CA1148017A - Electrophotographic member including a protective layer containing electron acceptor, binder resin and metallocene compound - Google Patents

Abstract

ABSTRACT

An electrophotographic member in which a photoconductive layer and a protective layer are superposed in order on a photoconductive support, wherein the improvement comprises:
said protective layer containing at least one metallocene or a compound having at least one metallocene nucleus in its molecular structure.

Description

ELECTROPHOTOGRAPHIC nal~MBER AND PROCESS

This invention relates to an electrophotographic member capable of yielding an image of good quality incorporating a metallocene compound in a 5 protective layer provided on the surface of a photoconductive layer.
A number of photosensitive members have been practically applied in electrophotographic systems including processes comprising charging, exposing and developing procedures tsee, for example, U.S. Patent 2,297,691).
For example, known photosensitive members include those which include a 10 layer of organic photoconductive material directly formed on a conductive substrate by coating or vacuum deposition or those in which the organic photoconductive material is combined with an organic polymeric binder, those using inorganic photoconductive materials such as ZnO, CdS, TiO2 and the like dispersed in a binder, those using vacuum-evaporated amorphous selenium and 15 its alloys, and those wherein different types of photoconductive layers are superposed on one another (see, for example, Japanese Patent Publication Nos.
5394/70, 3005/71 and 14271/74). In order to ensure certain levels of both electrical and optical properties and mechanical properties or to improve and stabilize these properties, or in some cases to improve the characteristics 20 required in a developing process, it has often been proposed to provide a protective layer on the photosensitive member surface.
Electrophotographic members having a surface layer on a photo-conductive layer have been known in the art. One type of such surface layers is an electrically insulating surface layer composed of a highly electrically 25 insulating material (e.g., see Tanaka, et al., U.S. Patent 3,438,706 and Watanabe, et al., U.S. Patent 3,457,070). This is advantageous in that the thickness of the electrically insulating surface layer can be thickened and in that materials having high mechanical strength can be used. However, in order to repeatedly us an electrophotographic member with this type of surface 30 layer, a specific latent image-forming process is required, such as: (A) first charging; second charging with an opposite polarity to that of the first charging; and imagewise exposure; or (B) first charging; second charging with opposite polarity and simultaneous imagewise exposure; and entire exposure, is required. Furthermore, the use of such a surface layer requires two or more 35 charging steps per one copying step, which results in complicating the apparatus, unstable properties, and high production costs.

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Another type of such surface layers is a protective layer composedof a relatively low electrically insulating material, i.e., a material having a low electric resistance. (See Joseph, U.S. Patent 3,434,832 and Polastri, U.S.
Patent 4,006,020.) In most cases, however, the use of such a protective layer S causes a high residual potential, and a great increase of cycle is required.
These electric variations result in scumming and do not result in a clear reproduction image.
In order to avoid such problems, an additive has been incorporated in the protective layer or a single protective layer of a specific type has been10 used. However, most of these techniques have involved problems sueh as a lossof transparency which is essential to a protective layer, a loss of image sharpness under high humidity conditions or fogging in the background under low humidity conditions, a reduction in charging property of a photoconductive layer, and a cyclic build-up of residual potential, and can thus not be put into15 practice. This is because these methods have been directed merely to loweringthe electric resistance of the protective layer or to improving its humidity dependence. In order to stabilize and ensure the charging property of the entire photoconductive layer over a long period of time under all practical conditions, various characteristics such as transport, injection and residence 20 of the electric charges occurring on the surface of a protective layer and atthe interface between the photoconductive layer and the protective layer must be collectively controlled. It is difficult to find a material which can improvethese characteristics while controlling ths electrical conductivity of the protective layer and which exhibits stable characteristics with variations in 25 humidity and temperature. There has never been known a material, which when contained in a binder resin can satisfy the above-mentioned characteris-tics, and provide the mechnical strength necessary to meet the requirements of an ordinary protective layer.
Extensive studies have been made and it has been found that an 30 electrophotographic member can be obtained by adding to a protective layer atleast one compound selected from the group consisting of metallocenes (i.e., biscyclopentadienyl complex salts), which the general formula (1):

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148~17 wherein ~ represents a metal atom and is, for example, selected from Fe, Ni, Co, V, Cr and Ti; and compounds having at least one metallocene nucleus in the molecular structure thereof, such as those having the formula (II):

