JPS6126044A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. adapted to an electrophotographic printer using laser beams as a light source by adding a specified pyrylium type dye as a sensitizer to a photoconductor. CONSTITUTION:The photosensitive compsn. is obtained by adding to the photoconductor, as a sensitizer, one of pyrylium type compds. represented by formula I in which Z is O, S, or Se; X1 is an atomic group forming pyran, benzopyran, naphthopyran, or the like; X2 is an atomic group forming pyrylium, benzopyrylium, or the like; each of Y1-Y4 is H, an aliphatic or aromatic group; R is H, halogen, or alkyl; A is an atomic group necessary to form a 5- or 6-membered ring; W<-> is an anion; and (m), (n) are each 0 or 1. This compd. is embodied by formula II. The photosensitive compsn. obtained by adding this sensitizer I to a photoconductor, such as poly-N-vinyl carbazole can be used as an excellent information recording medium.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to an organic photoconductive composition or an organic dye thin film suitable for an electrophotographic photoreceptor. The present invention relates to a heat mode optical information recording medium that performs recording and reproduction by causing a state change using a high-density energy beam.

``Prior Art'' Conventionally, many organic compounds have been known as photoconductive substances for single-child photographic materials, and it has been confirmed that some of these compounds have considerably high photosensitivity. . However, at present, there are very few examples of organic photoconductive substances t' actually being used as electrophotographic light-sensitive materials. Organic photoconductive materials have many superior properties compared to inorganic materials, and offer a wide range of applications in the field of electrophotography. For example, transparent photosensitive 7 (
Is organic photoconductive material suitable for the production of flexible photosensitive films or light and easy-to-handle photosensitive films? This is only possible by using 7'1m, film-forming properties during the production of photoreceptors, surface smoothness, and selectivity in charge polarity when applied to electrophotographic copying processes, all of which cannot be expected of inorganic photoconductive materials. It has characteristics. Although organic photoconductive materials have excellent performance properties in many respects, to date they have not been able to make a sufficient contribution to the field of electrophotography due to their low photosensitivity. It is.

Normally, if the photoconductive material itself has a low degree of photosensitivity and is in the short wavelength part of the spectrum, it is necessary to increase the photosensitivity by moving the photosensitivity to the longer wavelength part of the visible spectrum. A certain substance is added.

A large number of organic substances are known as sensitizers to improve sensitivity, but each has advantages and disadvantages, and although they are still in a satisfactory state in terms of increasing the sensitizing effect. do not have. Therefore, the development of effective spectral sensitizers for organic photoconductors has long been a challenge for those skilled in the art.

As one of these sensitizers, pyrylium-based dyes are reported to be useful, as described in U.S. Pat. No. 3/Ill, 70 by Davis et al.
No. 0, van Allanl et al., U.S. Pat.
U.S. Patent No. 3 to sl et al. 3t.

No. 9941, each specification further includes Research Disclosure/
63.2/, 1977, page j, etc.

However, such conventionally known thiopyrylium dyes have an absorption band in the visible range. Because these thiopyrylium dyes are used as sensitizers in photoconductors, they absorb in the visible range? It was not possible to obtain a colorless and transparent original conductive composition of purple color.

Furthermore, in recent years, electrophotographic printers using lasers as light sources have attracted attention. That is, the modulated IMlk of the laser is performed by an electrical signal corresponding to image information, and the modulated laser beam is scanned onto the photoreceptor by a violet galvano mirror or the like to form an electrostatic latent image sound.

By performing toner development and transfer, the desired reproduced image 1
1”k.

The laser used at this time is generally) 1 e −
These are gas lasers such as Cd lasers and He-Ne lasers, and the photoreceptors used for these light sources are 6s.
Conventionally known photoreceptors could be used as long as they were spectrally sensitized to about o11H1.

However, semiconductor lasers currently being developed and put into practical use, which are small, low cost, and capable of direct modulation, often have a long oscillation wavelength of 7j Onm or more. Therefore, a semiconductor laser like this? In order to manufacture a printer using this method, it is required that the photoreceptor has absorption characteristics in the near-infrared or infrared wavelength range, but conventionally known photoreceptors have sufficient sensitivity in the long wavelength range of 7j Onm or more. ? I couldn't.

On the other hand, conventionally, information recording media are irradiated with a beam of high energy density to determine physical property constants such as transmittance, reflectance, and refractive index. The recording method that records by changing the light has characteristics such as being able to form images with extremely high resolution and contrast, being able to add information later, and being able to record scales at the same time as exposure. It has advantages such as being suitable for recording computer output and transmitted time-series signals.

COM (Computer Output Micro).

It is applied to micro facsimiles, printing plates, optical discs, etc.

For example, recording media used in optical disk technology.

