JPH0211140B2 - - 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 performing 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 such as 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 photoconductor using a tellurium vapor-deposited layer sensitized by a method of photoreceptor, a selenium vapor-deposited layer is formed on a conductive layer as a charge transport layer, and a selenium-tellurium vapor-deposited layer is formed on this selenium vapor-deposited layer. Some use a photosensitive layer made of cadmium sulfide spectrally sensitized with a sensitizing dye, and others use functionally separated charge generation layers and charge transport layers containing organic pigments, and their photosensitive wavelengths There are known methods that use a photosensitive layer that is sensitized to the long wavelength side. On the other hand, recording coatings used in optical disk technology can store high-density information using optically detectable small (eg, about 1 micron) 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,
So far, 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 this laser is 750 nm.
It often has a wavelength of m or more. Therefore,
Recording and/or
When performing regeneration, the absorption characteristics of the laser sensitive coating have an absorption peak on the long wavelength side (generally from 750 nm to
850nm region). 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. To,
It has drawbacks 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 an organic coating containing a squareryllium dye disclosed in Feb. 1981, p. 105 to p. 109 is sensitive to a laser 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 a thermally stable organic coating. 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, A is

[Formula] or

[Formula] is shown. X ₁ and X ₂ represent a sulfur atom, an oxygen atom or a selenium atom. _Z1 is
Pyrylium, Thiopyrylium, Selenapyrillium, Benzopyrylium, Benzothiopyrillium,
Indicates the atomic group necessary to complete benzoselenapyrylium, naphtopyrylium, naphthothiopyrylium or naphthoselenapyrylium, and Z ₂ is pyran, thiopyran, selenapyran, benzopyran, benzothiopyran, benzoselenapyran, naphthopyran, naphthothiopyran or Shows the atoms needed to complete naphthoselenapyran. These rings contain alkyl groups (methyl, ethyl, n-
Propyl, isopropyl, n-butyl, t-butyl, n-acyl, t-acyl, n-hexyl, n
-octyl, t-octyl, 2-ethylhexyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl) , diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibenzylaminophenyl, etc.),
Styryl, 4-phenyl-1,3-butadienyl, methoxystyryl, dimethoxystyryl, ethoxystyryl, diethoxystyryl, dimethylaminostyryl, 4-(P-dimethylaminophenyl)-1,3-butadienyl, 4-(P -diethylaminophenyl)-1,3-butadienyl, a styryl group, or 4-phenyl-1,3-butadienyl or a substituted product thereof, or 3-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, Can be substituted by heterocyclic groups such as 9-carbazolyl. A is

[Formula] or

[Formula] is shown. R ₁ , R ₂ , R ₃ and R ₄ are: (a) a hydrogen atom; (b) an alkyl group, especially an alkyl group having 1 to 15 carbon atoms; for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl; , amyl, isoamyl, hexyl, octyl, nonyl, dodecyl (c) Alkoxy groups: e.g. methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, octoxy (d) Aryl groups: phenyl, α-naphthyl, β-
Naphthyl (e) substituted aryl group: tolyl, xylyl, biphenyl, ethyl phenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, Dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibenzylaminophenyl (f) Styryl group or 4-phenyl-1,3-butadienyl group: styryl, 4-phenyl-1,3
-butadienyl (g) substituted styryl group or 4-phenyl-1,3-
Butadienyl group: methoxystyryl, dimethoxystyryl, ethoxystyryl, diethoxystyryl, dimethylaminostyryl, diethylaminostyryl, 4-(P-dimethylaminophenyl)-1,3-butadienyl, 4-(P-diethylaminophenyl)- 1,3-Butadienyl (h) R ₁ and R ₂ and R ₃ and R ₄ may be combined to form benzene (i) Substituted or unsubstituted heterocyclic group: e.g. 3-carbazolyl, 9- Methyl-3-carbazolyl, 9
-Ethyl-3-carbazolyl, 9-carbazolyl. Representative examples of the compound represented by the general formula (1) are as follows.

