JPH06145550A - Phthalocyanine composition, its production, electro-photograhic photoreceptor containing same, and coating fluid containing same for change generation layer - Google Patents

Abstract

PURPOSE:To provide a phthalocyanine composition excellent in chargeability, resistance to dark decay and sensitivity, a production process therefor, and an electrophotographic photoreceptor. CONSTITUTION:A phthalocyanine mixture comprising titanyl phthalocyanine and a halogenated metallized phthalocyanine with a trivalent central metal is reprecipitated from water by the acid pasting process to obtain a precipitate having a characteristic diffraction peak at a Bragg angle (2theta+0.2 deg.) of 27.2 deg. in a CuKalpha X-ray diffraction spectrum, and this precipitate is subsequently treated with a water/organic solvent mixture to obtain a phthalocyanine composition having characteristic peaks at Bragg angles (2theta+0.2 deg.) of 7.5 deg., 24.2 deg. and 27.3 deg.. This composition is used to form an electrophotographic photoreceptor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phthalocyanine composition having high sensitivity, a method for producing the same, an electrophotographic photoreceptor using the same and a coating liquid for a charge generating layer.

[0002]

2. Description of the Related Art As a conventional electrophotographic photosensitive member, selenium (S) of about 50 μm is formed on a conductive substrate such as aluminum.
e) There is a film formed by a vacuum evaporation method. However, this Se photoconductor has a problem that it has sensitivity only up to a wavelength of about 500 nm. There is also a photoconductor in which a Se layer of about 50 μm is formed on a conductive substrate, and a selenium-tellurium (Se—Te) alloy layer of several μm is further formed on the Se layer. The higher the content of Te in the Te alloy, the longer the spectral sensitivity extends to the longer wavelength.
As the amount of e added increases, the surface charge retention property becomes poor, and there is a serious problem that it cannot be used as a photoreceptor in practice.

A chlorocyan blue or squarylium acid derivative of about 1 μm is coated on an aluminum substrate to form a charge generation layer, and a mixture of a polyvinylcarbazole or pyrazoline derivative having high insulation resistance and a polycarbonate resin is formed on the charge generation layer. There is a so-called composite two-layer type photoconductor in which a charge transport layer is formed by coating 10 to 20 μm, but in reality, this photoconductor does not have sensitivity to light of 700 nm or more.

In recent years, in this composite two-layer type photoreceptor,
The above drawbacks have been improved, that is, the semiconductor laser oscillation region 80.
Although many photoreceptors having a sensitivity of around 0 nm have been reported, most of them use a phthalocyanine pigment as a charge generating material, and use polyvinylcarbazole on a charge generating layer having a thickness of about 0.5 to 1 μm. A mixture of a pyrazoline derivative or a hydrazone derivative and a polycarbonate resin or a polyester resin having a high insulation resistance is used in an amount of 10 to 2
A 0 .mu.m coating is applied to form a charge transport layer to form a composite two-layer type photoreceptor.

Phthalocyanines differ not only in their absorption spectra and photoconductivity depending on the type of central metal, but also in their physical properties depending on the crystal type. Even with phthalocyanines of the same central metal, there are specific crystal types. Several examples have been reported that have been selected for electrophotographic photoreceptors.

For example, titanyl phthalocyanine has various crystal forms, and it has been reported that there are large differences in chargeability, dark decay, sensitivity, etc. due to the difference in the crystal forms.

Japanese Patent Application Laid-Open No. 59-49544 discloses that the crystal form of titanyl phthalocyanine is Bragg angle (2
θ ± 0.2 degrees) is 9.2 degrees, 13.1 degrees, 20.7 degrees,
Those which give a strong diffraction peak at 26.2 degrees and 27.1 degrees are described as being suitable, and an X-ray diffraction spectrum diagram is shown. The electrophotographic characteristics of the photoconductor using this crystalline form of titanyl phthalocyanine as a charge generating material are as follows: dark decay (DDR): 85%, sensitivity (E _1/2 ): 0.57lux.
・ It is sec.

Further, in JP-A-59-166959, a vapor-deposited film of titanyl phthalocyanine is allowed to stand in saturated steam of tetrahydrofuran for 1 to 24 hours to change its crystal form to form a charge generation layer. The X-ray diffraction spectrum has a small number of peaks and a wide width, and Bragg angles (2θ ± 0.2 degrees) of 7.5 degrees, 12.6 degrees, and 13.0 degrees.
It has been shown to give strong diffraction peaks at degrees, 25.4 degrees, 26.2 degrees and 28.6 degrees. The electrophotographic characteristics of the photoconductor using this crystalline form of titanyl phthalocyanine as a charge generating material are dark decay (DDR): 86% and sensitivity (E _1/2 ): 0.7 lux · sec.

