JPS58220143A - Organic film - Google Patents

Abstract

PURPOSE:To obtain an org. film having its absorption region at the side of longer wavelengths, especially >=750nm and suitable for use as a photosensitive film for an electrophotographic printer provided with semiconductor laser as a light source, by using a specified pyrylium compound. CONSTITUTION:An org. film is formed using a pyrylium compound represented by formula I (where A<-> is formula II or formula III; each of X1 and X2 is S, O or Se; Z1 is a group of atoms required to complete pyrylium, thiopyrylium, selenapyrylium, naphthoselenapyrylium or the like; Z2 is a group of atoms required to complete pyrane, thiopyrane, selenapyrane, naphthoselenapyrane or the like; each of R1-R4 is H, alkyl, alkoxy, aryl, styryl, 4-phenyl-1,3-butadienyl or a heterocyclic group; and each of m and n is 1 or 2). The pyrylium compound includes a compound represented by formula IV. For example, the pyrylium compound is vacuum deposited on a substrate or coated together with a binder to form an org. film having about <=10mum thickness, and the film is used in an optical disk recorder.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic coating that can effectively absorb a laser, particularly 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 electrophotographic photosensitive coatings for electrophotographic printers, coatings for optical discs that can be written and reproduced by semiconductor lasers, and infrared cut filters.

An electrophotographic printer that uses a laser as a light source modulates the laser using an electrical signal that corresponds to image information, and the modulated laser is optically scanned onto a photoreceptor using a lupanomirror, etc., to form an electrostatic latent image. After formation, 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
．． 6 nm) and helium-neon (oscillation wavelength: 6!
12.8 nm) gas laser.

Therefore, the photoreceptor used for such a light source is 6
It is sufficient that the photoreceptor is spectrally sensitized to about 50 nm, for example, a photoreceptor using a charge transfer complex of polyvinylcarbazole and trinitronefluorenone, or a photoreceptor using a tellurium vapor-deposited layer sensitized by selenium. One uses a photosensitive layer consisting of 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.Spectral enhancement using a sensitizing dye Those using sensitized cadmium sulfide as a photosensitive layer, and those using a photosensitive layer that is functionally separated into a charge generation layer and a charge transport layer containing organic pigments and sensitized to the longer wavelength range. etc. are known.

On the other hand, recording coatings used in optical disk technology can store high-density information by forming optically detectable small pits (eg, about 1 micron) in the form of spiral or circular tracks. To write information to such a disk,
The surface of the laser sensitive layer is scanned with a focused laser beam, and only the surface irradiated with the laser beam forms pits, and the pits are formed in the form of a spiral or circular track.

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 forms small pits at that location due to evaporation or melting.
can be formed. In addition, in another heat mode recording method,
By absorbing the irradiated laser energy, pits with an optically detectable concentration difference can be formed at that location.

The information recorded on this optical disk is detected by Lr when a laser is scanned along a track and optical changes in areas where pits are formed and areas where pits are not formed are read. 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 decreases, while when pits are formed, the laser beam is sufficiently reflected by the underlying reflective surface and the output of the photodetector increases.

As recording media for use in such optical discs, media that mainly use inorganic materials such as metal thin films such as aluminum evaporated films, bismuth thin films, tellurium oxide thin films, and chalcogenide-based amorphous glass films have been proposed so far.

Incidentally, in recent years, semiconductor lasers have been developed that are small, low-cost, and capable of direct modulation.
The oscillation wavelength of the laser 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 75 Q nm to 85 Q nm).
Q nm).

However, conventional laser-sensitive coatings, especially those formed mainly of inorganic materials, have the drawback of not being able to obtain high sensitivity characteristics (because of their high reflectance to laser light, the utilization rate of the laser is low). In addition, the sensitive wavelength range is 75
A value of Q nm or more may complicate the layer structure of the laser-sensitive coating, or the sensitizing dye used in the electrophotographic photosensitive coating may fade during repeated charging and exposure. It has disadvantages such as

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. 4,515,985, “Reeeac
h DiecloeureJ 20517 (198
1, 5) and [J, Va
c, S(!1゜Technol,, j8(1),
JLn, /Feb, 1981, pl 05-p1
It is known that organic coatings containing the square aryllium dye disclosed in 2009 are sensitive to lasers of 750 nm and above.

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. At present, it cannot be said that an organic film that is fully satisfactory in terms of practicality has been developed because it is necessary to satisfy certain characteristics.

Accordingly, a first object of the present invention is to provide a new and useful organic coating.

