JPH045383B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a photoconductive composition characterized by containing a novel trisazo compound. The present invention also 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'' Electrophotography has already been covered by Carlson's U.S. patent.
No. 2,297,691 discloses a photoconductive material consisting of a support coated with a dark insulating material whose electrical resistance changes depending on the dose 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. The material is then imagewise exposed to a pattern of radiation that has the effect of reducing the surface charge depending on the relative energy contained in different parts of the radiation pattern. The surface charge or electrostatic latent image thus left on the surface of the photoconductive material layer (electrophotographic photosensitive layer) then becomes a visible image when the surface is contacted with a suitable electrometric indicator material, i.e., toner. . 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 pattern.
The deposited display material can be fixed by known means such as heat, pressure, and solvent vapor. The electrostatic latent image can also be transferred to a second support (eg, 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 electrophotography are (1) ability to be charged to an appropriate potential in the dark, (2) less dissipation of charge in the dark, ( 3) The charge can be quickly dissipated by light irradiation. Conventionally, materials used as photoconductive materials for electrophotographic photoreceptors include selenium, cadmium sulfide,
These include zinc oxide. However, while these inorganic materials have many advantages, they also have various disadvantages. For example, selenium, which is currently widely used, satisfies conditions (1) to (3) above, but
It also has drawbacks such as difficult manufacturing conditions, high manufacturing costs, lack of flexibility, difficulty in processing it into a belt shape, and sensitivity to heat and mechanical shock, requiring careful handling. Cadmium sulfide and zinc oxide are used as electrophotographic photoreceptors by being dispersed in a resin as a binder, but they cannot be used as they are because of mechanical drawbacks such as smoothness, hardness, tensile strength, and abrasion resistance. Cannot be used repeatedly. 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, poly-N-vinylcarbazole and 2,4,7
-Electrophotographic photoreceptor consisting of trinitrofluoren-9-one (US Patent No. 3,484,237), poly-N-vinylcarbazole sensitized with pyrylium salt dye (Japanese Patent Publication No. 1983-25658), mainly composed of organic pigments. There are electrophotographic photoreceptors (Japanese Unexamined Patent Publication No. 47-37543), which are based on eutectic complexes consisting of dyes and resins (Japanese Unexamined Patent Application No. 47-10735). Electrophotographic photoreceptors using such organic materials are
Since it can be produced by coating by appropriately selecting a binder, a photoreceptor with extremely high productivity and low cost can be provided, and its mechanical properties and flexibility can also be improved. Furthermore, the wavelength of light sensitivity can be freely controlled by selecting the dye and organic pigment. 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 to eliminate the drawbacks of the conventional electrophotographic photoreceptors, the present inventors have found that an electrophotographic photoreceptor using a photoconductive composition containing a novel trisazo compound has been put into practical use. The present invention was achieved by discovering that it has high sensitivity and high durability to the extent that it can be used. On the other hand, conventional recording methods in which a high-energy-density beam 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 computer output and transmitted time-series signals, as it has the characteristics of being able to obtain information, add information later, and record simultaneously with exposure. have
COM (Computer Output Micro),
It is applied to microfacsimile, printing plates, optical disks, etc. For example, the recording medium used in optical disk technology is
Optically detectable small pits of around 1 μm can be formed into spiral or circular tracks to store high-density information. 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, and these pits are formed in the form of spiral or circular tracks. do.
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 disk in this way is
It is detected by scanning a laser along the track and reading the optical changes in the areas where pits are formed and those where pits are not formed. Conventionally, information recording media that can perform heat mode recording include thin films of metals and/or metal oxide semimetal derivatives on transparent supports such as plastics, or thin films containing self-oxidizing binders and dyes. A recording medium has been used in which a protective layer is provided on the recording layer. 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 the wavelength range increases and being easily decomposed by slight increases in temperature. Therefore, "direct read after write" capability [DRAW
(direct read and write)] is required for a recording medium that has high absorption efficiency for the laser beam used, a reflectance that allows sufficient focus control when reading records, or a stable recorded image. However, a recording medium containing an organic thin film that is sufficiently 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. Still another object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity and stable potential characteristics during 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 has been achieved by a photosensitive composition containing at least one trisazo compound represented by the following general formula [1]. In general formula [1], Ar is

