JPS59146063A - Organic film - Google Patents

Abstract

PURPOSE:To obtain an org. film which has an absorption band on a long wavelength side, is stable to heat, and is useful as a recording film of an optical disk by using a specific cyanine compd. CONSTITUTION:The cyanine compd. (e.g.; the formula II) expressed by formula I [Z1 is an atom group required for forming a nitrogenous heterocycle; Z2 is an atom group for forming (thia)pyrane, selenapyrane, benzo(thia)pyrane, naphtoselenapyrane, etc.; X is S, O, Se; Z3 is a bivalent hydrocarbon group necessary for forming 5-, 6-membered rings; R1 is H, alkyl; R2, R3 and H, halogen, a residual univalent org. group; R4 is H, halogen; A<-> is anion; m, n are 0, 1; l is 1, 2] is used. More specifically, an org. film of about <=10mu film thickness is formed by vacuum deposition of the above-mentioned cyanine compd. (may be coated together with a binder) on a substrate, by which the optical disc adapted to writing by using a semiconductor laser having about >=750nm wavelength is formed.

Description

[Detailed description of the invention]

The present invention relates to an organic film 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 film that can be applied to electrophotographic photosensitive coatings for printers, optical fibers that can be embedded and reproduced by semiconductor lasers, infrared cut filters, and the like. The Ichishikosha9 printer, which uses all lasers, modulates the laser using electrical signals corresponding to the information on both images, and then uses a galvano mirror or the like to combine the modulated laser with a sensor. After nine scans to form a static latent image,
By sequentially performing toner development and transfer, a desired reproduced image can be formed. Used in this case
Lasers that used to be used are generally helium-cadmium (oscillation wavelength: 4416 nn) or helium-neon (oscillation wavelength:
632.8 (formerly n)). Therefore, the photoreceptor used for such a light source is 6
It may be spectrally sensitized at 50 nm, % jf i, for example, polyvinyl carbazole and trinitrofluor I.
A charge transfer complex with /non is used as a photosensitive layer, a tellurium evaporated layer sensitized by selenium is used as a photoreceptor, and a selenium evaporated layer is formed on a conductive layer as a charge transport layer.
, those using a photosensitive layer formed by forming selenium-delul vapor on this selenium vapor-deposited layer, those using cadmium sulfide spectrally sensitized with a sensitizing dye, and those containing an organic pigment. A photosensitive layer is known in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer, and the photosensitive wavelength range of the photosensitive layer is sensitized on the wavelength side. On the other hand, the edge coating used in the amber disk technology consists of optically detectable small (e.g. H'', approximately 1/L) bits in the form of a spiral or circular track: L. to convey density information. To write information on such a disk, a focused laser beam is run on the surface of the laser-sensitive layer, and only the surface irradiated with this laser beam forms a pill. , this bit is formed entirely in the form of a helix or a circular track.
It is possible to form a functional bit. For example, in a heat mode recording method, the laser sensitive layer absorbs thermal energy and forms small bits at that location by evaporation or melting. In another heat mode recording method, a bit is formed at that location by the absorbed VC of the irradiated laser energy A-1, which increases the optical VCC detectability difference. Information recorded on this optical disk is detected by scanning a laser along a track (-7) and reading optical changes in areas where bits are formed and areas where no bits are formed. The energy scanned along the track and reflected by the disk is monitored by a photodetector. When no bits are being formed, the output LL of the photodetector is reduced, while when pits are being formed, the laser beam is The output of the photodetector increases due to sufficient reflection from the reflective surface of the optical disk.Up until now, recording media used for such optical discs have been made of metal thin films such as aluminum evaporated films, bismuth thin films, tellurium oxide thin films, and chalcogenide-based amorphous glass films. In recent years, semiconductor lasers have been developed that are compact, low-cost, and capable of direct modulation.
The excavation wavelength of this laser often has a wavelength of 750 nm or more. Therefore, when such a semiconductor laser is used for recording and/or reproduction, the absorption characteristics of the laser-sensitive coating have an absorption peak on the long wavelength side (generally 750 nm to 8!).
50nrn). However, conventional laser-sensitive coatings, especially coatings formed mainly of inorganic materials, have a high reflectance to laser light, resulting in a low laser utilization rate and the disadvantage that high sensitivity characteristics cannot be obtained. (7) The sensitive wavelength range is 75
Qn+η or higher means that the layer of laser sensitive coating (1
It has drawbacks such as complicating the q-formation, and fading of the color when the sensitizing dye used is repeatedly subjected to 2-band IPt, -1 light exposure, especially in the case of exposure removal for electrophotography. are doing. For this reason, in recent years, organic wave films have been proposed that exhibit quality sensitivity characteristics for light with wavelengths of 750 mm and above. For example, United States 11
Ke se a ch mountain 5c7 Fosure J
Bi IJ IJ disclosed in 20517 (1,981,5)
Umu thread dye and l' J, Vac, Sce. Techno7? , , 18(1), Jan, /F
'eb, 1,981. , PIO5-PIO9 contain an organic coating containing a square aryllium dye disclosed in 75