A second object of the present invention is to provide an organic coating having an absorption band on the long wavelength side, particularly at 750 nm or more.

A sixth 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 disk 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) % formula % X and x2 represent a sulfur atom, an oxygen atom or a selenium atom. 2. indicates the atomic group necessary to complete pyrylium, thiopyrylium, selenapyrylium, benzopyrylium, benzothiopyrylium, penzoselenapyrylium, naphtopyrylium, nandothiopyrylium, or naphthoselenapyrylium. , z2 represents an atom necessary to complete pyran, thiopyran, selenapyran, benzopyran, benzothiopyran, benzoselenapyran, naphthopyran, naphthothiopyran or naphthoselenapyran. These rings include 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), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, etc.).

biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, jetoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, fromophenyl, cyfromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibenzylaminophenyl nato), styryl, 4-phenyl -1,6-
butadienyl, methoxystyryl, dimethoxystyryl, ethoxystyryl, diethoxys f IJ /l/,
a styryl group such as dimethylaminostyryl, 4-(P-dimethylaminophenyl)-1,3-butadienyl, a-<P-diethylaminophenyl)-1,3-butajenyl, or 4-pheny#-1,3-butadienyl; It can be substituted by a substituent thereof or a heterocyclic group such as 6-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, 9-carbazolyl.

00 00 R1, R2, R3 and R4 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 group: For example, methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, octoxy (d) Aryl group = phenyl, α-naphthyl, β-naphthyl (e) [ Substituted aryl group nitrile, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl, jetoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, tetramophenyl, cyfuromophenyl, nitrophenyl, diethylaminophenyl, Dimethylaminophenyl, dibenzylaminophenyl (f) Styryl group or 4-phenyl-1,6-butadienyl group Nistyryl, 4-phenyl-1,6-butadienyl (ω substituted styryl group or 4-phenyl-1,3-butadienyl Group: methoxystyryl, dimethoxystyryl,
Ethoxystyryl, jetoxystyryl, dimethylaminostyryl, diethylaminostyryl, 4-(P-dimethylaminophenyl)-1,3-butadienyl, 4-(
p-diethylaminophenyl) -1,3-butadienyl (h) R, and R2 and R5 and R4 may combine to form benzene (1) f-substituted or unsubstituted heterocyclic group: for example 6- Carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3
-Carbazolyl represents 9-carbazolyl.

Representative examples of the compound represented by the general formula (1) are as follows.

Compound A Compound Example Compound Layer Compound Example 00 Compound M Compound Example Compound Layer Compound Example Compound Layer Compound Example 0 represents an anion such as berchlorate, fluoborate, sulfoacetate, iodide, bromide, etc.) and 6,4-dihydroxy-3-cyclobutene-1,2-dione or bacroconic acid or its derivatives (e.g. mono , dialkyl ester) in a solvent.

2-methyl-4,6-diphenylvirylium salt is 5c
Bar, Vol. 54, p. 2289 (19
21) and 2-methyl-4,6
-Diphenylthiopyrylium salt is described in He1v, Chin, Acta, Vol. 69, p. 221 (1) by Wisinger et al.
956). In addition to the above-mentioned compounds, known pyrylium salts having an active methyl group such as 2,6-di-t-butyl-4-methylthiopyrylium disclosed in U.S. Pat. No. 4,315,983 can be used as synthetic intermediates. can.

As the reaction solvent, a wide range of organic solvents can be used, but preferably alcohols such as ethanol, butanol and benzyl alcohol, nitriles such as acetonitrile and propionitrile, organic carboxylic acids such as acetic acid, acetic anhydride, etc. acid anhydrides are used. Further, aromatic hydrocarbons such as butanol, benzyl alcohol, and tonibenzene can also be mixed.

The ratio of the raw material compounds in the reaction system is 1.0 to 5.0 of the pyrylium salt to 1 equivalent mole of 3,4-dihydroxy-3-cyclobutene-1,2-dione or croconic acid.
It is equivalent mole, preferably 1.5 to 3.0 equivalent mole.

The reaction solvent is used in an amount of 0.5 to 100 yt, preferably 2 rtfL to 10 ml, per 1 g of the total amount of raw material compounds.

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 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, synthesis methods for representative examples of the above-mentioned compounds will be shown.

Synthesis Example 1 (Compound 167) 6,4-dihydroxy-
1.2 g of 3-cyclobutene-1,2-dione (0,01
05 mol) and 36 ml of n-butanol were added and heated to 100° C. with stirring to dissolve. quinoline 3m
7.3 g (0.0211 mol) of 1,2-methyl-4,6-cyphenylbyrylium perchlorate) and 15.1 mol of benzene were sequentially added to the flask to initiate the reaction.

