JPH0675395A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body excellent in electrification stability during repeated use, hardly increasing residual potential and hardly undergoing a change in the electrification ability and sensitivity even in a reactive gas. CONSTITUTION:This electrophotographic sensitive body contains a hydroquinone deriv. represented by formula I and a compd. having structural units of hindered amine represented by formula II and structural units of hindered phenol represented by formula III in the photosensitive layer. In the formula I, each of R1-R4 is H, halogen, alkyl, alkenyl, etc. In the formula II, each of R5-R8 is H, alkyl or aryl and Z is a nitrogen-contg. ring, etc. In the formula III, R9 is H or alkyl, each of R10-R12 is H, hydroxyl, alkyl, aryl, etc., and R13 is alkyl.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
In particular, the present invention relates to an electrophotographic photoreceptor having excellent gas resistance and excellent characteristics such as charge stability even after repeated use for a long period of time.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as Se, CdS and ZnO have been used as photoconductive materials for electrophotographic photoconductors, but in recent years, they have been disadvantageous in light sensitivity, thermal stability and toxicity. Now, electrophotographic photoreceptors using organic materials have been actively developed and put into practical use. The advantages of using an organic material include low cost, excellent mass productivity, wide variation, and the possibility of adopting various substances and compositions. However, in terms of durability, reduction in charging potential and residual potential There is a problem such as a rise in the price, which is not satisfactory.

One of the causes of the decrease in durability is the problem of deterioration of the organic material. Although much is not known about the mechanism of material deterioration, there are various hazards such as light irradiation, passage of electrons and holes, and reactive gases (O ₃ , NO _x, etc.) that the photoreceptor receives during the copying process. It is thought that it is caused by being entangled with.

It is known to add a specific antioxidant for the purpose of preventing such deterioration of the material, particularly oxidation by a reactive gas. For example, JP-A-57-122444,
JP-A-61-160552, JP-A-62-26566
6, JP-A-63-18356, JP-A-64-44451
Etc.

[0005]

However, even in these methods, there is a problem that the reaction gas resistance is not sufficient, and a problem that even if the reaction gas resistance is sufficient, the residual charge and sensitivity are increased. However, satisfactory results (characteristics) have not been obtained so far, and further improvement is desired. Therefore, it is an object of the present invention to provide an electrophotographic photosensitive member which is excellent in charging stability even when repeatedly used and has a small residual potential increase. Another object of the present invention is to resist reaction gases (O ₃ , NO _x , SO
_It is to provide an electrophotographic photosensitive member having excellent properties such as ( _X ).

[0006]

The present invention provides an electrophotographic photosensitive member having a photosensitive layer containing at least a charge generating substance and a charge transporting substance on a conductive support, wherein hydroquinone or a hydroquinone is contained in the photosensitive layer. An electrophotographic photoreceptor containing the derivative (a) and a compound (b) having at least a hindered amine structural unit.

Examples of the above hydroquinone or its derivative (a) include compounds represented by the following general formula (1).

[0008]

[Chemical 4]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group) A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acyl group,
Alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group,
Alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, aryloxycarbonyl group,
It represents an alkylacyloxy group, an arylacyloxy group, a silyl group or a heterocyclic group. In the above general formula (I), a compound having at least one substituent of R ₁ , R ₂ , R ₃ , and R ₄ has a group having a total number of carbon atoms of 4 or more is used as a particularly preferable compound.

Specific examples of the hydroquinone derivative preferably used in the present invention are shown below.

[0011]

[Chemical 5]

[0012]

[Chemical 6]

[0013]

[Chemical 7]

[0014]

[Chemical 8]

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[Chemical 9]

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[0017]

[Chemical 11]

[0018]

[Chemical 12]

[0019]

[Chemical 13]

[0020]

[Chemical 14]

[0021]

[Chemical 15]

[0022]

[Chemical 16]

[0023]

[Chemical 17]

[0024]

[Chemical 18]

[0025]

[Chemical 19]

[0026]

[Chemical 20]

[0027]

[Chemical 21]

[0028]

[Chemical formula 22]

[0029]

[Chemical formula 23]

[0030]

[Chemical formula 24]

[0031]

[Chemical 25]

[0032]

[Chemical formula 26]

[0033]

[Chemical 27]

[0034]

