JP2002322382A - Hydroxymetal phthalocyanine and method for production the same, electrophotorecepter, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydroxymetal phthalocyanine capable of attaining enough photosensitivity and duarability and of obtaining stable image quality for long term without image defect on using as an electrophotorecepter, to provide a manufacturing method therefor and an electrophotographic device. SOLUTION: The manufacturing method for the hydroxymetal phthalocyanine contains a process that a metal phthalocyanine having no hydroxy group bonded to a center metal is dissolved into an acid below 3.0 wt.% based on the total amount of a pigment solution to obtain the pigment solution and a process that the pigment solution is added to a prescribed solvent to deposit the hydroxymetal phthalocyanine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydroxymetal phthalocyanine and a method for producing the same, and an electrophotographic photosensitive member, a process cartridge and an electrophotographic apparatus using the same.

[0002]

2. Description of the Related Art Phthalocyanine compounds are useful as paints, printing inks, catalysts or electronic materials. Particularly, in recent years, phthalocyanine compounds have been widely studied as electrophotographic photoreceptor materials, optical recording materials and photoelectric conversion materials. I have.

[0003] The phthalocyanine compound usually shows a large number of crystal forms depending on the production method and the treatment method, and it is known that the photoelectric conversion characteristics of the phthalocyanine change depending on the difference in the crystal form. For example, as the crystal form of copper phthalocyanine, in addition to the stable β form, α, π, x,
It is known that there are crystal forms such as ρ, γ, and δ, and these crystal forms can be mutually transformed by mechanical strain, sulfuric acid treatment, organic solvent treatment, heat treatment, etc. Nos. 2,770,629 and 3,160,6
No. 35, No. 3,708,292, No. 3,
357, 989). Also, Japanese Patent Application Laid-Open No. 50-3854
No. 3 describes the relationship between the difference in crystal form of copper phthalocyanine and the electrophotographic sensitivity.

In addition to copper phthalocyanine, it has been proposed to use a metal-free phthalocyanine (non-metal phthalocyanine), hydroxygallium phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine or the like having a specific crystal type for an electrophotographic photosensitive member. ing. For example, JP-A-5-263007, JP-A-6-1923, and JP-A-7-26143
Japanese Patent Application Laid-Open No. 5 (1999) -2005 discloses an electrophotographic photoreceptor using hydroxygallium phthalocyanine having a specific crystal form.

[0005]

In the production of hydroxymetal phthalocyanine among the above-mentioned phthalocyanine compounds, usually, a precursor thereof is dissolved in an acid, and a solvent is added to the acid precursor to precipitate the hydroxymetal phthalocyanine. Is performed. However, hydroxygallium phthalocyanine obtained by a conventional acid pasting process is not suitable for obtaining good image quality, such as causing variations in characteristics such as chargeability and dark decay rate when used as a material for an electrophotographic photoreceptor. Was still not enough.

The present invention has been made in view of the above-mentioned problems of the prior art, and when used as an electrophotographic photoreceptor, achieves sufficient light sensitivity and sufficient durability to cause image quality defects. Hydroxymetal phthalocyanine capable of obtaining a stable image quality for a long period of time without any problem, a method for producing the same, and an electrophotographic photosensitive member using the same,
It is an object to provide a process cartridge and an electrophotographic apparatus.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that the shape of hydroxymetal phthalocyanine particles obtained in the conventional acid pasting treatment tends to be non-uniform, It has been found that variations in photoelectric characteristics occur due to the non-uniformity of the particles. And as a result of further diligent research based on such knowledge, metal phthalocyanine having no hydroxyl group bonded to the central metal is dissolved in acid at a predetermined concentration, and a solvent is added to the pigment solution to precipitate hydroxy metal phthalocyanine. The inventors have found that the above-mentioned problems can be solved by doing so, and have accomplished the present invention.

That is, in the method for producing a hydroxymetal phthalocyanine of the present invention, a metal phthalocyanine having no hydroxyl group bonded to a central metal is dissolved in an acid so as to be 3.0% by weight or less based on the total amount of the pigment solution. And obtaining a pigment solution by adding the pigment solution to a predetermined solvent to precipitate hydroxymetal phthalocyanine.

Further, the hydroxymetal phthalocyanine of the present invention is obtained by the production method of the present invention, and has an average particle size of 0.18 μm or less.

Further, an electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor comprising a conductive support and a photosensitive layer disposed on the conductive support, wherein the photosensitive layer is the above-mentioned present invention. Characterized by containing hydroxymetal phthalocyanine.

Further, the process cartridge according to the present invention includes the electrophotographic photoreceptor of the present invention, charging means for charging the electrophotographic photoreceptor, and a toner for transferring the electrostatic latent image formed on the electrophotographic photoreceptor to toner. And at least one member selected from the group consisting of a cleaning unit for removing toner remaining on the surface of the electrophotographic photoreceptor. .

Furthermore, an electrophotographic apparatus according to the present invention provides the electrophotographic photoreceptor of the present invention, charging means for charging the electrophotographic photoreceptor, and forming an electrostatic latent image on the electrophotographic photoreceptor. Image input means, developing means for developing the electrostatic latent image formed on the electrophotographic photoreceptor with toner to form a toner image, transfer means for transferring the toner image to a transfer target, Cleaning means for removing toner remaining on the surface of the photographic photoreceptor.

In the present invention, a metal phthalocyanine having no hydroxyl group bonded to the central metal is dissolved in an acid so as to be 3.0% by weight or less, based on the total amount of the pigment solution, to obtain a pigment solution. Since the shape of the obtained hydroxymetal phthalocyanine is sufficiently small and uniform, when the hydroxymetal phthalocyanine is used as a material for an electrophotographic photoreceptor, sufficient photosensitivity and sufficient durability are achieved, and image quality defects are reduced. It is possible to obtain a stable image quality for a long period of time without occurrence.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
In the drawings, the same or corresponding portions are denoted by the same reference characters.

(Hydroxymetal phthalocyanine and method for producing the same) In the method for producing hydroxygallium phthalocyanine according to the present invention, first, a metal phthalocyanine having no hydroxyl group bonded to the central metal was added to 3.0 parts by weight based on the total amount of the pigment solution. % By dissolving it in an acid to obtain a pigment solution.

