KR100754800B1 - Coating Composition for Forming Electrophotographic Photoconductor of Single Layer - Google Patents

Abstract

The present invention relates to a coating liquid composition of a single layer electrophotographic photosensitive member.

The present invention provides a coating liquid composition for forming an electrophotographic monolayer photoconductor comprising a charge generating material, a charge transporting material, an electron accepting material, a binder resin, an organic solvent, and an additive, wherein the electron accepting material is a cis type diphenoquinone-based. It is a feature to provide a coating liquid composition for forming a single layer electrophotographic photosensitive member, characterized in that the compound is a trans diphenoquinone-based compound.

The coating liquid for a single layer electrophotographic photosensitive member does not precipitate crystals, and can provide an effect having excellent solubility and excellent resin compatibility. Furthermore, when manufacturing the electrophotographic photosensitive member using the above-described coating solution, not only the sensitivity and stability are improved, but also excellent electrical characteristics such as electrostatic characteristics and dislocation characteristics can provide excellent image quality.

Electrophotographic photosensitive member, charge generating material, diphenoquinone, cis-type structure, trans-type structure

Description

Coating liquid composition of single layer electrophotographic photosensitive member {Coating Composition for Forming Electrophotographic Photoconductor of Single Layer}

1 is a cross-sectional view of a tomographic electrophotographic photosensitive member according to an embodiment of the present invention;

2 is a diagram showing a measurement result by ¹ HNMR spectrum of a trans-type diphenoquinone-based compound used in Example of the present invention;

FIG. 3 is a graph showing measurement results in a ¹ HNMR spectrum of a diphenoquinone compound having a ratio of cis-type and trans-type structures of 1: 1 (weight ratio) used in Examples of the present invention;

4 is a graph showing measurement results in a ¹ HNMR spectrum of a diphenoquinone compound having a ratio of cis-type and trans-type structure of 1: 2 (weight ratio) used in Examples of the present invention;

5 is a graph showing measurement results in a ¹ HNMR spectrum of a diphenoquinone compound having a ratio of cis-type and trans-type structures of 1: 5 (weight ratio) used in Examples of the present invention;

FIG. 6 is a graph showing measurement results in a ¹ HNMR spectrum of a diphenoquinone compound having a ratio of cis-type and trans-type structure of 1:10 (weight ratio) used in Examples of the present invention. FIG.

<Description of Symbols for Main Parts of Drawings>

110: conductor support layer 112: photosensitive layer

The present invention relates to a coating liquid composition of a single layer electrophotographic photosensitive member. More specifically, the structure of the diphenoquinone-based compound using the charge generating layer and the charge transport layer as a single layer and used as the electron accepting material included in the charge transport layer is obtained by using a cis type and a trans type structure in an appropriate ratio. A coating liquid composition of an electrophotographic photosensitive member having excellent compatibility.

In addition, the present invention relates to an electrophotographic photosensitive member which is improved in sensitivity and stability by using the above-described coating liquid composition and excellent in electrical characteristics such as electrostatic and dislocation characteristics.

Background Art Conventionally, as a photosensitive member for electrophotography, an inorganic photosensitive member having inorganic materials such as serene or a selenium alloy, zinc oxide, cadmium emulsion, and the like has been widely used. However, since the inorganic photoconductor has a problem of pollution or environmental pollution, research and development of an organic photoconductor including various organic photoconductive materials as a photosensitive layer material which can prevent the problem and adopt an advantageous coating method in terms of manufacturing cost. It is actively performed and put into practical use.

Recently, as a photosensitive layer for satisfying sensitivity and durability, many stacked organic photoconductors in which a charge generating layer containing a charge generating material and a charge transporting layer in which a charge transporting material is dispersed in a resin are laminated.

Such a laminated organic photosensitive member has good sensitivity and durability, but requires a uniform charging system or generates a large amount of ozone and deteriorates environmental conditions.

In order to remedy this problem, various types of electrostatic organic photoreceptors have emerged. However, in the case of the positive charge type, there are very few organic materials having excellent electron transporting ability, and even relatively good materials have toxic or carcinogenic properties, and thus, there is a problem that the practical use is poor.

In order to solve such a problem, the organic compound which introduce | transduced the functional group which has good solubility into the electron accepting structure of a molecule | numerator as an electron carrying material is proposed recently.