In Japanese Patent Application Laid-Open No. 2-198452, the crystal form of titanyl phthalocyanine is described as Bragg angle (2
High sensitivity (1.7 mJ / cm ² ) has a major diffraction peak at θ ± 0.2 °) of 27.3 °, and the production method thereof is 60 ° C. in a mixed solution of water and ortho-dichlorobenzene.
It is disclosed to heat and stir for a period of time.

In Japanese Unexamined Patent Publication No. 2-256059, a black angle (2θ) is used as a crystal form of titanyl phthalocyanine.
High sensitivity (0.62 lux.sec.) Has a main diffraction peak at 27.3 degrees (± 0.2 degrees), and the method for producing it is to stir in 1,2-dichloroethane at room temperature. It is disclosed.

As described above, the phthalocyanines have greatly different electrophotographic characteristics depending on the crystal form, and the crystal form is an important factor affecting the performance as an electrophotographic photoreceptor.

In Japanese Patent Laid-Open No. 62-194257, 2
Examples of using a mixture of two or more phthalocyanines, for example,
The use of a mixture of titanyl phthalocyanine and metal-free phthalocyanine as a charge generating material is also disclosed.

As described above, titanyl phthalocyanine has extremely high sensitivity due to the crystal form conversion and exhibits excellent characteristics. However, in the application such as laser printer,
Higher image quality and higher definition have been advanced, and there is a demand for an electrophotographic photoreceptor having higher sensitivity.

[0014]

SUMMARY OF THE INVENTION The present invention provides a phthalocyanine composition having high sensitivity, a method for producing the same, an electrophotographic photoreceptor using the same, and a coating liquid for a charge generating layer.

[0015]

The present invention relates to CuKα X
In the line diffraction spectrum, the Bragg angle (2θ ± 0.2
Degree) of the phthalocyanine composition having major diffraction peaks at 7.5 degrees, 24.2 degrees and 27.3 degrees.

Further, according to the present invention, a phthalocyanine mixture containing a titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent is reprecipitated in water by the acid pasting method, and the Bragg angle (2θ) is measured in the X-ray diffraction spectrum of CuKα. X-ray of CuKα, characterized in that a precipitate having a characteristic diffraction peak at 27.2 degrees (± 0.2 degrees) is obtained, and the precipitate is subsequently treated with a mixed solvent of an organic solvent and water. The Bragg angle (2θ ± 0.2 degrees) in the diffraction spectrum is 7.5 degrees, 24.2 degrees and 2
The present invention relates to a method for producing a phthalocyanine composition having a main diffraction peak at 7.3 degrees.

Generally, a phthalocyanine mixture is a mere physical mixture of phthalocyanines used as raw materials,
The X-ray diffraction pattern of the phthalocyanine mixture is formed by superposing the peak patterns of the individual phthalocyanines used as raw materials. On the other hand, the phthalocyanine composition of the present invention is a mixture of phthalocyanines used as a raw material at the molecular level, and the X-ray diffraction pattern is different from the peak pattern of each phthalocyanine simple substance used as a raw material. The pattern is shown.

The present invention also provides an electrophotographic photosensitive member having a photoconductive layer containing an organic photoconductive substance on a conductive substrate, wherein the organic photoconductive substance has a Bragg angle in an X-ray diffraction spectrum of CuKα. (2θ ± 0.2 degrees) is 7.5
The present invention relates to an electrophotographic photosensitive member which is a phthalocyanine composition having major diffraction peaks at 24.2 and 27.3 degrees.

The present invention also relates to a charge generation layer containing the phthalocyanine composition obtained by the above-mentioned production method as a charge generation material, and a compound represented by the following general formula [I] (R ₁ and R ₂ are:
Each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, fluoroalkyl group or fluoroalkoxy group, two R ₃ represents a hydrogen atom or an alkyl group independently, Ar ₁ And Ar ₂ each independently represent an aryl group, and m and n each independently represent an integer of 0 to 5) and a composite having a charge transport layer containing a benzidine derivative represented by the formula: Type electrophotographic photoreceptor.

[Chemical 2]

The present invention also relates to a charge generation layer coating liquid containing the phthalocyanine composition.

The present invention will be described in detail below. The titanyl phthalocyanine used in the present invention can be produced, for example, as follows. Phthalonitrile 18.
4 g (0.144 mol) of α-chloronaphthalene 120
4 ml titanium tetrachloride under nitrogen atmosphere
(0.0364 mol) is added dropwise. After the dropping, the temperature was raised and the mixture was reacted with stirring at 200 to 220 ° C. for 3 hours, and then 10
Filter hot at 0-130 ° C. and wash with α-chloronaphthalene and then methanol. Hydrolysis (140 ° C., 1 hour) is performed with 140 ml of ion-exchanged water, and this operation is repeated until the solution becomes neutral, and the solution is washed with methanol. Next, the substrate is thoroughly washed with NMP at 100 ° C., and then with methanol. The compound thus obtained is treated at 60 ° C.
Then, it is vacuum-dried under vacuum to obtain titanyl phthalocyanine (yield 46%).

