. vpo=-90
0V, E115=7.51UX-sec.

Examples 2 to 10 Electrophotographic photoreceptors were prepared in the same manner as in Example 1, except that the charge-generating materials and charge-transporting materials in Example 1 were replaced by those shown in Table 1. It was evaluated as follows. The results are shown in Table 1.

Table 1 Comparative Example 1 An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that a compound represented by the following structural formula was used as the charge transport material, and evaluation was performed in the same manner. .

Comparative Example 2 In Example 3, the following structural formula (I
An electrophotographic photoreceptor was prepared in the same manner as in Example 3, except that the compound represented by I[> was used, and evaluation was performed in the same manner.

Comparative Example 3 In Example 10, the above structural formula (
Example 1 except that the compound represented by I[I] was used.
An electrophotographic photoreceptor was prepared in the same manner as in Example 0 and evaluated in the same manner.

The results are shown in Table 2.

Table 2 Effects of the Invention In the present invention, by combining the charge generation layer containing the above-mentioned phthalocyanine pigment and the charge transport layer containing the above-mentioned benzidine compound, the chargeability is good and the potential attenuation due to light irradiation is fast. Therefore, an electrophotographic photoreceptor can be obtained which has high sensitivity, has little electric field dependence of potential attenuation, and is easily attenuated by light even at a relatively low potential, that is, has no tailing of the potential and almost no residual potential. In addition, the electrophotographic photoreceptor of the present invention has good potential stability and low temperature/humidity dependence.
Furthermore, it has the characteristics of extremely low optical fatigue, no deterioration in chargeability due to light, and no so-called optical memory effect, making it extremely easy to use.

The electrophotographic photoreceptor of the present invention is effectively used in electrophotographic copying machines, but can also be applied to various printers, microfilm readers, electrophotographic engraving systems, etc. that apply pyrography technology.

Patent applicant Fuji Xerox Co., Ltd. Agent
Patent attorney Tsuyoshi Seibe

Claims (1)

[Claims] (1) In a laminated electrophotographic photoreceptor in which a photosensitive layer consisting of a charge generation layer and a charge transport layer is provided on a conductive substrate, the charge generation layer has the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. Contains a phthalocyanine pigment represented by ▼ (I) (wherein, X represents two hydrogen atoms, or a divalent or higher metal to which an oxygen atom or a halogen atom may be bonded), and the charge transport layer is the following general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1 represents a hydrogen atom, an alkyl group, or an alkoxy group, and R_2 and R_3 are each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a substituted amino group, and when R_1 represents an alkyl group or an alkoxy group, each represents a hydrogen atom, a methyl group,
An electrophotographic photoreceptor comprising a benzidine compound represented by the following formula (representing an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a substituted amino group).