The reaction was carried out for 6 hours and 60 minutes at 95 to 110° C. while adding 60 ml of benzene and 20 ml of butanol in portions while azeotropically distilling off water.

After cooling, the reaction solution was suction filtered and washed with 30 g of n-butanol to obtain a crude dye. The crude dye was boiled and filtered 5 times with 200ml of methanol, then 100ml of tetrahydrofuran.
Dye 41 was obtained by boiling and filtering twice at 1.

Yield: 1.9g, Yield: 31.7% Melting point: 255-258°C Elemental analysis: Molecular formula C40H2604 Calculated value Analysis value 0: 84.18 84.02H:
4.60 4.76 Visible infrared absorption spectrum: 910 in dimethylformamide
rm 6.6X10' 815nm 6.2X10' Synthesis Example 2 (Compound A5) 3,4-dihydroxy-3 was placed in a 100-length Mitsuro flask.
- 1.0 g of cyclobutene-1,2-dione.

(0,0088 mo#) and n-butanol 50d,
The mixture was heated to 100° C. while stirring to cause dissolution. Next, 2.5 WfL of quinoline, 6.56 g of 2-methyl-4,6-cyphenylthiopyrylium perchlorate (0,
0176 mol) and benzene 10- were sequentially added into the flask to start the reaction. The reaction was carried out at 95 to 110° C. for 3 hours while adding 30 d of benzene and n-butano #10+4 in portions while azeotropically distilling water off.

After the reaction solution was left overnight, it was suction filtered and washed with 30 ml of n-butanol to obtain a crude dye.

The crude dye was boiled and filtered five times with 200 ml of methanol, and then boiled and filtered twice with tetrahydrone 100-ml to obtain dye layer 2.

Yield: 1.36. li' Yield: 25.7%
°Melting point: 232.5-235°C Elemental analysis: Molecular formula C4oH2602S2 calculated value Analysis value 0: 79.70 79.59
H: 4.5 6 4
．． 4 58: 10.64 1
0.69 Visible and infrared absorption spectrum: 975 nm in dimethylformamide 5.13X10' 885 nm 5.29X10' It may also be a eutectic complex with a polymer having a repeating unit.

A polymer having a repeating unit of an alkylidene diarylene moiety.

For example, it can be represented by general formula (5). In the formula, R6 and R7 are a hydrogen atom, an alkyl group (methyl, ethyl, globyl, isopropyl, butyl, t-butyl, pentyl, hexyl, octyl, nonyl, decyl), a substituted alkyl group (trifluoromethyl), an aryl group (phenyl, naphthyl), substituted aryl (tolyl, xylyl, ethylphenyl, flobylphenyl, amyl phenyl, chlorophenyl, dichlorophenyl, bromophenyl), frozen R6 and R7
can be combined to form cycloalkanes such as cyclohexyl or polycycloalkanes such as norbornyl.

R5 and R8 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen i atom (chloro, bromo, iodo), R2 is OSO II II
II-o-c-o-1-0-C-O-1-'c-o-
100 CH.

II II 1
- (! -0-0H2-1-0-0-CH-1O0 111 It is a group selected from the divalent residues consisting of.

Representative polymers are as follows.

