JPS6341857A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain high sensitivity and high durability which are substantially practicable by incorporating a specific bisazulenium salt compd. into a titled compsn. CONSTITUTION:This compsn. comprises at least one kind of the bisazulenium salt compd. expressed by the formula I, II or III. In the formulas, R<1> denotes a hydrogen atom, lower alkyl group, etc., or the substitution product thereof, R<2> and R<2> denote a hydrogen atom, halogen atom, etc., or the substitution product thereof, R<4> denotes a hydrogen atom, alkyl group, etc., or the substitution product thereof, R<5>-R<11> denote a hydrogen atom, hydroxy group, etc., or the substitution product thereof. A substd. or unsubstd. arom. ring may be formed by at least one combination among the combinations; R<5> and R<6>, R<7> and R<8>, R<8> and R<9>, R<9> and R<10>, and R<10> and R<11>. B<1>, B<2> denote a hydrogen atom, lower alkoxy group, etc., or the substitution product thereof, Y denotes -O-, etc., R<12>, R<13> denote a hydrogen atom, halogen atom, etc., or the substitution product thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a photoconductive composition characterized by containing a novel bisazurenium salt compound. The present invention also relates to a HEATMO P optical information recording medium that performs recording and reproduction by causing a state change using a high-density energy beam.

``Prior art'' The electrophotographic method has already been published by Carlson in US Patent No. 22976.
As disclosed in the specification of No. 91, a photoconductive material such as a support coated with an insulating substance is used in the dark, the electrical resistance of which changes depending on the amount of radiation received during image exposure. . The photoconductive material is generally first given a uniform surface charge in the dark after dark adaptation for a suitable period of time. next,
The material is imagewise exposed to radiation, a pattern of radiation which has the effect of reducing the surface charge depending on the relative energy contained in each part of the R-turn. The surface charge or electrostatic latent image thus left on the surface of the photoconductive material layer (electrophotographic photosensitive layer) is then brought into contact with a suitable electrometric display material, ie, toner, to form a visible image. Become.

The toner is contained in an insulating liquid or in a dry carrier, and in either case it can be deposited on the surface of the electrophotographic photosensitive layer depending on the charge nosetan.

The deposited display material can be fixed by known means such as heat, pressure, and solvent vapor. Also, the electrostatic latent image is the second
can be transferred to a support (for example, paper, film, etc.). It is likewise possible to transfer the electrostatic latent image to a second support and develop it there. Electrophotography is one of the image forming methods that forms images in this manner.

The basic characteristics required of an electrophotographic photoreceptor in such an electrophotographic method are (1) ability to be charged to an appropriate potential in a dark place, (2) less dissipation of charge in a dark place, ( 3) The ability to quickly dissipate charges by light irradiation.

Conventionally, materials used as photoconductive materials for electrophotographic photoreceptors include selenium, Pmium sulfide, and zinc oxide.

However, while these inorganic substances have many advantages, they also have various disadvantages.

For example, selenium, which is currently widely used, is
Condition (3) is fully satisfied, but the manufacturing conditions are difficult and the manufacturing cost is high), it is not flexible, it is difficult to process it into a belt shape, and it is sensitive to heat and mechanical shock. It also has some drawbacks, such as the need for careful handling. Sulfidation power) % Mium and zinc oxide are dispersed in resin as a binder and used as electrophotographic photoreceptors, but they have mechanical drawbacks such as smoothness, hardness, tensile strength, and abrasion resistance. Therefore, it cannot be used repeatedly as is.

In recent years, electrophotographic photoreceptors using various organic materials have been proposed in order to eliminate the drawbacks of these inorganic materials, and some of them have been put into practical use. For example, 4-N-vinylcarnozole and 2,4,7-dolinitrofluorene-9
- Electrophotographic photoreceptor (US Pat. No. 3,484)
, 237), poly N-vinylcarnozole sensitized with pyrylium salt dye (%Koshō 48-25658
), an electrophotographic photoreceptor whose main component is an organic pigment (Japanese Unexamined Patent Publication No. 4
7-37543), an electrophotographic photoreceptor whose main component is a eutectic complex consisting of a dye and a resin (Japanese Unexamined Patent Application Publication No. 1987-47-N).

785).

Electrophotographic photoreceptors using organic materials such as can also be improved. Furthermore, the wavelength of light sensitivity can be freely controlled by selecting dyes and organic pigments. However, on the other hand, it had low photosensitivity and was not suitable for repeated use, so it did not fully meet the requirements as an electrophotographic photoreceptor.

As a result of intensive research aimed at solving the drawbacks of the conventional electrophotographic photoreceptors, the present inventors have found that an electrophotographic photoreceptor using a photoconductive composition containing a novel bisazurenium salt compound is sufficiently effective. The present invention was achieved based on the discovery that it has high sensitivity and high durability that can be put to practical use.

On the other hand, conventional recording methods in which a beam of high energy density is irradiated onto an information recording medium to change physical property constants such as transmittance, reflectance, and refractive index, produce images with extremely high resolution and contrast. It has the advantages of being suitable for recording the output of electronic computers and transmitted time-series signals, as it has the characteristics of being able to record data at the same time as it is exposed, and that information can be added later. Has CO
It is applied to M (computer output micro), micro facsimile, original printing plates, optical discs, etc.

For example, recording media used in optical disk technology can store high-density information using optically detectable tables, small pits around 1 micron in the form of spiral or circular tracks. To write information on such a disk, a focused laser is scanned over 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. do.

