JPH03180851A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity, mobility, and printing resistance by incorporating specified titanyl phthalocyanine (composition) crystals and a specified polystyrene derivative. CONSTITUTION:This photosensitive body contains by titanyl phthalocyanine (composition) crystals comprising of 0 - 50pts.wt. of at least one of metal- or metal-free phthalocyanine and aza-porphyrin and metal- or metal-free naphthalocyanine, and 100pts.wt. of the titanyl phthalocyanine, and these crystals have intense absorption at each of (1490, 1415, 1332, 1119, 1072, 1060, 961, 893, 780, 751, and 730) + or - 2cm<-1> in an infrared spectra. As an electric charge transfer material, the polystyrene derivative composed of the structural units of formula I having a molecular weight of 1,000 - 50,000 is used and in formula I, R is H, 1 - 4C alkyl, or the like, and each of (m) and (n) is a positive integer.

Description

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

[Prior Art and its Problems] In recent years, with the development of non-impact printing technology, development of electrophotographic printers using laser light sources has been actively conducted. These devices are being made smaller in size and faster in speed, and photosensitive materials are also desired to have higher sensitivity and higher mobility.

In response to these needs, titanyl phthalocyanine crystals, which have high sensitivity particularly near the oscillation wavelength of semiconductor lasers, have been developed as charge generating agents.

However, as a charge transfer agent combined with this,
The previously known ones do not have sufficient mobility, so
Although this titanyl phthalocyanine crystal has high sensitivity, it was not possible to increase the speed very much.

It is known that the mobility of a charge transfer agent increases as the concentration of the transfer agent in the charge transfer layer increases.

However, as the concentration of the transfer agent in the charge transfer layer increases, the mechanical strength of the transfer layer as a film decreases, so it has been difficult to add the transfer agent into the charge transfer layer at a high tA degree. As a solution to this problem, a homopolymer of a styrene compound with a charge transfer agent in the side chain was developed, but it is still difficult to achieve both high-dimensional mobility of the charge transfer layer and mechanical strength of the membrane using this homopolymer. It wasn't.

An object of the present invention is to enable high-speed electrophotographic printers to be supported by combining a highly sensitive titanyl phthalocyanine crystal or its composition crystal with a charge transfer agent having high mobility and excellent mechanical strength. The object of the present invention is to provide an electrophotographic photoreceptor having high printing durability.

[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 penpin nucleus, and , metal-free naphthalocyanine and metal naphthalocyanine may have a substituent on the naphdyl nucleus) in a total amount of 0 to 50 parts by weight, and ditanyl phthalocyanine in TOOf
The active ingredient is a titanyl phthalocyanine crystal or a composition crystal thereof containing the fii part, and the crystal or composition crystal is
In the infrared absorption spectrum, 1490±2cm-fn
-1,1415±2cm-1.1332±2cm-m-
'1119±2cm-1ft", 1072±2cm-m
-1, 1060±2cm-IIt-'961±2cm
” 893±2 cm-' 780±2 cm-
m-'751 ± 2 cm-1 and 730 ± 2 cm-m-
1, and (b) the charge transfer agent has the general formula [I]; where m and n are each positive integers and m/n is 100 or less.〉 Consisting of the structural unit represented by, the molecular weight is 1000 to 50
This electrophotographic photoreceptor is characterized in that it contains a polystyrene compound having a hydrazone side chain of 0.000 as an active ingredient.

According to the present invention, by combining a ditanyl phthalocyanine crystal or a composition crystal thereof with a polymer consisting of a structural unit represented by the above general formula You can get a body.

The present invention will be explained in detail below.

The phthalocyanine compounds and naphthalocyanine compounds used in the present invention are described in "1 Phthalocyanine Compounds" by Moser and Thomas (Reinhold, 1963).
, “Phthalocyanine J (CRC Publishing, 19B3>
and other suitable methods.

For example, ditanyl phthalocyanine can be easily synthesized from 1,2-dicyanobenzine (0-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 synthesized according to the reaction formula shown in (2).

Pc+=0 (However, Pc indicates a phthalocyanine residue) Examples of organic solvents include nitrobenzene, quinoline, α-chloronaphthalene, β-chloro[1-naphthalene, α-methylnaphthalene, methoxynaphthalene, diphenyl ether, diphenylmethane, diphenylethane. , ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, and the like are preferred, and the reaction temperature is usually 150 to 300°C, particularly preferably 200 to 250'C.

