JPS6022348B2 - Photosensitive composition for electrophotography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a binder type electrophotographic photosensitive composition using a water-soluble prepolymer that is crosslinked to form a silk-like structure as a binder resin and a cadmium sulfide compound as a photoconductor. It is related to.

In general, photosensitive materials for electrophotography include a photosensitive composition obtained by mixing and dispersing a photoconductive inorganic compound in a solution obtained by dissolving amorphous selenium on a metal plate and a binder resin in an organic solvent. The present invention relates to a photosensitive composition for electrophotography (hereinafter simply referred to as a photosensitive composition) used in a binder type photosensitive material for electrophotography. . Conventional photosensitive compositions include photoconductive inorganic compounds such as ethylene, styrene, methacrylic esters, acrylic esters,
Resins made of monopolymers or multicomponent copolymers of vinyl acetate, vinyl chloride, hynylidene chloride, butadiene, silicone resins, epoxy resins, or alkyd resins, for example, acetone, benzene, toluene, ethyl acetate, trichlorethylene, etc. It is made by dispersing it in a solution dissolved in an organic solvent such as tyrene. However, cadmium sulfide compounds, which are a type of photoconductive inorganic compounds, have a higher affinity for water than the original organic solvent, and are difficult to disperse in solutions of resins dissolved in organic solvents. When a cadmium sulfide compound is dispersed in the above-mentioned solvent-based binder liquid, it is difficult to obtain a dispersion liquid with excellent dispersibility even though a great deal of cost and effort is required. Additionally, in order to improve the coating processability and to eliminate the problems caused by the use of organic solvents that are undesirable in terms of pollution, a photoguiding inorganic compound is mixed and dispersed in an aqueous dispersion resin (usually called latex). Although photosensitive compositions are known, they have not yet been put into practical use due to problems such as the presence of even microscopic water in the electrophotographic photosensitive layer, which greatly impedes electrophotographic performance. .

An object of the present invention is to provide a photosensitive composition that has excellent dispersibility and coating processability, does not use organic solvents that are undesirable from a pollution standpoint, and also has excellent moisture resistance and electrophotographic performance. An object of the present invention is to provide a photosensitive composition that can form an excellent electrophotographic light-sensitive material.

The above-mentioned object is achieved by using a photosensitive composition whose main components are a photoconductive cadmium sulfide compound and a water-soluble prepolymer (hereinafter referred to as prepolymer) that is crosslinked to form a network structure. .

That is, the photosensitive composition according to the present invention is prepared by mixing and dispersing a photoconductive cadmium sulfur compound powder in an aqueous solution of a prepolymer or a solution to which an appropriate amount of an alcoholic additive is added to improve solubility. There is an advantage in terms of pollution control that there is no need to use organic solvents, which are undesirable from the viewpoint of workability and safety and health.

Furthermore, as mentioned above, since a photosensitive composition in which photoconductive cadmium sulfide compound powder is dispersed in an aqueous prepolymer solution is used, it has excellent dispersibility and coating processability, and it is possible to form a photosensitive layer with a uniform and smooth surface. By thermosetting the photosensitive layer, it is possible to form a photosensitive layer composed of a resin having a strong network structure. Therefore, a photosensitive material made using the photosensitive composition according to the present invention can exhibit the effects of being excellent in electrical and mechanical durability, particularly in corona discharge characteristics. Further, in the photosensitive composition according to the present invention, the bleed polymer according to the present invention has a high affinity for the photoconductive cadmium sulfide compound powder, and can adsorb and coat the powder extremely well. Since a water-resistant film can be formed by carrying out a crosslinking reaction, a photosensitive layer with high moisture resistance can be formed.
On the other hand, in conventional photosensitive compositions that use resin solutions in organic solvents, the resin dissolved in the organic solvent has poor affinity and adsorption for photoconductive cadmium sulfide powders, resulting in poor photoconductivity. Not only is it not possible to sufficiently cover the cadmium sulfide compound powder with the resin, but the residual organic solvent present between the photoconductive cadmium sulfide compound powder and the resin may cause the photosensitive composition to be coated on the conductive substrate. During the drying process, it evaporates and leaves voids, which increase the hygroscopicity of the photosensitive layer and deteriorate the electrophotographic properties of the photosensitive layer. In addition, even in the case of a photosensitive composition made by dispersing photoconductive cadmium sulfide compound powder in an aqueous latex solution, when this composition is applied onto a meridian-conducting substrate and dried, gaps between the granular latex tend to form. It is difficult to obtain a photosensitive layer with good moisture resistance. Furthermore, the photosensitive layer prepared using the photosensitive composition according to the present invention has a high image density when an image is formed on the photosensitive layer, which is presumably due to the characteristics and dispersibility of the prepolymer used. In particular, it can exhibit excellent characteristics such as less fogging due to residual armament and high sensitivity.