【table】

【table】

【table】

【table】

[Table] These compounds, for example, have the general formula (In the formula, X ₁ means the same thing as defined above, and Z represents an anion such as perchlorate, fluoborate, sulfoacetate, iodide, bromide, etc.) and 3,4 It can be easily obtained by reacting -dihydroxy-3-cyclobutene-1,2-dione or croconic acid or a derivative thereof (eg, mono- or dialkyl ester) in a solvent. 2-Methyl-4,6-diphenylpyrylium salt is described in Schneider et al., Ber, Vol. 54, p. 2289 (1921).
By the method described, 2-methyl-4,6-
The diphenylthiopyrylium salt is from Wizinger et al.
It can be obtained by the method described in Helv.Chim.Acta, Vol. 39, p. 221 (1956). In addition to the above-mentioned compounds, pyrylium salts having a known active methyl group such as 2,6-di-t-butyl-4-methylthiopyrylium disclosed in U.S. Pat. No. 4,315,983 may be used as synthetic intermediates. Can be done. As the reaction solvent, a wide range of organic solvents can be used, preferably alcohols such as ethanol, butanol, benzyl alcohol,
Nitriles such as acetonitrile and propionitrile, organic carboxylic acids such as acetic acid, and acid anhydrides such as acetic anhydride are used. Furthermore, aromatic hydrocarbons such as benzene can be mixed with butanol, benzyl alcohol, and the like. The ratio of raw material compounds in the reaction system is 3,4-
The pyrylium salt is used in an amount of 1.0 to 5.0 equivalent mol, preferably 1.5 to 3.0 equivalent mol, per 1 equivalent mol of dihydroxy-3-cyclobutene-1,2-dione or croconic acid. The reaction solvent is used in an amount of 0.5 to 100 ml, preferably 2 ml to 1 g of the total amount of raw material compounds.
It is 10ml. The reaction temperature is 25°C to 200°C, preferably 60°C to 140°C, and the reaction time is 5 minutes to 30 hours.
Preferably it is from 20 minutes to 5 hours. Furthermore, a base can be added to promote the reaction. Specifically, bases such as triethylamine, pyridine, quinoline, and sodium acetate can be used. Next, methods for synthesizing representative compounds among the above-mentioned compounds will be shown. Synthesis Example 1 (Compound No. 7) 1.2 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione in a 100 ml three-necked flask
(0.0105 mol) and 36 ml of n-butanol were added and heated to 100° C. with stirring to dissolve. 3 ml of quinoline, 7.3 g (0.0211 mol) of 2-methyl-4,6-diphenylpyrylium perchlorate, and 15 ml of benzene were sequentially added into the flask to initiate the reaction. The reaction was carried out at 95-110°C while adding 30 ml of benzene and 20 ml of butanol in portions.
Water was azeotropically distilled off for 3 hours and 30 minutes. The reaction solution was cooled, filtered by suction, and diluted with n-butanol 30
ml to obtain the crude dye. The crude dye was boiled and filtered five times with 200 ml of methanol, and then boiled and filtered twice with 100 ml of tetrahydrofuran to obtain dye No. 1. Yield: 1.9g, yield: 31.7% Melting point: 255-258℃ Elemental analysis: Molecular formula C ₄₀ H ₂₆ O ₄ Calculated value Analysis value C: 84.18 84.02 H: 4.60 4.76 Visible infrared absorption spectrum: λmax ε in dimethylformamide 910nm 6.6×10 ⁴ 815nm 6.2×10 ⁴ Synthesis Example 2 (Compound No. 5) 1.0 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione in a 100 ml three-necked flask
(0.0088 mol) and 50 ml of n-butanol were added and heated to 100° C. with stirring to dissolve. next,
2.5 ml of quinoline, 6.36 g of 2-methyl-4,6-diphenylthiopyrylium perchlorate (0.0176
mol) and 10 ml of benzene were sequentially added to the flask to start the reaction. The reaction was carried out at 95-110℃.
While adding 30 ml of benzene and 10 ml of n-butanol in portions, water was azeotropically distilled off for 3 hours. After the reaction solution was left overnight, it was filtered under suction and washed with 30 ml of n-butanol to obtain a crude dye. The crude dye was boiled and filtered with 200ml of methanol 5 times.
Thereafter, the mixture was boiled and filtered twice with 100 ml of tetrahydrofuran to obtain dye No. 2. Yield: 1.36g Yield: 25.7% Melting point: 232.5-235℃ Elemental analysis: Molecular formula C ₄₀ H ₂₆ O ₂ S ₂ Calculated value Analysis value C: 79.70 79.59 H: 4.36 4.45 S: 10.64 10.69 Visible infrared absorption spectrum: Dimethyl λmax ε 975nm 5.13×10 ⁴ 885nm 5.29×10 ⁴ In the present invention, the pyrylium series compound represented by the above general formula (1) is a eutectic compound with a polymer having a repeating unit of an alkylidene diarylene moiety. It may also be a complex. A polymer having a repeating unit of an alkyldendiarylene moiety is, for example, represented by the general formula (5) It can be shown as In the formula, R ₆ and R ₇ are a hydrogen atom, an alkyl group (methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, octyl, nonyl, decyl), a substituted alkyl group (trifluoromethyl), Aryl group (phenyl, naphthyl), substituted aryl (tolyl, xylyl, ethyl phenyl, propylphenyl, amyl phenyl, chlorophenyl, dichlorophenyl, bromophenyl), and R ₆ and
They can be combined at R ₇ to form cycloalkanes such as cyclohexyl or polycycloalkanes such as norbornyl. _R5 and _R8
is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
Represents a halogen atom (chloro, bromo, iodo). _R9 is

【formula】 【formula】

【formula】

【formula】

【formula】

[Formula] or

【formula】 A group selected from the divalent residues consisting of. Representative polymers are as follows.

