JPH0211132B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an organic coating that can effectively absorb lasers, particularly semiconductor lasers having an oscillation wavelength on the long wavelength side, and convert them into other energy. The present invention relates to a novel organic coating that can be applied to photosensitive coatings, coatings for optical discs that can be written and reproduced by semiconductor lasers, infrared cut filters, and the like. An electrophotographic printer that uses a laser as a light source modulates the laser using an electrical signal that corresponds to image information, and scans the modulated laser light onto a photoreceptor using a galvano mirror or the like to create a static image. After forming the electrostatic latent image, a desired reproduced image can be formed by sequentially applying toner development and transfer. The laser used at this time was
Generally helium-cadmium (oscillation wavelength: 441.6n)
m) and helium-neon (oscillation wavelength: 632.8nm)
It was a gas laser. Therefore, the photoreceptor used for such a light source only needs to be spectrally sensitized to about 650 nm, such as one using a charge transfer complex of polyvinylcarbazole and trinitrofluorenone in the photosensitive layer, or one using selenium. A photoreceptor using a tellurium vapor-deposited layer sensitized by
A photosensitive layer comprising a selenium vapor deposited layer formed on a conductive layer as a charge transport layer, and a selenium-tellurium vapor deposited layer formed on the selenium vapor deposited layer,
The photosensitive layer uses cadmium sulfide that has been spectrally sensitized with a sensitizing dye, and is functionally separated into a charge generation layer and a charge transport layer containing organic pigments, and the photosensitive wavelength range is sensitized to the long wavelength side. There are known devices that use a photosensitive layer with a photosensitive layer. On the other hand, recording coatings used in optical disk technology can store high-density information by forming optically detectable small (eg, about 1 μm) pits in the form of spiral or circular tracks. To write information on such a disk, a focused laser beam is scanned over the surface of the laser-sensitive layer, and only the surface irradiated with this laser beam forms a pit, which is shaped into a spiral or circular track. to form. The laser sensitive layer can absorb laser energy to form optically detectable pits. for example,
In the heat mode recording method, the laser sensitive layer absorbs thermal energy and can form small pits at that location by evaporation or melting. In another heat mode recording method, absorption of irradiated laser energy can form pits with optically detectable density differences at the locations. The information recorded on this optical disk is detected by scanning a laser along the track and reading the optical changes in the pitted and non-pitted areas. For example, a laser is scanned along a track and the energy reflected by the disk is monitored by a photodetector. When pits are not formed, the output of the photodetector is reduced, while when pits are formed, the laser beam is sufficiently reflected by the underlying reflective surface and the output of the photodetector is increased. As a recording medium used for such optical discs,
Up to now, methods have been proposed that mainly use inorganic materials such as metal thin films such as aluminum vapor-deposited films, bismuth thin films, tellurium oxide thin films, and chalcogenite amorphous glass films. Incidentally, in recent years, semiconductor lasers have been developed that are small, low-cost, and capable of direct modulation, but the oscillation wavelength of these lasers often has a wavelength of 750 nm or more. Therefore, when recording and/or reproducing using such a semiconductor laser, the absorption characteristics of the laser sensitive coating have an absorption peak on the long wavelength side (generally between 750 nm and 850 nm).
