KR100431064B1 - Electrophotographic photoreceptor - Google Patents

Abstract

The present invention relates to an electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member including a hybrid composition of a porphyrin-based compound and an organic charge generating material. It is possible to provide an electrophotographic photosensitive member having a low level of afterimage occurrence and stable electrostatic properties.

Description

Electrophotographic photoreceptor {Electrophotographic photoreceptor}

The present invention relates to an electrophotographic organic photoconductor for use in an electrophotographic printer or copier.

The electrophotographic method Carlson introduced in US Pat. No. 2,297,691 is widely applied to copiers and printers, and in particular, laser printers using semiconductor lasers or LEDs as light sources suitable for digital processing according to the advancement and speed of information processing. Digital copiers are widespread. On the other hand, since the semiconductor laser has a light emission wavelength of approximately 790 nm long wavelength region, there is a strong demand for an electrophotographic photosensitive member having sufficient sensitivity to such long wavelength light.

An electrophotographic photosensitive member is generally formed on a conductive support (hereinafter referred to as a "support"), an insulating layer, a charge generation layer that generates charge by light irradiation, and a charge generated in the charge generation layer. It consists of a charge transport layer that transfers to the drum surface, sometimes forming a protective layer on the charge transport layer. The insulating layer is formed of a metal oxide film or an insulating polymer, and the charge generating layer is formed by coating a charge generating material of an inorganic pigment or an organic pigment and a binder resin together or applying a vacuum deposition method. The charge transfer layer is formed by applying a charge transfer material and a binder resin together on a charge generation layer. In some cases, only the charge generation layer and the charge transfer layer, or the charge generation layer and the charge transfer layer are composed of one layer, and the charge generation layer may be applied to the charge transfer layer. In particular, the charge generating material is an important material for generating charges by optical signals to form afterimages of data, and inorganic compounds such as zinc oxide (ZnO), cadmium sulfide (CdS), amorphous silicon (a-Si) and azo ( Azo), bis azo, indigo, perylene, and phthalocyanine-based organic compounds using organic pigments. Recently, inorganic charge generating materials can be easily changed and manufactured by electrostatic properties of photosensitive drums due to environmental pollution, human hazards, processing difficulty, etc., and drums of various characteristics can be manufactured according to the composition and crystal form of pigment used. Organic pigments have been spotlighted.

Many kinds of phthalocyanine compounds have been proposed as organic charge generating materials, and specific examples thereof include copper phthalocyanine, metal-free phthalocyanine, chloro aluminum phthalocyanine, chloro indium phthalocyanine, chloro gallium phthalocyanine, chloro germanium phthalocyanine, vanadiloxyphthalocyanine, and titanyl. Phthalocyanine, hydroxy germanium phthalocyanine, hydroxy gallium phthalocyanine and the like. In each of these phthalocyanine compounds, ε-type copper phthalocyanine as the copper phthalocyanine as the phthalocyanine-based charge generating material due to the difference in the crystalline form, and the Ｘ-type metal-free phthalocyanine as disclosed in US Pat. Τ-type metal-free phthalocyanine described in -182639, τ'-type metal-free phthalocyanine described in Japanese Patent Application Laid-Open No. 60-87332, and other high purity Ｘ-type free-walled materials described in Japanese Patent Application Laid-Open No. 60-243089. Metal phthalocyanine, metal-free phthalocyanine described in Japanese Patent Laid-Open No. 62-47054, metal-free phthalocyanine described in Japanese Patent Laid-Open No. 2-233769, and the like. As titanyl phthalocyanine, the type is disclosed in Japanese Patent Application Laid-Open No. 61-239248, the A-type in Japanese Patent Application Laid-Open No. 61-9066, Type I in Japanese Patent Application Laid-Open No. 61-109056, and A-type in Japanese Patent Application Laid-Open No. 62-67094. As for example, Japanese Patent Application Laid-Open No. 63-364 and Japanese Patent Laid-Open No. 63-366 describe a C crystal. Japanese Patent Application Laid-Open No. 61-239248 proposes a V-type, Japanese Patent Application Laid-Open No. 63-198067, and an M-type in Japanese Patent Application Laid-open No. Hei 1-123868 propose electrostatic charge generating materials.

Moreover, as a structure which uses two or more types of phthalocyanine as a charge generation material, Unexamined-Japanese-Patent No. 62-194257 shows using a mixture of titanyl phthalocyanine and a metal-free phthalocyanine as a charge generation material. Also, Japanese Patent Application Laid-Open No. 2-2702067 discloses a crystal-type composition of a metal-free phthalocyanine-based crystalline metal consisting of titanyl phthalocyanine and metal phthalocyanine, and Japanese Patent Laid-Open No. 5-2278, a crystal composition of titanyl phthalocyanine and vanadil phthalocyanine. Japanese Unexamined Patent Publication No. 8-176455 discloses a mixed crystal of gallium halide phthalocyanine and a metal-free phthalocyanine, and a phthalocyanine composition containing a titanyl phthalocyanine and a metal halide phthalocyanine trivalent.