【formula】

[expression] or

Represents [formula]. Z represents NR ¹ , -O-, -S- or -Se. However, R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group (the number of carbon atoms in an alkoxy group is 1 to 12
), an aryloxycarbonyl group having 6 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or a substituted product thereof. X represents an atomic group necessary to form an aromatic ring or a heterocycle (these rings may be substituted or unsubstituted) by condensation with a benzene ring. ^B1 , ^B2 ,
B ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a substituted product thereof, and B ¹ , B ² , and B ³ are the same or different groups; It's okay. R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 1 to 12 carbon atoms.
There are an alkoxycarbonyl group having an alkoxy group, an aryloxycarbonyl group having 6 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. When R ¹ is an unsubstituted alkyl group, specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group,
Examples include isobutyl group, isohexyl group, neopentyl group, and tert-butyl group. When R ¹ is a substituted alkyl group, the substituent is:
Hydroxy group, alkoxy group having 1 to 12 carbon atoms, cyano group, alkylamino group having 1 to 8 carbon atoms, dialkylamino group having two alkyl groups having 1 to 8 carbon atoms, halogen atom, having 6 to 15 carbon atoms There are aryl groups, etc. Examples thereof include hydroxyalkyl groups (e.g., hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, etc.), alkoxyalkyl groups (e.g., methoxymethyl group, 2-methoxyethyl group, 3-hydroxypropyl group, etc.), -methoxypropyl group, ethoxymethyl group, 2-ethoxyethyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group, 2-cyanoethyl group, etc.), (alkylamino)alkyl group (e.g.
(methylamino)methyl group, 2-(methylamino)
ethyl group, (ethylamino)methyl group, etc.), (dialkylamino)alkyl group (e.g., (dimethylamino)methyl group, 2-(dimethylamino)ethyl group, etc.), halogenoalkyl group (e.g., fluoromethyl group, chloro methyl group, bromomethyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.). When R ¹ is an unsubstituted alkoxycarbonyl group,
Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, and benzyloxycarbonyl group. When R ¹ is an unsubstituted aryl group, an unsubstituted aryl group, or an oxycarbonyl group, specific examples thereof include a phenyl group, a naphthyl group, a pyridyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group, and the like. When R ¹ is an unsubstituted acyl group, specific examples include an acetyl group, a propionyl group, a benzoyl group,
Examples include naphthoyl group and nicotinoyl group. When R ¹ is a substituted alkoxycarbonyl group, substituted aryloxycarbonyl group, or substituted acyl group, the substituent can be the same as the substituent for the substituted alkyl group in R ¹ described above, and the number of substituents is 1. from 3 to 3, and when multiple substituents are bonded, they may be the same or different from each other, and may be in any combination;
Further, the bonding position of the substituent is arbitrary. X is fused with a benzene ring to which a hydroxy group and -CONH-Ar are bonded to form a naphthalene ring or an anthracene ring. X is fused to a benzene ring to which a hydroxy group and Y are bonded to form a naphthalene ring or an anthracene ring. It is a group capable of forming an aromatic ring such as, or a heterocyclic ring such as an indole ring, a carbazole ring, a benzocarbazole ring, or a dibenzofuran ring. When X is an aromatic ring or a heterocyclic ring having a substituent, the substituent is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a lower alkyl group, preferably a lower alkyl group having 1 to 8 carbon atoms. (For example, methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, etc.), and the number of substituents is 1 or 2, and when there are 2 substituents, they are They can be the same or different. B ¹ , B ² , and B ³ are hydrogen atoms, halogen atoms (e.g., chlorine atoms, bromine atoms, iodine atoms),
Alkyl group having 1 to 6 carbon atoms (e.g. methyl group,
ethyl group, normal propyl group, etc.), carbon number 1 or more
There are 6 alkoxy groups (eg, methoxy group, ethoxy group, normal propoxy group, etc.). When B ¹ , B ² , and B ³ are a substituted alkyl group or a substituted alkoxy group, examples of the substituent include the same groups as the above-mentioned examples of the substituted alkyl group for R ¹ . Moreover, 1 to 4 B ¹ , B ² , and B ³ can be substituted at any position of each benzene ring. In the trisazo compound represented by the general formula [1], each of the three azo groups can be substituted at any position on the three benzene rings. Among the trisazo compounds represented by the general formula [1] of the present invention, a photoconductive composition with high photosensitivity can be provided, or an electrophotographic body with high photosensitivity and excellent durability can be provided. Alternatively, the trisazo compound represented by the following general formula [2] is preferable because the production raw material compound can be easily obtained and the trisazo compound can be produced at low cost, but it is limited to the compound of the general formula [2]. isn't it. In the formula, Z has the same meaning as Z in general formula [1]. Cp is

【formula】

【formula】

【formula】

[expression] or

Represents [formula]. Ar has the same meaning as Ar in general formula [1]. Further specific examples of Cp are the couplers shown in Table 1. (Table 1 is

【formula】 This shows the combination of and Ar. )

【table】

[Table] The novel trisazo compounds of the present invention can be easily produced by using known reactions. For example, the trisazo compound represented by the above general formula [2] can be synthesized by the following method. A compound in which R ² of the following general formula [3] is hydrogen,
The compound is nitrated under appropriate conditions, for example, using concentrated nitric acid or potassium nitrate in concentrated sulfuric acid, to give a compound of general formula [3] where R ² =NO ₂ . Next, this is reduced under appropriate conditions, for example, with iron powder and dilute hydrochloric acid or stannous chloride and hydrochloric acid in N,N-dimethylformamide to give a compound of general formula [3], where R ² =NH ₂ . Next, this was diazotized according to a conventional method and isolated as a trisdiazonium salt represented by the general formula [3], where R ² =N ₂ Q (Q represents an anionic functional group such as BF ₄ or ClO ₄ ). This can be easily synthesized by coupling reaction with the coupler (Cp) shown in Table 1 above in a suitable solvent such as N,N-dimethylformamide in the presence of an alkali such as sodium acetate or sodium hydroxide. .

