KR100371517B1 - Pruducing method of organic photoconducting drum with good abrasion resistance - Google Patents

Abstract

The present invention relates to a method for manufacturing an electrophotographic organic photosensitive drum, and more particularly, to a method for manufacturing an electrophotographic photosensitive drum including a charge generating layer and a charge transfer layer, wherein a wax dispersion is mixed with a polycarbonate-based The present invention relates to a method for manufacturing an electrophotographic organic photoconductive drum, wherein the resin is used as a binder resin of a charge transfer layer. According to the present invention, it is possible to provide an organic photoconductive drum having improved wear resistance and improved light sensitivity and dark attenuation characteristics. .

Description

Manufacturing method of organic photoconductive drum with excellent wear resistance {Pruducing method of organic photoconducting drum with good abrasion resistance}

The present invention relates to a method for manufacturing an electrophotographic organic photosensitive drum, and more particularly, to a method for manufacturing an electrophotographic photosensitive drum including a charge generating layer and a charge transfer layer, wherein a wax dispersion is mixed with a polycarbonate-based A method for producing an electrophotographic organophotoreceptor drum, wherein the resin is used as a binder resin of a charge transfer layer.

Electrophotographic photoreceptor drums used in printers, copiers and fax machines are an important part of expressing information by optical signals and consist of several thin layers. Generally, a metal oxide film or an insulating polymer is coated on an aluminum drum, 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, photo-sensitive oil and inorganic pigments are used, and azo, perylene, and phthalocyanine pigments are mainly used, and the electrostatic characteristics of the photosensitive drum can be easily changed. Organic pigments are used a lot because of the advantages of various crystal structures depending on the synthesis method and processing conditions. 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. The charge transfer layer transfers electrical signals generated from the charge generation layer to the surface of the drum and is composed of a charge generating material, a binder resin, an additive, and a solvent. As the charge transfer material, tertiary amines such as hydrazone-based, oxadiazole-based, butadiene-based and stilbene-based are used, and polycarbonate is generally used as the binder resin.

The charge transfer layer of the organic photosensitive drum is a place where friction with paper, a charging roller, a transfer roller, a developing roller, and the like occurs frequently. If the strength of this part is weak, the film is damaged and the electrostatic property is poor.

The present invention solves the above problems, and increases the film strength of the binder resin of the charge transfer layer used as the outer layer of the drum to improve the wear resistance and at the same time improve the photosensitivity and light attenuation characteristics electrophotographic organic photosensitive drum It relates to a method for producing.

That is, the present invention is a method for producing an electrophotographic photosensitive drum comprising a charge generating layer and a charge transfer layer, wherein the polyamide-modified castor wax, polyamide wax, active polyamide wax, oxidized polyethylene wax, polyethylene wax , Modified polyethylene wax, polypropylene-modified polyethylene wax, modified polypropylene wax, polytetrafluoroethylene-modified polyethylene wax, polytetrafluoroethylene-modified polypropylene wax, canova wax, canova-modified polyethylene wax, paraffin An electrophotographic organic photoconductor comprising a polycarbonate resin mixed with a wax dispersion liquid in which one or more polymer waxes selected from the group consisting of waxes and polytetrafluoroethylene waxes is dispersed in a solvent. It relates to a method for producing a drum.

Hereinafter, the present invention will be described in detail.

In the present invention, the charge generating material used in the charge generating layer is titanium oxide phthalocyanine, which has advantages of faster sensitivity and better attenuation than metal-free phthalocyanine. Titanium oxide phthalocyanine is dispersed together with the binder resin and the solvent. The binder resin that can be used at this time is 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-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 Alkyd Resin, Poly-N-Vinyl Car Sol resin, polyvinylformal resin, polyhydroxystyrene resin, polynovonyl resin, polycycloolefin resin, polyvinylpyrrolidone resin, poly (2-ethyl-oxazoline) resin, melamine resin, urea resin, amino It is resin, an isocyanate resin, an epoxy resin, etc. It can be used individually or in combination of 2 or more types. The amount used may be 10 to 100 parts by weight based on 5 to 30 parts by weight of the charge generating material. If it is less than 10 parts by weight, it is difficult to form a uniform charge generating layer, and the adhesive strength with the substrate is also weakened. If it exceeds 100 parts by weight, it is difficult to maintain the charge potential and make the mill base difficult.

In the present invention, the solvent used for forming 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, 1,2-dimethoxyethane, benzene, Toluene, xylene, methylbenzene, ethylbenzene, Clohexane etc. can be used individually or in combination of 2 or more types.

