JP3343268B2 - Phthalocyanine composition, process for producing the same, electrophotographic photoreceptor using the same, and coating solution for charge generation layer - Google Patents

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 process for producing the same, an electrophotographic photosensitive member using the same, and a coating solution 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) Some films are 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. Further, there is 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 thereon. The higher the Te content of the Te alloy, the longer the spectral sensitivity extends to longer wavelengths.
As the addition amount of e increases, there is a serious problem in that the surface charge retention characteristics become poor, and in fact, the photoreceptor cannot be used.

A charge generating layer is formed by coating a chlorocyan blue or squarylylate derivative of about 1 μm on an aluminum substrate, and a mixture of a polyvinyl carbazole or pyrazoline derivative having high insulation resistance and a polycarbonate resin is formed thereon. There is also a so-called composite two-layer type photoreceptor in which a charge transport layer is formed by coating with a thickness of 10 to 20 μm, but this photoreceptor does not have any sensitivity to light of 700 nm or more.

In recent years, in this composite two-layer type photoreceptor,
The above-mentioned disadvantage has been improved, that is, the semiconductor laser oscillation region 80
Many photoreceptors having a sensitivity around 0 nm have been reported, and many of them use a phthalocyanine pigment as a charge generating material, and have a polyvinyl carbazole, A mixture of a pyrazoline derivative or a hydrazone derivative and a polycarbonate resin or a polyester resin having a high insulation resistance is 10 to 2
A charge transport layer is formed by coating with 0 μm to form a composite two-layer type photoreceptor.

Phthalocyanines not only have different absorption spectra and photoconductivity depending on the type of the central metal, but also have different physical properties depending on the crystal type. Several examples have been reported that have been selected for electrophotographic photoreceptors.

[0006] For example, it is reported that titanyl phthalocyanine has various crystal forms, and there is a large difference in chargeability, dark decay, sensitivity, etc. depending on the crystal form.

JP-A-59-49544 discloses that the crystal form of titanyl phthalocyanine includes a Bragg angle (2
θ ± 0.2 degrees) are 9.2 degrees, 13.1 degrees, 20.7 degrees,
Those giving strong diffraction peaks at 26.2 degrees and 27.1 degrees are described as suitable, and the X-ray diffraction spectrum is shown. The electrophotographic characteristics of a photoreceptor using this crystalline form of titanyl phthalocyanine as a charge generation material are as follows: dark decay (DDR): 85%, sensitivity (E _1/2 ): 0.57 lux
-It is sec.

In JP-A-59-166959, a deposited film of titanyl phthalocyanine is left in saturated vapor of tetrahydrofuran for 1 to 24 hours to change the crystal form to form a charge generation layer. The X-ray diffraction spectrum has a small number of peaks and a wide peak, and has a Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees, 12.6 degrees, and 13.0 degrees.
, 25.4, 26.2 and 28.6 degrees are shown to give strong diffraction peaks. The electrophotographic characteristics of a photoreceptor 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 JP-A-2-198452, the crystal form of titanyl phthalocyanine has a Bragg angle (2
(θ ± 0.2 °) having a main diffraction peak at 27.3 ° has high sensitivity (1.7 mJ / cm ² ), and is produced at 60 ° C. in a mixed solution of water and ortho-dichlorobenzene at 1 ° C.
It is disclosed to heat and stir for hours.

In JP-A-2-256059, the crystal form of titanyl phthalocyanine has a black angle (2θ).
(± 0.2 °) having a main diffraction peak at 27.3 ° has high sensitivity (0.62 lux · sec), and it can be stirred in 1,2-dichloroethane at room temperature. It has been disclosed.

As described above, the electrophotographic characteristics of phthalocyanines greatly differ depending on the crystal form, and the crystal form is an important factor which affects the performance as an electrophotographic photosensitive member.

In Japanese Patent Application Laid-Open No. Sho 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 a very high sensitivity due to the conversion of the crystal form and exhibits excellent characteristics. However, in laser printers and the like,
Higher image quality and higher definition have been developed, and an electrophotographic photoreceptor having higher sensitivity characteristics has been demanded.