However, such a known organic charge generating material has a problem in that an afterimage occurs easily during image output or copying.

The present invention is to solve the problems of the prior art as described above, to provide an electrophotographic photosensitive member having a low sensitivity to the afterimage and stable electrostatic characteristics when performing image output or copying.

That is, the present invention relates to an electrophotographic photosensitive member comprising a hybrid composition of at least one porphyrin-based compound selected from the group consisting of substances represented by Formulas 1 and 2 and an organic charge generating material.

[Formula 1]

[Formula 2]

Where

R ₁ is a hydrogen atom, an unsubstituted or substituted alkyl group, an aryl group or an alkoxy group, may form a salt, may not be all the same,

R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group, an aryl group or an alkoxy group, and salts Can be done, not all the same,

M is Co, Cu, Ni, Sn, or an oxygen atom, or represents Al, Fe, Ga, Ge, In, Sn, Ti, V, or Zr to which a halogen atom or hydroxyl group is bonded.

1 is an X-ray diffraction diagram of the mixed crystal composition prepared in Example 1,

2 is an X-ray diffraction diagram of the mixed crystal composition prepared in Example 4,

3 is an X-ray diffraction diagram of the Y-type titanyl phthalocyanine used in Example 7,

4 is an X-ray diffraction diagram of Form B titanylphthalocyanine used in Example 10,

5 is an X-ray diffraction diagram of Form A titanylphthalocyanine used in Example 13, and

6 is an X-ray diffraction diagram of the τ-metal free phthalocyanine used in Example 16. FIG.

The present invention will be described in more detail below.

The present invention is characterized by including a porphyrin-based compound represented by the following formula (1) or (2) with the organic charge generating material in the charge generating layer.

Where

R ₁ is a hydrogen atom, an unsubstituted or substituted alkyl group, an aryl group or an alkoxy group, may form a salt, may not be all the same,

R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group, an aryl group or an alkoxy group, and salts Can be done, not all the same,

M is Co, Cu, Ni, Sn or an oxygen atom, or represents Al, Fe, Ga, Ge, In, Sn, Ti, V or Zr to which a halogen atom or hydroxyl group is bonded.

Forming a charge generating layer using a hybrid composition of at least one porphyrin-based compound selected from the group consisting of the compounds represented by Formulas 1 and 2 and an organic charge generating material such as phthalocyanine (Phthalocyanine) to obtain a photosensitive member having excellent characteristics Can be. In this case, the use weight ratio of the porphyrin-based compound and the charge generating material is preferably 50.0: 50.0 to 0.1: 99.9. When the charge generating layer is formed in this manner, it is possible to obtain a highly sensitive electrophotographic photosensitive member with low afterimage generation and stable electrostatic properties. In particular, when the phthalocyanine-based material is applied as a charge generating material in the manner of charging the photosensitive member surface with a negative charge, the effect is excellent.

These porphyrin-based compounds represented by formulas (1) and (2) can be prepared by known synthetic methods known in the art.

Hereinafter, a method of manufacturing the electrophotographic photosensitive member of the present invention will be described.

As a support body, what formed metal, such as aluminum, an aluminum alloy, nickel, stainless steel, or the like which carried out the conductive process on glass or a resin film, etc. in plate shape, cylindrical shape, film shape, etc. can be used.

On the surface of these supports, an insulating layer is formed uniformly and with good adhesion. This insulating layer is formed by forming an oxide film layer or a resin film layer on the metal surface. As the material of the resin coating layer, insulating polymers such as casein, polyvinyl alcohol, polyamide, polyimide, melamine, cellulose, or conductive polymers such as polythiophene, polypyrox and polyaniline, or metal oxide powders are added to these polymers. Is used.

The charge generating layer is formed by coating a composition consisting of at least one porphyrin-based compound selected from the group consisting of materials represented by Formulas 1 and 2, a charge generating material, a binder resin, a solvent, and an additive on an insulating layer. In this case, the charge generating material may be used alone or in combination of two or more thereof. Specifically, metal phthalocyanine and its derivatives, copper phthalocyanine (Cuppor Phthalocyanine), aluminum chloride phthalocyanine (Aluminium chloride Phthalocyanine), and titanyl substituted with a metal at the center of the phthalocyanine Phthalocyanine (Titanyl Phthalocyanine), Vanadium oxide Phthalocyanine, Indium chloride Phthalocyanine, Hydroxy gallium Phthalocyanine, Tin oxide Phthalocyanine, Tin oxide Phthalocine Derivatives thereof, and combinations of metal-free phthalocyanine with phthalocyanine having a central metal and the like can be used.