[Formula] (In the formula, Z has the same meaning as Z in general formula [1].) In addition, for compounds in which R ² in general formula [3] is hydrogen, when Z is an oxygen atom, J. Heinze and H.
Baumga¨rtel, Chem.Chem., 103 , 1572 (1970)
When Z is a nitrogen atom, according to the method described in
AHCook and DGJones, J.Chem.Soc., 1941 ,
By using the synthesis method described in J. 278 etc., when Z is a sulfur atom and a selenium atom, the above-mentioned J.
Heinze et al., Chem. Ber., 103 , 1572 (1970), P.
Karrer and F. Forster, Helv.chim.Acta, 28,
315 (1946), G. Hofmann, Jus. Liebigs Ann.
It can be easily synthesized by using the synthesis method described in Chem., 250, 294 (1889). Synthesis Example 1 (In the general formula [2], Z is an oxygen atom, Cp is No. (Cp
-1) Synthesis of trisazo compound) 2,4,5-triphenyloxazole 20g
(0.067 mol) was dissolved in 120 ml of concentrated sulfuric acid and cooled on ice.
While keeping the temperature of the solution below 5°C, 40 ml of concentrated nitric acid (1.38) was added dropwise. After completing the dropwise addition, the reaction mixture was left at room temperature overnight.
Pour into 2 ice water. The produced yellow precipitate was collected and washed with water. After further washing with hot ethanol in Step 1, recrystallization from pyridine yielded 18.8g (yield 65%).
2,4,5-tris(4-nitrophenyl)oxazole was obtained. Next, 4.32 g (0.01 mol) of this 2,4,5-tris(4-nitrophenyl)-oxazole was added with N,
Mix 200ml of N-dimethylformamide and 8g of iron powder, add 4ml of concentrated hydrochloric acid and 12ml of water to this mixture,
The mixture was heated to 100°C while stirring well. After reacting for 1 hour, the reaction solution was neutralized to pH=8 using a saturated sodium carbonate aqueous solution while maintaining it at 100° C., and the reaction solution was heated. Pour the liquid into ice water from Step 1.
The resulting white precipitate of 2,4,5-tris(4-aminophenyl)-oxazole was collected and dried.
Yield: 3.27 g (yield 96%) Furthermore, 3.27 g (9.56 mmol) of 2,4,5-tris(4-aminophenyl)-oxazole was added to dilute hydrochloric acid prepared from 25 ml of concentrated hydrochloric acid and 30 ml of water.
The mixture was stirred well for about 30 minutes on a water bath at ℃. The mixture was then cooled to 0°C and added with sodium nitrite.
A solution of 2.57 g dissolved in 10 ml of water was added dropwise at 0° C. over about 20 minutes. After that, stir at the same temperature for 1 hour,
After separating a small amount of unreacted substances, 20 ml of 42% hydroborofluoric acid was added to the liquid to collect precipitated crystals. After washing the crystals with a small amount of cold water and drying them, 3.93 g of red crystals of trisdiazonium fluoroborate were obtained.
(yield 65%). Next, the trisdiazonium salt 2 thus obtained
g and 3.11 g of 2-hydroxy-3-naphthoic acid 2'-trifluoromethylanilide (No. (Cp-1) in Table 1) as a coupler were dissolved in 200 ml of N,N-dimethylformamide, and acetic acid was added to the solution. A solution consisting of 3 g of sodium and 20 ml of water was added dropwise at a temperature of 0° C. over about 20 minutes, and then stirred at room temperature for about 2 hours. After that, the generated precipitate was collected, washed with 300 ml of water, washed with 100 ml of acetone, dried,
3.30 g (yield 81%) of trisazo compound was obtained. The decomposition temperature of this compound was 270°C or higher. The elemental analysis values and absorption spectrum are as follows. Elemental analysis C ₇₅ H ₄₅ F ₃ N ₁₀ O ₇ Calculated value C, 65.79% H, 33.13% N, 10.23% F, 12.49% Actual value C, 65.59% H, 33.37% N, 10.20% F, 12.20% IR Absorption spectrum (KBr tablet) The absorption spectrum is shown in Figure 1. Amide 1690 cm ^-1 Visible absorption spectrum Maximum absorption wavelength 574 nm (Contains 5% ethylenediamine, in N,N-dimethylformamide) Synthesis Examples 2 to 3 Coupler No. (Cp-1) in place of coupler (Cp-1) in Synthesis Example 1 2), No. (Cp-3)
A trisazo compound was synthesized in the same manner as in Synthesis Example 1 except that . Decomposition temperature of each compound, IR absorption spectrum (absorption value of amide, KBr
Table 2 shows the visible absorption spectra (absorption maximum wavelength value, in N,N-dimethylformamide containing 5% ethylenediamine).