[Chemical 28]

[0035]

[Chemical 29]

[0036]

[Chemical 30]

[0037]

[Chemical 31]

[0038]

[Chemical 32]

[0039]

[Chemical 33]

[0040]

[Chemical 34]

[0041]

[Chemical 35]

[0042]

[Chemical 36]

[0043]

[Chemical 37]

[0044]

[Chemical 38]

[0045]

[Chemical Formula 39]

[0046]

[Chemical 40]

[0047]

[Chemical 41]

[0048]

[Chemical 42]

[0049]

[Chemical 43]

[0050]

[Chemical 44]

[0051]

[Chemical formula 45]

[0052]

[Chemical formula 46]

[0053]

[Chemical 47]

A typical example of the hindered amine structural unit in the compound (b) having the hindered amine structural unit of the present invention is represented by the following general formula (II).

[0055]

[Chemical 48]

(In the formula, R ₅ , R ₆ , R ₇ , and R ₈ each represent a hydrogen atom, an alkyl group, or an aryl group, and may have a substituent. Z is necessary to form a nitrogen-containing ring. The compound (b) of the present invention preferably further has a hindered phenol structural unit, and the hindered phenol structural unit is preferably one represented by the following general formula (III). .

[0057]

[Chemical 49]

(In the formula, R ₉ represents a hydrogen atom and an alkyl group, R ₁₃ represents a substituted or unsubstituted branched alkyl group, R ₁₀ , R ₁₁ and R ₁₂ represent a hydrogen atom and a hydroxyl group, respectively. A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and R ₉ and R ₁₃ may combine with each other to form a ring.) Compound (b) having a hindered amine structural unit (hereinafter referred to as HA compound) Specific examples of the above) will be described below, but the compounds disclosed in JP-A Nos. 63-73255 and 63-73256 can also be used favorably.

[0059]

[Chemical 50]

[0060]

[Chemical 51]

[0061]

[Chemical 52]

[0062]

[Chemical 53]

[0063]

[Chemical 54]

[0064]

[Chemical 55]

[0065]

[Chemical 56]

[0066]

[Chemical 57]

[0067]

[Chemical 58]

In the electrophotographic photoreceptor of the present invention, the reason why the above object is achieved by incorporating the hydroquinone derivative and the HA compound in the photosensitive layer is not necessarily clear, but it is excellent in compatibility with the photosensitive layer constituent substances. That it does not act as a trap for electrons and holes,
The ability to react rapidly with radical substances and prevent the formation of traps is excellent, and the hydroquinone derivative and H
It is also possible that there is some interaction between the A compounds and a synergistic effect is expressed.

The present invention will be described below with reference to the drawings.

FIG. 1 is a sectional view showing a constitutional example of the electrophotographic photosensitive member of the present invention, which has a constitution in which a photosensitive layer 2 is provided on a conductive substrate 1.

2 and 3 are cross-sectional views showing another structural example of the present invention, in which the photosensitive layer is composed of a charge generation layer 3 and a charge transport layer 4 laminated.

FIG. 4 is another sectional view of the present invention, in which an undercoat layer 5 is provided between the conductive substrate 1 and the photosensitive layer 2.

FIG. 5 is a cross-sectional view showing still another structural example of the present invention, in which a protective layer 6 is provided on the photosensitive layer 2.

The conductive substrate 1 has a volume resistance of 10 ¹⁰ Ω.
Films or cylinders that have a conductivity of cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum, and metal oxides such as tin oxide and indium oxide by vapor deposition or sputtering. Plastic, paper-coated, aluminum, aluminum alloy, nickel, stainless steel, etc. plates and tubes that have been extruded and made into a raw tube by a method such as drawing, and then surface-treated by cutting, superfinishing, polishing, etc. Can be used.

In addition to the above, one obtained by dispersing conductive powder in a suitable binder resin and coating it on the above support can also be used as the conductive substrate 1 of the present invention. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as titanium black, conductive tin oxide and ITO. To be The binder resin used at the same time includes polystyrene, styrene-acrylonitrile copolymer, and styrene-
Butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, Ethyl cellulose resin,
Polyvinyl butyral, polyvinyl formal, polyvinyltoluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin, and other thermoplastic, thermosetting resin or photocurable resin Is mentioned. Such a conductive layer may be prepared by mixing these conductive powders and a binder resin with a suitable solvent such as THF, MDC, ME.
It can be provided by dispersing in K, toluene or the like and applying.

