JP2610861B2 - Electrophotographic photoreceptor - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an improvement in an electrophotographic photoreceptor having a layer in which a charge generating substance is dispersed.

(Prior art)

2. Description of the Related Art Conventionally, an electrophotographic photoconductor provided with a charge generation layer in which various resins are blended together with a charge generation material has been known. Examples of such resins include polyvinyl butyral (Japanese Patent Application Laid-Open No. 58-105154), fatty acid cellulose ester (Japanese Patent Application Laid-Open No. 58-166353), and an acrylic resin having a Tg of 70 ° C. or less and an acid value of 10 to 40 (Japanese Patent Application Laid-open No. 58-192040), a mixture of a resin having a Tg of 70 ° C. or lower and a resin having a Tg of 75 ° C. or higher (Japanese Patent Laid-Open No. 58-19 / 1983).
No. 3549), a resin-solvent system having lower compatibility with the charge-generating material-resin-solvent system and redispersion (Japanese Patent Application Laid-Open No.
-12646), polyvinylpyrrolidone (JP-A-56-11314)
No. 0), polyvinyl formal resin (JP-A-61-235844)
No.) and the like.

However, conventionally known photoconductors have a problem that the sensitivity and the chargeability against pre-exposure fatigue vary depending on the mixing ratio of the charge generating substance and the binder resin.

That is, the conventional photoreceptor can increase the sensitivity by reducing the amount of the binder resin used for the charge generating substance, but the chargeability with respect to the pre-exposure fatigue becomes remarkable,
Conversely, if the amount of the binder resin used relative to the charge generating substance is increased, a decrease in the chargeability due to pre-exposure fatigue can be suppressed, but the problem that the sensitivity is significantly reduced is included.

Further, the conventional photoreceptor also has a drawback that the charging potential is significantly reduced when charging and exposure are repeated.

〔Purpose〕

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotographic photoreceptor which has high sensitivity, has a remarkably small reduction in chargeability due to pre-exposure fatigue, and has a charge potential which does not decrease even when charging and exposure are repeated.

〔Constitution〕

According to the present invention, in an electrophotographic photoreceptor having at least a layer in which a charge generating substance is dispersed on a conductive support, the layer in which the charge generating substance is dispersed is an azo pigment which is a charge generating substance and a crown which is a binder. An electrophotographic photoreceptor characterized by comprising ether is provided.

Since the electrophotographic photoreceptor of the present invention contains crown ether in the layer in which the charge generating substance is dispersed, the photoreceptor is highly sensitive and has a remarkably small reduction in chargeability due to pre-exposure fatigue. Also has a remarkable effect that the charged potential does not decrease.

Generally, the chargeability of a highly sensitive photoreceptor is reduced due to pre-exposure fatigue. In the pre-exposure fatigue, as the time during which charges generated by light absorption remain in the photosensitive member in a movable state and the number of the charges are increased, the chargeability due to the pre-exposure fatigue is remarkably reduced. That is, even if the charging operation is performed in a state where the charge generated by the light absorption remains, the surface charge is neutralized by the movement of the remaining carrier, so that the surface potential does not increase until the residual charge is consumed. Therefore, the rise of the surface potential is delayed by the amount of the pre-exposure fatigue, and the apparent charging potential is lowered.

The present inventors have conducted intensive studies to improve this point, and as a result, have found that when the crown ether is contained in the layer in which the charge-generating substance is dispersed, the above-mentioned disadvantage is solved, and the present invention has been completed. .

The reason why the present invention has such a remarkable effect is not always clear at the local point, but since crown ether is chemically adsorbed to the charge generating substance and becomes a recombination center of the charge generated by light absorption, pre-exposure fatigue is caused. It is considered that the charge generated in the step (1) quickly recombine and the charge disappears, thereby suppressing a decrease in the charged potential of the photoconductor.