In more detail, the production of the charge generating layer is 5 to 30 parts by weight of the titanium oxide phthalocyanine, 10 to 100 parts by weight of the binder resin and 75 to 200 parts by weight of the solvent, glass beads, steel beads, zirconia beads, alumina beads, zirconia balls. Alternatively, steel balls are added and dispersed for 2 to 20 hours using a disperser. 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 individually or in combination of 2 or more types.

The charge generation layer coating solution thus prepared may be coated on the aluminite-treated aluminum tube using a sedimentation coating method, and then dried at 100 to 150 ° C. for 0.5 to 2 hours to form a charge generation layer.

In the present invention, the charge transfer material used in the charge transfer layer is 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-dimethyl-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-phenylhydrazone, 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-dihydro-1H-pyrazole, N, N'-di (4-methylphenyl) -N, N'-di Phenyl-1,4-phenylenediamine, 4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone, 4-dibenzylamino-3-methylbenzaldehyde De-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'-tetra Kis (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 (naphthalene -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) Gidine, 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-phenyl Amino) triphenylamine etc. can be used individually or in combination of 2 or more types by fixed ratio.

In the present invention, the binder resin used in the charge transfer layer may be a polycarbonate having good transparency and good strength, and a modified polycarbonate, a silicone modified polycarbonate using a bisphenol A derivative, and a copolymer of polycarbonate and other resins may also be used. have. In order to impart functionality to the charge transfer layer, additives such as charge attraction material, electron attraction material and antioxidant may be added.

In the present invention, mixing the wax dispersion in order to increase the film strength of the binder resin used in the charge transfer layer is the biggest feature. Waxes that can be used in the present invention include polyamide-modified caster waxes, polyamide waxes, active polyamide waxes, oxidized polyethylene waxes, polyethylene waxes, modified polyethylene waxes, polypropylene-modified polyethylene waxes, modified polypropylene waxes, polytetra Polymeric waxes such as fluoroethylene-modified polyethylene wax, polytetrafluoroethylene-modified polypropylene wax, canova wax, canova-modified polyethylene wax, paraffin wax, and polytetrafluoroethylene wax alone or in combination of two or more thereof It can be used by dispersing in the solvent used in the charge transfer layer.

The dispersing machine can be used as 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 stirrer , Microfluidizer, optimizer, ultrasonic grinder, etc. can be used. It is effective to use two or more dispersers. The wax dispersion thus prepared has a particle size of 1 micrometer or less.

The content of the wax dispersion is preferably used in the range of 0.005 to 10 parts by weight of the wax relative to 100 parts by weight of the polycarbonate resin. If the use amount of the wax is less than 0.005 parts by weight, the wear resistance is not effective, and if it is more than 10 parts by weight, the adhesion strength with the charge generating layer is reduced and the film strength of the polycarbonate is also weakened.

Hereinafter, the charge transfer layer manufacturing method will be described in more detail. 5 to 50 parts by weight of polycarbonate resin, 5 to 50 parts by weight of two or more types of charge transfer materials, 0.05 to 5 parts by weight of antioxidant, 0.05 to 5 parts by weight of charge attraction material, wax The wax dispersion liquid having a content of 0.005 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin is dissolved together with 50 to 200 parts by weight of the solvent and evenly coated on the charge generating layer by the sedimentation coating method. After coating the charge transfer layer and dried at 100 ~ 150 ℃ 0.5 ~ 2 hours. The thickness of the charge transfer layer thus prepared is 10-40 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

With 10 parts by weight of titanium oxide phthalocyanine, 50 parts by weight of polyvinyl butylal resin (Esrec BH-3, Sekisui), 85 parts by weight of 1,2-dimethoxyethane, 300 parts by weight of glass beads (0.5 to 0.75 mm) Ball milling for 24 hours. The dispersion was diluted with 600 parts by weight of 1,2-dimethoxyethane and ultrasonically scanned for 30 minutes to prepare a stable charge generating layer coating solution. The charge generating layer coating solution was uniformly coated on the anodized aluminum drum using the sedimentation coating method and then dried at 120 ° C. for 30 minutes to form a charge generating layer.