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wherein M has the same meaning as defined above. mus, the metallocene may be, e.g., an unsubstitute~ (I), or a substituted or polymeric (II) o~mpound.
Hereafter, these compounds are collectively referred to as metallocene compounds. m at is, the inclusion of these comFounds in the protective layer can eliminate a large dark decay of discharge potential frequently experienced in kncwn me~bers and can simultaneously suppress the residual potential after exposure to a sufficiently low level, making it possible to eliminate the cyclicbuildup of residual potential. When the metallocene compounds used in the present invention are oontained in the protective layer, their electrical conductivity is not changed by the charging or imagewise exposure steps, and they retain a substantially uniform latent image potential during repeated copying steps.
Thus, and in accordance with the present teachings, an electrophoto-graphic member is provided in which a photoconductive layer and a protective layer are superposed in order on a oonductive support. In the protective layer is present at least one electron acceptor, a resin binder and at least one metallocene or a compound having at least one metallocene nucleus in its lecular structure and present in an amount of from about 0.01 to about 70 weight percent, based on the weight of the protective layer.
An electrophotographic member having a protective layer according to the present invention does not require a specific latent image-forming process as is required by some of the previously described prior art techniques, and is advantageous in that a latent image can be formed merely by uniform charging and imagewise exposure.
The protective layer also exhibits st ble characteristics even though the ambient temperature and humidity vary. In addition, the resent invention has a number of the additional advantages.

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1148~17 -3a-For example, while the thickness of a kncwn protective layer is at most 5 ~, the protective layer according b~ the invention can be made several t~mes as thick. A conventional protective layer should have a relatively small thickness of about 0.1 to 5 ~ so as not to interfere with obtaining satisfactory electrical characteristics. Accordingly, the layer wears u~on repeated use and its characteristics vary to a significant extent.

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8~17 In the practice of the invention, the protective layer csn be formed in a thickness as great as 15 ~ or 20 ,u, which up to now would not be considered possible from the viewpoint of imparting reasonable electrical characteristics, by incorporating the foregoing compounds or adjusting the concentration of the 5 compound. In spite of such great thickness, a latent image can be formed by only uniformly charging an electrophotographic member of the present invention and imagewise exposure (i.e., the so-called Carlson process) without the use of any specific latent image-forming process such as first charging, second charging in the opposite polarity and imagewise exposure, or first 10 charging, simultaneous imagewise exposure and second charging, and uniform exposure. As a matter of course, the protective layer according to the present invention can be made as thin as desired.
The metallocenes and compounds having at least one metallocene nucleus in the molecular structure thereof contained in the protective layer of 15 the invention include, for example, ferrocene, nickelocene, titanocene, vinylferrocene and their oligomers or polymers, diferrocenylphosphine, 1,1'-ferrocene-bis~diphenylphosphine), acetylferrocene, dibenzferrocene, dimethyl-aminoethyl ferrocene, methylaminoethyl ferrocene, methylaminomethyl ferro-cene, ferrocenylacetonitrile, ferrocenylcarbonal, ferrocene sulfonic acid, 20 diferrocenylethane, diferrocenylmethane, phenylferrocene, phenyl cyclopenta-ferrocene, benzoylferrocene, acetylferrocene, and the like. Among these metallocene compounds, ferrocene, nickelocene and titanocene are preferred, with ferrocene being particularly preferred, due to good stability thereof.
These may be used alone or in combinations of two or more. These compounds 25 are generally used in the protective layer in an amount of about 0.01 to 79 wt.%, and preferably about 1 to 50 wt.%, based on the weight of the protective layer.
The thickness of the protective layer ranges from about 0.5 to 50 ,um and is chosen within such range depending on the use of the electrophoto-30 graphic member or the mechanical strength required for the protective layer.
The binder resins used in the protective layer of the electrophoto-graphic member according to the invention may be any of the resins which have been used in this field. Desirable characteristics of the binder for the protective layer include: film-forming ability, mechanical strength, moisture 35 resistance, corona resistance, good cleaning properties, chemical resistance, and good adhesiveness.