Polymer 1 Example 1: Poly(4,4'-isopropylidene diphenylene-〇〇-1,4-cyclohexyl-dimethyl carbonate) 2: PoIJ (3,3'-ethylenedioxyphenylenethiocarbonate) 6: Poly (4,4'-Isofuropylidene diphenylene carbonate CO-terephthalate) 4: Poly(4
, 4'-isopropylidene diphenylene carbonate) 5: Poly(4,4'-isopropylidene phenylene thiocarponate) 6: HoI) (2,2-f tanbis-4-phenylene carbonate) ) 7: Poly(4,4'-isofuropylidene diphenylene carbonate block ethylene oxide) 8: Poly(4,4'-isofuropylidene diphenylene carbonate block tetramethylene oxide) 9: Bo') ('+”-isopropylidene bis(2-
methylphenylene)-carbonate] Polymer & flJ lo: Poly(4,4'-isofuroylidenephenylene-co-1,4-phenylene carbonate) 11:
Poly(4,4'-isopropylidene diphenylene-c
o-1,3-phenylene carbonate) 12: poly(4,4'-isopropylidenediphenylene-co-
4,4'-diphenylene carbonate) 13: Poly(4,4'-isofuropylidene diphenylene/-co-4,4-oxydiphenylene carbonate) 14: Poly(4,4'-isofuropylidene carbonate) 15: Poly(4,4'-isopropylidene diphenylene-co-4,4'-ethylene diphenylene carbonate) 16: Poly [4,4'-methylenebis(2-methylphenylene)carbonate] 17: Poly(i,1-(p-bromophenylethane)bis(4-phenylene).1carbonate) 18:
poly[4,4'-isopropylidene diphenylene-c
o-sulfonyl bis-(4-7 enylene) carbonate] Polymer high Example 19: Poly(4,4'-isopropylidene bis(2
-chlorophenylene)-carbonate, ) 20: Poly(hexafluoroisofuropylidene di-4-phenylene carbonate) 21: Poly(4,4'-isopropylidene diphenylene-4,4'-isopropylidene dibenzoate) 22: Poly(4,4'-isopropylidene dibenzyl-4,4'-isopropylidene dipenzoate) 26
: Poly(2,2-(5-methylbutane)bis-4-
Phenylene carbonate] 24: Poly(2,2,-(ri,3-dimethylfurin)bis-4-phenylenecarbonate) 25: Poly(1,1-[1-(naphthyl)])bis-4-phenylenecarbo Poly(2,2-(4-methylpentane)bis-4-7enylene carbonate) These eutectic complexes are described, for example, in U.S. Pat. No. 3,684,502.
Australian Publication No. 87757/75. For example, the above-mentioned bicarbonate series compound and the above-mentioned polymer are dissolved in a halogenated hydrocarbon-containing solvent (dichloromethane), and this solution is mixed with a non-rodane-nonpolar solvent (hexane, octane, decane, etc.). , ligroin, toluene) can be injected to precipitate the eutectic complex.

The organic film of the present invention can be used for optical disc recording. For example, it is possible to use a recording medium in which the above-mentioned organic film 2 is formed on a substrate 1 as shown in FIG. Such an organic film 2 can be formed by vacuum deposition of the above-mentioned compound, or by applying a coating liquid containing a compound represented by the above-mentioned general formula (R) in a binder. When forming a film by
The above-mentioned compounds 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 esters such as nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, acetic acid, cellulose propionate, acetic acid, cellulose butyrate, and methyl cellulose. , cellulose ethers such as ethylcellulose, flobylcellulose, and methylcellulose, folystyrene, and Bo! J Vinyl resins such as vinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acecool, polyvinyl alcohol, polyvinylpyrrolidone, styrene-butadiene copolymer, styrene-acryloni) +7 / ni copolymer, styrene-butadiene-acrylonitrile copolymer, chloride Copolymer resins such as vinyl-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-6,3'-phenylene thiocarbonate), poly(4,4'-isopropylidene Poly(4゜4'-isopropylidene diphenylene carbonate), Poly(4,4'-5ee-butylidene diphenylene carbonate), Poly(4,4'-isopropylidene diphenylene carbonate) Polyarylate resins such as (carbonate-block-oxyethylene), polyamides, polyimides, epoxy resins, phenolic resins, polyolefins such as polyethylene, polypropylene, 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, methanol is used. , alcohols such as ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, N, N-
Amides such as dimethylformamide, N,N-dimethyl 7)amide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate, ethyl acetate, butyl acetate, Chloroform, methylene chloride, dichloroethylene.

Aliphatic halogenated hydrocarbons such as carbon tetrachloride and trichloroethylene, or benzene, toluene, xylene,
Aromatics such as refloin, monochlorobenzene, dichlorobenzene, etc. can be used.

Coating methods include dip coating, spray coating, spinner coating, bead coating,
This can be carried out using a coating method such as a Mayer bar coating method, a blade coating method, a roller coating method, or a curtain coating method.

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 film 2 is 1 to 90% by weight, preferably 20 to 70% by weight.
It is. However, 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, phenol resin, epoxy resin, polyamide, polyimide, glass, or metals can be used.

In addition, the present invention has a substrate 1 and an organic coating 2 as shown in FIG.
A reflective layer 6 can be provided between them. The reflective layer 6 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 with 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 the bit area, but will be absorbed in the non-pit area. Another method is to perform real-time writing with a laser beam of a first wavelength that is absorbed by the organic coating 2;
For readout, a laser beam of a second wavelength that is substantially transmitted through the organic coating 2 is used. The readout laser beam can respond to changes in the reflective layer caused by the different film thicknesses in the bit and non-pit areas.