Furthermore, since the photosensitive composition according to the present invention is a water-dispersed composition, a photosensitive layer can be formed by a military coat coating method on an endless drum installed in a copying machine. It has the above advantages and can exhibit many effects such as ease of mass production.

It was thought that it was impossible to use a water-soluble material as a binder in the photosensitive layer of an electrophotographic photosensitive material based on the electrical characteristics of the original electrophotography. Using a water-soluble prepolymer that can be crosslinked to form a silk-like structure as a binder,
The formation of an excellent photosensitive layer is a revolutionary new technology.

Examples of the photoconductive cadmium sulfide compound used in the present invention include cadmium sulfide, cadmium selenide,
Examples include cadmium sulfide selenide, zinc sulfide, and zinc selenide. Next, the prepolymer used in the present invention is a self-curing type that crosslinks with the action of light or heat to form a silk-like structure, and a self-curing type that forms a silk-like structure by crosslinking with the action of light or heat. There are those that form a crosslinked silk-like structure, and all of them can be effectively used in the present invention.

In addition, the prepolymer used is a relatively low-molecular compound, but it has many hydroxyl groups or carpoxyl groups, or
It may be a polymer or copolymer in which the carboxyl group is salt-formed with ammonia, and even in the case of such a polymer, it is preferable that the molecular weight is 50,000 or less from the viewpoint of dispersibility and processability. The prepolymers used in the present invention include condensed prepolymers and polymerized prepolymers. First, the condensed prepolymers will be explained below.

Examples of condensation prepolymers include prepolymers such as alkyd resins, phenolic resins, amino resins, epoxy resins, and urethane resins, and all of the prepolymers used in the present invention have many carboxylic acid groups or hydroxyl groups in their constituent components. and if necessary, some of the carboxylic acid groups are made hydrophilic by salt formation with ammonium groups, preferably one of alkyd resins, epoxy resins, phenol resins, and polyamide/resins. Bure polymers such as melamine resins are used in the present invention. A specific example of the alkyd resin prepolymer having a bifunctional acid as a constituent used in the present invention is, for example, a salt formed by subjecting phthalic acid and pentaestol to a dehydration condensation reaction and bonding an ammonium group to a carboxylic acid group. There is a product obtained by doing this, and its constituent components are roughly as follows. Specific examples of alkyd resin prepolymers containing trifunctional acids used in the present invention include, for example, those in which trimellitic anhydride, glycols, and adipic acid are combined, and the constituent components are roughly as follows. The structure is as follows.

In addition, there are water-soluble alkyd resin prepolymers using polyoxyethylene bonds that are used in the present invention, and a specific example is one in which phthalic anhydride, besotaerythritol, polyethylene glycol, and fatty acids are bonded. , its constituent components have the following structure.

Such prevolimers are already commercially available, and such commercial products include, for example, m Watersol S-123.
(Dainippon Ink Co., Ltd. acid) [2' Watersol S-12
6 (Dainippon Ink Co., Ltd.) Tsuyoshi Water Sol S-140
(Manufactured by Dainippon Ink Co., Ltd.) {4- Watersol S-10
A plate (manufactured by Dainippon Ink Co., Ltd.) is preferably used in the present invention.