The metal phthalocyanine having no hydroxyl group bonded to the central metal (hereinafter simply referred to as “metal phthalocyanine”) used in the production method of the present invention is specifically chloroaluminum phthalocyanine, chlorogallium phthalocyanine, Examples thereof include chloroindium phthalocyanine, dichlorosilicon phthalocyanine, dichlorogermanium phthalocyanine, and dichlorotin phthalocyanine. Further, di (oxogallium phthalocyaninyl) alkane (alkoxy-bridged gallium phthalocyanine dimer) such as 1,2-di (oxogallium phthalocyaninyl) ethane can also be used.

Further, specific examples of the acid used in the production method of the present invention include sulfuric acid, orthophosphoric acid, pyrophosphoric acid, chlorosulfonic acid, hydrogen bromide and the like. The average particle size of the resulting hydroxymetal phthalocyanine is smaller and more uniform, and higher photoelectric characteristics are obtained, which is preferable. These acids are preferably as pure as possible, and more specifically, those having a purity of 98% by weight or more.

In the pigment solution containing the metal phthalocyanine and the acid, the concentration of the metal phthalocyanine is 3.0% by weight or less, preferably 0.5 to 2.5% by weight based on the total amount of the pigment solution as described above. %. 2. The concentration of metal phthalocyanine is based on the total amount of the pigment solution.
If the content exceeds 0% by weight, it is very difficult to make the average particle size of the hydroxymetal phthalocyanine sufficiently small and uniform, for example, coarse particles are formed. As a result, the dark decay rate increases, and the film is used in the film forming process. Phenomena such as poor dispersion of the dispersion and occurrence of image quality defects such as black spots are likely to occur. In particular, when obtaining hydroxygallium phthalocyanine from chlorogallium phthalocyanine, when performing a crystal conversion on the obtained hydroxygallium phthalocyanine by solvent treatment or the like, the crystal conversion does not sufficiently proceed, and the crystal form inherently has The photoelectric characteristics become insufficient or the photoelectric characteristics tend to vary. The concentration of metal phthalocyanine is 0.5% by weight based on the total amount of the pigment solution.
If it is less than 1, the production efficiency tends to decrease, which is not preferable for practical use.

Next, by adding the pigment solution to a predetermined solvent, hydroxymetal phthalocyanine generated by hydrolysis of metal phthalocyanine precipitates in the mixed solution.

The predetermined solvent used in the present invention is not particularly limited as long as hydroxymetal phthalocyanine can be precipitated from the pigment solution.
Specifically, water, or a mixture of water and a water-soluble organic solvent can be used, as the water-soluble organic solvent, methanol, lower alcohols such as ethanol, acetone,
Lower ketones such as methyl ethyl ketone; ethers such as diethyl ether, methyl cellosolve and dioxane; dimethylformamide; dimethyl sulfoxide; In the present invention, it is preferable to use water among the above solvents.

In the present invention, when the predetermined solvent is obtained by adding a base to the above solvent,
This is preferable because the photoelectric properties of the obtained hydroxymetal phthalocyanine tend to be further improved. The base is not particularly limited as long as it shows water solubility and can be deprotonated, and specifically, alkali hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, potassium carbonate and the like. Examples include alkali carbonate, magnesium hydroxide, ammonia, and quaternary ammonium hydroxide. The amount of the base used is 0.1 to the acid in the pigment solution.
It is preferably from 5 to 3.0 molar equivalents,
More preferably, it is 1.2 molar equivalents.

The use amount of the above-mentioned predetermined solvent is preferably 2 parts by weight or more based on 1 part by weight of the pigment solution.
More preferably, it is 25 parts by weight. When the amount of the solvent used is less than the lower limit, coarse particles are formed, and it is extremely difficult to make the average particle size of the hydroxymetal phthalocyanine sufficiently small and uniform, and an anion generated at the time of hydrolysis Tends to be taken into the hydroxymetal phthalocyanine crystal, and the photoelectric characteristics tend to be insufficient.

Since the mixing of the pigment solution and the predetermined solvent is accompanied by heat generation, the solvent is sufficiently stirred, and the temperature of the mixture of the pigment solution and the predetermined solvent is lowered to -10 to 10 ° C. (more preferably, -10 to 10 ° C.). (5 ° C.), it is preferable to gradually add the pigment solution. The mixture of the pigment solution and the predetermined solvent is 1
If the temperature exceeds 0 ° C., it tends to be difficult to make the average particle size of the obtained hydroxymetal phthalocyanine sufficiently small and uniform, such as formation of coarse particles of 0.2 μm or more.

According to the production method of the present invention having the above structure, the formation of coarse particles is sufficiently suppressed, and the average particle diameter is 0.18 μm or less (preferably 0.05 to 0.15 μm).
m), the hydroxymetal phthalocyanine of the present invention can be efficiently and reliably obtained. When the average particle size exceeds the upper limit, when used for a material of an electrophotographic photoreceptor, light sensitivity and durability become insufficient, and as a result, image quality becomes stable for a long period of time, such as image quality defects. It is difficult to obtain.

The hydroxymetal phthalocyanine thus obtained can be converted into a desired crystal form by further subjecting it to a solvent treatment.

For example, in the case of hydroxygallium phthalocyanine, amides (N, N-dimethylformamide,
Solvent treatment using N, N-dimethylacetamide, N-methylpyrrolidone, etc.), esters (ethyl acetate, n-butyl acetate, iso-amyl acetate, etc.), ketones (acetone, methyl ethyl ketone, methyl iso-butyl ketone, etc.). By doing so, the Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum are 7.5 °, 9.9 °
Hydroxygallium phthalocyanine crystals having strong diffraction peaks at 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° are obtained; alcohols (methanol, ethanol, etc.), polyhydric alcohols (Ethylene glycol, glycerin, polyethylene glycol, etc.),
By performing a solvent treatment using a sulfoxide (such as dimethyl sulfoxide) or an aromatic compound (such as toluene or chlorobenzene), the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum becomes 7.7 °, 16 °. .5 °, 2
Hydroxygallium phthalocyanine crystals having strong diffraction peaks at 5.1 ° and 26.6 ° are obtained; amides (N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), organic amines (Pyridine, piperidine and the like), sulfoxides (dimethylsulfoxide and the like), and the like, to obtain a Bragg angle (2θ ±
0.2 °) is 7.9 °, 16.5 °, 24.4 ° and 2
A hydroxygallium phthalocyanine crystal having a strong diffraction peak at 7.6 ° is obtained; by performing a solvent treatment with an aromatic alcohol (such as benzyl alcohol) or the like, the Bragg angle (2θ) in the X-ray diffraction spectrum is obtained.
± 0.2 °) is 7.0 °, 7.5 °, 10.5 °, 1
1.7 °, 12.7 °, 17.3 °, 18.1 °, 2
A hydroxygallium phthalocyanine crystal having strong diffraction peaks at 4.5 °, 26.2 ° and 27.1 ° is obtained; solvent treatment is performed using polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.) and the like. Thereby, the Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum are 6.8 °, 12.8 °,
A hydroxygallium phthalocyanine crystal having strong diffraction peaks at 5.8 ° and 26.0 ° is obtained.