In the halogenated metal phthalocyanine compound having a trivalent central metal used in the present invention, the trivalent metal as the central metal may be In, Ga, Al or the like, and the halogen may be Cl, Br or the like. Further, the phthalocyanine ring may have a substituent such as halogen. Although the compound is a known compound, among these, for example, synthesis of monohalogenated metal phthalocyanine and monohalogenated metal halide phthalocyanine, Inorganic Chemistry [Inorganic Chemistry] 19, 3131
(1980) and JP-A-59-44054. Monohalogen metal phthalocyanine is, for example,
It can be manufactured as follows.

78.2 mmol of phthalonitrile and 15.8 mmol of metal trihalide were placed in 100 ml of quinoline which had been twice distilled and deoxygenated, and the mixture was heated under reflux for 0.5 to 3 hours, then gradually cooled, and then cooled to 0 ° C. After cooling and filtering, the crystals were washed with methanol, toluene, and then with acetone, and then
Dry at 0 ° C.

The monohalogen metal halogenphthaloanine can be produced as follows. 156 mmol of phthalonitrile and metal trihalide 37.
Mix 5 millimoles and melt at 300 ° C, then 0.5
Heat for ~ 3 hours to obtain a crude monohalogen metal halogen phthalocyanine, which is washed with α-chloronaphthalene using a Soxhlet extractor.

In the present invention, the composition ratio of the phthalocyanine mixture containing a titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent is such that the content of the titanyl phthalocyanine is from the viewpoint of electrophotographic characteristics such as charging property, dark decay and sensitivity. It is preferably in the range of 20 to 95% by weight, more preferably in the range of 50 to 90% by weight, particularly preferably in the range of 65 to 90% by weight, 7
Most preferably, it is in the range of 5 to 90% by weight.

The phthalocyanine mixture is reprecipitated in water by the acid pasting method to be made amorphous.
For example, 1 g of the phthalocyanine mixture is dissolved in 50 ml of concentrated sulfuric acid, stirred at room temperature, and then added to 1 liter of ion-exchanged water cooled with ice water for about 1 hour, preferably 40 minutes to 50 minutes.
Drop by minute and reprecipitate. After standing overnight, the supernatant is removed by decantation, and the precipitate is collected by centrifugation. Thereafter, the precipitate is repeatedly washed with ion-exchanged water as washing water until the pH after washing the washing water is 2 to 5, preferably around pH 3 and the conductivity is 5 to 500 μS / cm. Then, after thoroughly washing with methanol, vacuum heating and drying at 60 ° C. give a powder. The precipitate composed of the titanyl phthalocyanine thus produced and the halogenated metal phthalocyanine having a central metal of trivalent is the X of CuKα.
In the line diffraction spectrum, the black angle (2θ ± 0.2
Except that the analysis peak shows a clear analysis peak at 27.2 degrees, the peak is broad and its value cannot be clearly regulated.
When the pH exceeds 5, the characteristic peak intensity with a black angle (2θ ± 0.2 degrees) of 27.2 degrees in the X-ray diffraction spectrum of CuKα decreases, and the peak intensity newly increases to 6.8 degrees at 27. A peak stronger than the peak intensity of 2 degrees is generated, and the black angle (2θ ± 0.2 degrees) of the present invention is 7.5 degrees even if the powder is crystallized using a mixed solvent of organic solvent and water. It is not possible to obtain a composition having characteristic peaks at 24.2 and 27.3 degrees. PH after washing water is less than 2 or 5
If it exceeds, the chargeability, dark decay, sensitivity, etc. tend to be poor. If the conductivity is less than 5 μS / cm or exceeds 500 μS / cm, the charging property, dark decay, sensitivity, etc. tend to be poor.

