JPS5938752A - Electrophotographic receptor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor. In particular, the present invention relates to a positively and negatively chargeable electrophotographic photoreceptor containing a copolymer compound containing 11F lead oxide and a carbazole group as an active ingredient.

As a technique for imparting charging ability and photoresponsiveness to both positive and negative polarities to a zinc oxide photoreceptor, for example, the following technique is conventionally known.

■) Using zinc oxide heat-treated in hydrogen sulfide (US Patent No. 3,060.134) 2) Using zinc oxide heat-treated in the presence of hydrogen sulfide and ammonia gas (
3) Impregnating the photoconductive layer with an inorganic acid salt of manganese or cobalt (fl' JP 52-3303) 4) Impregnating the photoconductive layer with an organic manganese compound (Photogra
phic 5science and Engine
ee mouth ngvol, 16 11231 (1972)).

5) Using poly-N-vinylcarpanol as a binder for zinc oxide (circle+olographic Scn
ccand Engineering vol, 25
P39 (1981)).

6) A copolymer compound containing 50 to 95% acrylic acid alkyl ester and 1 to 5 organic acids having a vinyl group is used as a binder (#!i Kosho 51-16148).

The following techniques are known for imparting positive chargeability and photoresponsiveness to a luxurious zinc oxide photoreceptor.

7) A photoreceptor with a laminated structure consisting of a charge generation layer containing a sensitizing dye and a charge transport layer in which zinc oxide powder is bonded with a resin having a refractive index of 159 or more (Japanese Patent Application Laid-Open No. 55-60953). All of the prior art techniques 1) to 7) have problems in manufacturing and/or in the characteristics of the photoreceptor. For example, in 1) and 2), zinc oxide is also treated with a toxic substance called hydrogen sulfide, so special manufacturing equipment is required, and the allowable range of zinc oxide treatment conditions for the suspension is extremely limited to ensure good photoreceptor properties. In order to impart i/i charging ability in 3) and 4), photosensitivity decreases when the amount of additives is increased, and in 5) to obtain practical photosensitivity, poly- As the amount of zinc oxide added to N-vinylcarpanol increases, the two-banded heavy state virtually disappears (8) shows that the photosensitivity is slow, and (7) shows that the stacked layer consisting of a charge generation layer and a charge transport layer The problem is that the structure is difficult to manufacture because it is provided by coating. In particular, a characteristic problem common to the conventional technology is that the photosensitivity of the photoreceptor is slow, so the practical use of the photoreceptor is limited to photosensitive paper for direct copying machines, and P I) C, which can be used repeatedly. It had not been applied to photoreceptors for copying machines.

In view of the above circumstances, the present invention provides oxidation 111 for both positive and negative polarities.
The present invention was developed as a result of extensive research to solve various problems with E-lead photoreceptors.

That is, an object of the present invention is to provide a zinc oxide photoreceptor having practical charging ability and photoresponsiveness for both positive and negative polarities.

Another object of the present invention is to provide a zinc oxide photoreceptor that has excellent repeat durability. Another object of the present invention is to provide a zinc oxide photoreceptor that is inexpensive, non-polluting, and easy to manufacture.

The object of the present invention described above is (1) to prepare a copolymer compound containing zinc oxide, a carbazole group, and the following general formula (1) on a support for an electrophotographic photoreceptor.
) A positively and negatively charging electrophotographic photoreceptor characterized by being provided with a photoconductive layer containing a compound represented by the general formula (1), where R+, R2, Ra, and R4 are hydrogen atoms,
Substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group or aryl group, USIu is a hydrogen atom,
substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group or aryl group,
R7,R8゜R9,1L+o represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, or an amine group, and 1 (5 and The rings 6 may be cyclized with each other to form a saturated or unsaturated hydrocarbon ring having 3 to 10 carbon atoms.

2) The copolymer compound containing a carbazole group is a copolymer of N-vinyl carbazole A and a monomer I3 which is copolymerizable with A and does not contain a carbazole group,
13 is an acrylic acid ester, a methacrylic acid ester, an organic acid vinyl ester, a styrene, an N-vinyl-2-pyrrolidone 11゛ (71′ selected from -,
i,, i: and the composition molar ratio of the copolymer is A:13
- A positively and negatively chargeable electrophotographic photoreceptor, characterized in that the ratio is in the range of -95:5 to 50:50.

