JPH0222661A - Photosensitive body - Google Patents

Abstract

PURPOSE:To stably obtain high-quality images even at the time of repeated uses under conditions of high temperature and high humidity by incorporating a sulfonyl resin having specified structural units as main repeating units. CONSTITUTION:The photosensitive body contains the sulfonyl resin having as main repeating units the structural units each represented by formula I in which each of R<1>-R<6> is H, F, or substituent having F, or other substituents, and at least one of them is F or a substituent having F, and said resin is obtained by polycondensing only one kind among the various kinds of units represented by formula I, or the many kinds of units, thus permitting the obtained photosensitive body to be enhanced in mechanical strength, hardly scratchable, enhanced in releasability of attached matter to the surface of the photosensitive body, easy in cleanability, and to form a good image under high temperature and high humidity, and to stably obtain high-quality images at the time of repeated uses.

Description

DETAILED DESCRIPTION OF THE INVENTION A.8 Industrial Application Field The present invention relates to a photoreceptor, for example, an electrophotographic photoreceptor.

In conventional electrophotographic copying machines using the Carlson method, after the surface of a photoreceptor is charged, an electrostatic latent image is formed by exposure, and the electrostatic latent image is developed with toner, and then a visible image is formed. Transfer and fix onto paper, etc. At the same time, the photoreceptor is subjected to removal of adhered toner, neutralization of static electricity, and surface cleaning, and is used repeatedly over a long period of time.

Therefore, as an electrophotographic photoreceptor, it not only has electrophotographic properties such as good charging characteristics and sensitivity, and low dark decay, but also physical properties such as stiffness resistance, abrasion resistance, and moisture resistance after repeated use. It is also required to have good physical properties and resistance to ozone generated during corona discharge, ultraviolet rays during exposure, etc. (environmental resistance).

Conventionally, as electrophotographic photoreceptors, inorganic photoreceptors having a photosensitive layer mainly composed of an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide have been widely used.

On the other hand, the use of various organic photoconductive substances as materials for photosensitive layers of electrophotographic photoreceptors has been actively developed and researched in recent years.

For example, in Japanese Patent Publication No. 50-10496, poly-N vinylcarbazole and 2.4, 7. -)+7 An organic photoreceptor having a photosensitive layer containing nitro-9-fluorenone is described. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability. In order to improve these drawbacks, attempts have been made to develop organic photoreceptors with high sensitivity and durability by assigning the charge generation function and charge transport function to different substances in the photosensitive layer. ing. In such so-called function-separated type electrophotographic photoreceptors, substances that exhibit each function can be selected from a wide range of materials, so it is relatively easy to produce electrophotographic photoreceptors with arbitrary characteristics. Is possible.

Many substances have been proposed as charge-generating substances that are effective for such functionally separated electrophotographic photoreceptors. Examples of using inorganic substances include, for example, Japanese Patent Publication No. 43-1619
As described in Publication No. 8, there is amorphous selenium. This is combined with an organic charge transport material.

Furthermore, many electrophotographic photoreceptors using organic dyes or organic pigments as carrier-generating substances have been proposed. No. 22834, 54-
It is already known from No. 79632, Publication No. 56-116040, etc.

In recent years, development of organic electrophotographic photoreceptors using organic photoconductive substances has progressed, and they have been put to practical use in copying machines and printers. These have great advantages in terms of low cost, etc., and are expected to see great development in the near future.

However, these organic photoreceptors sometimes have insufficient durability to -71, which has been considered a drawback.

In other words, electrophotographic photoreceptors are required to have durability in terms of electrophotographic physical properties such as sensitivity, residual potential, and charging ability, as well as mechanical durability against abrasion and scratches on the photoreceptor surface due to rubbing. Currently, mechanical durability in particular is often a factor that determines the lifespan of a photoreceptor. However, none of the conventional binders had sufficient scratch resistance.

In addition, the surface layer of the photoreceptor is prone to adhesion of low-resistance substances due to ozone generated during corona charging under high humidity, toner filming due to poor toner cleaning, and fusion phenomena, which can cause image quality deterioration. ing. Therefore, it is also necessary to have good releasability of various deposits on the surface layer of the photoreceptor.

As a method to solve these problems, it is possible to disperse lubricating powder such as fluororesin in the surface layer.

This imparts lubricity to the surface layer, improving mechanical durability against wear and scratches.

In addition, mold releasability and water repellency can also be imparted.

However, fluororesin powder has problems with dispersibility and cohesion, making it difficult to form a uniform and smooth film.
Image defects such as image unevenness and pinholes are likely to occur. Use of binder resins or dispersion aids with good dispersibility often causes deterioration of electrophotographic properties, which is inconvenient.