[0014]

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

[0015]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a CuK.alpha.
Angle in the X-ray diffraction spectrum (2θ ± 0.2
Degree) is a phthalocyanine composition having main diffraction peaks at 7.5 degrees, 24.2 degrees and 27.3 degrees.

Further, according to the present invention, a phthalocyanine mixture containing titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent is reprecipitated in water by an acid pasting method, and the Bragg angle (2θ A precipitate having a characteristic diffraction peak at 27.2 degrees (± 0.2 degrees) and subsequently treating the precipitate with a mixed solvent of an organic solvent and water. In the diffraction spectrum, the Bragg angles (2θ ± 0.2 degrees) are 7.5 degrees, 24.2 degrees and 2 degrees.
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 phthalocyanine used as a raw material,
The X-ray diffraction pattern of the phthalocyanine mixture consists of a superposition of 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 phthalocyanine used as a raw material at a molecular level, and the X-ray diffraction pattern is different from the peak pattern of each phthalocyanine alone used as a raw material. Indicates a pattern.

The present invention also relates to 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 in an X-ray diffraction spectrum of CuKα. (2θ ± 0.2 degrees) is 7.5
, A phthalocyanine composition having main diffraction peaks at 24.2 degrees and 27.3 degrees.

Further, the present invention includes a charge generation layer containing a phthalocyanine composition obtained by the production method as a charge generating material, the following general formula [I] (R ₁ and R _2,
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), which has a charge transport layer containing a benzidine derivative represented by the following formula: The present invention relates to a type electrophotographic photosensitive member.

Embedded image

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

Hereinafter, the present invention will be described in detail. The titanyl phthalocyanine used in the present invention can be produced, for example, as follows. Phthalonitrile
4 g (0.144 mol) of α-chloronaphthalene 120
of titanium tetrachloride in a nitrogen atmosphere.
(0.0364 mol) is added dropwise. After dropping, the mixture was reacted at 200 to 220 ° C. for 3 hours while heating and stirring.
Filter hot at 0-130 ° C and wash with α-chloronaphthalene then methanol. Hydrolysis (90 ° C., 1 hour) is performed with 140 ml of ion-exchanged water, and this operation is repeated until the solution becomes neutral, and washed with methanol. Next, it is sufficiently washed with NMP at 100 ° C., and then washed with methanol. The compound obtained in this way is kept at 60 ° C.
To obtain titanyl phthalocyanine (yield 46%).

In the halogenated metal phthalocyanine compound having a trivalent central metal used in the present invention, examples of the trivalent metal as the central metal include In, Ga, and Al, and examples of the halogen include Cl and Br. Further, the phthalocyanine ring may have a substituent such as halogen. The compound is a known compound, and among these, for example, a method for synthesizing a monohalogen metal phthalocyanine and a monohalogen metal phthalocyanine is described in Inorganic Chemistry 19 , 3131.
(1980) and JP-A-59-44054. Monohalogen metal phthalocyanines are, for example,
It can be manufactured as follows.

78.2 mmol of phthalonitrile and 15.8 mmol of metal trihalide are placed in 100 ml of quinoline which has been distilled twice and deoxygenated, heated to reflux for 0.5 to 3 hours, then slowly cooled, and then cooled to 0 ° C. After cooling, the mixture was filtered, and the crystals were washed with methanol, toluene and acetone, and then washed with 11
Dry at 0 ° C.

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

In the present invention, the composition ratio of the titanyl phthalocyanine and the phthalocyanine mixture containing a trivalent halogenated metal phthalocyanine as the central metal is such that the content of the titanyl phthalocyanine in terms of electrophotographic properties such as chargeability, dark decay and sensitivity is reduced. The range is preferably from 20 to 95% by weight, more preferably from 50 to 90% by weight, particularly preferably from 65 to 90% by weight.
Most preferably, it is in the range of 5 to 90% by weight.