The organic coating of the present invention can be used with argon laser (oscillation wavelength 488
nm), helium-neon laser (oscillation wavelength 63 nm), helium-neon laser (oscillation wavelength 63 nm)
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).
A method of recording by irradiation with a laser beam having an oscillation wavelength in the near-infrared region or a certain infrared region such as a laser having a wavelength above the above, particularly a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) 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.

charge generation layer to obtain sufficient absorbance.

In order to contain as much of the above-mentioned photoconductive compound as possible and shorten the range of the generated charge carriers, the thin film layer 1 has a thickness of, for example, 5 microns or less, preferably 0.01 micron to 1 micron. It is preferable to form a thin film layer having the following properties. This means that most of the incident light is absorbed by the charge generation layer, generating many charge carriers, and that the generated charge carriers are not deactivated by recombination or trapping (togging). This is due to the need to inject into the transport layer.

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 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 polyvinylpyrene.

Preferably, polyvinyl butyral, polyarylate (
polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, cellulone resin, urethane resin, epoxy resin, casein, polyvinyl alcohol, Examples include insulating resins such as polyvinylpyrrolidone. The amount of resin contained in the charge generation layer is preferably 80% by weight or less, preferably 40% by weight or less.

The solvent that dissolves these resins depends on the type of resin. Specific organic solvents include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, N, N-
Amides such as dimethylformamide and 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, chloroform, methylene chloride, and Aliphatic halogenated hydrocarbons such as chloroethylene, carbon tetrachloride, trichlorethylene, etc., or aromatics such as benzene, toluene, xylene, ligatoin, monochlorobenzene, dichlorobenzene, etc. can be used.

Coating methods include dip coating method, spray coating method, spinner coating method, peed coating method,
This can be carried out using a coating method such as a Mayer barcoding method, a blade coating method, a roller coating method, or a curtain coating method. For drying, it is preferable to dry to the touch at room temperature and then heat dry. Heat drying at a temperature of 30°C to 200°C 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.

A function in the charge generation layer that is electrically connected to the charge generation layer described above and capable of receiving and receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. have. 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. "1! Magnetic waves" mentioned here include γ-rays, X-rays,
It encompasses a broad definition of "light rays" that includes ultraviolet rays, visible light, -Wf-4 light rays, 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 trap each other, resulting in a decrease in sensitivity.

Charge transporting substances include electron transporting substances and hole transporting substances, and electron transporting substances include chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4.7-dolinitro-9-fluorenone,
2,4,5.7-tetranitro-9-fluorenone, 2
, 4.7-) Leetrow 9-dicyanomethylenefluorenone, 2.4,5.7-titranitroxanthone, 2
, 4.8-trinidrothioxanthone and other electron-withdrawing substances, and polymerized products of these electron-withdrawing substances.

Examples of hole-transporting substances include pyrene, N-ethylcarbasol, N-isopropylcarbasol, N-)thyl-N
-Phenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-6-methylidene-10-ethylphenoxazine, P-diethylaminobenzaldehyde-N, N-diphenylhydrazone, P-
Diethylaminobenzaldehyde N-α-naphthyl-
N-phenylhydrazone, P-pyrrolidinobenzaldehyde-N, N-diphenylhuman dicine, 1,5.3-
) Dimethylindolenine-ω-aldehyde-N,N-diphenylhydrazone, p-diethylbenzaldehyde-
Hydrazones such as 3-methylbenzthiazolinone-2-hydracy, 2,5-bis(p-diethylaminophenyl)-1,5,4-oxadiazole, 1-phenyl-5-(p-diethylaminostyryl) -5-(P-diethylaminophenyl)pyrazoline, 1-[quinolyl(
2)"1l-(P-diethylaminostyryl)-5-(
P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2))-3-(P-diethylaminostyryl)-
5-(P-diethylaminophenyl)pyrazoline, 1-
[6-Medoxybilidyl(2))-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline,)-[pyridyl(5)]-5-(P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[lepidi A=(2))-1
(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)hilazoline, 1-phenyl-3-(p-diethylaminostyryl)-4-methyl-5 -(P-diethylaminophenyl)pyrazoline, 1-phenyl-6-(α-
benzyl-P-diethylaminostyryl)-5-(F-
pyrazolines such as diethylaminophenyl)pyrazoline and spiropyrazoline, 2-(P-diethylaminostyryl)-6-dinithylaminobenzoxazole, 2-
Oxazole compounds such as (p-diethylaminophenyl)-4-(p-dimethylaminophenyl)-5-(2-chlorophenyl)oxazole, 2-(P-diethylaminostyryl)-6-dinithylaminopenzothiazole, etc. Thiazole compounds, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane, 1,1-bis(4-N,N-diethylamine-2-methylphenyl)butane, 1, 1,
2.2-te) Polyarylalkanes such as lakis(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.