In the present invention, the thus obtained crude titanyl phthalocyanine compound is amorphized and then treated with tetrahydrofuran. At that time, the organic solvent used in the condensation reaction is removed in advance using an appropriate organic solvent, such as alcohols such as methanol, ethanol, and isopropyl alcohol, and ethers such as tetrahydrofuran and 1,4-dioxane. Preferably, it is treated. In particular, it is preferable to wash until the number of 0 ports of the washing liquid after hot water treatment becomes about 5 to 7.

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

Next, as phthalocyanine nitrogen isoconstructs, there are various porphines, such as Te1-lapyridinoborphyrazine, in which one or more of the penbin 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 amine groups, nitro groups, alkyl groups, alkoxy groups, cyano groups, and mercaptohalogen atoms, as well as sulfonic acid groups, carboxylic acid groups, or metal salts thereof. , aluminum salts, amine salts, etc. can be exemplified as relatively simple examples. Furthermore, various substituents can be introduced into the benzene nucleus via an alkylene group, a sulfonyl group, a carbonyl group, an imino group, etc., and these have been known as anti-agglomeration agents or crystal conversion inhibitors in the technical field of phthalocyanine pigments. % [ ] (e.g. U.S. Pat. No. 39
No. 73981 and No. 4088507). Kimiyaguchi's method for introducing each substituent is omitted. Also,
Items that are not publicly known will be described as examples of synthetic leather in the Examples.

In the present invention, ditanyl phthalocyanine and metal-free and metal phthalocyanine nitrogen isoconstructs which may have a substituent on the penbin nucleus, metal-free and metal phthalocyanines, or metal-free and metal phthalocyanine which may have a substituent on the nanodel nucleus. The composition ratio with phthalocyanine may be at least 100/150 (weight ratio), but is preferably 100/20 to 100/20.
<RAM ratio>.

That is, it includes titanyl phthalocyanine crystals alone and composition crystals of titanyl phthalocyanine and other phthalocyanines (hereinafter, these individual crystals and composition crystals are referred to as titanyl phthalocyanine compositions).

The titanyl phthalocyanine composition is prepared by mixing titanyl phthalocyanine with other phthalocyanines as necessary, and diluting the amorphous composition of the mixture with tetrahydrofuran for 90 minutes.
8. It can be produced by crystallization.

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 pasting method or an acid slurry method, and then grinding using a mechanical processing method. Equipment used during grinding includes a kneader, Banbury Mixer Attritor, Edge Runner Mill,
roll mill.

Examples include, but are not limited to, a ball mill, a sand mill, a 5PEX mill, a homomixer, a disperser, an agitator, a show crusher, a stamp mill, a cutter mill, and a micronizer. In addition, the acid pasting method, which is well known as a chemical treatment method,
This method involves dissolving the pigment in 95% or more sulfuric acid or making it into a sulfate salt, and then pouring it into water or ice water to re-precipitate it.
By keeping sulfuric acid and water desirably at 5° C. or lower and slowly injecting sulfuric acid into water that is stirred at high speed, amorphous particles can be obtained under fairly 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 1 q of new stable crystals. As a method for treating tetrahydrofuran, 5 to 300 parts by weight of tetrahydrofuran is placed in various stirring tanks per 1 part by weight of the amorphous titanyl phthalocyanine composition, and stirring is performed. Both heating and cooling are possible, but if the temperature is low, crystal growth will be faster, and if the temperature is low, it will be slower. As a stirring tank, in addition to a normal stirrer, an ultrasonic ball mill used for dispersion,
Mixers such as a Nando mill, a homomixer, a disper 1a, an agitator, a micronizer, and a concal blender type mixer can be used as appropriate, but are not limited to these.

These accompanying steps are typically followed by filtration, washing, and drying to obtain stabilized crystals of the titanyl phthalocyanine composition. At this time, it is also possible to add a resin or the like to the dispersion liquid as necessary without performing filtration or drying to form a coating. When used as a coating film for electrophotographic photoreceptors, etc., it is extremely effective as it saves a number of steps.

The infrared absorption spectrum of the titanyl phthalocyanine composition of the present invention thus obtained is shown in FIG. This titanyl phthalocyanine composition has an absorption wave number (cm", including an error of ±2) of 1490.1415.
．． 1332.1119.1072.1060.961,
893.780. It shows a characteristic strong peak at the point 751.730.