4.5 parts by weight of 4-dibenzylamino-2-methylbenzaldehydediphenylhydrazone (CTC191, ANAN), 1,1-bis- (para-diethylaminophenyl) -4,4-diphenyl-1,3 4.5 parts by weight of butadiene (T405, ANAN), 11 parts by weight of polycarbonate (PCZ-400, Mitsubishi Gas), 0.15 parts by weight of polyamide wax dispersion (10% by weight of wax), 0.5 parts by weight of tetracyanoquinodimethane Part, 0.2 parts by weight of n-octadecyl-3- (3,5-dibutylbutyl-4-hydroxyphenyl) propionate (IRGANOX1076, Ciba-Geigy), diphenyl monooctyl phosphite (MARK C, Asahi) Denka) 0.1 part by weight, 59.4 parts by weight of tetrahydrofuran and 19.3 parts by weight of toluene were stirred together to completely dissolve and then coated on the charge generation layer to form a charge transfer layer. This drum was dried at 120 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

Except for using the polyamide wax dispersion in Example 1 0.15 parts by weight of the polyethylene oxide dispersion (wax content 10% by weight) was carried out in the same manner as in Example 1, the results are shown in Table 1.

Example 3

Except for using a polyamide wax dispersion in Example 1 except that 0.15 parts by weight of polyethylene wax dispersion (wax content 10% by weight) was carried out in the same manner as in Example 1, the results are shown in Table 1.

Example 4

Except for using a modified polypropylene wax dispersion (wax content 10% by weight) 0.15 parts by weight in place of the polyamide wax dispersion in Example 1 was carried out in the same manner as in Example 1, the results are shown in Table 1.

Example 5

Except for using the polyamide wax dispersion in Example 1 polytetrafluoroethylene-modified polyethylene wax dispersion (wax content 10% by weight) 0.15 parts by weight was carried out in the same manner as in Example 1, the results are shown in Table 1 Shown in

Example 6

Example 1 except that 0.15 parts by weight of the active polyamide wax dispersion (10% by weight of wax) and 0.15 parts by weight of the polypropylene wax dispersion (10% by weight of wax) was used in place of the polyamide wax dispersion. The same was carried out, the results are shown in Table 1.

Comparative example

Except not adding a wax dispersion in Example 1 and was carried out in the same manner as in Example 1 and the results are shown in Table 1.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example Vr ¹⁾ 0 2 2 0 0 0 0 E1 / 2 ²⁾ 0.17 0.18 0.18 0.17 0.17 0.17 0.15 E1 / 5 ³⁾ 0.33 0.35 0.35 0.34 0.33 0.33 0.29 E100 ⁴⁾ 0.39 0.40 0.40 0.39 0.37 0.38 0.34 DD1 ⁵⁾ 98.9 97.2 97.0 98.0 98.1 97.8 96.5 DD5 ⁶⁾ 93.9 92.9 91.5 92.9 93.1 93.0 92.1 Wear resistance ⁷⁾ 0.0034 0.0028 0.0038 0.0030 0.0036 0.0030 0.0045

[Property evaluation method]

1) Vr (-V): Potential after 5 seconds after optical scanning

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

3) E1 / 5 (μJ / ㎠): Light sensitivity when 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

7) Wear resistance: TABER ABRASION TESTER (CALIBRASE CS-10, loss after 5000 seconds)

By increasing the film strength of the charge transfer layer by the present invention as described above to reduce the damage of the film due to friction and toner, such as paper, charging rollers, transfer rollers, developing rollers, so that the image can be printed without changing the electrostatic properties for a long time In addition to increasing wear resistance, it is possible to provide an organic photosensitive drum for electrophotographic having excellent light sensitivity and dark attenuation characteristics.

Claims (4)

In the method for producing an electrophotographic photosensitive drum comprising a charge generating layer and a charge transfer layer, a polyamide-modified castor wax, a polyamide wax, an active polyamide wax, an oxidized polyethylene wax, a polyethylene wax, a modified polyethylene wax, Polypropylene-modified polyethylene wax, modified polypropylene wax, polytetrafluoroethylene-modified polyethylene wax, polytetrafluoroethylene-modified polypropylene wax, canova wax, canova-modified polyethylene wax, paraffin wax, polytetrafluoro A method for producing an electrophotographic organic photoconductive drum, wherein the polycarbonate resin mixed with a wax dispersion liquid in which at least one polymer wax selected from the group consisting of low ethylene wax is dispersed in a solvent is used as a binder resin of a charge transfer layer. delete The method of claim 1, wherein the wax dispersion is used within an amount of 0.005 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin. The method of claim 1, wherein a metal phthalocyanine is used as the charge generating material of the charge generating layer.