Another water-dropping prepolymer of the condensed epoxy resin preferably used in the present invention is, for example, a reaction product of epichlorohydrin and diphenylolpropane treated with horse P04, French S04, etc. The end groups of the precipitated reaction product are reacted with the end groups to esterify them as or or or, and these are further reacted with an alkali metal atom or preferably ammonia to form a salt to make them water-soluble. It will be done.

Such prepolymers are already commercially available, and examples of commercially available products preferably used in the present invention include Watersol S-1 Group (manufactured by Dainippon Ink Co., Ltd.) '6} Kissol HF
(manufactured by Osaka Varnish Co., Ltd.).

Another water-soluble prepolymer of the condensed melamine resin preferably used in the present invention includes, for example, mono- or hexamethylolmelamine obtained by reacting melamine with formaldehyde, and examples include trimethylmelane and trimethylmelane having the following structure. There are derivatives of it.

Alternatively, there are mono- to hexamethoxymethylmelamines obtained by reacting the above-mentioned methylolmelamine and methanol, and one example is hexamethoxymethylmelamine and its derivatives having the following structure.

Furthermore, in addition to the initial condensate of methylol melamine,
There are prebolimers obtained by adding and condensing polyvalent amines such as alkylene polyvalent amines, hydroxy polyvalent amines, and guanidine.

Although such a prepolymer of melamine resin can be used in the present invention itself, it is preferably used as a curing agent for the prepolymer of the alkyd resin, epoxy resin, and acrylic resin, which is a polymeric water-soluble resin described later. is effectively used and is already commercially available under the following trade name. [71 Water Sol S
-695 (manufactured by Dainippon Ink Co., Ltd.) '8' Watersol S-616 (manufactured by Dainippon Ink Co., Ltd.) '9} Nikaratsuk M
w-12 (manufactured by Sanwa Chemical Co., Ltd.) 00 Nikaratsuku Mw
-22 (manufactured by Sanwa Chemical Co., Ltd.) (11) Nikaratsuku Mw
-30 (manufactured by Sanwa Chemical Co., Ltd.) (12) Nikaratsuku Mw-
Prepolymers of 40 (manufactured by Sanwa Chemical Co., Ltd.) or higher can also be appropriately mixed and used.

Furthermore, as another water-soluble prepolymer of condensed phenolic resin preferably used in the present invention, there are, for example, phenol alcohols obtained by reacting formaldehyde with phenols, and one example is 3, 5,
There is 3',5'-tetramethylol-4,4'-dioxydiphenylmethane. Furthermore, there are polynuclear phenolic resins, such as nopolac resins, in which a carboxyl group is introduced, a methylol group is further introduced, and then ammonia is added to form a salt, and a polymeric prepolymer can be obtained.

Although such a prepolymer can be used as such in the present invention, in the present invention, it is preferably used as a curing agent for the water-droppable prepolymer of the alkyd resin or the water-soluble polymeric resin described below. Other water-soluble polymers of condensation resins preferably used in the present invention include, for example, hydroxyalkylcellulose obtained by reacting alkylene oxide with alkali cellulose, and furthermore, hydroxyalkylcellulose obtained by reacting alkali cellulose with alkyl halide. Alkyl cell. There is a Such a water-soluble cellulose derivative can be cured to form a network structure by the action of a small amount of a crosslinking agent such as glyogysar, urea resin prepolymer, melamine resin prepolymer, or polybasic acid. It is something.

Examples of the water-dropping prepolymer of the polymeric resin preferably used in the present invention include polyacrylic acid and its derivatives, polyacrylamide, polyvinylpyrrolidone, polyvinyl ether, and polyvinyl alcohol.

As for the polyacrylic acid and derivatives.

