JP3538140B2 - How to store the electrophotographic photoreceptor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for storing an electrophotographic photoreceptor in which the photoreceptor is prevented from being deteriorated in a storage state before use and in an early stage of use.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have heretofore been Se, C
Inorganic materials such as dS and ZnO have been used, but in recent years, electrophotographic photoreceptors using organic materials exhibiting comparable properties have been developed and put into practical use. The advantages include inexpensiveness, mass productivity, and the like. However, since it is an organic substance, deterioration of the material cannot be avoided. On the other hand, an undercoat layer, a protective layer and the like are provided irrespective of an inorganic or organic material. However, since many of these are partially provided with an organic material, deterioration of the material cannot be avoided. Many such Deterioration mechanism of the material is not known, by light irradiation, due to passage of electrons, the reactive gases (NOx, SOx, O _3, etc.) or the like due are contemplated. It is known to add a specific antioxidant to the photosensitive layer in order to prevent such deterioration of the material, especially oxidation. For example, Japanese Patent Application Laid-Open Nos.
1-160552, JP-A-62-265666, JP-A-63-18356, JP-A-64-44451, and the like. However, in these inventions, the antioxidant is contained in the photosensitive layer, and from the viewpoint of storage, the antioxidant in the photoconductor is oxidatively deteriorated during the storage period of the photoconductor and cannot withstand storage. On the other hand, if an antioxidant is added more than necessary to the photoreceptor, it adversely affects the electrostatic characteristics when the photoreceptor is used, and an improvement in this respect has been strongly desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for preserving an electrophotographic photoreceptor which does not cause an abnormal image even after preservation in an oxidizing environment. Another object of the present invention is to provide a method for preserving an electrophotographic photosensitive member that does not cause deterioration of the photosensitive member in an early stage of use. Still another object of the present invention is to provide a method for preserving an electrophotographic photoreceptor capable of realizing an inexpensive and effective storage state.
Still another object of the present invention is to provide a method for preserving an electrophotographic photoreceptor which can always achieve effective preservation regardless of the preservation form.

[0004]

According to the present invention, the following inventions are provided. A method for preserving an electrophotographic photoreceptor, comprising: attaching an antioxidant to the surface of the electrophotographic photoreceptor after the photoreceptor is manufactured and before it is used in an electrophotographic process.

The present inventors have found that the above problems can be solved by attaching an antioxidant to the surface of the photoreceptor, and that the deterioration of the photoreceptor in the early stage of use can be prevented. Reached. Therefore, according to the present invention, the photosensitive member can be stored inexpensively and effectively without using an expensive photosensitive member storage method (for example, a photosensitive member storage container sealed with an inert gas). Also, regardless of the storage form of the photoconductor (inside or outside the actual machine, the degree of sealing of the cassette or storage container, etc.), effective storage can always be achieved. As a method of attaching such an antioxidant to the electrophotographic photoreceptor, a method of attaching the antioxidant powder as it is to the surface of the photoreceptor and attaching it, and attaching the microencapsulated antioxidant to the surface of the photoreceptor How to adhere,
A method in which an antioxidant powder or a microencapsulated antioxidant is applied to a photoreceptor by electrostatic force, a method in which an antioxidant is dissolved in an appropriate solvent, applied to the surface of the photoreceptor by an appropriate method, dried, and applied. And the like.

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Next, antioxidants which can be used in the present invention will be described. As an antioxidant that can be used in the present invention, plastics, rubber, petroleum, antioxidants for oils and fats, ultraviolet absorbers,
As the light stabilizer, all known materials can be used, and particularly, a material selected from the following compound group can be preferably used.

(1) Phenols described in JP-A-57-122444, phenol derivatives described in JP-A-60-188856 and JP-A-63-18356
Binder phenols described in Japanese Patent Application Publication No.

(2) Paraphenylenediamines described in JP-A-57-122444, JP-A-60-188
Paraphenylenediamine derivatives described in JP-A-956 and para-phenylenediamines described in JP-A-63-18356.

(3) Hydroquinones described in JP-A-57-122444, hydroquinone derivatives described in JP-A-60-188896, and JP-A-63-1
Hydroquinones described in No. 8356.

(4) Sulfur compounds described in JP-A-57-188956 and organic sulfur compounds described in JP-A-63-18356.

(5) Organic phosphorus compounds described in JP-A-57-122444 and organic phosphorus compounds described in JP-A-63-18356.

(6) Hydroxyanisols described in JP-A-57-122444.

(7) Piperidine derivatives and oxopiperazine derivatives having a specific skeleton structure described in JP-A-63-18355.