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1~8~7 For example, mention can be made of polyurethane resins, poly-styrene resins, polycarbonate resins, polyester resins, acrylic resins, siliconeresins, vinyl chloride resins, polyvinyl acetate resins, cellulose ester resins,nitrocellulose resins, alkyd resins and the like.
Additives may be added to improve the adhesiveness or smoothness of the fUm. For example, silane coupling agents and adhesive polyester resins (e.g., Myla~) 49000) can also be used as additives to improve the adhesiveness and sUicon block copolymers, fatty acids (e.g., stearic acid) and metal salts offatty acids (e.g., zinc stearate) can be used as additives to improve the smoothness of the film. Binder resins containing the _ 11 _ o bond are particularly preferred, such as polyurethane resins, polycarbonate resins and polyester resins; it is believed that these binder resins form a charge transfer complex with ferrocene, thereby conferring the desired electrical characteristics.
If necessary, a thin intermediate layer can be provided below the protective layer to improve the electrical characteristics. The intermediate layer may be composed of an inorganic compound such as SiO2, Se, S, As2O3, etc., or an organic compound such as polyester resins, epoxy resins, polyamide resins, polyurethane resins, nitrocellulose, vinylidene chloride resins, silicone resins, fluorine resins, etc. When the organic compound is uæd as the intermediate layer, both the electrical characteristics and the adhesion between the protective layer and the photoconductive layer are improved.
With respect to the thickness of the intermediate layer, it is sufficient that an exposed light transmits the photoconductive layer. A
suitable thickness of the intermediate layer which can be used varies with the type of material uæd, but ranges from about 50 A to 10 ~Im, preferably 100 A
to l IJm.
In constructing the electrophotographic member according to the invention, a conductive substrate is first provided on which a photoconductive layer has been formed in the usual manner.
Examples of inorganic crystalline photoconductors useful in the present invention are cadmium sulfide, cadmium sulfoselenide, cadmium selenide, zinc sulfide, zinc oxide, and mixtures thereof. Examples of inorganic photoconductive glasses are amorphous selenium, and ælenium alloys such as . ~ . . . .. .. . . . . . . . . . . .