area). However, conventional laser-sensitive coatings, especially those formed mainly of inorganic materials, have a high reflectance to laser light, resulting in a low laser utilization rate and the disadvantage that high sensitivity characteristics cannot be obtained. Moreover, setting the sensitive wavelength range to 750 nm or more complicates the layer structure of the laser-sensitive coating, and especially in the case of electrophotographic photosensitive coatings, the sensitizing dye used is subject to repeated charging and exposure. It has disadvantages such as fading. For these reasons, in recent years organic coatings have been proposed that exhibit high sensitivity to light with wavelengths of 750 nm or more. See, for example, U.S. Pat. No. 4,315,983, “Reseach
Pyrylium dyes disclosed in "Disclosure" 20517 (May 1981) and "J.Vac.Scl.Technol, 18(1), Jan./
It is known that the organic coating containing the squareylium dye disclosed in Feb. 1981, P105 to P109 is sensitive to lasers of 750 nm or more. However, in general, organic compounds have problems such as their absorption characteristics becoming unstable in the longer wavelength region and being easily decomposed by a slight temperature rise. Therefore, at present, it cannot be said that an organic film that is fully satisfactory in terms of practicality has been developed. Accordingly, a first object of the present invention is to provide a new and useful organic coating. The second object of the present invention is to
The object of the present invention is to provide an organic coating having an absorption band of 100 m or more. A third object of the present invention is to provide an organic coating that is stable to heat and sublimation. A fourth object of the present invention is to provide an electrophotographic photosensitive coating for an electrophotographic printer using a laser as a light source. A fifth object of the present invention is to provide a photosensitive film for electrophotography that has high sensitivity in a wavelength range of 750 nm or more. A sixth object of the present invention is to provide a coating for optical disc recording. A seventh object of the present invention is to provide an optical disc recording film that is highly sensitive in a wavelength range of 750 nm or more and has a sufficient S/N ratio. This object of the present invention is achieved by an organic coating containing a compound represented by the following general formula (1). General formula (1) (In the formula, R ₁ to _{R 2} and R ₄ represent an aryl group such as a phenyl group or a naphthyl group that may have a substituent, and may be the same or different. R ₁ ,
Substituents for R ₂ and R ₄ include dimethylamino,
Examples include substituted amino groups such as diethylamino, dipropylamino, dibutylamino, diphenylamino, phenylbenzylamino, and phenylethylamino, cyclic amino groups such as morpholino, piperidino, and pyrrolidinyl, and alkoxy groups such as methoxy, ethoxy, and butoxy. R ₃ is P-phenylene,
Two adjacent -CH= such as 1,4-naphthylene
Indicates an arylene group that forms a conjugated double bond system with a CH- group and may have a substituent. Examples of the substituent include halogen atoms such as chlorine, bromine, and iodine, alkyl groups such as methyl, and alkoxy groups such as methoxy and ethoxy. A is BF ₄ , ClO ₄ ,
Halogen atoms such as _{CF3OO , PF6} , Cl, Br, I, _{ClSO3 , CH3SO3} , _{C2H5SO3 ,
C3H7SO3 , C4H9SO3 , C5H11SO3 , _ _ _}
C ₆ H ₁₃ SO ₃ , CH ₃ CHClSO ₃ , ClCH ₂ CH ₂ SO ₃
,

[Formula], ICH ₂ SO ₃ ,

【formula】

【formula】

Alkylsulfonic acids such as [Formula], O ₃ SCH ₂ SO ₃ , O ₃ SCH ₂ SO ₃ ,
_{O3S ( CH2} ) _6SO3 , _{O3SCH2CH2 - O-}
Alkyl disulfonic acids, such as CH ₂ CH ₂ SO ₃

【formula】

It is an anionic residue such as benzenedisulfonic acid such as [Formula]. Specific compound examples are listed below. The organic coating of the present invention can be used for optical disc recording. For example, a substrate 1 as shown in FIG.