(8) Carotenes, amines, tocopherols, Ni described in JP-A-60-188956
(II) Complexes, sulfides and the like.

(9) US Pat. No. 1,968,906 and J. Pat. Am. Chem. Soc. 55, 1224 (1
933), a compound represented by the following general formula (I) (formula 1).

Embedded image (Wherein, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom,
Biloxy group, substituted or unsubstituted alkyl group, alkenyl group, aryl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, and substituted amino group, imino group, heterocyclic group, sulfoxide group, sulfonyl group , An acyl group or an azo group. )

(10) A compound represented by the following general formula (II):

Embedded image (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 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, arylcarbimoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, Alkyl acyloxy group, Represents a reel acyloxy group, a silyl group or a heterocyclic group, provided that at least one of R ₁ , R ₂ , R ₃ and R ₄ is a group having a total of 4 or more carbon atoms.)

(11) A compound represented by the following general formula (III):

Embedded image (Wherein, R ₅ represents —C—C _n H _{2n + 1-m} (R ₉ ) _m ,
R ₆ represents a substituted or unsubstituted alkyl group having 4 to 20 carbon atoms, an aryloxy group, an alkoxy group, a cycloalkyl group, an aryl group, an aralkyl group, or R ₅ ;
R ₉ may be combined with R ₉ to form a ring having 5 to 10 carbon atoms, but R ₇ and R ₈ are not simultaneously hydrogen, and R ₉ is a substituted or unsubstituted aryl group, arylthio group, An aryloxy group, an arylacylamino group, an arylcarbamoyl group, an arylsulfonyl group, an aryloxycarbonyl group, an arylacyloxy group, an arylamino group, an arylsulfonamide group, an arylsulfonyloxy group, n represents 1 to 5, m represents 1 or 2. ),

(12) A compound represented by the following general formula (IV):

Embedded image (Wherein, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aryl group, arylthio group, aryloxy group, benzyl group,
R ₁₀ and R ₁₁ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an acyl group, an alkylamino group, or an alkylcarbamoyl group. )

(13) A compound represented by the following general formula (V):

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ 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, arylcargimoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group , Alkyloxycarbonyl group, aryloxycarbonyl group, alkyl Acyloxy group, arylacyloxy group, a silyl group or a heterocyclic group.

(14) A compound represented by the following general formula (VI) (formula 6).

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ 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, arylcargimoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group , Alkyloxycarbonyl group, aryloxycarbonyl group, alkyl Acyloxy group, arylacyloxy group, a silyl group or a heterocyclic group.

(15) A compound represented by the following general formula (VII):

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Or an 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, arylcarbimoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group,
Alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, aryloxycarbonyl group,
Represents an alkylacyloxy group, an arylacyloxy group, a silyl group or a heterocyclic group.

(16) The following general formula (VIII)
A compound represented by the formula:

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ 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, Substituted or 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, arylcargimoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxycarbonyl group, aryloxycarbonyl Group, alkylacyloxy group, It represents reel acyl group, a silyl group, or a heterocyclic group.

(17) A compound represented by the following formula (IX):

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ 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, arylcargimoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group , Alkyloxycarbonyl group, aryloxycarbonyl group, alkyl Represents an acyloxy group, an arylacyloxy group, a silyl group or a heterocyclic group, and specific examples of the compounds represented by the general formulas (I) to (IX) are shown below, but it goes without saying that the compounds are not limited thereto. In the present invention, as a means for adhering these antioxidants to the surface of the photoreceptor, in addition to the above-described method, for example, the antioxidants may be added to the developer in the form of a toner or its surface, a carrier surface or a powder. [Specific examples of the compound of the general formula (I)]

[Table 1]

[Table 2] [Specific examples of compound of general formula (II)]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

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[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

[Table 19]

[Table 20]

[Table 21]

[Table 22]

[Table 23]

[Table 24]

[Table 25]

[Table 26]

[Table 27]

[Table 28]

[Table 29]

[Table 30]

[Table 31]

[Table 32]

[Table 33]

[Table 34] [Specific examples of compound of general formula (III)]

[Table 35]

[Table 36]

[Table 37]

[Table 38]

[Table 39]

[Table 40]

[Table 41] [Specific examples of compound of general formula (IV)]

[Table 42]

[Table 43] [Specific examples of compound of general formula (V)]

[Table 44]

[Table 45]

[Table 46]

[Table 47]

[Table 48]

[Table 49]

[Table 50]

[Table 51]

[Table 52]

[Table 53]

[Table 54]

[Table 55]