Approximately 72 small optically detectable pits can be in the form of spiral or circular tracks and stored in the pollution information. To write information on such a disk, a focused laser beam is scanned on the surface of the laser-sensitive layer, and only the surface irradiated with this laser beam forms pits, which are formed in the form of a spiral or circular track. .

In the heat mode recording method, the laser sensitive layer absorbs thermal energy when irradiated with a laser beam, and forms small pits at the affected locations by evaporation or melting.

The information recorded on the optical disc in this way.

It is detected by scanning along the laser track and reading optical changes in areas where pits are formed and areas where pits are not formed.

Conventionally, information recording media that can perform heat mode recording include thin films of metals and/or metal oxides, semimetallic dielectrics, etc. on transparent supports such as plastics.
Self-oxidizing binders and dyes? In recent years, recording media have been used in which a thin film containing a film is provided as a recording layer, and a protective film layer is provided on this.

On the other hand, as mentioned above, one oscillation wavelength is 7! With the spread of semiconductor lasers with long wavelengths of Onm or more, when recording and reproducing sound using such semiconductor lasers, the absorption characteristics of the recording layer have an absorption peak in the near-infrared or infrared wavelength region. required to have one.

However, conventional thin films mainly composed of S:-like substances.

There are problems such as the high reflectance of laser light reduces the efficiency of laser use, making it impossible to obtain high sensitivity characteristics, or the output of the laser light increases significantly during recording, and the absorption wavelength Area '77! In order to achieve a long wavelength range of On m or more, the layer structure of the recording layer must be made more complex.

In addition, when the recording layer is an organic thin film containing a dye, a binder, and t, 7! A dye that absorbs on the long wavelength side of Onm or more?
It is proposed to use For example, U.S. Patent No. μm7
Squamarillium dye shown in JRIJT issue, special public show JL-4LlOt/, etc.

Croconium color difference or US Patent No. 113/j9Ir
No. 3, rResearch Disclosure
J/rirλ 2nd year comic, ii'y~/Byrylium color chart shown on page 1, etc.? For example, JP-A-Sho!, which claims that the recording layer containing an organic thin film is adaptable to a racer with a thickness of 73 Onm or more. t-μA, 2co No. 1, JP-A-5R-i
i, 27 Octopus, JP-A Showa J'l-2/μ/4- issue, JP-A Showa 31-Co/7J Ri No. 1 1% Kai-Shojza-1,232μ
Fragrance publications etc. are presented.

However, in general, organic compounds have absorption characteristics that become unstable as the wavelength range increases, and are easily decomposed by a slight increase in temperature, or are used as dyes that are desired among the above-mentioned dye groups.
There is a problem that there are very few dyes having absorption characteristics in the region of jO-nm. Therefore, the 'direct read after write' capability (DRAW)
and write) ) required for all owned recording media. High absorption efficiency for the laser beam used;
It must satisfy various characteristics such as having a reflectance that allows sufficient focus control during recording reading and stability of recorded images, and it must not necessarily contain an organic thin film that is sufficiently satisfactory from a practical point of view. Recording media have not been developed.

``Object of the Invention'' Therefore, the object of the present invention is to contain a novel dye as a sensitizer that is colorless and transparent, absorbs in the far-infrared to near-infrared, and provides high sensitizing ability to photoconductive substances. It is an object of the present invention to provide a photosensitive composition comprising a photoconductive material. Another object of the present invention is to provide a photosensitive composition for use as a photoconductive composition for a photoconductive printer using a laser as a light source.

Another object of the present invention is to provide a novel and long-wavelength side, especially 7jOn
A photosensitive composition used as an optical information recording medium containing an organic thin film having an absorption band of m or more? It is to provide. Another object of the present invention is to provide a photosensitive composition for use as a recording medium that has very high storage stability. Another object of the present invention is to provide a photosensitive composition for use as an optical information recording medium that is highly sensitive in a wavelength range of +7 nm or more and has a sufficient S/N ratio. The present invention is achieved by an optical information recording medium characterized by containing at least one compound represented by the following general formula (Il). I) In the formula, Z represents an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom.Xl is an optionally substituted pyran, benzopyran, or naphthopyran.

Represents the atomic groups necessary to form thiopyran, benzothiopyran, naphthiopyran, selenapyran, benzoselenapyran, nandoselenapyran, ternapyran, penzoternapyran or naphthoternapyran.

Examples of the substituent include a halogen atom (for example, a salt atom, a bromine atom, etc.), and an optionally substituted alkyl group having a carbon number of λ (for example, a methyl group, an ethyl group).

Propyl group, butyl group, 1 is ethyl group, hexyl group.