As the binder resin, vinyl acetate, vinylpyrrolidine, acrylic, polyurethane, polycarbonate, polyester, polyamide, epoxy, polyvinyl butyral, polyvinyl acetal, phenoxy resin, silicone resin, vinyl chloride resin, vinyl chloride It may be used in the form of a lidene resin, a formal resin, a cellulose resin or a copolymer thereof, or a halide or a cyanoethyl compound thereof, or a mixture of two or more thereof.

As solvent, methyl isopropyl ketone, methyl isobutyl ketone, 4-methoxy-4-methyl-2-pentanone, isopropyl acetate, isobutyl acetate, tertiary butyl acetate, isopropyl alcohol, isobutyl alcohol, acetone, Methyl ethyl ketone, cyclohexanone, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, Dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 1-methoxy-2-propanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve, butyl Amine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N'-dimethylformamide, benzene, toluene, xylene, methylbenzene, ethylbenzene, cyclohexane, etc. Can be used.

Additives include dispersants, antifoams, surfactants and the like.

The charge transfer layer is formed by coating a composition consisting of a charge transfer material, a binder resin, a solvent, and an additive on the charge generating layer.

The charge transfer material that can be used at this time may be any one that can play a role in transferring the charge generated in the charge generating layer to the drum surface. Specifically 1,1-bis- (para-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene, N, N'-bis (olso, para-dimethylphenyl) -N, N'- Diphenylbenzidine, 3,3'-dimethyl-N, N, N'N'-tetrakis-4-methylphenyl- (1,1'-biphenyl) -4,4'-diamine, N-ethyl-3- Carbozolylaldehyde-N, N'-diphenylhydrazone, 4- (N, N-bis (para-toluyl) amino) -betaphenylstilbene, N, N, N ', N'-tetrakis (3 -Methylphenyl) -1,3-diaminobenzene, N, N-diethylaminobenzaldehydediphenyl-hydrazone, N, N-dimethylaminobenzaldehydediphenyl-hydrazone, 4-dibenzylamino-2-methylbenzaldehydedi Phenylhydrazone, 2,5-bis (4-aminophenyl)-[1,3,4] oxadiazole, (2-phenylbenzo [5,6-b] -4H-thiopyran-4-ylidene) -Propanedinitrile-1,1-dioxide, 4-bromo-triphenylamine, 4,4 '-(1,2-ethanediylidene) -bis (2,6-dimethyl-2,5-cyclohexa Dien-1-one), 3,4,5-triphenyl-1,2,4-triazole, 2- (4-methylphenyl) -6-phenyl-4H-thiopyran-4-yl Den-propanedinitrile-1,1-dioxide, 4-dimethylamino-benzaldehyde-N, N-diphenylhydrazone, 9-ethylcarbazole-3-aldehyde-N-methyl-N-phenylhydrazone, 5- (2-chlorophenyl) 3- [2- (2-chlorophenyl) ethenyl "-1-phenyl-4,5-dihydro-1H-pyrazole, 4-diethylamino-benzaldehyde-N, N-di Phenylhydrazone, N-biphenylyl-N-phenyl-N- (3-methylphenyl) amine, 9-ethylcarbazole-3-aldehyde-N, N-diphenylhydrazone, 3,5-bis (4- tert-butylphenyl) -4-phenyltriazole, 3- (4-biphenylyl) -4-phenyl-5-tert-butylphenyl-1,2,4-triazole, 4-diphenylamino-benzaldehyde- N, N-diphenylhydrazone, 5- (4-diethylaminophenyl) -3- [2- (4-diethylaminophenyl) -ethenyl] -1-phenyl-4,5-dihydro-1H -Pyrazole, N, N'-di (4-methylphenyl) -N, N'-diphenyl-1,4-phenylenediamine, 4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone, 4- Dibenzylamino-3-methylbenzaldehyde-N, N-diphenylhydrazone, 4,4'-bis (carbazol-9-yl) bipe , N, N, N ', N'-tetraphenylbenzidine, N, N'-bis (4-methylphenyl) -N, N'-bis (phenyl) -benzidine, N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) benzidine, N, N, N ', N'-tetrakis (4-methylphenyl) benzidine, N, N, N', N'-tetrakis (3-methylphenyl) benzidine, Di (4-dibenzylaminophenyl) ether, N, N'-di (naphthalen-2-yl) -N, N'-diphenylbenzidine, N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine, 1,3-bis (4 (4-diphenylamino) phenyl-1,3,4-oxadiazol-2-yl) benzene, N, N'-di (naphthalene-2- Yl) -N, N'-di (3-methylphenyl) benzidine, N, N'-di (naphthalen-1-yl) -N, N'-di (4-methylphenyl) benzidine, N, N'-di ( Naphthalen-2-yl) -N, N'-di (3-methylphenyl) benzidine, 1,1-bis (4-bis (4-methylphenyl) aminophenyl) cyclohexane, 4,4 ', 4 "-tris ( Carbazol-9-yl) -triphenylamine, 4,4 ', 4 "-tris (N, N-diphenylamino) -triphenylamine, N, N'-bis (biphenyl-1-yl)- N, N'-bis (naphth-1-yl) benzidine, 4,4 ', 4 "-tris (N-3-methylphenyl-N-phenylamino) triphenyl Min, N, N, N ', N'-tetrakis (biphenyl-4-yl) benzidine, 4,4', 4 "-tris (N- (1-naphthyl) -N-phenylamino) triphenyl Amine, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) triphenylamine, 4,4'4" -bis (4,4-diphenyl-1,3- Butadienyl) triphenylamine, 4,4'4 "-tris (4,4-diphenyl-1,3-butadienyl) triphenylamine, 4,4'4" -bis (4,4-di (4-methoxyphenyl) -1,3-butadienyl) triphenylamine, 4,4'4 "-tris (4,4-di (4-methoxyphenyl) -1,3-butadienyl) Triphenylamine, 4,4'4 "-bis (4,4-di (3-methoxyphenyl) -1,3-butadienyl) triphenylamine, 4,4'4" -tris (4,4 -Di (3-methoxyphenyl) -1,3-butadienyl) triphenylamine, 4,4'4 "-bis (4,4-di (2-methoxyphenyl) -1,3-butadier Phenyl) triphenylamine, 4,4'4 "-tris (4,4-di (2-methoxyphenyl) -1,3-butadienyl) triphenylamine, or the like may be used alone or in combination of two or more thereof. Can be.