For example, there are salts formed by reacting ammonia with the carboxyl group of an acrylic acid or methacrylic acid homopolymer or a copolymer of acrylic acid allester or methacrylic acid alkyl ester; In addition to the ester monomer, a multi-component copolymer is produced by copolymerizing monomers such as maleic anhydride, itaconic acid, methacrylamide, acrylamide, ammonium acrylate, ammonium methacrylate, and methyl vinyl ether. be. The water-soluble prepolymers of the polymeric acrylamide resin include acrylamide homopolymers, acrylamide and acrolein, acrylic esters, acrylic acid, methacrylic acid, acrylonitrile, butadiene, methacrylic esters, diallycyanamide, glycidyl acrylate, and maleic anhydride. Acid, methacrylamide, styrene, unsaturated fatty acid-modified alkyd resin monomer, vinyl acetate, vinyl chloride,
Examples include vinyl ether, pinyl ketone, vinylpyridine, and copolymers with vinylpyrrolidone.

Furthermore, there are also those containing a methylolated product of acrylamide or a methylolated product of a copolymer of acrylamide and N-vinyl lactam as a constituent component of the multicomponent copolymer.

The water-dropping prepolymers of acrylic acid and its derivatives and acrylamide-based resins are already commercially available, and commercially available products include, for example, (13) Watersol S-
727 (manufactured by Dainippon Ink Co., Ltd.) (1 core Water Sol S
-767 (manufactured by Dainippon Ink Co., Ltd.) (15) Watersol S-754 (manufactured by Dainippon Ink Co., Ltd.).

Furthermore, polyvinyl alcohol, polyvinylpyrrolidone, and polyvinyl ether, which are types of prepolymers according to the present invention, may be used alone, but they may also be copolymerized with the above-mentioned acrylic acid, methacrylic acid, or their esters or acrylamide. Can be used.

Furthermore, the prepolymers used in the present invention may be used alone or in combination, and in addition to the various prepolymers mentioned above, natural or synthetic compounds, water-soluble ones, or synthetic compounds having a large number of hydroxyl groups or carpoxyl groups can be used. Compounds that become water-dropable as a result of reactions such as chlorination or copolymerization, such as polymerization accelerators such as cobalt naphthenate, calcium naphthenate, and lead naphthenate, aldehydes, melamine resin prepolymers, phenolic resin prepolymers, and epoxy shesters. All resin prepolymers that can be cured by polymerization or condensation under the action of a curing agent are included in the present invention.
Next, in order to produce the photosensitive composition according to the present invention, for example, US Pat.
The solid content of the prepolymer is 10 to 10 parts by weight of a photoconductive cadmium sulfide compound having an average particle size of 2 or less, which is produced by the production method described in Ichigo Publication and Samurai Publication No. 47-20754, etc. 100 parts by weight preferably 2
0 to 8 parts by weight, optionally 0 to 10 parts by weight of a water-soluble or alcohol-soluble curing agent or 0 to 10 parts by weight of a polymerization accelerator
1 part by weight, 20 to 30 parts by weight as water, preferably 80 to 20 parts by weight, and optionally 0 to 30 parts by weight of an alcoholic amphipathic solvent to promote the solubility of the prepolymer in water. Furthermore, if necessary, an amine neutralizer to impart water solubility to the prepolymer and a surfactant to improve the coating condition are added, and these are processed using a homomixer, ball mill, sand mill, ultrasonic disperser, etc. It can be prepared by mixing and dispersing using a disperser.

Examples of the curing agent or polymerization accelerator used in the photosensitive composition of the present invention include polymerization accelerators such as cobalt naphthenate, calcium naphthenate, and lead naphthenate, aldehydes such as glyogyzal, and melamine resin prepolymers. , phenolic resin prepolymer, epixyester resin prepolymer, etc., considering the type of prepolymer, curing reaction time, reaction temperature, type of photoconducting inorganic compound, required performance of electrophotographic photosensitive layer, surface hardness, etc. Heals and is added in appropriate amounts.

Examples of the amphiphilic solvent used in the photosensitive composition according to the present invention include methyl alcohol, ethyl alcohol, inpropyl alcohol, n-propyl alcohol,
Inpropyl alcohol, secondary or tertiary butyl alcohol, methyl cellosolp, butyl cellosolp, ethoxybutyl alcohol or ethers are used, and the amount added is appropriately selected depending on the type of prepolymer and the concentration of the prepolymer in the aqueous solution. .