3) The composition ratio of the copolymer compound containing a carbazole group in the photoconductive layer is 50 weight/ξ-cents or more relative to zinc oxide. Next, the present invention will be explained in detail.

A feature of the present invention is that a copolymer compound containing a carpanol group (hereinafter abbreviated as lupasol copolymer compound) is used as a resin binder for zinc oxide, and at the same time, a compound represented by general formula (1) is used as a resin binder for zinc oxide. The process is to create a photoreceptor by adding The present inventor previously discovered that zinc oxide-bo IJ
It has been found that the charging ability of a -N-vinylcarbazole photoreceptor (prior art (5) described above) in positive and negative corona discharge can be arbitrarily controlled by adding compound (1) (Japanese Patent Application No. 1987- 126753), by using a carbazole copolymer as a binder instead of poly-N-vinylcarbazole as a binder for zinc oxide and further adding compound (1), the charging ability during positive and negative charging and We found that the photoresponsiveness was dramatically improved. At the same time, the adhesion of the photoconductive layer to the support and the flexibility of the photoconductive layer were significantly improved, and the present invention was completed after confirming that the photoreceptor had comprehensive characteristics that were sufficiently practical.

The carbazole copolymer suitable for the present invention is a copolymer compound of N-vinyl carbazole A and a nutrient B which is copolymerizable with A and does not contain a carpanol group, and 13
is a monomer selected from the group consisting of acrylic esters, methacrylic esters, organic acid vinyl esters, styrenes, and N-vinyl-2-pyrrolidone. Specific examples of monomers effective in the present invention are listed below, but the invention is not limited to these compounds.

A: N-vinylcarbasol, 3.6-ychloro-N
-vinyl carbazole, 3. (5-) Brom-N-vinyl force a, 6-/+yo IF -N
-Hinylcarnoζ sheet b,, 3-chloro-N-vinylcarbasonope 3-bromo-N-vinylcarbazole, 3-yoP-N-vinylcarbazole, 3-amino-
N-vinylcartumazole, 3-methylamino-N-vinylcarbazole, 3-methylamino-N-vinylcarbazole, 3-nitro-N-vinylcarbazole,
9-arylcarbazole and the like.

13 Methyl acrylate, ethyl acrylate, 11-propyl acrylate, isozorobyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid + (
・l-Butyl, acrylic acid/chlorhexyl, 2-ethylhexyl acrylate, octyl acrylate, acrylic acid: 3-trimethylaminoethyl, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, acrylic acid 24-) Estenope acrylates such as nitrophenol, methyl methacrylate, ethyl methacrylate,
n-propyl methacrylate, inzolopyl methacrylate, n-butyl methacrylate, isobutyl methacrylate,
terl -butyl methacrylate, rhohexyl methacrylate, octinope methacrylate 2-diethylaminoethyl methacrylate, 2-)methylaminoethinope methacrylate 2
Methacrylic acid esters such as 4-dinitropheninope.

Vinyl formate, vinyl acetate, vinyl propionate = /L/,
11- Organic acid vinyl esters such as vinyl butyrate, vinyl caprate, vinyl caprate, vinyl laurate, vinyl phenyl lumitate, vinyl stearate, vinyl trimethylacetate, vinyl benzoate, and vinyl 35-dinitrobenzoate.

Styrene, α-methylstyrene, 0-methylstyrene,
Styrene and its derivatives such as m-methylstyrene, p-methylstyrene, 0-methoxystyrene, 1o-methoxystyrene, p-methoxystyrene, 1n-dimethylaminostyrene, p-tsumethylaminostyrene, N-
Vinyl-2-pyrrolidone, etc.

The above carbazole copolymer can be synthesized using a known method such as a radical polymerization method or a cationic polymerization method. Monomer A in Cal, S sol copolymer
It is necessary that the compositional molar ratio A 50 95 (1) of B and A 50 95 falls within the range of 100 to 100%.