As the binder resin, polyvinyl butyl al resin, polyvinyl alcohol resin, polyamide resin, polyvinylacetate resin, polyvinyl chloride resin, polyacrylic resin, polyurethane resin, polycarbonate resin, polymethacryl resin, polyvinylidene chloride Resin, polystyrene resin, styrene-butadiene copolymer resin, styrene-methyl methacrylate resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinylacetate copolymer resin, vinyl chloride-vinylacetate-maleic anhydride copolymer Resin, Ethylene-Acrylic Acid Copolymer Resin, Ethylene-Vinyl Acetate Copolymer Resin, Methyl Cellulose, Nitrocellulose, Polysilicon Resin, Silicone Alkyd Resin, Phenol-Formaldehyde Resin, Cresol-Formaldehyde Resin, Styrene-Alkyd Resin, Poly -N-vinylcarbazole resin, polyvinyl cloth Resin, polyhydroxystyrene resin, polynorbornyl resin, polycycloolefin resin, polyvinylpyrrolidone resin, poly (2-ethyl-oxazoline) resin, melamine resin, urea resin, amino resin, isocyanate resin, epoxy Resin etc. can be used individually or in mixture of 2 or more types.

As solvent, methyl isopropyl ketone, methyl isobutyl ketone, 4-methoxy-4-methyl-2-pentanone, isopropyl acetate, isobutyl acetate, tertiary butyl acetate, isopropyl alcohol, isobutyl alcohol, acetone, Methyl ethyl ketone, cyclohexanone, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, Dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 1-methoxy-2-propanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve, butyl Amine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N'-dimethylformamide, benzene, toluene, xylene, methylbenzene, ethylbenzene, cyclohexane, etc. alone or in combination Can be mixed .

The additive may include an antioxidant, an antifoaming agent, and the like.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are provided for the purpose of description and are not intended to limit the present invention.

Example 1

Shake for 1.9 hours Titanyl Phthalocyanine (Aldrich) and 0.1 g Protoporphyrin (Aldrich) with 15 ml of glass beads (1 mm) in a paint shaker for 50 hours, then remove from glass beads and paint shaker. Washing with methyl alcohol was recovered by filtration and drying. This material was dispersed in 45 ml of water, then 3 ml of o-dichlorobenzene was added and stirred at 60 ° C. for 1 hour. 400 ml of methyl alcohol was added to the suspension, which was then stirred for 1 hour, cooled, filtered and dried to obtain a charge generating material. The X-ray diffraction diagram of the crystal composition obtained in this way showed the characteristics of Y-type oxo titanyl phthalocyanine having a clear and strong diffraction intensity at a Bragg angle of 27.3 ° as shown in FIG. 1.