The precipitate thus obtained is crystallized by treating with a mixed solvent of an organic solvent and water to obtain the phthalocyanine composition of the present invention. As for the use ratio of the organic solvent and water, the organic solvent / water (weight ratio) is preferably 3/97 to 97/3. This treatment can be carried out by contacting the precipitate with a mixed solvent of an organic solvent and water at 20 ° C to 100 ° C for 1 minute to 12 hours. Examples of the organic solvent used in this treatment include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, alicyclic hydrocarbons such as n-hexane, octane and cyclohexane, benzene,
Toluene, aromatic hydrocarbons such as xylene, tetrahydrofuran, dioxane, diethyl ether, ethylene glycol dimethyl ether, ethers such as ethylene glycol diethyl ether, acetate cellosolve, acetone, methyl ethyl ketone, cyclohexanone, ketones such as isophorone, methyl acetate, ethyl acetate Such as esters, dimethyl sulfoxide, dimethylformamide,
Phenol, cresol, anisole, nitrobenzene, acetophenone, benzyl alcohol, pyridine,
Non-chlorine organic solvents such as N-methyl-2-pyrrolidone, quinoline and picoline, dichloromethane, dichloroethane,
Trichloroethane, tetrachloroethane, carbon tetrachloride,
Chlorine-based organic solvents such as chloroform, chloromethyloxirane, chlorobenzene and dichlorobenzene can be used. Of these, chlorine-based organic solvents are preferred.

The electrophotographic photoreceptor of the present invention comprises a photoconductive layer provided on a conductive support. In the present invention,
The photoconductive layer is a layer containing an organic photoconductive substance, such as a film of an organic photoconductive substance, a film containing an organic photoconductive substance and a binder, a composite type film consisting of a charge generation layer and a charge transport layer, and the like. is there.

As the organic photoconductive substance, the phthalocyanine composition is used as an essential component, and known substances can be used in combination. Further, as the organic photoconductive substance, it is preferable to use an organic pigment and / or a charge transporting substance which generate an electric charge in the phthalocyanine composition. The charge generating layer contains the phthalocyanine composition and / or an organic pigment that generates a charge, and the charge transporting layer contains a charge transporting substance.

The organic pigments which generate the above-mentioned charges include azoxybenzene type, disazo type, trisazo type, benzimidazole type, polycyclic quinone type, indigoid type, quinacridone type, perylene type, methine type, α type and β type. , Γ
It is possible to use pigments known to generate electric charges, such as metal-free or metal-type phthalocyanine-based pigments having various crystal structures such as γ-type, δ-type, ε-type, and χ-type. These pigments are disclosed, for example, in JP-A-47-37543, JP-A-47-37544, and JP-A-47-18543.
JP-A-47-18544, JP-A-48-
No. 43942, No. 48-70538, No. 49-1231, No. 49-105536.
JP-A-50-75214, JP-A-53-
It is disclosed in JP-A-44028, JP-A-54-17732, and the like. Further, τ, τ ′, η and η ′ type metal-free phthalocyanines disclosed in JP-A-58-182640 and European Patent Publication No. 92,255 can also be used. In addition to these substances, any organic application that generates a charge carrier upon irradiation with light can be used.

As the charge-transporting substance, polymer compounds such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylindroquinoxaline, polyvinylbenzothiophene, polyvinylanthracene, polyvinylacridine are used. , Polyvinylpyrazoline, etc., and low molecular compounds include fluorenone, fluorene, 2,7-dinitro-9-fluorenone, 4H-indeno (1,2,6)
Thiofen-4-one, 3,7-dinitro-dibenzothiophen-5-oxide, 1-bromopyrene, 2-phenylpyrene, carbazole, N-ethylcarbazole, 3-phenylcarbazole, 3- (N-methyl-N).
-Phenylhydrazone) methyl-9-ethylcarbazole, 2-phenylindole, 2-phenylnaphthalene, oxadiazole, 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 1-
Phenyl-3- (4-diethylaminostyryl) -5-
(4-Diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline, 1-phenyl-3- (p
-Diethylaminophenyl) pyrazolin, p- (dimethylamino) -stilbene, 2- (4-dipropylaminophenyl) -4- (4-dimethylaminophenyl) -5
-(2-chlorophenyl) -1,3-oxazole, 2
-(4-Dimethylaminophenyl) -4- (4-dimethylaminophenyl) -5- (2-fluorophenyl)-
1,3-oxazole, 2- (4-diethylaminophenyl) -4- (4-dimethylaminophenyl) -5-
(2-fluorophenyl) -1,3-oxazole, 2
-(4-Dipropylaminophenyl) -4- (4-dimethylaminophenyl) -5- (2-fluorophenyl)
Examples include -1,3-oxazole, imidazole, chrysene, tetraphene, aclidene, triphenylamine, benzidine, and their derivatives. As the charge-transporting substance, the benzidine derivative represented by the general formula (I) is particularly preferable. In the general formula (I), examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and a tert-butyl group. As the alkoxy group, a methoxy group, an ethoxy group,
Examples include n-propoxy group and iso-propoxy group. Examples of the aryl group include a phenyl group, a tolyl group, a biphenyl group, a terphenyl group and a naphthyl group. Examples of the fluoroalkyl group include a trifluoromethyl group, a trifluoroethyl group, a heptafluoropropyl group and the like. As the fluoroorcoxy group, a trifluoromethoxy group, a 2,3-difluoroethoxy group,
2,2,2-trifluoroethoxy group, 1H, 1H-pentafluoropropoxy group, hexafluoro-iso-propoxy group, 1H, 1H-pentafluorobutoxy group,
2,2,3,4,4,4-hexafluorobutoxy group,
Examples thereof include fluoroalkoxy groups such as 4,4,4-trifluorobutoxy group. For example, the following compounds No. 1 to No. 6 and the like can be mentioned.