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11~8~7 selenium-tellurium, and selenium-arsenic. Selenium may also be used in its hexagonal crystalline form, commonly referred to as trigonal selenium.
Exsmples of organic photoconductors useful in the present invention are phthalocyanine pigments such as the X-form of metal free phthalocyanine described in Byrne, et ~, U.S. PHtent 3,357,989, and metal phthalocyanine pigments, such us copper phthalocyanine. Other typical organic photoconductors include photoinjecting pigments such as benzimidazole pig-ments, perylene pigments, quinacridone pigments, indigoid pigments, and polynuclear quinones.
A coating of 8 metallocene dissolved in a binder resin solution at a suitable concenttation is uniformly applied on the photoconductive layer using any of the widely employed techniques such as a spray coating, a dip coating or a coating using an applicator, after which the layer is dried.
Examples of solvents suitable for preparing the protective layer coating composition include dichloromethane, trichloromethane, tetrachloro-methane, methyl ethyl ketone, isobutyl acetate, ethylbenzene, cyclohexanone, diacetone alcohol, diethylene glycol diethyl ether, dimethylformamide, di-methyl sulfoxide, "Amsco" Mineral Spirits 66/3, "Exxon~ Aromatic Solvent 150, "Exxon" Aromatic Solvent 100, and so forth.
The thus fabricated electrophotographic member adequately satis-fies all the characteristic requirements discussed hereinbefore.
Further, it has been found that the characteristics Or the electro-photographic member are further improved by adding to the protective layer not only the metallocene or compound having at least one metallocene nucleus in the molecule thereof but also an electron acceptor, i.e., a compound exhibiting high electron affinity. The electron acceptor is added in an amount of from about 0.001 mol to 2 mols per mol of the metallocene compound.
Incorporation of an electron acceptor method is known, for exsmple, being described in British Patent 1,337,227. The essential functions of the eleotron acceptor are that: (i) it activates the ferrocene compound, i.e., increases a cation radical density; (ii) the acceptor per se can become a carrier; and (iii)the acceptor can improve the mobility of electron. &itable electron acceptors include, for example, anhydrides such as those of phthalic acid and tetrachlorophthalic acid, s-tricyanobenzene, picryl chloride, 2,4-dinitrochloro-benzene, 2,4-dinitrobromobenzene, 4-nitrobiphenyl, 4,4-dinitrobiphenyl, 2,4,6-trinitroanisole, trichlorotrinitrobenzene, trinitro~toluene, 4,6-dichloro-1,3-* Trademark .. . . . . . ..
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il~8i:717 dinitrobenezene, ~dinitrobenzene, chloranyl, bromanyl, tetracyanboethylene, hexacyanobutadiene, tetracyanoguinodimethane, benzoqufnone and ttheir halo-gen- or cyano-substituted compounds, aromatic or heterocyclic compounds substituted with a nitro group (-NO2), a sulfo (-SO3-) group, a carboxyl group (-5 COOH), a cyano group (-CN) and the like, monomers or polymers of 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitrofluoreneone, trinitroanthracene, di-nitroacridine, tetracyanopyrene, and dinitroanthraquinone. Examples of aromatic or heterocyclic compounds which can be used in the present invention are dicyanodichlorobenzoquinone, tetracyanobenzene, sulfonic acid, cyano-10 naphthalene, benzoic acid, nitronaphthalic anhydride, and so forth. Theheterocyclic compounds may include 5- to 7-membered ring compounds.
Suitable examples of hetero atoms are N, S and O.
In order to add these compounds together with the metallocene compounds to the protective layer, the compounds may be added to a binder 15 solution simultaneously or separately, or in some cases the compounds, which have been previously mixed uniformly, may be added to a binder soluffon. The application to the photoconductive layer is similar to fabricating other electrophotographic member of the invention described hereinbefore.
The present invention will be particularly illustrated by way of the 20 following examples.:
EXAMPLE I
Amorphous selenium was vacuum deposited on an aluminum substrate in a thickness of 60 y in a conventional manner to five a photoconductive layer. On the layer the ferrocene-organic binder-resin 25 solutions of the ollowing formulation Nos. 1 to 3 were applied by an automatic applicator in a thickness of 15 ym to provide Electrophotographic Members Nos. 1 to 3, respectively.
Solution No. 1 _ Ferrocene 10 g Polycarbonate (Panlite* a product of 100 g Teijin Chemicals Ltd.) Dichloromethane 1,000 g Solution No. 2 .
Ferrocene 10 g Polyurethane (Polyuremytilac Clear 260 g 8ase, a product of Dai Nippon Toryo Co., Ltd.) Solvent (polyuremytilac thinner) 150 g S~ * Trademark .. ..
: -, Solution No. 3 Perrocene * 10 g Polyester (Byron, a product of Toyo 100 g Spinning Co., Ltd.) Dichloromethane 1,000 g The resulting electrophotographic members having the protective layers obtained from Solutions Nos. 1 to 3 were tested in an ordinarily employed electric characteristic measuring apparatus for electrophotography to determine their characteristics. As shown in Table 1, the dark discharge 10 potential (DDP) was large and the residual potential (RP) was small, these potentials being very low in humidity dependence. Further, as indicated in Table 2, no accumulation of electrical charges was observed with regard to the dark discharge potential and residual potential, showing a very good repetitive characteristic.
TABLE I
Electro-photographic 20C 10% RH 20C 50% RH20C 95% RH
Member DDP RP DDP RP DDP RP
(V) (V~ (V)(V) (V) (V) No. 1 850 25 850 25 845 25 20No. 2 910 40 910 40 900 40 No. 3 970 70 970 70 970 70 Electro- DDP _ RP
25photographic 1 500 1 500 Member CYCLE CYCLES VCYCLE CYCLES V
(V) (V) '' ~ (V) (V) No. 1 850 850 0 25 25 0 No. 2 910 910 0 45 45 0 No. 3 970 975 5 70 70 0 EXAMPLE a On an aluminum substrate was vacuum deposited amorphous eeleni um in a thickness of 0.5 y, on which was applied a solution of 1 part by weight of polyvinylcarbazole in 10 parts by weight of tetrahydrofuran in a thickness of35 20 y using an applicator.

* Trademark -:1 ~48i3 17 g There were provided solutions containing metallocenes Nos. 4 to 6 as indicated in Table 3 in an amount of 10% by weight of polycarbonate resin (Panlite) and Example 1 was repeated to form protective layers for Electro-photographic Members 4 to 6, respectively. The electrical characteristics of 5 these members were measured similarly to Example 1, with good results shown in Table 3.