4.6 parts by weight of the mixed crystal composition prepared above, 3.1 parts by weight of polyvinyl butyral resin (Ethlec BM-2: SEKISUI Chemical Co., Ltd.), and 81.6 parts by weight of tetrahydrofuran solvent to form a charge generating layer (1 mm) together with a paint shaker and a ball mill to prepare a dispersion having an average particle size of about 250 nm. This dispersion was diluted with 3.8 times tetrahydrofuran solvent and sonicated for 30 minutes to prepare a stable coating solution. The coating solution was uniformly coated on the first anodized aluminum drum using the sedimentation coating method and then dried at 120 ° C. for 30 minutes.

The charge transfer layer comprises 4-dibenzylamino-2-methylbenzaldehydediphenylhydrazone (CTC-191: ANAN CORPORATION) 4.2 parts by weight, 1,1-bis- (para-diethylaminophenyl) -4,4-di Phenyl-1,3-butadiene (T-405: ANAN CORPORATION) 4.2 parts by weight, polycarbonate (Luplion Z400: Mtisubishi Gas Kagaku) 11 parts by weight, 2,6-di-t-butyl-4-methylphenol as antioxidant 0.4 parts by weight (2,6-di-t-butyl-4-methylphenol: cyanogenic), 55.7 parts by weight of tetrahydrofuran, and 24 parts by weight of toluene were stirred together to dissolve completely and then applied on a charge generating layer. The drum was dried at 120-130 degreeC for 30 minutes, and the photosensitive drum of 20 micrometers in thickness was obtained.

The photosensitive drum thus manufactured was charged with a -6KV to -7KV corona with an electrostatic charge tester (PDA-2000LA: QEA Inc.), and after 1.0 seconds of scanning 780 nm of light having an energy of 1.0 μJ / cm 2 for 1.0 seconds, After 1.0 second, the red LED light source erased the potential of the drum surface and left for 1.0 second. At this time, the initial charge potential V ₀ made on the drum surface before and after the fatigue test, the potential V _e of the drum surface after exposure, and the potential V _r value of the drum surface after 1.0 second of erasing operation were measured and compared. In addition, we measured the energy E _1/2 per unit area needed to reduce the initial charge potential to 1/2 by scanning 780 nm light into the drum, and the dark attenuation DD that maintains the potential after 1.0 second in the dark state after charging. Checked by Packard LaserJet 4050.

Example 2

5,10,15,20-tetra (4-pyridyl) porphyrin (5,10,15,20-Tetra (4-pyridyl) porphyrin: Fluka) instead of the protoporphyrin 의 of Example 1 in the preparation of the charge generating material It carried out similarly to Example 1 except having used.

Example 3

The preparation of the charge generating material was carried out in the same manner as in Example 1, except that meso-tetraphenylporphyrin (Fluka) was used instead of the protoporphyrin 의 of Example 1.

Comparative Example 1

The preparation of the charge generating material was carried out in the same manner as in Example 1, except that only 2 g of titanylphthalocyanine was used without using protoporphyrin Ⅸ.

Example 1 Example 2 Example 3 Comparative Example 1 Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change V ₀ (-V) 676 668 ↓ 3 675 669 ↓ 10 679 662 ↓ 7 681 668 ↓ 9 V _e (-V) 69 81 ↑ 23 68 80 ↑ 22 63 77 ↑ 19 66 76 ↑ 25 V _r (-V) 21 35 ↑ 26 20 30 ↑ 27 27 37 ↑ 23 24 33 ↑ 31 DD (%) 97.4 96.6 ↓ 1.2 98.2 96.6 ↓ 1.6 99.0 97.5 ↓ 1.5 96.9 94.8 ↓ 2.1 E _1/2 (uJ / ㎠) 0.110 0.110 0.112 0.113 burn ◎ ◎ ○ △

※ Observation of the image

×: Afterimage is very severe

△: slight afterimage occurrence

○: almost no afterimage

◎: no afterimage

Example 4

1.9 g of titanyl phthalocyanine (Aldrich) and 0.1 g of Protoporphyrin Al (Aldrich) were dissolved in 100 g of concentrated sulfuric acid (97%) cooled to 0 ° C, and the solution was poured into 1300 ml of distilled water little by little. The precipitate produced at this time was filtered, washed with dilute ammonia water, and then washed sufficiently with distilled water. The homogeneous composition thus obtained was kneaded with water so that 20% of the weight was solid, and a suspension added with tetrahydrofuran, which was 4 times the weight of the dough, was mixed with 15 ml of glass beads (1 mm) using a paint shaker. It was shaken for 20 hours while maintaining the ℃. The X-ray diffractogram of the crystal composition obtained by filtration and drying of the suspension thus obtained is shown in Fig. 2, which shows a clear and strong diffraction intensity of Y-type oxo titanyl phthalocyanine at a Bragg angle of 27.1 °. Showed characteristics.

Thereafter, the charge generation layer and the charge transfer layer were formed in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1.