It is known to be sensitive to lasers of Qnm or larger. E7 However, in general, organic compounds have absorption characteristics that are unstable in the longer wavelength region, and are easily decomposed by a slight temperature rise. However, the current situation is that not all isocovers have been developed that are fully satisfactory in terms of practicality. Accordingly, a first object of the present invention is to provide a new and useful organic coating. The object of the present invention is the long wavelength side, especially 750n
An object of the present invention is to provide an organic film having an absorption band above +'n. 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 preparation film 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 electrons to Jj, fi that has high sensitivity characteristics in a wavelength range of 750 nm or more. A sixth object of the present invention is to provide an optical tisf recording film. A seventh object of the present invention is to provide an optical disk recording film that is highly sensitive in the wavelength range of 750 nm or more and has a sufficient S/N ratio. The first objective of the present invention is achieved by an organic film containing a compound represented by the following general formula (1). General formula (1) Zl is II9. Hou size/ζ is unsubstituted 5〆 element 1M element j
i (a, for example, thiazole series nuclei (e.g. deazole, 4-methylthiazole, 4-phenylno-azole, 5-methylthiazole, 5-phenylthi]'zole, 4,5-dimethylthiazole, 4,5-diphenylthiazole) , 4-(2-chenyl)-thiazole, etc.),
Benzothiazole series nuclei (e.g. benzothiazole, 5-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5.6-)methylbenzodeazole, 5-bromobenzothiazole,
5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5,6-simethoxybenzothiazole, 5,6-cyoxymethylenebenzothiazole, 5-hydroxybenzothiazole,
6-hydroxybenzothiazole, 4,5,6,7-titrahydrobenzothiazole, etc.), naphthothiazole series nuclei (e.g. naphthoC2,1-d)) thiazole,
naphtho[1,2-a]thiazole, 5-methoxynaphtho[1,2-d)thiazole, 5-ethoxynaphtho[X,
2-a) Thitsuzole, 8-methoxynaphtho[2,1-
cl) Thiazole, 7-methoxynaphtho[2,i-d
]thiazole), thionafdene C7,6-d]thiazole series nuclei (e.g. 7-medoxythionaphthene [
7,6-(Ml chain), oxazole series nuclei (e.g. 4-methyloxazole, 5-methyloxazole)
f seanod, 4-phenyloxazole, 4.5-
Sifuenino L/oxazole, 4-ethyloxazole
) I7, 1,5-dimethyloxazole, 5-phenyl side → nozole), benzoxazole-based keratinium (e.g. benzoxazole, 5-chlorobenzo)
Kituzole, 5-methylbenzoxazole, 5-phenylbenzothiazole, 6-methylbenzoxazole, 5,6-dimethylbenzomexazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzothia sol, 6-hydro (1-xybenzogisazole, etc.), nuclei of the twoft oxazole series (1+11, such as natu C2,1-(1) oxazole, naph l-[1,2-tJ) oxazole, etc.],
Nuclei of the selenazole series (e.g. 4-methylselenazole/l', 4-phenylselenazole Ayfx), M of the benzoselenazole series (e.g. A-&j, '''n゛)'7-lenazole, 5-chlorobenzoselenium Sol, 5-methylbenzoselenazole, 5.6-dimethylbenzoselenazole, 5-methoxybenzoselenazole, 5-methyl-6-medoxybenzose(/nazole, 5.6-cyoxymethylenebenzoselenazole, 5- hydrogylbenzoselenazole, 4,5,6,7-tetoxyhydrobenzoselenazole, etc.), naphthocenazole series nuclei (e.g. nano l-(2,1-d ) selenazole, naphtho c
l, 2-d3 selenazole), thiazoline series nuclei (1
;IJ L f Yonazoli/, 4-methylthiazoline,
4-hydroxymethyl-4-methylthiazoline, 1
, 4-bis-hydroxymethylthiazoline, etc.), nuclei of the Saigipurine series (1+lI is ochryzoline), nuclei of the selenazoline series (1('II is selenozoline)
, 2-quinoline series nuclei (e.g. quinoline, 6-methylquinoline, 6-chloroquinoline, 6-methoxyquinoline, 6-nitoxyquinoline, 6-hydroxyquinoline),
4-quinoline series nuclei (e.g. quinoline, (j-methoxyquinoline, 7-methylquinoline, 8-methylquinoline), 1-isoquinoline series nuclei (e.g. inquinoline,
3.4-dihydroisoquinoline), 3-isoquinoline series nuclei (e.g. isoquinoline), 3.3-dialkylindolenine series nuclei (e.g. 3,3-dimethylindolenine, 3.;randimethyl-5- Chloroi Deaf L/Nin, 3.: U, 5-
pyridine series nuclei (1<1) e.g. pyridine, 5-methylpyridine), benzimidazole series nuclei (e.g. l-ethyl-5,6- Dichloropenzoimidazole, ■-Human Kogiethyl-5,+3-dichlorobenzimidazole, 1-ethyl-5-chloropenzoimidazole, 1-ethyl-5,6-dibromobenzimidazole, 1-ethyl-5-phenyl Benzimidazole, ■-ethyl-5-fluorobenzimidazole, 1-ethyl-5-/anobenzimidazole, ]-
(]β-ethyl-13-cyanobenzimidazole, ■-ethyl-5-[l1l-(j-, cyanobenzimidazole, ■-ethyl-5-fluoro-6
-anobenzimidazole, 1-ethyl-5-acylbenzimidazole, l-ethyl-5-carboxybenzimidazole, 1-ethyl-5-ethoxycarbonylbenzimidazole, ■=ethyl-5-sulfamidazole ruhensoimitasole, l-ethyl-5-N-ethylsulfamylbenzimidazole, 1-ethyl-s,
6- Cyfluoropensoimitasol, l-ethyl-5
, 6-dicyazbenzimitazole, I-ethyl-5-
Ethylsulfonylbenzimidazole, l-ethyl-5
-Mefsulfonylhensoimitasol, 1-ethyl-
5-Triple O[1-methylbenzimidazole, l-f-/l/-5-t') fluoromethylsulfonylbenzo-imidazole, ■-ethyl-5-drifluoromethylsulfinylbenzimitazole fxt) Represents a group of nonmetallic atoms necessary to form a metal. Z2(,;↓, optionally substituted biran, thiobilane,
Selenaviran, benzobilan, benzothioviran, penzoselenahiran, natsutoviran, natsutothioviran (
l indicates the atomic group necessary to form naphthoselenapyranwo, 11. We can specifically list things other than the hydrogen atoms shown in 1t2fu and 1mo in the lower part. Formation I" Two sets of hydrocarbon groups (-CH,, -C)-
42-, etc.) r indicates 7, this 7 these five members or Q: j, 5
j, i iVi &-, j: May be fused with a he7zene ring, canotalene ring, etc. it, tt, hydrogen atom or (・J: argyl group (for example, methyl, ethyl, n-7′-pyl, 15O-furovir, 1]-butyl, ・hex-butyl, 1so-butyl, 1
-butyl, +1-amyl, t-amyl, 11-'\gizol, n-ofnal, t-octyl, etc.) and further add other alkyl groups, such as i! rt Hou alkyl group (Ni-1d, 2-hydroxyethyl, 3-d fJ
xizolovir, 4-hydroxybutyl, 22-acetogyethyl, carboxymethyl, 2-carboxyethyl,
3-carboxypropyl 2-sulfoethyl, 3-sulfobutyl, 4-sulfobutyl, 3-sulfonyl toclopyl, 4-sulfatephthyl, N-(methylsulfonyl)-halhamylmethyl, 3-(acetylsulfamyl)
Furovir, 4-(acetylsulfamyl)butyl, etc.)