When a solvent containing no base is used as the predetermined solvent, the obtained hydroxymetal phthalocyanine is sufficiently washed with water, a dilute aqueous base solution, an organic solvent or the like to remove unreacted metal phthalocyanine, It is preferable to remove residues such as anions generated by hydrolysis of acid and metal phthalocyanine. The water used for washing is preferably purified water such as pure water, distilled water, or ion-exchanged water, and its electric conductivity is preferably 20.0 μS / cm or less (more preferably 10.0 μS / cm). Examples of the base used in the diluted basic aqueous solution include the bases exemplified in the description of the predetermined solvent.
Further, as the organic solvent, methanol, ethanol, n
-Propanol, n-butanol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate and the like. The amount of the water, dilute basic aqueous solution or organic solvent used is preferably 10 to 1000 times (more preferably 100 to 1000 times) the hydroxymetal phthalocyanine crystal in terms of weight.

(Electrophotographic Photoreceptor) Preferred embodiments of the electrophotographic photoreceptor of the present invention are shown in FIGS. The electrophotographic photoreceptor shown in FIGS. 1 to 3 has a layer containing a charge generating material (charge generating layer 5) and a layer containing a charge transporting material (charge transporting layer 6).
The electrophotographic photoreceptor 1 shown in FIG. 1 has an undercoat layer 4, a charge generation layer 5, and a charge transport layer 6 on a conductive support 2 in that order. Laminated structure; electrophotographic photoreceptor 1 shown in FIG.
A structure in which an undercoat layer 4, a charge generation layer 5, a charge transport layer 6, and a protective layer 7 are sequentially laminated thereon; the electrophotographic photoreceptor 1 shown in FIG.
Has a structure in which an undercoat layer 4, a charge transport layer 6, a charge generation layer 5, and a protective layer 7 are sequentially laminated on a conductive support 2. The electrophotographic photoreceptor shown in FIGS. 4 and 5 contains a charge generating substance and a charge transporting substance in the same layer (single-layer type photosensitive layer 8), and the electrophotographic photoreceptor 1 shown in FIG. A structure in which an undercoat layer 4 and a single-layer type photosensitive layer 8 are sequentially laminated on a conductive support 2; the electrophotographic photosensitive member 1 shown in FIG.
A subbing layer 4, a single-layer type photosensitive layer 8 on the conductive support 1,
And a structure in which the protective layer 7 is sequentially laminated. The charge generation layer 4 and the single-layer type photosensitive layer 8 contain the hydroxymetal phthalocyanine of the present invention.

Examples of the material of the conductive support used in the present invention include metals such as aluminum, nickel, chromium and stainless steel; aluminum, copper, gold, silver, platinum, palladium and titanium on paper, plastic or glass. A thin film provided by depositing or laminating a metal such as nickel-chromium, stainless steel, copper-indium or a conductive metal compound such as indium oxide / tin oxide; carbon black on paper, plastic or glass; Indium oxide, tin oxide-antimony oxide powder, metal powder, copper iodide and the like are dispersed and applied to a binder resin, and a conductive treatment is performed. The shape of the conductive support according to the present invention is not particularly limited, but those having a shape such as a drum shape, a sheet shape, and a plate shape are preferably used. Further, in the present invention, the surface of the conductive support, if necessary, mirror cutting, etching, anodic oxidation, rough cutting, centerless grinding,
Surface treatment such as sandblasting and wet honing may be performed. By roughening the surface of the conductive support by these surface treatments, it is possible to prevent grain-like density unevenness due to interference light in the electrophotographic photosensitive member, which can occur when using a coherent light source such as a laser beam. Can be.

The electrophotographic photosensitive member according to the present invention is shown in FIGS.
It is preferable to provide an undercoat layer on the conductive support as shown in FIG. When the undercoat layer is provided on the conductive support, the following (i) to (vi): (i) unnecessary carrier injection from the conductive support into the photosensitive layer is prevented, and the image quality is improved; ii) Environment dependence (temperature, humidity, etc.) of the light decay curve of the electrophotographic photoreceptor is reduced to obtain stable image quality; (iii) Due to a suitable charge transporting ability, even when used repeatedly for a long period of time, electric charge is obtained. Does not accumulate, and the occurrence of sensitivity fluctuation is suppressed; (iv) moderate pressure resistance to the charging voltage prevents the occurrence of image defects due to dielectric breakdown; (v) the photosensitive layer is used as an adhesive layer. (Vi) prevention of light reflection from the support tends to obtain the effect shown in (vi). Here, as the material of the undercoat layer, in addition to the crosslinked product according to the present invention, zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, titanate coupling Titanium compounds, aluminum chelate compounds, organoaluminum compounds such as aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, Suzuki Rate compound, aluminum silicon alkoxide compound, aluminum titanium alkoxide compound, aluminum zircon While organometallic compounds such um alkoxide compounds, among these, organic zirconium compound, an organic titanyl compound, the organoaluminum compound residual potential is used preferably for exhibiting good electrophotographic properties lower.

Further, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4 Silane coupling agents such as, -epoxycyclohexyltrimethoxysilane, and polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinylimidazole, and polyethylenoxide conventionally used in undercoat layers. Ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene,
Polyester, phenolic resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinylpyrrolidone, polyvinylpyridine, polyurethane, polyglutamic acid,
A binder resin such as polyacrylic acid can also be used as a material for the undercoat layer. One of the above materials may be used alone, or two or more thereof may be used in combination.