Octyl group, chloromethyl group, cyanomethyl group.

hydroxyethyl group, etc.), alkoxy groups with carbon number l-coO (e.g. methoxy group, ethoxy group, propioxy group,
butyloxy group, hexyloxy group, decyloxy group, etc.), optionally substituted aralkyl group having 7 to 7 carbon atoms (
(e.g., benzyl group, phenethyl group, etc.), optionally substituted aryl groups having t-carbon atoms (e.g., phenyl group, tolyl group, naphthyl group, chlorophenyl group, dichlorophenyl group, butylphenyl group, me, toxyphenyl group, ethoxy Phenyl group, hydroxyphenyl M, N.

N-dimethylaminophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group.

cyanophenyl group, methanesulfonylphenyl group, etc.),
Hydroxyl group, cyan group, alkyloxycarbonyl group having 1 or more carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, ?toxycarbonyl group, etc.) & aryloxycarbonyl group having 6 or more carbon atoms (e.g. F! phenyloxycarbonyl group, chlorophenyloxycarbonyl group, tolyloxycarbonyl group, butylphenyloxycarbonyl group, methoxyphenyloxycarbonyl group, etc.), carbon number 1 to +2
+2 alkanesulfonyl group C such as methanesulfonyl group, ethanesulfonyl group, furopanesulfonyl group, phthanesulfonyl group, hexylsulfonyl fi, etc. 1. Arylsulfonyl group having 6 to -1 carbon atoms (e.g. benzenesulfonyl group 1. carbon i number/-, -J lr optionally substituted amino group C e.g. amine, group, N-methylamino group, N, N- dimethylamino group, N-ethylamino group, N
, N-diethylamino group %N, N-dizolopylamino group, N.

N-dibutylamino group, N-methyl-N-phenylamino group, N-phenylated amino group, N-benzylamino group, etc.).

X2 may be S-substituted, pyrylium, benzopyrylium, naphtopyrylium, thiopyrylium, pen, zothiopyrylium, naphthopyryllium, selenapyrylium, benzoselenapyrylium.

Represents the atomic group necessary to form naphthoselenapyrilium, ternabililium, penzoternapyrylium, or naphthoselenapyrylium. represent.

Yl, Y2, Y3 and Y4 may be the same or different, and each is a hydrogen atom or an alkyl group having a carbon number of 1 to λ (for example, a methyl group), which may be substituted with lf.

Ethyl, propyl, and butyl groups are methyl groups.

Hexyl group, octyl group, decyl group, dodecyl group.

tetrodecyl group, etc.), number of carbon atoms that may be substituted with Il, j ~ -
1λ cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.), an optionally substituted aralkyl group with 7 to 7 carbon atoms (e.g., benzyl group, phenethyl group, etc.), an optionally substituted aralkyl group with 6 to 2 λ carbon atoms Aryl groups (e.g. phenyl groups).

t'J%fi, '#ruphenyl group, chlorophenyl group.

Dichlorophenyl group, methoxyphenyl group, naphthyl group, bromophenyl group, cyanophenyl group.

Methanesulfonylphenyl group, N,N-dibutylaminophenyl group, N,N-dibutylaminophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, etc.).

AFi, an element necessary to form a j-membered ring or a 6-membered ring.

Subgroups (e.g., formed fc cyclic residues include cyclopentenyl ring, cyclohexenyl ffi&4t+4L-
Represents a dimethylcyclohexenyl ring, indenylill.

R is: a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom), or an alkyl group having 1 to 1 carbon atoms (for example, a methyl group, an ethyl group, a propyl group).

butyl group, hexyl group, etc.).

Wθ represents an anion, for example... rogen ion (for example, chloride, bromide, iodide); 41. It represents barchlorate, periotide, tetrafluoroporate, sulfate, p-toluenesulfonate, alkylsulfone) (for example, methanesulfonate, ethanesulfonate, etc.).

n and m represent O or /i.

Specific examples of the dye represented by the general formula (I) are listed below. However, the compounds used in the present invention are not limited to these.

H3 QC4H9 The pyrylium dye of the present invention can be produced by a conventionally known method. It can be manufactured using That is, substituted biryllium salts are described in J. Kuthan, Advancesin Het.
erocyclic Che'1nistry, 34th
'Volume % No. 2 μ p. (1913), U.S. Patent No. μλe3
p7s or B+J, Murr)' etc.-J-
Org, Chem,, at, 1x3s (tqir co)
It can be produced according to the synthesis method described in et al. In addition, the compound required for the total synthesis of pentamethine color patches connected by forming a ring by reacting with the quaternary salt is 1, for example, Wilson, J.
An intermediate r obtained by monoetherifying a cyclic i,3-diketone is used as described in Chem, Soc, I it, (i y j3), etc. The dye of the present invention can be easily synthesized by reacting each of the above-mentioned compounds according to the method described in, for example, US Patent No. λ''yt<tPoo.

