JPS61238063A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. having high sensitivity and stable acceptance potential characteristics even at the time of repeated uses by using a photosensitive compsn. contg. an azo compd. substd. by perfluoroalkyl group as an electrostatic charge carrier for forming a photoconductive layer. CONSTITUTION:The electrophotographic sensitive body high in sensitivity and long in life can be obtained by forming on a conductive substrate a photosensitive layer prepared by dispersing into a binder or the charge transfer medium the azo compd. or by forming a charge generating layer composed essentially of this azo compd. and on this layer a charge transfer layer. This azo compd. is represented by formula I in which A<1> is an optionally substd. aromatic hydrocarbon ring or a hetero ring; X is an atomic group necessary to condense with a benzene ring and to form an optionally substd. aromatic hydrocarbon or hetero ring; Ar is an aromatic hydrocarbon or hetero ring substd. by at least one perfluoroalkyl group and optionally substd. another group except a perfluoroalkyl group; and n is 3, 4, 5, or 6. This compd. is embodied by a compd. of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a photoconductive composition characterized by containing an azo compound substituted with a perfluoroalkyl group. 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 published by Carlson in US Patent No. 2227T.
As disclosed in No. 1, a photoconductive material consisting of a support coated with an insulating substance in the dark whose electrical resistance changes depending on the amount of radiation received during image exposure is used. 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 with a pattern of radiation which has the effect of reducing the surface charge depending on the relative energy contained in the various parts of the radiation pattern. The surface charge or electrostatic latent image thus left on the surface of the photoconductive material layer (electrophotographic photosensitive 11) becomes a visible image when the surface is then 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/turn.

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 in which images are formed 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) Examples include scales that quickly dissipate charge when irradiated with light.

Conventionally, selenium, cadmium sulfide, zinc oxide, and the like have been used as photoconductive materials for electrophotographic photoreceptors.

However, it is true that while these inorganic substances have many advantages, they also have various disadvantages.

For example, the current bottom (the selenium used is
Condition (3) is fully satisfied, but the manufacturing conditions are difficult, 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). Therefore, there are drawbacks such as the need to be careful in handling.Cadmium sulfide and zinc oxide are used as electrophotographic photoreceptors by dispersing them in a resin as a binder, but they have problems with smoothness,
Due to mechanical defects such as hardness, tensile strength, and abrasion resistance, it cannot be used repeatedly as it 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, an electrophotographic photoreceptor (U.S. Patent J, 1
trll-, 237), poly-N-vinylcarbazole sensitized with pyrylium salt dye (Tokuko Sho μr-2
3tJ-1), an electrophotographic photoreceptor whose main component is an organic pigment (JP-A-7-473'A3), an electrophotographic photoreceptor whose main component is a eutectic complex consisting of a dye and a resin (JP-A-Show 7-473'A3), ≠7−
1073j).

Electrophotographic photoreceptors using such organic substances can be produced by coating by appropriately selecting a binder, so it is possible to provide photoreceptors with extremely high productivity and low cost, and they have excellent mechanical properties and flexibility. It can be improved. Furthermore, the wavelength of light sensitivity can be freely controlled by selecting dyes and organic pigments.

However, electrophotographic photoreceptors using reactive organic materials, ■Low light sensitivity.

■ Items with high photosensitivity have poor charging properties.

■ Items with high photosensitivity have a large charge dissipation in the dark (dark decay is large).

■ Characteristics such as light sensitivity, chargeability, and dark decay fluctuate significantly during repeated use.

■ When organic pigments are used, it is difficult to disperse the pigments and the surface quality of the coating is poor.

It has the following drawbacks and does not fully meet the requirements for an electrophotographic photoreceptor.

The present inventors aimed to eliminate the drawbacks of the conventional organic electrophotographic photoreceptors (as a result of intensive research, an electrophotographic photoreceptor using a photoconductive composition containing an azo compound substituted with a perfluoroalkyl group) Surprisingly, the inventors have discovered that the drawbacks of the organic electrophotographic photoreceptors described in (1) to (4) above can be solved all at once, and have arrived at the present invention.

The electrophotographic photoreceptor of the present invention has extremely high sensitivity, excellent charging properties, small changes in characteristics upon repeated use, and good coating surface condition.

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
M (computer output) Applied to microns, micro facsimiles, original printing plates, optical discs, etc.

For example, recording media used in optical disk technology can store high-density information using optically detectable small pits of around lμ in the form of spiral or circular tracks. To write information to such a disk, V-
A focused laser beam is scanned over the surface of the laser-sensitive layer, and only the surface irradiated with this laser beam forms pits, and the pits are formed in the form of a spiral or circular track.

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

Information recording media that can perform heat mode recording have conventionally been formed using thin films of metals and/or metal oxides, semimetallic dielectrics, etc. on transparent supports such as plastics, or those containing self-oxidizing binders and dyes. Recording media have been used in which a thin film is provided as a recording layer and a protective layer is provided on the thin film.

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, the absorption characteristics of organic compounds generally become unstable as the wavelength range increases, and the absorption efficiency of organic compounds is high for the laser beam used, which is required for recording media that slightly increases in temperature. The development of a recording medium containing an organic thin film that satisfies various characteristics such as sufficient reflectivity and stability of recorded images, and is not necessarily sufficient from a practical point of view. It has not been.

"Problems to be Solved by the Present Invention" The present inventors have arrived at the present invention as a result of intensive research in order to eliminate the above-mentioned drawbacks.

An object of the present invention is to provide a photoconductive composition that can be applied to various photoconductors. Still another object 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 Problems" The photosensitive composition of the present invention is characterized by containing at least one azo compound represented by the general formula [1].

(In the formula, A1: represents a substituted or unsubstituted hydrocarbon or heteroaromatic ring; X: to form a substituted or unsubstituted hydrocarbon or heteroaromatic ring by condensation with a benzene ring; Represents a necessary atomic group, Ar: hydrocarbon or heteroaromatic 11 substituted with at least one 4-fluoroalkyl group (may be substituted with a substituent other than -?4-fluoroalkyl group) represents.

n:3,≠,! or an integer. General formula [1
] Examples of A1 include hydrocarbon aromatic rings such as benzene, naphthalene anthracene, pinone, and anthraquinone, polynuclear quinone aromatic rings such as anthrone, furan,
Thiophene, pyridine, benzoxazole, benzothiazole.

