KR100532914B1 - New titanium oxide phthalocyanine polymorph, producing method thereof and method for producing organic photoconducting drum using thereof - Google Patents

Abstract

The present invention relates to a novel crystalline titanium oxide phthalocyanine, a method for preparing the same, and a method for preparing an electrophotographic organophotoreceptor drum using the same. More specifically, the XRD 2θ (degrees) has a value of 9.3, 10.5, 12.4, 13.1, and 15.1. The present invention relates to a new crystalline titanium oxide phthalocyanine having peaks at 15.6, 16.0, 20.7, 23.3, 26.2, 26.8 and 27.1, and a method for producing an electrophotographic organic photoconductive drum, which is used as a charge generating material. It is possible to provide an organophotoreceptor drum having excellent photosensitivity and excellent dark attenuation characteristics.

Description

New crystalline titanium oxide phthalocyanine, preparation method thereof and preparation method of electrophotographic organic photoconductive drum using the same

The present invention relates to a novel crystalline titanium oxide phthalocyanine, a method for preparing the same, and a method for manufacturing an electrophotographic organic photosensitive drum using the same. More specifically, the XRD 2θ (degrees) values are 9.3, 10.5, 12.4, 13.1, A new crystalline titanium oxide phthalocyanine showing peaks at 15.1, 15.6, 16.0, 20.7, 23.3, 26.2, 26.8 and 27.1 and a method for producing an electrophotographic organophotoreceptor drum characterized by using it as a charge generating material.

Electrophotographic photoreceptor drums used in laser printers, copiers and fax mills are an important part of expressing information by optical signals and are generally composed of several thin layers. A metal oxide film is coated on an aluminum drum or an insulating polymer is applied, and a charge generation layer is applied on the aluminum drum, and then a charge transport layer is applied. The charge generating layer is an electric signal generated by light and is composed of a charge generating material, a binder resin, an additive, and a solvent. As the charge generating material, organic and inorganic pigments having photosensitivity are used. Binder resins disperse pigments and allow them to adhere uniformly to aluminum drums, and solvents are used as media for uniform dispersion of charge generating materials and binder resins. Azo-based, perylene-based, and phthalocyanine-based pigments are mainly used as charge generating materials, and the electrostatic properties of photosensitive drums can be easily changed. Organic pigments are used a lot because of the advantage. When using a gallium-aluminum-arsonide laser, it is necessary to use a light absorbing pigment in the 700-800 nm range. Recently, a light source near the IR (Infra Red) range is frequently used due to the damage and danger of drums caused by short wavelength light. Doing. As the charge generating material, phthalocyanine is used which is excellent in heat resistance, chemical resistance, light resistance and excellent photoconductivity by light, and shows different electrostatic properties according to its crystal form and type. Is very important.

The charge generating materials used in the charge generating layer are copper phthalocyanine, aluminum chloride phthalocyanine, titanium oxide phthalocyanine, and vanadium oxide phthalocyanine. metal phthalocyanines and metal-free phthalocyanines and metal-free phthalocyanines such as oxide Phthalocyanine, Indium chloride Phthalocyanine, Hydroxy gallium Phthalocyanine, Tin oxide Phthalocyanine Is used alone or in combination, but its use has been limited because the crystal structure varies for each and the electrostatic properties vary depending on the crystal structure.

The present invention provides a titanium oxide phthalocyanine showing a new sensitivity characteristics by changing the crystal form of the existing A-type titanium oxide phthalocyanine, a method for preparing the same and an organic photosensitive drum having an excellent electrostatic effect and attenuating effect using the same. do.

In other words, the present invention provides a new crystalline titanium oxide phthalocyanine in which XRD 2θ (degrees) peaks at 9.3, 10.5, 12.4, 13.1, 15.1, 15.6, 16.0, 20.7, 23.3, 26.2, 26.8 and 27.1.