0 If the composition molar ratio is less than 50%, the photoresponsiveness during positive charging will decrease and a residual potential will occur, while if the composition molar ratio exceeds
- Differences in properties from vinyl carbazole become smaller and the effects of the present invention disappear. The monocarbazole copolymer desirably has a degree of polymerization capable of forming a film, and although this degree of polymerization varies depending on the composition of the copolymer, it is generally sufficient that it is about 200 or more.

Next, specific examples suitable for the present invention as compounds represented by the general formula (+) are listed below.

1, tl-bis(4-N,N-dimethylaminophenynoly-1-phenylmethane) 2, 1.1-bis(4-N,N-dimethylamino-2
-methylphenyl)-1-phenylmethane 311-bis(+-N,N-tmethylamino-2-methylphenyl)-1-(2-chlorophenyl)methane 4,
1.1-bis(4-N,N-trimethylamino-2-methylphenyl)-1-(4-methoxyphenynolimethane5, 1.1-bis(4-N,N-trimethylaminophenyl)-1 -(4-hydroxyphenyl)methane 6, 1.1-bis(4-N,N-dimethylaminophenyl)-1-(24-dimethoxyphenyl)methane 7,
11-bis(4-N,N-dimethylamino-2-ethylphenyl)-1-phenylmethane8, 1.1-bis(4-N,N-dimethylamino-2-ethylphenyl)
-methoxyphenyl)-1-phenylmethane 9, 1.1-bis(4-N,N-dimethylamino-2
-ethoxyphenyl)-1-phenylmethane 10, 1.1-bis(4-N,N-diethylaminophenyl)-1-phenylmethane 1111-bis(4-N,N-diethylamino-2-methylphenyliv)- 1-phenylmethane 12, 1.1-bis(4-N,N-diethylamino-
2-Methylphenyl)-1-(2-chlorophenyl)methane 18.1-bis(4-N,N-diethylamino-2-methylphenyl-1-(4-methoxyphenyl)
Methane 14, 1.1-bis(4-N,N-diethylaminophenyl)-1-(4-hydroxyphenyl)methane 15.1-bis(4-N,N-diethylaminophenyl)-1-(2 ,4-,)methoxyphenyl)methane 16, 1.1-bis(4-N,N-diethylamino-
2-ethylphe=)v) -1-phenylmethane 1711-bis(+-N,N-diethylamino-2-methoxyphenyl)-1-phenylmethane 18, 1.1-bis(4-N,N-diethylamino-
2-ethoxyphenyl)-1-phenylmethane 19, 1.1-bis(4-N,N-diethylamine-
2-methylphenyl)-1-(2,6-,)-rephenyl)methane 201゜l-bis(4-N,N-diethylamino-25-)methoxyphenyl/l/)-1-phenylmethane 21, 1.1-bis(4-N,N-nopendylaminophenynoly-1-phenylmethane22, 1.1-bis(4-N,N-dibenzylamino-2-methylphenynoly-1-phenylmethane) 2311-bis(4-N,N-dibenzylamino-25
-Tmethylphenyl)-1-phenylmethane
324 1.1-bis(+-N, N-dibenzylamino-2-methoxyphenyl)-1-phenyl #7 32511-bis(+-N
, N-trimethylamine-2-methylphenyl)-1-(
2,4-Jmethoxyphenyl)methane 3.26,
1.1.1-) Lis(4-N,N-dimethylaminophenyl)-1-phenylmethane
3127, 1. ],, ]1-tris4-
N,N-dimethylamino-2-methylphenylinomethane 3 (28, 1,
1-bis(4-N,N-diethylamino-25-dimethylphenyl)-1-(4-N,N-,diethylaminophenyl 3'i norimethane 29, 1.1-bis(4-N,N-diethylamino-25-dimethylphenyl) -2-methylphenyl 3 and enynoly-1-(4-N,N-dimethylamine-2-chlorophenynolimethane)