20 C 50% RH 20 C 95% RH
0 Electrophoto~raphic Member DDPRPDDP RP
No. 4 (Perrocene) 800 45 80540 No. 5 (Nickelocene) 710 35 70530 No. 6 (Dinitroferrocene) 81040810 40 Example 1 was repeated using resin Solutions Nos. 7 to 9 incorporated with the electron accepting materials indicated below, thereby forming protecting layers for Electrophotographic Members 7 to 9.
Solution No. 7 Perrocene 10 g Tetracyanoethylene 6.9 g Polycarbonate (Panlite, a product of 170 g Teijin Chemicals Ltd.) Dichloromethane 1,000 g Solution No. 8 Perrocene 10 g 7,7,8,8-Tetracyanoquinodimethane 11 g Polyurethane (polyuremytilac Clear 550 g Base, a product of Dai Nippon Toryo Co., Ltd.) Solvent (Polyuremytilac thinner)320 g Solution No. 9 Perrocene 10 g

2,3-Dichloro-5,6-dicyano-p-benzoquinone 3.5 g Polyester (Byron, Toyo Spinning Co., Ltd.) 135 g Dichloromethane 1,200 g . ' . : . ' ~ .:.' , . . ::,, ,: .
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--lo--Upon comparing the electrical characteristics of the electrophoto-graphic members using the protective layers obtained from Solutions Nos. 7 to 9 with those of the electrophotographic members using the protective layers from Solutions Nos. 1 to 3, it was revealed that the electrical characteristics 5 were superior compared with those using no electron accepting materials.

20 C 50% RH 20 C 95% RH
Electrophotographic Member DDPRP DDP RP

No. 1 85025 840 25 No. 7 875 0 875 0 No. 2 91040 900 40 No. 8 920 5 920 5 No. 3 97070 950 70 No. 9 95510 955 10 15 While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

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Claims (8)

CLAIMS:

1. An electrophotographic member in which a photoconductive layer and a protective layer are superposed in order on a conductive support, characterized in that said protective layer contains at least one electron acceptor, a binder resin and at least one metallocene or a compound having at least one metallocene nucleus in its molecular structure present in an amount from about 0.01 to 70 wt. %, based on the weight of the protective layer.

2. A member according to claim 1 wherein the metallocene nucleus is present in an amount of from 1 to 50 wt. percent.

3. A member according to claim 1 wherein said metallocene is a metallocene of Fe, Ni, Co, V ?r, or Ti, or said compound hav-ing at least one metallocene nucleus in its molecular structure includes Fe, Ni, Co, V, Cr, or Ti in the metallocene nucleus.

4. A member according to claims 1, 2 or 3 wherein said electron acceptor is present in an amount of from about 0.001 to 2 mols per mol of metallocene or the compound having at least one metallocene nucleus in its molecular structure.

5. A member according to Claims 1, 2 or 3 wherein said electron acceptor is selected from the group consisting of phthalic acid anhydride, tetrachlorophthalic acid anhydride, s-tricyanobenzene, picryl chloride, 2,4-dinitrochlorobenzene, 2,4-dinitrobromobenzene, 4-nitrobiphenyl, 4,4-dinitrobi-phenyl, 2,4,6-trinitroanisole, trichlorotrinitrobenzene, trinitro-o-toluene, 4,6-dichloro-1,3-dinitrobenzene, p-dinitrobenzene, chloranyl, bromanyl, tetra-cyanoethylene, hexacyanobutadiene, tetracyanoquinodimethane, benzoquinone and halo-or cyano-derivatives thereof, aromatic or heterocyclic compounds substituted with a nitro group, a sulfo group, a carboxyl group, or a cyano group, and monomers or polymers of 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitrofluorenone, trinitroanthracene, dinitroacridine, tetracyanopyrene, and dinitroanthraquinone.

6. A member according to Claim 1, 2 or 3, wherein said binder resin is a polyurethane resin, a polystyrene resin, a polycarbonate resin, a polyester resin, an acrylic resin, a silicone resin, a vinyl chloride resin, a polyvinyl acetate resin, a cellulose ester resin, a nitrocellulose resin, or an alkyd resin.

7, A member according to Claim 1, 2 or 3, wherein said protective layer is about 0.5 to 50 µ thick.

8. A process for forming a latent image characterized in using an electrophotographic member as in Claim 1, 2 or 3, wherein said member is first uniformly charged and then imagewise exposed.