In addition, the neutralizing agent used in the photosensitive composition according to the present invention is a basic compound that can neutralize acid groups such as carboxylic acid groups that are constituent components of the bleed polymer and make the prepolymer water-soluble. The resin used is one that can volatilize and be eliminated when heated and dried to generate free carboxyl groups to make the resin hydrophobic. Examples of such compounds include ammonia, triethylane, monogytriethanolamine, dimethylaminoethanol, diethylaminoethanol, etc., and the amount added is appropriate depending on the type and concentration of the prepolymer. Further, as the surfactant used in the photosensitive composition according to the present invention, preferably a fluorine-based surfactant is used, and this surfactant is already commercially available, for example, Megafax F-121, F-141, F-
150 (manufactured by Dainippon Ink & Chemicals) and FC-430 (manufactured by Sumitomo 3M).

The photosensitive composition according to the present invention is coated on a support, for example, a fin-guiding base paper, a plastic film laminated with a thin metal layer, etc., and optionally a polymeric quaternary amine salt,
It is coated with an intermediate layer of casein, polyvinyl alcohol, polyoxymethylcellulose, hydroxycellulose, alkylcellulose, water-soluble nylon, vinyl acetate, etc., so that the film thickness after drying is about 5 to 40 μm, and then After processing, at room temperature to 300°C, preferably 60 to 300°C.
A strong hydrophobic photosensitive layer for electrophotography is formed by heat curing at a temperature of 25 to 0 for 15 minutes to 3 hours. In the present invention, a single photosensitive layer may be provided, but photosensitive layers having different electrophotographic performance or physical properties may be provided as mirrors. For example, a lower photosensitive layer with excellent chargeability may be provided on an upper layer. Possible methods include providing a photosensitive layer with high sensitivity and excellent mechanical abrasion resistance, or providing a conventionally known solvent-based photosensitive layer as a lower layer and providing a photosensitive layer according to the present invention as an upper layer.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 [Photosensitive composition formulation A] Highly sensitive cadmium sulfide 1M with average grain size lr Exemplary compound '21 (water-soluble alkyd resin prepolymer solid content 5
0%). Exemplary compound [71 (Water-soluble melamine resin prepolymer solid content 66%)
1.5% water 4M methyl alcohol 2% inpropyl alcohol 2M [Photosensitive composition formulation B] Highly sensitive cadmium sulfide with 2 average grains 10
5 Ta Exemplary Compound (13) (Mottled acrylic resin prepolymer - solid content 60%) 5 Ta Exemplary Compound {7
} 2 ta water
6 [Methyl cellosolve
2 [FC-430 (base surfactant) 0
．． 08 evening [Photosensitive composition formulation C] 10 high-sensitivity cadmium sulfide microcrystals with an average particle size of 2 peaks Exemplary compound t31 (water-soluble alkyd resin brepolymer solid content 70%)
4.3 Water 4 Ethyl alcohol 4 [[Photosensitive composition formulation D] Highly sensitive cadmium sulfide microcrystals with an average particle size of 21 1M Exemplary compound '4} (Water-dropable alkyd resin prepolymer solid content 60%) 6 Calcium thanaphthenate 5% aqueous solution 0.08 Lead thanaphthenate2
After thoroughly mixing and dispersing each of the five types of photosensitive compositions in a 0% aqueous solution with an ultrasonic disperser using an ultrasonic disperser, each was coated on a 100R thick stainless steel sheet using a wire bar so that the film thickness after drying was 30 mm. Apply and dry depending on the method, and then apply these to the prescription.
Heat treated at 50oo for 3 minutes, and cured by heat treatment at 8pC for 1 hour.
．． 4).