3930, 1.1-bis(+-N,N-diethylamine-2-methylphenyl)-1-(4-N,N-,dimethylamine-2-methyl40lphenyl)methane 3111-bis(4-amino- 2-methylphenyl)-
1-41(4-N,N-dimethylaminophenyl)methane 211-bis(4-amino-25-tmethylphenyl)-1-(4-N,N-,)methylaminophenyl)methane 3.1- (+-N, N-, dimethylaminophenyl) -1,1,1-triphenylmethane L, 1-(4-N, N-diethylaminophenyl) -
1,1,1-triphenylmethane, 1.1-bis(4-N,N-2 methylaminophenyl)-11-diphenylmethane; 11-bis(+-N,N-2 ethylaminophenyl)- 1,1-diphenylmethane 1,1-bis(4-N,N-dibenzylamino-2-
methylphenyl)-1-cyclohexylmethane 1.1-
Bis(4-N,N-diben,dylamino-2-methoxyphenyl)-1-cyclohexylmethane 1,1-his(
4-N, N-)hendylaminophenynolyl-
Cyclohexylmethane 1,1-bis(4-N,N-nobenzylamino-25-
) methylphenyl)-1-cyclohexylmethane 11-
Bis(4-N,N-dibenzylamino-25-nomethymphenyl)-1-cyclohexylmethane 4211-Bis(3-N,N-diethylamino-4-methylphenyl)-1-phenylmethane 481 Bis(4- -N,N-diethylamino-2-
Methylaminolihebutane 441-bis(4-N,N-diethylamino-2-methoxyphenyl)-2-methylamino Methane 46 α, α, d, α′-tetrakis(+-N,N-noethylamine-2-methylphenyl)-p-xylene 4
711-bis(4-N,N-diethylamino-2-ethylphenyl)-2-phenylethane 48, 1.1.5.5-tetrakis(4-N,N-dimethylamine-2-methylphenyl)pentane 1 , 1.1-bis(4-N,N-diethylamino-2
-ethylphenynolyΦ-methylcyclohexane 5011-bis(4-N,N-dimethylamino-2-methylphenyl)cyclohexane 5111-bis(4-N-ethyl-N-methylamino-
2-methylphenyl)-3-methylcyclohexane 52
, 1.1.2.2-tetrakis(+-N,N-dimethylamine-2-methylphenyl)ethane53, 1.1-bis(4-N,N-diethylamino-2-methylphenyl)-3-phenyldi 0/8-5411-bis(4-N,N-dibenzylamino-2-
methylphenyl)pentane 55.1. l-bis(4-N,N-dibenzylamino-
2-Methoxyphenyl)-2-#-Ruzolonoξ 56, 1.1-Bis(4-N,N-dibenzylamino-2-methylphenyl)cyclohexane 5711-Bis(4-N,N-dibenzylamino -2-
58, 1.1-bis(4-N,N-diben,/;ruamino-2-methylphenyl)n-butane 59, 1.1-bis(4-N,N-dibenzylamino- 2-methoxyphenyl)pronoξne 60, 1.1-bis(4-N,N-2pennolamino-2-methoxyphenyl)n-butane 61, 1.1-bis(4-N,N-diethylaminophenyl)hezotane 6211-bis(4-N,N-dimethylaminophenyl)-2-methylzolonone63, 1. , l-his(4-N,N-dibenzylaminophenyl)penta/6411~bis(+-N,N-dibenzylaminophenyl)-2-methylzolonoξn05, 1. , l-bis(4-N,N-dibenzylaminophenyl)/chlorohexane 66, 1.1-bis(4-N,N-dibenzylaminophenyl)zolono(i7. 1.1-bis (4-N, N-dibenzylaminophenyl) normal butane 68, 1., l-bis(+-N, N-dibenzylamino-2,5=:; methylphenynolyhebutane 09, 1.1-bis( 4-N,N-2benzylamino-2,5-5;5methylphenyl) normal butane?0.1,1-bis(4-N,N-dibenzylamino-2,5-,/'methoxyphenyl) Normal butane?111-Bis[4-N,N-di(p-tolyl)aminophenyl]cyclohexane 7222-bis[4-N,N-di(p-tolyl)aminophenyl]zolonoS 7311-bis [4-N,N-di(p-tolyl)aminophenyl]-1-phenylethane 741 -bis[4-N,N-)(p-tolyl)aminophenyl]-1,1-)phenylethane 75 ■1-bisC4-N,N-no(p-tolyl)aminophenylcomethane 7(i, 1.1-bisC4-N,N-di(p-tolyl)aminophenyl]-1-phenylmethane 7711 -bis[4-N,N-di(p-tolyl)aminophenyl] -4-tcrt -butylcyclohexane 78 ■1-bis[4-”,N-,)(p-)yl)aminophenyl]-2 -Methylzolononξone 7911-BisC4-N+N-)(p-tolyl)aminonoenyl]ethane 8θ 11-bis[4-N,N-di(p-tolyl)aminophenyl]-8-methylbutane81.1.l- Bis [Φ-N, N-, di(p-tolyl)