[Table 56] [Specific examples of compound of general formula (VI)]

[Table 57]

[Table 58] [Specific examples of compound of general formula (VII)]

[Table 59]

[Table 60]

[Table 61]

[Table 62]

[Table 63]

[Table 64]

[Table 65] [Specific examples of the compound of the general formula (VIII)]

[Table 66]

[Table 67]

[Table 68]

[Table 69]

[Table 70] [Specific Examples of Compound of General Formula (IX)]

[Table 71]

[Table 72]

[Table 73]

[Table 74]

The photoreceptor to which the present invention is applied is not limited, and various types can be applied. FIG. 1 shows the most basic photoconductor, in which a photoconductive layer 12 is provided on a conductive substrate 11 (however, the photoconductive layer 12 is a single layer here), and FIG. ,
(B) is a photoconductor in which a photosensitive layer 12 composed of a stack of a charge generation layer 121 and a charge transport layer 122 is provided on a conductive substrate 11, and FIG. 3 is a conductive substrate of the photoconductor shown in FIG. 1 or FIG. 1
4A and FIG. 4B show a structure in which an intermediate layer 13 is provided between the photosensitive layer 12 and the photosensitive layer 12 on the photosensitive layer 12 of the photosensitive member shown in FIG. 1, FIG. 2 or FIG. This shows a type in which the protective layer 14 is provided.

The conductive substrate 11 has a volume resistance of 10 ^13.
Ωcm or less conductivity, for example, aluminum,
Metals such as nickel, chromium, nichrome, copper, silver, gold, platinum, etc., metal oxides such as tin oxide, indium oxide, etc. coated on film or cylindrical plastic or paper by vapor deposition or sputtering, or aluminum , Aluminum alloy, nickel, stainless steel, etc. I. , I .; I. A pipe or the like that has been surface-treated by cutting, superfinishing, polishing, or the like after forming into a liquid tube by a method such as extrusion or drawing can be used.

When the photosensitive layer 12 is of an inorganic type, the photosensitive layer 12 includes, for example, amorphous Se, CdS, ZnO, etc.
Representative examples include chemical substances and alloys such as Se-Te-Cl and Se-As, which are formed by a vapor deposition method or a form dispersed in a binder resin. The binder resin is the same as the binder resin used as needed in forming an organic photosensitive layer described later. Further, the inorganic photosensitive layer may be composed of a stack of photosensitive layers having different absorption wavelengths. On the other hand, if the photosensitive layer 12 is of an organic type, the photosensitive layer 12 may of course be a single layer.

First, the layered organic photosensitive layer (comprising the charge generation layer 121 and the charge transport layer 122) will be described. The charge generation layer 121 is a layer containing a charge generation substance as a main material. A resin may be used. As the binder resin, polyamide, polyurethane, polyester, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinyl carbazole, polyacrylamide and the like are used.

As the charge generating substance, for example, CI Pigment Blue 25 [Color Index (CI) 2
1180], C.I. Pigment Red 41 (CI21
200), CI Acid Red 52 (CI4510)
0), CI Basic Red 3 (CI4521)
0), phthalocyanine pigments having a porphyrin skeleton, azo pigments having a carbazole skeleton (described in JP-A-53-95033), and azo pigments having a distyrylbenzene skeleton (described in JP-A-53-133455). Azo pigments having a triphenylamine skeleton (described in JP-A-53-132547), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-217)
No. 28), an azo pigment having an oxadiazole skeleton (described in JP-A-54-12742), and an azo pigment having a fluorenone skeleton (described in JP-A-54-2283).
No. 4), an azo pigment having a bisstilbene skeleton (described in JP-A-54-17733), and an azo pigment having a distyryloxadiazole skeleton (described in JP-A-54-17733).
JP-A-2129), an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-17734), and C.I. Pigment Blue 16 (CI
Phthalocyanine pigments such as C.I. 74100); indigo pigments such as C.I.Vait Brown 5 (CI73410); C.I.D.D.D. (CI73030); And the like. Among these charge generating substances, azo pigments are preferred.

These charge generating substances may be used alone or in combination of two or more. The binder resin is suitably used in an amount of 0 to 100 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of the charge generating substance. The charge generating layer 121 is a charge generating material dispersed together with a binder resin, if necessary, using a solvent such as tetrahydrofuran, cyclohexane, dioxane, or dichloroethane using a ball mill, an attritor, or a sand mill.
It can be formed by appropriately diluting the dispersion and applying it. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like. Charge generation layer 12
The film thickness of 1 is suitably about 0.01 to 5 μm, and preferably 0.1 to 2 μm.

