JPH0594029A - Electrophotographic sensitive body - Google Patents

Abstract

(57) [Summary] (Correction) [Purpose] To provide a belt type photoreceptor having durability against bending action. [Structure] A charge-transporting layer of a belt-shaped electrophotographic photoreceptor in which a photosensitive layer on a conductive support comprises a charge-generating layer and a charge-transporting layer is mainly used, and a charge-transporting substance represented by I and II or II
It is composed of a resin having a repeating unit represented by I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and more particularly to a belt type photosensitive member having a high resistance to bending deformation.

[0002]

2. Description of the Related Art Conventionally, it has been known to use a hydrazone compound as a charge transport material for an electrophotographic photoreceptor. However, when hydrazone is used as the charge transport material of the belt type photoconductor, the problem is that the photoconductive layer cracks relatively early during repeated use, which causes image noise. It was

The usage of the belt type photoconductor will be specifically described with reference to FIG. 1. The belt type photoconductor 1 is stretched over three driving / supporting rollers 2 and the driving and supporting rollers are driven. Thus, the belt type photoconductor 1 is sequentially moved so as to circulate through the cleaner 5, the eraser 7, the charger 6, the image exposure 8, the developing sleeve 3, and the transfer charger 4. At that time, each drive / support roller 2 is always bent to a small radius. The cracking of the photosensitive layer is caused by the repeated bending action, but this bending action cannot be avoided because a belt-shaped photoreceptor is used.

[0004]

SUMMARY OF THE INVENTION The present invention is intended to provide an electrophotographic photosensitive member using a photosensitive layer material having high durability against bending action.

[0005]

The constitution of the present invention for solving the above-mentioned problems is an electrophotographic photosensitive member as set forth in the claims.

That is, the present invention has found that the use of the above-mentioned specific charge-transporting substance and the specific binder resin in the charge-transporting layer makes cracking of the photosensitive layer less likely to occur than conventional hydrazone compounds. It is based.

First, the photosensitive layer will be described.

In the laminated electrophotographic photosensitive member comprising an undercoat layer, a charge generation layer and a charge transport layer, the undercoat layer is polyamide, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl methyl ether, polyvinyl pyrrolidone, poly-N-. Thermoplastic resins such as vinyl imidazole, ethyl cellulose, nitrocellulose, ethylene-acrylic acid copolymer, casein, gelatin, etc., thermosetting resins such as phenol, urea resin, melamine, alkyd, unsaturated polyester, epoxy, etc. and titanium oxide for these resins. , Zinc oxide, indium oxide, antimony oxide, tin oxide, etc. are dispersed.

The solvent used here is cyclohexane,
Benzene, toluene, xylene, dichloromethane, 1,
1-dichloroethane, 1,2-dichloroethane, 1,
1,2-trichloroethane, 1,1,2,2-tetrachloroethane, monochlorobenzene, methanol, ethanol, butanol, methyl ethyl ketone, methyl-n-
Amyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-n-propyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl acetate, butyl acetate, dioxane, tetrahydrofuran and the like are preferable.

The thickness of the undercoat layer is 0.1 to 10 μm, preferably 0.3 to 5 μm.

The charge generating layer may be formed only of the charge generating substance, or may be formed by uniformly dispersing the charge generating substance in the binder. The charge-generating substance is formed by dispersing these components in a suitable solvent, coating this on the undercoat layer, and drying.

As the charge generating substance, for example, CI Pigment Blue 25 (Color Index (CI) 211
80), CI Pigment Red 52 (CI4510
0), CI Basic Red 3 (CI45210)
In addition to the above, phthalocyanine-based pigments having a porphyrin skeleton, azo pigments having a carbazole skeleton (Japanese Patent Laid-Open No. 5-212058).
3-95033), an azo pigment having a stilbene skeleton (described in JP-A-53-138229), and an azo pigment having a distyrylbenzene skeleton (JP-A-53-13).
3455), an azo pigment having a triphenylamine skeleton (described in JP-A-53-132547), and an azo pigment having a dibenzothiophene skeleton (JP-A-54-2).
1728), an azo pigment having an oxadiazole skeleton (described in JP-A-54-12742), an azo pigment having a fluorenone skeleton (described in JP-A-54-22834), an azo having a bisstilbene skeleton. Pigments (described in JP-A-54-17733), azo pigments having a distyryl oxadiazole skeleton (described in JP-A-54-2129), azo pigments having a distyryl carbazole skeleton (JP-A-54-17734). No.), a trisazo pigment having a carbazole skeleton (JP-A-57-19576).
No. 7, No. 57-195758), phthalocyanine-based pigments such as CI Pigment Blue 16 (CI74100), and CIVAT BROWN 5 (CI).
73410), sea butt die (CI73030)
Indigo pigments such as, indigo pigments such as Argos Scarlet B (manufactured by Violet), indense scarlet R (manufactured by Bayer), organic pigments such as square pigments: Se, Se alloy, CdS, inorganic such as amorphous Si Pigments can be used.