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

The information recorded on the optical disc in this manner is detected by scanning a laser along the track and reading optical changes in areas where pits are formed and areas where pits are not formed.

Conventionally, information recording media capable of recording HeatMoP include thin films of metals and/or metal oxides, semimetallic dielectrics, etc. on transparent supports such as plastics, or self-oxidizing binders and dyes. A recording medium has been used in which a thin film containing .

However, conventional thin films mainly composed of inorganic substances have a high reflectance to laser light, which reduces the efficiency of laser use and therefore makes it impossible to obtain high sensitivity characteristics, or the laser light during recording. There were problems such as a significant increase in output.

On the other hand, organic compounds generally have problems such as their absorption characteristics becoming unstable as they extend into longer wavelength ranges, and decomposition due to slight increases in temperature, resulting in poor quality.

Therefore, the direct read-after-write capability (DRAW)
A recording medium with a recording medium must have a high absorption efficiency for the laser beam used, a reflectance that allows sufficient focus control during record reading, or a recording medium that has a Various characteristics such as stability must be satisfied, and a recording medium containing an organic thin film that is fully satisfactory from a practical point of view has not yet been developed.

The present inventors have arrived at the present invention as a result of intensive research in order to eliminate the above-mentioned drawbacks.

"Problems to be Solved by the Invention" An object of the present invention is to provide a photoconductive composition that can be applied to various photoconductors. Another object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity and stable potential characteristics in repeated use.

Another object of the present invention is to provide an optical information recording medium that has high storage stability, high sensitivity, and a sufficient S/N ratio.

"Means for solving the problem" The present invention provides a photosensitive composition characterized by containing at least one of the bisazurenium salt compounds represented by the following - membrane force CD, (2) or [3] It is a thing.

- In membrane forces (1), (2) and [3], R1
represents a hydrogen atom, a lower alkyl group, an aryl group, an alkoxycarzenyl group, an aryloxycarzenyl group, an acyl group, or a substituted product thereof.

R and R represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, or a substituent thereof.

R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a substituent thereof.

R5, R6, R7, R8, R9, R10 and R are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an acyl group, a carxyl group, an alkali metal carboxyl group, or an alkali metal group. xylard group,
carnomoyl group, sulfonic acid group, sulfamoyl group,
It represents an alkali metal sulfonate group, nitro group, cyano group, amino group, hydroxyl group, or a substituted product thereof.

Also, R5 and R6, R7 and R8, R8 and R9, R9 and R1
0 and at least one combination of R and R may form a substituted or unsubstituted aromatic ring.

B, B are hydrogen atoms, halogen atoms, lower alkyl groups,
Represents a lower alkoxy group or a substituted product thereof, B1
, B2 may be the same or different groups. B1, B2
The position and number of the images are arbitrary. Y is N-R, -0-1-8
-1-8・-1, C=O.

RXR represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or a substituent thereof.

q represents an integer of 0.1 or 2.

ze represents an anion residue.

R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a 7-aryl group having 6 to 20 carbon atoms, an alkoxycarzenyl group having an alkoxy group having 1 to 12 carbon atoms, and an alkoxycarzenyl group having 6 to 20 carbon atoms.
There are aryloxycarfer groups and acyl groups having 1 to 20 carbon atoms.

When R1 is an unsubstituted alkyl group, specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Examples include hexyl group, isopropyl group, isobutyl group, inhexyl group, neopentyl group, tart-butyl group, and the like.

When R1 is a substituted alkyl group, the substituent includes a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a cyano group, an alkylamino group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. dialkylamino group, halogen atom,
Examples include aryl groups having 6 to 15 carbon atoms. As an example, a hydroxymethyl group, a hydroxyalkyl group,
2-hydroxymethyl group, 3-hydroxymethyl group, 2
-hiroxyprobyl group, etc.), alkoxyalkyl group (
For example, methoxymethyl group, 2-methoxyethyl group, 3
-methoxyprogyl group, ethoxymethyl group, 2-ethoxyethyl group, etc.), cyanoalkyl group (e.g. cyanmethyl group, 2-cyanethyl group, etc.), (alkylamino)alkyl group (e.g. Methyl group, 2-(
(methylamino)ethyl group, (ethylamino)methyl group, etc.), (dialkylamine)alkyl group (e.g., (dimethylamino)methyl group, 2-(dimethylamino)ethyl group, etc.), halogenoalkyl group (e.g., fluoromethyl chloromethyl group, bromomethyl group, etc.), and aralkyl groups (eg, benzyl group, phenethyl group, etc.).

When R1 is an unsubstituted alkoxycarnonyl group, specific examples include a methoxycarnonyl group, an ethoxyl group, a propoxycarbinyl group, a poxycarzenyl group, a penzyloxycarbinyl group, and the like.

R1 is an unsubstituted aryl group, unsubstituted aryloxycar2
In the case of a nyl group, specific examples thereof include a phenyl group, a naphthyl group, a pyridyl group, a phenoxycarbinyl group, a naphthoxycarbinyl group, and the like.

When R1 is an unsubstituted acyl group, specific examples include an acetyl group, a propionyl group, a benzoyl group, a naphthoyl group,
Examples include a nicotinoyl group.