[Table] Synthesis Example 4 (In general formula [2], Z is a sulfur atom, Cp is No.Cp
-1) Synthesis of trisazo compound) 2,4,5-triphenylthiazole 20g
(0.064 mol) was dissolved in 100 ml of concentrated sulfuric acid and cooled on ice.
To this was gradually added 21.4 g (0.212 mol) of potassium nitrate. At this time, the reaction temperature was kept below 5°C.
After the addition was complete, the reaction mixture was stirred for 3 hours under ice cooling,
Pour into ice water in step 2 and remove the yellow precipitate.
After washing with water and ethanol, recrystallized from DMF-ethanol, 18.5g (yield 80%) of 2,4,5-
Tris(4'-nitrophenyl)thiazole was obtained. Next, 15 g (0.034 mol) of this 2,4,5-tris(4'-nitrophenyl)thiazole was added to N,N-
500 ml of dimethylmamide and 20 g of iron powder were mixed, 10 ml of concentrated hydrochloric acid and 30 ml of water were added to this mixture, and the mixture was heated to 100° C. with thorough stirring. After 1 hour, the reaction temperature was increased to 100
While maintaining the temperature at °C, the reaction solution was neutralized using a saturated aqueous sodium bicarbonate solution, and the pH of the reaction solution was adjusted to 8, and the reaction solution was heated. 2,4,5-tris(4'-aminophenyl) was produced by pouring the liquid into ice water from Step 3.
A pale yellow precipitate of thiazole was collected and dried. Yield: 11.3g (yield 94%) Furthermore, 11g (0.03mol) of 2,4,5-tris(4'-aminophenyl)thiazole was added to diluted hydrochloric acid prepared from 60ml of concentrated hydrochloric acid and 180ml of water, and stirred on a 60°C water bath. After that, the solution was cooled to 0℃, and a solution of 7.6g of sodium nitrite dissolved in 30ml of water was added to this solution.
The mixture was added dropwise over a period of about 30 minutes at ℃. Then at the same temperature 1
After stirring for an hour and separating a small amount of unreacted materials, 80 ml of 42% borofluoric acid was added to the solution to collect precipitated crystals. After washing the crystals with a small amount of water and drying them, 17.4 g of colored crystals of trisdiazonium salt were obtained.
(yield 89%). Next, the trisdiazonium salt 2 thus obtained
g (3.15 mmol) and 3.03 g of 2-hydroxy-3-naphthoic acid 2'-trifluoromethylanilide (No. (Cp-1) in Table 1) as a coupler.
(9.16 mmol) in N,N-dimethylformamide
It was dissolved in 100ml and cooled to 0°C. 10 in this solution
% aqueous sodium acetate solution was added dropwise at 0°C, and the mixture was stirred at room temperature for 2 hours. Next, the generated precipitate was collected, washed with 300 ml of water, washed with 200 ml of acetone, and dried to obtain 3.44 g (yield: 79%) of the trisazo compound. The decomposition temperature of this compound was 270°C or higher. The elemental analysis values and absorption spectrum are as follows. Elemental analysis value C ₇₅ H ₄₅ F ₉ N ₁₀ O ₆ Calculated value as S C, 65.03% H, 3.27% F, 12.34% N, 10.11% S, 2.31% Actual value C, 65.31% H, 3.35% F, 12.05 % N, 10.06% S, 2.19% IR absorption spectrum (KBr tablet) Absorption of amide: 1685 cm ^-1 Visible absorption spectrum Absorption maximum wavelength 572 nm (in N,N-dimethylformamide containing 5% ethylenediamine) Synthesis examples 5 to 6 Synthesis examples A trisazo compound was synthesized in the same manner as in Synthesis Example 4, except that coupler Nos. (Cp-2) and (Cp-3) were used in place of coupler No. 4 (Cp-1). Decomposition temperature of each compound,
IR absorption spectrum (absorption value of amide, KBr tablet)
and visible absorption spectrum (absorption maximum wavelength value, 5%
ethylenediamine in N,N-dimethylformamide) are shown in Table 3.