The phthalocyanine mixture is reprecipitated in water by an acid pasting method to be made amorphous.
For example, after dissolving 1 g of the phthalocyanine mixture in 50 ml of concentrated sulfuric acid and stirring at room temperature, the mixture is added to 1 liter of ion-exchanged water cooled with ice water for about 1 hour, preferably 40 minutes to 50 minutes.
Drop and reprecipitate in minutes. After standing overnight, the supernatant is removed by decantation, and the precipitate is recovered by centrifugation. Thereafter, the precipitate is repeatedly washed with ion-exchanged water as washing water until the washed water has a pH of 2 to 5, preferably about 3 and a conductivity of 5 to 500 μS / cm. Then, after thoroughly washing with methanol, it is dried by heating under vacuum at 60 ° C. to obtain a powder. The precipitate formed in this way, comprising titanyl phthalocyanine and a metal halide phthalocyanine of which the central metal is trivalent, is the X of CuKα.
Angle (2θ ± 0.2)
Degree) shows a clear analysis peak at 27.2 degrees, and the peak is broad and its value cannot be regulated clearly.
When the pH exceeds 5, the characteristic peak intensity at 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 decreases to 6.8 degrees. A peak stronger than the peak intensity of 2 degrees is generated. Even if this powder is subjected to crystal transformation using a mixed solvent of organic solvent and water, the black angle (2θ ± 0.2 degrees) of the present invention is 7.5 degrees. , 24.2 ° and 27.3 ° cannot be obtained. PH after washing water is less than 2 or 5
When it exceeds, the chargeability, dark decay, sensitivity and the like tend to be inferior. If the conductivity is less than 5 μS / cm or more than 500 μS / cm, the chargeability, dark decay, sensitivity and the like tend to be poor.

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

The electrophotographic photoreceptor of the present invention has a photoconductive layer provided on a conductive support. In the present invention,
The photoconductive layer is a layer containing an organic photoconductive substance, and includes a coating of an organic photoconductive substance, a coating containing an organic photoconductive substance and a binder, and a composite coating composed of a charge generation layer and a charge transport layer. is there.

As the organic photoconductive substance, the above-mentioned phthalocyanine composition is used as an essential component, and a known substance can be used in combination. In addition, as the organic photoconductive substance, it is preferable to use an organic pigment and / or a charge transporting substance that generates a charge in the phthalocyanine composition. The charge generation layer contains the phthalocyanine composition and / or an organic pigment that generates charges, and the charge transport layer contains a charge transporting substance.

Examples of the organic pigments that generate electric charges include azoxybenzene, disazo, trisazo, benzimidazole, polycyclic quinone, indigoid, quinacridone, perylene, methine, α-type and β-type. , Γ
Pigments known to generate electric charges such as non-metal type or metal type phthalocyanine having various crystal structures such as type, δ type, ε type and χ type can be used. These pigments are described in, for example, JP-A-47-37543, JP-A-47-37544, and JP-A-47-18543.
JP-A-47-18544, JP-A-48-18544
43942, JP-A-48-70538, JP-A-49-1231, JP-A-49-105536
JP, JP-A-50-75214, JP-A-53-75214
No. 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 be used. In addition to these, any organic application that generates charge carriers by light irradiation can be used.

As the above-mentioned charge transporting substance, high molecular compounds include poly-N-vinyl carbazole, halogenated poly-N-vinyl carbazole, polyvinyl pyrene, polyvinyl indoloquinoxaline, polyvinyl benzothiophene, polyvinyl anthracene, and polyvinyl acridine. And low-molecular-weight compounds such as fluorenone, fluorene, 2,7-dinitro-9-fluorenone, and 4H-indeno (1,2,6).
Thiofen-4-one, 3,7-dinitro-dibenzothiophene-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) pyrazolin, 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, tetraphen, acridene, triphenylamine, benzidine, and derivatives thereof. As the charge transporting substance, a 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 isopropyl group, an n-butyl group, and a tert-butyl group. As the alkoxy group, a methoxy group, an ethoxy group,
Examples thereof include an n-propoxy group and an iso-propoxy group. Examples of the aryl group include a phenyl group, a tolyl group, a biphenyl group, a terphenyl group, a naphthyl group and the like. Examples of the fluoroalkyl group include a trifluoromethyl group, a trifluoroethyl group, and a heptafluoropropyl group. Examples of the fluoroalkoxy group include 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,
And a fluoroalkoxy group such as a 4,4,4-trifluorobutoxy group. For example, the following compounds No. 1 to No. 6 and the like can be mentioned.