R1 is a substituted alkoxycar2nyl group, a substituted aryl group,
In the case of the substituent R-roxycarunyl group and H-substituted acyl group, the same substituents as the substituents of the substituted alkyl group in 81 above can be mentioned, and the number of substituents is 1.
When a plurality of substituents are bonded, they may be the same or different from each other, or may be in any combination, and the bonding positions of the substituents may be arbitrary.

When R2 or R3 is a halogen atom, specific examples include a fluorine atom, a chlorine atom, a bromine atom, and the like.

When R2, R3 or R4 is an alkyl group, aryl group, aralkyl group or a substituent thereof, specific examples thereof include the above-mentioned R1 when it is an alkyl group, an aryl group, an aralkyl group or a substituent thereof; The same groups as in the specific examples can be mentioned.

R5, R6, R7, R8, R9, R1Q maku is H+ 1
When is a halogen atom, specific examples include a fluorine atom, a chlorine atom, a bromine atom, etc.

R5, R6, R7, R8, R9, n 10 or R11
When is an alkyl group, an aryl group, or an aralkyl group, specific examples thereof include the above-mentioned R1
The same examples as in the case where is an alkyl group, an aryl group, an aralkyl group, or a substituted product thereof can be mentioned. R5, R6, R7, R8, 6R10 or R11
When is an unsubstituted alkoxy group or aryloxy group, specific examples include a methoxy group, an ethoxy group, a pro4
Examples include alkoxy groups such as xy, and aryloxy groups such as phenoxy and naphthoxy groups. ms, R
When 6,17, R8, R9, ulo or R11 is an alkoxy group or aryloxy group having a substituent, specific examples of the substituent include the same substituent as the above-mentioned substituent when R1 is a substituted alkyl group. Other examples include alkyl groups such as methyl, ethyl, and isopropyl. R5, R6, Rtsu, R8, R9, R10 or R1
When 1 is an unsubstituted acyl group, examples of its variants include an acetyl group, a benzoyl group, a naphthoyl group, and the like. When R5, R', R', R8, R9, n10 or R11 is an acyl group, carnomoyl group or amine group having a substituent, specific examples of the substituent include the above-mentioned R1 being a substituted alkyl group. In addition to the same substituents as those mentioned above, alkyl groups such as a methyl group, an ethyl group, and an isopropyl group can be mentioned. R5, R6, R7, R8
, R9, H+ O or R is an alkali metal carboxylate group or an alkali metal sulfonate group,
Specific examples of alkali metals (cations) include Na0, K
o, Llo, etc.

R5 and R6, R7 and R8, R8 and R? , R9 and R10 or a combination of R and R to form an unsubstituted aromatic ring, specific examples include benzene ring, naphthalene ring, pyridine ring, thiophene ring, azulene ring, tropone ring, thiazole ring, oxazole ring, etc. I can give it to you. R
When an aromatic ring having a substituent is formed by a combination of 5 and B6.17 and R8, R and RXR and R, or R and R, specific examples of the substituent include the above-mentioned substitution when R1 is a substituted alkyl group. In addition to the same groups as the above groups, alkyl groups such as methyl, ethyl, and inpropyl groups can be mentioned.

When R12 and Rls are lower alkyl groups, specific examples thereof include methyl group, ethyl group, isopropyl group, etc., and when R and R are lower alkoxy groups,
Specific examples thereof include methoxy group, ethoxy group, propoxy group, etc. When R12 and R13 are halogen atoms, specific examples thereof include fluorine atom, chlorine atom,
I can list the bromine atom.

When B1 and B2 are halogen atoms, specific examples thereof include fluorine atom, chlorine atom, and bromine atom,
When B1 and B2 are lower alkyl groups, specific examples thereof include methyl group, ethyl group, isopropyl group, etc. When B1 and B2 are lower alkoxy groups, specific examples thereof include methoxy group, ethoxy group, Examples include propoxy groups.

ze represents all anionic residues, specific examples of which include verchlorate, fluorofrate, iodide, chloride, bromide, sulfate, nose iodide rX p-)luenesulfonate, and the like.

The bisazurenium compound of the present invention has the following general formula [4
], [5] or [6] and an azulene compound in the presence of a strong acid in a suitable solvent.

Reaction solvents used include alcohols such as ethanol, butanol, and tetrahedral alcohol, nitrile acids such as acetonitrile and zolobionitrile, organic calzes/acids such as acetic acid, acid anhydrides such as acetic anhydride, dioxane, and tetrahydropolymer. Alicyclic ethers such as lofuran are used.

Furthermore, aromatic hydrocarbons such as benzene can be mixed with butanol, benzyl alcohol, and the like. The temperature during the reaction can be selected from the range of room temperature to boiling point.

Examples of the strong acid that can be used include sulfuric acid, hydrochloric acid, hydrobromic acid, hydriodic acid, perchloric acid, periodic acid, and hydrofluoroboric acid.

[4] [5] [6] - Membrane force CI) The bis azulenium salt compounds of the present invention represented by (2) or [3] are listed below.

However, the compounds used in the present invention are not limited to these.

■ -1
To Hei
Heη
Sunrieto
Roro Φ e-opening■ ■clll
~ Mi Engineering O- 1
〇Senrai 8 C■ Agony- to N; 9-Shikou-Kuzu 8 Country Engineering S 8 壬8 S l-1-1e'I Q to Agonyt F9
RO ■ ■ 工 閤 2 meeting flash engineering ro words! xol] The electrophotographic photoreceptor of the present invention has the above-mentioned film strength (1), C2:
) or [3].