The charge transporting layer 122 can be formed by dissolving or dispersing a charge transporting substance and a binder resin in a suitable solvent, applying the solution on the charge generating layer 121, the conductive substrate 11 or the intermediate layer 13, and drying. . If necessary, a plasticizer, a leveling agent, and the like can be added.
The charge transport materials include a hole transport material and an electron transport material.

Examples of the hole transport material include poly-N-vinylcarbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene, polyvinylphenanthrene and oxazole derivatives ,
Oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazolin, phenylhydrazones, Electron donating substances such as α-phenylstilbene derivatives and benzidine derivatives are exemplified.

Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinonedimethane, 2,4,7-trinitro-9-
Fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6
Electron accepting substances such as 8-trinitro-4H-indeno [1,2-b] thiophen-4-one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide are exemplified. These charge transport materials are used alone or in combination 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 resin, phenoxy resin, polycarbonate,
Cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin,
Thermoplastic or thermosetting resins such as silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin can be used. As the solvent, tetrahydrofuran, dioxane, toluene, monochlorobenzene, dichloroethane, methylene chloride and the like are used. The thickness of the charge transport layer 122 is suitably about 5 to 50 μm.

Next, the case where the organic photosensitive layer 12 has a single-layer structure (single-layer organic photosensitive layer) will be described. In this case, too, a function-separated type composed of a charge generating substance and a charge transporting substance is often used. That is, the compounds described above can be used as the charge generating substance and the charge transporting substance.

The single-layer organic photosensitive layer can be formed by dissolving or dispersing a charge generating substance, a charge transporting substance, and a binder resin in an appropriate solvent, and applying and drying this. If necessary, a plasticizer, a leveling agent and the like can be added. As the binder resin, the binder resin described for the charge transport layer 122 may be used as it is, or the binder resin described for the charge generation layer 121 may be mixed and used.

The single-layer organic photosensitive layer is formed by dip coating or spray coating a coating liquid obtained by dispersing a charge generating substance, a charge transporting substance, and a binder resin using a solvent such as tetrahydrofuran, dioxane, dichloroethane, or cyclohexanone with a disperser or the like. And bead coating.
The thickness of the single-layer organic photosensitive layer is suitably about 5 to 50 μm.

The electrophotographic photosensitive member is shown in FIGS.
(B), the conductive substrate 11 and the photosensitive layer 12
By providing the intermediate layer 13 between the two, the effect as a photoreceptor can be further improved, and the adhesiveness can also be improved.

The intermediate layer 13 is formed by depositing an inorganic material such as Sio or Al ₂ O ₂ by vapor deposition, sputtering, or anodic oxidation, or a polyamide resin (Japanese Patent Application Laid-Open No. 58-3075).
7, JP-A-58-98739).
Alcohol-soluble nylon resin (JP-A-60-1967)
66, a water-soluble polyvinyl butyral resin (described in JP-A-60-232553), a polyvinyl butyral resin (described in JP-A-58-106549), and a resin layer such as polyvinyl alcohol. Can be. The intermediate layer 13 includes ZnO, TiO ₂ , Z
Pigment particles such as nS may be dispersed in an appropriate amount, and a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like may be used as the intermediate layer 13. The thickness of the intermediate layer 13 is suitably from 0 to 5 μm.

The above-mentioned photosensitive members are provided with a protective layer 14 on the photosensitive layer 12 as necessary (FIG. 4).
(A), (B)). Examples of the resin used for the protective layer 14 include ABS resin, ACS resin, olefin-vinyl copolymer resin, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyarylate, polyallyl sulfone, and polybutylene. , Polybutylene terephthalate, polycarbonate,
Polyether sulfone, polyethylene, polyethylene phthalate, polyimide, methacrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer resin, polyurethane, polyvinyl chloride, polyvinylidene chloride, epoxy resin, etc. Is mentioned.

To the protective layer 14, from the viewpoint of abrasion resistance, a polytetrafluoroethylene resin, a fluororesin, or a silicone resin is added as an additive to lower the friction coefficient and improve the abrasion resistance and the scratch resistance. The wear resistance can be improved even if an inorganic compound of titanium oxide, oxides, or potassium titanate is dispersed in the resin. Protective layer 14
Has a thickness of 0.5 to 10 μm, preferably 1 to 5 μm.

[0044]

The present invention will be described in more detail with reference to the following examples.