[0032]

Embedded image

Embedded image

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

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

The binders that can be used in all of the above cases include silicone resins, polyamide resins, polyurethane resins, polyester resins, epoxy resins, polyketone resins, polycarbonate resins, polyacryl resins, polystyrene resins, and styrene-butadiene copolymers. , Polymethyl methacrylate resin, polyvinyl chloride, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer,
Polyacrylamide resin, polyvinyl carbazole, polyvinyl pyrazoline, polyvinyl pyrene and the like can be mentioned. Further, a thermosetting resin and a photocurable 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 which 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. Examples of the fluidity-imparting agent include Modaflow (manufactured by Monsanto Chemical), Acronal 4F (manufactured by Basff) and the like. And as a pinhole inhibitor,
Benzoin, dimethyl phthalate and the like can be mentioned. These may be appropriately selected and used, and the amounts thereof may be appropriately determined.

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

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

To form a photoconductive substrate on a conductive substrate, a method of vapor-depositing an organic photoconductive substance on the conductive substrate,
Organic photoconductive substances and other components as necessary are converted into aromatic solvents such as toluene and xylene, halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, and alcohol solvents such as methanol, ethanol and propanol. There is a method of uniformly dissolving or dispersing, applying the solution on a conductive substrate, and drying. As a coating method, a spin coating method, a dipping method, or the like can be adopted. In the case where the charge generation layer and the charge transport layer are formed, the same operation can be performed.In this case, the charge generation layer and the charge transport layer may be either upper layers. It may be soaked.

When the phthalocyanine composition of the present invention is applied by a spin coating method, the number of revolutions is 50 using a coating solution obtained by dissolving the phthalocyanine composition in a halogenated solvent such as chloroform or toluene or a non-polar solvent.
It is preferable to perform spin coating at 0 to 4000 rpm, and when applying by a dipping method, methanol, dimethylformamide,
The conductive substrate is preferably immersed in a coating solution dispersed in a halogen solvent such as chloroform, methylene chloride, 1,2-dichloroethane or the like by using a ball mill, ultrasonic waves or the like.

The electrophotographic photoreceptor according to the present invention may further have a thin adhesive layer or barrier layer immediately above the conductive substrate, and may have a protective layer on the surface.

[0042]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Production Examples and Examples of phthalocyanine compositions.

Production Example 1 1 g of a phthalocyanine mixture composed of 0.75 g of titanyl phthalocyanine and 0.25 g of indium phthalocyanine was dissolved in 50 ml of sulfuric acid, stirred at room temperature for 30 minutes, and added to 1 liter of ion-exchanged water cooled with ice water.
In about 40 minutes, the solution was dropped and reprecipitated. The mixture was further stirred for 1 hour under cooling and then left overnight. After removing the supernatant by decantation, the precipitate was separated by centrifugation to obtain 700 mg of the precipitate. In the first washing, 120 mg 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 further continued five times. The pH and conductivity of the wash water separated and removed in the sixth operation (ie, wash water after washing) were measured (23 ° C.). Model PH51 manufactured by Yokogawa Electric Corporation was used for pH measurement. Also,
The conductivity was measured using a model SC-1 manufactured by Shibata Scientific Instruments.
7A was used. The pH of the washing water was 3.3, and the conductivity was 65.1 μS / cm. Then, methanol 60
After washing three times with ml, it was dried by heating under vacuum at 60 ° C. for 4 hours.
The X-ray diffraction spectrum of this vacuum dried product is shown in FIG. Next, 2 g of ion-exchanged water was added to 1 g of the vacuum dried product.
g and 1.5 ml of ortho-dichlorobenzene.
After heating and stirring at 1 ° C. for 1 hour, filtration, washing with methanol, and vacuum drying at 60 ° C. for 4 hours, crystals of the phthalocyanine composition of the present invention were obtained. The X-ray diffraction spectrum of this crystal is shown in FIG.