Polyvinyl chloride on a suitable cylindrical substrate,
The electrically conductive substrate 1 of the present invention is also one in which an electrically conductive layer is provided by a heat shrinkable tube containing the electrically conductive powder in a material such as polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, or Teflon. Can be used favorably as

The charge generating layer 3 may be formed of only the charge generating substance or may be formed by uniformly dispersing the charge generating substance in the binder. Therefore, the charge generating substance is formed by dispersing these components in a suitable solvent by using a ball mill, an attritor, a sand mill, ultrasonic waves or the like, coating this on a conductive support, and drying.

As the charge generating substance, for example, CI Pigment Blue 25 [Color Index (CI) 2118]
0], CI Pigment Red 41 (CI2120
0), CI Acid Red 52 (CI4510
0), CI Basic Red 3 (CI45210)
In addition to phthalocyanine pigments, azo pigments having a carbazole skeleton (described in JP-A-53-95033), azo pigments having a stilbene skeleton (JP-A-53-53).
138229), azo pigments having a distyrylbenzene skeleton (described in JP-A-53-133455), azo pigments having a triphenylamine skeleton (described in JP-A-53-132547), dibenzo. Azo pigments having a thiophene skeleton (JP-A-54-21728)
JP-A No. 54-12834), an azo pigment having an oxadiazole skeleton (described in JP-A-54-12742), an azo pigment having a fluorenone skeleton (described in JP-A-54-22834), and a bisstilbene skeleton. Azo pigments (described in JP-A-54-17733) and azo pigments having a distyryl oxadiazole skeleton (JP-A-54-54).
2129), an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-17734), and a trisazo pigment having a carbazole skeleton (JP-A-57-195767 and 57-195758). ), An azo pigment having an oxazole skeleton, and the like,
Furthermore, CI Pigment Blue 16 (CI74100)
Phthalocyanine-based pigments such as CIVAT BROWN 5
(CI73410), CI Bat Die (CI730
30) and other indigo pigments, Argoscar red B (manufactured by Violet), indanthren scarlet R (manufactured by Bayer), perylene pigments, square pigments, and polycyclic quinones such as 4,10-dibromoanthrone. Organic pigments such as pigments: Inorganic pigments such as Se, Se alloys, CdS and amorphous Si can be used.

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

The amount of the binder resin is 100
0 to 500 parts by weight, preferably 10 to 200 parts by weight
Parts by weight are suitable. The thickness of the charge generation layer is 0.01
It is preferably about 5 μm, and more preferably 0.1 to 2 μm.

As the solvent used here, tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, cyclohexane, methyl ethyl ketone, ethyl cellosolve and the like are preferable.

Examples of the coating method used here include a dip coating method, a spray coating method, a bead coating method and a nozzle coating method.

A hydroquinone derivative and an HA compound can be used in the charge generation layer 3. The addition amount of the hydroquinone derivative is 0.1 to 10 parts by weight and the HA compound is 0.5 to 100 parts by weight with respect to 100 parts by weight of the charge generation material. It is preferably 30 parts by weight.

The charge transport layer 4 can be formed by dissolving or dispersing a charge transport substance and a binder resin in a suitable solvent, coating the resultant on the charge generating layer, and drying. If necessary, a plasticizer, a leveling agent, etc. may be added.

The charge transport material includes a hole transport material and an electron transport material.

Examples of the electron transport material include chloranil, bromanil, tetracyanoethylene, tetracyanoquinone dimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone,
2,4,8-trinitrothioxanthone, 2,6,8-
Examples thereof include electron-accepting substances such as trinitro-4H-indeno [1,2-b] thiophen-4-one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide.

As the hole-transporting substance, poly-N-vinylcarbazole and its derivative, poly-γ-carbazolylethylglutamate and its derivative, pyrene-formaldehyde condensate and its derivative, polyvinylpyrene, polyvinylphenanthrene, oxazole derivative. ,
Oxadiazole derivative, imidazole derivative, monoarylamine derivative, diarylamine derivative, triarylamine derivative, stilbene derivative, α-phenylstilbene derivative, benzidine derivative, diarylmethane derivative, triarylmethane derivative, 9-styrylanthracene derivative, pyrazoline Other known materials such as derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives and butadiene derivatives can be used.