C.8 Purpose of the Invention The purpose of the present invention is to provide a photoreceptor that can exhibit the following characteristics.

(a) High mechanical durability and scratch resistance.

(b) High quality images can be stably obtained even under high temperature conditions.

(C) It has good cleaning properties and can prevent toner from adhering to and fusing to the surface of the photoreceptor.

(d) Scales to prevent image defects such as image unevenness and pinholes.

(e) High quality images can be stably obtained even during repeated use.

20 Structure of the Invention and Its Effects The present invention relates to a photoreceptor containing a resin having a structural unit represented by the following general formula [1] as a main repeating unit.

-Format (1) [-In Format (1), R', R2, R3, R4, R5, and R6 each represent a hydrogen atom, a substituent, a fluorine atom, or a substituent having a fluorine atom. However, at least one of R1, RzR3, R4, R5, and R6 represents a fluorine atom or a substituent containing a fluorine atom. ] As a result of studying binder resins with particularly high mechanical durability and scratch resistance, the present inventor found that good results can be obtained by incorporating a sulfone resin represented by formula (I) above. I discovered that.

That is, by employing the above-mentioned resin, the mechanical strength is increased and scratches are less likely to occur. Furthermore, the releasability of deposits on the surface of the photoreceptor was improved, cleaning performance was improved, and good images could be obtained even at high temperatures. As a result, high-quality images can now be stably obtained even during repeated use.

Furthermore, since it is no longer necessary to disperse something such as fluororesin fine powder, it is now possible to form a uniform coating film.

The reasons for this are not clear, but in addition to polysulfone (sulfone resin)'s inherent good electrical properties and high mechanical strength, the effects of fluorine atoms present in the resin improve the lubricity and release properties of the resin. It is speculated that the formability has improved.

The resin used in the photoreceptor of the present invention in (2) is one in which fluorine atoms are introduced into the structure of a so-called sulfone resin.

The sulfone resin of the present invention has a structural unit represented by -form [Ia] as a main repeating unit. Here, among the various structural units represented by the formula -i (CI), only one type may be co-condensed (or, many types may be co-condensed).

Furthermore, - R', R'', R'R in form (1)
4, R5, and a structural unit that does not have a fluorine atom in any of R6 (for example, a structural unit in which R1 to R4 are all hydrogen atoms and R5 and R6 are methyl groups, etc.), and -
It may also be a copolymer with a structural unit represented by format [I].

In this case, the proportion of the fluorine-containing structural unit represented by formula -a [I] is preferably 20 mol% or more, and more preferably 50 mol% or more.

Furthermore, if necessary, for the purpose of further improving physical, chemical, and electrical properties, - type (conceptual unit represented by N, structural unit other than the structural unit used in ordinary sulfone resins) may be contained in a small amount and co-condensed.

Furthermore, the following type (Ia) is preferably exemplified.

General formula (Ia) However, n is the degree of polymerization.

Next, the contents of the structural unit represented by the -format [1] will be described.

-C In formula (1), "a substituent having a fluorine atom"
Examples include alkyl groups, aryl groups, alicyclic alkyl groups,
Examples include alkoxy groups, and R5 and R6 may form a cyclic structure together with the bonded carbon atoms. Further, it may be further substituted with a halogen atom, a lower alkyl group, an aryl group, or the like.

Regarding R5 and Rh, examples of the "substituent" include an alkyl group, an aryl group, etc., and they may form a cyclic structure together with the carbon atoms bonded to R5 and R6. In this case, the alkyl group or aryl group may be further substituted with a halogen atom (excluding a fluorine atom), a lower alkyl group, an aryl group, or the like.

R', R'', R3, R' (7) r substituent, halogen atom (excluding fluorine atom), alkyl group,
Examples include alicyclic alkyl groups, aryl groups, alkoxy groups, etc., and these may be further substituted.

- In format (1), at least one of R5 and R6 can be a bulky group. Such a bulky group preferably has three or more carbon atoms and acts as a steric hindrance that hinders the molecular chain arrangement.

When one of R5 and R6 is a bulky group, the other may be a hydrogen atom, a fluorine atom, an alkyl group such as a methyl group, a perfluoromethyl group, or the like.

When forming a ring with R5 and R6, 5-membered or 6-membered
A carbocyclic or heterocyclic ring is preferred.

The above sulfone resins have mechanical strength, scratch resistance, abrasion resistance,
It has excellent rigidity resistance and good charging performance.