As for such an electron transporting material, Japanese Patent Laid-Open No. 1-206349, Japanese Patent Laid-Open No. 3-290666, Japanese Patent Laid-Open No. 4-360148, Japanese Patent Laid-Open No. 5-92936, and Japanese Patent Laid-Open Japanese Patent Application Laid-Open No. 7-179775, Japanese Patent Application Laid-Open No. 9-151157, Japanese Patent Application Laid-Open No. 10-73937, and the Korean Journal of Electrophotographic Publications No. 30, p. 1991), or in the general scientific and technical literature, such as "Japan Hard Copy '92 Proceedings p. 21-24.

However, the compounds described in these known documents have problems in practical use because of insufficient sensitivity and electrical properties in combination with existing charge generating materials.

Since there is no electron transport material capable of performing such an excellent function, the charge transport layer including the hole transport material is coated on the conductive support to separate the positively charged photosensitive layer into the charge generation layer and the charge transport layer according to the function. In this case, a structure for coating a thin film charge generating layer on the charge transport layer has been introduced. In this case, it is necessary to coat the surface protective layer to protect the charge generating layer of the thin film.

However, since coating of the surface protective layer becomes a factor of deterioration of sensitivity, it is difficult to design the photosensitive layer and a problem arises in that the manufacturing cost increases because the number of coatings increases due to an increase in the number of layers.

In order to solve such a problem, the monolayer type organic photoconductor which disperse | distributed a charge generating material and a charge transport material to a single film | membrane, or the composite type organic photoconductor which provided the charge transport layer in the lower layer of a single layer type is also proposed.

However, such an electrostatic organic photoreceptor may also cause crystallization or gelation due to lack of solubility or lack of compatibility, resulting in deterioration of electrophotographic properties or nonuniformity of local electrical properties in the coating. There is a problem that an image defect or a resolution decrease occurs.

In order to solve the problems as described above, an object of the present invention is to configure the structure of the diphenoquinone-based compound comprising the charge generating layer and the charge transport layer as a single layer and used as an electron accepting material contained in the charge transport layer, cis-type and trans It is to provide a coating liquid composition of a single-layer electrophotographic photosensitive member having excellent solubility and resin compatibility using a mold structure at an appropriate ratio.

It is another object of the present invention to provide an electrophotographic photosensitive member having improved electrical properties such as electrostatic and dislocation characteristics by using the above-described coating liquid composition.

In order to achieve the above object, the present invention provides a coating liquid composition for forming an electrophotographic monolayer photoconductor comprising a charge generating material, a charge transporting material, an electron accepting material, a binder resin, an organic solvent, and an additive, The electron accepting material is characterized by providing a coating liquid composition for forming a single-layer electrophotographic photosensitive member, characterized in that the compound of cis diphenoquinone and trans type diphenoquinone.

In addition, the present invention is characterized by providing a single-layer electrophotographic photosensitive member including a photosensitive layer prepared using the coating liquid composition.

The coating liquid for a photosensitive layer of the present invention comprises a charge generating material, a charge transporting material, an electron accepting material, a binder resin, an organic solvent, and an additive.

Oxotitanyl phthalocyanine as the charge generating material, triphenyldiamine (TPD) -based compound as the charge transport material, cis-type diphenoquinone-based compound of the formula (1) and trans-type diphenoquinone-based compound of the formula (2) Preferred but not limited to use.

　　　　　　

　　　　　　

Wherein R 1 is a methyl group, R 2 is an ethyl group, isopropyl group or t-butyl group.

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 Use may be made of, but not limited to, a dendene resin, a formal resin, a cellulose resin or a copolymer thereof, or a halide or cyanoethyl compound thereof, or a combination of two or more thereof.

Tetrahydrofuran is used as an organic solvent.

When using an additive, it is preferable to use a dispersing agent, an antifoamer, surfactant, etc.

It is recommended to use 0.5 to 10 parts by weight of the charge generating material, 1 to 20 parts by weight of the charge transport material, 1 to 10 parts by weight of the electron accepting material, 5 to 30 parts by weight of the binder resin, and 60 to 92.5 parts by weight of the organic solvent. Preferred but not limited to.