Heteroaromatic rings such as carbazole and phthalocyanine,
Furthermore, those in which the above-mentioned aromatic rings are bonded directly or with an aromatic or non-aromatic group, such as triphenyloxysol, triphenylthiazole, triphenylimidazole, triphenylselenazole, triphenylamine,
Examples include triphenylmethane, triphenylpyridine, triphenylto IJ 7zole, and tetraphenylthiophene.

In addition, substituents for these rings include lower alkyl groups having 1 to 2 carbon atoms (for example, methyl group, ethyl group, etc.), lower alkoxy groups having 1 to 2 carbon atoms (for example, methoxy group, ethoxy group, etc.), A lower haloalkyl group having carbon number/-A (e.g., chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), a dialkylamino group having λ alkyl groups having carbon number/-ig (e.g. dimethylamino group, Die JF -/I/amino group, etc.), -.rogen atom (e.g.,
Hydrogen groups, nitro groups, cyano groups, etc. can be exemplified for fluorine atoms, chlorine atoms, bromine atoms, etc., and the number of substituents is 1 to μ, and when multiple substituents are bonded, may be the same or different, and may be in any combination (and the bonding positions of the substituents may be arbitrary).

X is an aromatic ring such as a naphthalene ring or anthracene ring fused with a benzene ring to which a hydrocarbon group is bonded, or an indole ring, a carbazole ring, a benzocarbazole ring,
A group capable of forming a heterocycle such as a dibenzofuran ring.

When X is an aromatic ring or a heterocyclic ring having a substituent, specific examples of the substituent include the same substituents as those in A1[:, and the number of substituents is 1 to 5. When a plurality of substituents are bonded, they may be the same or different from each other, and may be in any combination, and the bonding positions of the substituents may be arbitrary.

Examples of perfluoroalkyl groups substituted with Ar include carbon ff/~/2 perfluoroalkyl groups (e.g., trifluoromethyl group, pentafluoroethyl group, k-fluorobutyl group, ylfluorohexyl group, etc.) be able to.

As Ar, benzene, naphthalene, anthracene,
Examples include hydrocarbon aromatic rings such as pyrene, and heteroaromatic rings such as furan, thiophene, pyridine, thiazole, benzoxazole, benzothiazole, and carbazole.

'! , TaAr When further substituted with a substituent other than the caberfluoroalkyl group, examples of the substituent include a hydroxy group, a cyano group, a nitro group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), Number of carbons/-/-
2 alkyl groups (e.g., methyl group, ethyl group, propyl group, isopropyl group, etc.), alkoxy groups having 1 to 2 carbon atoms (e.g., butoxy group, etoxy group, propoxy group, butoxy group, pentyl group) Oxy group, impropoxy group,
(inbutoxy group, inamyloxy group, tert-butoxy group, neonityloxy group, etc.), amino group, alkylamino group with carbon number /-/J (for example, methylamino group, ethylamino group, propylamino group, etc.) , number of carbons/−
/J dialkylamino group (e.g. dimethylamino group, diethylamino group, N-methyl-N-ditylamino group, etc.), arylamino group having 6 to /2 carbon atoms, (e.g.
phenylamino group, tolylamino group, etc.), carbon number t~/
! Diarylamino groups (e.g., diphenylamino groups, etc.) having λ aryl groups, carboxyl groups, alkali metal carboxyl groups (examples of alkali metals (cations), N2O, KΦ, Li'', etc.), alkali metal sulfonate groups ( Alkali metals (examples of cations, N2O, KO1L)
i■, etc.], alkylcarbonyl groups (e.g., acetyl group, propionyl group, benzylcarbonyl group, etc.), arylcarbonyl groups having an aryl group having 4 to 7.2 carbon atoms (e.g., benzoyl group, toluoyl group, carbon number 7~/
J(7) Can include an alkylthio group (e.g., methylthio group, ethylthio group, etc.) or an arylthio group having /-/2 carbon atoms (e.g., phenylthio group, tolylthio group, etc.), and the number of substituents is 1. to 3, and when multiple substituents are bonded, they are the same as each other.
They may be the same or different (any combination may be taken), and the bonding positions of the substituents are arbitrary. In particular, it is preferable that Ar has a halogen atom in addition to the perfluoroalkyl group.

n represents an integer of j, 44, j or 6, preferably 3 or ≠.

Among the azo compounds represented by the general formula (1) of the present invention,
It is possible to provide a photoconductive composition with high photosensitivity, or it is possible to provide an electrophotographic photoreceptor with high photosensitivity (and excellent durability), or it is possible to obtain a manufacturing raw material compound easily and at low cost. Since azo compounds can be produced, trisazo compounds represented by the following general formula [λ] and tetrakisazo compounds represented by the following general formula [3] are preferred, but general formulas [2] and [
3] is not limited to the compound.

[λ]

[3] As Ar and X in the general formula [-], the same specific examples as Ar and X in the general formula (1) can be given.

As Bl, B2 and B3 in the general formula [ko],
The same groups as the substituents in A1 above can be mentioned, and the number of Bl, B2 and B3 is 7 to 1000, and when a plurality of them are bonded, they may be the same or different from each other, and any number of substituents can be mentioned. (and the bonding position is arbitrary.

In the general formula [C], all 2 represent R1-1-〇-1-8- or -8e-.

R1 is a hydrogen atom, an alkyl group having carbon number/-J, or a carbon number of 6 to . There are an aryl group having 20 carbon atoms, an alkoxycarbonyl group having an alkoxy group having 1 to 1/J carbon atoms, an aryloxycarbonyl group having t to 0 carbon atoms, and an acyl group having 1 to 20 carbon atoms.

When R1 is an unsubstituted alkyl group, examples thereof include methyl group, ethyl group, propyl group, butyl group,
Examples include hexyl group, isopropyl group, isobutyl group, isohexyl group, neo-methyl group, and tert-butyl group.

When R1 is a substituted alkyl group, examples of the substituent include a hydrooxyl group, an alkoxy group having a carbon number of 1 λ, a cyano group, an alkylamino group having a carbon number of -4, and an alkyl group having a carbon number of -4. Examples include a dialkylamino group, a -.rogen atom, an aryl group having 4-/j carbon atoms, and the like. Examples thereof include hydroxyalkyl groups (e.g., hydrocarbon dimethyl group, co-hydroxypropyl group, 3-hydroxypropyl group, co-hydroxypropyl group, etc.), alkoxyalkyl groups (e.g., methoxymethyl group, λ-methoxyethyl group, etc.). , 3-methoxypropyl group, ethoxymethyl group, cone anoethyl group, etc.), cyanoalyl group (e.g. cyanomethyl group, cone anoethyl group, etc.), (alkylamino)
Alkyl group (for example, (ethylaminomethyl group, 2-
(methylamitsunoethyl group, (ethylamitsunomethyl group, etc.), (sial-based ruaminophalkyl group (e.g., (diethylamitunomethyl group, -1(dimethylamino)ethyl group, etc.), halogenoalkyl group (e.g. , fluoromethyl group, chloromethyl group, bromomethyl group, etc.), and aralkyl group (eg, benzyl group, phenethyl group, etc.).