In particular, it has the characteristics of a hard surface and moderate slipperiness, good transparency and insulation properties, and excellent compatibility with CTM.

In particular, it has been found that the sulfone resin of the present invention does not lose its transparency through polymerization even though it contains fluorine atoms. Even when used as a binder for the charge transport layer (upper layer side), it has the effect of not blocking light transmission.

In addition, if R5 and R6 are small (using a tall group on one side or forming a cyclic structure), it is possible to effectively prevent the molecular chains of the sulfone resin from arranging in a specific direction. Conceivable.

Therefore, it is considered that the crystallinity of the sulfone resin can be lowered.

Specific examples of the sulfone resin according to the present invention are listed below,
It is not limited to these. In addition, the following specific example shows a resin in which n structural units represented by the -format [I] are condensed, but these structural units can be used as one of the copolymerization components. As mentioned above.

Margin below C.F.

H, -1; 11-1; H.

CF2 C.F.

1. Next, an example of the structure of the photoreceptor of the present invention will be explained with reference to the drawings.

The photoreceptor of the present invention has a support 1 as shown in FIG.
(A conductive layer provided on a conductive support or sheet)
On top, a charge generating layer 2 (hereinafter sometimes referred to as CGL) containing a charge generating substance 5 (hereinafter sometimes referred to as CGM) and a binder resin as necessary is formed as a lower layer, and a charge transporting material ¥[6( A photosensitive layer 4 having a laminated structure consisting of a charge transport layer 3 (hereinafter sometimes referred to as CTL) containing a binder resin (hereinafter sometimes referred to as CTM) and a charge transport layer 3 (hereinafter also referred to as CTL) as an upper layer is shown in FIG. As shown, a photosensitive M4 having a laminated structure with CTL3 as a lower layer and CGL2 as an upper layer is provided on a support 1, and as shown in FIG. 3, a support 1 containing CGL, CTM and a binder resin. Examples include those provided with a photosensitive layer 4 having a single layer structure.

In addition, the upper CGL layer may contain both CGM and CTM in the same layer configuration as shown in FIG. 2 (a protective layer (OCL) may be provided on the photosensitive layer, and a An intermediate layer may be provided in between. An example thereof is shown in FIG.

That is, the intermediate layer 7 is provided on the support 1, and CTL3, C0M5, C
This photoreceptor has a photoreceptor layer 4 in which CGL2 containing TM and a binder resin is laminated, and is further provided with a protective layer 8 containing a binder as a main component.

The resin according to the present invention is applied to each of the photoconductor constituent layers, namely CGL, C
It may be contained in any of the TL, single-layer photosensitive layer, OCL, etc., or may be contained in a plurality of these layers.

In particular, the layer on the surface side of the photoreceptor (OCL, CTL3 in Figure 1)
, CGL2 shown in FIG. 2, etc.), the effects of the present invention become remarkable.

Fluororesin powder can be dispersed in the layer containing the resin, and the resin can be used as a dispersed binder.

That is, when a fluorine atom-containing sulfone resin is used as a binder, the dispersibility of the fluororesin powder is much improved compared to when a -m-type binder is used, and a uniform and smooth coating film can be obtained. This is presumed to be because the fluorine atoms contained as a constituent of the sulfone resin have an affinity for the fluororesin powder and thus play a role as a dispersion aid. Therefore, there is no need to add a dispersant or the like, and the adverse effects on electrophotographic properties (decreased sensitivity, increase in residual potential, increase in memory, etc.) caused by the addition of a dispersant can be avoided.

Further, since the characteristics such as abrasion resistance and high hardness that the sulfone resin generally has are maintained, it is extremely effective in improving mechanical durability by dispersing the fluororesin powder.

The content of the fluororesin powder is preferably 2 to 100% by weight, particularly preferably 5 to 30% by weight, based on the sulfone resin.

Fluorine resin powders include tetrafluoroethylene resin, trifluorochloroethylene resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, ethylene dichloride difluoride resin, and copolymers thereof. One or more types of powder selected from coalescence can be exemplified. The molecular weight of the resin, the particle size of the powder, etc. are also appropriately selected depending on the specifications of the photosensitive layer, protective layer, etc.

As the carrier generating substance (CGM), any inorganic pigment or organic pigment can be used as long as it absorbs electromagnetic waves and generates free carriers. Examples of CGM include the following.