Although various types of electrophotographic photoreceptors are known, the electrophotographic photoreceptor of the present invention may be any type of photoreceptor; Motsu.

(a) An electrophotographic photosensitive layer comprising a bis-azulenium salt compound dispersed in a non-inder or a charge carrier transport medium is provided on a conductive support.

(b) A charge carrier generation layer containing a bisazurenium salt compound as a main component is provided on a conductive support, and a charge carrier transporting medium layer is provided thereon.

The bis-azulenium salt compound of the present invention acts as a photoconductive substance, and when it absorbs light, it generates charge carriers with extremely high efficiency, and the generated charge carriers can also be transported using the bis-azulenium salt compound as a medium. However, it is more effective to use a charge carrier transport compound as a vehicle.

To prepare an electrophotographic photoreceptor of the type (,), fine particles of a pis azulenium salt compound are dispersed in an inder solution or a solution containing a charge carrier transport compound and an inder, and these are dispersed in a conductive support. The thickness of the "electrophotographic photosensitive layer" which can be coated on top and dried is preferably 3 to 30 .mu.m, preferably 5 to 20 .mu.m.

To prepare an electrophotographic photoreceptor of type (b), a bisazurenium salt compound is vacuum-deposited on a conductive support, or
Alternatively, fine particles of a bis-azulenium salt compound are dispersed in a suitable solvent or, if necessary, a solvent in which an inder is dissolved, and after coating and drying, a solution containing a charge carrier transport compound and an inder is applied thereon. Obtained by coating and drying. The thickness of the bis azulenium salt compound layer serving as the charge carrier generation layer at this time is preferably 4 μm or less, preferably 2 μm or less, and the thickness of the charge carrier transport medium layer is 3 to 30 μm, preferably 5 to 20 μm.

The bis-azurenium salt compound used in the photoreceptors of types (,) and (b) is used after being ground to a particle size of 5 μm or less, preferably 2 μm or less, using a dispersing machine such as a Zeel mill, a sand mill, or a vibration mill.

If the amount of bisazurenium salt compound used in the type (&) electrophotographic photoreceptor is too small, the sensitivity will be poor;
If it is too large, the charging property will deteriorate and the strength of the electrophotographic photosensitive layer will become weak.
1 to 2 times by weight, preferably 0.05 to 1 times by weight,
The ratio of the charge carrier transport compound added as needed is 0.1 to 2 times the weight of the binder, preferably 0.3 to 1 times the weight of the binder.
．． In the case of a charge carrier transport compound that can itself be used as an indium, the amount of the bis azulenium salt compound to be added is 0 to 0 in the noninder.
．． It is preferable to use 0.01 to 0.5 times the amount by weight.

Further, when forming a bis-azulenium salt compound-containing layer which becomes a charge carrier generation layer in the electrophotographic photoreceptor of type (b), the use Tit of the bis-azurenium salt compound relative to the binder resin is preferably 0.1 times or more by weight. If it is less than that, sufficient photosensitivity cannot be obtained. The proportion of charge carrier transport compounds in the charge carrier transport medium is 0 to
．． 2 to 2 times the weight, preferably 0.2 to 1.3 times [Takanobu is preferred. When using polymeric charge carrier transport compounds which themselves can be used as inders, other inders can be used without them.

In addition, for type (b) photoreceptor, patent application No. 59-531
No. 83, Patent Application No. 1983-109906, Patent Application No. 1987-1
As described in each specification of No. 18414, a charge carrier transport compound such as a hyplazone compound or an oxime compound can be added to the charge carrier generation layer.

When producing the electrophotographic photoreceptor of the present invention, additives such as a plasticizer or a sensitizer may be used in addition to Nononingoo.

The conductive support used in the electrophotographic photoreceptor of the present invention includes a metal plate made of aluminum, copper, zinc, etc., a plastic sheet made of polyester, or a plastic film on which a conductive material such as aluminum, indium oxide, SnO2, etc. is deposited by vapor deposition. Alternatively, dispersion coating or conductive treated paper may be used.

As the binder, it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. Examples of such high molecular weight polymers include, but are not limited to, the following.

Polycarbonate, polyester, polyester carbonate, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer , vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyra resin, phenol-formaldehyra+ resin, styrene-alkyra resin, poly-N-vinylcarbazole.

These binders can be used alone or in a mixture of 21 or more.

Plasticizers include piphenyl, chlorinated biphenyl, 0-terphenyl, p-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate,
Examples include triphenylphosphoric acid, methylnaphthalene, benzophenone, chlorinated nomirafine, polypropylene, polystyrene, dilaurylthiodipropionate, 3,5-dinitrosalicylic acid, various fluorohydrocarbons, and the like.

In addition, silicone oil or the like may be added to improve the surface properties of the electrophotographic photoreceptor.

Sensitizers include chloranil, tetracyanoethylene,
Methyl iolet, rhodamine B, cyanine dye,
Merocyanine dyes, pyrylium dyes, thiapyrylium dyes, etc. are praised.

Compounds that transport charge carriers are generally classified into two types: compounds that transport electrons and compounds that transport holes, and both can be used in the electrophotographic photoreceptor of the present invention. Compounds that transport electrons include compounds having an electron-withdrawing group, such as 2,4.7-dolinitro9-
Fluorenone, 2.4,5.7-tetranitro-9-fluorenone, 9-dicyanomethylene-2,4,7-dolinitrofluorenone, 9-dicyanomethylene-2゜4.
5.7-titranitrofluorenone, tetranitrofluorenazole chloranil, 2,3-diqua-5,6-diciatubenzoquinone, 2 + 4 + 7-dolinitro 9,10-phenanthrenequinone, tetrachlorophthalic anhydride, Examples include tetracyanoethylene and tetracyanoquinodimethane.