Further, since the effect on the pre-exposure fatigue as described above also appears during actual use in which charging and exposure are repeated, the electrophotographic photoreceptor according to the present invention is more electrically charged than the conventional one. Even when the exposure is repeated, the decrease in the charged potential is remarkably small.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

FIGS. 1 to 4 are drawings for explaining a typical layer structure of the electrophotographic photoreceptor of the present invention.

FIG. 1 shows a structure in which a charge generation layer 1 and a charge transfer layer 2 are sequentially laminated on a conductive support 3, and FIG. 2 shows a structure in which the charge generation layer 1 and the charge transfer layer 2 are laminated in FIG. The charge generation layer 1 is formed by a coating method that does not disturb the charge transfer layer 2, such as a spray coating method.

FIG. 3 is different from the laminated photosensitive layer of FIGS.
1 shows a photoconductor composed of a single-layer type photosensitive layer having a charge generation function and a charge transfer function in one layer.

FIG. 4 shows a structure in which an undercoat layer 5 is provided between the conductive support 3 and the charge generation layer 1 in FIG. Such an undercoat layer 5 can be similarly applied to the structure shown in FIGS. 2 and 3.

When the undercoat layer is intended to prevent light interference in a photoreceptor for a laser printer, a light-scattering undercoat layer or a light-absorbing undercoat layer is used. A resin undercoat layer such as polyamide, polyester, vinyl chloride-vinyl acetate copolymer, or polyvinyl butyral having good properties is used.

Next, each constituent material used in the present invention will be described.

The conductive support is intended to supply a charge having a polarity opposite to that of the charged charge to the substrate side, and has an electric resistance of
A material having a resistivity of 10 ⁸ Ωcm or less and capable of withstanding the conditions for forming the charge generation layer, the charge transfer layer, and the undercoat layer can be used. Examples of such materials include electrically conductive metals and alloys such as Al, Ni, Cr, Zn, and stainless steel; inorganic insulating materials such as glass and ceramics; and organic insulating materials such as polyester, polyimide, phenolic resin, nylon resin, and paper. The surface of the material is vacuum-evaporated, sputtered, spray-painted, etc., using Al, Ni, Cr, Zn, stainless steel, carbon,
Examples thereof include those obtained by coating an electrically conductive substance such as SnO ₂ or In ₂ O ₃ and performing a conductive treatment.

The layer in which the charge generating substance is dispersed is constituted as a charge generating layer in the laminated photosensitive layer as shown in FIGS. 1, 2 and 4, and a single layer type as shown in FIG. In the photosensitive layer, it is formed in the photosensitive layer.

In the multilayer photosensitive layer, the charge generation layer is composed of a charge generation substance and a binder.

In the present invention, crown ether is used as the binder.

As the crown ether used in the present invention, those having 3 to 8 oxygen atoms constituting a ring are preferable, and examples of such a crown ether include the following compounds.

The layer in which the charge generating substance of the present invention is dispersed contains crown ether as a binder, but if necessary, another resin binder used for this type of charge generating layer can be used in combination.

Such resin binders include polystyrene,
Styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer,
Polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyacrylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly- Thermoplastic or thermosetting resins such as N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin.

The total amount of the binder resin is 100
It is suitably used in an amount of 0.01 to 200 parts by weight, preferably 1 to 50 parts by weight based on parts by weight. Crown ether is used in an amount of at least 0.0
It is necessary to contain 1 part by weight, preferably 1 part by weight or more.

Examples of the charge generating substance include an azo pigment having a carbazole skeleton (described in JP-A-53-95033) and an azo pigment having a stilstilbene skeleton (described in JP-A-53-1382).
No. 29), azo pigments having a triphenylamine skeleton (described in JP-A-53-132547), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), Azo pigments having an azole skeleton (described in JP-A-54-12742), azo pigments having a fluorenone skeleton (described in JP-A-54-22834),
Azo pigments having a bisstilbene skeleton (JP-A-5-1773)
No. 3), an azo pigment having a distyryloxadiazole skeleton (described in JP-A-54-2129), and an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-2129).
17734), triazo pigments having a carbazole skeleton (described in JP-A-57-195767 and JP-A-57-195768), and C.I.
(CI 74100) and other phthalocyanine-based pigments, Sea Ivat Brown 5 (CI 73410), Sea Ivat Die (CI 7100)
Organic pigments such as indigo pigments such as 3030) and perylene pigments such as Argoscarlet B (manufactured by Violet) and Indus Scarlet R (manufactured by Bayer) can be used.