The undercoat layer according to the present invention may be formed by mixing and dispersing an electron-transporting pigment in the above-mentioned material. Examples of electron transporting pigments include organic pigments such as perylene pigments, bisbenzimidazole perylene pigments, polycyclic quinone pigments, indigo pigments, and quinacridone pigments; electron-withdrawing substituents such as cyano groups, nitro groups, nitroso groups, and halogen atoms. Bisazo pigments; organic pigments such as phthalocyanine pigments; inorganic pigments such as zinc oxide and titanium oxide. Among these charge transporting pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments are preferably used because they have high electron mobility. The content of these electron transporting pigments is preferably 95% by weight or less, more preferably 90% by weight or less, based on the total solid content in the undercoat layer. If the content of the electron-transporting pigment in the undercoat layer exceeds the above upper limit, the strength of the undercoat layer tends to decrease, and the coating film tends to have defects.

The method of mixing and dispersing these charge-transporting pigments includes a method of dispersing an electron-transporting pigment in a solution containing the material of the undercoat layer; A method of adding and mixing layer materials;
A method in which the material of the undercoat layer is added to and mixed with a liquid in which the electron transport pigment is dispersed in a resin; a method in which the material of the undercoat layer is added to the resin solution and mixed, and then the electron transport pigment is dispersed; A method in which the material for the undercoat layer is added to the transportable pigment, mixed, and then dispersed in a resin solution, may be mentioned. It is important to suppress the occurrence of gelation or aggregation in the mixed / dispersed liquid. When mixing and dispersing the electron transporting pigment, a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like can be used. This mixing / dispersion step is performed in an organic solvent. The organic solvent is one that dissolves a term metal compound or resin, and does not cause gelation or aggregation when mixing and dispersing the electron transporting pigment. There is no particular limitation, but specifically, methanol, ethanol, n-propanol, n-
Butanol, benzyl alcohol, methyl cellosolve,
Ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene, or a mixture thereof
Mixtures of more than one species.

The undercoat layer can be formed by applying the coating solution thus prepared on a conductive support, evaporating the solvent, and then drying. Examples of the application method of the coating liquid include a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method. The temperature in the drying step is preferably 80 to 1
70 ° C. The thickness of the undercoat layer thus obtained is preferably from 0.1 to 20 μm, more preferably from 0.2 to 10 μm.

The charge generation layer according to the present invention contains the hydroxymetal phthalocyanine of the present invention as described above, and the hydroxymetal phthalocyanine is usually dispersed in a binder resin. As such a binder resin, specifically, polyvinyl butyral resin, polyvinyl acetal resin, polyarylate resin, polycarbonate resin, polyester resin, phenoxy resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin , Acrylic resin, methacrylic resin, polyacrylamide resin, polyamide resin, polyvinyl pyridine resin, cellulosic resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, casein, vinyl chloride-vinyl acetate copolymer, modified vinyl chloride Vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-alkyd resin, phenol Formaldehyde resins. In addition, poly-N-
Organic photoconductive polymers such as vinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene can also be used as the binder resin. When another layer (such as a charge transport layer) is further laminated after the formation of the charge generation layer, a resin soluble in a solvent of a coating liquid for a layer laminated on the charge generation layer is not preferable.

Further, the charge generation layer according to the present invention comprises, as a charge generating material, a phthalocyanine pigment other than the hydroxygallium phthalocyanine of the present invention, a bisazo pigment, a triarylmethane pigment, a thiazine dye, an oxazine dye, Xanthene dye, cyanine dye, styryl dye, pyrylium dye, azo pigment, quinacridone pigment, indigo pigment, perylene pigment, polycyclic quinone pigment, bisbenzimidazole pigment, induthrone pigment, squarylium Organic pigments such as pigments or dyes may be contained.

The compounding ratio of the charge generating material and the binder resin in the charge generating layer is appropriately selected according to each kind, but is preferably 40: 1 to 1: 4 by weight. , 20: 1 to 1: 2. When the amount of the charge generating material exceeds 40 times (weight conversion value) the amount of the binder resin, the stability of the dispersion used for forming the charge generating layer tends to be insufficient. On the other hand, when the amount of the charge generation material is less than 1/4 (weight conversion value) of the amount of the binder resin, the sensitivity of the electrophotographic photosensitive member tends to be insufficient.

The charge generation layer according to the present invention comprises a coating solution obtained by dispersing a charge generation material and a binder resin in a predetermined solvent, into a predetermined layer (conductive support, charge transport layer, undercoat layer). Etc.) and dried. Here, as the organic solvent used for forming the charge generation layer, specifically, methanol, ethanol, n
-Propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone,
Methyl ethyl ketone, cyclohexanone, methyl acetate,
Examples include n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. One of these organic solvents may be used alone, or two or more thereof may be used in combination. Examples of the method of dispersing the charge generating material and the binder resin in these organic solvents include a sand mill, a colloid mill, an attritor, a ball mill, a dyno mill, a high-pressure homogenizer, an ultrasonic disperser, a coball mill, and a roll mill. In this case, it is preferable to perform the reaction under the condition that the crystal form of the charge generation material does not change due to the dispersion.

Examples of the method for applying the above-mentioned coating liquid include a sand mill, a colloid mill, an attritor, a ball mill, a dyno mill, a high-pressure homogenizer, an ultrasonic disperser, a coball mill, and a roll mill.

The thickness of the charge generation layer thus obtained is preferably 0.01 to 5 μm, more preferably 0.1 to 5 μm.
03 to 2 μm. If the thickness of the charge generation layer is less than the lower limit, the film formability tends to decrease and sufficient mechanical strength tends to be hardly obtained. On the other hand, when the thickness of the charge generation layer exceeds the upper limit, sufficient light attenuation tends to be hardly obtained in terms of electrical characteristics.

The charge transport layer according to the present invention contains a charge transport material and a binder resin. Here, the charge transporting material used in the present invention is not particularly limited as long as it has a function of transporting charge. Specifically, p-benzoquinone, chloranil,
Electron transport such as quinone compounds such as bromanil and anthraquinone, fluorenone compounds such as tetracyanoquinodimethane compound, 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds, cyanovinyl compounds and ethylene compounds And a hole transporting compound such as a triarylamine compound, a benzidine compound, an arylalkane compound, an aryl-substituted ethylene compound, a stilbene compound, an anthracene compound, or a hydrazone compound. One of these charge transport materials may be used alone, or two or more thereof may be used in combination. Among these charge transport materials, a triphenylamine-based compound and a benzidine-based compound are particularly preferable because they have high charge (hole) transport ability and excellent stability.

