JPH0350554A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve sensitivity, electrostatic charge holding characteristic and durability by using a specific titanyl phthalocyanine compsn. crystal as a charge generating agent and using a specific compd. as a charge transfer agent. CONSTITUTION:The charge generating agent consists of the titanyl phthalocyanine compsn. crystal contg. <=50 pts. wt. nitrogen isoconstitutional body of nonmetallic phthalocyanine and 100 pts. wt. titanyl phthalocyanine as its effective component. This compsn. crystal has a strong absorption at the prescribed wavelength of IR absorption spectra; in addition, the Bragg angle of the X-ray diffraction spectra with CuKalpha as a heat source exhibits the max. diffraction peak at 27.3 deg. and a strong diffraction peak at the other prescribed angle. In addition, the charge transfer agent contains the hydrozone compd. expressed by formula I and the compd. expressed by formula II as its effective component. In the formulas I, II, R<1> denotes a hydrogen atom, alkoxyl group, etc.; R<2> denotes a hydrogen atom, alkyl group, etc.; R<3>, R<4> denote a hydrogen atom, alkyl group, etc.; A denotes an electron-donating group, R<5> denotes a hydrogen atom, alkoxyl group, etc.; R<6>, R<7> denote a hydrogen atom, aralkyl group, etc. The high photosensitivity, electrostatic chargeability and durability are improved in this way.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor, and more specifically, the present invention relates to an electrophotographic photoreceptor, and more particularly, a novel titanyl phthalocyanine composition crystal is used as an active ingredient of a charge generation agent, and a predetermined compound is used as a charge transfer agent. The present invention relates to an electrophotographic photoreceptor containing the active ingredient as an active ingredient.

[Technology of auxiliary wood] Phthalocyanines and metal phthalocyanines have been known to exhibit excellent photoconductivity, and some of them are used in electrophotographic photoreceptors. In recent years, with the development of non-impact printer technology, electrophotographic optical printers that use laser light or LED as a light source and are capable of high image quality and high speed are becoming widespread, and the development of photoreceptors that can withstand these demands is becoming more and more popular. It's thriving.

In particular, when using a laser as a light source, semiconductor lasers are often used due to their compact size, low cost, and simplicity.However, the oscillation wavelength of the semiconductor lasers currently used for these is relatively long wavelength in the near-infrared region. It is limited. Therefore, it is inappropriate to use a photoreceptor sensitive to the visible region, which has been conventionally used in electrophotographic copiers, for semiconductor lasers, and a photoreceptor with photosensitivity extending into the near-infrared region is required. It has become to.

Conventionally known organic materials that meet this requirement include methine squaric acid dyes, indoline dyes, cyanine dyes, pyrylium dyes, polyazo dyes, phthalocyanine dyes, and naphthoquinone dyes. Among these, methine squaric acid dyes, indoline dyes, cyanine dyes, and pyrylium dyes can be made to have longer wavelengths, but they lack practical stability (repeatability), and polyazo dyes are difficult to make longer wavelengths. , and is disadvantageous in terms of production, and naphthoquinone dyes currently have difficulties in terms of sensitivity.

On the other hand, phthalocyanine dyes have a peak spectral sensitivity in the long wavelength region of 600 nm or more, and are also highly sensitive.The spectral sensitivity changes depending on the type of central metal and crystal type, so they are suitable as dyes for semiconductor lasers. It is believed that this technology has been developed, and research and development is being carried out vigorously.

Among the phthalocyanine compounds studied so far, 7
Examples of compounds that exhibit high sensitivity in a long wavelength range of 80 nm or more include X-type metal-free phthalocyanine, ε-type copper phthalocyanine, vanadyl phthalocyanine, and the like.

On the other hand, in order to achieve higher sensitivity, a laminated photoreceptor with a vapor-deposited phthalocyanine film as a charge generation layer was considered, and
Among the phthalocyanines whose central metals are group A and group IV metals, some have been obtained that have relatively high sensitivity. Documents related to such metal phthalocyanines include, for example, JP-A-57-211149, JP-A-57-148745@, JP-A-59-36254, JP-A-59-44054, and JP-A-59-3054.
Publication No. 1, Publication No. 59-31965, Publication No. 59-16
There are publications such as No. 6959. However, the preparation of the vapor deposited film requires a high vacuum evacuation device, which increases the equipment cost, so the above-mentioned organic photoreceptor inevitably becomes expensive.

In contrast, phthalocyanine is not deposited as a film, but
A multi-unit type photoreceptor has also been considered in which a resin decomposition layer is used as a charge generation layer, and a charge transfer layer is coated thereon.

As a charge transfer agent, as described in JP-A No. 54-59143, a hydrazone compound is used which has high sensitivity, low residual potential, little optical fatigue even when used repeatedly according to electrophotographic process, and excellent durability. has not yet been developed. In addition, as stated in Japanese Patent Application Laid-open No. 32850/1985, a triphenylmethane compound was developed that has high sensitivity and low residual potential, and has low optical fatigue and excellent durability even when used repeatedly according to the electrophotographic process. has been done.