Example 2 [Photosensitive composition formulation E] Highly sensitive cadmium sulfide microcrystals with an average particle size of 1 10 t Exemplary compound ■ 6.4 t Exemplary compound [51 (Epoxy shester prepolymer solid content 76%
) 0.5ta Exemplary Compound '71
0.6% water 7M ethyl alcohol 2 parts 30% ammonia water 1 part [FC-430
A photosensitive composition was prepared by thoroughly mixing and dispersing the 0.15-mL mixture using an ultrasonic disperser, and this was applied by a coating method using a wire bar.
The film was coated onto a 175 mm thick polyester film, which was to be peeled off in the final step and used as a temporary support, so that the film thickness after drying was 20 mm thick.

After heat-treating this at 140°C for 2 minutes, the layer was dried in the same manner as the lower layer except that the fluorocarbon surfactant FC-430 was added on top of the photosensitive layer until the film thickness including the lower layer was 30 mm. Apply and dry until smooth, and then heat at 140qC for 1 hour.
A laminated photosensitive layer was formed by heat treatment for a period of time.

Furthermore, a quaternary amine-based cationic conductive agent pq-T14 (manufactured by Souken Kagaku) is coated on top of the laminated photosensitive layer using a coating method using a wire bar so that the film thickness after drying is 5r', and then dried to form an intermediate undercoat layer. was formed.

Further, on this intermediate undercoat layer, a dispersion obtained by sufficiently dispersing a conductive agent with the following formulation using a ball mill was applied and dried using the same coating method using a wire bar, and then 1
Heat treatment was performed at 30 qo for 1 hour to form an intermediate conductive layer. [Guiding agent prescription] Guiding carbon HS-500 (manufactured by Asahi Carbon Co., Ltd.)
79 Thermosetting alkyd J-
555 (Dainippon Ink Co., Ltd.) 40 Butyl acetate
A dispersion obtained by thoroughly dispersing a mixed solution of the following formulation using a ball mill was coated on a stainless steel sheet with a thickness of 100 m thick, which was also used as a support for the present invention, and was operated at 10 picoC for 5 hours. Film thickness is 10
A conductive adhesive layer was formed so as to have zero peaks.

[Conductive attachment layer]

Conductive force bond HS-600 (manufactured by Asahi Carbon Co., Ltd.)
4-Year Epoxy Resin #1001
(Manufactured by Shell Petrochemicals)
Butyl acetate
Layering the adhesive layer of this main support and the intermediate conductive layer provided on the top layer of the laminated photosensitive layer having the temporary support,
After applying pressure and adhesion using a hot roller, the 100%
The thick polyester film for temporary support was peeled off to form a photosensitive plate with a smooth photosensitive layer surface, which was used as a sample (sample 5).

Example 3 [Photosensitive composition formulation F] Cadmium sulfide microcrystals with an average particle size of 11 20 ta Exemplary compound 12 Exemplary compound '71 3 ta Water
200 skin ethyl alcohol
A photosensitive composition was prepared by dispersing a mixture of 100% aqueous 30% ammonia and 5 parts using a sand mill, and this was coated onto a stainless steel sheet with an intermediate coating using a uniform coating method.

That is, the photosensitive composition is placed in a beaker, and one side of the pica is soaked in a 5% solution of isocyanate-modified quaternary amine cationic polymer Elecond B-13 (manufactured by Souken Kagaku Co., Ltd.) and then pulled up and applied. A stainless steel sheet with a thickness of 100 mm with an intermediate layer formed thereon was inserted as an anode, and 100 mm thick was inserted at a position facing the anode at a distance of 4 mm.
A thick stainless steel sheet was inserted and used as the cathode. Next, an initial voltage of 30 V was applied to both poles, a current was applied for 5 minutes, and a magnetic stirrer was used to thoroughly control the photosensitive layer using an electric ice motion system. After the coating was completed, the stainless steel sheet of the anode was pulled up. number 10
A yellow photosensitive layer was formed in the thickness of the film, and although this was washed with water, no leakage of the photosensitive layer occurred. Next, this photosensitive layer was dried and then heat treated at 15 mm for 1 hour to prepare a photosensitive plate, which was used as a sample (sample M.6). Example 4 [Photosensitive composition formulation G] Cadmium selenide sulfate with an average particle size of 1 μm Exemplary compound '2'
5.4 Exemplary Compounds (13
) 1.0 ta Exemplary compound OQ (Water-soluble melamine resin prepolymer solid content 70%)
2.0 t water 6'
A photosensitive composition was prepared by dispersing a mixture of isopropanol and n-butyl cellosolve 2 using an ultrasonic disperser.