Another aspect of the present invention provides a process for preparing new titanium oxide phthalocyanine by crystalline conversion of Form A titanium oxide phthalocyanine under alcohol or glycol dissolution for 10 to 150 hours.

Another aspect of the present invention provides a method for producing an electrophotographic organophotoreceptor drum, wherein the novel crystalline titanium oxide phthalocyanine is used as a charge generating material.

Hereinafter, the present invention will be described in more detail.

The present invention provides a new crystalline titanium oxide phthalocyanine through a crystalline conversion method and uses the same as a charge generating material to form a charge generating layer to provide an electrophotographic organic photosensitive drum having excellent light sensitivity and dark attenuation characteristics.

First of all, aluminum drum was used as a drum, and the surface deposited with metal oxide film, Al ₂ O ₃ or ITO (Indium Titanium Oxide) is used as it is, or the drum without metal oxide film coating is coated with BL (Block Layer) layer. use. BL liquid is a coating liquid consisting of polyamide and solvent, and 1-10% by weight of polyamide is dissolved in 90-99% by weight of alcohol and coated on an aluminum drum. A suitable BL layer is 0.3-2 micrometers thick and the drum is dried at 50-150 ° C. for 0.5-2 hours and then coated on the charge generating layer.

In the present invention, the charge generating layer is composed of a charge generating material, a binder resin, an additive and a solvent, and used a titanium oxide phthalocyanine in a new crystal form specially prepared as a charge generating material. This new crystalline titanium oxide phthalocyanine provides a charge generation layer suitable for gallium-aluminum-arthurne laser (780 nm) light sources. The new titanium oxide phthalocyanine has a different crystalline form than the existing type D titanium oxide phthalocyanine or type A titanium oxide phthalocyanine, which can be confirmed by Powder X-Ray Diffratometer (XRD). D-type titanium oxide phthalocyanine pigments have peaks at 2θ (degrees) at 4.3, 9.4, 9.6, 11.6, 13.2, 14.1, 14.9, 17.9, 18.4, 23.4, 24.0, 24.6, and 27.2 under Cu-K alpha1 light source. Titanium oxide phthalocyanine pigments of type A show peaks at 9.2, 10.4, 12.2, 13.0, 14.9, 15.5, 15.9, 20.6, 23.1, 26.1, and 27.0, but the new crystalline titanium oxide phthalocyanine pigment of the present invention is 9.3 It can be newly prepared by the crystalline conversion method to a new crystalline form showing peaks at 10.5, 12.4, 13.1, 15.1, 15.6, 16.0, 20.7, 23.3, 26.2, 26.8, and 27.1. The crystalline conversion method is a method of changing the crystalline form of A-type titanium oxide phthalocyanine in an alcohol or glycol solvent for 10 to 150 hours. In this case, alcohols that can be used include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, ethylene glycol, diethylene glycol, preethylene glycol, glycerin, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2- Methoxyethoxy) ethanol and the like can be used. Mechanical milling methods can be used for this purpose: kneader, banbury mixer, attritor, roll mill, ball mill, sand mill, spex mill, homogenizer, jaw crusher, stamp mill, cutter mill, dyno mill, micronizer, paint shaker, high speed A stirrer, a microfluidizer, an optimizer, an ultrasonic grinder, etc. can be used. 1 and 2 show X-ray diffraction (XRD) graphs of the titanium oxide phthalocyanine of the A-type titanium oxide phthalocyanine and the crystalline form converted in the same manner as the conventional A-type titanium oxide. The titanium oxide phthalocyanine photoreceptor in which the crystalline form is converted to this exhibits excellent photosensitivity and high electrostatic attenuation.