The PIIJ17ium dyes of the present invention are used as sensitizers in inorganic and organic photoconductive materials to improve the photoconductivity and sensitivity properties of a variety of photoconductive materials.

Inorganic photoconductive substances include zinc oxide, but particularly effective photoconductive substances are organic photoconductive substances. Examples of organic photoconductive materials include polymeric materials.

(Pyrivinylcarbazole and its derivatives described in 11 Japanese Patent Publication No. 341-109tls).

(2) Special Publication Shoke 3-7g4744 Publication %Special Publication Sho IJ-
Vinyl polymers such as polyvinylpyrene, polyvinylanthracene, borikovinyl-a-(a'-dimethylaminophenyl)-j-phenyl-oxazole, poly-3-pinyl-N-ethylcarbazole, etc., described in the /9/9J publication.

(3) Polymers such as polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 3.

(4) Tokuko Akira! Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in JP-A-36-90133 and Jim-/XIj of JP-A-36-90133, etc.
, various triphenylmethane polymers described in TO No. 6; and low-molecular ones (6) triazole derivatives described in U.S. Pat.

(7) Oxadiazole derivatives described in U.S. Patent No. 3/I μμ7 and the like.

(8) Imidazole derivatives described in Japanese Patent Publication No. 37/1983.

(9) United States Code No. 31. /! IIθλ No. Jl-
No. 2091, same 3jt4L2! Gu μ special public Sho μj-J
T! rK No. % Special Publication Shoj/-10913, Japanese Patent Publication Sho, i/
-23rd issue, Tokukai Sho! ,! r-/71oj, JP-A-JT-GLJR, JP-A-JJ-7OIrt-67, JP-A-5S-IJTR-53, JP-A-A-3TAjA
No. specification.

Boaryarylacacan derivatives described in publications, etc.

QO) U.S. Patent No. J/, I'07,19, U.S. Patent No.
-"7g7μ6, JP-A-Shojj-zarot-hiro, JP-A-33- and goti, %KAI-Shoμter-i.

JJ No. 37 & JP-A No. 53-31016, JP-A-
100jr1, JP-A-11r/It/, JP-A-57-μ5stts, JP-A-Sho! ;4A-//,2J
J7 issue, Tokukai Sho! Pyrazoline derivatives and pyrazolone derivatives in which jt-7≠jμ is described in the specification, publication, etc.

αυ U.S. Patent No. 37. Iju04 is the name Mei Tsumugi, special public show 3i-1010! No., JP-A-Sho-sa-za-3g-3j-1% Kai-Sho-j IA-110136, JP-A-Sho-jg-//9926
No., Special Publication, @'<tA-371λ No., Special Publication Show 1t7-
Specification No. 21336.

A phenylenediamine derivative described in official publications.

a2 US'Rglf-#! 1,7aj□, special public Sho μter No. 3370-, West German patent + DAS) //1os
ir, U.S. Pat. No. 3,110,703.

U.S. Patent No. 3λ≠Ojtri No. 7, U.S. Patent No. 3TSRS
No. θ, U.S. Patent No. 3λ103, U.S. Patent No. 41
/7jtYt1, U.S. Patent No. 4LO/Jj7A 1%
Kaisho! j-/GG, No. 1-to, JP-A-57. -//ri/32, Special Publication No. 3 Ter 27377, Japanese Patent Application Publication No. 1973-J
μ37 details 1. Arylamine derivatives described in publications, etc.

03) Direct amino-converted chalcone derivatives described in US Pat. No. 3j2tjO1.

(+41 Described in U.S. Pat. No. 35,25416, etc.) N,N-bicalpadil derivative.

(Oxazole derivatives described in 151 US Pat. No. 3,257, co03, etc.)

(Styryl anthracene derivatives described in JP-A No. 161, Sho st-μ6, Co. 3μ, etc.).

07) Fluorenone derivatives described in JP-A No. 10137 and the like.

0 barrels U.S. Patent No. J7/74A42, Japanese Patent Application Publication No. Akihiro-J
Tano μ3 (corresponding to US Patent No. U/30917), JP-A-Sho! , 1-! 043, JP-A No. 206μ, JP-A No. 53-4'4760, JP-A No. 33-1!419
No. 6, JP-A No. 77-1/#jθ No. 1% Kai-Sho j7-/4L
Examples include hydrazone derivatives disclosed in 17 μl specifications, publications, and the like. Two or more of these photoconductive substances may be used in combination depending on the case.

Among these photoconductive materials, poly-N-vinylcarbazole; triarylamines such as tri-p-tolylamine and triphenylamine; μ4/-bis(diethylamino l-J, #7.'-dimethyltriphenyl Boarylmethane such as methane; and 3
Unsaturated heterocycle-containing compounds represented by pyrazoline derivatives such as -c≠-dimethylaminephenyl)-i,j-diphenyl-pyrasolinato are preferably used.

