JPS58186747A - Electrophotographic receptor - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic receptor having high sensitivity and enabling repeated use by forming a photoconductive layer consisting essentially of zinc oxide, a compound having a carbazole group, and a specified compound on a support. CONSTITUTION:A photoconductive layer consisting essentially of zinc oxide, a compound having a carbazole group, and a compound represented by the formula is formed on a support at least the surface of which has electric conductivity to obtain an electrophotographic receptor. The compound having a carbazole group is a copolymer compound of a monomer A contg. a carbazole group with a monomer B copolymerizable with the monomer A and contg. no carbazole group. The receptor has very high sensitivity, a long life in repeated use and no toxicity, and it causes no pollution. In the formula, each of R1-R6 is H, optionally substituted alkyl, cycloalkyl, alkenyl or aryl, and each of R7-R10 is H, halogen, hydroxyl, optionally substituted alkyl, cycloalkyl, alkenyl, aryl, alkoxy or amino.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a reusable electrophotographic photoreceptor containing as active ingredients a compound containing zinc oxide and a carbazole group.

Conventionally, the photosensitive layer used in electrophotographic photoreceptors contains selenium,
Inorganic photoconductive materials such as cadmium sulfide and zinc oxide are widely used.

However, when using these inorganic materials as electrophotographic photoreceptor materials, there are still problems that need to be solved. For example, in a photoreceptor using seleno as a photosensitive material, the sensitivity range in the visible light wavelength range is limited, and as a solution to this problem, it is thought to expand the spectral sensitivity range by adding tellurium or arsenic. It is being However, the addition of tellurium, arsenic, etc. may expand the spectral sensitivity range, but it may also cause drawbacks such as lowering the crystallization temperature and increasing the dark decay rate, increasing optical fatigue, and increasing the spectral sensitivity range. When copying is carried out, an unstable image forming material is obtained in which the image of the previous document is likely to be copied as an afterimage.

Further, when a photoreceptor using seleno is continuously exposed to corona discharge, surface crystallization is induced, which often results in a decrease in electrical characteristics. Anotimono and the like are added to improve these properties. However, seleno, tellurium, arsenic, and chichimono are not harmless to the human body, and there are safety problems.

On the other hand, electrophotographic photoreceptors that use photoconductive materials such as zinc oxide and cadmium sulfide have a photoconductive layer in which fine particles of zinc oxide or cadmium sulfide are uniformly dispersed in a suitable binder resin. It is formed.

This photoconductive layer is a dispersed system, and due to complex interactions with the resin, there are many factors that govern its electrical, photoconductive, or physical properties, and a photoconductive layer with the desired properties can be obtained. is a difficult situation. In addition, since a dispersed system generally forms a porous layer with many voids, deterioration due to excessive current is likely to occur during corona charging, and its characteristics deteriorate rapidly, especially in a high humidity atmosphere, resulting in poor quality of copied images. This results in a significant decrease in quality. In addition, small pores in the photosensitive layer allow toner to enter during development, reducing its cleaning performance and forming a rough surface, resulting in poor mold releasability and a reduction in surface strength.

Recently, much research has been conducted on using organic compounds as new materials to replace inorganic photoconductive materials. This organic photoconductive material has many superior properties compared to inorganic materials, and has a wide range of applications in the field of electrophotography. For example, flexible photosensitive films and notebook-shaped films can be easily obtained, and they are lightweight and easy to handle. However, these organic materials have many drawbacks that need to be solved. For example, organic photoconductive materials generally have lower mobility of carriers generated by light than inorganic materials, and therefore require a greater burden on copying machine systems. When a vacuum deposition technique is required for layer formation, costs increase due to a decrease in yield due to a decrease in productivity and a decrease in reproducibility due to crystal polymorphism of the organic compound. Alternatively, compounds with the ability to transport charge carriers generated by light can be used as polymeric materials.
・In organic photoreceptors of the ``type'', the polymer matrix I-IJ wax glass transition temperature T
2 (e.g. M, Abkowitz et a
l, Journal of Applied Phys.
ics Vol, 52 P3453 (1981)) There is a decrease in characteristics such as an increase in the dark decay rate. Furthermore, phase separation of the charge transport material due to temperature occurs, causing a decrease in sensitivity.

On the other hand, examples of using polymer compounds as organic photoconductive materials are also known. A typical example thereof is poly-N-hinylcarhanol (PVK).

However, the spectral sensitivity region of PVK is in the ultraviolet region, and some kind of sensitization is required to apply this to electrophotography. Furthermore, serious drawbacks of PVK include its flexibility and poor adhesion to the support. Therefore, many efforts are required to use P V K as an organic photosensitive material.

There are several examples of studies on the synthesis and physical properties of N-hinylcarbadul copolymers with the aim of improving the coating properties of PVK and adhesion to substrates [e.g., M., DANIBL et al.
etal,, Journal of polymer
Science Vol, 15p57] (1977))
However, in this case, although the coating properties of the copolymer are improved, the photoconductive properties are significantly degraded, making it impossible to put it to practical use.