The new crystalline titanium oxide phthalocyanine is either alone or type A titanium oxide phthalocyanine, type D titanium oxide phthalocyanine, type B titanium oxide phthalocyanine, amorphous titanium oxide phthalocyanine, or titanium oxide phthalocyanine having one or more substituents on the molecule. A derivative, vanadium oxide phthalocyanine, a metal-free phthalocyanine, or a metal-free phthalocyanine derivative having one or more substituents on the molecule can be used in a mixture of 1/1 to 1 / 10.0. Substituents attached to titanium oxide phthalocyanine and metal-free phthalocyanine include amino group, nitro group, cyano group, alkyl group, alkoxy group, mercapto group, halogen group, sulfone group, carboxyl group, metal salt of carboxyl group, ammonium group, amine salt, alkyl A benzene group, a sulfonyl group, a carbonyl group, an imino group, and the like.

In the present invention, as the binder resin of the charge generation layer, polyvinyl butyl al resin, polyvinyl alcohol resin, polyamide resin, polyvinylacetate resin, polyvinyl chloride resin, polyacrylic resin, polyurethane resin, polycarbonate resin, polymeth Acrylic resin, polyvinylidene chloride resin, polystyrene resin, styrene-butadiene copolymer resin, styrene-methacrylic acid methyl resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinylacetate copolymer resin, vinyl chloride-vinyl Acetate-maleic anhydride copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-vinylacetate copolymer resin, methylcellulose, nitrocellulose, polysilicon resin, silicone-alkyd resin, phenol-formaldehyde resin, cresol-formaldehyde resin, Styrene-alkyd resin, poly -N-vinylcarbazole resin, polyvinylformal resin, polyhydroxystyrene resin, polynovonyl resin, polycycloolefin resin, polyvinylpyrrolidone resin, poly (2-ethyl-oxazoline) resin, melamine resin , Urea resins, amino resins, isocyanate resins, epoxy resins, etc. may be used alone or in combination of two or more thereof. More preferably, polyvinyl butyl al resin alone or polyvinyl butyl al resin and melamine resin, phenol resin and epoxy resin. It is preferable to mix one resin selected from the group consisting of 1: 0.5 to 1: 0.05.

In the present invention, the solvent of the charge generating layer is 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, butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N'-dimethylformamide, benzene, toluene, xylene, methylbenzene, ethylbenzene, cyclohexane Single back or two or more It can be used in combination.

In more detail, the production of the charge generating layer is 5-30 parts by weight of the new crystalline titanium oxide phthalocyanine, 1-60 parts by weight of the binder resin and 50-200 parts by weight of the solvent, and glass beads, steel beads, zirconia beads, and alumina. Add beads, zirconia balls or steel balls and disperse them for 1 to 20 hours using a disperser. At this time, the dispersing apparatus that can be used includes a high speed stirrer, a paint shaker, a ball mill, a sand mill, a dyno mill, a two roll mill, a three roll mill, an ultrasonic grinder, a microfluidizer, an optimizer and the like. The charge generating layer coating solution thus prepared was uniformly coated on an aluminum drum using a spin coater, bar coater, doctor blade, roller coater, curtain coater, bead coater, and sedimentation coater, and then dried at 50 to 200 ° C. for 0.1 to 4 hours. Let's do it. The thickness of the charge generation layer generated at this time is 0.01 to 3 micrometers. The coaters can also be used to coat BL and charge transfer layers.