The photoconductive composition of the present invention containing the pyrylium dye of the present invention as a sensitizer is obtained by dissolving these pyrylium dyes, the photoconductive substance, and an organic solvent. Spin coating, blade coating, knife coating, reverse roll coating, dip coating,
It can be used as a photoreceptor by coating and drying using a commonly used method such as rod coating or spray coating, or it can be used as a photoconductor by producing particles from the organic solvent solution using a mini-spray device or the like, and then applying the insulating liquid to the particles. It is used in photoelectrophoresis as a dispersion liquid.

Paper as a conductive support; Aluminum-paper laminate: Metal foil such as aluminum foil, zinc foil; Metal plate such as aluminum, copper, zinc, yachiyuu and galvanized plate - paper or cellulose acetate, polystyrene, etc. Nichrome, @, nickel, on regular photographic film base
There are also metals such as aluminum that are vapor-deposited. Preferably chromium, silver, nickel on paper, cellulose acetate, polyethylene terephthalate, etc.

Vapor-deposited metals such as aluminum and indium oxide are used.

As the organic solvent, a volatile hydrocarbon solvent with a boiling point of 200C or less is used, and immediately a halogenated carbonized solvent having a carbon number of 1 to 3 such as dichloromethane, chloroform, /, 2-dichloroethane, tetrachloroethane, dichloropronolyte or trichloroethane is used. Mizue is preferred. Various other solvents used in coating compositions, such as aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, ketones such as acetone or cobutanone, ethers such as tetrahydrofuran, and methylene chloride, and mixtures of the above solvents can also be used. It is. The solvent is dye,
7 to 700 t, preferably j to 20 t, based on the total amount of photoconductive material and other additives 11? Added.

The amount of the sensitizer used in the present invention is from 0.00 to 30 parts by weight, preferably from 0.00 to 10 parts by weight, per 10 parts by weight of the photoconductive material.

In particular, as a mode of use of the composition of the present invention, a sensitizer is incorporated into particles used in photoelectrophoresis.

Images can also be obtained by photoelectrophoresis. Particles used in the photoelectrophoresis method are produced using the mini spray device 2 from a solution consisting of a photoconductive substance such as the aforementioned poly-N-vinylcarbazole and the sensitizer of the present invention.

These particles further contain decane, dodecane, octane, /
Insulating liquid that combines saturated hydrocarbons such as e-roughin and isooctane.

Preferably, it is dispersed in a long chain alkyl hydrocarbon such as Iso, e-B% Isopar H, Isopar G (manufactured by Etsuo Kagaku Co., Ltd., trade name) to form a dispersion liquid, and this is used in the photoelectrophoresis method. Isopar E, Isopar H and Isopar Gt- are saturated hydrocarbons, respectively.
Tata, 3 and Tata.

FLIT%1 aromatic hydrocarbon purple O, Oj respectively.

Contains t% of O, Co, and O0λ weight. However, Isopar H contains olefins having a weight coefficient of θ of 3 or less. The respective points are ttjoc, tt, 2°C1/7110C,
/190C and tslr'c-777°C. The particle size in the dispersion is 0.3'-10 weights, preferably 7 to 3 weights, relative to the dispersion. The photoelectrophoresis method and its apparatus are described in Japanese Patent Publication No. Sho<Aj-206μθ.

Necessary additives may be appropriately added to the photoconductive layer and particles to improve the properties of the photoconductive layer and particles.

For example, an electrically insulating 79-inda component can also be present in the photoconductive compositions of the present invention. Preferred binders used to form the photoconductive compositions of the present invention are film-forming, hydrophobic polymeric binders with fairly high dielectric strength and good electrical insulation. Representative examples of such substances include: vinyl resin, gelatin, cellulose ester derivatives,
Natural resins such as cellulose nitrate; polycondensates contained in polyesters and polycarbonates; silicone resins; alkyd resins including styrene-alkyd resins; paraffin; and various mineral waxes; etc. Certain polymers useful as pinters! For an example of +'a quality,
Research Disclosure (ResearCh D
Volume A/-02 is also listed under the title 'Photographic Elements, Materials and Methods' on page A/-47.

Generally, the amount of binder present in the photoconductive compositions of the present invention can vary. Typically, useful amounts of binder range from about 10 to about 20 parts by weight, based on the total amount of the photoconductive material and binder mixture.

A charge control agent when preparing photoconductive particles.

Dispersion stabilizers may also be added. A copolymer of lauryl methacrylate and styrene (copolymerization ratio μ~22L) or a copolymer of low ethylhexyl methacrylate and styrene (copolymerization ratio μ~22L), which has the functions of both charge control and dispersion stability.
A copolymerization ratio of 1 to 1) can be advantageously used.