[0032]

[Chemical 3]

[Chemical 4]

The above-mentioned phthalocyanine composition and an organic pigment which generates an electric charge which is optionally used (both are the former).
And a charge-transporting substance (the latter) are used as a mixture (when a single-layer photoconductive layer is formed), the latter / the former is in a weight ratio of 10/1 to 2/1. It is preferable to mix them. At this time, the binder is 0 to 500% by weight, particularly 30 to 500% by weight based on the total amount of these compounds (the former + the latter).
It is preferably used in the range of weight%. When using these binders, additives such as a plasticizer, a fluidity-imparting agent, and a pinhole suppressor can be added, if necessary.

When a composite type photoconductive layer comprising a charge generating layer and a charge transporting layer is formed, the charge generating layer contains the above-mentioned phthalocyanine composition and, if necessary, a charge generating organic pigment, The agent may be contained in an amount of 500% by weight or less based on the total amount of the phthalocyanine composition and the organic pigment, and the above-described additive is 5% by weight or less based on the total amount of the phthalocyanine composition and the organic pigment. May be added in. Further, the charge transport layer may contain the above-mentioned charge transport material, and may further contain a binder in an amount of 500% by weight or less based on the charge transport material. When the charge transporting substance is a low molecular weight compound, it is preferable that the binder is contained in an amount of 50% by weight or more based on the compound.

Binders that can be used in all of the above cases include silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyacrylic resin, polystyrene resin, styrene-butadiene copolymer. , Polymethylmethacrylate resin, polyvinyl chloride, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer,
Examples thereof include polyacrylamide resin, polyvinylcarbazole, polyvinylpyrazoline, polyvinylpyrene and the like. Further, a thermosetting resin and a photocuring resin which are crosslinked by heat and / or light can also be used. In any case, there is no particular limitation as long as it is an insulating resin capable of forming a film in a normal state and a resin that is cured by heat and / or light to form a film.

Examples of the plasticizer as the additive include halogenated paraffin, dimethylnaphthalene, dibutyl phthalate and the like, and the fluidity-imparting agent is Modaflow (manufactured by Monsanto Chemical Co.), Acronal 4F (manufactured by Basuf Co.) and the like. As the pinhole inhibitor,
Examples thereof include benzoin and dimethyl phthalate. These may be appropriately selected and used, and the amount thereof may be appropriately determined.

In the present invention, the conductive substrate is a conductive material such as paper or plastic film subjected to conductive treatment, a plastic film laminated with a metal foil such as aluminum, or a metal plate.

The electrophotographic photoreceptor of the present invention comprises a photoconductive layer formed on a conductive substrate. The thickness of the photoconductive layer is preferably 5 to 50 μm. When the composite type of the charge generation layer and the charge transport layer is used as the photoconductive layer, the charge generation layer is preferably 0.001 to 10 μm, particularly preferably 0.2 to
Make a thickness of 5 μm. If it is less than 0.001 μm, it is difficult to uniformly form the charge generation layer, and if it exceeds 10 μm, the electrophotographic properties tend to deteriorate. The thickness of the charge transport layer is preferably 5 to 50 μm, particularly preferably 8 to 2
It is 5 μm. If the thickness is less than 5 μm, the initial potential tends to be low, and if it exceeds 50 μm, the sensitivity tends to decrease.

To form a photoconductive substrate on a conductive substrate, a method of depositing an organic photoconductive substance on the conductive substrate,
Organic photoconductive materials and other components as required in aromatic solvents such as toluene and xylene, halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, alcohol solvents such as methanol, ethanol and propanol. There is a method of uniformly dissolving or dispersing, coating on a conductive substrate, and drying. As a coating method, a spin coating method, a dipping method or the like can be adopted. When the charge generation layer and the charge transport layer are formed in the same manner, either of the charge generation layer and the charge transport layer may be an upper layer, and the charge generation layer may be a two-layer charge transport layer. It may be sandwiched.