【table】

[Table] These eutectic complexes are described, for example, in U.S. Patent No.
Publication No. 3684502, Australian Publication No. 87757/75
It can be similarly obtained by the method disclosed in the publication. For example, the above-mentioned pyrylium series compound and the above-mentioned polymer are dissolved in a halogenated hydrocarbon-containing solvent (dichloromethane), and a non-halogen-nonpolar solvent (hexane, octane, decane, ligroin, toluene) is injected into this solution. to precipitate the eutectic complex. 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 compound represented by the above-mentioned general formula (1) in a binder. be able to. 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, cellulose nitro, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate,
Cellulose esters such as cellulose palmitate, acetic acid, cellulose propionate, acetic acid, cellulose butyrate, cellulose ethers such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal , vinyl resins such as polyvinyl alcohol and polyvinylpyrrolidone, copolymer resins such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer,
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)
terephthalate), poly(4,4'-isopropylidene diphenylene carbonate), poly(4,
4'-sec-butylidene diphenylene carbonate), poly(4,4'-isopropylidene diphenylene carbonate-block oxyethylene)
Polyarylate resins such as 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 cyclohexanone, 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 compound represented by the above general formula (1) in the organic coating 2 is 1 to 90% by weight, preferably 20 to 90% by weight.
It is 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 the organic coating 2
real-time writing is performed with a laser beam of a first wavelength that is absorbed by the organic film 2, and a laser beam of a second wavelength that substantially transmits through the organic coating 2 is used 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:
It is also possible to record by irradiation with a gas laser such as a helium-cadmium laser (oscillation wavelength: 442 nm), but preferably at 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 a certain near-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 a thin film layer, for example, 5 microns or less, in order to shorten the range of the generated charge carriers. , 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. The solvent that dissolves these resins varies depending on the type of resin, and is 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, and curtain coating. For drying, it is preferable to dry to the touch at room temperature and then heat dry. Heat drying at a temperature of 30℃ to 200℃ for 5 minutes to 2
It can be carried out stationary or under blown air for a period of time within a range of hours. 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 display. ing. 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 transport substances include electron transport substances and hole transport substances, and electron transport 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 polymerization of these electron-absorbing 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-diethylaminobenzaldehyde-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)pyrazolene, 1-[quinolyl(2)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]- 3-(P-
diethylaminostyryl)-2-(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-dimethylaminophenyl)-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-
Examples include N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinyl acryldine, 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. Resins that can be used as binders are:
For example, acrylic resin, polyacrylate, polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone,
Examples include insulating resins such as polyacrylamide, polyamide, and chlorinated rubber, and organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and 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, resin, polyethylene fluoride, etc.), conductive particles (e.g. carbon black,
For example, a substrate made of plastic coated with silver particles (silver particles, etc.) together with a suitable binder, a substrate made of plastic or paper impregnated with conductive particles, a plastic containing a conductive polymer, 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 appropriate thickness of the undercoat layer is 0.1 micron to 5 micron, preferably 0.5 micron to 3 micron. . 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 a compound represented by the above-mentioned general formula (1) as a sensitizer for a photoconductive substance or an inorganic photoconductive substance such as zinc oxide, cadmium sulfide, or selenium.
This organic film is formed by coating these photoconductive substances and the above-mentioned compound together with a binder, and in another specific example, the above-mentioned general formula (1)
An organic film containing a compound represented by can be used as a photosensitive layer. In any of the photoreceptors, the present invention is based on the general formula (1).
For the purpose of increasing the sensitivity of a photoreceptor or obtaining a panchromatic photoreceptor, it contains at least one compound selected from the compounds shown in It is also possible to use a combination of two or more types of compounds represented by the general formula (1), 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 isodium 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 has 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, although it has 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 (11.2 g of casein, 1 g of 28% ammonia water, 222 ml of water) was coated on an aluminum cylinder by dip coating.
It was dried to form a subbing layer with a coating weight of 1.0 g/m ² . Next, 1 part by weight of the aforementioned compound No. (5), 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 were mixed and dissolved by stirring with a stirrer.This liquid was dissolved in the charge generation layer. Coated on top using dip coating method,
It was dried to form a charge transport layer. The film thickness at this time was 12μ. Corona discharge of -5 KV 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 leaving it in the dark for 5 seconds (dark decay).
_V5 ). Sensitivity was evaluated by measuring the exposure amount (E1/2 microjoule/ ^cm2 ) required to attenuate the potential _V5 after dark decay by half. 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 : -590 volts V ₅ : -550 volts E _1/2 : 1.2 microjoules/cm ² Examples 2 to 16 In place of the compound No. (5) used in Example 1, the compound shown in Table 1 was used. A photoreceptor was prepared in exactly the same manner as in Example 1, except that the compounds shown in the following were used, and the characteristics of this photoreceptor were measured. These results are shown in Table 1.