In the present invention, as the charge transporting material, a polymer charge transporting material having a charge transporting property, such as poly-N-vinylcarbazole and polysilane, can be used. In particular, the polyester-based polymer charge transporting materials disclosed in JP-A-8-176293 and JP-A-8-208820 have high charge transporting properties and are particularly preferable. When a polymer charge transport material is used as the charge transport material, the charge transport layer can be formed without using a binder resin, but a mixture of the polymer charge transport material and a binder resin described below is used. It may be used to form a film.

As the binder resin used in the charge transport layer according to the present invention, specifically, a polycarbonate resin,
Examples thereof include polyarylate resin, polystyrene resin, polyester resin, styrene-acrylonitrile copolymer, polysulfone, polymethacrylate, styrene-methacrylate copolymer, and polyolefin. One of these binder resins may be used alone,
Two or more kinds may be used in combination.

The charge transporting layer according to the present invention is obtained by dispersing a charge transporting material and a binder resin in a predetermined solvent, and coating the coating solution with a predetermined layer (conductive support, undercoat layer, charge generation layer). Etc.) and dried. Here, the compounding ratio (weight ratio) of the charge transport material and the binder resin in the coating liquid is preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3. . If the amount of the charge transporting material exceeds 5 times the weight of the binder resin, the mechanical strength of the charge transporting layer tends to decrease. On the other hand, when the amount of the charge transport material is less than 1/5 (weight conversion value) of the amount of the binder resin, the light sensitivity tends to decrease.

Examples of the solvent used in the coating solution include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; ketones such as acetone and 2-butanone; and halogen acids such as methylene chloride, chloroform and ethylene chloride. Aliphatic hydrocarbons; tetrahydrofuran,
One kind of organic solvent such as cyclic or straight-chain ethers such as ethyl ether, or a mixture of two or more kinds can be used. Further, examples of the application method of the coating liquid include a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method. The thickness of the charge transport layer thus obtained is preferably 5 to
It is 50 μm, more preferably 10 to 40 μm.

On the other hand, the single-layer type photosensitive layer of the electrophotographic photosensitive member shown in FIGS. 4 and 5 contains the hydroxymetal phthalocyanine of the present invention, a charge transport material and a binder resin.
Examples of the charge transport material and the binder resin include the charge transport material and the binder resin exemplified in the description of the charge transport layer. Further, the single-layer type photosensitive layer may contain a charge generating material other than the hydroxymetal phthalocyanine of the present invention.

The mixing ratio of hydroxymetal phthalocyanine to the charge transporting material in the single-layer type photosensitive layer is preferably 1:10 to 10: 1 by weight and 5: 1 to 1:20 by weight. It is preferable that the mixing ratio of the hydroxy metal phthalocyanine and the binder resin is 5: 1 to 1:20 by weight.

In the step of forming the single-layer type photosensitive layer, a coating solution is prepared in the same manner as the charge generation layer and the charge transport layer, and the coating solution is applied and dried to form the single-layer type photosensitive layer. Can be formed. The thickness of the single-layer type photosensitive layer thus obtained is preferably 5 to 50 μm,
More preferably, it is 10 to 40 μm.

In the electrophotographic photosensitive member according to the present invention, it is preferable to provide a protective layer 26 as shown in FIGS. When the electrophotographic photoreceptor is provided with a protective layer, both the stability against heat, electricity, and chemical substances and the mechanical strength are further improved, and the effect of preventing contamination by water, discharge products, toner, and the like. Tend to be more improved. In addition, the protective layer has a function as a charge transport layer in addition to a function of imparting stability and mechanical strength to the electrophotographic photoreceptor and a function of preventing contaminants from adhering to the surface. The protective layer can be used as it is as the charge transport layer of the laminated photoreceptor.

The material of the protective layer according to the present invention includes the organometallic compounds exemplified in the description of the undercoat layer,
Examples thereof include a silane coupling agent, a binder resin and the like, and further, the charge transporting materials exemplified in the description of the charge transporting layer.

The protective layer according to the present invention is obtained by applying a coating liquid obtained by dispersing the above-mentioned materials in a predetermined solvent onto a predetermined layer (such as a charge generation layer and a charge transport layer) and drying. Can be obtained by Here, examples of the solvent and the coating method used for the coating liquid include the solvent and the coating method exemplified in the description of the charge transport layer. The thickness of the protective layer thus obtained is not particularly limited as long as the photosensitive characteristics of the electrophotographic photoreceptor are not impaired. For example, when a protective layer is provided on the charge transport layer, the thickness is 0.5 to 20 μm. Preferably, 1 to 10
More preferably, it is μm.

(Electrophotographic Apparatus) FIG. 6 is a schematic structural view showing a preferred embodiment of the electrophotographic apparatus of the present invention. FIG.
In the above, the electrophotographic photoreceptor 1 of the present invention is held by a support 8, and the electrophotographic photoreceptor 1 is driven to rotate around the support 9 at a predetermined rotational speed in a direction indicated by an arrow. In the rotation process, the peripheral surface of the electrophotographic photosensitive member 1 is uniformly charged with a predetermined positive or negative potential by the charging member 10 supplied with a voltage from a power supply (not shown). Next, the electrophotographic photosensitive member 1 is subjected to optical image exposure by the image input means 11, and an electrostatic latent image corresponding to the exposure image is formed on the peripheral surface of the electrophotographic photosensitive member 1. Thereafter, a toner image is formed by the developing means 12 with the developer, and the toner image is transferred to the transfer target P by the transfer means 13. The transferred material P after the transfer of the toner image undergoes image fixing by the image fixing means 14 and is printed out as a copy. The electrophotographic photoreceptor 1 after the transfer step is cleaned by the cleaning unit 15 to remove the toner remaining on the peripheral surface thereof, and is repeatedly used for image formation.

Here, as the charging means according to the present invention, for example, a contact type charger using a roller-shaped, brush-shaped, film-shaped or pin-electrode-shaped conductive or semiconductive charging member, or corona discharge is used. And non-contact type chargers such as a scorotron charger and a corotron charger described above.