Next, Erecondo B-1 was placed on a 200mm thick aluminum plate.
After drying, 46 was coated to a thickness of about 5 mm to form an intermediate layer, and then the photosensitive composition was coated and dried to a thickness of 20 mm after drying, and then this was heated at 130°C. This was heat-treated for 30 minutes to harden and form a lower photosensitive layer. Matabetsu FC
A photosensitive composition was prepared in the same manner as [Photosensitive composition G] except that -430 was added for 0.10 minutes, and the film thickness after drying was as follows: The coating was coated to a thickness of 32 μm and dried, and then heat treated at 150 qo for 3 minutes to prepare a laminated photosensitive plate. This photosensitive plate was used as a sample (sample ship.7). Comparative Example 1 [Photosensitive Composition 1] Highly sensitive cadmium sulfide microcrystals with an average particle size of 1 mm 10 mm pure alkyd resin Beccosol J-555 (manufactured by Dainippon Ink Co., Ltd., solid content 50%) 8 mm butyl acetate
The mixture of 7' was dispersed using an ultrasonic disperser to prepare a photosensitive composition.

This was coated and dried on a 100mm thick stainless steel sheet using a wire bar coating method so that the film thickness after drying was 30mm thick, and then heat treated at 150°C for 30 minutes to prepare a photosensitive plate. This was used as a comparison sample (sample M.
8). Comparative Example 2 [Photosensitive Composition 1] Highly sensitive cadmium sulfide microcrystals with an average particle size of 1 French 10 evening heat-curable acrylic resin Dianal HR-116 (manufactured by Mitsubishi Rayon Co., Ltd. solid content 50%) 6.0 Tamelamine resin Nikaratsuku MS-1001 (manufactured by Sanwa Chemical Co., Ltd. solid content 5
0%) 2.6-butyl acetate
A photosensitive composition was prepared by dispersing the mixture in step 7' using an ultrasonic disperser.

This was coated and dried on a 100 mm stainless steel sheet by a coating method using a wire bar so that the film thickness after drying was 25 r', and then heat treated at 150 DEG C. for 30 minutes to prepare a photosensitive plate. This was used as a comparison sample (sample M
．． 9). Comparative Example 3 [Photosensitive Composition J] Highly sensitive cadmium sulfide microcrystals with an average particle size of 1 mm 10 Evening heat curing alkyd resin EZ-3650 (manufactured by Dainippon Ink Co., Ltd., solid content 60%) 60 Tabtylated melamine resin G-821 (60% solid content manufactured by Dainippon Ink Co., Ltd.)
2.0butyl acetate
A photosensitive composition was prepared by dispersing the mixture of [7] using an ultrasonic disperser.

This was coated and dried on a stainless steel sheet of 100 sheets by a coating method using a wire bar so that the film thickness after drying was 25 rl, and then heat treated at 150 DEG C. for 1 hour to prepare a photosensitive plate. This is a comparison sample (sample port.
10). Comparative Example 4 [Photosensitive Composition K] Highly sensitive cadmium sulfide microcrystals with average grain height lr 10 Evening heat curing acrylic resin HR-116 (manufactured by Mitsubishi Rayon Co., Ltd., solid content 50%) 6 Tabtylated melamine resin J-820 (large) Manufactured by Nippon Ink Co., Ltd. Solid content 60%)
0.8 Taepoxy Resin Epicoat #828 (
Made by Shell Petrochemicals (solid content 60%) 0.
8ta FC-430 0
．． 07 Butyl acetate 7
The above liquid mixture was dispersed using an ultrasonic disperser to prepare a photosensitive composition.