In addition, as a composite photoreceptor, metal-free phthalocyanine (
There are photoreceptors that use indium phthalocyanine (Japanese Patent Application No. 57-66963) and indium phthalocyanine (Japanese Patent Application No. 59-220493), and these are relatively highly sensitive photoreceptors; The latter has drawbacks such as a decrease in sensitivity, and the latter has drawbacks such as insufficient sensitivity for practical use when the charge generation layer is prepared from a resin dispersion system.

[Problems to be Solved by the Invention] Particularly in recent years, methods using titanyl phthalocyanine, which has relatively high sensitivity electrophotographic properties, have been studied (Japanese Unexamined Patent Publication Nos. 59-49544 and 61-23).
No. 928, No. 61-109056, No. 62-
275272], it is known that there are differences in properties depending on various crystal forms. Creating these various crystal forms requires special purification and special solvent treatments. The processing solvent is different from that used in forming the decomposition coating. This is because the various crystals obtained tend to grow in a certain long-treatment solvent, and when the same solvent is used as a coating solvent, it is difficult to control the crystal shape and particle size, resulting in poor paint stability. This is because the electrostatic properties deteriorate, making it unsuitable for practical use. For this reason, chlorinated solvents such as chloroform, which do not easily promote crystal growth, are usually used when making paints, but these solvents do not necessarily have good decomposition properties for titanyl phthalocyanine, making it difficult to stabilize the decomposition of paints. This is a problem in terms of sexuality.

On the other hand, titanyl phthalocyanine generally has a large ionization potential, and when used together with a hydrazone compound that has a small ionization potential, holes are easily injected from the titanyl phthalocyanine into the hydrazone compound because of the large difference in ionization potential. For this reason,
Poor charging properties and poor durability. When used in a dispersed photoreceptor containing a charge generation agent and a charge transfer agent in a single layer,
There is a problem in that it is difficult to include a large amount of a charge generating agent in order to improve sensitivity while maintaining chargeability.

The present invention has been made in order to solve the conventional problems as described above, and uses a titanyl phthalocyanine composition crystal having excellent photoconductivity in an electrophotographic photoreceptor containing a charge generating agent and a charge transfer agent. It is an object of the present invention to provide an electrophotographic photoreceptor with high sensitivity and excellent charge retention and durability by using a specific compound as a charge generation agent and a specific compound as a charge transfer agent.

[Means for Solving the Problems] The present invention provides an electrophotographic photoreceptor containing a charge generating agent and a charge transfer agent, in which (a) the charge generating agent is a non-metallic phthalocyanine nitrogen isomer, a metal phthalocyanine nitrogen isomer, or a non-metallic phthalocyanine nitrogen isomer. Metal phthalocyanine, metal phthalocyanine, metal-free naphthalocyanine or metal naphthalocyanine (however, metal-free phthalocyanine nitrogen isoform, metal phthalocyanine nitrogen isoform, metal-free phthalocyanine and metal phthalocyanine may have a substituent on the benzene nucleus, , a metal-free naphthalocyanine and a metal naphthalocyanine which may have a substituent on the naphthyl nucleus, in a total amount of 50 parts by weight or less of one or more of the following, and 100 parts by weight of titanyl phthalocyanine. In the infrared absorption spectrum, the composition crystal has a compound crystal as an active ingredient,
1490±2cm-I! J”, 1415±2cm-In
", 1332 ± 2 cm-m-', 1119 ± 2 Cm Kazutomi, 1o72 ± 2 cm", , 1060 ± 2 cm-'
961±2 cm-1, 893±2 cm-IA-
'780±2cm"751±2cm-Il-'
and 730 ± 2 cm-I! In the X-ray diffraction spectrum using CuKδ as a radiation source, the maximum diffraction peak is at a Bragg angle (2θ±0.2 degrees) of 27.3 degrees. and shows a strong diffraction peak at θ±0.24.1 degrees, or in the X-ray diffraction spectrum using CLIKδ as the radiation source, Bragg angle {2θ±0.
2 degrees} shows the maximum diffraction peak at 27.3 degrees, and 7.4
(b) The charge transfer agent exhibits strong diffraction peaks at 22.3 degrees, 24.1 degrees, 25.3 degrees, and 28.5 degrees; , a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a halogen, a substituted or unsubstituted amino group, a morphorno group, a piperidino group or a phenyl group, and R2 may form a carbazono group. Represents a hydrogen atom, a substituted or unsubstituted alkyl group, and R3 and R4 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a ring such as a pyridyl group, pyrrolodino group, or carbazono group. ) and a hydrazone compound represented by the general formula [■]: (wherein A is an electron donating group, R5 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group) , R6 and R7 are the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted 7-ralkyl group, a substituted or unsubstituted aryl group> The active ingredient is a compound represented by This is an electrophotographic photoreceptor characterized by the following.