, cyclic alkyl group (e.g., cyclohegycyl, etc.), allyl group ((C11,=CH-CH,Q aralgyl group (e.g., benzyl, noenethyl, α-naphthylmethyl, β-nanothylmethyl, etc.), substituted aralgyl, 14S
? (eg, carboxybenzyl, sulfobenzyl, hydroxybutyl). 1 et al. and l also. III:, each (a) hydrogen 1. Gt atom, (h)...Rogen atom: chlorine atom, dog atom, iodine atom, or monovalent organic residue, such as (C) an argyl group, especially a carbon atom number of 1 to □ 1.
Argyl group of 5: 191J, for example, methyl, ethyl, propyl, isobutyl, butyl, 1-butyno-1, amyl, iso-amyl, -xyl, octyl, nonyl, dodecyl (d) Alkoxy group: for example, Methoxy, - ``toxy, propoxy, butoxy, amyloxy, hexoxy,
Octoxy (e) 71J- group: phenyl, α-#7f, β
-naphthyl (f) +1・'4 aryl group nitrile, gysilyl, biphenyl, ethylphenyl, methoxyphenyl,
: [: l- xy2-dynyl, ``amyloxyphenyl, dimethoxyphenyl, shed=v□ymph J-2,
, hydroquinphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyfuromonofyl, di-
r+noenyl, diethylami/phenyl, dimethyl γ
Minophenyl, cybenzyl-aminenoenyl (g) Styryl (11) Substituted styryl group: methoxystyryl, dimethoxystyryl, ethoxystyryl, diethoxystyryl, dimethylaminostyryl, diethyl-rminostyryl (i) + a: substituted or unIIQI! l! Heterocyclic group of 8: For example, 3-carbazolyl, 9-,-methyl-3-carbazolyl, 9-ethyl-3-nonolhazolyl, 9-1 can be used to form a flubazolyl ring. 1 represents a hydrogen atom or a halogen atom (eg, a chlorine atom, a bromine atom, an iodine atom). ■ A is chloride ion, bromide ion, iodide II ion, perchlorate ion, benzenesulfonate ion,
It does not exist when it contains P-toluenesulfonate ion, methyl sulfate ion, or ethyl sulfate ion. In and n represent 0 or l, l is 0, ■ or 2
shows. The compound of the general formula (1) forms a resonant body with the compound represented by the following general formula (2), and the present invention includes such a resonator. General formula (2) (In the formula, Otsu1 to Z3, R, -R4, X, A", l
, m J, □ and 11 have the same meanings as above. However, Z, Bapyl, thiopyrylium, selenapyrilium, benzobyrylium, penzothymebilirium A, benzoselenapyrylium, natutopyrylium, natuthiopyrylium or nandoselenapyrilium. IJ IJ is expressed in the salt series. ) Next, the ananine compound represented by the general formula (1)/f i
Compound Examples (4) These 7' anine compounds can be synthesized by the method described in US Pat. No. 2.73/1, No. 4100. In general formula (1), /=O compound is represented by general formula (3)
and the compound of general formula (3) (where Z, , Z3.1(,,,1,(4,Aet,
・N IrJ, represents the same thing as the previous 4-C definition.) General formula (4) or - official (5), and a compound whose size is Δ is expressed by the general formula (,1). 1--7, -11, it, , -9Sgo22℃cc, ,x(j:'A("1 ■ et al. 1%. (In the formula Z2.X, It, , R3, A'' and ni &:j, Mif description to see fixed page/, - thing 1
100 J! Hep's stuff, 1 too, I/-1, no 1-
-rlkyl group such as rusen, ethyl J, Q, etc. ゎ4-8)
General formula (5) % formula % (same as %), represents the . ) By heating in a suitable solvent (l 41 (-曾7.ru. ), general formula (() in general formula (6), ---Z2---5, (in the formula Z2. it2. R, , X, A'' b f
Him represents the same thing as defined above, and horse is a tonoacyl group such as an acetyl group, zolovanyl group, benzoyl group, and f(, is a phenyl group, toruyl group, etc.). represents a phenyl group. k represents 1 or 2) A4 can be obtained by heating the compound shown above in a suitable solvent. These compounds represented by the general formula (1) or t and the general formula (2) can form a eutectic complex with the claw coalescence, and 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, it may be an 11-layer recording medium in which the above-mentioned organic film Q2 is formed on a substrate 1 as shown in FIG. Such a coating film 2 (7i, the above-mentioned cyanine compound can be formed by A micro-steaming, and a coating solution containing the above-mentioned cyanine compound/rostol in the mata binder can be applied). (It is also possible to form 6 or 2 pieces. Coating (
Therefore, when forming a film, the above-mentioned compound may be contained in the binder in a fractional state, or may be contained in an amorphous state. Drop-compatible binders (7) can be selected from a wide range of resins, including nitrocellulose, phosphor-rt cellulose, cellulose sulfate, auto-tE + hirulose, prepropionic cellulose, cellulose acetate, myristic acid. Cellulose, valmitinated cellulose, cellulose ethers such as vinegar e and cellulose globionic acid X, vinegar M and cellulose butyrate, methyl cellulose, ethyl cellulose,)
t1 vinyl cellulose, cellulose ethers of methylcellulose, polystyrene, ka-vinyl,
Vinyl compounds such as polyvinyl vinegar, polyvinyl butyral, polyvinyl gamma cetal, polyvinyl alcohol, polyvinylpyrrolidone, -styrene/butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylic rJ, ==
Copolymer resins such as vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic, polymethacrylic acid, polyacrylamide, polyacrylonitrile, etc. acrylic resins, polyesters such as polyethylene derephthalate, poly(4,4-isopropylidene diphenylene-co-1,