(1,) Inorganic materials such as amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium selenide sulfide, mercury sulfide, lead sulfide, zinc oxide, amorphous silicon, etc. Pigments (2) Ab-based pigments such as monoazo pigments, polyazo pigments, metal complex azo pigments, pyrazolone azo pigments, stilbene azo and thiazole azo pigments (3) anthraquinone derivatives, antoanthrone derivatives, dibenzpyrenequinone derivatives, vilanthrone derivatives,
Anthraquinone or polycyclic quinone pigments such as violanthrone derivatives and isoviolanthrone derivatives (4) Indigoid pigments such as indigo derivatives and thioindigo derivatives (5) Diphenylmethane pigments, triphenylmethane pigments, xanthine pigments, acridine pigments, etc. Carbonium pigments (6) Quinoneimine pigments such as azine pigments, oxazine pigments and thiazine pigments (7) Methine pigments such as cyanine pigments and azomethine pigments (8) Quinoline pigments (9) Nitro pigments (10) Nitroso pigments (11) Benzoquinone and naphthoquinone pigments (12)
Naphthalimide pigments (13) Perylene pigments such as bisbenzimidazole derivatives (14) Fluorenone pigments (15) Squarylium pigments (16) Azulenium compounds (17) Perylene pigments such as perylene anhydride and perylene imide (18) ) Metal-free phthalocyanine pigments such as alpha-type, beta-type, Ab-based pigments and phthalocyanine-based pigments are particularly preferred.

As the ab-based pigment, for example, the following exemplified compound group (It)
There is one represented by ~(Vl).

The following margin shows the exemplified compound group [■]: The following margin shows the exemplified compound [V]: The below margin also shows the following exemplified compound group consisting of the polycyclic bovine non-pigment [■]
] ~ (IXI can be most preferably used as CGM.

The following blank exemplified compound group [■]: U4 Yunol/Gaketsu group [■): Next, there are no particular restrictions on the charge transport substance that can be used in the present invention, but for example, oxazole derivatives, oxadiazole derivatives, Thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidasilone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, oxacylone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives,
These may include benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, polyvinylpyrene, poly-9-vinylanthracene, and the like.

However, it is preferable to use a CTM that has an excellent ability to transport holes generated during light irradiation to the support side and is suitable for combination with the carrier-generating substance, such as the following exemplified compound group (X) or A styryl compound of (XI) is used.

Exemplary compound group [X]: In addition, the following exemplary compound groups (XII) to (X
It is also possible to use hydrazone compounds of VI).

I14 Compound rXrV]: Exemplified compound group (Xll): Exemplified compound group (XVI): In addition, pyrazoline compounds represented by the following exemplary compound [X■] can also be used as CTM.

The following margin exemplified compound group [X■]: Furthermore, amine derivatives shown in the following exemplified compound group [X■] can also be used as CTMs.

Exemplary compound group [Xνl]: The following margin The layer structure of the photosensitive layer of the photoreceptor of the present invention has a laminated structure and a single layer structure as described above.
, either the single-layer photosensitive layer or OCL, or multiple layers may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, etc. can.

Electron-accepting substances that can be used in the photoreceptor of the present invention include:
For example, succinic anhydride, maleic anhydride, dibromaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride,
Tetrabromo phthalic anhydride, 3-nitro phthalic anhydride,
4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, 0-dinitrobenzene, m-dinitrobenzene, 1.3.5-) dinitrobenzene, varanitrobenzonitrile , picryl chloride, quinone chlorimide,
Chloranil, bromanil, 2-methylnaphthoquinone, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone, trinitrofluorenone, 9-
Fluorenonedene [dicyanomethylenemalonodinitrile], polynitro-9-fluorenonedene [dicyanomethylenemalonodinitrile], picric acid, O-nitrobenzoic acid, P-nitrobenzoic acid, 3.5-dinitrobenzoic acid, pentafluoro Benzoic acid, 5-nitrosalicylic acid,
3.5-dinitrosalicylic acid and a filler can be added.

Typical examples of such antioxidants are shown below, but the invention is not limited thereto.

Group (1): Hindered phenols dibutylhydroxytoluene, 2.2'-methylenebis(6-t-butyl-4-methylphenol), 4.4'
-butylidenebis(6-mo-butyl-3-methylphenol), 4,4'-thiobis(6-L-butyl-3-methylphenol), L2,2'-butylidenebis(6-t-butyl-4-methylphenol), α-tocopherol,
β-tocopherol, 2,2.4-trimethyl-6-hydroxy-7-t-butylchroman, pentaerythyltetrakis (3-(3,5-di-L-butyl-4-hydroxyphenyl)propionate L 2,2'- Thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis(3-(3゜5-di-t-butyl-4-hydroxyphenyl)propionate) , butylhydroxyanisole, dibutylhydroxyanisole, 1-(2
-[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl)-4-(3
-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)-2,2°6.6-titramethylpiperidyl and the like.