When R1 is an unsubstituted alkoxycarbonyl group, specific examples thereof include a methoxycarmenyl group, an etquin carbonyl group, a proboxycarzenyl group, a butodicarbonyl group,
Examples include benzyloxycarbonyl group.

When R1 is an unsubstituted aryl group, an unsubstituted aryl group, or an oxycarbonyl group, specific examples include a phenyl group, a naphthyl group, a pyridyl group, a phenoxydicarbonyl group, and a napht-
=y'dicarbonyl group, etc. can be mentioned.

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

When R1 is a substituted alkoxycarbonyl group, a substituted aryloxycarbonyl group, or a substituted acyl group, the substituent can be the same as the substituent of the substituted alkyl group in R described above, and the number of substituents is 1 to 3. and when multiple substituents are bonded, they may be the same or different from each other (and may be in any combination (
, and the bonding position of the substituent is arbitrary.

As Ar and X in general formula [3], the same specific examples as Ar and X in general formula (1) can be given.

As Z in the general formula [3], the same specific examples as 2 in the above-mentioned general formula [λ] can be given.

represents an integer. ), or a divalent organic residue having aromaticity.

Examples of covalent organic residues include the divalent organic residues and their substituents shown below, and the substituents include the same groups as the examples of substituents in A1 above. .

In the above specific examples, R1 can be the same specific example as R1 in the above-mentioned general formula [λ].

B and B represent a hydrogen atom or an electron-withdrawing group. Specific examples of electron-withdrawing groups include halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.), nitro groups,
Examples include a cyano group and an alkoxycarbonyl group (methoxycarbonyl group, ethocarmenyl group, etc.).

Q2 represents a divalent aromatic carbocyclic group, a divalent aromatic heterocyclic group, or a substituent thereof. Specific examples thereof include a covalent aromatic carbocyclic group, a divalent aromatic carbocyclic group, and a substituted product thereof as shown in the following structure.

As the substituent, the same groups as the above-mentioned examples of the substituent in A1 can be mentioned.

In addition to the trisazo compound represented by the general formula [≠], trisazo compounds represented by the following general formula [≠] are also useful.

HOC0N) i-Ar [Hiro] Y in the general formula [Hiro], X and Ar in the general formula [μ] represent the same meanings as X and Ar in the general formula [μ].

Also, among the trisazo compounds represented by the general formula [!], the following general formula [!] ] More preferred are trisazo compounds represented by the general formula [! ] is not limited to the compounds.

(In the formula, Z represents the same meaning as 2 in the above general formula [λ]. Cp represents a coupler residue, and Ar represents the same meaning as Ar in the above general formula [/J], preferably benzene, Represents naphthalene.

Furthermore, the perfluoroalkyl group substituted with Ar is preferably a trifluoromethyl group, and when it is further substituted with a substituent other than a perfluoroalkyl group, it is preferably a -rogen atom (e.g. fluorocarbon atoms, chlorine atoms, bromine atoms, etc.).

Furthermore, among the tetrakisazo compounds represented by the general formula [3], the tetrakisazo compounds represented by the following general formula [6] are more preferred, but are not limited to the compounds of the general formula (JJ).

[≦]

(In the formula, 2 is the same specific example as Z and Cp in the above-mentioned general formula [J]) as Cp in the above-mentioned general formula [J].

Specific examples of the azo compound of general formula [1] include the following, but the azo compound of the present invention is not limited to the following. For the sake of simplicity, let's start with A1
The structure and substitution positions are shown.

(In the case of lln=3 (trisazo compound), the compound layer
In the case of AI N -N (II) r+-' (tetrakisazo compound) Next, specific examples of cp show the coupler residue combinations shown in Table 1, and the symbols in the table represent coupler hawks. ) The azo compound used in the present invention can be easily produced by using a known reaction. For example, the trisazo compound represented by the above general formula [λ] can be synthesized by the following method.

A compound in the following general formula [7] in which R2 is hydrogen is nitrated under appropriate conditions, for example, using concentrated nitric acid or potassium nitrate in concentrated sulfuric acid, to give a compound in the general formula [7] in which R2=NO2. Next, this is treated under appropriate conditions, for example, N, N
- R2 = NH2 of the general formula [7] by reducing iron powder and dilute hydrochloric acid or stannous chloride and hydrochloric acid in dimethylformamide.
Let it be a compound of Next, this is diazotized according to a conventional method and isolated as a trisdiazonium salt represented by the general formula % (representing an anionic functional group such as 04). Among them, the couplers (Cp) shown in Table 7 above and an alkali such as sodium acetate,
It can be easily synthesized by coupling reaction in the presence of sodium hydroxide.

(In the formula, 2 has the same meaning as Z in the general formula [λ].) In addition, in the compound where R2 in the general formula [7] is hydrogen, when 2 is an oxygen atom, [Chemi
she Berichte) J, / Oj.

/j7J(/ri70), (J-Hefnze an
According to the description of Z.
If is a nitrogen atom, the ``Journal of the Chemical Society''
chemical 5ociety) J, /Rihiro/,
27F (A, H, Cook and D, G, Jone
When 2 is a sulfur atom and a selenium atom, by using the synthesis method described in
emishe Berichte month, to3, 1r72
(/ri70) (J, Helnze et al.), “Helvetica Chimi Acta (Helvetica Chimi Acta)”
ca Acta Month, 21. ．． 3/j' (/ri 4ct)
.

(P-Karrer and F. Forster) % [Jutus Liebigs Annalen der Hemie
derChemie Mon, 230, 2ri 1A (lrry
)<G.

It can be easily synthesized by using the synthesis method described in J. Hofman et al.

Further, the couplers shown in Table 7 can be easily synthesized according to known methods. Typical synthesis methods are shown below, but the synthesis method is not limited to this method.