The electrophotographic photosensitive member of the present invention is manufactured by the following method.

1 is a cross-sectional view of an electrophotographic photosensitive member according to an embodiment of the present invention. An electrophotographic photosensitive member according to an embodiment of the present invention is formed by sequentially stacking a photosensitive layer 112 including a charge generating material, a charge transporting material, and an electron accepting material on a conductor support layer 110.

First, as a support of the conductor support layer 110, a metal, such as aluminum, an aluminum alloy, nickel or stainless steel, or a material formed by conducting a conductive treatment on glass or a resin film or the like in a plate shape, a cylindrical shape, or a film shape may be used. Can be.

The structure which forms an insulating layer on the surface of the support body of these conductor support layers 110 is also possible. In this case, the insulating layer is formed on the surface of the support of the conductor support layer 110 to have uniformity and good adhesion. This insulating layer is formed by forming an oxide film layer or a resin film layer on a 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, polypyrrole and polyaniline, or metal oxide powders are added to these polymers. Is used.

Next, a coating liquid composition for a photosensitive layer composed of a charge generating material, a charge transporting material and an electron accepting material, a binder resin, an organic solvent, and an additive is coated on the photosensitive layer 112 and then dried at a high temperature for a predetermined time. In coating, conventional coating apparatuses such as a dip coater, spray coater, wire bar coater, applicator, doctor blade, roller coater, bead coater and the like can be used.

Examples of the charge generating material include oxo titanyl phthalocyanine, copper phthalocyanine, metal phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine, chlorogermanium phthalocyanine, vanadil oxide phthalocyanine, titanyl oxide phthalocyanine, hydroxy gelatininine and hydroxy Gallium phthalocyanine etc. can be used individually or in mixture of 2 or more types. The content of the charge transport material according to the embodiment of the present invention is 0.5 to 10 parts by weight.

The charge transport material serves to transfer charges generated in the photosensitive layer 112 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-tol) Luyl) 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-4-ylidene) -propanedinitrile-1,1-dioxide, 4-bromo-triphenylamine, 4,4 '-( 1,2-ethanediylidene) -bis (2,6-dime -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-phenyl triazole, 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-di 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) -triphenyl Amine, 4,4 ', 4 "-tris (N, N-diphenylamino) -triphenylamine, N, N'- Su (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, 4,4'4" -bis (4,4-diphenyl-1,3-buta Dienyl) 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) tri Phenylamine, 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-butadienyl ) Triphenylamine, 4,4'4 "-tris (4,4-di (2-methoxyphenyl) -1,3-butadienyl) triphenylamine, N, N'-bis (3-methylphenyl) -N, N'- Scan (2-naphthalene) - [1,1'-biphenyl] -4,4' etc. can be used alone or in mixture of two or more kinds diamine. As the charge transport material according to the embodiment of the present invention, a triphenyldiamine-based compound is suitable. The content of the charge transport material according to the embodiment of the present invention is 1 to 20 parts by weight.

Diphenoquinone-based compounds are used as the electron accepting material. The content of the electron accepting material according to the embodiment of the present invention is 1 to 10 parts by weight. In addition, 2- (1,1-dimethylethyl) -4- [3- (1,1-dimethylethyl) -5-methyl-4, which is one of diphenoquinone compounds, is an electron accepting material according to an embodiment of the present invention. -Oxo-2,5-cyclohexa-diene-1-iridine] -6-methyl-2,5-cyclohexadien-1-one can be used, and the cis structure and the trans structure in an appropriate ratio It may contain. As for the ratio of a cis diphenoquinone type compound and a trans type diphenoquinone type compound, 1: 1: 1: 5 (weight ratio) are suitable. As for the ratio of the diphenoquinone type compound of a cis-type and a trans-type structure, 1: 1: 1: 2 (weight ratio) are preferable. Furthermore, the ratio of the triphenyldiamine-based compound, which is a charge transporting material, and the diphenoquinone-based compound, which is an electron-accepting material, according to an embodiment of the present invention is from 1: 1 to 1:10 (weight ratio).

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. The content of the binder resin according to the embodiment of the present invention is 5 to 30 parts by weight.