[Table] Other trisazo compounds can also be synthesized by following the above synthesis example, except for changing the coupler and the corresponding trisdiazonium salt. The electrophotographic photoreceptor of the present invention has an electrophotographic photosensitive layer containing one or more trisazo compounds represented by the above general formula. Various forms of electrophotographic photoreceptors are known, and the electrophotographic photoreceptor of the present invention may be any type of photoreceptor, but it usually has an electrophotographic photoreceptor structure of the type exemplified below. . (a) An electrophotographic photosensitive layer comprising a trisazo compound dispersed in a binder or a charge carrier transport medium is provided on a conductive support. (b) A charge carrier generation layer containing a trisazo compound as a main component is provided on a conductive support, and a charge carrier transporting medium layer is provided thereon. The trisazo 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 trisazo compound as a medium. It is more effective to transport it as a medium. To create an electrophotographic photoreceptor of type (a), fine particles of a trisazo compound are dispersed in a binder solution or a solution containing a charge carrier transport compound and a binder, and this is coated on a conductive support and dried. . The thickness of the electrophotographic photosensitive layer at this time is preferably 3 to 30 microns, preferably 5 to 20 microns. To create an electrophotographic photoreceptor of type (b), a trisazo compound is vacuum-deposited on a conductive support, or dissolved in a solvent such as amine and applied.
Alternatively, it can be obtained by dispersing fine particles of a trisazo compound in a suitable solvent or, if necessary, a solvent in which a binder is dissolved, coating and drying, and then coating and drying a solution containing a charge carrier transport compound and a binder thereon. The thickness of the trisazo compound layer serving as the charge carrier generation layer at this time is preferably 4 microns or less, preferably 2 microns or less, and the thickness of the charge carrier transport medium layer is 3 to 30 microns, preferably 5 to 20 microns. The trisazo compound used in the photoreceptors of types (a) 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 ball mill, sand mill, or vibration mill. If the amount of the trisazo compound used in the electrophotographic photoreceptor of type (a) is too small, the sensitivity will be poor, and if it is too large, the charging property will be poor, the strength of the electrophotographic photoreceptor will be weakened, and the electrophotographic photoreceptor will have poor sensitivity. The proportion of the trisazo compound in the layer is 0.01 to 2 times the weight of the binder, preferably 0.05 to 1 weight, and the proportion of the charge carrier transport compound added as necessary is 0.1 to 2 times the weight of the binder.
The preferred range is 0.3 to 1.3 parts by weight. In the case of a charge carrier transporting compound which itself can be used as a binder, the amount of the trisazo compound added is preferably 0.01 to 0.5 times the weight of the binder. In addition, when forming a trisazo compound-containing layer that becomes a charge carrier generation layer in the type (b) electrophotographic photoreceptor, the amount of trisazo compound used is preferably 0.1 times or more by weight relative to the binder resin, and if it is less than that, sufficient photosensitivity is obtained. is not obtained. The proportion of the charge carrier transport compound in the charge carrier transport medium is preferably 0.2 to 2 times, preferably 0.2 to 1.3 times by weight, the binder. When using polymeric charge carrier transport compounds that can themselves be used as binders,
Can be used without other binders. In addition, for the type (b) photoreceptor, a patent application was filed in 1983.
No. 53183, Patent Application No. 109906, Patent Application No. 1983-
As described in each specification of No. 118414, charge carrier transport compounds such as hydrazone compounds and oxime compounds 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 together with the binder. The conductive support used in the electrophotographic photoreceptor of the present invention includes a metal plate such as aluminum, copper, or zinc, a plastic sheet such as polyester, or a plastic film on which a conductive material such as aluminum, indium oxide, or SnO ₂ is deposited. , dispersed coating, or conductive treated paper. 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-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole These binders may be used alone or in combination of two or more. It can be used as a mixture of Plasticizers include biphenyl, biphenyl chloride,
o-terphenyl, p-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, dilaurylthiodipropionate, 3,5-dinitrosalicylic acid, various Examples include fluorohydrocarbons. In addition, silicone oil or the like may be added to improve the surface properties of the electrophotographic photoreceptor. Examples of the sensitizer include chloranil, tetracyanoethylene, methyl violet, rhodamine B, cyanine dye, merocyanine dye, pyrylium dye, thiapyrylium dye, and the like. 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-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 9-dicyanomethylene-2,4 , 7-trinitrofluorenone, 9-dicyanomethylene-
2,4,5,7-tetranitrofluorenone, tetranitrocarbazole chloranil, 2,3-dichloro-5,6-dicyanobenzoquinone, 2,
Examples include 4,7-trinitro-9,10-phenanthrenequinone, tetrachlorophthalic anhydride, tetracyanoethylene, and tetracyanoquinodimethone. Compounds that transport holes include compounds having an electron-donating group, such as polymers, such as (1) polyvinylcarbazole and its derivatives described in Japanese Patent Publication No. 34-10966, (2) Japanese Patent Publication No. 43-18674. Polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4-(4'-dimethylaminophenyl)-5-phenyl-oxazole, poly-3-vinyl-N-ethyl described in Japanese Patent Publication No. 43-19192 Vinyl polymers such as carbazole, (3) Polymers such as polyacenaphthylene, polyindene, copolymerization of acenaphthylene and styrene, etc. described in Japanese Patent Publication No. 19193-1973, (4) Polymers such as those described in Japanese Patent Publication No. 1984-13940, etc. Condensation resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in . (5) Various triphenylmethane polymers described in JP-A-56-90883 and JP-A-56-161,550. In addition, low molecular weight ones include (6) triazole derivatives described in U.S. Patent No. 3,112,197, etc., (7) oxadiazole derivatives described in U.S. Pat. No. 3,189,447, etc., (8) Imidazole derivatives described in Japanese Patent Publication No. 37-16096, etc., (9) U.S. Patent Nos. 3615402, 3820989,
No. 3542544, Special Publication No. 1977-555, Special Publication No. 1971-
No. 10983, JP-A-51-93224, JP-A-55-108667
No., JP-A-55-156953, JP-A-56-36656,
Polyarylalkane derivatives described in specifications, publications, etc., (10) U.S. Patent No. 3180729, U.S. Patent No. 4278746
No., JP-A-55-88064, JP-A-55-88065,
JP-A-49-105537, JP-A-55-51086, JP-A-56-80051, JP-A-56-88141, JP-A-Sho
No. 57-45545, JP-A No. 112637-1983, JP-A-55
Pyrazoline derivatives and pyrazolone derivatives described in -74546 specification, publications, etc. (11) U.S. Patent No. 3615404, Japanese Patent Publication No. 1973-
No. 10105, JP-A No. 1983-83435, JP-A No. 1983-
No. 110836, Japanese Patent Application Publication No. 119925, Publication No. 119925, Publication No. 119925, Publication No. 119925-
Phenylenediamine derivatives (12) described in US Pat.
No., West German Patent (DAS) No. 1110518, US Patent No. 3180703, US Patent No. 3240597, US Patent No. 3658520, US Patent No. 4232103, US Patent No. 4175961, US Patent No. 4012376, JP-A-Sho 55
−144250, JP-A-56-119132, JP-A-1983-