Besides these organic charge transport substances, selenium.

Inorganic materials such as selenium-tellurium amorphous silicon and cadmium sulfide can also be used.

Further, these charge transport substances can be used alone or in combination of two or more.

Can be formed. Examples of resins that can be used as binders include acrylic resins and boria (relate).

Insulating resins such as polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber, or poly-N-vinylcarbazole, polyvinylanthracene, Mention may be made of organic photoconductive polymers such as polyvinylpyrene.

Since the charge transport layer has a limit in its ability to transport charge carriers, it cannot be made thicker than necessary. Generally it is 5 microns to 60 microns, with a preferred range of 8 microns to 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. Examples of substrates having a conductive layer include those in which the substrate itself is conductive;
For example, aluminum, aluminum alloy, copper, zinc, stainless steel.

vanadium, molybdenum, chromium, titanium, nickel,
It can be made using indium, gold, platinum, etc. In addition, aluminum, aluminum alloy, indium oxide,
Plastics (e.g. polyethylene, polypropylene, polyvinyl chloride,
(polyethylene terephthalate, acrylic resin, polyethylene fluoride, etc.), conductive particles (e.g. carbon black, steel particles, etc.) coated on plastic with a suitable binder, and substrates made of plastic or paper impregnated with conductive particles. or plastics containing conductive polymers.

A subbing layer having barrier and adhesive functions can also be provided between the conductive layer and the photosensitive layer. The subbing layer is casein,
Polyvinyl alcohol, nitrocellulose, ethylene-
Acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon 610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin,
The thickness of the undercoat layer that can be formed from aluminum oxide or the like is 0.1 micron to 5 micron.

Preferably, the thickness is between 0.5 micron and 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 1 of the charge transport layer must be positively charged, and after charging, When exposed to light, electrons generated in the charge generation layer are injected into the charge transport layer in the exposed area, and then reach the surface and neutralize the positive charge, resulting in attenuation of the surface potential and an electrostatic contrast between it and the unexposed area. arise.

A visible image can be obtained by developing the electrostatic latent image thus formed with a negatively charged toner. Either fix this directly, or transfer the toner image to paper or plastic film, etc.
It can be 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, developing method, and 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, and when exposed to light after charging, holes generated in the charge generation layer are injected into the charge transport layer in the exposed area. , which then reaches the surface and neutralizes the negative charges, resulting in attenuation of the surface potential and an electrostatic contrast between the surface potential and 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, the above-mentioned hydrazones,
Organic photoconductive substances such as pyrazolines, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, lJ phenylamine, poly-N-vinylcarbazoles, and inorganic photoconductive substances such as zinc oxide, cadmium sulfide, and selenium. The organic film may contain a compound represented by the above-mentioned general formula (1) as a sensitizer for the substance. This organic film is formed by coating the photoconductive substance and the above-mentioned compound together with a binder.
In another specific example, an organic film containing a compound of the general formula (Rideso) described above can be used as the photosensitive layer.

In any of the photoreceptors, the present invention contains at least one compound selected from the compounds represented by the general formula (1), and if necessary, pigments with different light absorptions are used in combination to improve the sensitivity of the photoreceptor. It is also possible to use a combination of two or more types of compounds represented by general formula (1), or to use them in combination with a charge-generating substance selected from known dyes and pigments, for the purpose of increasing the photoreceptor's performance or obtaining a panchromatic photoreceptor. It is possible.

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 sandwiching the above-mentioned organic film therebetween.

The organic film of the present invention can have significantly higher sensitivity in the wavelength range of 75 Q nm or more compared to conventional laser electrophotographic photoreceptors, and also has higher sensitivity than conventional optical disk recording materials. Moreover, it is possible to provide a sufficiently improved S/'N ratio. Furthermore, the compound used in the present invention has 7
Although it has an absorption peak at 50 nm or more, it has the advantage of being extremely stable against heat.

Hereinafter, the present invention will be explained according to examples.

Example 1 An aqueous solution of casein (11.2 g of casein, 1 g of 28% ammonia water, 222 m of water) was coated on an aluminum cylinder using a dip coating method, and dried to give a coating amount of 1.0.9/m2. A subbing layer was formed.

Next, 1 part by weight of the aforementioned compound A (5), 1 part by weight of butyral resin (Eslec BM-2, manufactured by Sekisui Chemical Co., Ltd.), and 30 parts by weight of inpropyl alcohol were dispersed for 4 hours using a ball mill disperser.