According to the present invention, as a charge transfer agent, the general formula [I]
By using compounds represented by An electrophotographic photoreceptor with low optical fatigue and excellent durability can be obtained.

The present invention will be explained in detail below.

The phthalocyanine compounds and naphthalocyanine compounds used in the present invention are described in "Phthalocyanine Compounds" by Moser and Thomas (Reinhold Co., 1963).
), “Phthalocyanine J (CRC Publishing, 1913
Those obtained by known methods such as 3) and other suitable methods are used.

For example, titanyl phthalocyanine can be easily synthesized from 1,2-dicyanobenzene (O-phthalodinitrile) or a derivative thereof and a metal or metal compound according to a known method.

For example, in the case of titanyl phthalocyanines, the following (1)
Alternatively, it can be easily combined according to the reaction formula shown in (2).

(Left below) PcTi=0 (PC indicates phthalocyanine residue) Organic solvents include nitrobenzene, quinoline, α-chloronaphthalene, β-chloronaphthalene, α-methylnaphthalene,
A high boiling point organic solvent inert to the reaction of methoxynaphthalene, diphenyl ether, diphenylmethane, diphenylethane, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, etc. is preferable, and the reaction temperature is usually 150 to 300'C, especially 200-250°C is preferred.

In the present invention, the thus obtained crude titanyl phthalocyanine compound is used as it is or after being purified by the method described below. In the case of purification, treatment is performed with tetrahydrofuran after the amorphization treatment. At that time, after removing the organic solvent used in the condensation reaction using an appropriate organic solvent, for example, alcohols such as methanol, ethanol, and isopropyl alcohol, and ethers such as tetrahydrofuran and 1,4-dioxane. , preferably hydrothermal treatment. In particular, it is preferable to wash until the p-day of the washing solution after hot water treatment reaches about 5 to 7.

Subsequent treatment with an electron-donating solvent such as 2-ethoxyethanol, diglyme, dioxane, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, and morpholine is more preferred.

Next, as phthalocyanine nitrogen isoconstructs, there are various volfins, such as tetrapyridinovolphyrazine, in which one or more of the benzene nuclei of phthalocyanine is replaced with a quinoline nucleus, and as metal phthalocyanines, copper,
Various materials such as nickel, cobalt, zinc, tin, aluminum, and titanium can be mentioned.

Substituents for phthalocyanines and naphthalocyanines include amino groups, nitro groups, alkyl groups, alkoxy groups, cyano groups, mercapto groups, halogen atoms, etc., sulfone M groups, carboxylic acid groups, or metal salts thereof. , ammonium salts, amine salts, etc. can be exemplified as relatively simple examples. Furthermore, an alkylene group is added to the benzene nucleus,
Various substituents can be introduced via a sulfonyl group, a carbonyl group, an imino group, etc., and these are known as anti-aggregation agents or crystal conversion inhibitors in the technical field of phthalocyanine pigments, for example, in US Pat. 39
Nos. 73981 and 4088507), or unknown ones. Known methods for introducing each substituent are omitted. In addition, things that are not publicly known will be described as examples in the Examples.

In the present invention, titanyl phthalocyanine and metal-free and metal phthalocyanine nitrogen isoconstructs that may have a substituent on the benzene nucleus, metal-free and metal phthalocyanines, or metal-free and metal naphthalocyanines that may have a substituent on the naphthyl nucleus. It is sufficient that the ratio is 100/50 (weight ratio) or more, but preferably 100/20 to 0
．． 1 (weight ratio). If it is 100/0.1 or more, the crystal will contain many single crystals in addition to the mixed crystal composition, and the infrared absorption spectrum and X-ray diffraction spectrum of the new material of the present invention will be Identification may become difficult (hereinafter, these mixed groups are referred to as titanyl phthalocyanine groups).

The titanyl phthalocyanine composition of the present invention can be produced by mixing titanyl phthalocyanine and other phthalocyanines, and treating the amorphous composition of the mixture with tetrahydrofuran to crystallize it.

The amorphous titanyl phthalocyanine composition can be obtained by a single chemical or mechanical method, but more preferably by a combination of various methods.

For example, amorphous particles can be obtained by weakening agglomeration between particles using a method such as an acid basing method or an acid slurry method, and then grinding using a mechanical processing method. Equipment used during grinding includes seconder, Banbury mixer attritor, edge runner mill,
Roll mill, ball mill, sand mill, SPEX mill,
Examples include, but are not limited to, homomixers, dispersers, agitators, jaw crushers, stamp mills, cutter mills, and micronizers. In addition, the acid pasting method, which is well known as a chemical treatment method, is a method in which a pigment is dissolved or made into a sulfate in 95% or more sulfuric acid and then poured into water or ice water to re-precipitate. By keeping the temperature preferably at 5° C. or lower and slowly injecting sulfuric acid into water that is being stirred at high speed, amorphous particles can be obtained under roughly good conditions.

Other methods include a method in which crystalline particles are directly milled using a mechanical processing device for a very long time, and a method in which particles obtained by an acid pasting method are treated with the above-mentioned solvent or the like and then milled.