In the present invention, the charge transfer layer is composed of a charge transfer material, a binder resin, an additive, and a solvent. The charge transfer material that can be used serves to transfer charges generated in the charge generating layer to the drum surface, and 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-methylbenzaldehydediphenylhydrazone, 2,5-bis (4-aminophenyl)-[1,3,4] oxadiazole, (2 -Phenylbenzo [5,6-b] -4H-thiopyran-4ylidene) -propanedinitrile-1,1-dioxide, 4-bromo-triphenylamine, 4,4 '-(1,2- Ethanediylidene) -bis (2,6-dime Yl-2,5-cyclohexadien-1-one), 3,4,5-triphenyl-1,2,4-triazole, 2- (4-methylphenyl) -6-phenyl-4H-thiopyran- 4-ylidene] -propanedinitrile-1,1-dioxide, 4-dimethylamino-benzaldehyde-N, N-diphenylhydrazone, 9-ethylcarbazole-3-aldehyde-N-methyl-N-phenylhydra Zone, 5- (2-chlorophenyl) 3- [2- (2-chlorophenyl) ethenyl "-1-phenyl-4,5-dihydro-1H-pyrazole, 4-diethylamino-benzaldehyde-N , N-diphenylhydrazone, 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-di Hydro-1H-pyrazole, N, N'-di (4-methylphenyl) -N, N'-diphenyl-1,4-phenylenediamine, 4-dibenzylaminobenzaldehyde-N, N-dipe Nylhydrazone, 4-dibenzylamino-3-methylbenzaldehyde-N, N-diphenylhydrazone, 4,4'-bis (carbazol-9-yl) biphenyl, 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 (naphthalen-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) triphenylamine, N, N, N ', N'- tetrakis (biphenyl-4-yl) benzidine, 4,4', 4 "-tris (N- (1-naphthyl) -N- Phenylamino) triphenylamine, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) triphenylamine, etc. can be used individually or in combination of 2 or more types by a fixed ratio. The binder resin and solvent used for a charge transfer layer can use those used by the charge generation layer.

The charge attraction material may be applied to the charge generation layer or the charge transfer layer, and the charge attraction material serves to improve the durability of the drum by reducing the fatigue caused by the light by speeding up the sensitivity by light. do. Substances which can be used as charge gravitational materials are tetracyanoethylene, tetracyanoquinomimethane, anthraquinone, o-dicyanobenzene, p-dicyanobenzene, 2,6,2 ', 6'-tetraphenyldiphenoquinone , Succinate anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, m-dinitrobenzene, p-dinitro Benzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, quinonechloroimide, chloranyl, bromanyl, dichlorodicyano-p-benzoquinone, anthraquinone, dinitroanthraquinone, 2,7-di Nitrofluorenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 2- (2-phenylbenzo [5,6-b] -4H-thiopyran-4-yl Den) -propanedinitrile-1,1-dioxide, 4,4 '-(1,2-ethanediylidene) -bis (2,6-dimethyl-2,5-cyclohexadien-1-one) , 2- (4-methylphenyl ) -6-phenyl-4H-thiopyran-4-ylidene] -propanedinitrile-1,1-dioxide, 2- (4- (1-methylethyl) phenyl) 6-phenyl-4H-thiopyran- 4-ylidene] -propanedinitrile-1,1-dioxide and the like.

In the present invention, the method for preparing the charge transfer layer will be described in more detail. 5 to 50 parts by weight of binder resin, 3 to 30 parts by weight of two or more types of charge transfer materials, 0.05 to 5 parts by weight of antioxidant, and 0.05 to 5 parts by weight of charge attraction material Then, 50 to 200 parts by weight of the solvent are dissolved together, and the coating is evenly coated on the charge generating layer by the sedimentation coating method, followed by drying at 50 to 200 ° C. for 0.1 to 4 hours. The thickness of the charge generating layer thus prepared is 10 to 40 micrometers.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1

The new crystalline titanium oxide phthalocyanine converts the existing A-type titanium oxide phthalocyanine into crystalline form for 10 to 150 hours in 1-propanol or 1-butanol solvent. 5 parts by weight of the new crystalline titanium phthalocyanine, 3.2 parts by weight of polyvinylbutylal resin (Esrec BH-3, Sekisui), 41.8 parts by weight of 1-methoxy-2-propanol 300 parts by weight of glass beads (0.5 to 0.75 mm) The ball milling was repeated three times for 1 hour after 1 hour dispersion in a paint shaker. This dispersion was diluted with 100 parts by weight of 1-methoxy-2-propanol and ultrasonically scanned for 30 minutes to prepare a stable coating solution. The charge generating layer coating solution was uniformly coated on an aluminum drum coated with polyamide using a sedimentation coating method, and then dried at 120 to 130 ° C. for 30 minutes to form a charge generating layer.