Group (II): paraphenylenediamines N-phenyl-
N-isopropyl-p-phenylenediamine, N,N'
-di-5ec-butyl-p-phenylenediamine, N-phenyl-N-5ec-butyl-p-phenylenediamine, NN'-diisopropyl-p-phenylenediamine,
N,N'dimethyl to N,N-di-L-butyl-p-phenylenediamine, etc.

Group (III): Hydroquinones 2.5-di-L-octylhydroquinone, 2゜6-sidodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-1-
Octyl-5-methylhydroquinone, 2-(2-octadecenyl)-5-methylhydroquinone, etc.

Group (IV): organic sulfur compounds dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, etc.

Group (V): mphosphorus compounds such as triphenylphosphine, tri(nonylphenyl)phosphine, tri(dinonylphenyl)phosphine, tricresylphosphine, tri(2,4-dibutylphenoxy)phosphine, and the like.

Group (Vl): Hindered amines There are those described in Japanese Patent Application No. 162867/1986.

These compounds are known as antioxidants for rubbers, plastics, oils and fats, and can be easily prepared commercially.

These antioxidants may be added to the carrier transport layer.

In that case, the amount of antioxidant added is carrier transport material ￥t1
0.00 parts by weight, the amount is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 1 to 25 parts by weight.

In addition to the resin according to the present invention, other binder resins can be used in the photosensitive layer. For example, the sulfone resin of the present invention can be used for CTL, and other binder resins can be used for CGL.

Such binder resins include, for example, polyethylene,
Addition polymer resins and polyaddition resins such as polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, etc. , polycondensation type resins, and copolymer resins containing two or more of the repeating units of these resins, such as vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate maleic acid copolymer resins, etc. In addition to insulating resins, polymeric organic semiconductors such as polyJ-N-vinylcarbazole may be used.

Further, the intermediate layer functions as an adhesive layer or a barrier layer, and in addition to the binder resin, for example, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- maleic acid copolymer, casein,
N-alkoxymethylated nylon, starch, etc. are used.

Next, the conductive support supporting the photosensitive layer is a metal plate made of aluminum or nickel, a metal drum or metal foil, a plastic film deposited with aluminum, tin oxide, indium oxide, etc., or paper coated with a conductive substance. , a film or drum of plastic or the like can be used.

The CGL can be provided by vacuum-depositing the above-mentioned CGM on the support, or by applying a solution or dispersion of CGM alone or together with a suitable binder resin in a suitable solvent and drying it.

When the above CGM is dispersed to form a CGL, the CGM is preferably in the form of powder having an average particle size of 2 μm or less, preferably 1 μm or less.

That is, if the particle size is too large, dispersion in the layer will be poor, and some of the particles will protrude from the surface, resulting in poor surface smoothness. In some cases, discharge may occur at the protruding parts of the particles, or toner may Particles tend to adhere and toner filming phenomenon occurs easily.

However, if the above particle size is too small, it tends to aggregate,
It is desirable to set the lower limit of the average grain size to 0.01 μm because the resistance of the layer increases, the sensitivity and repeatability decrease due to an increase in crystal defects, or there is a limit to miniaturization.

CGL can be provided by the following method.

That is, this is a method in which the CGM described above is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., a binder resin is added, and a dispersion obtained by mixing and dispersing is applied. Dispersing particles under the action of ultrasound in this method results in
Uniform dispersion is possible.

Examples of solvents used to form CGL include N, N
-dimethylformamide, benzene, toluene, xylene, monochlorobenzene, 1.2 dichloroethane, dichloromethane, 1,1.2 trichloroethane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, butyl acetate, and the like.

2 CGM per 100 weight of binder resin in CGL
The amount is 0 to 500 parts by weight, preferably 40 to 250 parts by weight. If CGM is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, dark decay will increase.
and the acceptance potential decreases.

The film thickness of the CGL formed as described above is preferably 1 to 10 μm, particularly preferably 3 to 7 μm in the case of a configuration for positive charging, and preferably 0 to 7 μm in the case of a configuration for negative charging.
．． 01 to 10 μm, particularly preferably 0.1 to 3 μm.

Further, CGL can be formed by using the CTM described above in the same manner as the CGL described above (that is, by coating the CTM alone or by dissolving and dispersing it together with the binder resin described above and drying it).

CTM is 20 to 200 parts by weight, preferably 30 to 150 parts by weight per 100 parts by weight of binder resin in CTL.

If the content of CTM is less than this, the photosensitivity will be poor and the residual potential will tend to be high (and if it is more than this, the solvent solubility will be poor).