4-cyclohexylidene dimethylene carbonate), poly(ethylenedioxy-3,3'-phene; t1/thiocarbonate), poly(4,4'-ingrohylidene diphenylene carbonate) rate), poly(
4,4'-isozolopylidene diphenylene carbonate), poly(4,4,'--Sec-butylidene diphenylene carbonate), poly(4,4'-isopropylidene diphenylene carbonate), poly(4,4'-isopropylidene diphenylene carbonate) Phenylene carpone +---Block-A
Polyarylate %J Fats, Aru, I (-) Long aryamides, polyimides, Evogine sensin, phenolics [fats, white, polyethylene, polypropylene]

【two. It can be used for whitening, whitening, etc., such as polyethylene, chlorinated polyethylene 7T, etc. [Organic foil cutting that can be used for festivals J41] When applying binder A (class 11 or previous +% compound) to binder ``1 bow C included'', fractional 1δI and -] or i:l non-product'h-like j?smell and 1'crab'2 are different, but -WZ f is used for alcohol such as methanol, ethanol, isozolopanol, '7 Chthone, mecal ethyl ketone, cyclohexanone, N,
N--dimer f-form 11 amide, i4. N-dimenaracetamide, etc. -rmido river, dimer f-rusulbogicide, etc.
Ethers such as Noran', Cyogylline, ethylene glycol 11 methyl ether, -V-sulfurs such as methyl acetate, ethyl acetate, and butyl acetate, gloroporum, methylone tetrachloride, and cyclo-L1 aliphatic halogenated stratified hydrogens such as carbon tetrachloride, trichlorethylene, benzene, toluene, cylene,
Aromatic groups J, q, etc. such as ligroin, monochlorobenzene, dichlorobenzene, etc. can be used. Coating & J: Can be carried out using coating methods such as i-2 dip coving method, spray coating method, spinner coating method, bead coating method, Mayer bar coating method, blade coating method, roller coating method, curtain coating method, etc. can. When forming the 41 film 2 together with the binder, the cyaninated material 11 is
-, rJCK. Sir, 41 aircraft membrane rupture 2 drying I1
The thickness (or vapor thickness) is less than 10 ζ microns, preferably less than 2 microns. 17; As IJil! Plastics such as Zli2, polyester, acrylic resin, polyolefin resin, phenol resin, epoxy resin, polyamide, polyimide, glass, or gold L (Ii class) can be used. As shown in Figure 2, a reflective layer 3 is provided between the substrate 1 and the organic coating 20. It can be combined with a vapor-deposited layer of gold maple or a non-laminated layer.
A hit 5 can be formed by the irradiation flC of the ζ/ζ laser likelihood line 4. bit 5 depth organic al I
If the llf and lI thickness of Iψ2 are made the same, the pit gt
It is possible to increase the reflectance by 1-, - in the range <>. +tW protrusion [1 when 7. The growth of the laser beam and the laser beam used for incorporation is shown in Figure 1. However, using a small laser beam with a small intensity fj, fj, tY; However, the non-pit region (〆coi-rfd is absorbed.-mafC) Another method is to perform real-time pre-implantation with the first laser beam absorbed by the organic film 2, The method of reading (-7) is to use a laser beam between the second waves that substantially transmits through the coating 2; It is possible to respond to the change in the reflection phase caused by the change in reflection phase.
880m), helium-neon laser (oscillation i(+
633 nm), recording by gas radar irradiation such as helium-cadmium laser (oscillation wavelength 4420 m) is also a technique, but preferably 12 < is 750 nm.
Lasers with wavelengths longer than nm;
The near-infrared or infrared region (by irradiation with a laser beam with a wavelength of
l, the aforementioned laser)'f: #i! can be used. This process, loading and reading can be performed with a laser of a different wavelength, or can be performed with a laser of a different wavelength. Another specific example of Mikagemei is 1, which can be used as a photosensitive layer for electronic photography and 9 bodies. However, such a photosensitive layer can be functionally separated into a charge generation layer and a charge transport layer.
! 1. It can also be applied to the photoreceptor in one layer and one layer. city; load generation layer &t, (-' minute absorption-1c: YN-
'＋! +2) In order to contain as many of the above-mentioned cyanide compounds as possible, and to keep the range of the generated mold surface carriers as short as possible, a thin film layer, e.g. It is preferable to use a thin film layer with a thickness of 0.01 to 1 micron. This thing C
2. The part of the incident light +44H is 'fli', which is absorbed by the redundant layer and generates a lot of Tl (and 5i' carriers). Recombining N・capturing (trap)(・without losing (predicting) °'small, I; The green layer can be formed by diluting the Cyan compound of A'lt'ls with a suitable f(binder Q) for one minute and coating it on the substrate 1-, and A vapor-deposited film can be formed by vacuum deposition ν 200 and V 6). 1j By using the vine binder and L7 used when forming the evaporated film from 6 wide'-c' ???