As the binder resin, polyamide, polyurethane, polyester, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, polyacrylamide and the like are used. Be done.

The amount of binder resin is 100
5 to 100 parts by weight, preferably 10 to 50 parts by weight
Parts by weight are suitable.

The solvent used here is tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, cyclohexane, methyl ethyl ketone, 1,1,1.
A single solvent or a mixed solvent such as 2-trichloroethane, 1,1,2,2-tetrachloroethane, dichloromethane and ethyl cellosolve is preferable.

The average film thickness of the charge generation layer is 0.01 to 2 μm.
m, preferably 0.1 to 1 μm.

The charge transport layer is formed by dissolving a charge transport material, a binder resin and, if necessary, a plasticizer and a leveling agent in a suitable solvent, coating the solution on the charge generating layer and drying. As the charge transport substance, a compound represented by the general formula [I]
An electron donating substance represented by

The binder resin has the general formula [II],
The resin represented by [III] may be mentioned.

As the solvent for forming the charge transport layer, tetrahydrofuran, 1,2-dichloroethane, cyclohexanone, dichloromethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane and a mixed solvent thereof are used. preferable. The thickness of the charge transport layer is 10 to
It is 100 μm, preferably 20 to 40 μm.

The protective layer is a layer in which ultrafine powder of metal or metal oxide is dispersed in a binder resin. It is desirable that the binder resin be substantially transparent to visible light and infrared light and have excellent electric insulation, mechanical strength and adhesiveness. For example, polyester resin, polycarbonate resin, polyurethane resin, epoxy resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, silicone resin, alkyd resin, melamine resin, phenol resin, polyvinyl chloride resin cyclized butadiene rubber, fluorine resin, etc. Can be used. As the metal powder, gold, silver, aluminum, iron, nickel, and as the metal oxide, zinc oxide, titanium oxide, tin oxide, bismuth oxide, antimony oxide, indium oxide and the like can be used.

The composition ratio of the binder resin of the protective layer and the metal or metal oxide varies depending on the combination of materials, but the binder resin 1
5 to 500 parts by weight of metal or metal oxide for 100 parts by weight
Used in the range of parts by weight.

The thickness of the protective layer may be 0.5 to 30 if necessary.
It can be set between μm.

[0023]

EXAMPLES The structure and operation of the present invention will be described below with reference to examples.

The amounts (parts) of the respective components described in the examples are parts by weight.

Example 1 Al vapor-deposited PET film (Metalmy DMSX-43)
Toyo Metallizing (thickness: 75 μm), the following disazo pigment was dispersed, and a charge generation layer coating solution prepared by using polyvinyl butyral resin (manufactured by XYHL Union Carbide) as a binder was bead-coated and dried, .2 μm
The charge generation layer of was formed.

[0026]

[Chemical 5]

Further, as a charge transporting material represented by the general formula I, 9 parts of the following structural formula, and a resin having a repeating unit represented by the general formula II, Panlite L12
50 (Teijin Kasei average molecular weight 25,000) 10 parts,
Silicone oil KF50 (made by Shin-Etsu Silicone) 0.0
A charge transport layer coating solution prepared by dissolving 02 parts in 100 parts of THF was nozzle-coated on the charge generation layer and dried to give a thickness of 2
A 0 μm charge transport layer was formed.

[0028]

[Chemical 6]

The belt-shaped photoreceptor of the present invention was produced by the steps of cutting, punching and ultrasonic bonding the belt-shaped photoreceptor coated as described above.

The structure of Panlite L1250 is shown below.

[0031]

[Chemical 7]

Example 2 The present invention was carried out in the same manner as in Example 1 except that Panlite K1300 (produced by Teijin Kasei Co., Ltd., average molecular weight 30000) was used as the resin having the repeating unit represented by the general formula II in Example 1. Was prepared.

The structure of Panlite K1300 is the same as that of Panlite L1250.

Example 3 The present invention was carried out in the same manner as in Example 1 except that Panlite C1400 (average molecular weight 37500 manufactured by Teijin Chemicals Ltd.) was used as the resin having the repeating unit represented by the general formula II of Example 1. Was prepared.

The structure of Panlite C1400 is the same as that of Panlite L1250.