4.2 parts by weight of 4-dibenzylamino-2-methylbenzaldehydediphenylhydrazone (CTC191, ANAN), 1,1-bis- (para-diethylaminophenyl) -4,4-diphenyl-1,3 Butadiene (T405, ANAN) 4.2 parts by weight, polycarbonate (PCZ-400, Mitsubishi Gas) 12 parts by weight, tetracyanoquinomimethane 0.5 parts by weight, n-octadecyl-3- (3,5-diter 0.2 part by weight of butylbutyl-4-hydroxyphenyl) propionate (IRGANOX1076, Ciba-Geigy), 0.1 part by weight of diphenyl monooctyl phosphite (MARK C, Asahi Denka), 55.7 part by weight of tetrahydrofuran, toluene 24 parts by weight were stirred together to completely dissolve and then coated on the charge generating layer to form a charge transfer layer. This drum was dried at 120-130 degreeC for 30 minutes.

The electrophotographic photosensitive drum thus manufactured was electrostatically charged with a electrostatic charge tester (Cynthia 91KSE, Gentec Co., Ltd.) at -6KV and corona line speed of 160 mm / sec. The damping and residual potentials were measured and the results are shown in Table 1.

Example 2

In Example 1, except that 3 parts by weight of polyvinyl butylal and 0.5 parts by weight of butylated urea resin were used in the same manner as in Example 1, and the results are shown in Table 1.

Example 3

In Example 1, except that 3 parts by weight of polyvinyl butylal and 0.5 parts by weight of butylated melamine resin were used, the same procedure as in Example 1 was conducted, and the results are shown in Table 1.

Example 4

In Example 1, except that 3 parts by weight of polyvinyl butylal and 0.5 parts by weight of epoxy resin were used, the same procedure as in Example 1 was conducted, and the results are shown in Table 1.

Comparative Example 1

10 parts by weight of Type A titanium oxide phthalocyanine (Japan), 3.5 parts by weight of polyvinyl butylal, 86.5 parts by weight of 1-methoxy-2-propanol, and 3 parts in a paint shaker together with 300 parts by weight of glass beads (0.5 to 0.75 mmφ). Time milling. This dispersion was diluted with 100% by weight of 1-methoxy-2-propanol and then ultrasonically scanned for 30 minutes to prepare a stable charge generating layer coating solution. The coating solution was first coated on a polyamide-coated aluminum drum using the sedimentation coating method and then dried in an oven at 120 to 130 ° C. for 30 minutes. Coating of the charge transfer layer was the same as in Example 1. Physical properties test was carried out in the same manner as in Example 1 and the results are shown in Table 1.

Comparative Example 2

In Comparative Example 1 except that A-type titanium oxide phthalocyanine (SYNTEC) was used in the same manner as in Comparative Example 1 and the results are shown in Table 1.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Vr ¹⁾ 8 7 9 11 13 14 E1 / 2 ²⁾ 0.45 0.45 0.46 0.47 0.58 0.54 E1 / 5 ³⁾ 0.98 0.97 1.00 1.19 1.29 1.26 E100 ⁴⁾ 1.10 1.11 1.19 1.51 1.54 1.47 DD1 ⁵⁾ 99.2 99.3 99.3 97.8 99.7 97.6 DD5 ⁶⁾ 97.7 97.0 98.4 94.0 96.9 94.4

[Measurement of physical properties]

1) Vr (-V): Residual potential after 5 seconds from Gwangjusa Temple

2) E1 / 2 (μJ / ㎠): Light sensitivity at the time when initial surface potential decreases to 1/2

3) E1 / 5 (μJ / ㎠): Light sensitivity when the initial surface potential decreases to 1/5

4) E100 (μJ / ㎠): Light sensitivity when surface potential is -100V

5) DD1 (%): Darkness attenuation (V1 / VO) × 100, V0: initial surface potential, V1: maximum surface potential 1 second after surface potential

6) DD5 (%): Darkness attenuation (V5 / VO) × 100, V0: Initial surface potential, V5: Surface potential after 5 seconds maximum surface potential

The use of the new crystalline titanium oxide phthalocyanine as described above is superior to the case of using the titanium oxide phthalocyanine of the conventional type A, which is suitable for fast printing speed and digital environment, and also has excellent attenuation characteristics electrophotographic organic photosensitive drum Can be provided.