The recording medium can have the above-mentioned organic film 2 formed thereon. Such an organic film 2 can be formed by vacuum deposition of the above-mentioned compound, or by applying a coating liquid containing the above-mentioned polymethine compound in a binder. When forming a film by coating, the above-mentioned compound may be contained in the binder in a dispersed state or in an amorphous state. Suitable binders can be selected from a wide variety of resins. Specifically, nitrocellulose, cellulose phosphate, cellulose sulfate,
Cellulose esters such as cellulose acetate, cellulose propionate, cellulose acetate, cellulose myristate, cellulose palmitate, acetic acid, cellulose propionate, cellulose acetate/butyrate, cellulose ethers such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, polystyrene, Vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, and polyvinylpyrrolidone; Polymer resins, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyacrylonitrile, polyesters such as polyethylene terephthalate, poly(4,4'-
Isopropylidene diphenylene-co-1,4-cyclohexylene dimethylene carbonate), poly(ethylenedioxy-3,3'-phenylene thiocarbonate), poly(4,4'-isopropylidene diphenylene carbonate) poly(4,4'-isopropylidene diphenylene carbonate), poly(4,4'-sec-butylidene diphenylene carbonate), poly(4,4'-sec-butylidene diphenylene carbonate),
Polyarylate resins such as isopropylidene diphenylene carbonate-block oxyethylene), polyamides, polyimides,
Epoxy resins, phenolic resins, polyolefins such as polyethylene, polypropylene, and chlorinated polyethylene can be used. The organic solvent that can be used during coating varies depending on the type of binder and whether the above-mentioned compound is contained in the binder in a dispersed or amorphous state, but in general, , alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexane, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, tetrahydrofuran, dioxane,
Ethers such as ethylene glycol monomethyl ether, esters such as methyl acetate, ethyl acetate, butyl acetate, aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichloroethylene, or benzene, toluene. , xylene, ligroin, monochlorobenzene, dichlorobenzene, and other aromatic compounds can be used. Coating can be carried out using coating methods such as dip coating, spray coating, spinner coating, bead coating, Meyer bar coating, blade coating, roller coating, and curtain coating. When forming the organic film 2 together with the binder, the content of the above-mentioned polymethylene compound in the organic film 2 is 1 to 90% by weight, preferably 20 to 70% by weight. Further, the dry film thickness or vapor deposited film thickness of the organic film 2 is 10 microns or less, preferably 2 microns or less. As the substrate 1, plastics such as polyester, acrylic resin, polyolefin resin, phenolic resin, epoxy resin, polyamide, and polyimide, glass, or metals can be used. Further, in the present invention, a reflective layer 3 can be provided between the substrate 1 and the organic coating 2 as shown in FIG.
The reflective layer 3 can be a deposited layer or a laminate layer of a reflective metal such as aluminum, silver, or chromium. The organic coating 2 can be formed into pits 5 by irradiation with a focused laser beam 4 as shown in FIG. By making the depth of the pits 5 the same as the thickness of the organic coating 2, the reflectance in the pit region can be increased. When reading, if a laser beam having the same wavelength as the laser beam used for writing but with low intensity is used, the reading light will be largely reflected in pit areas, but will be absorbed in non-pit areas. Another method is to perform real-time writing with a laser beam of a first wavelength, which is absorbed by the organic coating 2, and to use a laser beam of a second wavelength, which is substantially transmitted through the organic coating 2, for reading. The readout laser beam can respond to changes in the reflection phase caused by different film thicknesses in pitted and non-pitted regions. The organic coating of the present invention can be used with argon laser (oscillation wavelength: 488 nm), helium-neon laser (oscillation wavelength: 488 nm), helium-neon laser (oscillation wavelength:
633 nm), or by irradiation with a gas laser such as a helium-cadmium laser (oscillation wavelength 442 nm), but preferably 750 nm.
Lasers with longer wavelengths, especially gallium-aluminum-arsenic semiconductor lasers (oscillation wavelength 780nm)
A method of recording by irradiation with a laser beam having an oscillation wavelength in the near-infrared or infrared region is suitable. Furthermore, the aforementioned laser beam can be used for reading. At this time, writing and reading can be performed using a laser of the same wavelength, or can be performed using lasers of different wavelengths. In another embodiment of the present invention, it can be applied as a photosensitive layer of an electrophotographic photoreceptor. Further, such a photosensitive layer can be applied as a charge generation layer in an electrophotographic photoreceptor in which the functions are separated into a charge generation layer and a charge transport layer. The charge generation layer contains as much of the above-mentioned photoconductive compound as possible in order to obtain sufficient absorbance, and is preferably a thin film layer, for example, 5 microns or less, in order to shorten the range of the generated charge carriers. is preferably a thin film layer having a thickness of 0.01 micron to 1 micron. This means that most of the incident light is absorbed by the charge generation layer and generates a large number of charge carriers, and that the generated charge carriers are not deactivated by recombination or trapping, and the charge transport layer This is due to the need to inject. The charge generation layer can be formed by dispersing the above-mentioned compound in a suitable binder and coating it on the substrate, or it can be obtained by forming a vapor deposited film using a vacuum vapor deposition apparatus. . The binder that can be used when forming the charge generation layer by coating can be selected from a wide range of insulating resins.