Organic solvents usable in the present invention include 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 Back alone or It can mix and use 2 or more types. The content of the organic solvent according to the embodiment of the present invention is 60 to 92.5 parts by weight.

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

Hereinafter, the present invention will be described in detail with reference to preferred embodiments. In the description of the present invention, when the detailed description of the related well-known technology is obvious to those skilled in the art or it may be determined that the subject matter of the present invention may be obscured, the detailed description thereof will be omitted.

Synthesis Example

Synthesis Example 1

Into a three-necked reactor equipped with a Reflux device and an oxygen bubbling device, 100 g of 2-3-butyl-6-methylphenol (TVMP) and 300 g of methanol were added, stirred to mix well, and again, Pd (dba) was used as a catalyst. 0.5 wt% of ₃ compared to tBMP.

Oxygen is flowed into the reactor and the reaction temperature is 30 ° C. for 24 hours. After the reaction, the reaction product is filtered to remove the catalyst, and the filtrate is recrystallized from hexane to obtain the target material.

¹ HNMR measurement resulted in 65 parts by weight of the trans-type diphenoquinone (DQ) compound. The prepared trans-type diphenoquinone (DQ) compound was measured by a spectrum of Varian Unity 300 (300 MHz) ¹ HNMR as shown in FIG. 2.

Synthesis Example 2

In Synthesis Example 1, 72 parts by weight of a diphenoquinone (DQ) compound was obtained in the same manner as in Synthesis Example 1 except that the reaction temperature was changed from 60 ° C to 60 ° C.

This is measured with a spectrum of Varian Unity 300 (300MHz) ¹ HNMR is shown in FIG.

[Production example]

Preparation Example 1

Y-type oxo titanyl phthalocyanine (ST10 / 10.2; Syntec) 2.0 parts by weight, 중량 N, N'-bis (3-methylphenyl) -N, N'-bis (2-napthyl)-[1,1'-biphenyl ] 4,4'-diamine (DPND; Hitachi Chemical Co., Ltd.) 65 parts by weight, 85 parts by weight of polycarbonate resin (PCX-300; Mitsubishi Gas Kagaku Co., Ltd.), 555 parts by weight of THF, 185 parts by weight of toluene, Synthesis Example 2 10 parts by weight of diphenoquinone (DQ) compound having a ratio of cis-type and trans-type structure prepared in 1: 1 together was dispersed by an ultrasonic disperser (unisonized ultrasonic wave) for 1 hour to prepare a stable monolayer coating solution.

Preparation Example 2

In Preparation Example 1 of the monolayer coating solution, the same procedure as in Preparation Example 1 except for changing the diphenoquinone (DQ) compound having a 1: 1 ratio of cis-type and trans-type structure to a diphenoquinone (DQ) compound having a 1: 2 ratio. To prepare a coating solution.

The diphenoquinone (DQ) compound used herein was measured with a spectrum of Varian Unity 300 (300 MHz) ¹ HNMR as shown in FIG. 4.

Preparation Example 3

In Preparation Example 1 of the monolayer coating solution, the same procedure as in Preparation Example 1 except for changing the diphenoquinone (DQ) compound having a ratio of 1: 1 to cis-type and trans-type structure to a diphenoquinone (DQ) compound having a 1: 5 ratio. To prepare a coating solution.

The result of measuring the diphenoquinone (DQ) compound used here by the spectrum of Varian Unity 300 (300 MHz) ¹ HNMR is shown in FIG. 5.

Comparative Production Example

1.0 parts by weight of Y-type oxo titanyl phthalocyanine (ST10 / 10.2: Syntec), N, N'-bis (3-methylphenyl) -N, N'-bis (2-napthyl)-[1,1'-biphenyl ] 4,4'-diamine (DPND; manufactured by Hitachi Chemical Co., Ltd.) 8.4 parts by weight, 11 parts by weight of polycarbonate resin (PCX-300; manufactured by Mitsubishi Gas Kagaku KK), HF 55.7 parts by weight, toluene 24 parts by weight 10 parts by weight of the trans-type diphenoquinone (DQ) compound prepared in Synthesis Example 1 were added together and dispersed in an ultrasonic disperser (only ultrasonic wave) for 1 hour to prepare a stable monolayer coating solution.