Amino-2-methylphenyl]ethane 82, 1. , l-bis[cow-N,N-di(p-tolyl)amino-2-methylphenylcocyclohexane 83, 1.1. -His(4-N,N-,;;benzylaminophenyl)ethane8411-Bis(4-N,N-dibenzylaminophenynorilalopane8511-bis(4-N,N-dibenzylaminophenyl)n Butane 8(+, 11-bis(4-N+N-dibenzylaminophenyl)-2-methylbutane 871-bis(4-N,N-dibenzylaminophenyl)-■-hexane 88, 1.1-bis(4 -N,N-dibenzylaminophenynoly2-ethylhexa/8911-bis(4-N,N-dibenzylaminophenyl)-'1-dobgan90, 1,1-bis[small-N+N-7 (p-tribenzyl)aminophenyl]ethane9111-bis[hand-N,N-di(0-chlorobenzyl)anophenyl]-0-butane92.1.l-bis[4-N,N -di(p-bromobennor)aminophenyl 1-n-butane' 93. 1.1-bis[4-N,N-,di(
p-Methylbenzinolyaminophenyl]zomisaki 94.1. l-bis[4-N,N-di(p-nitrobenzyl)ami/phenyl]-2-ethylhexane95, 1.1-bis(4-N,N-dibenzylamino-2-methylphenynolimethane) 9611-bis(4-N,N-dibenzylamino-2-
Ethylphenynolimethane 97, 1,1-bis[4·-N,N-di(p-chlorobenzyl)amino-2-ethylphenyl]methane 9811-bis(+-N,N-dibenzylamino-2-
methylphenyl)ethane 99, 1.1-bis(4-N,N-nobennolamino-2-ethylphenyl)ethane' 100. 1.1-bis(4-N,N-dibenzylamino-2-methylphenyl)zoronoξ' 101. 1.1-bis(4-N,N-di(0-
Chlorbenzyl)amino/-2-ethylphenyl)solonξone102. 1. , l-bis(4-N,N-dibenzylamino-2-methylphenyl)butane [131,1-bis(4-N,N-di(p-chlorobenzyl)amino-2-ethylphenyl)butane 1 (+4.1-bis(+-N,N-dibenzylamino-2-methylphenyl)-2-methylpropane105.1.1-bis(4-N,N-,dibenzylamino-2- methoxyphenyl)butane 100, ],]1-bis4-N,N-dibenzylamino-2-methylphenyl)hezotane 107, 1. , l-bis[4-N,N-di(p-tolylamino)-2-methoxyphenyl]hebutane[18,1,1-bis(4-N,N-dibenzylamino-2-methylphenyl)hexane 109.2-bis(4-N,N-dibenzylamino-2-methylphenynobutane) 110 2.2-bis(4-N,N-dibenzylamino-2-methylphenyl)prono The electrophotographic photoreceptor of the invention is produced by using zinc oxide powder together with the above carbazole copolymer, a compound represented by the general formula (+), and a dispersing solvent using a dispersing machine such as a ball mill, attritor, kedimir, sand mill, or three-roll mill. Mix and disperse uniformly to prepare a photoconductive layer coating solution (-1
This coating liquid is applied onto a support for an electrophotographic photoreceptor using a coating machine such as a blade coater, Ronto coater, knife coater, reverse roll coater, Tinozo coater, or spray coater, and then dried. be done.