[Table] Example 17 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. 1 g of this charge transfer complex compound and the aforementioned compound No. (5)
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 : 530 volts V ₅ : 490 volts E _1/2 : 4.2 microjoules/cm ² Example 18 A polyvinyl alcohol film having 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. (5) used in Example 1 was applied onto the previously formed polyvinyl alcohol layer using a Meyer 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 : -540 volts V ₅ : -510 volts E _1/2 : 2.4 microjoules/ ^cm2 As can be seen from the above-mentioned examples, the electrophotographic photoreceptor of the present invention has a remarkable high temperature in the wavelength range of 750 nm or more. It has excellent sensitivity characteristics and charging characteristics such as initial potential and dark decay. Example 19 Nitrocellulose solution (Daicel Chemical Industries, Ltd.)
Manufactured by Ohares Latzker: Nitrocellulose 25
12 parts by weight of a methyl ethyl ketone solution, 3 parts by weight of the aforementioned compound No. (5) and 70 parts by weight of methyl ethyl ketone were mixed and thoroughly dispersed. This dispersion 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 performed 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 20 500 mg of the above compound No. (7) was placed in a molybdenum boat for vapor deposition, and after evacuating 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. When information was recorded on the produced optical disc recording medium in the same manner as in Example 1, Example 19
Clear pits similar to those of Example 19 were observed.
Information was reproduced in the same manner as above, and a waveform with a sufficient S/N ratio was observed. Example 21 The aforementioned compound No. (5) was vapor-deposited on an aluminum vapor-deposited glass plate in the same manner as in Example 20, and 0.2
An optical disc recording medium having a micron recording layer was prepared. When information was stored on this optical disk recording medium in the same manner as in Example 19 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 22 The aforementioned compound No. (13) was deposited on an aluminum-deposited glass plate in the same manner as in Example 20, and
An optical disk recording medium having a recording layer of 0.2 microns was prepared. When information was stored on this optical disk recording medium in the same manner as in Example 19 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 23 The aforementioned compound No. (15) was deposited on an aluminum-deposited glass plate in the same manner as in Example 20, and
An optical disk recording medium having a recording layer of 0.2 microns was prepared. When information was stored on this optical disk recording medium in the same manner as in Example 19 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 24 2.0 g of the above-exemplified compound No. (5) and 2.0 g of poly(4,4'-isopropylidene diphenylene carbonate) were dissolved in 100 ml of dichloromethane with stirring. 50 g of toluene was added to this solution to precipitate it, and enough dichloromethane was injected to redissolve the precipitate, followed by n-hexane.
When 500 g of the solution was injected under stirring, purple-blue crystals were precipitated. After separating the crystals, recrystallization was repeated. This crystal was used as Compound No. (5) in Example 19 above.
An optical disc recording medium was prepared in exactly the same manner as in Example 19, except that the compound was used in place of
As a result of repeating information recording and reproduction, similar results were obtained. Example 25 A photoreceptor was prepared in exactly the same manner as in Example 1, except that the eutectic complex prepared in Example 24 was used in place of compound No. (5) used in Example 1. The characteristics of this photoreceptor were measured. The results at this time were as follows. V ₀ : -590 volts V ₅ : -550 volts E _1/2 : 0.8 microjoules/cm ²

[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. FIG. 4 is an explanatory diagram showing the infrared absorption spectrum of compound No. (7). 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, A represents [Formula] or [Formula], X ₁ and _{X 2} represent a sulfur atom, an oxygen atom, or a selenium atom. Indicates the atomic group necessary to complete benzopyrylium, benzothiopyrylium, benzoselenapyrylium, naphthopyrylium, naphthothiopyrylium or naphthoselenapyrylium. Z ₂ is pyran, thiopyran, which may be substituted, respectively. Selena Piran,
Indicates the atomic groups necessary to complete benzopyran, benzothiopyran, benzoselenapyran, naphthopyran, naphthothiopyran, or naphthoselenapyran. R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, alkyl groups, alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted styryl groups, substituted or unsubstituted 4-phenyl-1,3 - represents a butadienyl group or a substituted or unsubstituted heterocyclic group. Furthermore, R ₁ and R ₂ may form a substituted or unsubstituted benzene ring, and R ₃ and R ₄ may form a substituted or unsubstituted benzene ring. m and n are 1 or 2. )