A carboxylic acid in which R3 of the following general formula (r) is -COOH is acid halogenated with an appropriate acid halogenating reagent (e.g., thionyl chloride, oxalyl chloride, etc.) in an organic solvent such as benzene or chloroform to obtain the general formula R3 of (r) is -
Co-X'(X' represents a chlorine atom, a bromine atom, etc.

). Next, this was prepared as A r -N R2 (A
r represents the same meaning as Ar in general formula [1]. It can be easily synthesized by condensation with an amine represented by:

(In the formula, X has the same meaning as X in the general formula (/J) described above.) Synthesis Example 1 (Synthesis of Cp-j in Table 1 Nocohydroxy-3-naphthoic acid 4A7.iil (0
.

2zmol) was mixed with chloroform/20ynl, and 22ml (0.3mol) of thionyl chloride was added to this mixture. This mixture was then heated under reflux on an oil bath for 3 hours. After cooling to room temperature, the solvent was distilled off to obtain an ocher solid. This solid was dissolved in acetone/jOryd and o
After cooling to 'c, Koamino! -Chloropenzotrifluoride IO'7nl (0.7, tmol) was added dropwise. After the dropwise addition was completed, the reaction mixture was heated under reflux on an oil bath for 3 hours. After cooling to room temperature, the formed crystals were counted, washed with acetone, and recrystallized from ethanol-water to give 629 (yield: 76
%) of pale yellow crystals of Cp-r were obtained. Melting point is λ-3.1
-22≠, it was 0C.

Synthesis Example 2 (Synthesis of a trisazo compound in the general formula [!], where Z is an oxygen atom and Cp is cp-+ in Table 1) 2Iμ, j-
triphenyloxazoleco0y(0,0A7mo))
was dissolved in concentrated sulfuric acid ioomt and cooled on ice. Add potassium nitrate to this, Hirog<o.

2-2 ml) was gradually added. At this time, the reaction temperature is j
'Kept below C. After the addition was completed, the reaction mixture was stirred for 3 hours under water cooling, poured into ice water, and the resulting yellow precipitate was filtered out, washed with water and ethanol, and then recrystallized from pyridine. -Nitrophenylnooki length sea 12.2.P9 (obtained $7P chino).

Next, this λ, Hiro, j-)ris (≠′-nitrophenyl)
Oxazole t3/i (o, oJrnol) is N, N-
Dimethylmuamide! 00111. Mix with 26g of iron powder,
Add 10 g of concentrated hydrochloric acid and JO ml of water to this mixture (stir and heat to 100 ml). After 1 hour, while maintaining the reaction temperature at 100 ml, add saturated aqueous sodium bicarbonate solution to the solution. The pH after the reaction was adjusted to 1, and the reaction solution was filtered while hot.The filtrate was poured into ice water of 31 to produce 2.
, 44, j-tris(μ′-aminophenyl)
The pale yellow precipitate of oxazole was counted and dried. Hiromu Haruyoshi,
≠7 g (yield: 7 g) In addition to λ,4C,j-)lith(Hiroshi'-aminophenyloxazole/λi (0,0 J! mol)'1 dilute hydrochloric acid prepared from 1 jod of concentrated hydrochloric acid and 100 tIIl of water, to After stirring on a water bath at 0C, cool to 0C and add sodium nitrite to this solution in water J Om1VC.
The dissolved solution was added dropwise at 00c over about 30 minutes. Thereafter, the mixture was stirred at the same temperature for 7 hours, and after removing a small amount of unreacted materials, ≠λ borohydrofluoric acid (jOd) was added to the filtrate, and the precipitated crystals were collected. The crystals were washed with a small amount of water and then dried to obtain brown crystals of trisdiazonium salt iz, rg (yield 7/%).

Next, the trisdiazonium salt 2fi (
J, / j mmol) and as a coupler, 2-
Hydroxy-3-su7toic acid co'-chloro-j'-trifluoromethylanilide (@cp-4 in Table 1) J
, j&gC, λmmol was dissolved in N-dimethylformamide to Omlvcf8 and cooled to OoC. Add 10 rttl of 10% sodium acetate aqueous solution to this solution.
After addition, the mixture was stirred at room temperature for 2 hours.

Next, the generated precipitate was collected, washed with JOOml of water, washed with 200ml of acetone, and dried to obtain the trisazo compound μ, 2IiC yield j%.The decomposition temperature of this compound is 2700C or higher. there were.

The elemental analysis values and absorption spectra for Cuttle are as follows.

Calculated value as elemental analysis value c75H42C4i'3F9N1007 C, Ai, ly% H92, ♂7chi α, 7. Mui'
f', I1. t/% N, ri, 57% actual measurement value c, ti
,orchi H,,2,74%,7.33%F,//,
λ% N, 7.3 ≠ IR absorption (KBr tablet amino acid absorption: / & !r 0an-' visible absorption spectrum absorption thick wavelength j 720 m (! in N, N-dimethylformamide containing thiethylenediamine) Synthesis example 3 (General formula (l, Z is a sulfur atom, Cp is C in Table 1)
Synthesis of trisazo compounds that are p-s. )2, IA,!
-triphenylthiazole 20g (0,01,1Am
ol) was dissolved in iooml of concentrated sulfuric acid and cooled on ice. Potassium nitrate λ/,4Ali (0°21 comol) was gradually added to this. What is the reaction temperature at this time? The temperature remained below 0C.

After the addition was completed, the reaction mixture was stirred for 3 hours under water cooling, poured into 21 ice water, the resulting yellow precipitate was collected, washed with water and ethanol, and then recrystallized from DMF-ethanol.
jg (yield 1096) 0')2. IA! -) Squirrel (4
c'-nitrophenyl)thiazole and then the λ, μ,! -tris(lA/-nitrophenyl)thiazo-hlzl(o,o3timol) with N,N-
200 g of dimethylmamide and 20 g of iron powder were mixed, 10 rrdl 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, while maintaining the reaction temperature at 100°C, the reaction solution was neutralized using a saturated aqueous sodium bicarbonate solution to bring the pH of the reaction solution to r, and the reaction solution was filtered while hot. The filtrate was poured into 31 ice water to produce a
The pale yellow precipitate of er l'lis(4c'-aminophenyl)thiazole was separated and dried. Yield i1.3g (
Add λ, tA, t-4 lith (μ'-aminophenylnotiazo A // 29 (0, Oj 3m01) to diluted hydrochloric acid prepared from concentrated hydrochloric acid tort and water/lrOml). After stirring on a water bath at 60 °C and cooling to o 'C, add 7.69 g of sodium nitrite to this solution in water.
was added dropwise at 00C over about 30 minutes.