Amorphous particles can also be obtained by sublimation. For example, each raw material obtained by various methods under vacuum is
It can be obtained by heating to 600° C. to sublimate it and immediately co-evaporating it onto a substrate.

The amorphous titanyl phthalocyanine composition obtained as described above is treated in tetrahydrofuran to obtain new stable crystals. As a method for treating tetrahydrofuran, 5 to 300 parts by weight of tetrahydrofuran are placed in various stirring tanks per 1 part by weight of the amorphous titanyl phthalocyanine composition, and the mixture is stirred. Both heating and cooling are possible, but heating speeds up crystal growth.
It also slows down at low temperatures. As the stirring tank, in addition to a normal stirrer, an ultrasonic ball mill, a sand mill, a homomixer, a disperser, an agitator, a micronizer, etc., which are used for classification, or a mixer such as a concal blender type mixer, etc., can be used as appropriate. However, it is not limited to these.

After these stirring steps, filtration, washing, and drying are usually performed to obtain stabilized crystals of titanyl phthalocyanine complex. At this time, without filtration or drying, it is possible to add a resin or the like to the separated liquid as necessary to make it into a paint, which is extremely effective as it saves a number of steps when used as a coating film for electrophotographic photoreceptors and the like.

The infrared absorption spectrum of the crude titanyl phthalocyanine of the present invention thus obtained is shown in FIG. This titanyl phthalocyanine composition has an absorption wave number (c'1, including an error of ±2) of 1490 and 141.
5, 1332, 1119, 1072, 1060,961
, 893, 780, 751, and 730 show characteristic strong peaks.

For reference, Figure 2 shows the infrared absorption spectrum of titanyl phthalocyanine treated with N-methylpyrrolidone. FIG. 3 shows an infrared absorption spectrum of titanyl phthalocyanine treated by the treatment method for obtaining phthalocyanine.

These infrared absorption spectra show that the titanyl phthalocyanine composition obtained by the above method is novel.

Further, X-ray diffraction patterns using CuKδ rays are shown in FIGS. 4 to 6. This titanyl phthalocyanine compound exhibits a maximum diffraction peak at a Bragg angle 2θ (with an error range of ±0.2 degrees) of 27.3 degrees in the X-ray diffraction diagram, and a maximum diffraction peak of θ±0.24 degrees. Those showing a strong peak at once, and those showing a strong peak at two times.
Some of them show a maximum peak at 7.3 degrees, and others show strong peaks at 7.4 degrees, 22.3 degrees, 24.1 degrees, 25.3 degrees, and 28.5 degrees.

These differences are thought to be due to the difference in the growth rate of each crystal plane of a crystal with the same structure, since the intensity of a diffraction line is generally approximately proportional to the size of each crystal plane.

The titanyl phthalocyanine compound of the present invention shows no major change in the infrared absorption spectrum even when heated and stirred in tetrahydrofuran to promote crystal growth, and is an extremely stable and good crystal.

One of the charge transfer agents used in the present invention has the general formula [I]
(wherein RS , R2 , R3 and R4 have the same meanings as above) Particularly effective are compounds represented by formula [III].

The compounds represented by the general formula [I] can be easily synthesized by conventional methods. For example, J. Pacansky et al.
Radiat. Phys. CheIll. )
, Volume 29, No. 3, Pages 219-225, 198
It can be easily obtained by method 7).

Specifically, <In the formula, R1, R2, R3 and R4 have the same meanings as above> is added in a molar ratio of 1:1 to 2:1, and a mineral acid such as hydrochloric acid is used as a catalyst. , can be easily mixed in ethanol.

Specific examples of the compound represented by the general formula [IIl] include those shown in Table 1, but similar compounds are effective, and the invention is not necessarily limited thereto.

(Left below) Table 1 Table-1 (Continued) These can be synthesized by conventional methods. For example, Furuno (Y
oshino) et al., Tokyo Industrial Research Institute Report (Rep.G
ov. Chem. Ind. Res. Inst.
Tokyo), 37, 95, 111 (1942
), and US Pat. No. 3,739,000@.

Specifically, the compound represented by the general formula [■] is a phenyl compound represented by the general formula [IV]: (wherein A and R5 have the same meanings as above), and the compound represented by the general formula [V ]:R6 R
7 C-0 - [V] (wherein R6 and R7 have the same meanings as above) are added in a molar ratio of 4:1 to 2=1, and a mineral acid such as hydrochloric acid or By using anhydrous zinc chloride or the like as a catalyst, the reaction can be easily carried out. Also, if necessary, a solvent such as methanol, ethanol, dioxane, chloroform, benzene or the like may be used.

The electrophotographic photoreceptor of the present invention preferably has an undercoat layer, a charge generation layer, and a charge transfer layer laminated in this order on a conductive substrate. It may be a layered structure or a structure in which a charge generating agent and a charge transfer agent are dispersed and coated on an undercoat layer with a suitable resin.

Furthermore, these undercoat layers can be omitted if necessary.