Example 5

5,10,15,20-tetra (4-pyridyl) porphyrin (5,10,15,20-Tetra (4-pyridyl) porphyrin: Fluka) instead of the protoporphyrin 의 of Example 4 in the preparation of the charge generating material It carried out similarly to Example 4 except having used.

Example 6

The preparation of the charge generating material was carried out in the same manner as in Example 4, except that meso-Tetraphenylporphyrin (Fluka) was used instead of the protoporphyrin 의 of Example 4.

Comparative Example 2

The preparation of the charge generating material was carried out in the same manner as in Example 4, except that only 2 g of titanylphthalocyanine was used without using protoporphyrin 린.

Example 4 Example 5 Example 6 Comparative Example 2 Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change V ₀ (-V) 680 669 ↓ 11 672 663 ↓ 9 682 672 ↓ 10 681 669 ↓ 12 V _e (-V) 62 74 ↑ 12 67 81 ↑ 14 60 73 ↑ 13 60 76 ↑ 16 V _r (-V) 18 34 ↑ 16 20 31 ↑ 11 17 27 ↑ 10 17 34 ↑ 17 DD (%) 97.5 96.6 ↓ 0.9 97.2 96.2 ↓ 1.0 97.0 96.7 ↓ 0.3 96.0 95.3 ↓ 0.7 E _1/2 (uJ / ㎠) 0.107 0.106 0.108 0.109 burn ◎ ○ ◎ △

Example 7

4.5 parts by weight of Y-type titanyl phthalocyanine (ST10 / 10.2: SynTec), 0.09 parts by weight of Protoporphyrin Al (Aldrich), 3.1 parts by weight of polyvinyl butyral resin (XYHL: Union Carbide Crop.) Part and 81.6 parts by weight of a tetrahydrofuran solvent were dispersed together with glass beads (1 mm) using a paint shaker and a ball mill to prepare a dispersion having an average particle size of about 250 nm. The dispersion was diluted with 3.8 times of tetrahydrofuran solvent to inject ultrasonic waves for 30 minutes to prepare a stable coating solution, and the same method as in Example 1 was used to form a charge generating layer. It measured in the same way.

The X-ray diffractogram of the Y-type titanyl phthalocyanine (ST10 / 10.2: SynTec) used at this time has a clear and strong diffraction intensity at a Bragg angle (2Θ) 27.3 °, as shown in FIG.

Example 8

5,10,15,20-tetra (4-pyridyl) porphyrin (5,10,15,20-Tetra (4-pyridyl) porphyrin: Fluka) instead of the protoporphyrin 의 of Example 7 in the preparation of the charge generating layer It carried out similarly to Example 7 except having used.

Example 9

The preparation of the charge generating layer was carried out in the same manner as in Example 7, except that meso-tetraphenylporphyrin (Fluka) was used instead of the protoporphyrin Ⅸ of Example 7.

Comparative Example 3

4.5 parts by weight of Y-type titanyl phthalocyanine (ST10 / 10.2: SynTec), 3.1 parts by weight of polyvinyl butyral resin (XYHL: Union Carbide Crop.), And 81.6 parts by weight of tetrahydrofuran solvent in glass beads ( 0.5 ~ 0.75mm) together with a paint shaker and a ball mill to prepare a dispersion having an average particle size of about 250 nm. The dispersion was diluted with 3.8-fold tetrahydrofuran solvent and then subjected to ultrasonic scanning for 30 minutes to prepare a stable coating solution, and using the same method as in Example 7, except that a charge generating layer was formed. Again measured in the same way.

Example 7 Example 8 Example 9 Comparative Example 3 Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change V ₀ (-V) 676 668 ↓ 8 675 669 ↓ 6 679 662 ↓ 17 681 668 ↓ 13 V _e (-V) 67 81 ↑ 14 65 80 ↑ 15 60 77 ↑ 17 63 76 ↑ 13 V _r (-V) 20 35 ↑ 15 18 30 ↑ 12 22 37 ↑ 15 19 33 ↑ 15 DD (%) 97.4 96.6 ↓ 0.8 97.2 96.5 ↓ 0.7 97.0 96.5 ↓ 0.5 97.0 96.2 ↓ 0.8 E _1/2 (uJ / ㎠) 0.114 0.111 0.112 0.110 burn ◎ ◎ ○ △

Example 10

4.5 parts by weight of B-type titanyl phthalocyanine (TPL-364: 日本 資 材), 0.1 part by weight of Protoporphyrin Al (Aldrich), polyvinyl butyral resin (Ethlec BM-S: SEKISUI Chemical Co. , Ltd.) 3.1 parts by weight, and 81.6 parts by weight of tetrahydrofuran solvent were dispersed together with glass beads (0.5-0.75 mm) using a paint shaker and a ball mill. The dispersion was diluted with 3.8-fold tetrahydrofuran solvent and then ultrasonically scanned for 30 minutes to prepare a stable coating solution, which was used in the same manner as in Example 1 except for forming a charge generating layer. The X-ray diffractogram of the B-type titanylphthalocyanine used at this time has a clear and strong diffraction intensity at a Bragg angle of 7.6 ° as shown in FIG. 4.