A dispersion of the above was first formed and coated on the subbing layer by a dip coating method, and dried to form a charge generating layer. The film thickness at this time was 0.3μ.

Next, 1 part by weight of P-diethylaminobenzaldehyde-N-phenyl-N-α-naphthylhydrasone, 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 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.

Corona discharge at -5 V was applied to the photoreceptor thus prepared. The surface potential at this time was measured (initial potential Vo).

Furthermore, the surface potential of this photoreceptor was measured after it was left in a dark place for 5 seconds (dark decay Vs). Sensitivity was evaluated by measuring the amount of exposure ('F-% microjoules/d2) required to dark decay and attenuate the post-mortem potential v5 to %. At this time, a gallium, aluminum/arsenic semiconductor laser (oscillation wavelength: 780 nm) was used as a light source. These results were as follows.

v(1: -590 volts v5: -5so volts B,: 1.2f icloj/I//cm2 Example 2~
16 In place of the compound in compound layer (5) used in Example 1, each of the compounds shown in Table 1 was used.A photoreceptor was prepared in exactly the same manner as in Example 1, and this photoreceptor was We measured the characteristics of These results are shown in Table 1.

Table 1 2 Compound layer (1) -570-5401,5
6 compound layer (2) -580-5401,314 compound layer (5), -580-5501,65 compound layer (4) -590-5701,56 compound layer (+5
) -570-5501,87 Compound 4 (7)
-550-5301,48 compound 4(8) -5
80-ssoo, 99 compound layer (13) -5
70-5401; 110 compound layer (14)
-560-5301,711 Compound (15) -5
70-5361,412 compound layer (16) -570
-5401,51! I compound layer (17) -
560-530,0,9 Example The above-mentioned exemplified compound Vo (
V) Vs (v)F' M (microjoule yv/
cm2)14 Compound layer (18) -570-
5500,815 compound layer (19) -580-54
01,516 compound/16(2o) -570-54
01, 2 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, 2,4.7-) dinitro-9-fluorenone 5
II and poly-N-vinylcarbazole (number average molecular weight 3
00,00.0 ) to form a charge transfer complex compound by dissolving 5g in 70g of tetrahydrofuran. This charge transfer complex compound and 1 g of the compound of the aforementioned compound layer (5) were added to a solution in which 5 g of polyester resin (manufactured by Pylon Toyobo) was dissolved in 70 d of tetrahydrofuran, and dispersed therein.・Place this dispersion on the undercoat layer to a film thickness of 12 microns after drying.
It was applied and dried.

The charging characteristics of the photoreceptor prepared by Kouji Zuko were measured in the same manner as in Example 1. The results of this were as follows.

However, the charging polarity was set to ■.

V (1: Q: +530 volts Vs: 0490 volts EM: 4.2 microunits/unit 2 Example 18 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 A(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, a solution prepared by dissolving pyrazoline compound 5y of the structural formula and 5 g of polyarylate resin (condensation product of bisphenol A and terephthalic acid-isophthalic acid) in 70 ml of tetrahydrofuran was placed on the charge generation layer to give a film thickness after drying. It was applied to a thickness of 10 microns and dried to form a charge transport layer.

The charging characteristics of the photoreceptor thus prepared were measured in the same manner as in Example 1. The results of this were as follows.

vo: -540 volts Vs: -510 volts F, %: 2.4 microjoules/32 As can be seen from the above-mentioned examples, the electrophotographic photoreceptor of the present invention has a voltage of 750 volts.
It has remarkable high sensitivity characteristics in the wavelength range of nm or more, and has excellent charging characteristics such as initial potential and dark reduction quality.

Example 19 =) Cellulose solution (manufactured by Daicel Chemical Industries, Ltd.; Ohares Lacquer 12 parts by weight of a 25% by weight dinitrocellulose solution in methyl ethyl ketone, the above-mentioned compound* (5)
6 parts by weight of the compound and 70 parts by weight of methyl ethyl ketone were mixed and sufficiently dispersed. This dispersion was coated on an aluminized glass plate by dip coating and dried to obtain a recording layer of 0.6 g/m2.

The optical disc recording medium thus created was mounted on a turntable, and the turntable was turned on with a motor f1800 rpm.
Recording was performed by irradiating the surface of the recording layer in a track shape with a 5 mW and 8 MHz gallium-aluminum-arsenide semiconductor laser (oscillation wavelength: 780 nm) focused to a spot size of 1.0 microns while giving a rotation of .