After that, it was stirred at the same temperature for 1 hour, and after removing a small amount of unreacted materials, the p liquid was added with ψ2% borohydrofluoric acid. OM was added and the precipitated crystals were collected in a furnace. After washing the crystals with a small amount of water and drying them, 17.1 Ag of brown crystals of trisdiazonium salt were obtained.
(Yield 10%) was obtained.

Next, 2 g of the trisdiazonium salt thus obtained (J
, t jmmol) and euhydroxy-3-naphthoic acid co'-trifluoromethyl-≠'- as coupler.
Chloronaphthoic acid anilide (Cp −j in Table 1
) J,! Ajll (P, 'Ajmmol
) was dissolved in ioml of N,N-dimethylformamide and cooled to o'c. To this solution, 10tttl of :/(7q6 sodium acetate aqueous solution was added dropwise at o'C, and the mixture was stirred at room temperature for 2 hours.

Next, the generated precipitate was collected, washed with 300 rnl of water, washed with 200 ml of acetone, and dried to obtain 33 g (yield: 3%) of tetrakisazo compound a.

The decomposition temperature of this compound was 2700C or higher.

The elemental analysis values and absorption spectra for Cuttle are as follows.

Elemental analysis value C75H42α3F9N1oo,, Calculated value as s C
, tO, ni/% H, ko, lμ% α, 7. lμchi1',
//, Hirotachi N, Ri, ≠7% S, 2.11% Actual value C, 40,22% H, 3,02%, 7.0/%)
', //, Hiroj Chi N, ri, ≠t% S, 2.0W Chi I
R absorption spectrum (KBr tablet) Absorption of amide: /&r0cIrL-"Visible absorption is the maximum wavelength of Cuttle absorption! 7/nm (J in thiethylenediamine-containing N,N-dimethylformamide) Other azo compounds of the present invention It can be synthesized according to the above synthesis example except for changing the coupler and the corresponding diazonium salt.

The electrophotographic photoreceptor of the present invention has an electrophotographic photosensitive layer containing seven or more types of azo compounds represented by the above general formula. Although various forms of electrophotographic photoreceptors are known,
The electrophotographic photoreceptor of the present invention may be any type of photoreceptor, but usually has an electrophotographic photoreceptor structure of the type exemplified below.

(a) An electrophotographic photosensitive layer comprising an azo compound dispersed in a binder or a charge carrier transport medium is provided on a conductive support.

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

The azo 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 be transported using the azo compound as a medium, but the charge carrier transport compound It is more effective to transport it as a medium.

To prepare an electrophotographic photoreceptor of type fa), fine particles of an azo compound are dispersed in a binder solution or a solution containing a charge carrier transporting 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 3 to 30 .mu.m, preferably j-20 .mu.m.

To prepare an electrophotographic photoreceptor of type (b), an azo compound is vacuum-deposited on a conductive support, or dissolved in a solvent such as amine and coated, or fine particles of an azo compound are coated on a conductive support with a suitable solvent or If necessary, it can be obtained by dispersing it in a solvent in which a binder has been dissolved, coating and drying, and then coating and drying a solution containing a charge carrier transport compound and a binder thereon. At this time, the thickness of the azo compound layer serving as the charge carrier generation layer is preferably ψμ or less, preferably 2μ or less, and the thickness of the charge carrier transport medium layer is 3 to 30μ, preferably j-
The azo compound used in photoreceptors of types (a) and (b) has a particle size of 20 μm. It is used after being pulverized to a size of less than μ, preferably less than 2 μ.

If the amount of the azo 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 photosensitive layer will be weak), and the The proportion of the azo compound in the photographic photosensitive layer is 0.01 to 2 times the weight of the binder, preferably 0.0
2 to 1 times by weight is preferable, and the ratio of the charge carrier transport compound to be added as necessary is a,/-2 times by weight, based on the binder.
Preferably, the range is from O,j to /,3 times by weight. In addition, in the case of a charge carrier transport compound that itself can be used as a binder, the amount of the azo compound added is 0 to the binder.
．． It is preferable to use 0/-0.1 times by weight.

In addition, when forming an azo compound-containing layer which becomes a charge carrier generation layer in a type (b) electrophotographic photoreceptor, the amount of azo compound used is preferably 0.1 times or more by weight relative to the binder resin, and if it is less than that, it is sufficient. Photosensitivity cannot be obtained. The proportion of the charge carrier transport compound in the charge carrier transport medium is 0.2 to 2 times the weight of the binder, preferably 0.2 to 2 times the weight of the binder.
i, 3 times by weight is preferred. When using polymeric charge carrier transport compounds which themselves can be used as binders, other binders can also be used without the need for other binders.

In addition, special requests can be made for type (b) photoreceptors! ? -! 3i
r3 issue, special application 1975'-10 tata 0≦ issue, special application show! As described in each of the specifications of Tar//Ir≠1, a charge carrier transporting compound such as a hydrazone 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 together with the binder.

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 such as polyester, or a plastic film on which a conductive material such as aluminum, indium oxide, 5N02, 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 Polymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alcoholic acid f
m fat, phenol-formaldehyde resin, styrene-
Alkyd resin, poly-N-vinylcarbazole These binders can be used alone or as a mixture of two or more.

Examples of plasticizers include biphenyl, chlorinated biphenyl, 0-terphenyl, p-terphenyl, cyphthyl 7-trivalent, dimethyl glycol 7-talate, dioctyl phthalate,
Triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin polypropylene, polystyrene, dilauryl thiodipropionate, 3. ! -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,
Examples include 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 Eva λ, ≠ 17 t"J Ni rotor fluorenone, λ, 4t, r, 7-titranitro 2
-Fluorenone, Terdicyanomethinone-'+''
+ 7h') Nitrofluoronone, terdicyanomethylene-2゜'A,j,7-titranitrofluorenone,
Tetranitrocarbasol chloranil, co, 3-dichlororu! , 6-dicyazbenzoquinone, λ, ,7-dolinitrota, 10-7 enanthrene, tetrachlorophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, and the like.