Eyes! 1fjj, j4-insulating 4+14 resins, DOU/V poly-N-biyl; organic photoconductive materials such as lucarbazole, polyvinylanthracene and polyvinylpyrene;
You can choose from a variety of polymers. Good size, polyvinyl butyral, polyester (bisphenol, A/A
and phthalic acid condensation polymers, polycarbonate-1, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, Boribi J
Niruhinojin, cellulose resin, methane fat,
Examples include insulating resins such as ebony resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. Charge ``V in the Ryusei layer (-411.1 fat ti
, below 80%μ, preferably i):l 40140i
Over ゛%゛ are monks. The Z1 solvent that dissolves these resins varies depending on the type of resin, and the Z1 solvent that dissolves the above-mentioned charge transport layer and F-side layer [2]
It is preferable to select from those that do not have any. Specific organic solvents include methanol, ethanol, isopro-(
r-nodocols such as Mer, ketones such as acetone, methinodoethyl ketone, cyclohexanone, 14, N,
N-dimethylformamide, N,N-dimethylani7adamide, other amides, sulfoxides such as dimethylsulfoginde, ethers such as tetrahydrolane, dioquinane, ethylene glycol monomethyl ether, If'lE+ ``esters such as methyl and acetic acid, chloroformo 1, methylene, dichloroethylene, carbon tetrachloride) 17 aliphatic halogenated hydrocarbons such as ethylene, benzene, etc. , Toluene, Kinshimen, Ligroin, Monochlorobenzene, Dichlorobenzene I Depends on which aromatic group it is in.
-Niryo-teing method, Subinner Koj-I/G θ2,
Bead coach ink rll ha Meyer Burny 1-D/G method, Pt node coating method, [''-Rah-J
-i-ing method, Cunydenkote-Ingua f,
H can be used in the 21-ting method. φ: Drying (1, Murosho V (after drying to the touch, heat drying)
I don't like the h method. Power IJ heat dry smoke, 30℃ ~ 200℃
'C's 1 island and 5 minutes to 2 hours of Han 1 river till',
It can be carried out between ', static + I-1 r/, i, and under ventilation. It is electrically connected to the charge generation layer, and receives and takes charge carriers transferred from the charge generation layer in the presence of an electric field.
It has the ability to transport these 'heavy carriers' to the surface. At this time, this charge transport layer may be layered on top of the charge generation layer or may be layered on the bottom of the layer. [tl]]7 cities, freight transport bureaus
It is desirable that the material is layered on the soil of the load generation layer. The substance that transports all of the charge carriers in the charge transport layer (hereinafter simply referred to as i, charge transport material) is the above-mentioned charge carrier (Wr
Preferably, the material 9 is also substantially insensitive to the range of electromagnetic waves to which the living layer is sensitive. The "electromagnetic waves" referred to here are r
Includes a broad definition of "rays" that includes rays, X-rays, ultraviolet rays, ``rays'', near-infrared rays, infrared rays, far-infrared rays, etc. When the photosensitive wavelength range of the charge transport layer coincides with or overlaps that of charge generation j@, generation occurs in both]-
However, the charge carriers trap each other, resulting in a decrease in sensitivity. In the charge transport substance and E~, there is a ``child transport'' with the subject substance (IF), and there is an electron transport substance t4, chrono-1-anyl, bromoanil, detracyanoethylene,
Tetracyanoquinodimethane, 2,4.7-dolinitro-9-flumerenone, 2.4.5.7-tetranitro-
9-Fluorenone, 2.4.7-) Rinitro! (-dicyanomethy1/fluorenone, 2, 4., 5.7-titranitroxantrinitrodiogizanton TI of tatami)
, polymerization of child-attracting substances and these electron-attracting substances 1-7
There is Rikomo's residence. +JE pore-transporting substances tEi include pyrene, N-ethylcarbazole, N-inzolovyl-ruvasol, N-tanal-N-phenylhydrazino-3-methylythene-9
-Ethylcarbazole, N,N-diphenylhydrazole: U-methylidene- 9-Ethylcarbazole, N
, N-sifgonylhydrazino-3-methylidene~l
(+-Ethylnoenothiazine, N,N-diphenylhydrazino-3-methylidene-1()-ethylphenoxazine, P-diethylaminostyryldehyl'-1, N-
Diphenylhydrazone, P-diethylaminobenzaldehyde-N-α naphthalene-N-phenylhydrazone, P-bicolidinobenzaldehyde-N,N-
Diphenylhydrazone, 1. , 3. 3-Trimethylindolenine-aldehyde-N,N-diphenylhydrazone l)-Hydrazones such as diethylbenzaldehyde-3-methylbenzthiazo 1nonone-2-hydrazone, 2,5-bis(P-diethylaminophenyl) −
1. 3. 4-Ogisadiazole, 1-phenyl-3-(P-diethylaminostyryl)-5~(P
-diethylamine phenyl)pyrazoline, 1. -[quinolyl(21)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, i-(pyridyl(2)]-3-(P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, l-[6-medoxybilidyl(2+]-3-(1)-diethyl "aminostyryl)-5-(P-9ethylaminophenyl) Pyrazoline, 1-[pyridyl (3
)]-:3-(P-diethylaminostyryl)~5
~(P~diethylaminophenyl)pyrazoline, i. −
(Levidyl f2+ 1-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2+ LL-
3~(P-diethylaminostyryl)-4-methyl~
5-(II'-diethylaminophenyl)pyrazoline, x-r)pyridyl(21]-3-(α-methyl-
P ~ diethylaminostyryl) -, -5 - (
P-diethylaminostyryl)-pyrazoline, -phenyl-3-(P-diethylaminostyryl)-4-methyl-5(p)ethylaminophenyl)pyrazoline, 1-
Phenyl-3-(α-benzyl-P-diethylaminostyryl)-5-(P-diethylaminophenyl)
Pyrazolines such as pyrazoline and spiropyrazoline, 2
-(IJ-diethylaminostyryl)-6-jethylaminobenzoosasol, 2-(P-shetylaminophyl)-4-(p-dimethylaminophenyl)
-Oxazole compounds such as 5-(2-chlorophenyl)oxazole, thiazole compounds such as 2-, (P-diethylaminostyryl)-6-dinithylaminobenzothiazole, bis(4-diethylamine-2-methylphenyl)- Triarylmethane compounds such as phenylmethane, ■, 1-bis(4-N, N-diethylamino-2
-methylphenyl)hebutane, 1,1,2,2-te]・