A conductive support is used as the support for the electrophotographic photoreceptor. More specifically, metal plates such as aluminum, nickel, and chromium; metals such as aluminum, nickel, and ξranium deposited or splattered on paper or plastic; and metal foils such as aluminum and paper. Alternatively, materials laminated with silastic film, carbon-mixed paper, low-resistance paper coated with and/or impregnated with an organic or inorganic conductive treatment agent, glass with a conductive transparent film such as soot oxide or indium oxide. A board etc. can be used. Further, the shape of the support may be selected from a seven-piece belt, a long low-knope endless belt, an endless belt, a drum, and the like.

As the zinc oxide powder constituting the photoconductive layer, those conventionally used in electrophotographic photoreceptors can be used to the same extent. Furthermore, conventionally known dye sensitizers for zinc oxide can be used. Among these, dye compounds having a xanthine skeleton or a triphenylmethane skeleton and having a difficult acid group or a lactone ring are preferred from the viewpoint of solubility and adsorption to zinc oxide. Particularly suitable dye sensitizers include dibromofluorescein, Joe 15 fluorescein, tetrachlorfluorescein, tetrabromofluorescein, tetraiodofluorescein, tetrachlortetraiodofluorescein, tetrabromtetraiodofluorescein, bromophenol blue, tetrabromophenol blue, Examples include tetraiodophenol sol, bromothymol blue, and bromocresol bar blue from cresol green.

The amount of dye sensitizer added to zinc oxide is 1 (1
It is effective to use 10-31 parts to 5 parts by weight per 0 parts by weight, and a particularly preferable addition amount is 10-2 parts by weight to 2 parts by weight. As a method for adsorbing the dye sensitizer onto zero lead oxide, known techniques can be used. Of these, a coating solution prepared by dissolving the pigment in a suitable solvent and adding 1F lead oxide is thoroughly mixed and dispersed in a ball mill etc. to obtain 111t oxide, Saito +
f + iM This dye is adsorbed, and then this coating liquid is used to remove the solvent of the dye solution and prepare zinc oxide powder (hereinafter abbreviated as sensitized 111-lead oxide) on which the dye has been adsorbed on the surface. This method is a dye adsorption method suitable for the present invention. The solvent of the dye solution can be removed by Δ゛1 filtration, heat drying, freeze drying, spray drying, or Japanese Patent Publication No. 5G-398.
All 19 techniques are effective.

Solvents used for preparing the coating solution for the photoconductive layer include benzene, toluene, quinolene, aromatic hydrocarbons, methylene chloride, halogenated hydrocarbons such as 12-dichloroethane, chloroform, monochlorobenzene, tetrahydrofuran, Cyclic ethers such as 4-nooxane, 7-chlorohexanone, and mixed solvents thereof can be used.

The blending ratio of Cal/ζ-nol copolymer to zinc oxide is 50 parts by weight of carbazole copolymer per 100 parts by weight of zinc oxide.
Parts by weight or more are required.

If the blending ratio of the carbazole copolymer is less than 50 parts by weight, practical charging ability cannot be improved.

The blending ratio of the compound represented by the general formula (1) varies depending on the blending ratio of the copolymer and the composition of the copolymer, but
Generally, 5 parts by weight to 40 parts by weight per 100 parts by weight of zinc oxide.
0 parts by weight is preferred.

The thickness of the photoconductive layer formed on the electrophotographic photoreceptor support as described above is 5 μm to 100 μm, preferably 10 μm to 50 μm.

The electrophotographic photoreceptor of the present invention produced in this manner has charging ability, photosensitivity, and mechanical strength sufficient for practical use in corona discharge of both positive and negative polarities. Furthermore, since the blending ratio of the cal/ζ sol copolymer, which functions as a binder, is 500 parts by weight relative to tlli lead oxide, the durability against repeated use is extremely good. Further, the photoreceptor of the present invention has no problem of toxicity including the raw materials. Therefore, the electrophotographic photoreceptor of the present invention is suitable for use in yen)() type electrophotographic copying machines, and particularly as a photoreceptor for PPO type microfilm readers and printers that produce copies from negative and positive microfilms. Furthermore, it can be applied as a photoreceptor for a two-color color copying machine or a photoreceptor for a PPCE type color cylinder making machine.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited by these examples.