Among these charge generating substances, azo pigments are particularly preferred, and among the azo pigments, the following disazo pigments or trisazo pigments are most preferred.

 Specific examples of the azo pigment are shown below.

The thickness of the charge generation layer 1 is suitably about 0.05 to 2 μm, and preferably 0.1 to 1 μm.

The charge generation layer 1 can be formed by dissolving or dispersing a resin binder and a charge generation substance in an appropriate solvent, and applying and drying this. As a solvent, benzene, toluene, xylene, methylene chloride, dichloroethane, monochlorobenzene, dichlorobenzene, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxane, tetrahydrofuran, cyclohexanone, methyl cellosolve, ethyl cellosolve, etc. may be used alone or in combination. it can.

The charge transfer layer 2 is formed by dissolving or dispersing a charge transfer material and a resin binder in an appropriate solvent,
It can be formed by coating and drying on the top. If necessary, a plasticizer or a leveling agent can be added.

Examples of charge transfer materials include poly-N-vinylcarbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, oxadiazole Derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazolin, phenylhydrazones, α-phenyl Electron donating substances such as stilbene derivatives;

Examples of the resin binder include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, and vinyl chloride-vinyl acetate copolymer used in the charge generation layer. Coalescence, polyvinyl acetate, polyvinylidene chloride, polyacrylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin And a thermoplastic or thermosetting resin such as melamine resin, urethane resin, phenol resin and alkyd resin.

As the solvent at this time, tetrahydrofuran, dioxane, toluene, monochlorobenzene, dichloroethane, methylene chloride and the like can be used.

The thickness of the charge transfer layer 2 is suitably about 5 to 100 μm.

In the case where the layer in which the charge generating substance is dispersed is a single-layer type photosensitive layer as shown in FIG. 3, the charge generating substance, crown ether, resin binder and, if necessary, It can be formed by mixing the charge transfer materials used in the charge transfer layer, and applying and drying these coating solutions on a conductive support or the like.

Further, in the present invention, as described above, an undercoat layer can be provided between the conductive support and the photosensitive layer, if necessary.

The light-scattering subbing layer and the light-absorbing subbing layer are layers for preventing light interference in the photoreceptor for a printer as described above. The light-scattering undercoat layer is constituted by dispersing a conductive pigment such as tin oxide and antimony oxide and a white pigment such as zinc oxide, zinc oxide and titanium oxide in the following thermosetting resin, The light-absorbing undercoat layer is formed by dispersing a conductive light-absorbing pigment such as carbon or various metals and / or a light-absorbing organic pigment in a similar thermosetting resin. The thermosetting resin used here is, for example, active hydrogen (-OH group,-
It is obtained by thermally polymerizing a compound containing a plurality of hydrogens such as NH ₂ groups and —NH groups) with a compound containing a plurality of isocyanate groups and / or a compound containing a plurality of epoxy groups. Examples of the compound containing a plurality of active hydrogens include, for example, acrylic resins containing active hydrogens such as polyvinyl butyral, phenoxy resin, phenol resin, polyamide, polyester, polyethylene glycol, polypropylene glycol, polybutylene glycol, and hydroxyethyl methacrylate groups. And the like. As the compound containing a plurality of isocyanate groups, for example,
Examples include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and prepolymers thereof. Examples of the compound having a plurality of epoxy groups include bisphenol A epoxy resin.

In any case, the light-scattering or light-absorbing undercoat layer is applied on a substrate with a solution obtained by dissolving or dispersing the above components on a substrate.
It is formed by thermal polymerization at 200 ° C. The thickness of the undercoat layer is suitably from 1 to 10 μm. The weight ratio of the conductive powder, the white pigment, and the thermosetting resin is suitably 2 to 6/1 to 5/2 to 6, and the weight ratio of the light absorbing pigment to the thermosetting resin is 4%. ~ 9/1 ~ 6 is suitable.