A compound that transports holes is a compound having an electron-donating group, such as a polymer, as described in (1) Japanese Patent Publication No. 34-1
Polyvinyl carnozole and its derivatives as described in Japanese Patent Publication No. 0966, (2) polyvinylpyrene as described in Japanese Patent Publication No. 18674-1974 and Japanese Patent Publication No. 19192-1972,
Polyvinylanthracene, poly-2-vinyl-4-(4
vinyl polymers such as '-umethylaminophenyl)-5-phenyl-oxazole and 4+7-3-vinyl-N-ethylcarnosol; Polymers such as copolymers of acenaphthylene and styrene, (4) Japanese Patent Publication No. 56-139
Condensation resins such as birene-formaldehye P resin, brompyrene-formaldehyde resin, and ethyl carnocesol-formaldehye P resin described in Publication No. 40, (5
) JP-A-56-90883 and JP-A-56-1615
Various triphenylmethane polymers described in Publication No. 50, and among low molecular weight ones, (6) triazole derivatives described in US Patent No. 3112197, etc., (7) US Patent filE 3189447, etc. (8) Imidazole derivatives described in Japanese Patent Publication No. 37-16096, (9) U.S. Patent A: 3615402, U.S. Patent No. 38209
No. 89, No. 3542544, Equity No. 1845-555, Japanese Patent Publication No. 10983-1983, Japanese Patent Publication No. 93224-1983
No., JP-A-55-108667, JP-A-55-156
Polyarylalkane derivatives described in No. 953, JP-A No. 56-36656, publications, etc., αO U.S. Patent No. 3180729, U.S. Patent No. 4278
No. 746, JP-A-55-88064, JP-A-55-8
No. 8065, JP-A-49-105537, JP-A-55
-51086 No. 1 JP-A-56-80051, JP-A-5
Pyrazoline derivatives and pyrazolone derivatives described in JP-A No. 6-88141, JP-A-57-45545, JP-A-54-112637, JP-A-55-74546, publications, etc., 0υ US Pat. No. 3,615,404 , 'Sho 51-1
No. 0105, JP-A-54-83435, JP-A-54-
110836, JP-A No. 54-119925, JP-B No. 413-3712, JP-B No. 28336-Sho 47-28336, and gazettes, etc.; 49-35
No. 702, West German Patent (DAS) No. 1110518, US Patent No. 3180703, US Patent No. 3240597
No. 3,658,520, U.S. Pat. No. 4,232
No. 103, U.S. Patent No. 4,175,961, U.S. Patent No. 4
012376, JP-A-55-144250, JP-A-56-119132, JP-A-39-27577, JP-A-56-22437 specification, official gazette, etc., (19 Amino-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501, α9 N,N-bicalnodyl derivatives described in U.S. Pat. No. 3,542,546, etc., U.S. Pat. No. 32
oxazole derivatives described in JP-A No. 57203, etc., αG styryl anthracene derivatives described in JP-A-56-46234, etc., αD fluorenone derivatives described in JP-A-54-110837, etc., α9 U.S. Patent No. 3717462, Japanese Patent Application Publication No. 1983-59
No. 143 (corresponding to U.S. Pat. No. 4,150,987), JP-A-55-52063, JP-A-55-52064, Jikai W355-46760, JP-A-55-85495, JP-A-57-11350 , Japanese Patent Publication No. 57-14874
9, hyP lazone derivatives disclosed in JP-A-57-104144, etc., α9 U.S. Patent No. 4047948, U.S. Patent No. 404
No. 7949, U.S. Patent No. 4,265,990, U.S. Patent No. 4
Benzidine derivatives described in US Pat. No. 273,846, US Pat. No. 4,299,897, US Pat. No. 4,306,008, etc.;
No. 40, JP-A-59-97148, JP-A-59-19
Examples include stilbene derivatives described in Japanese Patent No. 5658 and the like.

In the present invention, the compound that transports charge carriers is (1
The present invention is not limited to the compounds listed in 1 to 2, and all charge carrier transport compounds known to date can be used.

Two or more types of these charge transport materials may be used in combination depending on the case.

In the photoreceptor obtained as described above, an adhesive layer or a rear layer may be provided between the conductive support and the photosensitive layer, if necessary. Materials used for these layers include the high molecular weight polymer used in the above-mentioned non-ingu, gelatin, casein, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose,
The vinylidene chloride polymer latex described in JP-A No. 59-84247, the styrene-butadiene polymer latex or aluminum oxide described in JP-A No. 59-114544, and the thickness of these layers is 1.
It is preferably less than μm.

The electrophotographic photoreceptor of the present invention has been described in detail above, and the electrophotographic photoreceptor of the present invention generally has characteristics such as high sensitivity (excellent durability).

The electrophotographic photoreceptor of the present invention can be widely applied in fields such as photoreceptors for printers using lasers and cathode ray tubes as light sources, as well as electrophotographic copying machines.