In addition, as a method using organic photosensitive materials, the carrier generation function and the key-IJ transport function are provided in separate layers.
A technique for creating a so-called functionally separated photoreceptor is known, but in this case too, problems arise due to the low mobility of photocarriers in the organic material phase and the injection of photocarriers between the charge generation layer and the charge transfer layer. It is not easy to obtain a useful photoreceptor as there are many cases where problems arise. Further, as an example of a single-layer type functionally separated photoreceptor, a technique is known in which an organic photoconductive material is dispersed in a polymer 7 trix to form a eutectic complex with a matrix to generate light carriers. (For example, Japanese Patent Application Laid-Open No. 47-10785
, JP-A-50-16538, JP-A-51-t-8822
6, etc.) However, this type of photoreceptor has the disadvantage that the eutectic complex formed lacks heat resistance. or,
As an example of a pigment-dispersed organic photoreceptor, a photoreceptor in which a relatively small amount of photoconductive particles (such as cadmium selenide) is dispersed in an activated 7-trix resin (PVK/TNli'') is known.

(For example, JP 53-2093O, USP 376431
5) However, this system cannot be said to have sufficient photosensitivity, and
It is not practical due to the poor coating properties of PVK and the toxicity of 'II'NF'.

The present inventors hereby provide a technique for obtaining a new photoreceptor that improves the disadvantages of organic and inorganic photosensitive materials without impairing their advantages. That is, carbazole
A copolymer compound obtained by copolymerizing monomer A containing a carbazole group and monomer B, which is copolymerizable with humans and does not contain a carbazole group, is used as a polymer 7trix, and is Zinc oxide, which obtained spectral sensitivity in the visible range, was
The present invention provides an electrophotographic photoreceptor that is dispersed in a trix. As a method for obtaining a photoreceptor using a technique similar to this method, an example is provided in which P V K i7 trix is used and Zno is used as the photoconductive material (for example, N, C-K
he etal.

Photographic, 5science and
Engineering Vo125゜P39 (198
1) ). In this example, it has been reported that some kind of interaction occurs at the interface between PVK and zinc oxide, PVK at the interface is activated, and the properties of the photoreceptor are improved.

However, the photosensitivity of this type of photoreceptor depends on the zinc oxide content, and when the photosensitivity is increased to a satisfactory level, the charging ability almost disappears. In order to solve this drawback, it has been proposed to use the photoconductive layer as a charge generation layer and provide a charge transport layer (PVK) thereon to apply it to a so-called functionally separated photoconductor, but the photosensitivity is low. It has the disadvantage that it deteriorates.

Yet another solution is to add polyester to the PVK-zinc oxide dispersion layer to restore the charging ability and to
Attempts have also been reported to improve the adhesion to the support and coating properties, which are serious drawbacks of VK. [Gueno・
However, according to research by the present inventors, the addition of a small amount of resin such as polyester can improve the coating film properties of the photosensitive layer. However, it is not possible to recover sufficient charging ability.Also, when resins such as polyester (1-) are added to obtain sufficient charging ability, the bulk of photocarriers generated on the surface of zinc oxide is In view of the above circumstances, the present inventors have developed an organic photoconductive material that has several excellent properties and an organic photoconductive material that is the only harmless inorganic photoconductive material. As a result of earnestly pursuing the development of a photoreceptor system that can effectively utilize zinc oxide, which is also inexpensive, the present invention has been completed.

That is, in the present invention, a photoconductive layer comprising at least a compound containing zinc oxide and a carbazole group, and a compound represented by the following general formula (■) is provided on a support having at least a conductive surface. An electrophotographic photoreceptor in which the carbazole group-containing compound is a copolymer compound of a carbazole group-containing monomer A and a monomer B that is copolymerizable with A and does not contain a carbazole group. The present invention provides an electrophotographic photoreceptor characterized by the following.

General formula (I) However, in the formula, R, R,, R, and R4 are hydrogen atoms, substituted or unsubstituted alkyl groups, cycloalkyl groups, alkenyl groups, or aryl groups, and R, 5, and R6 are hydrogen atoms. , a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, or aryl group, R7゜R8'``9'' ``10 is a hydrogen atom, - Riken atom, hydroxyl group, substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group, alkoxy group or amino group, and R5 and R6 may be cyclized with each other to form a saturated or unsaturated hydrocarbon ring having 3 to 10 carbon atoms. .

The above objects of the present invention are: (1) to provide a new electrophotographic photoreceptor using a copolymer compound containing at least zinc oxide and a carbazole group, (2) to provide an electrophotographic photoreceptor with extremely high sensitivity, and (2) to be used repeatedly. (1) To provide an electrophotographic photoreceptor that is non-toxic and pollution-free; (2) To provide an electrophotographic photoreceptor that is inexpensive and easy to manufacture.

Next, the present invention will be explained in detail.

The conductive support used in the present invention includes aluminum,
Metal plates such as nickel, metals such as aluminum and nickel vapor-deposited or sputtered onto paper or plastic films, metal foils such as aluminum bonded to paper or plastic films, carbon-containing paper, organic or Examples include low-resistance paper treated with an inorganic conductive treatment agent. The shape of the conductive support can be sheet-like, long roll-like, or
An endless belt shape or a drum shape can be selected and used.