Arylamine derivatives described in No. 27577, JP-A-56-22437, publications, etc. (13) Amino-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501, (14) U.S. Pat. No. 3,542,546 (15) Oxazole derivatives described in U.S. Pat. 17) Fluorenone derivatives described in JP-A-54-110837 and the like. (18) U.S. Patent No. 3717462, JP-A-54-59143 (corresponding to U.S. Patent No. 4,150,987), JP-A-55-
No. 52063, JP-A-55-52064, JP-A-55-
46760, JP-A-55-85495, JP-A-57-11350
Examples include hydrazone derivatives disclosed in JP-A-57-148749, JP-A-57-104144, and the like. In the present invention, the compound that transports charge carriers is not limited to the compounds listed in (1) to (18), and all hitherto known charge carrier transporting compounds can be used. Two or more types of these charge transport materials may be used in combination depending on the case. In addition, the photoreceptor obtained in the above manner has the following properties:
An adhesive layer or barrier layer can be provided between the conductive support and the photosensitive layer, if necessary. Materials used for these layers include, in addition to the high molecular weight polymer used for the binder, gelatin, casein, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, and JP-A-59-
84247, the styrene-butadiene polymer latex or aluminum oxide described in JP-A-59-114544, and the thickness of these layers is 1μ.
m or less is preferable. The electrophotographic photoreceptor of the present invention has been described in detail above, and the electrophotographic photoreceptor of the present invention generally has the characteristics of high sensitivity and 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 trisazo 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 that perform known signal transfer or scanning. It can be used as a photoconductive layer of a solid-state image sensor having a light-receiving layer (photoconductive layer). Also, A.K.
Ghosh, Tom Feng, J.Appl.Phys., 49(12),
5982 (1978), it can also be used as a photoconductive layer in solar cells. The trisazo compound of the present invention can also be used as photoconductive colored particles in a photoelectrophoresis system and colored particles in a dry or wet electrophotographic developer. In addition, the trisazo compound of the present invention can be
No. 17162, JP-A-55-19063, JP-A-55-161250
As disclosed in the specifications of JP-A No. 57-147656, the compound is dispersed in an alkali-soluble resin solution such as a phenolic resin together with the aforementioned charge carrier transporting compounds such as oxadiazole derivatives and hydrazone derivatives, By coating on a conductive support such as aluminum, drying, image exposure, toner development, and etching with an alkaline aqueous solution, printing plates with high resolution, high durability, and high sensitivity can be obtained, and printed circuits can also be created. can. 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 trisazo compound of the present invention on a support. It can be formed using various methods. When using the coating method, examples of organic solvents include alcohols (e.g., methanol, ethanol, isopropanol, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, citroxanone, etc.), amides (e.g., 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.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, methylchloroform, carbon tetrachloride, monochlorobenzene, diglyme, etc.) chlorobenzene, 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 (e.g., nitrocellulose, cellulose phosphate, cellulose acetate, cellulose butyrate, methylcellulose, ethylcellulose) , butyl cellulose, etc.), acrylic resins (e.g., polymethyl methacrylate, polybutyl methacrylate, polybutyl acrylate, polymethacrylic acid, polyacrylamide, polymethacrylamide, polyacrylonitonyl, etc.), vinyl resins (e.g., polystyrene, polyacetic acid) vinyl, polyvinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, etc.),
Polycarbonates, polyesters, polyamide resins, epoxy resins, phenol resins, oligoolefin resins (eg, polyethylene, polypropylene, etc.), synthetic copolymer resins, and the like can be used. Application can be carried out using a general-purpose coating method such as spraying, roller coating, spinner coating, or blade coating. When forming an organic thin film together with a resin, the content of the trisazo compound in the thin film is 5 to 90% by weight, preferably 15 to 80% by weight, with the remainder being a binder. Further, the vapor deposited thickness or dry thickness of the organic thin film is 10 μm or less, preferably 2 μm or less. 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. Specific examples include glass, quartz, ceramics, paper, metals, plastics (eg, 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 read and reproduced using transmitted light, it must be transparent to the read laser beam. 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. can 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. Reproducing information has the same wavelength as the laser beam used for writing, but if a laser beam with low intensity is used, the reading light will be largely reflected at the pit area.
It will be absorbed in the non-pit area,
This is performed by detecting the difference in reflected light from the pit-formed portion and the non-pit-formed portion. Another method may be to perform real-time recording with a laser beam of a first wavelength that is absorbed by the organic thin film, and use a second wavelength laser beam that substantially passes through the organic thin film for reproduction. The regeneration laser beam is activated by responding to changes in the reflection phase 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, it can be protected from dust, scratches, and contact with harmful gases, and the preservation of the recording layer is significantly improved. Laser beams applied to the optical information recording medium of the present invention include Ar laser, He-Ne laser, He-Ne laser, and He-Ne laser.
Gas lasers such as CD lasers are also possible. EXAMPLES Next, the present invention will be specifically explained using Examples, but the present invention is not limited to the Examples. In the examples, "parts" indicate "parts by weight." Example 1 It is shown by the general formula [2] synthesized in Synthesis Example 1, and Z
is an oxygen atom, Cp is No. (Cp-1) in Table 1, 1 part of a trisazo compound, 5 parts of 4,4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane, and bisphenol A. Add 5 parts of polycarbonate and 95 parts of dichloromethane, grind and mix in a ball mill to prepare a solution, and apply this coating solution to the surface of a conductive transparent support (100 μm polyethylene terephthalate film) using a wire round rod. Provided with a vapor-deposited film of indium oxide.
Coated on surface resistance 10 ³ Ω) and dried to a thickness of approximately 8μ
An electrophotographic photoreceptor having a single-layer electrophotographic photosensitive layer of m was prepared. This electrophotographic photoreceptor was tested at +5KV using an electrostatic copying paper tester (SP-428 model manufactured by Kawaguchi Electric Co., Ltd.).
The surface is charged to +400V by corona discharge, and then the surface is irradiated with light at 4lux using a tungsten lamp with a color temperature of 2854〓, and the time required for the surface potential to attenuate to half of the initial surface potential. When the half-reduced exposure amount E ₅₀ (lux.sec) was measured, it was 2.6lux.sec. Examples 2 to 23 In Example 1, in place of the trisazo compound synthesized in Synthesis Example 1, a trisazo compound shown in Table 3 was used, and in the same manner as in Example 1, a single-layer electrophotographic photoreceptor was prepared. It was prepared, and the half-reduced exposure amount E ₅₀ due to positive charging was measured in the same manner as in Example 1. The results obtained are shown in Table 4.