When the phthalocyanine composition of the present invention is applied by a spin coating method, the phthalocyanine composition is dissolved in a halogenated solvent such as chloroform or toluene or a non-polar solvent to obtain a coating solution at a rotation speed of 50.
Spin coating at 0 to 4000 rpm is preferable, and when applying by a dipping method, the phthalocyanine composition is treated with methanol, dimethylformamide,
It is preferable to immerse the conductive substrate in a coating liquid which is dispersed in a halogen solvent such as chloroform, methylene chloride or 1,2-dichloroethane using a ball mill, ultrasonic waves or the like.

The electrophotographic photosensitive member according to the present invention may further have a thin adhesive layer or a barrier layer directly on the conductive substrate, or may have a protective layer on the surface.

[0042]

EXAMPLES The present invention will be described in detail below with reference to production examples and examples of phthalocyanine compositions.

Production Example 1 1 g of a phthalocyanine mixture consisting of 0.75 g of titanyl phthalocyanine and 0.25 g of indium phthalocyanine chloride was dissolved in 50 ml of sulfuric acid and stirred at room temperature for 30 minutes, and this was added to 1 liter of ion-exchanged water cooled with ice water.
The solution was dropped in about 40 minutes and reprecipitated. Further, the mixture was stirred under cooling for 1 hour and then left overnight. After removing the supernatant liquid by decantation, the precipitate was separated by centrifugation to obtain 700 mg of precipitate. As the first washing, 120 ml of ion-exchanged water as washing water was added to 700 mg of the precipitate and stirred, and then the precipitate and the washing water were separated and removed by centrifugation.
The same washing operation was performed 5 times in succession. The pH and conductivity of the wash water separated and removed in the sixth operation (that is, the wash water after washing) were measured (23 ° C.). Model PH51 manufactured by Yokogawa Electric Corporation was used for the measurement of pH. Also,
The conductivity is measured by model SC-1 manufactured by Shibata Scientific Instruments Co., Ltd.
7A was used. The pH of the wash water was 3.3 and the conductivity was 65.1 μS / cm. After that, methanol 60
After being washed with ml three times, it was vacuum dried at 60 ° C. for 4 hours.
The X-ray diffraction spectrum of this vacuum dried product is shown in FIG. Next, 12.5 g of this vacuum dried product was added with 22.5 ion-exchanged water.
g and 1.5 ml of ortho-dichlorobenzene, 60
After heating and stirring at 1 ° C for 1 hour, filtration, washing with methanol, and vacuum drying at 60 ° C for 4 hours to obtain crystals of the phthalocyanine composition of the present invention. The X-ray diffraction spectrum of this crystal is shown in FIG.

Production Example 2 To 1 g of the vacuum dried product obtained in the same manner as in Production Example 1 was added 9 g of ion-exchanged water and 100 ml of 1,2-dichloroethane, and the mixture was stirred at room temperature for 2 hours to obtain the phthalocyanine composition of the present invention. Crystals were obtained. The X-ray diffraction spectrum of this crystal is shown in FIG.

Production Example 3 A phthalocyanine composition was prepared in the same manner as in Production Example 1, except that the number of washings after the treatment with sulfuric acid was changed to wash the washing water to a pH of 4.0 and a conductivity of 17.8 μS / cm. Manufactured. The X-ray diffraction spectrum of the obtained composition was the same as in FIG.

Comparative Production Example 1 Crystals of the phthalocyanine composition were prepared in the same manner as in Production Example 1, except that the washing water was washed up to pH 6.0 and conductivity 3.4 μS / cm by changing the number of washings after the sulfuric acid treatment. Manufactured. The X-ray diffraction spectrum of the vacuum dried product before treatment with the halogen solvent is shown in FIG. The X-ray diffraction spectrum of the crystal obtained after the halogen treatment is shown in FIG.

Comparative Production Example 2 A phthalocyanine composition was prepared in the same manner as in Production Example 2 except that the number of washings after the treatment with sulfuric acid was changed to wash the washing water to a pH of 6.0 and a conductivity of 3.4 μS / cm. Crystals were produced. The obtained crystal X-ray diffraction spectrum is shown in FIG.

Comparative Production Example 3 To 1 g of the vacuum dried product obtained in the same manner as in Production Example 1 was added 10 ml of isopropyl alcohol and the mixture was heated with stirring at 90 ° C. for 8 hours to obtain crystals of a phthalocyanine composition. The X-ray diffraction spectrum of this crystal is shown in FIG.

Production Examples 4 to 6 Crystals of a phthalocyanine composition were obtained according to Production Examples 1 to 3 except that indium phthalocyanine bromide was used instead of indium phthalocyanine chloride in Production Examples 1 to 3.

Comparative Production Examples 4 to 6 Crystals of a phthalocyanine composition were obtained according to Comparative Production Examples 1 to 3 except that indium phthalocyanine bromide was used instead of indium phthalocyanine chloride in Comparative Production Examples 1 to 3.