It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene. Preferably, polyvinyl butyral, polyarylate (condensation polymer of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, cellulose resin, urethane. Examples include insulating resins such as resin, epoxy resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. The resin contained in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or less. Solvents that dissolve these resins vary depending on the type of resin, and are preferably selected from those that do not dissolve the charge transport layer or undercoat layer described below. Specific organic solvents include alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, N,N-dimethylformamide,
Amides such as N,N-dimethylacetamide,
Sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aliphatic halogens such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, and trichloroethylene. Hydrocarbons or aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorobenzene, etc. can be used. Coating can be carried out using coating methods such as dip coating, spray coating, spinner coating, bead coating, Meyer bar coating, blade coating, roller coating, curtain coating, and the like. For drying, it is preferable to dry to the touch at room temperature and then heat dry. Heat drying can be carried out at a temperature of 30° C. to 200° C. for a period of time ranging from 5 minutes to 2 hours, either stationary or under ventilation. The charge transport layer is electrically connected to the charge generation layer described above, and has the function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. There is. At this time, this charge transport layer may be laminated on or under the charge generation layer. However, it is desirable that the charge transport layer is laminated on the charge generation layer. The substance that transports charge carriers in the charge transport layer (hereinafter simply referred to as charge transport substance) is preferably substantially insensitive to the wavelength range of electromagnetic waves to which the charge generation layer is sensitive. The term "electromagnetic waves" used herein includes a broad definition of "light rays" that includes gamma rays, X-rays, ultraviolet rays, visible light, near infrared rays, infrared rays, far infrared rays, and the like. When the photosensitive wavelength range of the charge transport layer coincides with or overlaps that of the charge generation layer, charge carriers generated in both layers capture each other, resulting in a decrease in sensitivity. Charge-transporting substances include charge-transporting substances and hole-transporting substances, and charge-transporting substances include chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, and 2,4,7-trinitro-9-fluorenone. , 2, 4, 5, 7-
Tetranitro-9-fluorenone, 2,4,7-
trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitroxanthone,
Examples include electron-withdrawing substances such as 2,4,8-trinitrothioxanthone, and polymerized versions of these electron-withdrawing substances. Examples of hole-transporting substances include pyrene, N-ethylcarbazole, N-isopropylcarbazole,
N-Methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-
3-methylidene-10-ethylphenothiazine,
N,N-diphenylhydrazino-3-methylidene-10-ethylphenoxazine, P-dimethylaminobenzaldehyde-N,N-diphenylhydrazone, P-diethylaminobenzaldehyde-N
-α-Naphthyl-N-phenylhydrazone, P-
Pyrrolidinobenzaldehyde-N,N-diphenylhydrazone, 1,3,3-trimethylindolenine-ω-aldehyde-N,N-diphenylhydrazone, P-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone hydrazones such as 2,5-bis(P-diethylaminophenyl)-1,3,4-oxadiazole, 1
-Phenyl-3-(P-diethylaminostyryl)
-5-(P-diethylaminophenyl)pyrazoline, 1-[quinolyl(2)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]- 3-(P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[6-methoxy-pyridyl(2)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1- [Pyridyl(3)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[Lepidyl(2)]-3-(P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]-
3-(P-diethylaminostyryl)-4-methyl-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]-3-(α-methyl-P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-phenyl-3-
(P-diethylaminostyryl)-4-methyl-5
-(P-diethylaminophenyl)pyrazoline,
1-Phenyl-3-(α-benzyl-P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, spiropyrazoline and other pyrazolines, 2-(P-diethylaminostyryl)
-6-diethylaminobenzoxazole, 2-
Oxazole compounds such as (P-diethylaminophenyl)-4-(P-diethylaminophenyl)-5-(2-chlorophenyl)oxazole, 2
Thiazole compounds such as -(P-diethylaminostyryl)-6-diethylaminobenzothiazole, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane, 1,1-bis(4-N,N -diethylamino-2-methylphenyl)heptane, 1,
Polyarylalkanes such as 1,2,2-tetrakis(4-N,N-dimethylamino-2-methylphenyl)ethane, triphenylamine, poly-
N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine,
Examples include poly-9-vinylphenylanthracene, pyrene-formaldehyde resin, and ethylcarbazole formaldehyde resin. In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium amorphous silicon, and cadmium sulfide can also be used. Moreover, these charge transport substances may be one or two types.