Preparation of sensitized zinc oxide 1.0 parts by weight of tetraiodofluorescein is added to 100 parts by weight of tetrahydrofuran and completely dissolved. Next, 100 parts by weight of zinc oxide powder (Sakai Chemical Industry Co., Ltd. Sazenox 4-000) was added to this solution, and the mixture was placed in a porcelain ball mill and mixed and dispersed for 3 hours.Then, the resulting coating liquid was transferred to a beaker. , completely evaporate the tetrahydrofuran while stirring at 70'C.
．． Oxidized IJr stained with detraiodofluorescein
i Lead powder was used as sensitized zinc oxide in the following Examples and Comparative Examples.

Method for Preparing Photoreceptor A predetermined amount of carbazole copolymer is dissolved in a predetermined amount of methylene chloride. A predetermined amount of the compound of general formula (1) is added and dissolved in this solution, and then a predetermined amount of the above-mentioned sensitized zinc oxide is added, and the mixture is placed in a porcelain ball mill and dispersed for 2 hours. The resulting coating liquid was applied to the aluminum side of a laminated film made by bonding polyethylene terephthalate and aluminum together using a blade coating method to a dry thickness of 25 μm, and dried at 110°C for 30 minutes to form a photoreceptor. create.

Method for Measuring Electrostatic Charging Characteristics The electrostatic charging characteristics of the photoreceptor were measured using an electrostatic copying paper tester (model 5P428 manufactured by Kawaguchi Electric Seisakusho Co., Ltd.). Attach the sample to the test equipment by charging the sample under the conditions of corona discharge voltage ± (i, OkV, scanning speed 25 (1 mm/s), and measure the potential ■0 [4] immediately after charging. Then, after dark decaying for 5 seconds ( Potential v5 [■''), color temperature 2854°, 1 illuminance 51u
The amount of exposure necessary to attenuate the surface potential by 50% by irradiating light on the tungsten layer x, i.e., half the exposure) j'
(', l'+ l/21- l II X・Sec
] is recorded as the photosensitivity. Ushita l 50 [-1LI
Xsec] The potential after irradiation is the residual potential Vu[,V]
Measure as.

Example 1 A copolymer of N-vinylcarbazole (A) and 11-butyl acrylate (13) (composition molar ratio A/il = 90710) was used as the tunorpazole copolymer, and the formula of general formula (1) was used. Compound 411 [],, as a compound
l-bis(4-N,N-diethylamino-2-methylphenyl)-1-phenylmethane] Photoreceptor samples 1 to 5 with different blending ratios of compound/1611 and carbazole copolymer according to the following formulation It was created.

Table 1 shows the measurement results of the electrostatic charging properties of the samples.

Table 1 As is clear from the results in Table 1, the positive and negative charging potentials increase in proportion to the amount of Compound 11 added. It is also seen that the optimum value for photosensitivity E1/2 exists in the amount of compound/l611.

Example 2 Using the copolymer used in Example 1 as the carbazole copolymer and compound 1622 as the compound of general formula (1), the carbazole copolymer and sensitized zinc oxide were combined according to the following formulation. Photoreceptor samples 7 to 11 were prepared with different blending ratios, and the electrostatic charging characteristics were measured. The results are shown in Table 2.

As is clear from Table 2, by setting the blending ratio of carbazole copolymer to sensitized zinc oxide to 50% by weight or more, a practical surface potential (1 Vol) of 300 [4] can be achieved.
It was raised.

Example 3 A copolymer shown in Table 1 was used as a carbazole copolymer, and compound 430 (
1,1-bis(4-N,N-diethylamino-2-methylphenyl)-1,-(4-N,N-dimethylamine-2-methylphenyl)methane] and prepared samples 12 to 20f according to the following formulation. :Created.

The electrostatic charging characteristics are shown in Table 4.