Production Examples 7 to 9 Crystals of a phthalocyanine composition were obtained according to Production Examples 1 to 3 except that gallium phthalocyanine chloride was used instead of indium phthalocyanine chloride in Production Examples 1 to 3.

Comparative Production Examples 7 to 9 Crystals of a phthalocyanine composition were obtained according to Comparative Production Examples 1 to 3 except that gallium phthalocyanine chloride was used instead of indium phthalocyanine chloride in Comparative Production Examples 1 to 3.

Production Examples 10 to 12 Crystals of a phthalocyanine composition were obtained according to Production Examples 1 to 3 except that aluminum phthalocyanine chloride was used instead of indium phthalocyanine chloride in Production Examples 1 to 3.

Comparative Production Examples 10 to 12 Crystals of phthalocyanine composition were obtained according to Comparative Production Examples 1 to 3 except that aluminum phthalocyanine chloride was used instead of indium phthalocyanine chloride in Comparative Production Examples 1 to 3.

Example 1 1.5 g of the phthalocyanine composition produced in Production Example 1, 0.9 g of polyvinyl butyral resin S-REC BL-S (manufactured by Sekisui Chemical Co., Ltd.), melamine resin ML351W (manufactured by Hitachi Chemical Co., Ltd.) 0 0.1 g, ethyl cellosolve 49 g and tetrahydrofuran 49 g were mixed and dispersed by a ball mill. The obtained dispersion is applied on an aluminum plate (conductive substrate 100 mm x 100 mm x 0.1 mm) by a dipping method,
It was dried at 140 ° C. for 1 hour to form a charge generation layer having a thickness of 0.5 μm. 1.5 g of the above No. 4 charge-transporting substance,
A coating solution obtained by mixing 1.5 g of polycarbonate resin Iupilon S-3000 (manufactured by Mitsubishi Gas Chemical Co., Inc.) and 15.5 g of methylene chloride was applied on the above substrate by a dipping method, and dried at 120 ° C. for 1 hour. To form a charge transport layer having a thickness of 20 μm. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate, photoresponsiveness) were evaluated by Cynthia 30HC (manufactured by Midoriya Electric Co., Ltd.). Corrosion charging method to -65
It was charged to 0 V and monochromatic light of 780 nm was exposed on a 50 mS photoconductor to measure various characteristics. The definition of the above characteristics is
It is as follows. Sensitivity (E ₅₀ ) is the initial charging potential -6
780 required to halve 50V after 0.2 seconds of exposure
The amount of irradiation energy of monochromatic light of nm, and the residual potential (V
r) is 50 mS exposure of monochromatic light of 20 mJ / m ² of the same wavelength,
It is the potential remaining on the surface of the photoreceptor after 0.2 seconds and 0.5 seconds of exposure. The dark decay rate (DDR) is the initial charging potential of the photoconductor of -650 V and the surface potential V after the initial charging and left for 1 second in the dark.
₁ defined (-V) with the _{(V 1/650) × 100} . Photoresponsiveness (T _1/2 ) is 20mJ / m ^{2 at} wavelength 780nm
Was defined as the time (sec) required to halve the initial charging potential of -650 V by exposing 50 mS of monochromatic light.

Examples 2 and 3 An electrophotographic photosensitive member was produced and evaluated according to Example 1 except that the titanyl phthalocyanine composition obtained in Production Examples 2 and 3 was used. The results are shown in Table 1.

Comparative Examples 1 to 3 Electrophotographic photosensitive members were produced and evaluated according to Example 1 except that the titanyl phthalocyanine composition obtained in Comparative Production Examples 1 to 3 was used. The results are shown in Table 1. Although it seems that the sensitivity is high in appearance, the dark decay rate was not a value that can be practically used.

Comparative Example 4 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the dry powder before the treatment with the ortho-dichlorobenzene solution was used in Production Example 1, but it was charged to −650V. I couldn't.

[Table 1]

Examples 4 to 6 The titanyl phthalocyanine compositions obtained in Production Examples 4 to 6 in Example 1 were used, and N was used as the charge transport material.
Example 1 except that No. 2 was used in place of the o.4 compound
The electrophotographic photosensitive member was manufactured and evaluated according to 3 to 3. The results are shown in Table 2.

Comparative Examples 5 to 7 Other than using the titanyl phthalocyanine composition obtained in Comparative Production Examples 4 to 6 in Example 1 and using No. 2 as the charge transport material instead of the No. 4 compound. Was manufactured and evaluated in accordance with Example 1. The results are shown in Table 2.