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

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

Moreover, X-ray diffraction patterns using CuKδ rays are shown in FIGS. 4 to 7. In the X-ray diffraction diagram, this titanyl phthalocyanine composition exhibits a maximum diffraction peak at a Bragg angle of 20 (including an error range of ±0.2 degrees) of 27.3 degrees, 9.7 degrees, 24. Those that show a strong peak at one time,
The maximum peak was at 27.3 degrees, 7.4 degrees, and 22.3 degrees.
Some exhibit strong peaks at 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.

Even when the titanyl phthalocyanine composition of the present invention is further heated in tetrahydrofuran to promote crystal growth, it shows no major change in the infrared absorption spectrum from 1 to A3, and is an extremely stable and good crystal. .

The polystyrene compound used as the charge transfer agent of the present invention is represented by the general formula [E], and concrete examples thereof include those shown in Table 1. but are not limited to these.

These styrene compounds have the general formula [■1; (wherein, R
is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms,
A styrene compound containing an alkoxyl group or a dialkylamino group as shown in Table 1゜) and a hydrazone group-containing styrene compound of the formula [■
]; It can be produced by copolymerizing with the sudrene monomer shown in the following in an appropriate ratio.

As a more specific production method, first, a Grignard reagent of 4-chlorostyrene is produced, and then 7JD of dimethylformamide (DMF) is added to produce 4-formylstyrene (J, W, Date, L.

5 tarr and C, W, 5 trobel
, J, Org, Chem, , 26゜1
965, 2225>. Then, 7Jn of the desired 1,1-diarylhydrazine compound was added to 4-formylstyrene.
After the condensation process in the presence of an acidic catalyst, the compound of the general formula [Il
A hydrazone group-containing styrene compound represented by l is produced. The polystyrene compound used in the present invention can be obtained by mixing this monomer and the styrene monomer represented by the general formula [111] in an appropriate ratio and copolymerizing the mixture using a polymerization initiator if necessary. It will be done.

The polymer of the present invention is easily soluble in solvents such as benzene, chloroform, and methylene chloride, and is insoluble in methanol and ethanol. In addition, a hard film can be produced by cheresting a solution dissolved in methylene chloride, and no cracks are observed, making it extremely useful as a charge transfer agent for electrophotographic photoreceptors. It is.

The electrophotographic photoreceptor of the present invention preferably has a conductivity of t on a single plate, and an undercoat layer, a charge mediating layer, and a charge transfer diagram, which are laminated in this order. It may be one in which a charge generation layer is laminated in this order, or one in which a charge generation agent and a charge transfer agent are dispersed and coated with a suitable resin on an undercoat layer.

Furthermore, these undercoat layers can be omitted if necessary.

By coating the titanyl phthalocyanine composition according to the present invention as a charge generating agent on a substrate together with a suitable binder, 1q of charge generating layers with extremely good dispersibility and extremely high photoelectric conversion efficiency can be obtained.

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 at 40 to 200°C with 13-bit heat drying. , for a period of 10 minutes to 6 hours, under static or ventilated conditions. Film thickness after drying is 0.01 to 5 feet,
It is preferably applied so that the ratio is between 0.1 and 1.

The binder that can be used in forming the charge generating layer by coating can be selected from a wide variety of insulating resins and organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthrasenya polyvinylpyrene, and the like. Preferably, polyvinyl butyral, polyarylate (condensation polymer of bisphenol octane and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, polyacid-resistant vinyl, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, hirulose resin, urethane resin , Epo V resin, silicone resin,
Examples include vA edge chronic resins such as polystyrene, polyketone, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, polyacrylonitrile, phenolic resin, melamine resin, kaviin, polyvinyl alcohol, and polyvinylpyrrolidone. 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, and cyclohexanone, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl acetate and methyl cellosolve, carbon tetrachloride, and chloroborm.

Aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane and trichlorethylene, ethers such as tetrahydrofuran, dioxane and ethylene glycol monomethyl ether, N,N-dimethylformamide, N
, amides such as N-dimethylacetamide, and sulfoxides such as dimethylsulfoxide.

The charge transfer layer in the electrophotographic photoreceptor of the present invention is prepared by dissolving a polystyrene compound composed of IrPi structural units represented by the above film type [I] in an appropriate organic solvent, coating the solution, and drying it. used.