These charge transport materials may be used alone or in admixture of two or more.

As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate , Polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinylholmar, polyvinyltoluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, Thermoplastic or thermosetting resins such as urethane resin, phenol resin and alkyd resin can be mentioned.

A hydroquinone derivative and an HA compound can be used in the charge transport layer 4. The addition amount is 0.01 to 2 parts by weight of the hydroquinone derivative and 0.01 of the HA compound with respect to 100 parts by weight of the charge transport material. It is preferably from 10 to 10 parts by weight.

Tetrohydrofuran, dioxane, toluene, monochlorobenzene, dichloroethane, methylene chloride and the like are used as the solvent.

A suitable thickness of the charge transport layer 4 is about 5 to 50 μm.

In the present invention, a plasticizer or a leveling agent may be added to the charge transport layer 4. As the plasticizer, those used as general plasticizers for resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount of the plasticizer used is preferably about 0 to 30% by weight based on the binder resin. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a bar fluoroalkyl group in the side chain are used, and the amount thereof is 0 to 1% by weight based on the binder resin. Is appropriate.

Next, the case where the photosensitive layer 2 has a single layer structure will be described. In this case as well, in most cases, a function-separated type composed of a charge-generating substance and a charge-transporting substance can be mentioned.

That is, the compounds shown above can be used as the charge generating substance and the charge transporting substance.

The single-layer photosensitive layer can be formed by dissolving or dispersing the charge-generating substance, the charge-transporting substance and the binder resin in a suitable solvent, coating and drying the solution.
If necessary, a plasticizer, a leveling agent, etc. may be added.

As the binder resin, the binder resins mentioned above in the charge transport layer 4 may be used as they are, or the binder resins mentioned in the charge generation layer 3 may be mixed and used.

A photoconductor obtained by adding a hole-transporting substance to a eutectic complex formed of a pyrylium dye, bisphenol dye, or polycarbonate can also be used as the single-layer photoconductor. A hydroquinone derivative and an HA compound can be used in the single-layer photosensitive layer, but the addition amount is 10
The hydroquinone derivative is 0.01 to 5 parts by weight based on 0 part by weight.
It is preferable that the parts by weight and the HA compound are 0.01 to 10 parts by weight.

The single-layer photosensitive layer is a coating solution prepared by dispersing a charge-generating substance, a charge-transporting substance, a binder resin, the hydroquinone derivative and the HA compound using a solvent such as tetrahydrofuran, dioxane, dichloroethane or cyclohexane with a disperser or the like. It can be formed by coating with a dip coating method, spray coating, bead coating, or the like.

The film thickness of the single-layer photosensitive layer is preferably about 5 to 50 μm.

In the present invention, as shown in FIG. 4, an undercoat layer 5 can be provided between the conductive support and the photoconductor 2. The undercoat layer 5 generally contains a resin as a main component,
Considering that the photosensitive layer may be coated with a solvent on these resins, it is desirable that these resins have high solvent resistance to general organic solvents. Examples of such resins include polyvinyl alcohol, casein, water-soluble resins such as sodium polyacrylate, copolymer nylon, alcohol-soluble resins such as methoxymethylated nylon, polyurethane,
Examples thereof include melamine resins, phenol resins, alkyd-melamine resins, epoxy resins, and other curable resins that form a three-dimensional network structure.

To the undercoat layer 5, fine powder pigments of metal oxides such as titanium oxide, silica, alumina, zirconium oxide, tin oxide and indium oxide can be added to prevent moire and reduce residual potential. Good.

These undercoat layers can be formed by using an appropriate solvent and coating method as in the above-mentioned photosensitive layer.

Further, as the undercoat layer 5 of the present invention, a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like can be used.

In addition to the above, the undercoat layer 5 of the present invention contains Al ₂ O ₃
Provided by anodic oxidation, organic substances such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , and I
Those provided with an inorganic substance such as TO or CeO ₂ by the vacuum thin film forming method can also be favorably used.

The thickness of the undercoat layer 5 is preferably 0 to 5 μm.