[Table] Example 24 Shown by the general formula [2] synthesized in Synthesis Example 4, Z
A solution prepared by dissolving 5 parts of a trisazo compound in which sulfur atom is a sulfur atom and Cp is No. (Cp-1) in Table 1 and 5 parts of a polyester resin (trade name: Vylon 200, manufactured by Toyobo Co., Ltd.) in 50 parts of tetrahydrofuran. After dispersing with a ball mill for 20 hours, using a wire round rod, conductive support (75 μm polyethylene terephthalate film with a vapor-deposited aluminum film on the surface. Surface electrical resistance: 4 x 10 ² Ω)
A charge generation layer having a thickness of 0.5 μm was prepared by coating and drying. Next, p-(diphenylamino) is added on top of the charge generation layer.
Benzaldehyde N'-methyl-N'-phenylhydrazone 3.6 parts of polycarbonate 4 with bisphenol A
A solution prepared by dissolving 13.3 parts of dichloromethane and 26.6 parts of 1,2-dichloroethane was coated using a wire round rod and dried to form a charge transport layer with a thickness of 11 μm, thereby forming an electrophotographic photosensitive layer consisting of two layers. An electrophotographic photoreceptor was created. This photoconductor is charged with -6KV corona discharge for 5 seconds to obtain an initial surface potential Vo.Next, light from a tungsten lamp is irradiated to the photoconductor surface with an illuminance of 30 lux, and the surface potential is initially The surface potential (residual potential) V _R was measured when exposed to light at an exposure amount E of ₅₀ and 60 lux.sec, which is required to attenuate the surface potential to half of the surface potential Vo. Similar measurements were also repeated 3000 times.
The results are shown in Table 5.