At this time, any solvent can be used as long as it dissolves polystyrene, but it is preferable to select a solvent that does not affect the electrodynamic diagram or the undercoat layer, which will be described later, during coating. Specifically, benzene and xylene.

Aromatic hydrocarbons such as monochlorobenzene, acetone,
Ketones such as methyl ethyl ketone, esters such as ethyl acetate, fats such as chloroform and dichloromethane
Used are lj group halogenated hydrocarbons, ethers such as tetrahydrofuran and dioxane, amides such as N,N-dimethylformamide, and sulfoxides such as dimethyl sulfoxide.

Furthermore, it is effective to appropriately add various additives commonly used for resins, such as ultraviolet absorbers and antioxidants, to the crotch meat in order to prevent deterioration.

The coating method is performed using equipment such as a spin coater, applicator spray coater, bar coater, dip coater, doctor blade, roller coater, curtain coater, bead coater, etc., and the film thickness after drying is 5 to 50 mm, preferably 10 mm. It is best to apply the coating to a length of ~20m.

In addition to these layers, an undercoat layer can be provided on the conductive veneer for the purpose of preventing a decrease in chargeability and improving adhesion. As the undercoat layer, nylon 6, nylon 66, nylon 11, nylon 610. Alcohol-soluble polyamides such as copolymerized nylon and alkoxymethylnylon, cavin, polyvinyl alcohol, cellulose 21-0, ethylene-acrylic acid copolymer, gelatin, polyurethane, polyvinyl butyral, and metal oxides such as aluminum oxide are used.

It is also effective to incorporate conductive particles such as metal oxides and carbon black into the resin.

[Examples] Examples of the present invention will be described below. In addition, in the example,
Parts refer to parts by weight.

Synthesis of charge generating agent Synthesis example 1 20.4 parts of O-phthalodinitrile, 7.6 parts of titanium tetrachloride
After heat reaction in 50 parts of quinoline at 200'C for 2 hours, the solvent was removed by steam distillation, the solution was purified with a 2% aqueous hydrochloric acid solution, followed by a 2% aqueous solution of sodium hydroxide, methanol, N , washed with N-dimethylformamide, dried, and added 21.3 parts of titanyl phthalocyanine (Ti0Pc) to 2+
It was 9.

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

Synthesis Example 3 1 to 20 parts of 0-naphthalodiny to 50 st of quinoline
After a heating reaction at 200'C for 4 hours, the reaction 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.

Synthesis 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 heated at 60-180'C for 8
The mixture was stirred for a period of time, then poured into water, and the solid content was filtered, washed with water, and dried to obtain a compound represented by the following formula.

MPc (COC (2cm-1l) 1.
3 (in the formula, M represents 2, Cu, Ti0.Zn, etc., MPc
indicates a phthalocyanine residue, and the number outside parentheses indicates the average number of substitutions determined by analysis (2 or less). Various phthalocyanine derivatives were obtained by reacting this with amines by a known method.

By reducing these various phthalocyanine derivatives by a known method, -film form; ) to obtain a phthalocyanine derivative represented by

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
1 part 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.

(See blank below) Table 2 Synthesis of charge transfer agent Synthesis example 5 Into a 1 fl flask, 14.79 ml of magnesium metal, 20 mI of ethyl ether, and a small amount of ethyl bromide were added, and the magnesium was activated by heating. , 4
-chlorostyrene81. E I was bored. During the reaction, heat was generated and the temperature reached a high temperature, so the reaction solution was cooled in a water bath to maintain the temperature below 50'C.

After the dropwise addition was completed, the reaction was continued for another 2 hours at room temperature.

Dimethylformamide (DMF) 43.89 was added dropwise over a period of 2 hours, and the mixture was allowed to stand overnight at room temperature.

500 d of ethyl ether was added, and the reaction solution was added to a dilute aqueous hydrochloric acid solution. Extraction was performed, and the ether layer was washed with pure water and dried over magnesium WL acid. After distilling off the ether, it was distilled to produce 4-formylstyrene.

Next, this 4-formylstyrene 66 cJ, 1.1
-Diphenylhydrazine 92,5 9, Benpine 300
+1.