Compounds that transport holes include compounds having an electron-donating group, such as polymers, as described in (1) Japanese Patent Publication No. 3 μ-1
Polyvinylcarbazole and its derivatives described in No. 09tt, (2) Japanese Patent Publication No. Sho IAJ-llr67,
Polyvinylpyrene, polyvinylanthracene, poly(lambda)-vinyl-Hiro-(
Vinyl polymers such as ≠'-dimethylaminophenyl)-j-phenyl-oxazole, poly-3-vinyl-N-ethylcarbazole, (3) Special Publication Showa 4t! -/ri/ri3
copolymers such as polyacenaphthynones, polyindenes, copolymers of acenaphthylene and styrene, etc., described in the publication;
(4) Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin and ethylcarbazole-formaldehyde resin described in Japanese Patent Publication No. Shojt-/J Rihiro θ.

(5) JP-A Sho zt-yorr 3 and JP-A Shoyo 6-/
Various triphenylmethane polymers described in Specification A/110.

In addition, low-molecular compounds include (6) triazole derivatives described in U.S. Patent No. J//2/RI No. 7, etc.; (7) triazole derivatives described in U.S. Patent No. Described Ohosadiazole derivatives, (8) Tokuko Sho 3
Imidazole derivatives described in Publication No. 7-/60 and others, (9) U.S. Patent No. Jt/! No. 1402, No. 3120, No. 3! Hiroko j Hirohiro issue, special public Sho≠J--jyo 3, special public Shoj/-IOYIJ, JP-A 5/-5'J-ko 3, JP-A 1! -10161, No. 7.

JP-A-77-/14-ri No. 53, JP-A-4L-36AjJ
Polyarylalkane derivatives described in the specifications, publications, etc.,
JP-A Show 1s-trots issue, JP-A Show 149-7 Or! 3
No. 7, Japanese Patent Application Publication No. 1973-
4001/issue, JP-A-74-1rl/IA/, JP-A-74-μ! ! 4AJ' issue, Tokukai Sho! Hiro-7/12637
No., Tokukai Shoj! Pyrazoline derivatives and pyrazolone derivatives described in -7 μrat specification, publications, etc.

(11) U.S. Patent No. 3616≠Oa Specification, Special Publication!
/-1010! No., Tokukai Shoj4cmrj! Jj issue, Tokukai Sho! Hiro-/No. 10136, Tokukai Sho tlL-/IF Octopus No., Tokuko Sho 4t't-47/2, Tokukai Akihiro 7-213
Phenylenediamine derivatives (2) described in US Pat.
r, U.S. Patent No. 3/1r0703, U.S. Patent No. 32
1AOJ-97, U.S. Patent No. JtJ'rj20, U.S. Patent No. Vco 32103, U.S. Patent No. 4A/7JrP
t1, U.S. Patent No. 140/2374, JP-A-1J-
11AtA2!70, JP-A-Shoj+-ii Ri No.132,
Arylamine derivatives described in Japanese Patent Publication No. 3 Ta-27177, Japanese Patent Application Laid-Open No. 4-22≠37, publications, etc.
0gua2≠2, US Patent No. u, 2tryyo, US Patent IA27Jr4ct, US Patent IA2 Tata T27
04) Amino-substituted chalcone derivatives as described in US Patent No. 3jλ410/, (15) N as described in US Patent No. jjlJjlL4, etc. N-bicalbasil derivatives, (1→ oxisazole derivatives described in U.S. Pat. No. 3,217,203, etc., (lη styryl anthracene derivatives described in JP-A-56-μ42 JIA, etc., Fluorenone derivatives described in Patent No. 10137 and the like.

(barrel U.S. Patent No. 3717 Hiro62, Japanese Patent Application Publication No. Sho J'μ-j
RIlμ3 (corresponding to U.S. Patent No. Hiroshi/Yo0917), JP-A-ShojJ--120tJ, JP-A-Sho! ! -J-206μ
No., Tokukai Akira! rr-IA471. Q, JP-A-Sho sr-,r
Rari! No., JP-A No. 17-/, IJjO No., JP-A No. 17-Sho.
-/1Ar71A No., JP-A-67-104t14L4
Examples include hydrazone derivatives disclosed in the specification of No. L and the like.

In the present invention, the compound that transports charge carriers is (1
) to 0 so, 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 addition, in the photoreceptor obtained as described above, an adhesive layer or a 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, $lihinyl alcohol, ethyl cellulose, carboxymethyl cellulose, and JP-A-Sho! Vinylidene chloride polymer latex described in TarrlA2447, JP-A-Sho! Tar／／! styrene-butadiene polymer latex or aluminum oxide described in No. J@4C, and the thickness of these layers is preferably 1 μm or less.

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 to photoreceptors for printers using lasers and cathode ray tubes as light sources, in addition to electrophotographic copying machines.

The photoconductive composition containing the azo compound of the present invention can be applied as a photoconductive layer of an 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 photosensitive layer (photoconductive layer).
urnal of Applied Physics
s) J *μri (/2), J-PF3 (/ri71), (
A, K.

It can also be used as a photoconductive layer in solar cells, as described in J. Ghosh, Tom Feng.

The azo 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.

Moreover, the azo compound of the present invention is disclosed in Japanese Patent Publication No. 37-17742, Japanese Patent Application Publication No. 1987-17742, Japanese Patent Application Publication No. 1987-17742, Japanese Patent Application Publication No. 1987-17742, Japanese Patent Application Publication No. 1987-17742, Japanese Patent Publication No. 1987-17742, Japanese Patent Application Publication No. 1987-17742, Japanese Patent Application Publication No. 1987-17742, Japanese Patent Application Publication No. 1987-17742. ! -/Riots issue, Tokukai Akira! j-/6121
No. 0, JP-A-17-1999/Hiroi-76!6, an alkali-soluble resin solution such as a phenolic resin together with the charge carrier transporting compounds described above such as oxadiazole derivatives and hydrazone derivatives. By dispersing it in the medium, coating it on a conductive support such as aluminum, drying, image exposure, toner development, and etching with an alkaline aqueous solution, a printing plate with high resolution, high durability, and high sensitivity can be obtained, as well as printed circuits. You can also create .

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 azo compound of the present invention on a support. It can be formed using various methods.

When using the coating method, organic solvents include alcohols (e.g. methanol, ethanol, isopronominol, etc.), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), faamides (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 (
For example, methylene chloride, chloroform, dichloroform, carbon tetrachloride, monochlorobenzene, dichlorobenzene, etc.) can be used alone or in combination. The binder for the dye can be selected from known natural or synthetic resins, and specifically, cellulose resins (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, polyacrylonitrile, etc.), vinyl resins (e.g., polystyrene, polyvinyl acetate, (polyvinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, etc.), polycarmenates, polyesters, polyamide resins, epoxy resins, phenol resins, polyone fin resins (e.g., polyethylene, polypropylene, etc.), or synthetic copolymer resins, etc. Can be applied by spray, roller coach ink, spinner coating,
This can be done using a general-purpose coating method such as flade coating.