Conductive substrates used in the present invention include metal plates, metal drums, or metal foils made of aluminum, nickel, chromium, etc., plastic films with thin layers of aluminum, tin oxide, indium oxide, chromium, etc., and conductive materials. Paper or plastic film coated or impregnated with is used.

By coating the titanyl phthalocyanine composition according to the present invention as a charge generating agent on a substrate with a suitable binder,
It is possible to produce 1 q of charge generation layer with extremely good decomposition property and extremely high photoelectric conversion efficiency.

Coating is performed using a spin coater, applicator, spray coater, bar coater, dip coater, doctor blade, roller coater, curtain coater, or bead coater, and drying is preferably performed by heating at 40 to 200°C. The test is carried out for a period of 10 minutes to 6 hours under static or ventilated conditions.

The film thickness after drying is o. It is coated in such a way that it has an oi~5 base, preferably a 0.1~1 instant.

Binders that can be used to form the charge generating layer by coating can be selected from a wide variety of insulating resins and organic photoconductive polymers such as poly-N-vinyl rubber, polyvinyl anthracene, and polyvinyl pyrene. can. Preferably, polyvinyl butyral, polyarylate (condensation polymer of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, cellulose resin, urethane resin , epoxy resin, silicone resin, polystyrene, polyketone, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, polyacrylonitrile, phenol resin, melamine resin, casein, polyvinyl alcohol, polyvinylpyrrolidone, and other insulating resins. I can do it. The resin contained in the charge generation layer is suitably 100% by weight or less, preferably 40% by weight or less. Further, these resins may be used alone or in combination of two or more.

The solvent for dissolving these resins varies depending on the type of resin, and is preferably selected from those that do not affect the charge transfer layer and undercoat layer, which will be described later, during coating. Specifically, aromatic hydrocarbons such as benzene, xylene, ligroin, monochlorobenzene, dichlorobenzene, ketones such as acetone, methyl ethyl ketone, cyclohexanone, alcohols such as methanol, ethanol, isopropanol, ethyl acetate, methyl cellosolve, etc. Esters, carbon tetrachloride, aliphatic halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, trichloroethylene, tetrahydrofuran,
Ethers such as dioxane, ethylene glycol monomethyl ether, N,N-dimethylformamide, N
, N-dimethylacetamide, and sulfoxides such as dimethyl sulfoxide.

Further, the charge transfer layer can be formed by dissolving the compounds represented by the general formulas [I] and [■] in a suitable binder and coating the solution. The mixing ratio is
The compound represented by general formula [II] is 0. 05-90wt%, especially 20-50wt
% is preferred. Regarding the binder and organic solvent used when forming the charge transfer layer by coating, those used when forming the charge generation layer as described above can be used in the same manner. The total amount of the compounds represented by formulas [I] and [II] contained in the charge transfer layer is suitably 10 to 90% by weight, preferably 30 to 65% by weight. Furthermore, a plasticizer or the like can be used together with the binder as necessary.

The charge transfer layer is electrically connected to the charge generation layer described above, receives charge carriers injected from the charge generation layer in the presence of an electric field, and transfers these charge carriers to the photoreceptor surface or support surface. It has the function of
The charge transport layer may be laminated on the charge generation layer,
Moreover, it may be laminated thereunder. However, it is preferable that the charge transport layer is laminated on the charge generation layer.

At this time, the thickness of the charge transfer layer is 3 to 50, preferably 5
~20 legs.

In addition, for the binder resin normally used for the charge transfer layer,
5-40% by weight of the titanyl phthalocyanine composition of the present invention and 10-70% by weight of the charge transfer agent, 5-50 liters
! It is also possible to produce a single layer photoreceptor with IR1 preferably 15 to 30 IjIri. As a result, a positively charged photoreceptor with stable charging properties, sensitivity, etc. can be obtained.

Further, an undercoat layer having a barrier function and a contact function can be provided between the conductive support and the photoreceptor. The undercoat layer contains casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane, gelatin, aluminum oxide,
It can be formed using zinc oxide or the like. The thickness of the undercoat layer is 0.1 to 5 mm, preferably 0.5 to 3 tII! 1
The degree is appropriate.

The electrophotographic photoreceptor of the present invention has an absorption peak at a wavelength around 800 nn+, as shown in the spectral sensitivity characteristic diagram in FIG. It can also be applied to various optical storage devices.

[Examples] The present invention will be specifically described below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In addition, in the examples, parts indicate parts by weight.

Production synthesis example of phthalocyanines 1 20.4 parts of 0-phthalodinitrile, 7.6 parts of titanium tetrachloride
After heating reaction for 2 hours at 200'C in 50 parts of quinoline, the solvent was removed by steam distillation, purified with 2% aqueous hydrochloric acid solution, then 2% aqueous sodium hydroxide solution, methanol, N
, N-dimethylformamide and dried to obtain 21.3 parts of titanyl phthalocyanine (TiOPc).