Then, a small amount of para-toluenesulfonic acid was placed in a 500-flask equipped with a Dean-Starck receiver and heated.
Time passed quickly. After the reaction was completed, benzene was distilled off and recrystallized with methanol to produce 4-(N,N-diphenylhydrazotumethyl)styrene.

Next, 11.5 g of the above compound, 49 styrene monomers, and 15 benzene were charged into a 50 d flask, and further 0.5 g of azobisisobutyronitrile (AIBN) was charged.
added. After polymerization was carried out at 60''C for 24 hours, the polymerization solution was poured into a large amount of methanol.The obtained solid was dried at 50°C under reduced pressure.

Yield 112g, Mw=40000, m/n=1 (where m/n is the abundance ratio of styrene structural units and styrene Ir14kA units containing styrene structural units and dracine groups) of 4-(N,N-diphenylhydrazo 1 q of styrene (dimethyl)styrene-styrene copolymer.

Synthesis Example 6 A copolymer was obtained by performing synthesis in the same manner as in Synthesis Example 5 except that m/n=1 in Synthesis Example 5 was changed to m/rl=3.

Synthesis Example 7 A copolymer was obtained by performing synthesis in the same manner as in Synthesis Example 5 except that m/n=1 in Synthesis Example 5 was changed to m/n=5.

Packaging Example 1 of Electrophotographic Photoreceptor 100 parts of titanyl phthalocyanine obtained in Synthesis Example 1 and each derivative (4-a to 4-e) shown in Table 2 obtained in Synthesis Example 4
> 10 parts of each were dissolved in ice-cooled 98% sulfuric acid, precipitated in water, filtered, washed with water, and dried to obtain 1 q of a homogeneous composition of both. 10 parts of this composition was entrained in 200 parts of tetrahydrofuran (THE>200 parts) for about 5 hours, filtered and washed, and after drying, 9.5 parts of a titanyl phthalocyanine composition 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.

In this way, 1q titanyl phthalocyanine composition 0
．． 49, polyvinyl butyral 0.33, Tl-IF
It was dispersed together with 509 in a ball mill. This dispersion was applied onto a polyester film having an aluminum vapor-deposited layer using a film applicator so as to have a dry film thickness of 0.2js, and dried at 100° C. for 1 hour to obtain a charge generation layer.

On the charge generation layer thus obtained, 10 parts of the 4-(N,N-diphenylhydrazotumethyl>styrene-styrene copolymer obtained in Synthesis Example 5) was added as a charge transfer agent in 50 parts of methylene chloride. A charge transfer material was formed by applying a solution dissolved in the above to a dry film thickness of 15 mm.

In this way, electrophotographic photoreceptors (1-a to 1-e) having laminated photosensitive layers were obtained. The half-decreased exposure ff1 (E1/2) of this photoreceptor was measured using an electrostatic copying paper tester (107δI).
Measured by JjW Seisakusho E, P/l-8100>.

That is, it is charged by -5.5 kV corona discharge in a dark place, then exposed to white light with an illuminance of 5 lux, and the exposure amount E (ILJX・1/
2 sec> was calculated.

Example 2 A sample was prepared in the same manner as in Example 1 except that ditanyl phthalocyanine was used alone in Example 1, and the infrared absorption spectrum was the same as that in Figure 1, and the X-ray diffraction image was as in Figure 5. After confirming that this was the case, a photoreceptor was manufactured and its electrophotographic characteristics were measured and evaluated.

Example 3 1 part of titanyl phthalocyanine obtained in Synthesis Example 1 and Synthesis Example 2
0.05 part of the metal-free phthalocyanine obtained in
Dissolve in portions in 30 parts of 8% hydrochloric acid and entrain the mixture for about 1 hour while maintaining the temperature below 5°C. Subsequently, the mixture was slowly poured into 500 parts of ice water containing a sulfuric acid solution at high speed, and the precipitated homogeneous composition was filtered. This is washed with distilled water until no acid remains, to obtain a wet cake.

The cake (containing 1 part of phthalocyanine) was stirred in 100 parts of tetrahydrofuran for about 1 hour,
Filtration and washing with tetrahydrofuran were performed to obtain a tetrahydrofuran dispersion of titanyl phthalocyanine composition crystals containing 0.95 parts of pigment. Let it dry partially,
Infrared absorption spectra and X-ray diffraction images were examined. the result,
The infrared absorption spectrum was similar to that in FIG. 1, and the X-ray diffraction pattern was similar to that in FIG. 6.