Example 4 PET film with Al vapor deposition (Metal Me DMSX-43)
The following trisazo pigment is dispersed in Toyo Metallizing's thickness of 75 μm, and a phenoxy resin (PK is used as a binder.
The charge generation layer coating liquid prepared using HH Union Carbide) was dried to form a 0.2 μm charge generation layer.

[0037]

[Chemical 8]

Further, as the charge transporting material represented by the general formula I, 8 parts of the following structural formula, and a resin having a repeating unit represented by the general formula III, Panlite T
S2050 (Teijin Kasei average molecular weight 40,000) 1
0 parts, silicone oil KF50 (made by Shin-Etsu Silicone)
A charge transport layer coating solution prepared by dissolving 0.002 part in 100 parts of toluene was nozzle-coated on the charge generation layer and dried to form a charge transport layer having a thickness of 90 μm.

[0039]

[Chemical 9]

The belt-shaped photoreceptor coated as described above was cut, punched, and ultrasonically bonded to produce the belt-shaped photoreceptor of the present invention.

The structure of Panlite TS2050 is shown below.

[0042]

[Chemical 10]

Comparative Example 1 The present invention was carried out in the same manner as in Example 1 except that Panlite L1225 (average molecular weight 22500 manufactured by Teijin Chemicals) was used as the resin having the repeating unit represented by the general formula II in Example 1. Was prepared.

The structure of Panlite L1225 is the same as that of Panlite L1250.

Comparative Example 2 The present invention was carried out in the same manner as in Example 4 except that Panlite TS2050 (average molecular weight 20000 manufactured by Teijin Kasei) was used as the resin having the repeating unit represented by the general formula III in Example 1. Was prepared.

Comparative Example 3 An electrophotographic photosensitive member of the present invention was produced in the same manner as in Example 3, except that the charge transporting material represented by the general formula I in Example 3 having the following structure was used.

[0047]

[Chemical 11]

The belt-shaped photoconductors produced as described above were used in Examples 1, 2 and 3 and Comparative Examples 1 and 3 in the copying machine M-10.
A modified machine (manufactured by Ricoh), a laser beam printer LP3320-SP4 (manufactured by Ricoh) in Example 4 and Comparative Example 2
A copy was made with a modified machine, and the state of occurrence of cracks on the surface of the photoreceptor was visually observed. In addition, a black solid image was copied to confirm the presence or absence of image noise (white spots) due to cracks.
The results are shown in the table.

[0049]

[Table 1] Example 1

[0050]

Table 2 Example 2

[0051]

Table 3 Example 3

[0052]

Table 4 Example 4

[0053]

[Table 5] Comparative Example 1

[0054]

[Table 6] Comparative Example 2

[0055]

[Table 7] Comparative Example 3

[0056]

As described above, the electrophotographic photosensitive member of the present invention has excellent durability against bending action.

[Brief description of drawings]

FIG. 1 is a conceptual diagram of a copying apparatus for explaining the operation of a belt-shaped photoreceptor.

[Explanation of symbols]

 1 photoconductor belt 2 drive / support roller 3 developing sleeve 4 transfer charger 5 cleaner 6 charger 7 eraser 8 image exposure

Claims (3)

[Claims] 1. A belt-shaped electrophotographic photoreceptor having a photosensitive layer comprising at least a charge generation layer and a charge transport layer on a conductive support, wherein the charge transport layer is mainly a charge transport substance represented by the following general formula I: An electrophotographic photosensitive member comprising a resin having a repeating unit represented by the general formula II or the general formula III. [Chemical 1] However, in the above general formula I, R ₁ is any of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group, and R ₂ , R ₃ and R ₄ are respectively Hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, Ar ₁ is a substituted or unsubstituted aryl group, Ar ₂ is a substituted or unsubstituted arylene group, Ar ₁ may form a ring together with R ₁ . n is 0 or 1. [Chemical 2] [Chemical 3] However, in the above general formulas II and III, R ₅ and R ₆ are each a hydrogen atom, an aliphatic group which may have a substituent, a carbocyclic group, or an aromatic group, and Z is a substituent. carbocyclic ring which may have, either in the atomic group necessary for forming a heterocyclic ring, R ₇ to R ₁₄ is a hydrogen atom, a halogen atom, an optionally substituted aliphatic group, It is either a carbocyclic group or an aromatic group. 2. The electrophotographic photosensitive member according to claim 1, wherein the resin represented by the general formula II or the general formula III has an average molecular weight of 25,000 or more. 3. The electrophotographic photosensitive member according to claim 1, wherein the resin represented by the general formula II or III has a repeating unit represented by the following chemical formula. [Chemical 4]