The protective layer 6 is provided for the purpose of protecting the surface of the photoconductor, and the materials used therefor are ABS resin and AC.
S resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallyl sulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene, polyethylene terephthalate,
Polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone,
Examples thereof include resins such as polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin. In addition to the protective layer, a fluororesin such as polytetrafluoroethylene, a silicone resin, and a dispersion of an inorganic material such as titanium oxide, tin oxide, or potassium titanate in these resins for the purpose of improving wear resistance. Can be added.

As a method of forming the protective layer, a usual coating method is adopted. The protective layer preferably has a thickness of about 0.1 to 10 μm.

In addition to the above, known materials such as aC and a-SiC formed by the vacuum thin film forming method can be used as the protective layer.

In the present invention, it is possible to provide another intermediate layer (not shown) between the photosensitive layer and the protective layer.

A binder resin is generally used as a main component in the intermediate layer. Examples of these resins include polyamide, alcohol-soluble nylon resin, water-soluble vinyl butyral resin, polyvinyl butyral and polyvinyl alcohol.

As a method for forming the intermediate layer, a usual coating method is employed as described above. The thickness of the intermediate layer is 0.05 to
About 2 μm is suitable.

The mixing ratio of the hydroquinone derivative and the HA compound contained in the photosensitive layer is hydroquinone derivative /
HA compound = 5/1 to 1/20 is preferable.
If the mixing ratio is larger or smaller than this mixing ratio, the synergistic effect of mixing will be small.

[0114]

EXAMPLES Next, the present invention will be described with reference to examples.

Example 1 5 parts by weight of butyral resin [XYHL (manufactured by UCC)] was dissolved in 150 parts by weight of cyclohexanone, 10 parts by weight of trisazo pigment of the following structural formula (IV) was added, and dispersed by a ball mill for 48 hours. . Further cyclohexanone 21
0 part by weight was added and dispersion was carried out for 3 hours. This was diluted with cyclohexanone while stirring so that the solid content concentration became 0.9% by weight. The charge generation layer coating solution thus obtained was coated on a 75 μm thick aluminum vapor-deposited polyethylene terephthalate film with a doctor blade, and the temperature was maintained at 80 ° C. for 2
After drying for a minute, a charge generation layer having a thickness of 0.2 μm was formed.
Next, 8 parts by weight of a charge transport material having the following structural formula (V) and a polycarbonate resin [K-1300 (manufactured by Teijin Chemicals)] 10
Parts by weight, 0.04 parts by weight of trimethylhydroquinone as a hydroquinone derivative, 0.30 part by weight of an HA compound of Exemplified Compound No. II-14, silicone oil [KF-
50 (manufactured by Shin-Etsu Chemical Co., Ltd.)] 0.002 parts by weight was dissolved in 85 parts by weight of tetrahydrofuran. The charge transport layer coating solution thus obtained was applied onto the charge generating layer with a doctor blade and dried at 130 ° C. for 10 minutes to give a film thickness of 20 μm.
The charge transport layer of 1 was formed to prepare an electrophotographic photosensitive member of Example 1.

[0116]

[Chemical 59]

Example 2 The hydroquinone derivative of Example 1 was treated with 2-methyl-
An electrophotographic photoreceptor of Example 2 was prepared in the same manner as in Example 1 except that 5-chlorohydroquinone was used instead.

Example 3 The hydroquinone derivative in Example 1 was exemplified as Compound N.
An electrophotographic photosensitive member of Example 3 was prepared in the same manner as in Example 1 except that the HA compound was changed to the exemplified compound No. II-6 in o.I-5.

Example 4 Exemplified compound N is the hydroquinone derivative in Example 1.
An electrophotographic photosensitive member of Example 4 was prepared in the same manner as in Example 1 except that the HA compound was changed to the exemplified compound No. II-13 in o.I-242.

Example 5 Exemplified compound N is the hydroquinone derivative in Example 1.
An electrophotographic photosensitive member of Example 5 was prepared in the same manner as in Example 1 except that the HA compound was changed to the exemplified compound No. II-4 in o.I-267.

Comparative Examples 1 to 9 Electrophotographic photosensitive members of Comparative Examples 1 to 9 were prepared in the same manner as in Example 1 except that the hydroquinone derivative and HA compound in Examples 1 to 5 were used alone as shown in Table 1. Created.