Comparative Production Example 2

In Comparative Preparation Example 1 of the monolayer coating solution, the trans-type diphenoquinone (DQ) compound was changed to the diphenoquinone (DQ) compound having a cis-to-trans structure ratio of 1: 10, in the same manner as in Preparation Example 1. A coating solution was prepared.

The diphenoquinone (DQ) compound used herein was measured with a spectrum of Varian Unity 300 (300 MHz) ¹ HNMR as shown in FIG. 6.

The solubility evaluation results of the diphenoquinone (DQ) compound used above are shown in Table 1.

division NMR ratios of cis- and trans-structure DQ (7.6 to 7.8 ppm peak) Solubility ^a) (wt%) Crystal precipitation TEST ^b) Article 1 1: 1 40 Not Occurred 2 1: 2 40 Not Occurred 3 1: 5 30 Microgeneration Comparative Production Example 1 Trans-solo 10 Large quantities 2 1: 10 15 Large quantities

a) Tetrahydrofuran: toluene = 3: 1 mixed solvent conditions

b) 20 wt% of a diphenoquinone (DQ) compound was dissolved in a mixed solvent, and then dropped on a glass substrate.

EXAMPLE

Example 1

After primary processing on the conductive cylindrical support (30 mm Φ), the monolayer coating solution prepared in Preparation Example 1 was subjected to hot air drying at 120 ° C. for 30 minutes using a dip coating method on an aluminite-treated aluminum drum, and having a thickness of 24 μm. A dark green monolayer type body was obtained. The surface of the photoconductive drum manufactured as described above was observed to show the results of crystal precipitation and appearance defects in Table 2.

In addition, a +6 KV to +7 KV corona charge is performed using an electrostatic checker tester to charge the potential of the drum surface to about +650 V, and then a unit required to halve the charge potential by scanning light of 780 nm wavelength into the drum. The potential Vr was measured after erasing the potential of the drum surface with the energy E 1/2 per area, red LED light source. And dark attenuation DD1 and DD5 which hold | maintain the electric potential after 1 second and 5 second in the dark after charging were measured, respectively.

Then, using the Brother company printer (HL-1470), the black potential and the potential of 300 dpi and 600 dpi were measured using JIG manufactured by itself, and again using the Brother company printer (HL-1470), Fig. 600 dpi was measured using a densitometer (model name: RD918, manufactured by Mechves) and shown in Table 2, respectively.

Example 2

Example 1 was prepared and evaluated in the same manner as in Example 1 except that the monolayer coating solution prepared in Preparation Example 2 was used instead of the monolayer coating solution prepared in Preparation Example 1 for the preparation of the single layer photosensitive member.

Example 3

Example 1 was prepared and evaluated in the same manner as in Example 1 except for using the monolayer coating solution prepared in Preparation Example 3 instead of the monolayer coating solution prepared in Preparation Example 1 for the preparation of the monolayer photosensitive member.

Comparative Example 1

After primary processing on the conductive cylindrical support (30 mm Φ), the monolayer coating solution prepared in Comparative Preparation Example 1 was hot-dried at 120 ° C. for 30 minutes using a dip coating method on an aluminite-treated aluminum drum, and having a thickness of 24 μm. The dark green monolayer photosensitive member of was obtained. The surface of the photosensitive drum thus prepared was observed, and the results of crystal precipitation and appearance defects are shown in Table 2.

In addition, a +6 KV to +7 KV corona charge was performed with the electrostatic beaker tester to charge the potential of the drum surface to about +650 V, and then the light potential of the 780 nm wavelength was injected into the drum to halve the charge potential. The potential Vr was measured after erasing the potential of the drum surface with the energy E 1/2 per unit area necessary for the red LED light source. And the dark attenuation DD1 and DD5 which hold | maintain the electric potential after 1 second and 5 second in the dark after the charging were measured, respectively.

Then, using the Brother company printer (HL-1470), the black potential and the potential of 300 dpi and 600 dpi were measured using JIG manufactured by itself, and again using the Brother company printer (HL-1470), In addition, the 600 dpi concentration was measured using a densitometer (model name: RD918, Mechves Co., Ltd.), and is shown in Table 2, respectively.