〔effect〕

Since the electrophotographic photoreceptor of the present invention contains crown ether in the layer in which the charge generating substance is dispersed, the photoreceptor is highly sensitive and has a remarkably small reduction in chargeability due to pre-exposure fatigue. Also has a remarkable effect that the charged potential does not decrease.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

Example 1 [Coating solution for charge generation layer] A ball mill was prepared by mixing 5 parts by weight of an azo pigment (pigment No. 1) shown in Table 1 with 160 parts by weight of a 0.78% by weight cyclohexanone solution of crown ether (dibenzo 18 crown 6 ether) for 72 hours. To obtain a pigment dispersion, and then the pigment dispersion
To 100 parts by weight, 90 parts by weight of methyl ethyl ketone was additionally mixed with stirring to prepare a charge generating layer coating liquid.

(Coating liquid for charge transfer layer)

α-phenylstilbene-based charge transfer material (the following compound) 100 parts by weight Polycarbonate (trade name, Panlite C 1400: 100 parts by weight of Teijin Limited) Silicone oil (trade name, KF 50: Shin-Etsu Silicone Co., Ltd.)
1 part by weight tetrahydrofuran 800 parts by weight Next, the above-mentioned coating solution for a charge generation layer was coated on a 75 μm polyester film substrate on which Al was vacuum-deposited with a blade, and was heated and dried at 120 ° C. for 10 minutes to about 0.2 μm. A charge generation layer was formed. Then, the above-mentioned resuscitation coating solution for a charge transfer layer was coated on the charge generation layer with a blade, and dried by heating at 120 ° C. for 20 minutes to form a charge transfer layer having a thickness of about 20 μm to prepare a photoreceptor.

Example 2 A photoconductor was prepared in the same manner as in Example 1, except that the azo pigment in the coating layer for the charge generation layer was changed to Pigment No. 39.

Example 3 A coating solution for a charge transfer layer used in Example 1 was coated on a 75 μm polyester film substrate on which Al was vacuum-deposited with a blade in the same manner as in Example 1, and then dried to transfer a charge of about 20 μm. A layer was formed. Then, the coating liquid for a charge generation layer used in Example 1 was spray-coated on the charge transfer layer, and dried by heating at 120 ° C. for 30 minutes to form a charge generation layer of about 0.2 μm. Created.

Example 4 A photoconductor was prepared by the same way as that of Example 1 except that the α-phenylstilbene compound in the coating solution for the charge transfer layer was changed to a compound having the following structure.

Example 5 A 0.78% by weight cyclohexanone solution of crown ether (dibenzo 18 crown 6 ether) used for preparing the coating solution for the charge generation layer was converted to a 0.39% by weight cyclohexanone solution of crown ether (dicyclohexano 24 crown 8 ether). A photoconductor was prepared in the same manner as in Example 2 except for the above.

Example 6 90 parts by weight of methyl ethyl ketone used for preparing a coating liquid for a charge generation layer was polyvinyl butyral (trade name: XYHL,
A photoconductor was prepared in the same manner as in Example 5, except that a 0.43 wt% methyl ethyl ketone solution (manufactured by Union Carbide Plastics Co., Ltd.) was 90 parts by weight.

Example 7 Fine powder of tin oxide containing 10% by weight of antimony oxide 8
Parts by weight, 5 parts by weight of titanium oxide white pigment powder, and 68 parts by weight of a 1% by weight solution of polyvinyl butyral (trade name: BL-1, manufactured by Sekisui Chemical Co., Ltd.) in a methyl ethyl ketone for 72 hours. Additional parts by weight were processed again in the ball mill for 48 hours. Next, while stirring 80 parts by weight of the pigment dispersion, 8 parts by weight of a 20% by weight solution of tolylene diisocyanate in methyl ethyl ketone was added and mixed to obtain an undercoat layer coating liquid for light scattering.