Comparative Example 10 An electrophotographic photosensitive member of Comparative Example 10 was prepared in the same manner as in Example 1 except that the hydroquinone derivative and HA compound in Example 1 were not added.

Example 6 An electrophotographic photoreceptor of Example 6 was prepared in the same manner as in Example 3 except that the trisazo pigment of Example 3 was replaced with titanyl phthalocyanine and the charge transport material was replaced by the following structural formula (VI). Created.

[0124]

[Chemical 60]

Example 7 The hydroquinone derivative in Example 6 was exemplified as Compound N.
An electrophotographic photosensitive member of Example 7 was prepared in the same manner as in Example 6 except that the HA compound was changed to the exemplified compound No. II-4 in o.I-267.

Comparative Examples 11 to 14 Hydroquinone derivatives and H in Examples 6 and 7
Electrophotographic photoreceptors of Comparative Examples 11 to 14 were prepared in the same manner as in Example 6 except that the compound A was used alone as shown in Table 1.

Comparative Example 15 An electrophotographic photosensitive member of Comparative Example 15 was prepared in the same manner as in Example 6 except that the hydroquinone derivative and HA compound were not added.

Example 8 1 part by weight of an alcohol-soluble polyamide resin [CM-8000 (manufactured by Toray Industries, Inc.)] was dissolved in a mixed solvent of 80 parts by weight of methanol and 20 parts by weight of n-butanol, and this was 75 μm.
Apply on a thick aluminum vapor-deposited polyethylene terephthalate film with a doctor blade, dry at 130 ° C for 5 minutes,
An undercoat layer having a thickness of 0.1 μm was provided. Next, 2 parts by weight of titanyl phthalocyanine, 7 parts by weight of the charge-transporting substance of the structural formula (VI), 10 parts by weight of a polycarbonate resin [K-1300 (manufactured by Teijin Chemicals)], 1,2-dichloroethane 2
00 parts by weight, 0.005 parts by weight of a hydroquinone derivative of Exemplified compound No. I-272, H of Exemplified compound No. II-8
Disperse 0.40 parts by weight of compound A in a sand mill for 5 hours,
This is coated on the undercoat layer with a doctor blade, 130 ° C,
After drying for 10 minutes, a photosensitive layer having a film thickness of 20 μm was formed to prepare an electrophotographic photosensitive member of Example 8.

Comparative Example 16 Comparative Example 16 was carried out in the same manner as in Example 8 except that the hydroquinone derivative and the HA compound were not added.
An electrophotographic photoconductor of was prepared.

The electrophotographic photosensitive member obtained as described above was measured in a dynamic mode using EPA-8100 (manufactured by Kawaguchi Denki Seisakusho). First, -6kV to the photoconductor
Is discharged for 5 seconds, and the potential V ₂ (-
V) is measured, and after dark decay, a 6lux tungsten lamp is irradiated when the surface potential becomes −800 V, and the exposure amount E _{1 /} required to optically attenuate the surface potential to −80 V. The surface potential V ₃₀ (−V) after exposure for ₁₀ (lux · sec) and 30 seconds after exposure was measured. Also, the color temperature 2856
The same characteristics as above were measured after repeating the irradiation of the tungsten lamp of 5 lux at 5 ° K and the charging at -6 kV for 60,000 times (after fatigue). Table 1 shows the results before and after fatigue.

Further, the NO _X concentration (NO + NO ₂ ) 20 ppm
V ₂ (−V), E _1/10 (lux · sec), V ₃₀ (−) after being kept in an atmosphere of (20 ° C./30% RH) for 5 days
Table 2 shows the measurement results of V). The photoreceptors of Example 6 and Comparative Example 13 were evaluated in the same manner as above, with the charging polarity and the evaluation potential all being positive.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Table 4]