Lakis(4-,-N,N-1-dimethylamine-2-methylphenyl)ethane Valley polyarylalkane, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly- 9-vinylphenylanthracene,
pyrene-pormaldehyde resin, ethyl carbazole formaldehyde resin, etc. In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium amorphous silicon, and cadmium can also be used. , these mountains: Cf1iii1mX !lNaguga,
111/ko can be used in combination of two or more. Can be formed. Resins that can be used as binders include, for example, acrylic resins, polyester, polycarbonate, polystyrene, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulpo/, polyacrylamide, polyamide, Insulation such as chlorinated rubber (, + l- resin, or j-
Examples include highly versatile polymers such as polyN-hinylcarbazole, polyvinyla/thracene, and polyvinylpyrene. 714', load width + A 1m I/': l, 'I
K (fif 4 yari)” lti.ii
a) Since there is a pie field, the film Il# cannot be made thicker than necessary. Generally fl:
i, 5 microns to 30 microns, preferably range 1
The size is 8 microns to 20 microns. By applying 'd', load rxi r. (1/17U forming the circumference)
Any suitable coating method such as those described above may be used. Such a charge generation layer. A photosensitive layer having a laminated structure of a load transfer station is provided on a substrate having a four-electrode layer. 4
iM. The substrate having a layer may be one in which the substrate itself is conductive, such as aluminum, aluminum alloy, copper,
lead, stainless steel, vanadium, molybdenum, chromium,
Titanium, nickel, indium, gold, platinum, etc. can be used, and in addition, aluminum, aluminum alloy, indium oxide, tin oxide, indium oxide-tin oxide alloy, etc. can be used to prevent the layer formed by the vacuum evaporation method. Plastics (e.g. polyethylene, polypropylene,
Polyvinyl chloride, polyethylene terephthalate, acrylic resin, polyfluorinated ethylene, etc.), tetraelectric particles (e.g. carbon black, silver particles, etc.) are coated on a piece of plastic together with a suitable binder, and then the substrate and conduit particles are coated. It is possible to use a substrate made of plastic or paper impregnated with a substance or a plastic containing a conductive polymer. A barrier layer and a subbing layer may be provided between the conductive layer and the photosensitive layer. F separate layer (li, casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyramide (norylon 6, nylon 66, nylon 610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, 1-component The film thickness of the undercoat layer is 0.1 to 5 microns, preferably 0.5 to 3 microns.
be. 41 layers, 'small, idling original life 1 (to), 'nii;
What if I use a photoreceptor that has been installed on 111 of the I-cho Chuo transmission station? When the charge transport material consists of a child transport substance, it is a burden! li*ii Transport layer Table 1 There is a necessary charge to the river Kinmasa, and when it is exposed after the emperor, it is '14+ in the exposed part, the Toyo generated in the charge generation layer is transferred to the transport layer, and then Neutralizes positive charges by reaching the surface1,
,table! MI IIF, decrease I is a cow [] not 4.1K)l
(: same as part 1jp 7f; contrast is cow-<
, 1, (-no(gu(・(tet-,-r de sa/? !ii
'Bow 11', along 1゛ (6-self, 111 hoods if developed with one packing box of toner) -b<: (H4 et al.・Transfer the shoulder-1 toner image onto paper or plastic film 1-!J, then develop it.
So, I can speak the knee. 1 puko, impression ν (7 objects, static 1 (1, latent image on 1118 paper insulating layer (・C・Pak・, copy (ρ11) + elephant 12, constant a-t method can also be used .Currently Ward Ha11 (□!1.1'1
The current 1st room method and the 714th method may be used for public 1.11 and public withdrawal. ＼Work 1. A) It is not d. - 10,000, charge ring;, = 4g is a field consisting of tE pore transport fat □t (, ・i-+', φ+F i'ilN including 8Nj
60, 141, 7, 7, 60, 141, 7
If 'e, then D'g Mube will have Ichigoben, ↓, + 1.
Generated with 4 1. It is injected into the 1st layer of the hollow hole,
The child's f reached the clothes rlii (2-te direct market delivery order: Nakakkl
L, surface 'city's 1st place decrease b (111 with Gushishi still I falling light section)
In 1, Shizu'C14, Con[・Last is Ushishiru, at the current 1φ time l1t (+, child J consignment trade is / Kodeai and (li Moei
/It is safe to use IE chargeable toner. Book: 'JI', Book 1q1 for the Ming Dynasty
(ll, moe (ji<'s += l・razon/L('', parazolin husband 11.4 for Kirinol, L azole 1
[1, triarylmethane i, 1j, poly 1′
) -N-Vinyl force/“Level cold” and I1,1
・Initiate Jl: 'fi: Sex! 1 force negative, 1-β 11 hill lead, 1 fuka cadmium l3,) Niren etc., 1
Jjli 机尤ノj:f, 71. ；Sex I J da′↓”“
11 feels firm and 2 contains 111 [Boσ) non-neen conversion'
Contains σ and has (riyu he 1i1: + and i 3cm (ki/). Kono Yu 4 ryo 41i21i'zs izl:,
Koit et al. (1) Light 1'X l\+', fl'I'a
'iT and 1ii+;・1('s compound kebainter and ('(- coating [-fil') form a film;
3゜Also, another concrete 4<-1-1 contains shi, 1, front and bo's n-aninized batters, 44th +1・':! ip;;
It would be possible to use -C as the source of the impression. i) 4 of 7 directions) and body smell - C, 1) 1 Z) notification to f + γ horn 6.1 In general formula (1), ノJ, scolding' proboscis or death] 尤(・+b, x: talent, 'X, / Shifr Kudomo 1 惺)''
4, Ji "i"',) Y, path of absorption 17+" a) Yumida i, ti i: , i, II negative 1j two
- in ゛ I History Month 1 Shino Ai 1) 7 catties, 1 book of 4□t & fJj - + j-, '1 -' J) 7, bank low 1 tick II <catty', 1 book 31 ~
I:'l 411 Jb. L1 general formula 11) T /Jk 't\7L/)
Convert 'r 1', ZJ f 2 God V, +'+ l゛, J
Hikin included/ζsu, Dota d Kori, 11 no Gin・i, [, f2
11, 1, ``)'') It is also possible to use it in combination with a substance that causes sprouting.