The thickness of the formed CTL is preferably 5 to 50 μm,
Particularly preferably, it is 5 to 30 um. Also, CGL and C
The film thickness ratio of TL is preferably 1:(1 to 30).

In the case of the single-layer structure, the proportion of CGM contained in the binder resin is 20 parts by weight per 100 parts by weight of the binder resin.
~500 parts by weight, preferably 40 to 300 parts by weight.

If the CGM content is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, dark decay and acceptance potential will decrease.

Next, the ratio of JM to the binder resin is 20 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the binder resin.

If the CTM content is less than this, the photosensitivity will be poor and the residual potential will tend to be high, and if it is more than this, the solvent solubility will be poor.

The ratio of CTM to CGM in the single-layer photosensitive layer is preferably 1:3 to 1:2 in terms of stacking ratio.

In the present invention, the protective layer provided as necessary has a volume resistivity of 10'Ω·cm or more, preferably 1010Ω·cm or more, more preferably 10"Ω·c as a binder.
A transparent resin having a diameter of m or more is used. Further, the binder may contain a resin that is cured by light or heat.

Examples of such resins that harden with light or heat include thermosetting acrylic resins, silicone resins, epoxy resins, urethane resins, urea resins, phenol resins, polyester resins, alkyd resins, melamine resins, photocurable/cinnamic acid resins, etc. Alternatively, copolymerization of these resins (or cocondensation resins are available, as well as all of the photo- or thermosetting resins used in electrophotographic materials). In addition, the protective layer may contain materials with improved processability and physical properties. A thermoplastic resin may be contained if necessary for the purpose of preventing cracks, imparting flexibility, etc. Examples of such thermoplastic resins include polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, and epoxy resin. , butyral resin, polycarbonate resin, silicone resin, or copolymer resins thereof, such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic acid copolymer resin, poly-N-vinyl carbazole, etc. Molecular organic semiconductors and other thermoplastic resins used in electrophotographic materials can all be used.

Further, the protective layer may contain an electron-accepting substance,
In addition, if necessary, an ultraviolet absorber or the like may be included for the purpose of protecting the CGM, which is dissolved in a solvent together with the binder, and applied and dried to a thickness of 2 μm by, for example, dip coating, spray coating, blade coating, roll coating, etc. Hereinafter, the layer thickness is preferably 1 μm or less.

The photoreceptor of the present invention can be used in electrophotographic copying machines, laser beam printers, CRT printers, electrophotographic plate-making systems, and the like.

In this case, various light sources such as a He-Ne laser, a semiconductor laser (780 nm, 680 nm, etc.), an LED, a halogen lamp, etc. can be used as the light source.

E. Examples More specific examples will be described below, but the embodiments of the present invention are not limited thereto.

[Synthesis method]

was synthesized by copolymerizing the sodium salt of

Below are the blank spaces: 1. Vinyl chloride/vinyl acetate/on Egami aluminum cylinder
A 0.1 μm thick undercoat layer was formed using a 1% acetone/cyclohexanone solution of maleic acid copolymer (S-LEC MF-10, manufactured by Block Chemical Industry Co., Ltd.).

Next, sublimed 4, 10 dibrom anthron (
■-3) 40g in a porcelain ball mill at 4Orpm for 24 hours
Pulverized for a time, polycarbonate resin (Panlite L-1
250, manufactured by Kijin Kasei Co., Ltd.) was dissolved in 1,2-dichloroethane (1,300 d), and a binder liquid was added thereto, and further 24
This was dispersed over time to obtain a CGL coating solution.

This was applied by dip coating on the undercoat layer to form a CGL film with a thickness of 1 μm.
has been established.

Then, the exemplified compound Natsu-2/CTM (X-61)=1
A 1,2-dichloroethane-U solution of 0.00/75 (weight ratio) was dip-coated on the CGL to form a CTL having a film thickness of 20 Wrm, thereby forming a photoreceptor of an example.

Example 2 A photoreceptor was prepared in the same manner as in Example-1 except that 1-35 was used in place of Exemplified Compound 1-2 in Example-1.

A photoreceptor was prepared in the same manner as in Example 1, except that r-14 was used in place of exemplified compound r-2 in Practical Benefit ■Double Example-■.

A photoreceptor was prepared in the same manner as in Example 1, except that Exemplified Compound 1-2 in Example 1 was replaced with the following compound (A).

An undercoat layer was formed in the same manner as in Example-1. Then, CTM
(X -75) /Panlight L -1250=75
/100 (weight ratio) 1,2-dichloroethane solution was dip-coated on the undercoat layer to form a CTL of 20 μm.