Production Example 2 9 g of ion-exchanged water and 100 ml of 1,2-dichloroethane were added to 1 g of the vacuum-dried product obtained in the same manner as in Production Example 1, 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 The phthalocyanine composition was prepared in the same manner as in Production Example 1 except that the number of washings after the sulfuric acid treatment was changed, and the washing water was washed to a pH of 4.0 and a conductivity of 17.8 μS / cm. Manufactured. The X-ray diffraction spectrum of the composition obtained was the same as in FIG.

Comparative Production Example 1 The crystals of the phthalocyanine composition were prepared in the same manner as in Production Example 1 except that the number of washings after the sulfuric acid treatment was changed, and the washing water was washed to a pH of 6.0 and a conductivity of 3.4 μS / cm. Manufactured. FIG. 4 shows an X-ray diffraction spectrum of the vacuum dried product before the halogen solvent treatment. 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 sulfuric acid treatment was changed, and the washing water was washed to pH 6.0 and conductivity to 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, 10 ml of isopropyl alcohol was added, and the mixture was heated and stirred 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.

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

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

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

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

Comparative Production Examples 10 to 12 Crystals of the phthalocyanine composition were obtained in the same manner as in Comparative Production Examples 1 to 3, except that aluminum chloride phthalocyanine was used in place of indium phthalocyanine chloride.

Example 1 1.5 g of the phthalocyanine composition produced in Production Example 1, 0.9 g of polyvinyl butyral resin ESLEK BL-S (manufactured by Sekisui Chemical Co., Ltd.), and melamine resin ML351W (manufactured by Hitachi Chemical Co., Ltd.) 0 .1 g, 49 g of ethyl cellosolve and 49 g of tetrahydrofuran 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,
After drying at 140 ° C. for 1 hour, a charge generation layer having a thickness of 0.5 μm was formed. 1.5 g of the above-described No. 4 charge transporting substance,
A coating solution obtained by blending 1.5 g of a polycarbonate resin Iupilon S-3000 (manufactured by Mitsubishi Gas Chemical Company) and 15.5 g of methylene chloride is applied on the substrate by a dipping method, and dried at 120 ° C. for 1 hour. Thus, a charge transport layer having a thickness of 20 μm was formed. Electrophotographic characteristics (sensitivity, residual potential, dark decay rate, photoresponsiveness) were evaluated by Cynthia 30HC (manufactured by Midoriya Electric Co., Ltd.). -65 photoconductor by corona charging
After charging to 0 V, a monochromatic light of 780 nm was exposed to a 50 mS photoreceptor, and various characteristics were measured. The definition of the above characteristics is
It is as follows. Sensitivity (E ₅₀ ) is the initial charge potential −6.
780 required to halve 50 V after 0.2 seconds of exposure
nm is the irradiation energy of monochromatic light, and the residual potential (V
r) exposes monochromatic light of the same wavelength of 20 mJ / m ² for 50 mS,
This 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 -650 V, and the surface potential V after leaving the dark for 1 second after the initial charging.
₁ defined (-V) with the _{(V 1/650) × 100} . The optical response (T _1/2 ) is 20 mJ / m ^{2 at} a wavelength of 780 nm.
Is defined as the time (sec) required for exposing the monochromatic light of 50 mS to 50 ms and halving the initial charging potential -650 V.

Examples 2 and 3 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the titanyl phthalocyanine compositions obtained in Production Examples 2 and 3 were used. The results are shown in Table 1.

Comparative Examples 1 to 3 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the titanyl phthalocyanine compositions obtained in Comparative Production Examples 1 to 3 were used. The results are shown in Table 1. Although apparently high sensitivity, the dark decay rate was not a value that could withstand practical use.

Comparative Example 4 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Production Example 1 except that the dried powder before the treatment with the ortho-dichlorobenzene solution was used. Could not.

[Table 1]

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

Comparative Examples 5 to 7 Except that the titanyl phthalocyanine compositions obtained in Comparative Production Examples 4 and 6 were used in Example 1 and that No. 2 was used instead of the No. 4 compound as the charge transporting material. Was used to produce and evaluate an electrophotographic photosensitive member according to 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 dried powder before the treatment with the ortho-dichlorobenzene solution was used. I couldn't do that.