On the other hand, when measuring physical properties, the image was confirmed by Samsung ML-6060.

Example 11

5,10,15,20-tetra (4-pyridyl) porphyrin (5,10,15,20-Tetra (4-pyridyl) porphyrin: Fluka) instead of the protoporphyrin 의 of Example 10 in the preparation of the charge generating layer. It carried out similarly to Example 10 except having used 0.1 weight part.

Example 12

The preparation of the charge generating layer was carried out in the same manner as in Example 10, except that 0.1 part by weight of meso-tetraphenylporphyrin (Fluka) was used instead of the protoporphyrin Ⅸ of Example 10.

Comparative Example 4

4.5 parts by weight of B-type titanylphthalocyanine (TPL-364), 3.1 parts by weight of polyvinyl butyral resin (Ethlec BM-S (SEKISUI Chemical Co., Ltd.), and tetrahydrofuran A solvent having an average particle size of about 250 nm was prepared by dispersing 81.6 parts by weight of solvent with glass beads (0.5-0.75 mm) using a paint shaker and a ball mill. This dispersion was diluted with 3.8-fold tetrahydrofuran solvent and then subjected to ultrasonic scanning for 30 minutes to prepare a stable coating solution, and the same procedure as in Example 10 except that the charge generating layer was formed using the dispersion.

Example 10 Example 11 Example 12 Comparative Example 4 Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change V ₀ (-V) 671 645 ↓ 26 680 672 ↓ 8 675 660 ↓ 15 683 663 ↓ 21 V _e (-V) 110 112 ↑ 2 108 110 ↑ 2 110 115 ↑ 5 113 119 ↑ 6 V _r (-V) 18 34 ↑ 16 17 30 ↑ 13 20 32 ↑ 12 21 40 ↑ 19 DD (%) 98.1 96.3 ↓ 1.8 98.4 97.8 ↓ 0.3 98.3 96.7 ↓ 1.6 98.1 96.8 ↓ 1.3 E _1/2 (uJ / ㎠) 0.29 0.28 0.28 0.31 burn ◎ ◎ ○ ×

Example 13

4.5 parts by weight of type A titanylphthalocyanine (TPL-363: Aldrich), polyvinyl butyral resin (Ethlec BM-2: SEKISUI Chemical Co. , Ltd.) The same process as in Example 10 was carried out except that the dispersion was prepared using 3.1 parts by weight and 81.6 parts by weight of a tetrahydrofuran solvent. The X-ray diffraction diagram of the A-type titanyl phthalocyanine (TPL-363: 日本 資 材) used at this time has a clear and strong diffraction intensity at a Bragg angle (2Θ) 26.3 ° as shown in FIG.

Example 14

5,10,15,20-tetra (4-pyridyl) porphyrin (5,10,15,20-Tetra (4-pyridyl) porphyrin: Fluka) instead of the protoporphyrin Ⅸ of Example 13 in the preparation of the charge generating layer It carried out similarly to Example 13 except having used 0.1 weight part.

Example 15

The preparation of the charge generating layer was carried out in the same manner as in Example 13, except that 0.1 part by weight of meso-Tetraphenylporphyrin (Fluka) was used instead of the protoporphyrin 의 of Example 13.

Comparative Example 5

4.5 parts by weight of A-type titanylphthalocyanine (TPL-363), 3.1 parts by weight of polyvinyl butyral resin (Ethlec BM-2 (SEKISUI Chemical Co., Ltd.), and tetrahydrofuran 81.6 parts by weight of glass beads (0.5-0.75 mm) were dispersed together with a paint shaker and a ball mill to prepare a dispersion. The dispersion was diluted with 3.8 times of tetrahydrofuran solvent and then ultrasonically injected for 30 minutes. It carried out similarly to Example 13 except having prepared the stable coating liquid.