The photoconductive composition containing the bis-azulenium salt compound of the present invention can be used as a photoconductive layer in the image pickup tube of a video camera, or on the entire surface of a one-dimensional or two-dimensional array of semiconductor circuits for performing known signal transfer or scanning. It can be used as a photoconductive layer of a solid-state image sensor having a light receiving layer 78i (photoconductive layer) provided in the photoconductive layer. Also, A, ni, :P-sh et al. (fi-ni,
Ghosh, Tom Feng, J.

Appl, Phys, 49 (12), 598
2 (1978)), it can also be used as a photoconductive layer in solar cells.

The bis-azurenium salt compound of the present invention can also be used as photoconductive colored particles in a photoelectrophoresis system and any colored particles in a dry or wet electrophotographic developer.

In addition, the bis azulenium salt compound of the present invention was
-17162, JP-A-55-19063, JP-A-5
K as disclosed in No. 5-161250 and Japanese Unexamined Patent Publication No. 57-147656.

It is dispersed in an alkali-soluble resin solution such as phenol resin together with the above-mentioned charge carrier transporting compounds such as oxadiazole derivatives and hydrazone derivatives, coated on a conductive support such as aluminum, and after drying, image exposure, toner development, Etching with alkaline aqueous solution provides high resolution,
In addition to producing highly durable and highly sensitive printing plates, it is also possible to create printed circuits.

Next, an example of using the photosensitive composition of the present invention as an optical information recording medium will be described.

That is, the optical information recording medium of the present invention is constructed by forming an organic thin film containing at least the bisazurenium salt compound of the present invention on a support. It can be formed using various methods such as coating.

When using a coating method, organic solvents include alcohols (e.g., methanol, ethanol, impropatol, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amyl compounds (e.g., N, N-dimethylformamide P, N, N-dimethylacetamide S, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane, monoglyme, diglyme, etc.) etc.), halogenated hydrocarbons (for example, methylene chloride, chloroform, methylchloroform, carbon tetrachloride, monochlorobenzene, dichlorobenzene, etc.) can be used alone or in combination. The pigments can be selected from known natural or synthetic resins, and specifically include cellulose resin C; nitrocellulose, cellulose phosphate, cellulose acetate, cellulose butyrate, Methyl cellulose, ethyl cellulose, butyl cellulose, etc.), acrylic resins (e.g., polymethyl methacrylate, polydityl methacrylate, polybutyl acrylate, ?rimethacrylic acid, polyacrylamide P1 polymethacrylamide, ?lyacrylonitrile, etc.), vinyl resins ( For example, polystyrene, polyvinyl acetate, polyvinyl chloride, norivinyl alcohol, polyvinyl pylori P
polycarbonates, polyesters, polyamide resins, epoxy resins, phenolic resins, polyolefin resins (e.g. polyethylene, I-lipropylene, etc.)
Alternatively, a synthetic copolymer resin or the like can be used. Application can be carried out using general-purpose coating methods such as spraying, roller coach ink, spinner coach ink, and spray coating.

When forming an organic thin film together with a resin, the content of the bisazurenium salt compound in the thin film is 5 to 90% by weight.
The amount is preferably 15 to 80% by weight, and the remainder is noninder. Also, the vapor deposited film thickness or dry film thickness of the organic thin film is 10
The thickness is not more than μm, preferably not more than 2 μm.

Furthermore, an anti-fading agent and a coloring agent can be contained in 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 transparent or opaque to the laser beam 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.).

When writing and recording is performed by irradiating a laser beam from the support side, it must be transparent to the laser beam.On the other hand, when writing and recording is performed from the opposite side of the support, that is, the surface of the recording layer. , need not be transparent to laser light. However, when reading and reproducing using transmitted light,
Must be transparent to readout laser light. On the other hand, when reading and reproducing are performed using reflected light, it may be transparent or opaque to the reading laser beam. Further, the support may be provided with guide grooves formed of unevenness, if necessary, or may be provided with an undercoat layer made of, for example, an ultraviolet curing resin.

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, silver, chromium, etc. may be added between the support and the organic thin film. A reflective layer such as a vapor deposited layer or a laminate layer of a reflective metal such as tin can be provided.

The recording of information is carried out by the formation of pits in the organic thin film by the thermal effect of irradiation with a focused laser beam on the organic thin film. When the depth of the pit is made the same as the thickness of the organic thin film, the reflectance in the pit region can be increased. The reproduction of 1 yen information has the same wavelength as the laser beam used for writing, but if a laser beam with low intensity is used, the read light will be largely reflected in the bit area, but will be absorbed in the non-pit area. This is done by detecting the difference in reflected light from the pit-formed area and the non-pit-formed area. 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 substantially passes through the organic thin film for reproduction. This is achieved by the reproduction laser beam responding to changes in the reflective layer caused by the different film thicknesses in pitted and non-pitted areas.

Further, it is also possible to use a recording medium having a configuration in which two recording media having the same configuration as described above are arranged so that the organic thin films face each other.

In this case, since the organic thin film is isolated from the outside air, preservation of the recording layer is significantly improved since it can be protected from dust adhesion, generation of dust, and contact with harmful gases.

As the laser beam applied to the optical information recording medium of the present invention, gas lasers such as Hs-Ne laser and He-Cd laser, and semiconductor lasers having a wavelength of 750 nm or more can be used.

Furthermore, the recording medium containing the novel photosensitive composition of the present invention provides high sensitivity and a sufficiently improved S/N ratio to lasers that have absorption in the long wavelength range of 750 nm or more. be able to.