In addition to being used as a laser-sensitive coating on a photoreceptor, it can also be used for infrared cut filters, solar sensors, light sensors, etc. A solar cell can be prepared, for example, by sandwiching the organic film described above between indium oxide and alkyl dipoles and the organic film described above. The organic coating of the present invention can achieve higher sensitivity in the wavelength range of 75Qnrn or more compared to conventional electrophotographic photoreceptors for l/- laser, and compared to conventional C) Y disk recording materials. (It is possible to provide a sufficiently improved S/N ratio with high sensitivity even if the compound is used in the present invention.
Despite having an absorption peak at
It has the advantage of being extremely stable. Hereinafter, the present invention will be explained with reference to Examples. Example 1 An ammonia aqueous solution of casein (Casein L, 2 g, 28' / ammonia water 1 g, water 222 d) was coated on an aluminum cylinoder by dip coating method. Og/+r?
A complete rust layer was formed. Next, 1 ton of the above-mentioned compound Afll, 14 parts of the compound, 111 parts of the compound Afll (varnished knock 13 M-2 = locally produced by Sekisui Chemical)] and 11 francs of tetrahedral. 30 parts by weight was milled into a ball mill using a M machine for 4 u; 7
The interval is 11t1-7. This dispersion was first formed [7 liters]
-Apply on rust layer 1- by dip coating method (7, dry, form 0 layer of (l ttC) [7. At this time 1
The thickness of the tube 4 was (13 tt).Next, 1 part of P-diethylaminobenzaldehyde-N-phenyl-N-α-naphthylhydrazone, 1 part of polysulfone resin (P1700: - manufactured by On Carbide, 1 part of h1 part and monoku ``2 rubenzene 6, ME +
Mix 17 parts and stir with a stirrer to dissolve 2 parts. This liquid was applied to the charge generation layer by the tδ coating method and dried to form a heavy transport layer. At this time, the film thickness was 12μ.
I did Fi. The surface level at this time is 4111
(Initial?l-m (X'rVo)
The photoconductor of t was repaired in the dark for 5 seconds, and then the surface potential was +
tttl has been established (grade reduction ai V,). Sensitivity t: 1, Ifθ・
By measuring the potential W < light intensity (1 joule/c, 1 joule/c, and At this time, a gallium, aluminum arsenide semiconductor laser (isolation wavelength 780 former Tl) was used.The results of Tono'1 et al. were as follows.Vo: -620 volts V5: 580 volts b!/2", 8.5 microjoules/,,I Examples 2 to 17 Compound A used in 1 A photoreceptor was prepared in exactly the same manner as in Example 1, except that each of the compounds shown in the table was used, and the characteristics of this photoreceptor were measured.The results are shown in Table 1. 4 l Table 2 Compound tb (sword -570 to 51 (125
,03〃(3+ -570-5(+(17,84〃
(4) 590 -54 (110,55〃 (
5) -58 (1-5:30+44+6 〃f
6) ~600 -550 9.87
n (71580-5209, (')3 u
(8) −56(> −52017,59
〃(9) -570-52011,31,0”
(1,0) -610-550+5(111n
u+) -590~550 9.412
” (12) -570-5:30
22.013 N (13) -560
-51029,414" (I4) -570
-5]-013,515” (151-590-5
708,516 (161-58(1-5:), (
1] 6.417” (I7] 5
50 -500 33.0 Example 18 An ammonia water bath solution of casein was applied onto an aluminum plate with a thickness of 100 microns, and dried to form a sublayer 1→ with a thickness of 11 microns. Next eko, 2.4.7-dolinitro9-fluoreno75
g and poly-N-vinylcarbasol (number 4 average molecular weight 3
00,000) 5 g of tetrahydrofuran 70
ml V, to form an engineered transfer complex compound. 1 g of the compound of this transfer complex compound and the above-mentioned compound 46m was added to 5 g of polyester resin (Vylon: manufactured by Toyobo).
and tetrahydrofuran 70. d to γ4 and liquid) J
IJ, it's dispersed. This dispersion was applied onto the F rust layer to give a film thickness of 12 mm after drying. Measurements were made in the same manner as in Example 1.The results were as follows:
? It was ri. However, band 1E polarity 1.'', (→.Vo: m550 volts V,: e1490 ports)!≦: 485 micro unit/c+i Example 19 Aluminum evaporated polyethylene prephthalate l/-) Aluminum surface of film 1. Forming a polyvinyl alcohol film with a thickness of 11 microns on top. the law of nature. Next, a dispersion of the compound □/6 (1) used in the example process was applied to the polyvinyl alcohol layer formed earlier using VC so that the film thickness after drying was 0.5 microns. It was coated with a Mayer bar and dry-fried to form a 100% solid layer. Next, 5 g of virasoline compound 17A of the structural formula and polyaryl L/l" +
'lJ 1lrr (bisphenol A and prephthalic acid
Dissolve 5 g of -f Soft Tar 1 in 70 ml of tetrahydrofuran and apply the solution to 7 of the electric generation layer so that the strength or thickness after drying is 10 μTff.