When forming an organic thin film with a resin, the content of the tetrakisazo compound in the thin film! -0% by weight, preferably 1t-to% by weight.

The rest is a binder. Further, the vapor deposition thickness or dry thickness of the organic thin film is 10 μm or less, preferably 2 μm or less.

Furthermore, an anti-fading agent 1 colorant 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 V-day 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 a guide groove 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. Reproducing information uses 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 in the pit area;
It will be absorbed in the non-pit region, and this is done by detecting the difference between the 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. The reproduction laser beam is activated by 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, it can be protected from dust, scratches, and contact with harmful gases, and the preservation of the recording layer is significantly improved.

The laser beam applied to the optical information recording medium of the present invention is
Gas lasers such as Arv laser, ) le-Ne laser, He-Cd laser, etc. 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 One part of the trisazo compound synthesized in Synthesis Example 2 (denoted by J-J, Z is an oxygen atom, and Cp is Cp-4 in Table 1) and ≠, lAl-bis(diethylamino)-u ,
Add 75 parts of u'-dimethyltriphenylmeth and 5 parts of polycarbonate of bisphenol A to the dichloromethantana part, grind this in a ball mill, mix and prepare a liquid,
An indium oxide vapor-deposited film was applied to the surface of a conductive transparent support (iooμ door polyethylene tele7 V-) film using this coating solution using a wire round rod.

The coating was coated on a surface resistor (1030) and dried to prepare an electrophotographic photoreceptor having a single-layer electrophotographic photosensitive layer with a thickness of about tμ.

This electrophotographic photoreceptor was charged with a +≠oovyr- charge by corona discharge of +jKV using an electrostatic copying paper tester (model SP-≠2 manufactured by Kawaguchi Denki ■), and then the color temperature λ
Irradiate the surface with light using a tungsten lamp at rJIt 0 so that the surface becomes 'A flux, find the time required for the surface potential to attenuate to half of the initial surface potential, and calculate the half-decreasing exposure amount E5olux, 5ec) When measured, A lux.

It was sec.

Examples 2 to 26 In Example 1, an electrophotographic photoreceptor with a single layer structure was produced in the same manner as in Example 1, except that the azo compounds shown in Table 1 were used instead of the trisazo compound synthesized in Synthesis Example 2. Then, in the same manner as in Example 1, the half-decreased exposure amount E50 due to positive charging
was measured. The results obtained are shown in Table 2.

In Table 2, the azo compounds are shown by the combination of the above-mentioned compound position and Cp4 in Table 7.

Table 2 Table 2 Table 2 Example 52 Trisazo compound synthesized in Synthesis Example 3 and represented by the general formula C6), where Z is a sulfur atom and Cp is cp-J- in Table 1! and polyester resin (product name: Pylon J
, 00, manufactured by Toyobo ■) and 3 parts of tetrahydrofuran.
After dispersing for 1.20 hours in a mail mill with a solution dissolved in 0 parts, using a wire round rod, conductive support (a 73μ polyethylene terephthalate film with an aluminum vapor deposited film on the surface.Surface electricity) Coated on resistor IAX10 O) and dried to a thickness of 0633
A charge generation layer of m was prepared.

Next, a hydrazone compound represented by the following structural formula [3] is placed on the charge generation layer. parts, μ parts of polycarbonate of bisphenol A, 13.3 parts of dichloromethane/, 4 parts of 2-dichloroethane λ. A solution dissolved in part A was applied and dried using a wire round rod to form a charge transport layer having a thickness of 71 μm, thereby producing an electrophotographic photoreceptor having a two-layer electrophotographic photosensitive layer.

The surface potential vo when this photoreceptor was charged for 3 seconds with a corona discharge of 14 KV and the surface potential V30 when left in a dark place for 30 hours were measured. J Olux
The surface potential (residual potential) Vn when exposed to light at the exposure amount E50 and &01ux・Sec required for the surface potential to attenuate to half of the surface potential v3o. Each was measured.

Further, similar measurements were repeated 1000 times. The results are shown in Table 3.

Table 3 Comparative Example 1.2 Trisazo compound used in Example 52 (general formula [
! ], 2 is a sulfur atom, and Cp is Cp in Table 1.
-! Instead of , the following structural formula [103 (JP-A-Sho!r-/2
3144/), (//) (Patent Application ShojP-
An electrophotographic photoreceptor having a two-layer structure was prepared in the same manner as in Example 52, except that the method described in JOP/r specification was used.
50 and residual potential vR were measured. Further, the same procedure as in Example 52 was repeated 3000 times, and the results are shown in Table μ.

As is clear from the results in Table 1 and above, the electrophotographic photoreceptor of the present invention containing an azo compound substituted with a 4-fluoroalkyl group (in Example 52, a trifluoromethyl group) Compared to the electrophotographic photoreceptor of the comparative example containing an azo compound not substituted with a group, it is extremely superior in terms of surface potential, sensitivity, residual potential, and stability during repeated use.

Examples 53 to 127 In Example 52, a two-layer electrophotographic photoreceptor was prepared in the same manner as in Example 52, except that the azo compounds shown in Table 5 were used instead of the trisazo compound synthesized in Synthesis Example 3. , The half-decrease exposure amount E5o was measured in the same manner as in Example 52. The results are shown in Table 1.

In Table 5, azo compounds are shown by combinations of the above-mentioned compound positions and cp-/% in Table 1.

Table 5 Table 5 Table 3 Table 5 Example 128 Trisazo compound synthesized in Synthesis Example 3 and represented by the general formula Cj3, where Z is a sulfur atom and Cp is Cp-1 in Table 1!
and the hydrazone compound used in Example 52 [ri]4cO
copolymer of benzyl methacrylate and methacrylic acid ([η] 300C methyl ethyl ketone = 0, /
u, 3 parts containing methacrylic acid, and 4) ioo parts were added to 610 parts of dichloromethane and dispersed by ultrasonication.

This dispersion was applied onto a grained aluminum plate with a thickness of 0.21 mm and dried to a dry film thickness of 1. An electrophotographic printing plate material having an electrophotographic photosensitive layer of mm was prepared.