Comparative Example 8 An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 1 except that the dry powder before the treatment with the ortho-dichlorobenzene solution was used in Manufacturing Example 4, but the charging was performed up to −650V. I couldn't.

[Table 2]

Examples 7 to 9 The titanyl phthalocyanine compositions obtained in Production Examples 7 to 9 in Example 1 were used, and N was used as the charge transport material.
Example 1 except that No. 5 was used instead of the o.4 compound
The electrophotographic photosensitive member was manufactured and evaluated according to 3 to 3. The results are shown in Table 3.

Comparative Examples 9 to 11 In Example 1, except that the titanyl phthalocyanine compositions obtained in Comparative Production Examples 7 to 9 were used and No. 5 was used as the charge transport material instead of the No. 4 compound. Was manufactured and evaluated in accordance with Example 1. The results are shown in Table 3.

Comparative Example 12 An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 1 except that the dry powder before the treatment with the ortho-dichlorobenzene solution was used in Manufacturing Example 7, and was charged to −650V. I couldn't.

[Table 3]

Examples 10 to 12 Except that the titanyl phthalocyanine compositions obtained in Production Examples 10 to 12 were used in Example 1 and that No. 1 was used as the charge transport material instead of the No. 4 compound. An electrophotographic photosensitive member was manufactured and evaluated according to Examples 1 to 3. The results are shown in Table 4.

Comparative Examples 13 to 15 Other than using the titanyl phthalocyanine compositions obtained in Comparative Production Examples 10 to 12 in Example 1 and using No. 1 as the charge transport material instead of the No. 4 compound. Is
An electrophotographic photosensitive member was produced and evaluated according to Example 1. The results are shown in Table 4.

Comparative Example 16 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the dry powder before the treatment with the ortho-dichlorobenzene solution was used in Production Example 10, but it was charged up to −650V. I couldn't.

[Table 4]

[0068]

The electrophotographic photosensitive member using the phthalocyanine composition according to the present invention has excellent electrophotographic characteristics such as chargeability, dark decay and sensitivity, and is required to have higher density and higher image quality than ever before. It can be suitably applied to the electrophotographic process. In particular, when it is applied to a laser beam printer, the life of the semiconductor laser can be greatly extended due to its excellent sensitivity. In full-color copying, the halftone gradation tolerance corresponding to the sensitivity can be increased, which is extremely advantageous.

[0069]

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum of a vacuum dried product obtained in Production Example 1.

2 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Production Example 1. FIG.

FIG. 3 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Production Example 2.

FIG. 4 X of the vacuum dried product obtained in Comparative Production Example 1
Line diffraction spectrum.

5 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Comparative Production Example 1. FIG.

6 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Comparative Production Example 2. FIG.

7 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Comparative Production Example 3. FIG.

Front Page Continuation (72) Inventor Mikio Itagaki 4-13-1, Higashi-cho, Hitachi-shi, Ibaraki Hitachi Chemical Co., Ltd. Ibaraki Research Center

Claims (5)

[Claims] 1. A phthalocyanine composition having major diffraction peaks at Bragg angles (2θ ± 0.2 degrees) of 7.5 degrees, 24.2 degrees and 27.3 degrees in an X-ray diffraction spectrum of CuKα. 2. A phthalocyanine mixture containing a titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent is reprecipitated in water by an acid pasting method to produce a Bragg angle (2θ ± 0.2 in an X-ray diffraction spectrum of CuKα. A CuKα, characterized in that a precipitate having a characteristic diffraction peak at 27.2 degrees is obtained, and the precipitate is subsequently treated with a mixed solvent of an organic solvent and water.
Of the Bragg angle (2θ ± 0.
2 degrees) has a major diffraction peak at 7.5 degrees, 24.2 degrees and 27.3 degrees. 3. An electrophotographic photoreceptor having a photoconductive layer containing an organic photoconductive substance on a conductive substrate, wherein the organic photoconductive substance has a Bragg angle (2θ ± 0) in an X-ray diffraction spectrum of CuKα. (2.degree.) Is a phthalocyanine composition having major diffraction peaks at 7.5.degree., 24.2.degree. And 27.3.degree. 4. A charge generation layer containing the phthalocyanine composition obtained by the production method according to claim 2 as a charge generation material, and the following general formula [I] (R ₁ and R ₂ are each independently hydrogen. An atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, two R ₃ 's each independently represent a hydrogen atom or an alkyl group, and Ar ₁ and Ar ₂ are A composite electrophotographic photoreceptor having a charge transport layer containing a benzidine derivative represented by the formula (1), each independently representing an aryl group, and m and n each independently represent an integer of 0 to 5). . [Chemical 1] 5. A charge generating layer coating liquid containing the phthalocyanine composition according to claim 1.