More than one species can be used in combination. When the charge transport material does not have film-forming properties,
A film can be formed by selecting an appropriate binder. What resins can be used as binders?
For example, insulating resins such as acrylic resin, polyarylate, polyester, polycarbonate, polystyrene acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber, or poly-N-vinyl Mention may be made of organic photoconductive polymers such as carbazole, polyvinylanthracene, polyvinylpyrene. Since the charge transport layer has a limit in its ability to transport charge carriers, it cannot be made thicker than necessary. Typically it is between 5 microns and 30 microns, with a preferred range between 8 microns and 20 microns. When forming the charge transport layer by coating, an appropriate coating method as described above can be used. A photosensitive layer having such a laminated structure of a charge generation layer and a charge transport layer is provided on a substrate having a conductive layer. As the substrate having the conductive layer, materials that are themselves conductive can be used, such as aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, and platinum. In addition, plastics (such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic, conductive particles (e.g. carbon black, etc.), conductive particles (e.g. carbon black,
A substrate made of plastic coated with silver particles, etc.) together with a suitable binder, a plastic having a conductive polymer made by impregnating plastic or paper with conductive particles, etc. can be used. A subbing layer having barrier and adhesive functions can also be provided between the conductive layer and the photosensitive layer. The subbing layer is made of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon
610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide, etc. The thickness of the undercoat layer is 0.1 micron to 5 micron.
Preferably, 0.5 micron to 3 micron is appropriate. When using a photoreceptor in which a conductive layer, a charge generation layer, and a charge transport layer are laminated in this order, and the charge transport material is an electron transport material, the surface of the charge transport layer must be positively charged, and exposure after charging is required. Then, in the exposed area, electrons generated in the charge generation layer are injected into the charge transport layer, and then reach the surface and neutralize the positive charge, causing a decrease in surface potential and creating an electrostatic contrast with the unexposed area. . A visible image can be obtained by developing the electrostatic latent image thus formed with a negatively charged toner. This can be directly fixed, or the toner image can be transferred to paper, plastic film, etc. and then developed and fixed. Alternatively, a method may be used in which the electrostatic latent image on the photoreceptor is transferred onto an insulating layer of transfer paper, then developed and fixed. The type of developer, the developing method, and the fixing method may be any known ones or known methods, and are not limited to specific ones. On the other hand, when the charge transport material consists of a hole transport material, the surface of the charge transport layer must be negatively charged.
After charging, when exposed to light, holes generated in the charge generation layer in the exposed area are injected into the charge transport layer, and then reach the surface and neutralize the negative charge, causing a decrease in the surface potential and static electricity between the exposed area and the unexposed area. Electrocontrast occurs. During development, it is necessary to use a positively charged toner, contrary to the case where an electron transport material is used. In another specific example of the present invention, organic photoconductive materials such as the aforementioned hydrazones, pyrazolines, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, triphenylamines, poly-N-vinylcarbazoles, etc. The organic film may contain the above-mentioned polymethylene compound as a sensitizer for photoconductive substances or inorganic photoconductive substances such as zinc oxide, cadmium sulfide, and selenium. This organic coating is formed by coating these photoconductive substances and the above-mentioned compounds together with a binder. Furthermore, in another specific example, an organic film containing the aforementioned polymethine compound can be used as the photosensitive layer. In any of the photoreceptors, the pigment used is at least one selected from the compounds represented by the general formula (1).