A roller as a contact-type charger according to the present invention
When using a roller with a charging member,
By bringing the electrical member into contact with the electrophotographic photoreceptor,
Electrophotography of roller-shaped charging member without moving means
It can be rotated at the same peripheral speed as the photoconductor. Also,
Attach predetermined drive means to the roller-shaped charging member,
It may be rotated at a peripheral speed different from the peripheral speed of the photoreceptor
No. Iron, copper, true
Conductivity of brass, stainless steel, aluminum, nickel, etc.
Or a resin molded product in which conductive particles are dispersed.
Which can be used. In addition, the roller-shaped charging member
EPDM, polybutadiene, heavenly
Rubber, polyisobutylene, SBR, CR, NBR,
Recon rubber, urethane rubber, epichlorohydrin rubber,
SBS, thermoplastic elastomer, norbornene rubber,
Rubber such as loro silicone rubber and ethylene oxide rubber
Materials include carbon black, zinc, aluminum, copper,
Metals such as iron, nickel, chromium and titanium, ZnO
-Al_TwoO_Three, SnO_Two-Sb_TwoO_Three, In_TwoO_Three-SnO_Two,
ZnO-TiO_Two, MgO-Al_TwoO_Three, FeO-Ti
O_Two, TiO_Two, SnO_Two, Sb _TwoO_Three, In_TwoO_Three, Zn
Conductive particles such as metal oxides such as O and MgO
Is preferably a material in which semiconductive particles are dispersed.
Furthermore, the material of the resistance layer and the protective layer of the roller-shaped charging member
The conductive particles or semiconductive particles described above.
Kuril resin, cellulose resin, polyamide resin, methoki
Nylon, ethoxymethylated nylon, poly
Urethane resin, polycarbonate resin, polyester tree
Fat, polyethylene resin, polyvinyl resin, polyarelay
Resin, polythiophene resin, PFA, FEP, PET
Such as polyolefin resin and styrene butadiene resin
Those that are dispersed and whose resistance is controlled are preferably used.
You. The resistivity of the resistance layer and the protective layer is preferably 10
^Three-10¹⁴Ωcm, more preferably 10⁶-10¹²Ωc
m, more preferably 10⁷-10¹²Ωcm. Ma
The thickness of each of the resistance layer and the protective layer is preferably 0.1.
01-1000 μm, more preferably 0.1-500 μm
m, more preferably 0.5 to 100 μm. Further
In addition, if necessary, add hindered
Antioxidants such as enols and hindered amines, clay,
Fillers such as kaolin and lubricants such as silicone oil
Can be added. The means to form these layers
Blade coating method, Meyer bar coating
Coating, spray coating, dip coating,
Bead coating method, air knife coating method,
A curtain coating method or the like can be used.

When the electrophotographic photosensitive member is charged by using the above-mentioned contact-type charger, a voltage is applied to the roller-shaped charging member, and the applied voltage is preferably a DC voltage or a voltage obtained by superimposing an AC voltage on a DC voltage. . As the voltage range, the DC voltage is preferably 50 to 2000 V, positive or negative, depending on the required charging potential of the photoreceptor.
More preferably, it is 00V. On the other hand, when the AC voltage is superimposed on the DC voltage, the peak-to-peak voltage is 400 to 18
The voltage is preferably 00 V, more preferably 800 to 1600 V, and even more preferably 1200 to 1600 V. The frequency of the AC voltage to be superimposed is preferably 50 to 20,000 Hz, more preferably 1 to 2000 Hz.
It is 00-5000 Hz.

As an exposure means, a semiconductor laser, an LED (light e
an optical system capable of exposing a light source such as a liquid crystal shutter to a desired image in a desired image form; a developing means using a regular or reversal developer such as a one-component type or a two-component type; And the like; Examples of the transfer device include a contact-type transfer charger using a belt, a roller, a film, a rubber blade, or the like, a scorotron transfer charger using corona discharge, a corotron transfer charger, and the like.

Although not shown in FIG. 6, the electrophotographic apparatus of the present invention may include an intermediate transfer unit. As the intermediate transfer means according to the present invention, those having a structure in which an elastic layer containing rubber, an elastomer, a resin and the like and at least one coating layer are laminated on a conductive support can be used. Materials used as materials include polyurethane resin, polyester resin, polystyrene resin, polyolefin resin, polybutadiene resin, polyamide resin, polyvinyl chloride resin,
Examples thereof include resins in which conductive carbon particles, metal powder, and the like are dispersed and mixed in a resin such as a polyethylene resin or a fluororesin. The shape of the intermediate transfer means may be a roller shape, a belt shape, or the like.

Further, in the present invention, by using the process cartridge of the present invention comprising the above-described electrophotographic photosensitive member of the present invention and at least one member selected from the group consisting of charging means, developing means and cleaning means. In addition, it is possible to efficiently and reliably perform the attachment / detachment work between the predetermined means provided in the process cartridge and the electrophotographic apparatus.

[0059]

EXAMPLES Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 Synthesis of chlorogallium phthalocyanine 30 parts by weight of 1,3-diiminoisoindoline and gallium trichloride
1 part by weight was added to 230 parts by weight of dimethyl sulfoxide,
After reacting at 150 ° C. for 4 hours, the product was separated by filtration, washed with ion-exchanged water, and then the obtained wet cake was dried to obtain 28 parts by weight of chlorogallium phthalocyanine crystal.

(Synthesis of hydroxygallium phthalocyanine) 20 parts by weight of the obtained chlorogallium phthalocyanine crystal was dissolved in 800 parts by weight of 98% concentrated sulfuric acid in an ice bath.
The mixture was stirred for 2 hours to prepare a pigment solution (chlorogallium phthalocyanine concentration: 2.4% by weight). This pigment solution is
The mixture was dropped into a mixed solution of 1500 parts by weight of 25% aqueous ammonia and 500 parts of distilled water over 14 hours to precipitate hydroxygallium phthalocyanine crystals. In this step, the mixed solution was dropped while mechanically stirring constantly. The liquid temperature of the mixed solution at the start of dropping was −3 ° C., the solution temperature in the system during dropping was less than 2 ° C., and the temperature at the end was 1 ° C.

Next, the precipitated crystals are separated by filtration, washed with distilled water until the conductivity of the filtrate becomes less than 20 μS / cm, and the obtained wet cake is dried under vacuum at 50 ° C. for 48 hours. , Hydroxygallium phthalocyanine crystal 19
Parts by weight were obtained. FIG. 7 shows a powder X-ray diffraction diagram of the obtained hydroxygallium phthalocyanine crystal.