Next, the above-mentioned undercoat layer coating solution for light scattering was coated on a 75 μm polyester film substrate on which Al was vacuum-deposited with a blade, and heated and cured at 120 ° C. for 30 minutes to form an undercoat layer for light scattering of about 2.5 μm. Was formed.

Next, a photoreceptor having a charge generation layer and a charge transfer layer formed on the light scattering subbing layer in the same manner as in Example 2 was prepared.

Comparative Examples 1 and 2 Photoconductors were prepared in the same manner as in Examples 1 and 2, except that the crown ether of the coating solution for the charge generation layer was polyvinyl butyral (trade name: XYHL, manufactured by Union Carbide Plastics). Example 3 A photoconductor was prepared in the same manner as in Example 3, except that the crown ether of the coating solution for the charge generation layer was changed to polyvinyl butyral (trade name: XYHL, manufactured by Union Carbide Plastics).

Comparative Example 4 A photoconductor was prepared in the same manner as in Example 4, except that the crown ether of the coating solution for the charge generation layer was changed to polyvinyl butyral (trade name: XYHL, manufactured by Union Carbide Plastics).

Comparative Example 5 A photoconductor was prepared in the same manner as in Example 2, except that the crown ether of the coating solution for the charge generation layer was polyester (trade name: Byron 200, manufactured by Toyobo Co., Ltd.).

Comparative Example 6 0.78 of crown ether during preparation of coating solution for charge generation layer
A photoreceptor was prepared in the same manner as in Example 1, except that the weight percent cyclohexanone solution was changed to a 5.88 weight percent cyclohexanone solution of polyvinyl butyral (trade name: XYHL, manufactured by Union Carbide Plastics).

Comparative Example 7 A photoconductor was prepared in the same manner as in Example 1, except that the azo pigment of the coating solution for the charge generation layer was changed to titanyl phthalocyanine.

The electrophotographic photoreceptor prepared as described above was evaluated for electrophotographic characteristics as follows using an electrostatic copying paper test apparatus (Kawaguchi Electric Mfg. Co., Ltd., Model SP 428). First, a -6 KV corona discharge was applied to each photoconductor for 20 seconds, during which a charge potential V ₂ (volt) was measured 2 seconds after the start of corona discharge.
Thereafter, when the device was left in a dark place and the surface potential became -800 V, it was irradiated with tungsten light, and an exposure amount S (lux sec) required for light attenuation of the surface potential to -400 V was obtained. Then, after irradiating 100000 lux sec with tungsten light having a color temperature of 2856 ° K, charging potential V ₂ ′ (vo
lt) and the exposure amount S ′ (lux sec). Table 1 shows the above results.

In addition, the type photoreceptor shown in FIG.
The measurement was performed for 0 second, during which the charged position V ₂ was measured 2 seconds after the start of corona discharge, and then placed in a dark place to increase the surface potential to +80.
At the time when the voltage reached 0v, the film was irradiated with tungsten light, and the exposure amount S required for light attenuation of the surface potential to + 400v was obtained. Thereafter, in the same manner as described above, the charged sheet position V ₂ ′ and the light amount S ′ after the light fatigue after irradiation of 100,000 lux sec were obtained.

[Brief description of the drawings]

1 to 4 are schematic sectional views of various electrophotographic photosensitive members according to the present invention. 1; charge generation layer 2; charge transfer layer 3; conductive support 4; single-layer photosensitive layer 5; undercoat layer

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Katsuichi Ota 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd. (72) Inventor Kayoko Yokoyama 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (56) References JP-A-59-36254 (JP, A)

Claims (1)

(57) [Claims] 1. An electrophotographic photoreceptor having at least a layer in which a charge generating substance is dispersed on a conductive support, wherein the layer in which the charge generating substance is dispersed is an azo pigment which is a charge generating substance and a crown ether which is a binder. A photoconductor for electrophotography, comprising: