JPH0211137B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an organic coating that can effectively absorb a laser, especially a semiconductor laser having an oscillation wavelength on the long wavelength side, and convert it into another 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 read 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 photoreceptor in which a tellurium vapor-deposited layer sensitized by Those using a photosensitive layer, those using cadmium sulfide that has been spectrally sensitized with a sensitizing dye, and those that are functionally decomposed into a charge generation layer and a charge transport layer containing organic pigments, and their photosensitive wavelength range There are known devices 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 such disc information, 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 then shaped into a spiral or circular track. Form. The laser sensitive layer can absorb laser energy to form optically detectable pits. For example, in a heat mode recording method, the laser sensitive layer absorbs thermal energy and can form small pits at that location by evaporation or melting. In addition, in another heat mode recording method, the irradiated laser
The absorption of energy can form pits with optically detectable concentration differences at that location. 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.
In many cases, the wavelength is longer than that. 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 750nm to 850nm).
m 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 drawback of not being able to achieve high sensitivity characteristics. Ori,
Moreover, setting the sensitive wavelength range to 750 nm or more means that
It has drawbacks such as making the layer structure of the laser-sensitive coating complex, and especially in the case of electrophotographic sensitive coatings, the sensitizing dye used fades during repeated charging and exposure. There is. For this reason, in recent years, organic coatings have been proposed that exhibit high sensitivity to light with a wavelength 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 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 film containing a compound represented by the following general formula (1). General formula (1) Z ₁ is a substituted or unsubstituted nitrogen-containing heterocycle, for example, a thiazole series nucleus (for example, thiazole, 4
-Methylthiazole, 4-phenythiazole, 5
-Methylthiazole, 5-phenylthiazole,
4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)-thiazole, etc.), benzothiazole series nuclei (e.g. benzothiazole, 5-chlorobenzothiazole, 5-
Methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5
-Promobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6
-methoxybenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 4,
5,6,7-tetrahydrobenzothiazole, etc.), naphthothiazole series nuclei (e.g. naphtho[2,1-d]thiazole, naphtho[1,2-d]
Thiazole, 5-methoxynaphtho [1,2-d]
Thiazole, 5-ethoxynaphtho [1,2-d]
Thiazole, 8-methoxynaphtho [2,1-d]
Thiazole, 7-methoxynaphtho[2,1-d]
thiazole, etc.), thionaphthene [7,6-d]
Thiazole series nuclei (e.g. 7-methoxythionaphthene[7,6-d]thiazole), oxazole series nuclei (e.g. 4-methyloxazole, 5
-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole), benzoxazole series nuclei (e.g. benzoxazole, 5-phenyloxazole),
-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole series nuclei (e.g. naphtho[2,1-d]
oxazole, naphtho[1,2-d]oxazole, etc.), selenazole series nuclei (e.g. 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazole series nuclei (e.g. benzoselenazole, 5-chloro Benzoselenazole, 5-methylbenzoselenazole, 5,6-dimethylbenzoselenazole, 5-methyloxybenzoselenazole, 5-methyl-6-methoxybenzoselenazole, 5,6-dioxymethylbenzoselenazole, 5-hydroxybenzoselenazole, 4,5,6,7-tetrahydrobenzoselenazole, etc.), naphthoselenazole series nuclei (e.g. naphtho[2,1-d]selenazole, naphtho[1,2-d]selenazole) , thiazoline series nuclei (e.g. thiazoline, 4-methylthiazoline,
4-hydroxymethyl-4-methylthiazoline,
4,4-bis-hydroxymethylthiazoline, etc.), oxazoline series nuclei (e.g. oxazoline), selenazoline series nuclei (e.g. selenazoline), 2-quinoline series nuclei (e.g. quinoline,
6-methylquinoline, 6-chloroquinoline, 6-
Methoxyquinoline, 6-ethoxyquinoline, 6-
hydroxyquinoline), 4-quinoline series nucleus,
(e.g. quinoline, 6-methoxyquinoline, 7-
methylquinoline, 8-methylquinoline), 1-isoquinoline series nuclei (e.g. isoquinoline, 3,
4-dihydroisoquinoline), 3-isoquinoline series nuclei (e.g. isoquinoline), 3,3-dialkylindolenine series nuclei (e.g. 3,3-dimethylindolenine, 3,3-dimethyl-5-chloroindolenine, 3 , 3,5-trimethylindolenine, 3,3,7-trimethylindolenine), pyridine series nuclei (e.g. pyridine, 5-
methylpyridine), benzimidazole series nuclei (e.g. 1-ethyl-5,6-dichlorobenzimidazole, 1-hydroxyethyl-5,6-dichlorobenzimidazole, 1-ethyl-chlorobenzimidazole, 1-ethyl-5, 6-dipromobenzimidazole, 1-ethyl-5-phenylbenzimidazole, 1-ethyl-5-pheolobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-(β-acetoxyethyl)-5- Cyanobenzimidazole, 1-ethyl-5-chloro-6-cyanobenzimidazole, 1-ethyl-5-fluoro-6-cyanobenzimidazole, 1-ethyl-5-acetylbenzimidazole, 1-ethyl-5-carboxybenzo Imidazole, 1-ethyl-5-ethoxycarbonylbenzimidazole, 1-ethyl-5-
Sulfamylbenzimidazole, 1-ethyl-
5-N-ethylsulfamylbenzimidazole, 1-ethyl-5,6-difluorobenzimidazole, 1-ethyl-5,6-dicyanobenzimidazole, 1-ethyl-5-ethylsulfonylbenzimidazole, 1-ethyl- 5-methylsulfonylbenzimidazole, 1-ethyl-5
-trifluoromethylbenzimidazole, 1-
ethyl-5-trifluoromethylsulfonylbenzimidazole, 1-ethyl-5-trifluoromethylsulfinylbenzimidazole, etc.). Z ₂ is optionally substituted pyran, thiapyran,
Indicates an atomic group necessary to complete selenapyran, benzopyran, benzothiapyran, benzoselenapyran, naphthopyran, naphthothiapyran, or naphthoselenapyran, and X is a sulfur atom, an oxygen atom, or a selenium atom. As substituents, the following
Specific examples include atoms other than hydrogen atoms shown in R ₂ and R ₃ . Z ₃ is a substituted or unsubstituted divalent hydrocarbon group forming a 5- or 6-membered ring (-CH ₂ -CH ₂ -, -
CH ₂ −CH ₂ −CH ₂ −,

[Formula] -CH=CH-, etc., and these 5- or 6-membered rings may be fused with a benzene ring, a naphthalene ring, etc. R ₁ is a hydrogen atom or an alkyl group (e.g. methyl, ethyl, n-propyl, iso-propyl,
n-butyl, sec-butyl, iso-butyl, t-butyl, n-amyl, t-amyl, n-hexyl,
n-octyl, t-octyl, etc.), and also other alkyl groups, such as substituted allyl groups (e.g., 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl, carboxymethyl, - carboxiel,
3-carboxypropyl, 2-sulfoethyl, 3
-Sulfopropyl, 4-sulfobutyl, 3-sulfatepropyl, 4-sulfatebutyl, N
-(methylsulfonyl)-carbamylmethyl, 3-
(acetylsulfamyl)propyl, 4-(acetylsulfamyl)butyl, etc.), cyclic alkyl groups (e.g. cyclohexyl, etc.), allyl groups ( _CH2
=CH- _CH2- ), aralkyl groups (e.g., benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, etc.), substituted aralkyl groups (e.g., carboxybenzyl, sulfobenzyl, hydroxybenzyl, etc.). R ₂ and R ₃ each represent (a) a hydrogen atom, (b) a halogen atom: a chlorine atom, a bromine atom, an iodine atom or a monovalent organic residue, such as (c) an alkyl group, especially a carbon atom number of 1 to 15 Alkyl groups: For example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl, hexyl, octyl, nonyl, dodecyl (d) Alkoxy groups: For example, methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy , octoxy(e) Aryl group: phenyl, α-naphthyl, β-
Naphthyl (f) substituted aryl group: tolyl, xylyl, biphenyl, ethyl phenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, Promophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibenzylaminophenyl (g) styryl (h) Substituted styryl group: methoxystyryl, dimethoxystyryl, ethoxystyryl, diethoxystyryl, dimethylaminostyryl, Diethylaminostyryl (i) Substituted or unsubstituted multi-ring group: e.g. 3-carbazolyl, 9-methyl-3-carbazolyl, 9
-Ethyl-3-carbazolyl, 9-carbazolyl ring can be formed. R ₄ is a hydrogen atom or a halogen atom (for example,
chlorine atom, bromine atom, iodine atom). A is a chloride ion, bromide ion, iodide ion, perchlorate ion, benzenesulfonate ion, P-toluenesulfonate ion,
Represents anions such as methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion, etc.
R ₁ itself is an anionic group, e.g. -SO ₃ , OSC ₃
, −COO, SO ₂ NH−,

【formula】

Does not exist when [expression] is included. m and n represent 0 or 1, and l represents 0, 1 or 2. The compound represented by the general formula (1) forms a resonator with the compound represented by the following general formula (2), and the present invention includes such a resonator. General formula (2) (In the formula, Z ₁ to _{Z 3} , R ₁ to R ₄ , X, A , l, m and n have the same meanings as above. However, Z ₂ is pyrylium, thiapyrylium, selenapyrylium,
It is expressed in the pyrylium salt series such as benzopyrylium, benzothiapyrylium, benzoselenapyrylium, naphthopyrylium, naphthothiapyrylium or naphthoselenapyrylium. ) Next, representative examples of the cyanine compound represented by the general formula (1) will be listed.

【table】

【table】

【table】

【table】

[Table] These cyanine compounds are listed in U.S. Patent No.
It can be synthesized by the method described in Japanese Patent No. 2734900. In the general formula (1), the compound with l=0 has the general formula (3)
Compound represented by and general formula (3) (In the formula, Z ₁ , Z ₃ , R ₁ , R ₄ , A and n represent the same as defined above.) The compound represented by the general formula (4) or the general formula (5) Formula (4) (In the formula, Z ₂ , X, R ₂ , R ₃ , A and m represent the same as defined above, and R ₅ represents an alkyl group such as a methyl group or an ethyl group.) General formula (5 ) (In the formula, Z ² , R ₂ , R ₃ , X and m are the same as defined above.) It can be obtained by heating in a suitable solvent. In the general formula (1), the compound in which l=1 or 2 is a compound represented by the above-mentioned general formula (3) and a compound represented by the general formula (6). (In the formula, Z ₂ , R ₂ , R ₃ , X, A and m represent the same as defined above, R ₆ represents an acyl group such as an acetyl group, a propionyl group, a benzoyl group, and R ₇ represents a phenyl group such as a phenyl group or a tolyl group. k represents 1 or 2) It can be obtained by heating the indicated compound in an appropriate solvent. These compounds represented by general formula (1) or general formula (2) can form a eutectic complex with a polymer,
These eutectic complexes are included in the present invention. The organic coating of the present invention can be used for optical disc recording. For example, a substrate 1 as shown in FIG.
It is possible to provide a recording medium on which the organic film 2 described above is formed. Such an organic film 2 can be formed by vacuum deposition of the above-mentioned cyanine compound, or by applying a coating liquid containing the above-mentioned cyanine 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, cellulose nitro, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, cellulose acetate/propionate,
Cellulose esters such as cellulose acetate and butyrate, cellulose ethers such as methyl cellulose, ethyl cellulose, propyl cellulose, and butyl cellulose, vinyl resins such as polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, and polyvinylpyrrolidone. Copolymer resins such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile polymer, vinyl chloride-vinyl acetate polymer, polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, poly Acrylic resins such as methacrylic acid, polyacrylamide and 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) poly(4,4'-isopropylidene diphenylene carbonate), poly(4,4'-sec-butylidene diphenylene carbonate), poly(4,4'-sec-butylidene diphenylene carbonate),
Polyarylate resins such as 4'-isopropylidene diphenylene carbonate-block oxyethylene), or polyolefins such as polyamides, polyimides, epoxy resins, phenolic resins, polyethylene, polypropylene, and chlorinated polyethylene, etc. 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-dimethylacetonamide; sulfoxides such as dimethyl sulfoxide; tetrahydrofuran and 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, trichlorethylene, or benzene, Aromatics such as 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. When forming the organic film 2 together with the binder,
The content of the aforementioned cyanine compound in the organic coating 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 the different film thicknesses in the pit region and the pit region. 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 750 nm).
Lasers with wavelengths longer than m, especially gallium-aluminum-arsenic semiconductor lasers (oscillation wavelength 780n)
m) 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 aforementioned cyanine compound as possible to obtain sufficient absorbance;
In addition, in order to shorten the range of the generated charge carriers, a thin film layer, for example, 5 microns or less, preferably
A thin film layer having a thickness of 0.01 micron to 1 micron is preferable. This means that most of the incident light is absorbed by the charge generation layer and generates a large number of carriers, and that the generated charge carriers are not deactivated by recombination or trapping and are transferred to the charge transport layer. This is due to the need for injection. The charge generation layer can be formed by dispersing the above-mentioned cyanyl 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. can. Binders that can be used to form the charge generating layer by coating can be selected from a wide variety of insulating resins, and can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylprene. . Preferably, polyvinyl butyral, polyarylate (condensation polymer of busphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin,
Polypynylacetate, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, cellulose resin, urethane resin, epoxy resin,
Examples include insulating resins such as 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 dimethysulfoxide, ethers such as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, and 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 surface. 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" including r-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 polymerized versions of these electron-withdrawing substances. Examples of hole-transporting substances include pyrene, N-ethylcarbazone, N-isopropylcarbazone, and 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-
Hydrazones such as 3-methylbenzthiazolinone-2-hydrazone, 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)pyrazolyl, 1-[6-methoxy-pyridyl(2)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)
Pyrarizone, 1-[pyridyl(3)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)prazolin, 1-[lepidyl(2)]-3-
(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]-3-(P-diethylaminostyryl)-4
-Methyl-5-(P-diethylaminophenyl)
Birazoline, 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-(P-diethylaminophenyl)-4-
(P-dimethylaminophenyl)-5-(2-chlorophenyl)oxazole and other oxazole compounds, 2-(P-diethylaminostyryl)-6-
Thiazole compounds such as diethylaminobenzothiazole, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane, 1,1-bis(4-N,N-diethylamino-2-methylphenyl)hebutane,
Polyarylalkanes such as 1,1,2,2,-tetrakis(4-N,N-dimethylamino-2-methylphenyl)ethane, triphenylamine,
Poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-bilylphenylanthracene,
Examples include 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 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, 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 conductive themselves such as aluminum, aluminum alloy, copper, zinc, stainless steel, panadium, molybdenum, chromium, titanium, nickel, indium, gold, and platinum can be used. In addition, plastics (e.g., polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin) have a layer formed by vacuum deposition of aluminum, aluminum alloy, indium oxide, tin oxide, indium tin monoxide alloy, etc. conductive particles (e.g., carbon black, etc.), conductive particles (e.g., carbon black,
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 a Bayer function and an adhesive function 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, which eventually reaches the surface and neutralizes 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 treating 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 is made of a hole transport material, it is necessary to charge the charge transport material negatively, and when exposed to light after being charged, holes generated in the charge generation layer are injected into the charge transport layer in the exposed area. Thereafter, it reaches the surface and neutralizes the negative charge, causing a decrease in surface potential and creating an electrostatic contrast with the unexposed area.
During development, it is necessary to use a positively charged toner, contrary to the case where an electron transport material is used. Further, in another specific example of the present invention, organic light such as the above-mentioned hydrazones, pyrazolines, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, tripheniamine, poly-N-vinylcarbazoles, etc. The organic coating may contain the aforementioned cyanine compound as a sensitizer for conductive substances and inorganic photoconductive substances such as zinc oxide, cadmium sulfide, and selenium. The organic film is formed by coating these photoconductive substances and the above-mentioned compounds together with a binder. In another embodiment, an organic film containing the aforementioned cyanine compound can be used as the photosensitive layer. In any of the photoreceptors, the compound used contains at least one compound selected from the compounds represented by the general formula (1), and if necessary, pigments with different light absorptions may be combined to increase the sensitivity of the photoreceptor. ,
For the purpose of obtaining a panchromatic photoreceptor, it is also possible to combine two or more compounds represented by general formula (1), or to use them in combination with a charge-generating substance selected from known dyes and pigments. be. The organic coating of the present invention can be used not only as a laser-sensitive coating for an electrophotographic photoreceptor in the above-mentioned optical disk recording medium, 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 has high sensitivity and sufficient sensitivity compared to conventional disk recording materials. It is possible to provide an improved S/N ratio. 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, 28%, 1 g of aqueous ammonia, 222 ml of water) was coated on an aluminum cylinder using a dip coating method, dried, and coated with a coating amount of 1.0 g/ ^m2. formed a layer. Next, 1 part by weight of the cyanine compound of Compound No. (1) mentioned above, 1 part by weight of butyral resin (Eslec BM-2, manufactured by Sekisui Chemical Co., Ltd.), and 30 parts by weight of tetrahydrofuran were dispersed for 4 hours using a ball mill dispersion machine. . 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-diethylaminobenzaldebide-N
1 part by weight of -phenyl-N-α-naphthylhydrazone, 1 part by weight of polysulfone resin (P1700 manufactured by Union Carbide Co., Ltd.) and 6 parts by weight of monochlorobenzene were mixed and dissolved by stirring with a stirrer.This liquid was added to the charge generation layer. A charge transport layer was formed by coating on top using a dip coating method and drying.The film thickness at this time was:
It 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 it was left in a dark place for 5 seconds (dark decay V ₅ ).
Sensitivity is the amount of exposure required to attenuate the potential V ₅ to 1/2 after dark decay (E1/2 microjoule/cm ² )
It was evaluated by measuring. 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 : -620 volts V ₅ : -580 volts E1/2: 8.5 microjoules/cm ² Examples 2 to 17 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】

[Table] Example 18 An ammonium aqueous solution of casein was applied on a 100 micron thick aluminum plate and dried to a film thickness of 1.1
A micron subbing layer was formed. 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)
5g of polyester resin (Vylon: manufactured by Toyobo)
was added to a solution of 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 The charging characteristics of the photoreceptor thus adjusted
It was measured in the same manner as. The results of this were as follows. However, the charging polarity was determined. V ₀ : 550 volts V ₅ : 450 volts E1/2: 48.5 microjoules/cm ² Example 19 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. (1) used in Example 1 was applied onto the polyvinyl alcohol layer formed earlier using a Meyer bar so that the film thickness after drying was 0.5 microns. and dried to form a charge generator. Next, the structural formula 5 g of pyrazoline compound and 5 g of polyarylate resin (condensation polymer of bisphenol A and terephthalic acid-isophthanic acid) were dissolved in 70 ml of tetrahydrofuran and applied onto the charge generating layer so that the film thickness after drying was 10 microns. , 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 : -580 volts V ₅ : -520 volts E1/2: 10.5 microjoules/cm ² As can be seen from the above-mentioned examples, the electrophotographic photoreceptor of the present invention has extremely high sensitivity in the wavelength range of 750 nm or more. It has excellent charging characteristics such as initial potential and dark decay. Example 20 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. (1) and 70 parts by weight of methyl ethyl ketone were mixed and thoroughly dispersed.
This dispersion was applied onto an aluminum vapor-deposited glass plate by dip coating method, and then dried to give a coating density of 0.6 g/m ^{2 .}
A recording layer was obtained. 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 4 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 21 500 mg of the above compound No. (1) 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. Example 20 was applied to the optical disk recording body thus prepared.
When information was stored in the same manner as in Example
Clear pits similar to those in Example 20 were observed.
Information was reproduced in the same manner as in No. 20, and a waveform with a sufficient S/N ratio was observed. Example 22 The above-mentioned compound No. (5) was coated on an aluminum vapor-deposited glass plate in the same manner as in Example 20 to form a light beam having a recording layer with a dry coating weight of 0.6 g/ ^m2 . A disk recorder was created. When information was recorded on this optical disk recording medium in the same manner as in Example 20 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 above compound No. (8) was coated on an aluminum vapor-deposited glass plate in the same manner as in Example 20 to produce an optical disc having a recording layer with a dry coating weight of 0.6 g/ ^m2 . A record was created. When information was stored on this optical disk recording medium in the same manner as in Example 20 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 The aforementioned compound No. (14) was coated on an aluminum vapor-deposited glass plate in the same manner as in Example 20.
An optical disc recording medium having a recording layer with a dry coating weight of 0.6 g/m ² was prepared. When information was stored on this optical disk recording medium in the same manner as in Example 20 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 coating 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, Z ₁ represents an atomic group necessary to complete a substituted or unsubstituted nitrogen-containing heterocycle. Z ₂ represents an optionally substituted pyran, thiapyran, selenapyran, bempyran, benzothiapyran, benzoselenapyran, Indicates the atomic group necessary to complete naphthopyran, naphthothiapyran or naphthoselenapyran,
X is a sulfur atom, an oxygen atom or a selenium atom.
Z ₃ represents a substituted or unsubstituted 5- or 6-membered divalent hydrocarbon group. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R ₂ and R ₃ are hydrogen atoms, halogen atoms, or 1
Indicates the organic residue of valence. R ₄ represents a hydrogen atom or a halogen atom. A represents an anion, m and n are 0 or 1, and l is 0, 1 or 2. )