When the surface of this recorded optical disc was observed using a scanning electron microscope, clear bits were observed. Furthermore, when a low-output gallium-aluminum-arsenide semiconductor laser was incident on this optical disk and one reflected light was detected, a waveform with a sufficient S/'N ratio was obtained.

Example 20 500 μm of the compound of the compound layer (7) described above was added to molybdenum powder for vapor deposition, and the mixture was evacuated to less than 1×10 HF, and then vapor-deposited on an aluminum-deposited glass plate. During the deposition, the heater was controlled so that the pressure in the vacuum chamber did not rise above 10@-5 mHf, and a 0.2 micron thick deposited film was formed.

When information was stored on the produced optical disc recording medium in the same manner as in Example 1, clear bits similar to those in Example 19 were observed, and information was reproduced in the same manner as in Example 19. At this time, a waveform with a sufficient -fi S/N ratio was observed.

Example 21 The above-mentioned compound (5) was vapor-deposited on an aluminum-deposited glass plate in the same manner as in Example 2o to prepare an optical disc recording medium having a recording layer of 0.2 microns.

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/)J ratio was observed. Further, when the surface of the recording layer after information was written was observed with a scanning electron microscope, clear bits were found to have been formed.

Example 22 The above-mentioned compound 4 (13) was vapor-deposited on an aluminum-deposited glass plate in the same manner as in Example 20 to produce an optical disc recording medium having a recording layer of 0.2 microns.

A waveform with a sufficient A ratio was observed, indicating that information was recorded on this optical disc recording medium in the same manner as in Example 19 and then reproduced. Furthermore, when the surface of the recording layer on which information had been written was observed using a scanning electron microscope, clear bits were found to have been formed.

Example 23 The above-mentioned compound A (15) was vapor-deposited on an aluminum-deposited glass plate in the same manner as in Example 20 to produce an optical disk recording medium having a recording layer of 0.2 microns.

When information was stored on this optical disk recording medium in the same manner as in Example 19 and then reproduced, a waveform with sufficient s and M ratios was observed. Further, when the surface of the recording layer after information was written was observed with a scanning electron microscope, clear bits were found to have been formed.

Example 24 Compound 2.0I of the exemplified compound 4 (5) and poly(
4,4'-isopropylidene diphenylene carbonate)
) 2.0# was dissolved in dichloromethane 100° while stirring. 50 g of toluene was added to this solution to precipitate it, and after injecting enough dichloromethane to redissolve the precipitate, 500 g of n-hexane was injected with stirring, and purple-blue crystals were precipitated. After distributing this crystal from house to house, it is recrystallized repeatedly.

Compound A (5) using this crystal in Example 19 above
An optical disk recording medium was prepared in exactly the same manner as in Example 19, except that the compound was used in place of the following compound, and then information recording and reproduction were repeated, and the same results were obtained.

Example 25 Example 1 except that the eutectic complex prepared in Example 24 was used in place of compound 4 (5) used in Example 1.
A photoreceptor was prepared in exactly the same manner as described above, and the characteristics of this photoreceptor were measured. The results at this time were as follows.

Vn: -590 volts V5: -550 volts To E: 0.8 microjoules/trust 2

[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. 6 is an explanatory view showing an embodiment of this optical disk recording medium. FIG. 4 is an explanatory diagram showing an infrared absorption spectrum of compound rot (7). 1...Substrate 2...Organic coating 3...Reflection layer 4...Laser beam 5...Bit □

Claims (1)

[Scope of Claims] An organic film characterized by containing a compound represented by the following general formula (1). General formula (1) X and X2 represent a sulfur atom, an oxygen atom or a selenium atom. 2. are optionally substituted pyrylium, thiopyrylium, selenapyrylium, benzopyrylium,
z2 represents the atomic group necessary to complete benzothiopyrylium, benzoselenapyrylium, naphthopyryllium, naphthothiopyrylium or naphthoselenapyrylium,
The atomic groups necessary to complete biran, thiobilane, selenapyran, benzobylane, benzothiobilane, benzoselenabilane, naphthopyran, naphthothiobilane, or naphthoselenabilane, which may each be substituted, are shown. R,,
R2, R, and R4 are a hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted styryl group, a substituted or unsubstituted 4-phenyl-1,5-butadienyl group, or a substituted Or it represents an unsubstituted heterocyclic group. Further, R1 and R2 may form a substituted or unsubstituted benzene ring, and R5 and R4 may form a substituted or unsubstituted benzene ring. m and n are 1 or 2. )