This is peeled off in the final step by a coating method using a wire bar, and is used as a temporary support.
The film thickness after drying is 2 on the 00mm thick polyester film.
The coating was coated and dried to give 0A, and then heat treated at 14,000 for 1 hour to form a lower photosensitive layer. Matabetsu F
A photosensitive composition was prepared in the same manner as [Photosensitive composition K] except that C-430 was removed, and this was applied onto the lower photosensitive layer so that the film thickness after drying including the lower photosensitive layer was 30 mm. The coating was coated and dried, and then heat treated at 140° C. for 1 hour to form a laminated photosensitive layer on the temporary support. Furthermore, pq-T14 was coated on this laminated photosensitive material by a coating method using a wire bar so that the film thickness after drying was five peaks, and dried to form an intermediate undercoat layer. Next, on this intermediate undercoat layer, a dispersion obtained by sufficiently dispersing a military guide agent having the following formulation using a ball mill was applied and dried by the same coating method using a wire bar, and then heat treated at 13,000°C for 1 hour to form an intermediate guide agent. formed a layer.

[Conductive agent prescription]

Conductive carbon HS-500 (manufactured by Asahi Carbon Co., Ltd.)
7 Evening heat curing alkyd J-
555 (manufactured by Dainippon Ink Co., Ltd.)
40 butyl acetate 1
A dispersion obtained by thoroughly dispersing a mixture of the following formulation using a ball mill was coated on a stainless steel sheet with a thickness of 100 mm and 100 mm to be used as a support.
A conductive adhesive layer was formed by drying at ℃ for 5 hours to a thickness of 100 mm.

[Military guiding adhesive layer]

Tortoise conductive carbon HS-500 (manufactured by Asahi Carbon Co., Ltd.)
4-Year Epoxy Resin #100
1 (manufactured by Shell Petrochemical Company)
Butyl acetate 1
00m' The adhesive layer of this main support and the intermediate conductive layer provided on the top layer of the laminated photosensitive layer having the temporary support are superimposed,
After applying pressure and adhesion using a hot roller, the 100%
A photosensitive plate with a smooth photosensitive layer was prepared by peeling off the final thick polyester film for use as a temporary support.

This was used as a comparison sample (sample port.11). The initial potential, residual potential, and sensitivity of the sample and comparative sample were measured using an Ichiro V charging device and a vibrating capacitive surface potentiometer equipped with a tungsten light source set so that the sample surface illuminance was 5 lux. Shown in the table. In addition, the initial potential is the potential (in volts) after 5 seconds have passed after the end of charging, the residual potential is the potential in volts when 5 seconds have passed after the start of exposure, and the sensitivity is the exposure amount in lux seconds required for the initial potential to reach the half value. It is represented. Also sample M. 1~No. 5 and sample M. 7 and the comparative sample were each mounted on a drum-type durability test machine equipped with a magnetic brush phenomenon device and a charging device, each containing only a carrier that does not contain toner, and operated at a speed of 2 m/min, at a charging voltage of V, and at 30°C. A high-temperature test was conducted in which the charging and phenomenon cycles were repeated 5000 times in an 80% atmosphere. The value of each initial potential at this time is
Shown in the table. Table 1 also shows the initial potential residual rates of the sample and comparative sample after the aforementioned 500 Tsukasa durability test was performed on the sample at the initial stage of the test and the comparative sample.

Furthermore, using a stylus electric surface roughness measuring device (manufactured by Tokyo Seimitsu Co., Ltd., Surgomu 2) for the samples (Samples M.1 to M.4) and comparative samples (Kaijou.8 to M.10), Table 1 shows the results of measuring the surface roughness. From the results shown in Table 1, it can be seen that the samples according to the present invention are significantly superior to the comparative samples in terms of residual potential, sensitivity, durability, surface roughness, etc.

Claims (1)

[Claims] 1. A photosensitive composition for electrophotography, the main components of which are a photoconductive cadmium sulfide compound and a water-soluble polymer that is crosslinked to form a network structure.