Zinc oxide is used as a dye sensitizer in the thinned photoconductive layer.
Conventionally known dyes can be used, such as xanthine dyes such as fluorescein, erythrosin B1, phloxine 81, rosebenogal, rhodamine B1, rhodami 76 G, acid red, bromophenol blue, tetrabromophenol blue,
Triphenylmethane dyes such as bromcresol purple, bromthymol blue, fromphenol red, crystal violet, and malachite green, acridine dyes such as acridine orange, noanine dyes such as merocyanine, indoaniline dyes, and anothraquinones such as anthraquinone violet. Examples include inodigo dyes, inodigo dyes, and azo dyes. Among these, compounds having a xanothene skeleton or triphenylmethane skeleton and an acid or lactone structure are preferred from the viewpoint of solubility and adsorption to zinc oxide. Examples of particularly preferred sensitizers are tetrachlortetraiodofluorescein, tetrabromtetrachlorfluorescein, tetraiodofluorescein, dibromofluorescein, tetrabromof-14-fluorescein, tetrachlorfluoresceino, bromophenol blue, tetrabromophenol Blue, tetraiodophenol blue.

The amount of the sensitizer added to zinc oxide is 10
A range of 10 parts to 3 parts per 0 parts by weight is effective, preferably 10 to 2 parts, and a particularly preferred addition amount is 10 parts to 1 part. As a method for adsorbing these sensitizers onto zinc oxide, known techniques can be used. For example, zinc oxide is added to a dye solution dissolved in an appropriate solvent, thoroughly dispersed and mixed using a ball mill, etc., and then the dispersion is dried by heat drying, freeze drying, spray drying, etc. to remove the solvent. However, there is a method in which the dye is fixed on zinc oxide as a precursor, by adding zinc oxide to the dye solution and thoroughly dispersing and mixing it, without going through the solvent removal process.
This method includes adding a resin binder solution.

Alternatively, a method may be used in which zinc oxide is simply added to a solution containing a dye and a resin binder, and the mixture is dispersed and mixed, thereby adsorbing the dye and dispersing the paint at the same time.

Also, JP-A-54-99635, JP-A-55-8984
It is also possible to use known techniques such as No. 5, ie microencapsulation methods in the presence of hydrophilic or lipophilic resins.

In the present invention, a compound effective as a 7-trix polymer for uniformly dispersing zinc oxide is obtained by copolymerizing a monomer containing a carbazole group with a monomer B that can be copolymerized with A but does not contain a carbazole group. It is a copolymer compound obtained by. Monomers effective in the present invention are listed below, but are not limited to these compounds.

A: N-vinylcarbazole, 3,6-cyclo-N-
vinylcarbaso) Ii, 3,6-dibrome-N-
Vinylcarbazole, 3.6-syodo N-hinylcarbazole 370 Ru N-vinylcarbazole, 3-
Bromo-N-vinylcarbazole, 3-iodo-N-vinylcarbazole, 3-amino-N-vinylcarbazole, 3-methylamino-N-vinylcarbazole, 3-
Dimethylamino-N-vinylcarbazole, 3-nitro N-vinylcarbazole, 9-arylcarbazole, and the like.

B Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate
-butyl, isobutyl acrylate, ter acrylate
t-butyl, cyclohequinyl acrylate, 2-ethylhexynol acrylate, octyl acrylate, 3-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,4-dinitrophenol acrylate, etc. Acrylic acid ester, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-17-monohexyl methacrylate, nclohexyl methacrylate , octyl methacrylate, 2-diethylamine ethyl methacrylate,
Methacrylic acid esters such as 2-dimethylaminoethyl methacrylate and 2,4-dinitrophenyl methacrylate.

Vinyl oxate, vinyl acetate, propionate H=/L', n
-buty-17yl, vinyl cafuroate, vinyl caprylate,
Organic acid vinyl esters such as vinyl caprate, vinyl laurate, vinyl balmitinoate, vinyl stearate, vinyl trimethylacetate, vinyl benzoate, vinyl 3,5-dinitrobenzoate.

Styrene, α-methylstyrene, 0-methylstyrene,
Styrene and its derivatives such as m-methylstyrene, p-methylstyrene, 0-methoxystyrene, m-methkinstyrene, p-methkinstyrene, m-dimethylaminostyrene, p-dimethylaminostyrene, N-vinyl-2 -Pyrrolide=18-7 etc.

Examples of compounds represented by the general formula (I) include those shown below, but the invention is not limited thereto.