Synthesis Example 2 14.5 parts of aminoiminoisoindolenine and 5 parts of quinoline
After the reaction, the solvent was removed by steam distillation, purified with a 2% aqueous hydrochloric acid solution, then a 2% aqueous sodium hydroxide solution, and then purified with methanol and N,N-dimethylformamide. After sufficient washing and drying, 8.8 parts of metal-free phthalocyanine (yield 70%) was obtained.

Synthesis Example 3 20 parts of 0-naphthalodinitrile in 50 parts of quinoline
After a heating reaction at 00° C. for 4 hours, the product was purified with a 2% aqueous hydrochloric acid solution, washed with methanol and N,N-dimethylformamide, and dried to obtain 15 parts of metal-free naphthalocyanine.

Example 4 A mixture of 15 parts of metal-free or metal phthalocyanine, 500 parts of dichlorotoluene, 25 parts of acetyl chloride and 70 parts of aluminum chloride was stirred at 60 to 80°C for 8 hours, then poured into water to determine the solid content. was filtered, washed with water, and dried to obtain a compound represented by the following formula.

MPc (COC 2 C! > 1.3 (in the formula, M is 2, Cu, Tie, Zn, etc., MPC is a phthalocyanine residue, and the number outside the box indicates the average number of substitutions by analysis. Similarly> Various phthalocyanine derivatives were obtained by reacting this with amines by a known method.

By reducing these various phthalocyanine derivatives by a known method, the general formula; A phthalocyanine derivative represented by the following formula is obtained.

For example, to reduce a phthalocyanine derivative represented by the following formula, dissolve 6 parts of potassium hydroxide in 80 parts of diethylene glycol, add 6 parts of the above phthalocyanine derivative after sufficiently finely grinding it, and roughly add hydrazine hydrate. 10
gradually add the solution and reflux for about 10 hours. The resulting deep blue slurry is poured into water, filtered, washed with water, and dried.

The obtained phthalocyanine derivatives are shown in Table 2.

(Leaving space below) Table 2 Synthesis Example 5 Metal-free phthalocyanine, copper phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine, and titanyl phthalocyanine, which had been chlorosulfonated by a conventional method, were reacted with various amines to obtain the phthalocyanine derivatives shown in Table 3. .

(Leaving space below) Table 3 Table 3 (Continued) Example 6 Preparation of 4 hydrans represented by general formula [I] Diphenylhydrazine 2.02 9 and p-diethylaminobenzaldehyde 1,77 9 were added as a catalyst. 1 drop of 1 ft of 1N salt was added, stirred in 5 cc of ethanol at room temperature for about 1 hour, filtered and washed with ethanol, and after drying, 2.2 g of crystals were obtained. Yield: 76%.

Example 7 Diphenylhydrazine 2.13 (j and p-diphenylaminobenzaldehyde 2.80 9, 1 as a catalyst
One drop of N-hydrochloric acid was added, and the mixture was stirred in 5 cc of ethanol at room temperature for about 1 hour, filtered, washed with ethanol, and dried to obtain 1.9 g of crystals.

Yield 53%.

Example 8 {Illustrated Compound No. 2 (See Table-1}〉N, N
16.4 Ij of -diethylamino-toluidine and 4.89 Ij of benzaldehyde are heated and stirred at an internal temperature of 80 DEG C., and as soon as a homogeneous solution is obtained, 10.0'J of concentrated hydrochloric acid is added dropwise.

Afterwards, the internal temperature was raised to 120°C, and the mixture was heated and stirred at the same temperature for about 10 hours. The reaction solution was cooled to room temperature, then 10
% aqueous sodium bicarbonate solution until neutral. Furthermore, the target product was extracted with 150 cc of ethyl acetate. After dehydration with sodium sulfate, ethyl acetate is distilled off using an evaporator. The residual candy-like substance was recrystallized from ethanol ioo cc to obtain 9.2 g of white powder. The melting point of this substance is 1
The temperature was 10.0 to 111.5°C.

Synthesis Example 9 (Exemplary Compound No. 10) N,N-diethylamino-Yamaichi Toluidine 16.4 9
and 4-dimethylamine-2-methylbenzaldehyde 6
．． 4g was reacted in the same manner as in Example 8, and the melting point was 124-12.
9.2 g of white powder at 7°C was obtained.

Synthesis Example 10 (Exemplary Compound No. 20> N,N-dimethylamino-toluidine 10.39 and p-methylbenzaldehyde 4,8T were reacted in the same manner as in Synthesis Example 8, and the melting point was 130-140'C. white powder of 7.7
I got a 9.

EXAMPLE 1 100 parts of the titanyl cyanine obtained in Example 1 and 10 parts of the derivative shown in Table 2 obtained in Synthesis Example 4-a were mixed with ice-cooled 98% Dissolve in sulfuric acid, precipitate in water, filter, wash with water,
By drying, a uniform composition of both is obtained. 10 parts of this composition was stirred in tetrahydrofuran (THE>200 parts) for about 5 hours, filtered and washed, and after drying,
9.5 parts of titanyl phthalocyanine complex was obtained.