[Table] Examples 25 to 53 In Example 24, a two-layer electrophotographic photosensitive material was prepared in the same manner as in Example 24, except that the trisazo compound shown in Table 6 was used instead of the trisazo compound synthesized in Synthesis Example 4. A body was prepared, and the half-life exposure amount E ₅₀ was measured in the same manner as in Example 24. The results are shown in Table 6.

【table】

[Table] Example 54 Synthesized in Synthesis Example 1, expressed by the general formula [2], Z
is an oxygen element, Cp is No. (Cp-1) in Table 1, 5 parts of a trisazo compound, 40 parts of the hydrazone compound used in Example 24, and a copolymer of benzyl methacrylate and methacrylic acid ([η] 30°C methyl ethyl ketone) = 0.12, methacrylic acid content 32.9%)
100 parts of the solution was added to 660 parts of dichloromethane and dispersed by ultrasonication. This dispersion was coated on a grained aluminum plate with a thickness of 0.25 mm and dried to prepare an electrophotographic photosensitive printing plate material having an electrophotographic photosensitive layer with a dry film thickness of 6 mm. The surface potential of the photosensitive layer was charged to about +600V by corona discharge (+6KV) on this sample in a dark place, and then the sample surface was exposed to tungsten light with a color temperature of 2854〓 at an illuminance of 2.0lux, which caused a half-reduced exposure. The amount is
It was 2.4lux.sec. Next, raise the surface potential of this sample to about + in the dark.
After being charged to 400V, the image was exposed by bringing it into close contact with a transparent original with a positive image. Contains a toner prepared by adding 5 parts of polymetal methacrylate (toner) dispersed in fine particles in 1000 parts of Isoper H (Etsuso Standard Co., Ltd., petroleum-based solvent) and 0.01 part of soybean oil lecithin. It was immersed in a liquid developer and a clear positive toner image could be obtained. The toner image was further fixed by heating at 100° C. for 30 seconds. This printing plate material was mixed with 70 parts of sodium metasilicate hydrate, 140 parts of glycerin, and ethylene glycol.
By immersing it in a solution of 550 parts and 150 parts of ethanol for about 1 minute and washing it with a stream of water while gently brushing it, the electrophotographic photosensitive layer in the areas to which toner was not attached was removed, and a printing plate was obtained. . In addition, instead of a liquid developer, the obtained electrostatic latent image is used as a toner for Xerox 3500 (Fuji Xerox Co., Ltd.).
After developing with a magnetic brush using a commercially available product (manufactured by J.D. Co., Ltd.), the image was fixed by heating at 80°C for 30 seconds. 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 made in this way is used as a Hamada star.
Using a 600CD offset printing machine, we were able to print 50,000 sheets of extremely clear prints with no spot stains using conventional methods. Example 55 Nitrocellulose solution (manufactured by Daicel Chemical Industries, Ltd.,
10 g of methyl ethyl ketone (25 wt% solution), 3.0 g of the trisazo compound synthesized in Synthesis Example 6, and 100 g of tetrahydrofuran were mixed and sufficiently dispersed.
After applying this dispersion liquid to an acrylic substrate using a spinner coating method (1000 rpm),
It was dried for an hour (film thickness 0.3 μm). The recording medium produced in this manner was mounted on a turntable, and while the turntable was rotated by a motor at 1800rpm, a 10mW and 8MHz helium-neon laser beam (oscillation wavelength 633nm) focused on the spot side 1.0μm was emitted. Recording was carried out by irradiating the surface of the recording layer in the form of tracks. When the surface of the recorded recording layer was observed using a scanning electron microscope, clear pits were observed. Furthermore, when the above laser beam with a low output was made incident on this recording medium and the reflected light was detected, a waveform with a sufficient S/N ratio was obtained.

[Brief explanation of drawings]

FIG. 1 shows the IR absorption spectrum (KBr tablet method) of the trisazo compound of the present invention [the compound synthesized in Synthesis Example 1]. Moreover, FIG. 2 shows the trisazo compound of the present invention [compound synthesized in Synthesis Example 5]
The IR absorption spectrum (KBr tablet method) of

Claims (1)

[Scope of Claims] 1. A photosensitive composition containing at least one trisazo compound represented by the following general formula [1]. In general formula [1], Ar represents [formula] [formula] or [formula]. Z represents NR ¹ , -O-, -S- or -Se. However, R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group (the number of carbon atoms in an alkoxy group is 1 to 12
), an aryloxycarbonyl group having 6 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or a substituted product thereof. X represents an atomic group necessary to form an aromatic ring or a heterocycle (these rings may be substituted or unsubstituted) by condensation with a benzene ring. ^B1 , ^B2 ,
B ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a substituted product thereof, and B ¹ , B ² , and B ³ are the same or different groups; It's okay.