It was. To improve flexibility and strength, plasticizers such as chlorinated diphenyl, remethyl phthalate and epoxy resin (trade name Epicote), 100 N parts of a leading conductive material are added.

It is also possible to add up to 60 parts, preferably +i10 to Hiroo parts.

In addition, in order to improve the sensitivity, JP-A Sho sr-+jμ3 is increased by % JP-A 5R-6SU3, JP-A Show,! rl210
．． 22J9, JP-A No. 1022440, JP-A No. 31-707jt4tμ, JP-A SR-/J-4t
These are described in each of the J4A publications. Chemical sensitizers such as urea compounds, thio-based compounds, carbonylamine compounds, thiocarbonylamine compounds, sulfonylamine compounds, dicarbonylamine compounds, etc., preferably 7 to 100 parts by weight per 100 parts by weight of the photoconductive substance. can also be added in an amount of 3 to jO parts by weight.

The coating thickness of the photoconductive composition of the present invention on a suitable support is:
Can vary widely. Generally, it can be coated within a range of about 70 microns to about 300 microns (before drying), has an optical density of about 0.03 or less for visible light, and is substantially colorless and transparent photoconductive. Composition layer? can be formed. The preferred range of coating thickness before drying is:
It was found to be in the range of about 7 microns to about tsoirons. However, useful results can be obtained even outside this range. The dry thickness of this coating may range from about 7 microns to about 7 microns. The thickness of the dried coating is about 01
! It is possible to obtain a photoconductive composition Ns that is colorless and transparent to visible light even in the range of 200 to 200 microns, and is sensitive only to far-infrared to near-infrared regions.

On the other hand, the photosensitive composition of the present invention can also be used as an optical information recording medium. That is, the optical information recording medium of the present invention is constructed by forming an organic thin film containing at least the pyrylium dye of the present invention on a support.
The organic thin film can be formed using various methods such as the aforementioned compound coating by vacuum evaporation. It can be formed using

When a coating method is used, the organic solvents include alcohols (for example, methanol, ethanol, isopronochloride, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (for example).

N,N-dimethylformamide, N,N-dimethylacetamide, etc.)% Esters (e.g. methyl acetate, ethyl acetate, butyl acetate, etc.), Ethers (e.g. tetrahydrofuran, dioxane, monoglyme, diglyme, etc.)
, hydrogen halides C such as methylene chloride, chloroform, methyl chloroform, 4 [ftJ], monochlorobenzene.

Dichlorobenzene, etc.) can be used alone or in combination. The binder for the dye can be selected from known natural or synthetic resins, and specifically, cellulose resins (eg, nitrocellulose, cellulose phosphate, cellulose acetate X & cellulose butyrate, methyl cellulose).

ethyl cellulose, butyl cellulose, rose, etc.), acrylic resins (e.g. polymethyl methacrylate).

polybutyl methacrylate, polybutyl acrylate,
Polymethacrylic acid, polyacrylamide.

polymethacrylamide, polyacrylonitrile, etc.).

Vinyl resins (e.g. polystyrene, polyvinyl acetate,
Poly, hinyl chloride, polyvinyl alcohol.

polyvinylpyrrolidone, etc.), polycarbonates.

Polyesters, polyamide resins, epoxy resins, phenolic resins, polyolefin resins (eg.

Polyethylene, polypropylene, etc.) or synthetic copolymer resins can be used. As for the application.

It can be carried out using general-purpose coating methods such as xi'v+, roller coating, spinner coating, and blade coating.

When an organic thin film is formed together with a resin, the content of the biryllium dye in the thin film is from j to 10% by weight, preferably from /j to 10% by weight, and the remainder is a binder. Further, the vapor deposition thickness or dry thickness of the organic thin film is 19 μm or less, preferably 2 μm or less.

Furthermore, an anti-fading agent, a coloring agent, etc. can be incorporated into the organic thin film as required.

The material of the support used in the present invention is known to those skilled in the art and may be either transparent or opaque to the laser light used. Specifically, glass, quartz,
Ceramics, paper, metals.

Plastics (e.g. acrylic resin, methacrylic resin, polyester resin, polyolefin resin, polystyrene resin, polyamide resin, polycarbonate resin, etc.)
etc. can be mentioned.

When writing and recording is performed by irradiating a laser beam from the support side, the support must be transparent to the laser beam, whereas when writing and recording is performed from the opposite side of the support, that is, the surface of the recording layer. does not need to be transparent to laser light. However, when read and reproduced using transmitted light, it must be transparent to the read laser beam. On the other hand, when reading and reproducing sound reflected light is used, it may be transparent or opaque to the reading laser beam.

Further, the support may be provided with guide grooves formed by unevenness as necessary, or may be provided with an undercoat layer made of, for example, an ultraviolet curing resin. It may be provided.