111-His(4-N,N-dimethylaminophenyl)
-1-phenylmethane 2, 1,1-bis(4-N,N-dimethylamino-2
-methylphenyl)-1-phenylmethane 3,11-bis(4-N,N-dimethylamino-2-methylphenyl)-1-(2-chlorophenyl)methane 4
, 1.1-bis(4-N,N-dimethylamino-2-
methylphenyl)-1-(4-7toki/phenyl)mekun 5, 1.1-his(4-N,N-dimethylaminophenyl)-1-(4-hydroquinophenyl)methane 6, 1.1- Bis(4-N,N-dimethylaminophenyl)-1-(2,4-dimethoquinophenyl)methano 7
, 1.1-bis(4-N,N-dimethylamino-2-
ethylphenyl)-1-phenylmethane 8, 1,1-his(4-N,N-dimethylamino-2
-methquinphenyl)-1-phenylmethane 9, 1.1-bis(4-N,N-dimethylamine-2
-toquinophenyl)-1-phenylmethane 1011-bis(4-N,N-diethylaminephenyl)-1-phenylmethane 1111-his(4-N,N-diethylamino-2-methylphenyl)-1-phenylmethane 12,],]1-bis4-N,N-diethylamino-2
-methylphenyl)-1-(2-di0)diphenyl)methane 13.1-bis(4-N,N-diethylamino-2-methylphenyl)-1-(4-methoxyphenyl)methane 1411-bis (4-N,N-diethylaminophenyl)-1-(4-phenyl)methane 15.1.1-bis(4-N,N-diethylaminophenyl-1-(2,4-dimethoxyphenyl))6 11 -bis(4-N,N-diethylamine-2-
ethylphenyl)-1-phenylmethane 17,], ]1-his 4-N,N-diethylamino-2
-7quinphenyl)-1-phenylmethane18 11-bis(4-N,N-diethylamino-2-
1-phenylmethano-19 11-bis(4-N,N-diethylamino-2-
methylphenyl)-1-(2,6-chlorophenyl)
Methane 20] l-His(4-N,N-diethylamine-25-nomethoxy/phenyl)-1-phenylmethano 21 11-bis(4-N,N-dibenzylaminophenyl-22 11-bis( 4-N,N-dibenzylamino-2
-methylphenyl)-l-phenylmethano23, 1.1-his(4-N,N-dibenodylaminoni25-dimethylphenyl)-1-phenylmethano24 11-bis(4-N.N-dimethylphenyl)-1-phenylmethano24 benzylamino-2
-methoxyphenyl)-1-phenylmethane25 11-bis(4-N.N-dimethylamino-2
-methylphenyl)-1-(2,4-dimethoxyphenyl)methane 26, 1.1. l-tris(4-N,N
-dimethylaminophenyl)-1-phenylmethane 27, 1.1.1-tris(4-N.N-dimethylamino-2-methylphenyl)methane 28, 1.1-his(4-N,N- diethylamino-
25-Dimethylphenyl)-1-(4-N,N-diethylaminophenyl)-methane29 11-His(4-N,N-diethylamino-2-
methylphenyl)-l-(4-N,N-dimethylamine-2-chlorophenyl)methane 30 11-His(4-N,N-diethylamino-2-
methylphenyl)-■-(4-N,N-dimethylamino-2-methylphenyl)methano31,1.1-bis(4-amino-2-methylphenyl)-1-(4-N,N-dimethyl Aminophenylramethane 32 11-bis(4-amino-25-dimethylphenyl)-1-(4-N,'N-dimethylaminophenyl)methane 33, 1-(4-N,N-dimethylaminophenyl)- 1.1.1-triphenylmethane 34, 1-(4-N,N-diethylaminophenyl)-1.1., 1-triphenylmethane 35 11-bis(4-N,N-dimethylaminophenyl)- 11-diphenylmethane 36 11-bis(4-N,N-diethylaminophenyl)-11-diphenylmethane 37, 11-bis(4-N,N-dibenzylamino-2
-Methyl = 2 2-phenyl)-1-chlorohexyl/lumetano 38] l-his(4-N,N-dibenol-amino-2-methquinphenyl)-1-chlorohegin lumetano 39] l-bis(
4-N,N-dibenzylaminophenyl)-1-k40, 1,1-bis(t-N,N-di/\nodylamino-25-dimethylphenyl)-1-7chlorohex normethane 41.1-bis(4-N,N-dibenzylamino-25-lame-1-t-diphenyl)-1-chlorohequinylmethane 4211-bis(3-N,N-diethylamino-4- methylphenyl)-1-phenylmethane 43, 1.1-his(4-N,N-diethylamino-
2-methylphenyl)heptano 441-bis(4-N,N-diethylamino-2-cryquinophenyl)-2-methylpropane 45, 1. ], l-1 helis (4-N, N-diethylamino-2-methylphenyl) methane 46 α, α2 α', α'-detrakis (4-N, N-
diethylamino-2-methylphenyl)-p-xyleno47.1.1-bis(4-N,N-diethylamino-2
-ethylphenyl)-2-phenylethane 48, 1.1.5.5-tetrakis(4-N,N-dimethylamino-2-methylphenyl)bearthane 4911-bis(4-N,N-diethylamino-2- ethyl phenyl)-4-methyl7-chlorohexane 5011-bis(4-N,N-metelamin-2-methylphenyl)/chlor\gisa1 5111-bis(4-N-diL-thyl-N-methylamino- 2-methylphenyl)-3-methyl7chlorohexane 52, 1.1.2.2-tetrakis(4-N,N-dimethylamino-2-methylphenyl)ethane 5311-his(4-N,N-diethylamino -2-methylphenyl)-3-phenylpropane 54, 1.1-bis(4-N,N-dibenzylamino-2-methylphenyl)beartan 5511-bis(4-N,N-di\nodylamino-2
-methoxyphenyl)-2-methylpropane 5611-bis(4-N,N-dibenzylamino-2-