Compounds represented by general formula (1) that contain different types of pigments and are used in combination of pigments with different light absorption as necessary to increase the sensitivity of photoreceptors or to obtain panchromatic photoreceptors. It is also possible to use a combination of two or more types, or a combination with a charge generating substance selected from known dyes and pigments. The organic coating of the present invention can be used not only as a laser-sensitive coating for the above-mentioned optical disk recording bodies and electrophotographic photoreceptors, but also for infrared cut filters, solar cells, optical sensors, and the like. A solar cell can be prepared, for example, by using indium oxide and aluminum as electrodes and forming the above-mentioned organic film between them in a sandwich structure. The organic film of the present invention can have significantly higher sensitivity in the wavelength range of 750 nm or more compared to conventional electrophotographic photoreceptors for lasers, and can have significantly higher sensitivity than conventional optical disk recording materials. A sufficiently improved S/N ratio can be provided. Furthermore, the compound used in the present invention has the advantage of being extremely stable against heat despite having an absorption peak at 750 nm or higher. Hereinafter, the present invention will be explained according to examples. Example 1 An ammonia aqueous solution of casein (casein 11.2 g, 28%, ammonia water 1 g, water 222 ml) was coated on an aluminum cylinder by dip coating method, and dried to form a subbing layer with a coating amount of 1.0 g/m ² was formed. Next, 1 part by weight of the aforementioned compound No. 1, butyral resin (Eslec BM-2: Sekisui Chemical Co., Ltd.)
1 part by weight) and 30 parts by weight of isopropyl alcohol were dispersed for 4 hours using a ball mill disperser. This dispersion was applied onto the previously formed subbing layer by a dip coating method and dried to form a charge generation layer. The film thickness at this time was 0.3μ. Next, P-diethylaminobenzaldehyde-
1 part by weight of N-phenyl-N-α-naphthylhydrazone, 1 part by weight of polysulfone resin (P1700: manufactured by Union Carbide), and 6 parts by weight of monochlorobenzene.
Parts by weight were mixed and dissolved by stirring with a stirrer. This liquid was applied onto the charge generation layer by dip coating and dried to form a charge transport layer. The film thickness at this time was 12μ. A -5 kV corona discharge was applied to the photoreceptor thus prepared. The surface potential at this time was measured (initial potential V ₀ ). Furthermore, the surface potential of this photoreceptor was measured after it was left in a dark place for 5 seconds (dark decay V ₅ ). The degree of reduction was evaluated by measuring the amount of exposure (E1/2 microjoule/ ^cm2 ) required to attenuate the potential _V5 after dark decay to 1/2. At this time, a gallium, aluminum arsenide semiconductor laser (oscillation wavelength 780 nm) was used as a light source. These results were as follows. V ₀ : -475 volts V ₅ : -460 volts E1/2: 5.3 microjoules/cm ² Examples 2 to 13 In place of the compound No. (1) used in Example 1, the compounds shown in Table 1 were used. A photoreceptor was prepared in exactly the same manner as in Example 1, except that the compounds shown were used, and the characteristics of this photoreceptor were measured. These results are shown in Table 1.

[Table] Example 14 An ammonia aqueous solution of casein was coated on an aluminum plate with a thickness of 100 microns and dried to form a subbing layer with a thickness of 1.1 microns. Next, 5 g of 2,4,7-trinitro-9-fluorenone and 5 g of poly-N-vinylcarbazole (number average molecular weight 300,000) were added to 70 ml of tetrahydrofuran.
to form a charge transfer complex. This charge transfer complex compound and 1 g of the above compound No. (1)
was added to a solution in which 5 g of polyester resin (manufactured by Byron Toyobo) was dissolved in 70 ml of tetrahydrofuran and dispersed. This dispersion was applied onto the undercoat layer so that the film thickness after drying was 12 microns, and dried. Example 1 shows the charging characteristics of the photoreceptor thus prepared.
It was measured in the same manner as. The results of this were as follows. However, the charging polarity was determined. V ₀ : +580 volts V ₅ : +555 volts E1/2: 7.2 microjoules/cm ³ Example 15 A polyvinyl alcohol film with a thickness of 1.1 microns was formed on the aluminum surface of an aluminum vapor-deposited polyethylene terephthalate film. Next, a dispersion of the aforementioned compound No. (7) used in Example 1 was applied onto the polyvinyl alcohol layer formed earlier using a Mayer bar so that the film thickness after drying was 0.5 microns. , and dried to form a charge generation layer. Next, the structural formula A solution prepared by dissolving 5 g of pyrazoline compound and 5 g of polyarylate resin (condensation polymer of bisphenol A and terephthalic acid-isophthalic acid) in 70 ml of tetrahydrofuran is placed on the charge generation layer so that the film thickness after drying is 10
It was applied to a micron thickness and dried to form a charge transport layer. Example 1 shows the charging characteristics of the photoreceptor thus prepared.