'i・shi:) At the end, a cargo transport layer was formed. This is how ril'fl made Kankyutai obi ta tF4￥
All genders were measured by the same method as in Example 1. Ko-11
The results were as follows. Vo: -580 volts V: -520 volts E%: 10.5 microjoules/rJ As per each of the above-mentioned embodiments, the present invention's ? to. Child Ij Shinkanme L: The body is extremely sensitive in the wavelength range of 750 nm or more! 1! In addition to having U-character,
, 5th place, dark decay, etc. 1st place waiting case 11; I love you. Mi゛ichi 1tari 2 〇Nitrocellulose solution (Daicel Chemical) Z L <4i
Made by Ohares Lacquer Nitrocellulose 25% i, l % methyl ethyl ketone iW 12x H6';
(+,, AiJ 1) Compound 1f; 3 parts ψ of the compound (1) and 70 parts 2 parts of mesalethyl ketone were mixed, and -(- part V was dispersed. The dispersion was coated on an all-aluminum vaporized glass, IVC, and dip coating method, and then dried to obtain a recording layer of 0.6 g/m''. 8. Take it on the table with a motor.
7 dot size while applying rotation of 00 rpm]
,,5 rnW and 4 illll focused to O micron
The recording layer was irradiated with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 78011 nm) in the form of a track of 1 and 0, and a recording of 71 was achieved. The surface of this recorded optical disc was scanned 4 times (ta1) (
] When observed with a fine weight, it was found that 1 bright bit force ≦
M? It's mere. Still, a low-power gallium-aluminum fiber half η゛h body was injected into this disk.
By detecting the reflected light, a waveform with a sufficient S/N ratio was obtained. Example 21 Compound 50 ()η total deposition j) of the aforementioned compound, % (])
1Put it in a molybdenum boat,
/After exhausting the air, the aluminum vapor-deposited glass was removed.
child. During steaming 4, the pressure inside the Wataru chamber is I O-'lffm H7
More than that ,,)−,? The heater was controlled □7 so as not to cause a 0.02 micron thick vapor deposited film to form. When the 1'l'f information was stored on the optical disc recording body prepared in the above 2 in the same manner as in Example 20, Example 2
Clear bits similar to 0 were observed, and although information was still reproduced in the same manner as in Example 20, a waveform with a sufficient S/N ratio was observed. Example 22 The above-mentioned compound P(5) was coated on an aluminum vaporized glass plate in the same manner as in Example 20, and then dried and coated.
A W disc recording body having a recording layer of , 6y/i was prepared. After one blue report was recorded on this disc recording medium in the same manner as in Example 20, a waveform with a sufficient S/N ratio was observed. In addition, after the information has been captured, the surface of the recording layer is examined using a scanning electron microscope to see that clear bits have been formed. Example 23 [Compound described in 11■ 1f; Compound (8) was carried out in 1+
This was coated on a temporary aluminum-deposited glass in the same manner as IJ 20 to prepare a disc recording body having a recording layer with a dry coating weight of 0.6 y/die. When information was stored on this optical disc recording medium in the same manner as in Example 20 and then reproduced, a waveform with a sufficient SIN ratio was observed. My father, after listening to the information, looked at the surface of the recording layer using a scanning electron microscope, and found that there were clear bits formed there. Example 24 The above compound A (14) was added to Example 20,! 2) Coat the temporary aluminum-deposited glass in the same manner (7).
Dry f]21-IlO65Y/n? Record of ￥ [
) 6 self-recorded optical discs were created. After storing information on this optical disk 1.1 recording medium in the same manner as in Example 20, a waveform with a sufficient S/N ratio was observed at the 11f raw (-). When I put it in and inspected it with a microscopic mirror, clear bits were formed.

[Brief explanation of drawings]

Figures 1 and 2 are views showing one part of the optical disk recording body when the coating of this invention is used, and Figure 3 is an explanation showing an embodiment of this optical disc recording body. It is a diagram. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Organic film, 3... Reflective layer, 4
... Laser beam, 5... Bit special [Created by ^X11 people Canon Co., Ltd. r, I
,'E=! □1 All tab p th? Closing stone 3 Amendment to closing procedure (voluntary) Commissioner of the Patent Office Kazuo Sugi 1 Display of the case 1982 Patent application No. 2078 (S 2)
Name of the invention Organic coating 33 Person who makes the correction! Relationship with If I'1
Address Higashireito Yoyo Ward F Maru f-3-30-25,710
Positive object clear # UI book 6 amendment contents (1) Special MF t:l'J request range is different; correct as stated. (2) Ming Chao 1 Ming 16 shell line 19, 2B16 page river line 20, page 14 '>'r line 2, page 18 line 6, gu 18@
Correct 1-thio] in line 7 and line 9 of the 18th line to [thia]. (6) Similarly, on page 39, line 19, ``Selenium-deral amorphous silicon'' is used as ``Se(/Netherle, amorphous silicon J).''2.1Far' 1) An organic coating characterized by containing a compound represented by the general formula (1) (wherein Zl is an atomic group necessary to complete a substituted or unsubstituted nitrogen-containing ring) Zz is optionally substituted biran, thiapyran, selenaviran, benviran,
Indicates the atomic group necessary to complete benzothiapyran, penzose V nabilane, naphthopyran, naphthothiapyranshanaphthoselenaviran, and X is a sulfur atom, a 1'12 elementary atom, or a selenium atom.

Claims (1)

[Scope of Claims] An organic film characterized by containing a compound represented by the following general formula (+). General formula (1) (wherein, Zl represents an atomic group necessary to form a substituted or unsubstituted 9-containing heterocycle.
Indicates an atomic group essential for completing benzothiobilane, benzoselenabilane, naphthopyran, naphthothiobilane or naphthoselenabilane, and is a sulfur atom, an oxygen atom, or a selenium ji<child. Z represents a set of two hydrocarbon groups forming a substituted or unsubstituted 5-membered or 7-membered or 0-negative group. ■
[7] represents a hydrogen atom or an unsubstituted alkyl group. 1(,2 and 1mo, are hydrogen atoms, halogen atoms or monovalent organic residue capos.H,4(,-,J:
, ■ A hydrogen atom or a halogen atom. A indicates an anion/ion, +11 and n I:t O or 1, e &:
, L (1, l or 2)