methylphenyl)ncrohex→notu, 5711-bis(4-N,N-dihe7dylamino-2-
methylphenyl)p0/guno5811-his(4-N,N-dibenzylamino-2=
methylphenyl) normanobutano 5911-bis(4-N,N-dibenzylamino-2-
70 Ropan 60] l-bis(4-N,N-dibenzylamino-2
-Me1~ki/phenyl) normal butane6111-his(4-N,N-diethylaminephenyl)butano6211-bis(4-N,N-dimethylaminophenyl)-2-methylpropane6311-bis(4- 1. 1-bis(4-N,N-dibenzylaminophenyl)furononoro 711-bis(4-N,N-dibenzylaminophenyl)no 25-rumalubuk 7 68, 1.1-his(4-N, N-7 to 7dylamino-25-dimethylphenyl)l\pukuno69, 1.1-his(4-N,N-dibenosolamino-25-dimethylphenyl)n-butane 7011-bis(4-N,N-dihenonol T minnow 25
-dimeI-quinophenyl) normal butane7111-bis(4-N,N-(p-tolyl)aminephenyl)/chloro/\xanoa222-bis(4-N,I'J-cy(p-tolyl) aminophenyl]propane 73, 1,1-his(4-N,N-di(p-tolyl)
[aminophenyl]-1-phenylethane741-bis(4-N,N-di(p-tolyl)aminophenyl-11-diphenylethane7511-bis(4-N,N-(p-1□lyl)amino) phenyl]methane7611-his(4-N,N-di(p-tolyl)aminophenyl)-1-phenylmethane7711-his[:4-N,N-di(p-tolyl)aminophenyl 26-l) -4-tert-bunal 7-lylohexane 7811-
His[:4-N,N-di(p-tolyl)aminophenyl]-2-methylpropane 79, 1.1-bis(4-N,N-di(p-tolyl)
aminophenyl]ethane 80, 1.1-his[:4-N,N-di(p-tolyl)aminophenyl]-3-methylbutane8], 1.1-bis['4-N,N-di( p-tolyl)amino-2-methylphenyl]ethane 8211-bis(4-N,N-di(p-tolyl)amino-2-methylphenylconclohexane8311-bis(4=N,N-dibenzylamino phenyl)ethane 8411-bis(4-N,N-dibenzylaminophenyl)prone 8511-bis(4-N,N-dibenzylaminophenyl)nbutano8611-his(4-N,N-dibenzylaminophenyl) Dylaminophenyl→-2-metelphytano871-bis(4-N,N-dibenzylaminophenyl)-n-・\xa7 8811-bis(4-N,N-dibenodylaminophenyl 2-ether /\Kizano8911-bis(4-N,N-sylaminephenynolyn-tochikat9011-bis(4-N,N-di(p-rimachihenozyl)aminophenyl)ethane91, 11- Bis(4-N,N-di(0-chlorohenozyl)aminophenyl]-n-butane9211-Bis(4-N,N-di(p-promobenozyl)aminephenyl]-n-butane93)1-bis( 4-N,N-di(p-methylhenozyl)aminophenyl]propane 9411-bis(4-N,N-di(p-nitrobenonyl)aminophenyl)-2-ethelhexane9511-bis(4-N,N- Dibenzylamino-2-
methylphenyl)methane 9611-bis(4-N,N-di＼fudylamino-2
-ethylphenyl)methane 97.1.1-bis(4-N,N-di(p-chlorohenozyl)ami7-2-ethylphenylcomethane 9811-bis(4-N,N-dibenzylamino-2-
methylphenyl)ethane 9911-bis(4-N,N-dibenzylamino-2-
eterphenyl)ethane 100.1-bis(4-N,N-dihe7dylamino-2-methylphenyl)propane 101, 1.1-bis(4-N,N-di(0-chlorohenodyl)amino-2 -ethylphenyl)furopane 102.1.1-bis(4-N,N-dibenzylamino-2-methylphenyl)butane 103.1.1-his(4-N,N-di(p-chlorohenozyl)amino -2-ethylphenyl)butano104.1.1-bis(4-N,N-dibenzylamino-2-methylphenyl)-2-methylpropane105.1.1-bis(4-N,N-dibenzylamino-2-methylphenyl) benzylamino-2-methquinphenyl)butane 106, 1.1-bis(4-N,N-dibenzylamino-2-methylphenyl)butano 107.1-bis(4-N,N-di (p-tolylamino)-2-129-methquinphenyl]l\butano10B, 1.1-bis(4-N,N-benodylamino-2-methylphenyl)7\xano109.2.2 -bis(4-N,N-dibenzylamino-2-methylphenyl)butane 1]0.2.2-bis(4-N,N-dibenzylamino-2-methylphenyl)propane Electrophotography of the present invention The photoreceptor consists of zinc oxide adsorbed with a sensitizing dye, a copolymer containing the above carbazole group, and the general formula (
The compound represented by D is dispersed and mixed with the solvent to prepare a coating solution for forming a photosensitive layer, which is coated on a conductive support and dried. In this case, the blending ratio of the copolymer containing a carbazole group is 10 to 400 parts by weight, particularly 50 to 30 parts by weight, per 100 parts by weight of zinc oxide.
0 parts by weight is preferred. The compounding ratio of the compound represented by general formula (I) is 10 to 100 parts by weight per 100 parts by weight of zinc oxide.
400 parts by weight, particularly preferably 50 to 300 parts by weight.