Further, a transmission electron microscope (H-9000,
The particle shape of the obtained crystal was observed by Hitachi, Ltd.). As a result, it was confirmed that the obtained hydroxygallium phthalocyanine crystal was fine and uniform with the formation of coarse particles being sufficiently suppressed, and the average particle size was 0.15 μm.

[0064] Example 2 Dimethyl formamide 110 parts by weight of hydroxygallium phthalocyanine crystals 10 parts by weight obtained in Example 1 (solvent treatment of hydroxygallium phthalocyanine), 5 m
After milling for 24 hours together with 250 parts by weight of mφ glass beads, the crystals were separated, washed with 900 parts of distilled water, and the obtained wet cake was dried under vacuum at 80 ° C. for 24 hours to obtain hydroxygallium phthalocyanine crystals. One part by weight was obtained. FIG. 8 shows a powder X-ray diffraction pattern of the obtained hydroxygallium phthalocyanine crystal.

In the same manner as in Example 1, the grain shape of the obtained crystal was observed with a transmission electron microscope. As a result, it was confirmed that the obtained hydroxygallium phthalocyanine crystal was fine and uniform with the formation of coarse particles being sufficiently suppressed, and the average particle size was 0.15 μm.

(Preparation of Electrophotographic Photoreceptor) 8 parts by weight of polyvinyl butyral (trade name: Eslec BM-1, manufactured by Sekisui Chemical Co., Ltd.) was added to 152 parts by weight of n-butyl alcohol, and the mixture was stirred and 5% by weight. Was prepared. Next, a 50% toluene solution of tributoxy zirconium acetylacetonate (trade name: ZC
540, manufactured by Matsumoto Kosho Co., Ltd.), 10 parts by weight of γ-aminopropyltriethoxysilane (trade name: A1100, manufactured by Nippon Unicar Co., Ltd.) and 130 parts by weight of n-butyl alcohol. Then, the mixture was added to the above polyvinyl butyral solution and stirred with a stirrer to prepare a coating liquid for forming an undercoat layer. This coating solution is
Dip coating on aluminum pipe of × 319mm, 150 ℃
For 10 minutes to form an undercoat layer having a thickness of 1.0 μm.

Next, the above hydroxygallium phthalocyanine crystal 1 was added to a solution in which 1 part by weight of polyvinyl butyral (trade name: ESLEC BM-S, manufactured by Sekisui Chemical Co., Ltd.) was previously dissolved in 49 parts by weight of n-butyl acetate. A part by weight was added thereto, and a dispersion treatment was performed for 1.5 hours using a dyno mill. This dispersion was diluted with n-butyl acetate to prepare a charge generation layer forming coating solution having a solid content of 3.0% by weight. The obtained coating liquid is applied to the undercoat layer by a ring coating machine,
The resultant was dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.20 μm. Further, when the crystal form of the hydroxygallium phthalocyanine crystal after the dispersion treatment was examined by X-ray diffraction, it was confirmed that the crystal form was the same as that before the dispersion, and there was no change.

Further, N, N'-bis- (p-tolyl)-
N, N'-bis- (p-ethylphenyl) -3,3'-
4 parts by weight of dimethylbenzidine and 6 parts by weight of polycarbonate Z resin are dissolved in 40 parts of monochlorobenzene, and the resulting solution is applied on the above-mentioned charge generating layer by a dip coating apparatus, and heated and dried at 115 ° C. for 60 minutes to form a film. A charge transport layer having a thickness of 18 μm was formed to obtain a desired electrophotographic photosensitive member.

(Preparation of Electrophotographic Apparatus) Using the obtained electrophotographic photosensitive member, an electrophotographic apparatus having the configuration shown in FIG. 6 was prepared, and the following evaluation tests were performed. Note that a scorotron charger was used as a charging unit.

(Charging Characteristics Evaluation Test) Grid Applied Voltage−
The electrophotographic photosensitive member is charged at 600 V (Step A), and one second later, 7.0 mJ using a 780 mm semiconductor laser.
/ M ² to discharge electricity (Step B), and after 3 seconds, irradiate 50 mJ / m ² red LED light to remove electricity (Step C).
And the dark decay (V0-V1) one second after Step A was measured. Table 1 shows the obtained results.

Incidentally, in the column of “initial potential” in Table 1, 2
When the above measurement was performed under the conditions of 0 ° C. and 50% RH,
The charge potentials in steps A to C in the first process are shown. A large absolute value of the potential in Step A means that the electrophotographic photosensitive member has a high accepting potential and can increase contrast; a small absolute value of the potential in Step B means that the electrophotographic photosensitive member has high sensitivity. Means;
The fact that the absolute value of the potential in the step C is small means that the residual potential of the electrophotographic photosensitive member is small, and that image memory and fog are small.

In Table 1, the column “Environmental stability”
The initial potential measured under the conditions of 20 ° C. and 50% RH is used as a reference value, and the conditions are 10 ° C. and 15% RH or 30 ° C. and 85%
The difference between the initial potential measured under the RH condition and the reference value is shown. The values in Table 1 are at 10 ° C., 15% RH or 30%.
This is the value of the initial potential measured under the condition of 85 ° C. and 85% RH, which has a larger variation from the reference value.

Further, in the column of “potential fluctuation after 10,000 times” in Table 1, the difference between the 10,000th time and the initial potential when the above process was repeated 10,000 times under the conditions of 20 ° C. and 50% RH is shown. Indicated.

(10000-sheet print test) 30 ° C., 8
A print test for 10,000 sheets was performed under 5% RH conditions, and the occurrence of black spots in the obtained image quality was observed. Table 1 shows the obtained results.

Example 3 (Synthesis of 1,2-di (oxogallium phthalocyaninyl) ethane) 10 parts by weight of gallium chloride was added to 75 ml of toluene.
Then, 33 ml of a methanol solution of 28% sodium methoxide was added dropwise while cooling. After stirring for about 30 minutes, 33.5 parts by weight of phthalonitrile and 150 ml of ethylene glycol were added, and the mixture was stirred at 180 ° C. for 24 hours under a nitrogen atmosphere. The product is filtered and then N, N-
After sequentially washing with dimethylformamide and distilled water and drying, 27.8 parts by weight of 1,2-di (oxogallium phthalocyaninyl) ethane crystal was obtained.