Next, as CGM, sublimed 4,10-dibromoanthrone (■-3) was ground in a ball mill for 24 hours, and 1 to (■-3)/exemplified compound ■-2 = 50/100 (weight ratio) , 2-dichloroethane solution was added at a concentration of 9% by weight, and the mixture was further dispersed for 24 hours. Next, 75% CTM (X-75
) was added thereto, and further monochlorobenzene was added so that the ratio of monochlorobenzene/1.2-dichloroethane was 3/7 (volume ratio) to prepare a CGL coating liquid. This coating liquid was spray-coated onto the CTL to form a CGL with a thickness of 5 μm, thereby producing a photoreceptor.

A photoreceptor was prepared in the same manner as in Examples to 4, except that 1-35 was used in place of Exemplified Compound 1-2 in Example 4.

Exemplary compound of Example-4! A photoreceptor was produced in the same manner as in Example-4 except that 1-14 was used instead of -2.

Comparative Basis 2l A photoreceptor was prepared in the same manner as in Example-4, except that Compound (A) of Comparative Example-1 was used in place of Exemplified Compound 1-2 of Example-4.

EXAMPLE 2 A subbing layer was formed on the aluminum cylinder in the same manner as in Example 1. Next, butyral resin (S-LEC BX-1, manufactured by Block Chemical Co., Ltd.)/CTM (X-75) =
Prepare a methyl ethyl ketone solution so that the weight ratio is 100/75, and apply it on the undercoat layer by dip coating,
A CTL with a film thickness of 15 μm was formed.

Next, CGM (V-7) was pulverized for 30 minutes using a paint conditioner (Red Devi 1), and exemplified compound 1-2 was added to it in 1.2-dichloroethane/1.1.
．． A solution dissolved in a 2-trichloroethane mixed solution to a concentration of 0.5% by weight was added and dispersed for 3 minutes.
A solution obtained by dissolving 1.2-dichloroethane/1,1.2-trichloroethane in a mixed solution of 3% by weight and 1% by weight of 2.6% was added, and the mixture was further dispersed for 30 minutes.
A liquid L was prepared.

Next, the CGL liquid was spray coated on the CTL layer to prepare a photoreceptor.

Example 2 A photoreceptor was prepared in the same manner as in Example 7 except that 1-35 was used in place of Exemplified Compound 1-2.

A photoreceptor was prepared in the same manner as in Example 7, except that I14 was used in place of Exemplified Compound 1-2 in Example 7.

A photoreceptor was prepared in the same manner as in Example 7, except that Compound (A) of Comparative Example-1 was used in place of Exemplified Compound I-2 of Example-7.

Implementation M1 Rule The undercoat layer, CGL, and CTL were formed in the same manner as in Example-1, except that Compound (A) of Comparative Example-1 was used instead of Exemplary Compound I-2 of the CTL binder of Example-1. .

Then, 1,2-dichloroethane/of Exemplified Compound 1-2
A mixed solution of 1,1,2-trichloroethane was prepared (I
-2:1,2-dichloroethane:1.1.2-1-dichloroethane=5:100:100).

The binder liquid was spray-coated onto the CTLJi to form a protective layer with a thickness of 0.5 μm to obtain a photoreceptor.

A photoreceptor was prepared in the same manner as in Example 10, except that 35 was used in place of Exemplified Compound 1-2 in Example 10.

A photoreceptor was prepared in the same manner as in Example 10, except that 14 was used in place of Exemplified Compound 1-2 in Example 10.

Comparative Example-1 instead of Exemplified Compound 1-2 of Example-10
A photoreceptor was prepared in the same manner as in Example 10 except that compound (A) was used.

Pointed fat ■2U 1. On the aluminum cylinder. An undercoat layer was formed in the same manner as in Example-1.

Next, CGM (V-7)/acrylic resin (Elvasite 2010, manufactured by Dapon) = 100 / 40 (
Mix and adjust 1.2-dichloroethane/monoethanolamine-1000/l (volume ratio) to 2.1% by weight, pulverize with paint conditioner,
Dispersion was performed to prepare a CGL coating liquid.

This CGL coating solution was dip coated onto the undercoat layer, and 0.
A CGL with a film thickness of 3 μm was created.

Then CTM (X-43) / Exemplary compound ■-2 = 7
A 1.2-dichloroethane solution (coating liquid for CTL) was prepared so that the ratio was 5/100 (weight ratio), and dip coating was performed on the CGL to form a CTL and obtain a photoreceptor.