The infrared absorption spectrum of the composition thus obtained is the first
It was new as shown in the figure. Also, the X-ray diffraction diagram is the 4th one.
It looked like the picture.

The titanyl phthalocyanine complex thus obtained was 0.
49, polyvinyl butyral 0.39, Chome F 30
I was defeated in a ball mill with g. This separation solution was applied onto a polyester film having an aluminum vapor layer using a film applicator so that the dry film thickness was 0.2 μs, and dried at 100° C. for 1 hour to obtain a charge generation layer.

On the charge generation layer thus obtained, 70 parts of the hydrazone compound shown in Synthesis Example 6 as a charge transfer agent and 3 parts of the triphenylmethane derivative of the exemplified compound (No. 2) were added.
0 parts and polycarbonate resin (Mitsubishi Gas Chemical Z-2
00) 100 parts toluene/tetrahydrofuran (
1/1) A solution dissolved in 500 parts has a dry film thickness of 1
The charge transfer layer was formed by applying the coating to a thickness of 5 layers to obtain an electrophotographic photoreceptor having a laminated photosensitive layer.

This photoreceptor was tested using an electrostatic copying paper tester (Kawaguchi Electric Seisakusho EP).
A-8100), the photoreceptor was first exposed to light for 0.8 seconds, and then exposed to -5. The measurement was repeated 2,000 times by charging by OkV corona discharge and leaving for 0.9 seconds, then exposed to white light with an illuminance of 5 lux for 0.2 seconds, and then resting for 8 seconds. amount of change in potential (dVo>, potential holding rate for 0.9 seconds (V
o. 9/VQ) and the exposure amount E1/2 (lux-sec) required to attenuate the surface potential by half,
The results are shown in Table 4 (vo is the initial charging potential, ■0.
9 is the charged potential after 0.9 seconds.

Examples 2 to 6 Exemplary compounds No. 1 were synthesized in the same manner as in Examples 8 to 10 using the above-mentioned synthesis method of Yoshino et al. 2.4,1
Photosensitization was carried out in the same manner as in Example 1 by combining triphenylmethane of 0, 20, 30 (see Table 1) and using these compounds together with the hydrazone compound shown in Example 6 as a charge transfer agent. A body was prepared and its potential characteristics were investigated.The results are shown in Table 4.

Example 7 Combination of 1 part of titanyl phthalocyanine obtained in Example 1 and Example 2
Metal-free phthalocyanine obtained in 0. 05 parts and 9 at 5℃
It is dissolved little by little in 30 parts of 8% sulfuric acid and the mixture is stirred for about 1 hour while maintaining the temperature below 5°C. Subsequently, the sulfuric acid solution was slowly poured into 500 parts of ice water that was stirred at high speed, and the precipitated homogeneous precipitate was filtered. This is washed with distilled water until no acid remains, to obtain a wet cake. The cake (assuming the amount of phthalocyanine contained is 1 part) was stirred in 100 parts of tetrahydrofuran for about 1 hour, filtered, and washed with tetrahydrofuran, and the titanium hydroxide containing 0.95 parts of pigment was stirred in 100 parts of tetrahydrofuran. A tetrahydrofuran dispersion of cyanine composition crystals was obtained.It was partially dried and examined for its infrared absorption spectrum and X-ray diffraction image.As a result, the infrared absorption spectrum was similar to that shown in Figure 1, and the X-ray The diffraction pattern looked like the 5th one.

Next, 1.5 parts by dry weight of this composition, butyral resin (Sekisui Chemical BX-5>1 part, tetradidrofuran 80
The paint was prepared using an ultrasonic dissociator.

This separated liquid was treated with polyamide resin (Toray CM-8000).
) to 0. A charge generation layer was obtained by applying the mixture to a dry film thickness of 0.2 sM on an aluminum plate coated with 5NI.

The subsequent steps were similar to those in Example 1 to produce a photoreceptor,
Its characteristics were evaluated. The results are shown in Table 4.

Example 8 0.05 part of the metal-free naphthalocyanine obtained in Comprehensive Example 3 was used instead of the metal-free phthalocyanine in Example 7.
A sample was prepared in the same manner as in Example 7, and it was confirmed that the infrared absorption spectrum was the same as that shown in FIG. 1, and the X-ray diffraction image was as shown in FIG. It was produced in the same manner, and its characteristics were measured and evaluated. The results are shown in Table 4.

Example 9 Copper tetrapyridinoporphyrazine was synthesized by a known method.

100 parts of butanylphthalocyanine and 10 parts of the above copper tetrapyridinoporphyrazine were dissolved in concentrated sulfuric acid, poured into water, filtered, washed with water, and dried to obtain uniform, fine crystals. Furthermore, as in Example 7, the product was washed with tetrahydrofuran, and as a result, the infrared absorption spectrum was as shown in FIG. Hereinafter, a photoreceptor was prepared in the same manner as in Example 1, and its characteristics were measured and
evaluated.