After charging the surface potential of the photosensitive layer to approximately +6oov by subjecting this sample to corona discharge (+JKV) in a dark place,
When the sample surface was exposed to tungsten light with a color temperature of 2rJ-IAo at an illuminance of -2.01ux, the half-reduced exposure amount was -0.
It was 6ux, sec.

Next, this sample was charged to a surface potential of about +μQov in a dark place, and then brought into close contact with a transparent original with a positive image, and imagewise exposed. A toner was prepared by adding 1 part of polymethyl methacrylate (toner) dispersed in fine particles and 0.0 part of soybean oil lecithin to 1000 parts of l5oper H (Esso Standard Co., Ltd., petroleum solvent). It was possible to obtain a clear positive toner image by immersing the toner in the liquid developer containing the toner.

Further, the toner image was fixed by heating at 1000C for 3C seconds. This printing plate material was mixed with 70 parts of sodium metasilicate hydrate, 7 μθ parts of glycerin, 130 parts of ethylene glycol,
Soak it in a solution dissolved in ethanol and iodine for about 7 minutes, and wash it with water (while brushing).
The portions of the electrophotographic photosensitive layer to which toner was not attached were removed to obtain a printing plate.

Also, the electrostatic latent image obtained instead of liquid developer? , Xerox 3J00 toner (manufactured by Fuji Xerox Co., Ltd.) was developed with a magnetic brush and then heated at RO0C for 30 seconds to fix it.Next, the photosensitive layer in the area where the toner was not attached was removed with an alkaline solution. A version was obtained.

The printing plate made in this way is /S Madastar 600C.
Very clear prints with no spot stains printed using a D-offset printing machine using a conventional method! I was able to print out the cane.

Example 129 Nitrocellulose solution (Daicel Chemical Industry M, methyl ethyl ketone λj wt% bath solution 10fi, trisazo compound J synthesized in Synthesis Example 2, Og and tetrahydrofuran/00g were mixed and thoroughly dispersed. This dispersion liquid on an acrylic substrate using spinner coating method (10
00 rpm) and then dried at a temperature of ro0c for 2 hours (film thickness 0.3 μm).

The recording medium produced in this way was mounted on a turntable, and the turntable was moved by a motor.
p.m. Spot side l while rotating.

oμmvc focused 10 rnW and I MHz helium-neon laser light (oscillation wavelength 1.33 nm)
Recording was performed by irradiating the surface of the recording layer in the form of a track. When the surface of the recorded recording layer was observed using a scanning electron microscope, clear pits were observed.

Furthermore, when the above-mentioned laser beam with a low output was incident on this recording medium and the reflected light was detected, a wavelength having a sufficient S/N ratio was obtained. Comparative Example 3.4 Used in Example 52 Trisazo compound (general formula C
j), Z is a sulfur atom, and cp is Cp in Table 1.
The two-layer electron A photographic photoreceptor was prepared, and the surface potential Vo, v3o, half-exposure E50, and residual potential v were prepared in the same manner as in Example 52.
R was measured. Table 4 shows the results of repeating the same measurements 5000 times in the same manner as in Example 52.

As is clear from the results above, the present invention contains an azo compound substituted with a fluoroalkyl group (trifluoromethyl group in Example 52 and a halogen atom (halogen atom in Example 52)). The electrophotographic photoreceptor has lower surface potential, sensitivity, residual potential, sensitivity, and residual potential than a comparative electrophotographic photoreceptor containing an azo compound that is not substituted with a perfluoroalkyl group or an azo compound that is substituted only with a halogen atom. It is also slightly superior in terms of stability during repeated use.

Procedural amendment (side Showa/ρ year? month r day Taku

Claims (5)

[Claims] (1) A photosensitive composition containing at least one azo compound represented by the following general formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, A^1: represents a substituted or unsubstituted hydrocarbon or heteroaromatic ring, and X: represents a substituted or unsubstituted aromatic ring fused with a benzene ring. Represents an atomic group necessary to form a hydrocarbon or heteroaromatic ring, Ar: a hydrocarbon or heteroaromatic ring substituted with at least one perfluoroalkyl group (substitution other than perfluoroalkyl group) n: represents an integer of 3, 4, 5 or 6.) (2) In the azo compound represented by general formula [1],
Hydrocarbon or heteroaromatic in which Ar is substituted with at least one perfluoroalkyl group and at least one halogen atom (may be substituted with a substituent other than the perfluoroalkyl group and halogen atom)
The photosensitive composition according to claim 1. (3) The photosensitive composition according to claim 1, wherein the azo compound represented by the general formula [1] is a trisazo compound represented by the following general formula [2]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [2] (In the formula, Z: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-, -S
- or -Se-. 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. X: Represents an atomic group necessary to form a substituted or unsubstituted hydrocarbon or heteroaromatic ring by condensation with a benzene ring, Ar: Hydrocarbon substituted with at least one perfluoroalkyl group Or it represents a heteroaromatic ring (which may be substituted with a substituent other than a perfluoroalkyl group). B^1, B^2, B^3: Represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a substituted product thereof. ) (4) The photosensitive composition according to claim 1, wherein the azo compound represented by the general formula [1] is a tetrakisazo compound represented by the following general formula [3]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [3] (In the formula, Z: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-, -S
- or -Se-. 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. X: represents an atomic group necessary to form a substituted or unsubstituted hydrocarbon or heteroaromatic ring by condensation with a benzene ring; Ar: a hydrocarbon substituted with at least one perfluoroalkyl group; represents a system or a heteroaromatic ring (which may be substituted with a substituent other than a perfluoroalkyl group). Q^1: There are single bonds, ▲mathematical formulas, chemical formulas, tables, etc.▼(
However, n represents an integer from 1 to 3. ), or a divalent organic residue having aromaticity. B^1 and B^2 represent a hydrogen atom or an electron-withdrawing group. ) Q^2: Represents a divalent hydrocarbon type or heteroaromatic ring group or a substituted product thereof. (5) The photosensitive composition according to claim 1, wherein the azo compound represented by the general formula [1] is a trisazo compound represented by the following general formula [4]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [4] [In the formula, Y: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ Represents ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. X: Represents an atomic group necessary to form a substituted or unsubstituted hydrocarbon or heteroaromatic ring by condensation with a benzene ring, Ar: Hydrocarbon substituted with at least one perfluoroalkyl group Or it represents a heteroaromatic ring (which may be substituted with a substituent other than a perfluoroalkyl group).