Comparative Example 2

Example 1 was prepared and evaluated in the same manner as in Example 1 except that the monolayer coating solution prepared in Comparative Preparation Example 2 was used instead of the monolayer coating solution prepared in Preparation Example 1 for the preparation of the monolayer photosensitive member.

 Electrostatic characteristics  Dislocation characteristics  Image characteristics   Exterior judgment division DD1 (%) DD5 (%) E1 / 2 (μJ / ㎠) Vr (-V) Black potential (VL) (-V) 600 dpi potential (-V) Black concentration 600 dpi concentration Example 1 93.0 82.9 0.44 60 190 605 1.55 0.53 ○ Example 2 93.2 83.4 0.45 62 195 610 1.53 0.56 ○ Example 3 92.5 82.2 0.47 69 199 619 1.50 0.49 △ Comparative Example 1  Not measurable x Comparative Example 2 83.0 68.4 0.62 95 310 695 1.18 0.30 x

※ appearance judgment legend

○: Good appearance

△: Small amount of appearance defects (crystallization) occurs (appearance defects 1 to 5)

×: A large amount of appearance defects (crystallization) occurred (more than 5 appearance defects)

As can be seen from Table 1 and Table 2, the solubility and dissolution of the crystal form of the diphenoquinone (DQ), which is an electron-accepting substance used in the preparation of the coating solution, in the ratio of cis-type and trans-type structures of 1: 1 to 1: 5. Appearance characteristics are shown to be much better than the trans type monostructure and 1: 5 or more. Preferably, the ratio of the cis-type and trans-type structures of the diphenoquinone (DQ) in the ratio of 1: 1 to 1: 2 indicates more excellent solubility and appearance characteristics.

The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and changes without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

As described above, according to the present invention, the coating liquid for monolayer electrophotographic photosensitive members does not precipitate crystals, and can provide an effect excellent in solubility and excellent in resin compatibility. Furthermore, when manufacturing the electrophotographic photosensitive member using the above-described coating solution, not only the sensitivity and stability are improved, but also excellent electrical characteristics such as electrostatic characteristics and dislocation characteristics can provide excellent image quality.

Claims (9)

A coating liquid composition for forming an electrophotographic monolayer photoconductor comprising a charge generating material, a charge transporting material, an electron accepting material, a binder resin, and an organic solvent, The electron accepting material is a coating liquid composition for forming a single-layer electrophotographic photosensitive member, characterized in that the cis-type diphenoquinone-based compound and the trans-type diphenoquinone-based compound. The method of claim 1, A coating liquid composition for forming a single layer electrophotographic photosensitive member, wherein the ratio of the cis-type diphenoquinone-based compound and the trans-type diphenoquinone-based compound is 1: 1 to 1: 5 by weight. The method of claim 1, A coating liquid composition for forming a single-layer electrophotographic photosensitive member, wherein the ratio of the cis-type diphenoquinone-based compound and the trans-type diphenoquinone-based compound is 1: 1 to 1: 2 by weight. The method of claim 1, A coating liquid composition for forming a monolayer type electrophotographic photosensitive member, wherein the diphenoquinone-based compound and the charge transporting material are in a weight ratio of 1: 1 to 1:10. The method of claim 1, 0.5 to 10 parts by weight of the charge generating material; 1 to 20 parts by weight of the charge transport material; 1 to 10 parts by weight of the electron accepting material; 5 to 30 parts by weight of the binder resin; And 60 to 92.5 parts by weight of the organic solvent Coating liquid composition for forming a single-layer electrophotographic photosensitive member comprising a. The method of claim 1, The coating liquid composition for forming a monolayer electrophotographic photosensitive member, wherein the charge generating material is oxo titanyl phthalocyanine. The method of claim 1, Coating composition for forming a single-layer electrophotographic photosensitive member, characterized in that the charge transport material is triphenyldiamine-based. The method of claim 1, The diphenoquinone compound is 2- (1,1-dimethylethyl) -4- [3- (1,1-dimethylethyl) -5-methyl-4-oxo-2,5-cyclohexa-diene-1 -Iridine] -6-methyl-2,5-cyclohexadien-l-one, The coating liquid composition for forming the single-layer electrophotographic photosensitive member. A tomographic electrophotographic photosensitive member comprising a photosensitive layer prepared using the coating liquid composition of any one of claims 1 to 8.

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