The thickness of the photoconductive layer formed as described above is 530- ~50 μm, preferably 10 to 30 μm.

As shown in FIG. 1, the electrophotographic photoreceptor of the present invention includes a monomer A containing a carbazole group on a conductive support 1;
Monomer B copolymerizable with N and containing no carbazole group
The basic structure is that the matrix is a copolymer compound obtained by copolymerizing and the compound represented by the general formula (I), and a layer 4 in which zinc oxide 3 is uniformly dispersed is provided on the 7 Trix 2. However, it is also possible to adopt forms as shown in FIGS. 2, 3, and 4. In both FIGS. 2 and 3, a photoconductive layer 4 is provided on a conductive support l, and a charge carrier transport layer 5 is further provided thereon. Further, in FIG. 4, a photoconductive layer 4 is provided on a conductive support 1, and an insulating layer 6 is further provided thereon. In the photoreceptor of FIG. 2, the thickness of the photoconductive layer 4 is 5 to 50 μm, preferably 10 to 30 μm.
The thickness of the charge carrier transport layer 5 is 0.2 to 5 μm, preferably 0.5 to 2 μm. In the photoreceptor of FIG. 3, the photoconductive layer 4 has a thickness of 05 to 101 tm, preferably 05 to 57 tm, and the charge carrier transport layer has a thickness of 5 to 57 tm.
50 μm/10 to 30 μm. Also the fourth
In the photoreceptor shown in the figure, the thickness of the photoconductive layer 4 is 5 to 50 μm.
The thickness of the insulating layer 6 is preferably 01 to 100 μm, preferably 05 to 50 μm.

By adopting the configurations shown in FIGS. 2, 3, and 4, the electrical, chemical, and physical stress applied to the photoconductive layer 4 from the outside is significantly reduced, and the repeatable life of the photoreceptor is dramatically increased. It is possible to improve the Furthermore, the second
The photoreceptor of the form shown in the figure can be selected and used for the purpose of placing more emphasis on sensitivity, and the photoreceptor of the form of FIG. 3 can be selected and used for the purpose of placing more importance on the repeat life.

Any known charge carrier transport layer can be used in the present invention. For example, polyvinylcarbazole, a copolymer compound containing a carbazole group, a polymer layer such as borihinylpyrene, triarylmethanes, triarylalkanes, detraarylmethanes, diarylalkanes, distyryl-containing aromatic compounds, birapurin N,N-dibenozylaniline derivatives, 1'lytolylamino, tetraphenyldiaminobiphenyls, 4-diarylamino-substituted chalconos, oxadiazoles, 5
- Solid solution layers in which low molecular weight charge carrier transport substances such as aminothiazoles, triazoles, imidaprones, quinadurinos, benzofurans, hydrazo7s, and diamines are dispersed in the form of molecules in an electrically insulating polymer.

Further, the photoreceptor having the form shown in FIG. 4 is disclosed in US Pat.
67, Special Publication No. 42-25223, Special Publication No. 43-15
52 Publication, Special Publication No. 42-19748, Special Publication No. 4
Publication No. 3-4958, Japanese Patent Publication No. 43-24748,
etc. Publication No. 13437/1987, Special Publication No. 1787/1973
Publication No. 1, Japanese Patent Publication No. 48-2965, Japanese Patent Application Publication No. 1987-
By applying the latent image forming method disclosed in Publication No. 133056, etc., it is possible to significantly extend the repeat life.

In this case, the following layer made of thermoplastic resin or thermosetting resin is used as the insulating layer.

■ Thermoplastic resins polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyfluoroethylene propylene, tetrafluoroetereno/perfluoroalkoxy-substituted perfluorovinyl copolymer, polyvinylformyl
polyvinyl butyral, polycarbonate, polyester, polyacrylate, polyvinyl chloride, polyvinyl acetate, vinyl chloride/vinyl acetate copolymer, etc.

■ Thermosetting resins, alkyd, aminoalkyd, epoxy, epoxy ester, acrylic polyester, acrylic evoquino, curable cyclized butadieno rubber, curable cyclized triazine rubber, curable cyclized natural rubber, thermosetting polyurethane, Moisture-curable polyurethane, photo-curable polyurethane, photo-curable polyester, photo-curable polyester acrylate-1-1, etc.

The insulation layer can be formed by bonding method, shrink method, roll coating method,
Formed by coating by dip coating, spray coating, electrodeposition coating, etc., and further processing such as heat curing, photocuring, electron beam curing, heating and melting of powder depending on the material of the insulating layer. I can do it.

The photoreceptor disclosed by the present invention has a number of excellent properties, and is sufficiently practical in terms of flexibility and adhesion to a support. For example, even if a 204 m thick photosensitive layer of the present invention in the form shown in Fig. 1 is formed using a film made of aluminum laminated onto a polyethylene terephthalate film as a support, and then the layer is bent by 180°, no peeling of the layer occurs. -Also, no destruction of the interlaminar bodies was observed.

However, several drawbacks have been pointed out in the past in the so-called bike-type photoreceptor in which photoconductive powder is dispersed in a polymer as in the present invention. For example, since the photosensitive layer is essentially composed of a porous composite, it does not have sufficient surface strength, and the layer is porous, resulting in developer intrusion, cleaning problems, or deterioration due to electrical conduction. It is easily affected by this and has a low printing capacity. Furthermore, since zinc oxide and sensitizing dyes are directly exposed to NOx, SOX, etc. in ozone, corona, etc. generated during the compound calyx process, deterioration of the photoreceptor progresses rapidly.