Example 13 Example 14 Example 15 Comparative Example 5 Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change V ₀ (-V) 679 673 ↓ 6 680 668 ↓ 12 678 667 ↓ 11 682 675 ↓ 7 V _e (-V) 128 139 ↑ 11 135 144 ↑ 9 131 138 ↑ 7 140 150 ↑ 10 V _r (-V) 20 33 ↑ 13 21 31 ↑ 10 20 26 ↑ 6 22 33 ↑ 11 DD (%) 98.7 98.5 ↓ 0.2 98.2 97.6 ↓ 0.6 98.4 97.7 ↓ 0.7 98.4 97.6 ↓ 0.8 E _1/2 (uJ / ㎠) 0.32 0.33 0.33 0.35 burn ◎ ◎ ◎ △

Example 16

4.5 parts by weight of τ-type metal-free phthalocyanine (TPA-891: 日本 資 材), 0.1 part by weight of Protoporphyrin Al (Aldrich), polyvinyl butyral resin (XYHL: Union Carbide Crop.) 3.1 It carried out similarly to Example 10 except having prepared the dispersion liquid using a weight part and 81.6 weight part of tetrahydrofuran solvents. The X-ray diffraction diagram of the τ-type metal-free phthalocyanine (TPA-891: 日本 資 材) used at this time has a clear and strong diffraction intensity at the Bragg angle (7.5) and 9.1 ° as shown in FIG.

Example 17

5,10,15,20-tetra (4-pyridyl) porphyrin (5,10,15,20-Tetra (4-pyridyl) porphyrin: Fluka) instead of the protoporphyrin 의 of Example 16 in the preparation of the charge generating layer It carried out similarly to Example 16 except having used 0.1 weight part.

Example 18

The preparation of the charge generating layer was carried out in the same manner as in Example 16, except that 0.1 part by weight of meso-Tetraphenylporphyrin (Fluka) was used instead of the protoporphyrin 의 of Example 16.

Comparative Example 6

4.5 parts by weight of τ-type metal-free phthalocyanine (TPA-891: Nihon Carbide), 3.1 parts by weight of polyvinyl butyral resin (XYHL: Union Carbide Crop.), And 81.6 parts by weight of tetrahydrofuran solvent (0.5 ~ 0.75mm) together with a paint shaker and a ball mill to prepare a dispersion, which was diluted with 3.8 times of tetrahydrofuran solvent, and then ultrasonically injected for 30 minutes to prepare a stable coating solution. The same procedure as in Example 16 was performed except for the above.

Example 16 Example 17 Example 18 Comparative Example 6 Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change Early Fatigue Experiment change V ₀ (-V) 679 662 ↓ 17 680 674 ↓ 6 672 661 ↓ 11 669 664 ↓ 5 V _e (-V) 119 130 ↑ 10 120 128 ↑ 8 120 132 ↑ 12 134 144 ↑ 10 V _r (-V) 22 38 ↑ 17 20 36 ↑ 16 23 33 ↑ 10 25 39 ↑ 14 DD (%) 96.9 96.2 ↓ 0.4 97.0 96.2 ↓ 0.8 96.8 96.8 ↓ 0.0 97.1 97.0 ↓ 0.1 E _1/2 (uJ / ㎠) 0.31 0.31 0.32 0.33 burn ◎ ○ ○ ×

The above results show that the electrophotographic photosensitive member containing a porphyrin-based compound is superior to the conventional photosensitive member in terms of image resolution and afterimage, but almost identical in electrostatic properties. .

The photoconductor including the charge generating layer according to the present invention has a stable electrostatic characteristic with less afterimage generation when performing image output or copying.

Claims (6)

An electrophotographic photosensitive member comprising a hybrid composition of at least one porphyrin-based compound selected from the group consisting of substances represented by Formulas 1 and 2 and an organic charge generating material. [Formula 1] [Formula 2] Where R ₁ is a hydrogen atom, an unsubstituted or substituted alkyl group, an aryl group or an alkoxy group, may form a salt, may not be all the same, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group, an aryl group or an alkoxy group, and salts Can be done, not all the same, M is Co, Cu, Ni, Sn, or an oxygen atom, or represents Al, Fe, Ga, Ge, In, Sn, Ti, V, or Zr to which a halogen atom or hydroxyl group is bonded. The electrophotographic of claim 1, wherein the organic charge generating material is at least one selected from azo, biszo, indigo, perylene, and phthalocyanine. Photoreceptor. The electrophotographic photosensitive member according to claim 1, wherein the organic charge generating material is a phthalocyanine-based material. According to claim 3, The phthalocyanine-based compound is metal-free phthalocyanine, Copper Phthalocyanine, Aluminum chloride Phthalocyanine, Titanyl Phthalocyanine, Vanadium oxide Phthalocyanine (Vanadium oxide Phthalocyanin) Indium chloride Phthalocyanine, Hydroxy gallium Phthalocyanine, Tin oxide Phthalocyanine, Tin Phthalocyanine, or derivatives thereof, or combinations of metal phthalocyanines with metal phthalocyanines Electrophotographic photosensitive member. The electrophotographic photosensitive member according to any one of claims 1 to 4, wherein a weight ratio of the porphyrin-based compound and the phthalocyanine-based compound is 50.0: 50.0 to 0.1: 99.9. delete