Table-3 12N-vinylcarpanol-n-butyl methacrylate copolymer (composition molar ratio 40/54
) 12t N-vinylcarbazole-n-butyl methacrylate copolymer (composition molar ratio 7
1/29) 1Φ N-vinylcarbazole-n-butyl methacrylate copolymer (composition molar ratio 96/4) L5 N-vinylcarbazole-acrylic acid-〇-octyl copolymer (composition molar ratio 68/32) 1 (i N-vinylcarbazole-vinyl stearate copolymer (composition molar ratio 90/l O) 17: 5-) Brome-N
-Vinylcarbazole-acrylic acid-fl-butyl copolymer (composition molar ratio 75/25) 18"A
, ('r-)bromo-N-vinylcarpanol-α-methylstyrene positive polymer (composition molar ratio 73/27)
J9 3.6-diiodo N-vinylorganol-11-octyl acrylate copolymer (composition molar ratio 7
8/22) 20 N-vinyl carboxy--N-vinyl-2-pyrrolidone copolymer (composition molar ratio 65/35) From Table 4, when the copolymer composition molar ratio A/13 becomes 5o150 or less (sample 12) The photoresponsiveness during positive charging is decreased, and a decrease in sensitivity and an increase in residual potential are observed. Moreover, when the composition molar ratio A/l'3 exceeds 9515 (sample 14)
The positive and negative chargeability decreased, and practical characteristics could not be changed.

Example 4 The copolymer used in Sample 17 of Example 3 was selected as the h-lupanol copolymer, and the compound of general formula (1) was
Photoreceptor sample 2 was prepared using the compound shown in 5 according to the following formulation.
1 to 26 were created.

The electrostatic charging characteristics are shown in Table-5.

Table 5 It was found that all of the photoreceptor samples in Table 5 had practical charging potential and photosensitivity in both positive and negative charging.

Example 5 Photoreceptor sample 23 of the Example Committee was installed in a commercially available Carlson type selenium RPC copying machine, and positive charging - image exposure - two-component dry development - plain paper transfer - A (by repeating 3 static elimination - fur brush cleaning) As a result of a running test, good image characteristics were shown up to 10,000 cycles.

Example 6 The photoreceptor sample 23 of Example 4 was installed in a commercially available Carlson type IIF lead oxide C copying machine, and the photoreceptor sample 23 was subjected to negative charge-image exposure-two-component dry development-plain paper transfer-A O static elimination-fur As a result of a running test with repeated brush cleaning, it showed good image characteristics after 10,000 cycles.

patent applicant Tomoekawa Paper Mill Co., Ltd.

Claims (1)

[Scope of Claims] 1) A copolymer compound containing zinc oxide and a cal-guzole group and the following general formula (1) on a support for an electrophotographic photoreceptor;
) A positively and negatively chargeable electrophotographic photoreceptor characterized by being provided with a photoconductive layer containing a compound represented by the general formula (1), where ribs, IL2. Formerly, IL4 is a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl or aryl group, ILs, R6 is a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group,
Alkenyl group, cycloalkenyl group or aryl group, R? , Rs, R9, Rh. represents a hydrogen atom, a hydrogen atom, a hydroquine group, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, or an amine group; and R6 are cyclized with each other and have a carbon atom number of 3 to 1. (
may form one saturated or unsaturated hydrocarbon ring. 2) The copolymer compound containing a carpanol group is a copolymer with a monomer 11 which is copolymerizable with N-vinylcarbazoles A and 8 and does not contain a carbazole group,
13 is a monomer selected from the group consisting of acrylic acid ester, methacrylic acid ester, organic acid vinyl ester, styrene i, and N-vinyl-2-pyrrolidone, and the composition molar ratio of the copolymer is A:11-・95:5~50:50
'Jf: The positively and negatively chargeable electrophotographic photoreceptor according to claim 1. 3) The positive and negative components according to claims 1 and 2, characterized in that the composition ratio of the copolymer compound containing a carbazole group in the photoconductive layer is 50% by weight or more based on zinc oxide. Chargeable electrophotographic photoreceptor.