The photoreceptor of the present invention has advantageous conditions for overcoming these drawbacks. That is, in conventional Beitzter type photoreceptors, the amount of binder used is usually 2 times the amount of the photoconductive powder.
It is composed of 0 to 35% by weight, and is used to increase ffi' of the binder for the purpose of improving repeat copying characteristics and surface strength.
! When the weight of f40 is exceeded, the sensitivity decreases significantly and the photoreceptor cannot be used, which is a serious drawback.

On the other hand, in the photoreceptor of the present invention, the ratio of the copolymer as a binder to zinc oxide is 10 to 400%.
It can be used in a range of 50% to 300% by weight, and in particular, it has the distinctive feature that there is virtually no decrease in the sensitivity of the photoreceptor even when the total amount of copolymer used is 50 to 300% by weight, and it has sufficient practical characteristics. ing. The photoreceptor of the present invention, which is formed by using the copolymer as a binder in such a ratio, has an extremely low porosity, which causes deterioration when energized.
The surface is smooth and strong, and the sensitizing dye and zinc oxide, which are susceptible to deterioration due to light and Ozu 7, are protected by Bitstar, which dramatically improves the repeated printing durability of the photoreceptor. I can do it. A further important advantage is that it can be manufactured using a simple technique of dispersion coating in the manufacturing department, and that commercially available and inexpensive materials can be used for cutting, so manufacturing costs can be reduced. Furthermore, the photoreceptor of the present invention has no problems with respect to the pollution and toxicity of photoreceptors, which have often been a problem in recent years, and can provide a useful photoreceptor.

The reason why a carbazole copolymer and zinc oxide exhibit such good properties as described above when applied to a photoconductive material is not clear, but it may be due to the ease of movement of the carbazole groups present in the polymer. 1, which is presumed to be involved. In polyvinylcarbanol, carbazole groups are strongly structured in the polymer, but in copolymers, the interaction between carbazole groups is weakened. As a result, it appears that the carbazole group is effectively activated by interaction with zinc oxide.

Examples of the present invention will be described below.

Method for Preparing Sensitized Zinc Oxide 10 parts of tetraiotofluoresceino was added to 100 parts of tetrahydrofurano and dissolved, and then 100 parts of zinc oxide (manufactured by Sakai Kagaku Co., Ltd., 5azex #4000) was added. This mixture was milled in a porcelain ball mill (inner volume 1.5 t, outer diameter 15
cm) and mixed and dispersed at 78 rpm for 3 hours. Next, the resulting dispersion was transferred to a container with an open top, and the tetrahydrofuran was completely evaporated while stirring at 70°C. The zinc oxide powder dyed with tetraiodofluor 38-olescein thus obtained was used as sensitized zinc oxide in the following Examples and Comparative Examples.

Method for Preparing Photoreceptor A predetermined amount of a copolymer compound containing a carbazole group is dissolved in methidichloride. Add a predetermined amount of the general formula (1
) was added and dissolved, then the above-mentioned sensitized zinc oxide was added in a predetermined amount, and this mixture was milled in a porcelain ball mill (inner volume: 15 t, outer diameter: 15 m) at a rotational speed of 78 r-p=m for 2 hrs.
Spread out the time. The obtained dispersion was coated on the aluminum side of a laminated filter made by laminating Boriethelene Telefuku 1/-1. and aluminum together using a blade coating method so that the thickness after drying was 25 μm, and the mixture was heated at 110°C. A photoreceptor was prepared by drying for 5 minutes.

Examples 1 to 7 A copolymer of N-vinyl Rubadur and n-butyl meccrylate with a molar ratio of 75 to 25 was used as a copolymer compound (the composition ratio of the copolymer was all monomers). (expressed as a molar ratio), photoreceptors were prepared by changing the type of compound of general formula (1) according to the following formulation.

Examples 8 to 14 11-His (4-N, N-
Photoreceptors were prepared using diethylamine-2-methylphenyl)1-phenylmethane (abbreviated as TPM) and changing the type of copolymer compound containing a carbazole group according to the following formulation.

Example 15 I) V K (BAS
Luvican M l 70) glue D/l manufactured by P- Company
A 5 wt.

Example 16 The photoreceptor shown in Example 1 (however, the thickness of photoconductive layer 1 was changed to 3
The chlorbenose 7 solution of PVK used in Example 15 was applied on top of the PVK layer (μm coating) so that the thickness of the PVK layer after drying would be 10 μm, and the layer composition was dried at 90°C for 10 minutes to form the layer structure shown in Figure 3. A laminated photoreceptor was obtained.

Comparative Examples 1 to 3 Photoreceptors were prepared using the following compounds in place of the compound of general formula (I) in the formulation of Example 1.

Comparative Example 4 A mixture having the following formulation was dispersed and coated according to the procedure described in the section of the photoreceptor manufacturing method, and a thickness of 25 μm was obtained.
A photoreceptor was fabricated.

For each of the photoreceptor samples of Examples 1 to 16 and Comparative Examples 1 to 3 prepared as described above, electrostatic charging characteristics and actual copying tests using a copying machine were conducted.