The photosensitive composition of the present invention can be used not only as an electrophotographic photoreceptor, a photoconductive composition, or an optical information recording medium, but also as an infrared cut filter, a photosensor, or other recording material using laser light sensitivity. Can be used.

"Examples" Next, the present invention will be specifically explained using synthesis examples and examples, but the present invention is not limited to the examples. In the examples, "parts" indicate "parts by weight."

Synthesis Example 1 (Synthesis of the above-mentioned exemplary compound (2)) 4.4'-
Diformyl-N-methyl-N,N-diphenylamine 4
78 ■ and Higeia Azulene 792 Misaki with 2 oi of acetic anhydride
After dissolving, 1.92 ml of p-)luenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 1 hour. Next, pour the reaction mixture into 200 g of ice water.
After pouring into m1 and stirring for 1 hour, ethyl alcohol is
omj was added and stirred for an additional 30 minutes. Furthermore, a solution of 630 η of sodium iodide dissolved in Sml of water was added to this solution, and the mixture was stirred at room temperature for 2 hours, and then left at room temperature overnight. Next, count the formed precipitate and add water (200 + 1!7).
, ethyl alcohol (50:nl), vinegar m ethyl (50
-), green crystals of 863119 were obtained after drying. Yield 50%.

The properties of the compound were as follows.

Decomposition point 138-140℃, maximum absorption wavelength 657 nm Elemental analysis value C45H47N Calculated value as I2 C, 63, 17%H, 5,53%N, 1.64
%I, 29.66% Actual value C, 62.95%H, 5.77%N, 1.58
I
The above-mentioned exemplified compound (3) was synthesized in the same manner as in Synthesis Example 1 except that Jiumum was changed to 1.08F. Black-purple crystals of 889~ were obtained. Yield 56%.

The properties of the compound were as follows.

Decomposition point 143-145℃ Maximum absorption wavelength 654 nm Elemental analysis value C45) 147 N Calculated value as C1204 C,6
7,50%H, 5,92%N, 1.75%α, 8.8
5% Actual value C, 67, 35% H, 6,03% N, 1.70
% α, 8.59% Example 1 Bis azulenium salt compound synthesized in Synthesis Example 1 2.1
4.4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane 5 parts and bisphenol A polycarbonate (trade name: Lexan 121 GE)
A conductive transparent support (100 parts
An indium oxide vapor deposited film is provided on the surface of a 3m polyethylene terephthalate film. Surface resistance 10'Ω
) and dried to prepare an electrophotographic photoreceptor having a single-layer electrophotographic photosensitive layer with a thickness of about 8 μm.

This electrophotographic photoreceptor was statically charged to +400V by leaving the corona at +5kV using an electrostatic copying paper tester (Model 5P-428 manufactured by Yoro Denki ■).
The exposure amount required for the potential to attenuate by half, that is, the half-reduction exposure amount Eka (:erg/cj) was measured. A gallium, aluminum arsenide semiconductor laser (oscillation wavelength: 780 nm) was used as a light source. As a result, E. =
It was 30.3 erg/-.

Examples 2 to 7 In Example 1, an electrophotograph of a single layer structure was prepared in the same manner as in Example 1, except that the bis azulenium salt compound shown in Table 1 was used instead of Compound Part 2 synthesized in the Synthesis Example. A photoreceptor was prepared, and the half-reduced exposure amount Eso due to positive charging was measured in the same manner as in Example 1. The results obtained are shown in Table 1.

Table 1 Example 8 Bis azulenium salt compound pigeon 3.5 synthesized in Synthesis Example 2
After dispersing in a ball mill for 20 hours with a solution of 5 parts of Noryester resin (trade name: Noceilon 200, manufactured by Toyobo ■) dissolved in 50 parts of Tetrahyprofuran, conductive Support (75 μm
An aluminum vapor-deposited film is provided on the surface of a polyethylene terephthalate film. Surface electrical resistance 4×1o2
Ω) and dried to produce a charge generation layer with a thickness of 0.5 μm.

Next, on the charge generation layer, p-(diphenylamino)benzaldehyde N'-methyl-N'-phenyl was applied.
．． 6 parts of polycarbonate of bisphenol A and 13.3 parts of dichloromethane and 2 parts of 1,2-dichloroethane.
A 6.6 part solution was applied and dried using a wire round iron to form a charge transport layer with a thickness of 11 μm, thereby producing an electrophotographic photoreceptor consisting of two layers.

The initial surface potential (2) of this electrophotographic photoreceptor was charged by -6 kV corona discharge for 2 seconds using an electrostatic copying paper tester (Model 5P-428 manufactured by Yoro Denki (1)).

Then, after measuring the potential v3 when left in a dark place for 30 seconds, we measured the potential v3 of the gallium, aluminum, arsenic semiconductor laser (
The photoreceptor was exposed to light using a light source with an oscillation wavelength of 780 nm. At this time, the amount of exposure required to attenuate the potential v3 by half when left for 30 seconds in a dark place, that is, half-decreased exposure i E5
0 (erg/-)].The results were as follows.

V=-630V V=-590V E50: 15.3 erg/cJ Similar measurements were repeated 3000 times.

As a result, it was found that the fluctuations in vo, vs, and E5o described above were extremely small, and that this photoreceptor had good edge-turning characteristics.

Examples 9 to 21 In Example 8, the compound NEL3 synthesized in Synthesis Example 2
A two-layer electrophotographic photoreceptor was prepared in the same manner as in Example 8, except that the bisazurenium salt compound shown in Table 2 was used instead of , and the half-decreased exposure amount E5o was measured in the same manner as in Example 8. did. The results are shown in Table 2.