COMPARATIVE EXAMPLE 1 A coating liquid for an undercoat layer, a coating liquid for a charge generation layer, and a coating liquid for a charge transport layer were sequentially coated and dried on a polyester film on which Al had been deposited by vapor deposition. A 2 μm-thick undercoat layer was formed with a 0.3 μm-thick charge generation layer and a 22 μm-thick charge transport layer to prepare a photoconductor of a comparative example. [Undercoat layer coating solution] Methanol 80 parts n-butanol 20 parts Alcohol-soluble nylon (Alamine CM-8000, manufactured by Toray) 3 parts Alcohol-soluble nylon is dissolved in a methanol / n-butanol mixed solvent having the above composition, and the undercoat is performed. A layer coating solution was prepared. [Charge generating layer coating liquid] Azo pigment having the following structure

Embedded image Cyclohexane 100 parts Tetrahydrofuran 50 parts [Coating solution for charge transport layer] Dichloromethane 83 parts Polycarbonate (Panlite K-1300, manufactured by Teijin Chemicals) 10 parts Charge transport material (Chemical formula 11) 7 parts

Embedded image The above photoreceptor was processed with a grounding conductive layer, and was bonded to form a photoreceptor for mounting.

Examples 1 to 9 The antioxidants shown in Table 11 were directly adhered to the photoreceptor of Comparative Example 1 to obtain an electrophotographic photoreceptor of the present invention. Example 1
Each of the photoreceptors of Comparative Examples 1 to 9 and Comparative Example 1 was mounted on a cassette for LP-4080, and allowed to stand in a nitrogen dioxide exposure tester under conditions of a NO ₂ concentration of 5 ppm, 25 ° C. and a humidity of 35% for 5 days. Then, Ricoh laser printer LP-40
Printing was performed at 80, and the image density of the image portion was measured with a Macbeth densitometer. Table 11 shows the values of the first sheet and the 1000th sheet.

[Table 75]

COMPARATIVE EXAMPLE 2 Thickness was determined by plasma CVD on an aluminum cylinder having a diameter of 40 mm. A 5 μm amorphous silicon (a-Si: H) layer was provided to serve as a charge generation layer. Next, a charge transport layer coating solution having the following composition was applied thereon and dried to form a 20 μm charge transport layer, thereby preparing an electrophotographic photoreceptor of Comparative Example. [Charge transport layer coating solution] Toluene 320 parts Polycarbonate resin (Iupilon Z-200, manufactured by Mitsubishi Gas Chemical) 10 parts Charge transport material (Chemical formula 12) 49 parts

Embedded image

Examples 10 to 18 The photoreceptor of Comparative Example 2 was uniformly charged with a corona charger having a discharge pressure of -5.3 kV, and immediately applied with the antioxidant shown in Table 12 in a dark place. By attaching to the surface, an electrophotographic photoreceptor of the present invention was prepared. Each of the photoreceptors of Examples 10 to 18 and Comparative Example 2 was mounted on a cassette for LP-1060, and left in an ozone exposure tester at an ozone concentration of 5 ppm and 35 ° C. for 5 days. Then Ricoh Laser Printer LP-
Printing was performed at 1060 and SP-3, and dirt on the background portion of the image was visually evaluated on a five-point scale. However, rank 5
Is good and rank 1 is bad. Table 12 shows the results.

[Table 76]

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[0081]

According to the method for storing an electrophotographic photosensitive member of the present invention, it is possible to suppress a decrease in the charged potential without losing high sensitivity by repeated use. That is, in the negative-to-negative development that prevents a decrease in image density in the positive-positive development, it is possible to prevent the background portion from being stained.
In addition, since the method of storing the electrophotographic photosensitive member is excellent in environmental resistance (reaction gas resistance) in a copying machine or the like, it is highly durable and can prevent occurrence of an abnormal image.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a single-layer type electrophotographic photosensitive member according to the present invention.

FIGS. 2A and 2B are schematic cross-sectional views of a laminated electrophotographic photosensitive member according to the present invention.

FIG. 3 is a schematic cross-sectional view of an electrophotographic photoreceptor provided with an intermediate layer to which the present invention is applied.

FIGS. 4A and 4B are schematic cross-sectional views of an electrophotographic photosensitive member provided with a protective layer to which the present invention is applied.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-181298 (JP, A) JP-A-59-135477 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 5/00 G03G 21/00

Claims (1)

(57) [Claims] 1. A method of manufacturing a photoconductor in which at least a charge generation layer and a charge transport layer are laminated on a conductive support, and until the photoconductor is mounted on an electrophotographic apparatus until it is used in an electrophotographic process. A method for preserving an electrophotographic photosensitive member, wherein an antioxidant is attached to the surface of the electrophotographic photosensitive member for storage.