The optical information recording medium of the present invention basically has an organic thin film provided on the above-mentioned support, but if necessary, aluminum, -, chromium,
A reflective layer of a reflective metal such as tin or a laminate layer can be provided.

Information is recorded by irradiating the organic thin film with a focused laser beam and by forming pits in the organic thin film due to thermal effects. When the pit depth t is made the same as the thickness of the organic thin film, it is possible to increase reflected heavy sound in the pit region. Does the reproduction of information use the same wavelength as the laser beam used for writing? If a laser beam with low intensity is used, the readout light will be largely reflected in the pit area, but will be absorbed in the non-pit area. This is done by detecting the difference. or.

Another method is to perform real-time recording with a laser beam of a first wavelength that is absorbed by the organic thin film, and use a laser beam of a second wavelength that is substantially transmitted through the organic thin film for reproduction. Laser beam for reproduction.

This is done by responding to changes in the reflective layer caused by different film thicknesses in pitted and non-pitted areas.

Also, there are two recording media with the same configuration as described above.

It is also possible to provide a recording medium in which the organic thin films are arranged so as to face each other.

In these cases, the organic thin film is isolated from the outside air, so
Preservation of the recording layer is significantly improved because it can be protected from dust, scratches, and contact with harmful gases.

The laser beam applied to the optical information recording medium of the present invention is
ArL'-za* He Ne laser 1He-c
Although a gas laser such as a d-laser is also possible, a semiconductor laser having a wavelength of 75011 m or more is preferred.

In addition to being used as a photoconductive composition or a source information recording medium, the photosensitive composition of the present invention can also be used as an infrared cut filter, a solar cell one-source sensor, or a laser light sensitive 8? It can also be used for other recording materials.

The photoconductive composition, which is the photosensitive composition of the present invention, is a highly sensitive photoreceptor that exhibits a sufficient sensitizing effect.

Also, compared to conventional laser electrophotographic photoreceptors.

It was possible to achieve extremely high sensitivity in a long wavelength region of 7j Onm or more, and also to improve stability. Further, a recording medium containing the novel photosensitive composition of the present invention is 7j (7yly11
Absorption on the longer wavelength side? The pyrylium dyes used in the present invention are highly sensitive and can provide a sufficiently improved ratio of 7 vS/l"i to a laser with
Although it has an absorption peak of more than 7JOnm, it is extremely stable against heat and light, and has significantly improved stability compared to the dyes described in JP-A-111111, for example. It is. Therefore, the stability of the recorded image on the recording medium of the present invention is significantly improved.

Specific examples of the present invention will be described below.

The scope of the present invention is not limited to these.

Examples 1 to 7 BoIJ-N-vinylcarbazole (trade name Rubican ty
o, manufactured by BASF, intrinsic viscosity [η]=l.

/'lf, coj0c, in THF) 52%M1 Dye JjIlv&3, J'-dinitrobenzanilide 30mQ and tmethylene chlorite coA
ltt and ethylene chloride 1-aJVc'l were dissolved to prepare a photosensitive solution. This photosensitive solution was coated onto a conductive transparent support (a 700 μm polyethylene terephthalate support with a surface resistivity of io + 10 with an indium oxide evaporation film) using a wirer's land rod. lμ
An organic thin film with a photosensitive layer was obtained.

Due to the corrosive discharge of this organic thin film i +jKV, a o
The amount of exposure required to attenuate the potential of the OVK band to +72, that is, the half-reduced exposure ILEt/2Cerg/c
m) Of course, it was measured.

As a light source, a Galiliu aluminum-arsenic semiconductor laser (oscillation wavelength: 130 nm) was used.

Example 8 As an organic photoconductive substance, g,4t'-bis(diethylamino)-1,λ'~dimethyltriphenylmethane 19
and Bisphenol A (bolicarbonate) (manufactured by GE,
Product name: Lexanlco/)jf.

The dyes 〇~ of Compound Specific Example (1) are used as chemical sensitizers.

Anilide compound of the following structural formula 0. , lf, Kura, methylene chloride JOtrl, and 30 ml of ethylene chloride were dissolved to prepare a photosensitive solution. An organic thin film was prepared in the same manner as in Example 5 and measured at -Ex/21.

El/2 is 6u, J (erg/cm2) T atyt.

(anilide compound) Examples 9-13 A specific example of the compound of Example 8 (in place of the dye in 11).

Soreso i-L l product Ac1Il (21, (51, (il
E l/2 k was measured in the same manner as in Example 8 except that the color x was used. The results are shown in Table λ.

4 Example 14 Compound Specific Example (2) in color @Jt00~ is placed in an MO boat for deposition in a vacuum evaporator, evacuated to 1x10 llllHg or less, and then deposited on a Pyrex substrate.