Example 9 5 parts by weight of butyral resin [XYHL (manufactured by UCC)] was dissolved in 150 parts by weight of cyclohexanone, 10 parts by weight of trisazo pigment represented by the following structural formula (VII) was added, and dispersed by a ball mill for 48 hours. . Further cyclohexanone 2
10 parts by weight was added and dispersed for 3 hours. This was diluted with cyclohexanone while stirring so that the solid content concentration became 0.9% by weight. The thus-obtained coating liquid for charge generation layer was applied onto a 75 μm thick aluminum-deposited polyethylene terephthalate film with a doctor blade and dried at 80 ° C. for 2 minutes to form a charge generation layer having a thickness of 0.2 μm. Next, 8 parts by weight of the charge transport material represented by the following structural formula (VIII),
Polycarbonate resin [K-1300 (manufactured by Teijin Chemicals)] 10 parts by weight, 0.005 parts by weight of trimethylhydroquinone as a hydroquinone derivative, and 4-benzoyloxy-2,2,6, as a hindered amine compound.
0.04 parts by weight of 6-tetramethylpyridine and 0.002 parts by weight of silicone oil [KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.)] were dissolved in 85 parts by weight of tetrahydrofuran. The thus-obtained charge transport layer coating liquid was applied onto the charge generation layer with a doctor blade and dried at 130 ° C. for 10 minutes to form a charge transport layer having a thickness of 20 μm. Created.

[0137]

[Chemical formula 61]

Example 10 The hydroquinone derivative of Example 9 was treated with 2-methyl-
An electrophotographic photosensitive member of Example 10 was prepared in the same manner as in Example 9 except that 5-chlorohydroquinone was used instead.

Example 11 The hydroquinone derivative in Example 9 was exemplified as Compound N.
o. I-26 is exemplified by a hindered amine compound Compound No.
Example 11 is carried out in the same manner as in Example 9 except that it is II-19.
An electrophotographic photoconductor of was prepared.

Example 12 The hydroquinone derivative in Example 9 was exemplified as Compound N.
o Hindered amine compound exemplified in I-240 Compound N
Example 1 as in Example 9 except that o.II-26 was used.
No. 2 electrophotographic photosensitive member was prepared.

Example 13 Exemplified compound N is the hydroquinone derivative in Example 9.
O.I-267 exemplified hindered amine compound Compound N
o.II-33 Example 1 similar to Example 9 except that
The electrophotographic photoconductor of No. 3 was prepared.

Comparative Examples 17 to 25 Electrophotographic photosensitive members of Comparative Examples 17 to 25 were prepared in the same manner as in Example 9 except that the hydroquinone derivative and the hindered amine compound in Examples 9 to 13 were used alone as shown in Table 1. Created.

Comparative Example 26 An electrophotographic photosensitive member of Comparative Example 26 was prepared in the same manner as in Example 9 except that the hydroquinone derivative and the hindered amine compound in Example 9 were not added.

Example 14 An electrophotographic photoreceptor of Example 14 was prepared in the same manner as in Example 11 except that the trisazo pigment of Example 11 was replaced with titanyl phthalocyanine and the charge transport material was replaced by the following structural formula (IX). Created.

[0145]

[Chemical formula 62]

Example 15 Electrophotographic sensitization of Example 15 was repeated in the same manner as in Example 14 except that the hydroquinone derivative in Example 14 was changed to Exemplified Compound No. I-54 and the hindered amine compound was changed to Exemplified Compound No. II-22. Created the body.

Comparative Examples 27 to 30 Electrophotographic photosensitive members of Comparative Examples 27 to 30 were prepared in the same manner as in Example 14 except that the hydroquinone derivative and the hindered amine compound in Examples 14 and 15 were used alone as shown in Table 1. Created.

Comparative Example 31 An electrophotographic photosensitive member of Comparative Example 31 was prepared in the same manner as in Example 14, except that the hydroquinone derivative and the hindered amine compound were not added. Example 16 1 part by weight of an alcohol-soluble polyamide resin [CM-8000 (manufactured by Toray Industries, Inc.)] was dissolved in a mixed solvent of 80 parts by weight of methanol and 20 parts by weight of n-butanol, and this was 75 μm.
Apply on a thick aluminum vapor-deposited polyethylene terephthalate film with a doctor blade, dry at 130 ° C for 5 minutes,
An undercoat layer having a thickness of 0.1 μm was provided. Next, 2 parts by weight of titanyl phthalocyanine, 7 parts by weight of the charge transport material of the structural formula (VIIII), and a polycarbonate resin [K-1300
(Manufactured by Teijin Kasei)] 10 parts by weight, 200 parts by weight of 1,2-dichloroethane, 0.007 parts by weight of hydroquinone derivative of Exemplified compound No. I-273, Exemplified compound No. II-3
6 hindered compounds of 0.07 parts by weight in a sand mill
After time dispersion, this was coated on a subbing layer with a doctor blade and dried at 130 ° C. for 10 minutes to form a photosensitive layer having a film thickness of 20 μm, to prepare an electrophotographic photosensitive member of Example 16.