The electrostatic charging properties were measured using an electrostatic copying paper tester model 5P-428 (manufactured by Kawaguchi Electric Seisakusho). The sample is attached to a test device and charged under the conditions of a corona discharge voltage of -6 KV and a charging speed of 250.7 seconds, and the potential Vo (V) immediately after charging is measured. After dark decaying for 5 seconds (potential v5 [V]),
Color temperature 285 (.K1 illuminance 5 lux, then half exposure amount E
+(lux·see) was measured. The results are shown in Tables 1 and 2.

In the photocopying test 1-, the sample was mounted on a commercially available electrophotographic copying machine and ranoninok test was carried out.
Measure the maximum image density and fog of the copied image when copying the 1st, 2000th, 5000th, 10,000th, and 15,000th copy, as well as the optimum exposure amount of the photoconductor when the copying machine is installed. did. The results are shown in Table 3.

Table 1 Table 2 Background fog = (interwhiteness of non-image area after copying)
- (value expressed in Hunter whiteness of paper before copying).

As judged from the results in these tables, the electrophotographic photoreceptor according to the present invention has extremely high sensitivity, can withstand copying of 15,000 sheets or more, and forms good copied images. On the other hand, the photoreceptor of comparative sample 1 had a
Although it can withstand copying of 00 or more sheets, it has the problem that the image density is somewhat low. In addition, the sensitivity of the photoreceptor of Comparative Sample 4 was slow, and when more than 2,000 copies were made, the image density decreased significantly, making it impossible to continue the running nog test.

Example 17 A 20 μm thick Mylar film was laminated on the surface of the photoreceptor of Example 1 to form an insulating layer, and a fourth insulating layer was formed.
A photoreceptor of the present invention in the form shown in the figure was obtained.

48- 47- Comparative Example 5 An insulating layer was formed on the surface of the photoreceptor of Comparative Example 1 by the method of Example 15 to obtain an insulation-coated photoreceptor for comparison.

Using the thus obtained photoreceptor of Example 17, the surface potential was first raised to 180 by corona discharge at 6 KV.
The surface potential of the photoreceptor is charged to 0V, and then the surface potential of the photoconductor is removed by discharging AC6KV to 0V, and at the same time 2
Light image irradiation was carried out at 51 x-sec, then 10 x-sec.
After irradiating the entire surface with 01ux-aec to form an electrostatic latent image on the surface of the insulating layer, it is developed with O toner using a dry development method, and then corona charging is performed on the photoreceptor so that it becomes □tooV, and paper is placed on top of this. By adhering and transferring, an image with high image density and no fog/yap was obtained. The above process i was repeated 50,000 times, and the image characteristics were good without any problems.

On the other hand, the image density of the photoreceptor of Comparative Example 5 was slightly lower than that of the photoreceptor of Example 17, but the image density was improved after 50,000 uses.

Furthermore, the surface potential V d (V) of the unexposed part of the photoreceptor and the surface potential V + (
V) Measure the difference and convert it into an electrostatic image: ]/truss 1-
It was designated as VC (V). Table 4 shows the changes in the electrostatic conotruses 1 to 1 after repeating the process described in - 50,000 times.

Table 4 From the results in Table 4, it was confirmed that the photoreceptor of the present invention (Example 15) had a higher electrostatic conolast than Comparative Example 5 and had excellent characteristics.

[Brief explanation of drawings]

1 to 1 are enlarged sectional views of a photoreceptor according to the present invention. l... Conductive support 2... Copolymer compound and carbazole derivative etc. 71-Lix 3... Zinc oxide 4... Photoconductive layer 5... Charge carrier transport layer 6 ... Insulating layer 7 ... Photoreceptor patent applicant Tomogawa Paper Mills Co., Ltd.

Claims (6)

[Claims] (1) An upper surface of a support having at least a conductive surface;
An electrophotographic photoreceptor of general formula (I) characterized in that it is provided with a photoconductive layer comprising at least a compound containing zinc oxide and a carbazole group, and a compound represented by the following general formula CI>. In the formula, R4 is a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, or a haaryl group, and R6 is a hydrogen atom, a substituted or unsubstituted alkyl group. group, 7-chloroalkyl group, alkenyl group, cycloalkenyl group or aryl group, "7'""8""9""10
represents a hydrogen atom, /%(]gen atom, hydroxyl group, substituted or unsubstituted alkyl group, 7-chloroalkyl group, alkenyl group, aryl group, alkokino group, or amine group, and it and R6 are mutually exclusive. 7 to form a saturated or unsaturated hydrocarbon ring having 3 to 10 carbon atoms. (2) The compound containing a carbazole group is a copolymer compound of a monomer A containing a carbazole group and a monomer B which is copolymerizable with A and does not contain a carbazole group. Electrophotographic photoreceptor 93 according to claim 1 (3) In the copolymer compound, A is N-hinylcarbanol, and B is acrylic ester, methacrylic ester, organic acid vinyl ester, styrene, N
3. The electrophotographic photoreceptor according to claim 2, wherein the monomer is selected from the group consisting of: -vinyl-2-pyrrolidone L. (4) In the copolymer compound, the composition molar ratio is A:
The electrophotographic photoreceptor according to claim 3, characterized in that B=95:5 to 5:95. (5) The electrophotographic photoreceptor according to claim 1, further comprising a charge carrier transport layer on the photoconductive layer. (6) The electrophotographic photoreceptor according to claim 1, characterized in that an insulating layer is provided on the photoconductive layer.