Measured using the same method as above. The result of this is
It was as follows. V ₀ : -460 volts V ₅ : -435 volts E1/2: 5.5 microjoules/cm ² As can be seen from the above-mentioned examples, the electrophotographic photoreceptor of the present invention has a remarkable high sensitivity in the wavelength range of 750 nm or more. It has excellent charging characteristics such as initial potential and dark decay. Example 16 Nitrocellulose solution (Daicel Chemical Industries, Ltd.)
Manufactured by Ohares Latzker: Nitrocellulose 25
12 parts by weight of methyl ethyl ketone solution), 3 parts by weight of the aforementioned compound No. (4), and 70 parts by weight of methyl ethyl ketone were mixed and thoroughly stirred.
This solution was applied onto an aluminized glass plate by dip coating and dried to obtain a recording layer of 0.6 g/m ² . The optical disk recording medium created in this way is mounted on a turntable, and the turntable is driven by a motor.
Spot size while giving 1800rpm rotation
Recording was carried out by irradiating the surface of the recording layer in the form of a track with a 5 mW and 8 MHz gallium-aluminum-arsenide semiconductor laser (oscillation wavelength 780 nm) focused at 1.0 micron. When the recorded surface of the optical disc was observed using a scanning electron microscope, clear pits were observed. Furthermore, when a low-output gallium-aluminum-arsenic semiconductor laser was incident on this optical disk and reflected light was detected, a waveform with a sufficient S/N ratio was obtained. Example 17 500 mg of the above-mentioned compound No. 2 was placed in a molybdenum boat for vapor deposition, and after evacuated to 1×10 ^-6 mmHg or less, it was vapor-deposited on an aluminum vapor-deposited glass plate. During the deposition, a 0.2 micron deposited film was formed while controlling the heater so that the pressure in the vacuum chamber did not rise above 10 ^-5 mmHg. Example 16
When information was stored in the same manner as in Example
Clear pits similar to those in Example 16 were observed.
Information was reproduced using the same method as in No. 16, and a waveform with a sufficient S/N ratio was observed. Example 18 The above compound No. (3) was vapor-deposited on an aluminum-deposited glass plate in the same manner as in Example 17 to produce an optical disk recording medium having a recording layer of 0.2 microns. When information was stored on this optical disc recording medium in the same manner as in Example 16 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, when the surface of the recording layer after information was written was observed with a scanning electron microscope, clear pits were found to have been formed. Example 19 The aforementioned compound No. (6) was vapor-deposited on an aluminum vapor-deposited glass plate in the same manner as in Example 17, and 0.2
An optical disc recording medium having a micron recording layer was prepared. When information was stored on this optical disc recording medium in the same manner as in Example 16 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, when the surface of the recording layer after information was written was observed with a scanning electron microscope, clear pits were found to have been formed. Example 20 The aforementioned compound No. (10) was vapor-deposited on an aluminum vapor-deposited glass plate in the same manner as in Example 17, and 0.2
An optical disc recording medium having a micron recording layer was prepared. When information was stored on this optical disc recording medium in the same manner as in Example 16 and then reproduced, a waveform with a sufficient S/N ratio was observed. Further, when the surface of the recording layer after information was written was observed with a scanning electron microscope, clear pits were found to have been formed.

[Brief explanation of drawings]

1 and 2 are cross-sectional views when the organic film of the present invention is used in an optical disk recording medium, and FIG. 3 is an explanatory view showing an embodiment of this optical disk recording medium. 1...Substrate, 2...Organic coating, 3...Reflection layer,
4... Laser beam, 5... Pit.

Claims (1)

[Scope of Claims] 1. An organic film characterized by containing a compound represented by the following general formula (1). General formula (1) (In the formula, R ₁ , R ₂ and R ₄ represent a substituted or unsubstituted aryl group. _{R 3} represents a substituted or unsubstituted arylene group. A is an anionic residue.)