Next, 1.5 parts by dry weight of the water composition and butyral resin (
The paint was adjusted using an ultrasonic dispersion machine so that it contained 1 part of Katsuzu Kagaku MBX-5) and 80 parts of tetrahydrofuran. This dispersion was applied onto an aluminum plate coated with 0.5 ml of polyamide resin (CH-8000 manufactured by Toshi Co., Ltd.) so that the film thickness after drying at 92° C. was 0.2 μs, and the charge generation layer was removed.

On top of that, 4-(N,N
-Diphenyldirazonomedyl> An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that 10 parts of the styrene-styrene copolymer was used, and its electrophotographic properties were measured and evaluated.

Example 4 4-(N
, N-diphenylhydrazotumethyl)styrene styrene copolymer was used, a photoreceptor was prepared in the same manner as in Example 3, and its electrophotographic properties were measured and evaluated.

Example 5 Synthesis Example 3 was used instead of the phthalocyanine derivative of Example 1.
A sample was prepared in the same manner as in Example 1 except that 0.05 part of the metal-free naphthalocyanine obtained in Example 1 was used, and the infrared absorption spectrum was the same as that in Figure 1, and the X-ray diffraction image was as in Figure 7 After confirming that it was the same, the electrophotographic properties of the photoreceptor were measured and evaluated.

Example 6 1 part of titanyl phtha[l cyanine i11 obtained in Example 5 and 10 parts of 4-(N,N-diphenylhydrazotumethyl)styrene styrene copolymer obtained in Synthesis Example 5 were mixed with ~Rahydrofuran/1~Luene (1/1) mixture 4
0 parts and J: After dispersing with paint conditioner in a glass container with σ glass beads, the dry film thickness is 121J.
! A single-layer electrophotographic photoreceptor was prepared by coating an aluminum plate in such a manner as to give n. The characteristics were evaluated in the same manner as in Example 1 except that the charging applied voltage was +5.5 kV.

Comparative Example 1.2 The titanyl phthalocyanine obtained in Synthesis Example 1 before the sulfuric acid treatment was washed with N-methylpyrrolidone to obtain the crystals shown in Figure 2 in the infrared absorption spectrum (Comparative Example 1).
〉.

Further, the infrared absorption spectrum of the amorphous phthalocyanine obtained immediately after the sulfuric acid treatment was as shown in FIG. 3 (Comparative Example 2).

Using these, photoreceptors were prepared in the same manner as in Example 1 except that the fractional solvent was changed to a dichloromethane/trichloroethane mixture (1/1), and the characteristics thereof were evaluated.

Table 3 summarizes the initial surface potential, dark decay rate after 2 seconds, half-reduced exposure amount, and surface potential after 5 seconds of light irradiation for Examples 1 to 6 and Comparative Examples 1 and 2 shown above.

(Left below) Table vo: V2: V2 /Vo: El/2' VR: Initial surface potential Surface potential after 2° seconds Charge retention rate halved after 2 seconds Exposure amount Surface potential after 5 seconds of light irradiation [Effects of the invention] Above As explained above, according to the present invention, titanyl phthalocyanine, which is a charge generating agent with high sensitivity, is combined with a polystyrene compound, which is a charge transfer agent with high mobility and excellent mechanical strength of the coating film. As a result, 1q of electrophotographic photoreceptors with high sensitivity and high printing durability can be used in high-speed printers.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the titanyl phthalocyanine composition used in one example of the present invention, and FIGS. Absorption spectrum diagram, 4th
Figures 7 to 7 are X-ray diffraction patterns of butanyl phthalocyanine compositions used in one example of the present invention.

Claims (1)

[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 crystal or a composition crystal thereof containing a total of 0 to 50 parts by weight of one or more of the following (which may have a substituent on the naphthyl nucleus) and 100 parts by weight of titanyl phthalocyanine. , the crystal or composition crystal has an infrared absorption spectrum of 1490±2 cm^-^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 and 730±2cm^-^
(b) The charge transfer agent has the general formula [I]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R is a hydrogen atom, represents a lower alkyl group, alkoxyl group, or dialkylamino group having 1 to 4 carbon atoms, m and n are each positive integers, and m/n is 100 or less, and has a molecular weight of 10
An electrophotographic photoreceptor characterized in that the active ingredient is a polystyrene compound having a hydrazone side chain of 00 to 50,000.