Comparative Example 32 An electrophotographic photosensitive member of Comparative Example 32 was prepared in the same manner as in Example 16 except that the hydroquinone derivative and the hindered amine compound were not added.

The electrophotographic photosensitive member obtained as described above was measured in a dynamic mode using EPA-8100 (manufactured by Kawaguchi Denki Seisakusho). First, -6kV to the photoconductor
Is discharged for 5 seconds, and the potential V ₂ (-
V), and after dark decay, further irradiate a 6lux tungsten lamp when the surface potential becomes −800V, and e exposure amount E _{1 /} required to optically attenuate the surface potential to −80V. The surface potential V ₃₀ (−V) after exposure for ₁₀ (lux · sec) and 30 seconds after exposure was measured. Also, the color temperature 2856
The same characteristics as described above were measured after repeating the irradiation of the tungsten lamp 5lux at a temperature of 5 K and the charging at -6 kV for 60,000 times (after fatigue). Table 3 shows the results before and after fatigue.

Further, the NO _X concentration (NO + NO ₂ ) 20 ppm
V ₂ (−V), E _1/10 (lux · sec), V ₃₀ (−) after being kept in an atmosphere of (20 ° C./30% RHF) for 5 days
Table 4 shows the measurement results of V). The photoreceptors of Example 14 and Comparative Example 29 were evaluated in the same manner as above with the charging polarity and the evaluation potential all being positive.

[0152]

[Table 5]

[0153]

[Table 6]

[0154]

[Table 7]

[0155]

[Table 8]

[0156]

EFFECT OF THE INVENTION The electrophotographic photosensitive member of the present invention is excellent in charging stability by repeated use and has a small increase in residual potential.
Further, it is a photoconductor that has little charging property and sensitivity fluctuation even in a reactive gas.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a configuration example of an electrophotographic photosensitive member of the present invention.

FIG. 2 is an explanatory diagram of another configuration example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is an explanatory diagram of another configuration example of the electrophotographic photosensitive member of the present invention.

FIG. 4 is an explanatory diagram of another configuration example of the electrophotographic photosensitive member of the present invention.

FIG. 5 is an explanatory diagram of another configuration example of the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 1 Conductive Substrate 2 Photosensitive Layer 3 Charge Generation Layer 4 Charge Transport Layer 5 Undercoat Layer 6 Protective Layer

Claims (5)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer containing at least a charge-generating substance and a charge-transporting substance on a conductive support, wherein hydroquinone or its derivative (a) and a hindered amine are contained in the photosensitive layer. An electrophotographic photoreceptor containing the compound (b) having a structural unit. 2. The electrophotographic photosensitive member according to claim 1, wherein the compound (b) having a hindered amine structural unit further has a hindered phenol structural unit. 3. Hydroquinone or its derivative (a)
Is a compound represented by the following general formula (I), and the electrophotographic photosensitive member according to claim 1 or 2. [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted Unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, alkylthio group, arylthio group, alkylamino group, arylamino group, acyl group, alkylacylamino group, arylacylamino group, Alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylacyloxy Group Represents a reel acyloxy group, a silyl group or a heterocyclic group.) 4. The electrophotographic photoreceptor according to claim 1 or 3, wherein the hindered amine structural unit is represented by the following general formula (II). [Chemical 2] (In the formula, R ₅ , R ₆ , R ₇ , and R ₈ each represent a hydrogen atom, an alkyl group, or an aryl group, and may have a substituent.
Z represents an atomic group necessary for forming a nitrogen-containing ring) 5. The electrophotographic photoreceptor according to claim 2, wherein the hindered phenol structural unit is represented by the following general formula (III). [Chemical 3] (In the formula, R ₉ represents a hydrogen atom or an alkyl group, R ₁₃ represents a substituted or unsubstituted branched alkyl group, R ₁₀ and R
₁₁ and R ₁₂ each represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ₉ and R ₁₃ may combine with each other to form a ring. )