A photoconductor was prepared in the same manner as in Example 13, except that Exemplified Compound I-35 was used instead of Exemplified Compound I-2 in Example-13.

A photoreceptor was prepared in the same manner as in Example 13, except that Exemplified Compound I-14 was used instead of Exemplified Compound I-2 in Example-13.

Comparative Example-1 instead of Exemplified Compound 1-2 of Comparative Example-13
A photoreceptor was prepared in the same manner as in Example 13 except that compound (A) was used.

Sharp application 2■ In the same manner as in Example-1, a subbing layer was formed on an aluminum cylinder.

Next, 1. A 2-dichloroethane solution was prepared, and a dispersion liquid was prepared using a paint conditioner.

This composition was dip-coated on the undercoat layer to a thickness of 15 μm to form a single-layer photosensitive layer, thereby producing a photoreceptor.

11'' Toni U A photoreceptor was prepared in the same manner as in Example-16 except that Exemplified Compound 1-35 was used in place of Exemplified Compound 1-2 in Example-16.

A photoreceptor was prepared in the same manner as in Example-16 except that Exemplified Compound 1-14 was used in place of Exemplified Compound 1-2 of Example-17.

Comparative Example-1 instead of Exemplified Compound 1-2 of Example-16
A photoreceptor was prepared in the same manner as in Example 16 except that compound (A) was used.

(Measurement of photoreceptor characteristics) Each electrophotographic photoreceptor sample obtained as described above was
-The black paper potential vb was installed on the Bix 2812M R modified machine (manufactured by Konica Corporation) and after repeating the process of charging → exposure → development → transfer → cleaning 10,000 times.
And the white paper potential Vw was measured.

However, Examples 4 to 9.16 to 18 and Comparative Example 2.3.6
The photoreceptor was tested by changing the charging and transfer polarity from negative to positive, and by changing the developer to a negatively chargeable two-component developer.

Note that the black paper potential here refers to the surface potential of the photoreceptor when the above-mentioned copying cycle is performed using a black paper original with a reflection density of 1.3, and the white paper potential refers to the photoreceptor surface potential when a blank paper is used as the original. Represents the surface potential of the body.

In addition, the following indicators, which are important for electrophotographic photoreceptors, were evaluated.

Evaluation method 1, image Various photoreceptor samples were mounted on a modified 11-Bix2812MR machine (manufactured by Konica), and the process of charging → exposure → development → transfer → cleaning was repeated 10,000 times, and then an image was produced and image unevenness was detected. , image defects such as pinholes were evaluated, and the results were shown as ○, Δ, and ×.

2. Poor cleaning The conditions for measuring cleaning properties are as follows.

After development by the above process, the sample photoreceptor is sufficiently neutralized by light irradiation to keep the toner floating, and the toner is separated using a specific force using a centrifugal separation method. Adhesion amount: Area Duck 150
0 (manufactured by Konica), and the separation rate is calculated by dividing the difference by the amount of toner adhering before separation, and the larger the value is, the better the cleaning performance is.
Evaluation was made with ×.

3. Photoconductor surface Various photoconductor samples were mounted on a modified U-Bix2812MR machine (manufactured by Konica), and after repeating the process of charging → exposure → development → transfer → cleaning 10,000 times, the photoconductor surface was observed. The presence or absence of scratches was evaluated and indicated as ○, Δ, or ×.

The results of these measurements are shown in FIGS. 5 and 6.

Poetry As is clear from the above, the photoreceptor of the example has excellent cleaning properties and scratch resistance, and even when a large number of copies are made in succession, there is little variation in black paper potential IVbl and white paper potential Vwl, so stable copying is possible. An image is obtained.

[Brief explanation of the drawing]

FIG. 1, FIG. 2, FIG. 3, and FIG. 4 are sectional views of each side of the electrophotographic photoreceptor. FIGS. 5 and 6 are tables showing the characteristics of the electrophotographic photoreceptor, respectively. In addition, in the symbols shown in the drawings, 1... Support 2... Charge generation layer (CGL) 3...
...Charge transport layer (CTL) 4...
Photosensitive layer 5...Charge generating substance (CG, M) 7
. . . Intermediate layer 8 . . . Protective layer (OCL).

Claims (1)

[Claims] 1. A photoreceptor containing a resin having a structural unit represented by the following general formula [I] as a main repeating unit. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the general formula [I], R^1, R^2, R^3, R^4, R^5, and R^6
each represents a hydrogen atom, a substituent, a fluorine atom, or a substituent containing a fluorine atom. However, R^1, R^2R^3
, R^4, R^5, and R^6 represent a fluorine atom or a substituent having a fluorine atom. ]