The pressure inside the vacuum chamber during vapor deposition was controlled so as not to rise above 10 waHg. In this manner, an optical information recording medium having a dye thin film of 0025 .mu.m2 provided on the /ξirex substrate was prepared.

The above optical recording medium was irradiated with smW and fMHz gallium-aluminum-arsenic semiconductor laser light @(oscillation wavelength rJ Onm)' (oscillation wavelength rJ Onm)' (on the recording layer surface for lμ seconds) focused to a spot size of O6gμm. When observed with a scanning electron microscope, clear pits were observed.In addition, when the low-power laser light and sound were incident on this medium,
When the reflected light was detected, a waveform with a sufficient S/N ratio was obtained.

After the recorded medium was left for λ weeks under dry conditions at a temperature of 100° C., it was reproduced under the same conditions as described above, and no change was observed at all compared to before the passage of time. On the other hand: Separately, a recorded recording medium was prepared in the same manner as above, and the temperature was 30±.
Tungsten light (jμooO1ux)k under the condition of j0C
After irradiation, playback was performed under the same conditions as above, and it was found that the S/N ratio was almost the same as before the light emission test.

(Comparative example) Using the known dye j00f shown below.

A film thickness of 0.2 was formed on the Pyrex substrate by the same operation as in Example 1.
A recording medium provided with a 6 μm thick organic thin film was printed.

Comparison dye fAl After writing and reproducing one line under the same conditions as Example 4, was there a sufficient S/N ratio? Indicated. Further, data was written under the same conditions as in Example 4, and after each heat resistance test and light emission test (kW) were performed, the IS/N ratio was compared with the sample before the durability test. decreased by JO-40.

As shown in the above results, the recording medium using the dye ligature of the present invention is
It has been confirmed that the recording medium is significantly more durable against heat and light than known recording media using dyes.

Example 15 Nitrocellulose solution (manufactured by Daicel F-Higaku Kogyo.

Methyl ethyl ketone J jw t% solution) 10ff,
Pigment compound example (2) dye 3.0? and tetrahydrofuran 100? "z Mixed and dissolved. This solution was applied to the acrylic substrate using the spinner coating method (ioo).

rpm), and dried for 2 hours at a temperature of 1oo0c (film thickness: 0.Jμynl.The recording medium thus prepared was mounted on a turntable, and while rotating at /g00rpm with a turntable motor, the spot size was The jmW and I MHz gallium-aluminum-arsenic semiconductor laser light (oscillation wavelength r
, tonm) Y5 Recording The recording was performed by irradiating the recording surface in a track shape. When the surface of this recorded recording layer was examined using a scanning electron microscope, clear bits were observed.

Furthermore, the above laser source with low output for this recording medium? When the incident and one reflected light was detected, a waveform with a sufficient S/N ratio was obtained.

On the other hand, in the same manner as in Example 14, the heat resistance and four-way tests were conducted under the same conditions, and then the Nyu-bon was recorded, and the S/N ratio tM was almost the same as before the durability test.

Example 16 An optical recording medium was prepared in the same manner as in Example 15, except that the dye ligature of Compound Specific Example (5) was used in place of the dye compound (2) used in Example 15, and then the same procedure was carried out. Laser light irradiation by operation? Sufficient S/N when recording and playing back
The ratio was obtained.

Example 17 An optical recording medium was prepared in the same manner as in Example 15, except that the color of compound specific example αυ; tt was used in place of the dye compound (2) used in Example 15, and then the same When the laser beam was emitted and recorded and played back, sufficient S/
The N ratio was obtained.

Claims (1)

[Scope of Claims] A photosensitive composition comprising at least one compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z represents an oxygen atom, an ion atom, a selenium atom, or a tellurium atom. X_1 represents an atomic group necessary to form optionally substituted pyran, benzopyran, naphthopyran, thiopyran, benzothiopyran, naphthothiopyran, selenapyran, benzoselenapyran, naphthoselenapyran, ternapyran, benzoternapyran, or naphthoselenapyran . X_2 is optionally substituted pyrylium, benzopyrylium, naphthopyryllium, thiopyrylium, benzothiopyrylium, naphthothiopyrylium, selenapyrylium, benzoselenapyrylium, naphthoselenapyrylium,
Represents the atomic group necessary to form ternapyrylium, benzoternapyrylium, or naphthoselenapyrylium. Y_1, Y_2, Y_3 and Y_4 may each be the same or different and represent a hydrogen atom, an optionally substituted aliphatic group, or an optionally substituted aromatic group. R is a hydrogen atom, a halogen atom, or an alkyl group, and A is
Represents a five-membered ring or a group of atoms necessary to form a five-membered ring. W^Θ represents an anion, and n and m represent 0 or 1.