The results are shown in Table 4.

Comparative Example 1 A photoreceptor was prepared in the same manner as in Example 1 except that only the hydrazone compound shown in Comparative Example 6 was used as a charge transfer agent, and its potential characteristics were measured and evaluated. The results are shown in Table 4.

Comparative Example 2 A photoreceptor was prepared in the same manner as in Example 1 except that only the hydrazone compound shown in Comparative Example 7 was used as a charge transfer agent, and its potential characteristics were measured and evaluated. The results are shown in Table 4.

(Leaving space below) Table 4 Amount of change in surface potential during the ? period from the 1st to the 2000th time V,,: Surface potential after 0.9 seconds Vg.g /V
■: (}.Dark decay rate after 9 seconds dvO E1/2: Half-decreased exposure amount ■R: Surface potential after 1.1 seconds of light irradiation [Effects of the Invention] As described above, the electrophotographic photoreceptor of the present invention has a novel By using a stable composition crystal as a charge generating agent, the composition crystal is stable against solvents, so when used as a paint, it becomes easy to select a solvent, and it has a long life with good separation. Since a coating material can be obtained, it becomes easy to form a homogeneous film, which is important in the production of photoreceptors.

In particular, an electrophotographic photoreceptor obtained by combining the compounds of the general formulas [I] and [II] as a charge transfer agent has high photosensitivity, especially in the semiconductor laser wavelength range, and has excellent charging properties. It has excellent durability because it has little optical fatigue even after repeated use, and is particularly useful as a photoreceptor for high-speed, high-quality printers.

[BRIEF DESCRIPTION OF THE DRAWINGS] FIG. 1 is an infrared absorption spectrum diagram of a titanium fluoride cyanine composite used in an embodiment of the present invention, and FIGS. Infrared absorption spectrum diagram of Yuguchi cyanine, Figures 4 to 6 are X-ray diffraction diagrams of titanyl phthalocyanine composition used in one embodiment of the present invention, and Figure 7 is spectral sensitivity of one embodiment of the present invention. It is a characteristic diagram.

Claims (4)

[Claims] (1) In an electrophotographic photoreceptor containing a charge generating agent and a charge transfer agent, (a) the charge generating agent is a metal-free phthalocyanine nitrogen isoconstruct, a metal phthalocyanine nitrogen isoassembly, a metal-free phthalocyanine, a metal phthalocyanine, a metal-free naphthalocyanine; or metal naphthalocyanine (however, metal-free phthalocyanine nitrogen isoform, metal phthalocyanine nitrogen isoform, metal-free phthalocyanine and metal phthalocyanine may have a substituent on the benzene nucleus, and metal-free naphthalocyanine and metal naphthalocyanine The active ingredient is a titanyl phthalocyanine composition crystal containing 100 parts by weight of titanyl phthalocyanine and a total of 50 parts by weight or less of one or more of the above (which may have a substituent on the naphthyl nucleus); In the infrared absorption spectrum of the crystal,
1490±2cm^-^1, 1415±2cm^-^1
, 1332±2cm^-^1, 1119±2cm^-^
1, 1072±2cm^-^1, 1060±2cm^-
^1, 961±2cm^-^1, 893±2cm^-^
1,780±2cm^-^1,751±2cm^-^1
In the X-ray diffraction spectrum with characteristic strong absorption at 730±2cm^-^1 and CuK@α@ as the radiation source, the Bragg angle (2θ±0.2 degrees) is 27.3 degrees. The Bragg angle (2θ±
0.2 degrees) shows the maximum diffraction peak at 27.3 degrees, and 7
．． 4 degrees, 22.3 degrees, 24.1 degrees, 25.3 degrees, 28.
(b) The charge transfer agent has a general formula [I]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R^1 is a hydrogen atom, a substituted or Unsubstituted alkyl group, substituted or unsubstituted alkoxyl group, halogen, substituted or unsubstituted amino group, morphono group,
A carbazono group may be formed together with a piperidino group or a phenyl group, R^2 represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R^3 and R^4 represent a hydrogen atom or a substituted or unsubstituted alkyl group. , a substituted or unsubstituted aryl group, or a ring such as a pyridyl group, pyrrolodino group, carbazono group, etc.) and a hydrazone compound represented by the general formula [II]; Yes▼...[II] (In the formula, A is an electron donating group, R^5 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, R^6 and R^7 are the same or An electrophotographic photoreceptor characterized by containing as an active ingredient a compound represented by the following formulas, each representing a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. . (2) As a charge transfer agent, a hydrazone compound of the formula [III
] The electrophotographic photoreceptor according to claim (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[III] (3) As a charge transfer agent, R^6 in general formula [II]
The electrophotographic photoreceptor according to claim 1 or 2, further comprising a compound in which R^7 is a substituted or unsubstituted aryl group. (4) As a charge transfer agent, R^5 in general formula [II]
The electrophotographic photoreceptor according to claim 1, containing a compound in which A is a methyl group and A is a dialkylamino group.