[Table 2]

Examples 7 to 9 In Example 1, the titanyl phthalocyanine compositions obtained in Production Examples 7 to 9 were used, and N was used as a charge transport material.
Example 1 except that No. 5 was used instead of the compound of o.4
An electrophotographic photoreceptor was manufactured and evaluated according to Comparative Examples Nos. 1 to 3. Table 3 shows the results.

Comparative Examples 9 to 11 Except that the titanyl phthalocyanine compositions obtained in Comparative Production Examples 7 to 9 were used in Example 1 and that No. 5 was used in place of the compound of No. 4 as a charge transporting material. Was used to produce and evaluate an electrophotographic photosensitive member according to Example 1. Table 3 shows the results.

Comparative Example 12 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the dried powder before the treatment with the ortho-dichlorobenzene solution was used. I couldn't do that.

[Table 3]

Examples 10 to 12 In Example 1, the titanyl phthalocyanine compositions obtained in Production Examples 10 to 12 were used, and No. 1 was used in place of the compound of No. 4 as the charge transporting material. An electrophotographic photosensitive member was manufactured and evaluated according to Examples 1 to 3. Table 4 shows the results.

Comparative Examples 13 to 15 Except that the titanyl phthalocyanine compositions obtained in Comparative Production Examples 10 to 12 were used in Example 1 and that No. 1 was used instead of the compound of No. 4 as the charge transport material. Is
An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 1. Table 4 shows the results.

Comparative Example 16 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the dried powder before the treatment with the ortho-dichlorobenzene solution was used. I couldn't do that.

[Table 4]

[0068]

The electrophotographic photoreceptor using the phthalocyanine composition according to the present invention has excellent electrophotographic properties such as chargeability, dark decay and sensitivity, and is required to have higher density and higher image quality than before. It can be suitably applied to an electrophotographic process. In particular, since the sensitivity is excellent, when applied to a laser beam printer, the life of a semiconductor laser can be greatly extended. Further, in full-color copying, the latitude of halftone gradation corresponding to sensitivity can be increased, which is extremely advantageous.

[0069]

[Brief description of the drawings]

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

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

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

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

FIG. 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.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Mikio Itagaki 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Ibaraki Research Laboratory (56) References JP-A-6-175382 (JP, A) JP-A-5-345866 (JP, A) JP-A-5-6013 (JP, A) JP-A-3-217462 (JP, A) JP-A-3-220392 (JP, A) JP-A-3-54264 ( JP, A) JP-A-2-256059 (JP, A) JP-A-2-198452 (JP, A) JP-A-2-28265 (JP, A) JP-A-1-299874 (JP, A) JP Hei 3-9962 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 67/00

Claims (5)

(57) [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 titanyl phthalocyanine and a metal halide phthalocyanine whose central metal is trivalent is reprecipitated in water by an acid pasting method, and the Bragg angle (2θ ± 0.2) is obtained in the X-ray diffraction spectrum of CuKα. CuKα, wherein a precipitate having a characteristic diffraction peak at 27.2 ° 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), wherein the phthalocyanine composition has main diffraction peaks at 7.5 degrees, 24.2 degrees and 27.3 degrees. 3. 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 (2θ ± 0) in an X-ray diffraction spectrum of CuKα. (2 °) is a phthalocyanine composition having main diffraction peaks at 7.5 °, 24.2 ° and 27.3 °. 4. A charge-generating layer containing the phthalocyanine composition obtained by the production method according to claim 2 as a charge-generating material, and the following general formula [I] (R ₁ and R ₂ are each independently hydrogen Represents an atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, two R ₃ each independently represent a hydrogen atom or an alkyl group, and Ar ₁ and Ar ₂ are Each of which independently represents an aryl group, and m and n each independently represent an integer of 0 to 5), which has a charge-transporting layer containing a benzidine derivative as a charge-transporting substance. . Embedded image 5. A coating liquid for a charge generation layer containing the phthalocyanine composition according to claim 1.