Table 2 Furthermore, the electrophotographic photoreceptors of Examples 9 to 21 were repeatedly measured 3000 times in the same manner as in Example 8, and the VoSV, E5o values were all very stable and excellent with little fluctuation. Ta.

Example 22 Bisazurenium salt compound magnetic compound synthesized in Synthesis Example 1 2.5
parts, 40 parts of the hyP lazone compound used in Example 8, a copolymer of benzyl methacrylate and methacrylic acid ([η
[Methyl ethyl ketone = 0.12 at 30°C, methacrylic acid content 32.9%) 100 parts and dichloromethane 66
It was added to 0M and subjected to ultrasonic dispersion.

This dispersion was coated on a grained aluminum plate with a thickness of 0.25 m and dried to prepare an electrophotographic photosensitive printing plate material having an electrophotographic photosensitive layer with a dry film thickness of 6 m.

This sample was charged with corona discharge (+6 kV') in the dark to bring the surface potential of the photosensitive layer to about +6 QOV, and then exposed to a gallium, aluminum, and arsenic semiconductor laser (oscillation wavelength 780 nm). The half-decrease exposure amount was 22.3 crg/-.

Next, this sample was charged to a surface potential of about +400 in a dark place, and then brought into close contact with a transparent original with a positive image, and imagewise exposed. As a light source, a gallium, aluminum, arsenic semiconductor laser (oscillation wavelength: 780 nm') was used. This was mixed with 5 parts of polymethyl methacrylate (toner) dispersed in the form of fine particles in 1000 parts of l5oper H (Tuso Standard Co., Ltd., petroleum solvent) and 0.0 parts of soybean oil lecithin.
It was possible to obtain a clear positive toner image by immersing the toner in a liquid developer containing the toner prepared by adding 1 part of 0.01 parts.

The toner image was further fixed by heating at 100° C. for 30 seconds. When this printing plate material is immersed in a solution of 70 parts of sodium metasilicate hydrate dissolved in 140 parts of glycerin, 550 parts of ethylene glycol, and 150 parts of ethanol for about 1 minute, and washed with a stream of water while lightly brushing, Remove the electrophotographic photosensitive layer in areas where toner is not attached,
A printing plate was obtained.

Instead of a liquid developer, the obtained 'Fp' DL latent image was developed with a magnetic brush using toner for Xerox 3500 (manufactured by Fuji Xerox ■), and then heated at 80° C. for 30 seconds to fix it. Next, a printing plate was also obtained by removing the photosensitive layer in the areas to which toner was not attached using an alkaline solution.

The printing plate produced in this way was used as Hamadastar 600C.
It was possible to print 50,000 sheets of very clear printed matter with no spot stains by printing using a D-offset printing machine in a conventional manner.

Example 23 Nitrocellulose solution (Daicel Chemical Industries 'B, 25 wt% methyl ethyl ketone solution) 102, bis azulenium salt compound Nl synthesized in Synthesis Example! L4.3, Of and TetrahyP Lofuran 1002 were mixed and well dispersed. This dispersion was applied to an acrylic substrate using a spinner coating method (lQOOrprr+), and then heated to 80°C.
It was dried at ℃ for 2 hours (film thickness 0.3 μm). The recording medium prepared in this way was mounted on a turntable, and while the turntable was rotated by a motor at 180 Or, p, rn, a spot size of 5 was focused to a spot size of 0.8 μm.
Recording was performed by irradiating the surface of the recording layer in a track-like manner with a rnW and 8h1& gallium, aluminum, arsenic semiconductor laser (oscillation wavelength 780 nm). When the surface of the recorded recording layer was observed using a scanning electron microscope, clear bits were observed.

Furthermore, the above laser beam with low output power is incident on this recording medium, and the reflected light is detected. However, a waveform with a sufficient S/N ratio was obtained.

Claims (1)

[Scope of Claims] 1) A photosensitive composition characterized by containing at least one bisazurenium salt compound represented by the following general formula [1], [2] or [3]. thing. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [2] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [3] General formulas [1], [2] and [ 3], R^1 represents a hydrogen atom, a lower alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, or a substituted product thereof. R^2 and R^3 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, or a substituent thereof. R^4 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a substituent thereof. R^5, R^6, R^7, R^8, R^9, R^1^0
and R^1^1 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group,
It represents an aralkyl group, an acyl group, a carboxyl group, an alkali metal carboxylate group, a carbamoyl group, a sulfonic acid group, a sulfamoyl group, an alkali metal sulfonate group, a nitro group, a cyano group, an amino group, a hydroxy group, or a substituted product thereof. Also R^5 and R^6, R^7 and R^8, R^8 and R^9
, R^9 and R^1^0, and at least one combination of R^1^0 and R^1^1 may form a substituted or unsubstituted aromatic ring. B^1 and B^2 represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a substituent thereof, and B^1 and B^2 may be the same or different groups. The positions and numbers of B^1 and B^2 are arbitrary. Y has ▲mathematical formula, chemical formula, table, etc.▼, -O-, -S-, -Se
−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R^1^2 and R^1^3 are hydrogen atoms, lower alkyl groups,
Represents a lower alkoxy group, a halogen atom, or a substituted product thereof. q represents an integer of 0, 1 or 2. Z^■ represents an anionic residue.