1 is a X-ray diffraction (XRD) graph of the conventional A-type titanium oxide phthalocyanine,

Figure 2 is an XRD graph of the new crystalline titanium oxide phthalocyanine according to the present invention.

Claims (7)

New crystalline titanium oxide phthalocyanine with peaks at XRD 2θ (degrees) at 9.3, 10.5, 12.4, 13.1, 15.1, 15.6, 16.0, 20.7, 23.3, 26.2, 26.8 and 27.1. A process for preparing the new phthalocyanine of claim 1 by crystalline conversion of Form A titanium oxide phthalocyanine under alcohol or glycol dissolution for 10 to 150 hours. A method of manufacturing an electrophotographic photosensitive drum comprising a charge generating layer and a charge transferring layer, wherein the titanium oxide phthalocyanine of claim 1 is used as a charge generating material. The binder resin used in the charge generating layer is polyvinyl butyl al resin, polyvinyl alcohol resin, polyamide resin, polyvinylacetate resin, polyvinyl chloride resin, polyacrylic resin, polyurethane resin, poly Carbonate resin, polymethacrylic resin, polyvinylidene chloride resin, polystyrene resin, styrene-butadiene copolymer resin, styrene-methacrylic acid methyl resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinylacetate copolymer resin , Vinyl chloride-vinylacetate-maleic anhydride copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-vinylacetate copolymer resin, methylcellulose, nitrocellulose, polysilicon resin, silicone-alkyd resin, phenol-formaldehyde resin, cresol Formaldehyde resin, styrene Kid resin, poly-N-vinylcarbazole resin, polyvinylformal resin, polyhydroxystyrene resin, polynobornyl resin, polycycloolefin resin, polyvinylpyrrolidone resin, poly (2-ethyl-oxazoline) A resin, melamine resin, urea resin, amino resin, isocyanate resin and epoxy resin manufacturing method of an organic photoconductor film, characterized in that at least one member selected from the group consisting of. The method of claim 3, wherein the binder resin used in the charge generation layer is mixed with a polyvinyl butyl al resin, one selected from the group consisting of melamine resin, phenol resin and epoxy resin in a ratio of 1: 0.5 to 1: 0.05 Method for producing an electrophotographic organic photosensitive drum, characterized in that used. The method of claim 3, wherein the new crystalline titanium oxide phthalocyanine is A-type titanium oxide phthalocyanine, D-type titanium oxide phthalocyanine, B-type titanium oxide phthalocyanine, amorphous titanium oxide phthalocyanine, amino group to the molecule, nitro group At least one substituent selected from the group consisting of a cyano group, an alkyl group, an alkoxy group, a mercapto group, a halogen group, a sulfone group, a carboxyl group, a metal salt of a carboxyl group, an ammonium group, an amine salt, an alkylene group, a sulfonyl group, a carbonyl group and an imino group Titanium oxide phthalocyanine derivatives, vanadium oxide phthalocyanine, metal-free phthalocyanine and amino groups in the molecule, nitro group, cyano group, alkyl group, alkoxy group, mercapto group, halogen group, sulfone group, carboxyl group, metal salt of carboxyl group, ammonium group, Consisting of an amine salt, an alkylene group, a sulfonyl group, a carbonyl group and an imino group The method of manufacturing an organic photosensitive drum for electrophotography, characterized by using a mixture in a proportion of metal-free phthalocyanine derivative at least one selected from the group consisting of a 1/1 to 1 / 0.01 or more with a substituent selected from one kinds of picture. delete