(Synthesis of hydroxygallium gallium phthalocyanine) 20 parts by weight of the obtained 1,2-di (oxogallium phthalocyaninyl) ethane crystal was mixed in an ice bath with 98 parts by weight.
After dissolving in 800 parts by weight of concentrated sulfuric acid and stirring for 2 hours, the solution was filtered through a glass filter to obtain a pigment solution (1, 1).
2-di (oxogallium phthalocyaninyl) ethane concentration: 2.4% by weight). This pigment solution was added dropwise over 14 hours to a mixed solution of 1500 parts by weight of 25% aqueous ammonia and 500 parts by weight of distilled water to precipitate hydroxygallium phthalocyanine crystals. In this step, the mixed solution was dropped while mechanically stirring constantly. The liquid temperature of the mixed solution at the start of dropping was −3 ° C., the solution temperature in the system during dropping was less than 3 ° C., and the temperature at the end was 0 ° C.

Next, the precipitated crystals are separated by filtration, washed with distilled water until the conductivity of the filtrate is less than ²⁰ μS / m ² , and the obtained wet cake is dried under vacuum at 50 ° C. for 48 hours. 19 parts by weight of hydroxygallium phthalocyanine crystals were obtained. FIG. 9 shows a powder X-ray diffraction pattern of the obtained hydroxygallium phthalocyanine crystal.

In the same manner as in Example 1, the grain shape of the obtained crystal was observed with a transmission electron microscope. . The obtained electron micrograph is shown in FIG. It was confirmed that the obtained hydroxygallium phthalocyanine crystal was fine and uniform with the formation of coarse particles being sufficiently suppressed, and the average particle size was 0.10 μm.

Example 4 (Solvent treatment of hydroxygallium phthalocyanine) 10 parts by weight of the hydroxygallium phthalocyanine crystal obtained in Example 3 was mixed with 110 parts by weight of dimethylformamide and 5 m
After milling with 250 parts by weight of mφ glass beads for 24 hours, the crystals were separated, washed with 900 parts of distilled water, and the obtained wet cake was dried at 80 ° C. under vacuum for 24 hours to obtain hydroxygallium phthalocyanine crystals. 8 parts by weight were obtained. FIG. 11 shows a powder X-ray diffraction pattern of the obtained hydroxygallium phthalocyanine crystal.

Further, in the same manner as in Example 1, the grain shape of the obtained crystal was observed with a transmission electron microscope. As a result, it was confirmed that the obtained hydroxygallium phthalocyanine crystal was fine and uniform with the formation of coarse particles being sufficiently suppressed, and the average particle size was 0.10 μm.

(Preparation of Electrophotographic Photoreceptor and Electrophotographic Apparatus) An electrophotographic photoreceptor and an electrophotographic apparatus were prepared in the same manner as in Example 2 except that the hydroxygallium phthalocyanine crystal thus obtained was used. Then, a charging characteristic evaluation test and a 10,000-sheet print test were performed. Table 1 shows the obtained results.

Comparative Example 1 20 parts by weight of a chlorogallium phthalocyanine crystal obtained in the same manner as in Example 1 was dissolved in 480 parts by weight of 98% concentrated sulfuric acid in an ice bath, and stirred for 2 hours to prepare a pigment solution. Pigment concentration 4 wt%). The pigment solution was added dropwise over 6 hours to a mixed solution of 1500 parts by weight of 20% aqueous ammonia and 500 parts by weight of distilled water to precipitate hydroxygallium phthalocyanine crystals. In this step, the mixed solution was dropped while mechanically stirring constantly. The liquid temperature of the mixed solution at the start of dropping is -3 ° C, and the temperature of the solution in the system during dropping is 5 ° C.
The temperature at the end was less than 0 ° C. and 38 ° C.

Next, the precipitated crystals are separated by filtration, washed with distilled water until the conductivity of the filtrate is less than ²⁰ μS / m ² , and the obtained wet cake is dried under vacuum at 50 ° C. for 48 hours. 19 parts by weight of hydroxygallium phthalocyanine crystals were obtained. FIG. 12 shows a powder X-ray diffraction pattern of the obtained hydroxygallium phthalocyanine crystal.

Further, in the same manner as in Example 1, the grain shape of the obtained crystal was observed with a transmission electron microscope. As a result, it was confirmed that the obtained hydroxygallium phthalocyanine crystal was a non-uniform crystal containing coarse particles having a particle diameter of 0.7 μm or more, and the average particle diameter was 0.5 μm.

Comparative Example 2 (Solvent treatment of hydroxygallium phthalocyanine) The procedure of Example 1 was repeated, except that the hydroxygallium phthalocyanine crystal obtained in Example 1 was replaced with 10 parts by weight of the hydroxygallium phthalocyanine crystal obtained in Example 1. 2
And 8.8 parts by weight of hydroxygallium phthalocyanine crystal was obtained. FIG. 13 shows a powder X-ray diffraction pattern of the obtained hydroxygallium phthalocyanine crystal.

When the grain shape of the obtained crystal was observed with a transmission electron microscope in the same manner as in Example 1,
It was confirmed that the obtained hydroxygallium phthalocyanine crystal was a non-uniform crystal containing coarse particles having a particle size of 0.5 μm or more, and the average particle size was 0.4 μm.

(Preparation of Electrophotographic Photoreceptor and Electrophotographic Apparatus) An electrophotographic photoreceptor and an electrophotographic apparatus were prepared in the same manner as in Example 2 except that the hydroxygallium phthalocyanine crystal thus obtained was used. Then, a charging characteristic evaluation test and a 10,000-sheet print test were performed. Table 1 shows the obtained results.

Comparative Example 3 20 parts by weight of 1,2-di (oxogallium phthalocyaninyl) ethane crystal obtained in the same manner as in Example 3 was dissolved in 480 parts by weight of 98% concentrated sulfuric acid in an ice bath. After stirring for 2 hours, the solution was filtered through a glass filter to obtain a pigment solution (1,2-di (oxogallium phthalocyaninyl) ethane concentration: 4.0% by weight). The pigment solution was added dropwise over 6 hours to a mixed solution of 1500 parts by weight of 25% aqueous ammonia and 500 parts by weight of distilled water to precipitate hydroxygallium phthalocyanine crystals. In this step, the mixed solution was dropped while mechanically stirring constantly. The liquid temperature of the mixed solution at the start of the dropping was −3 ° C., the solution temperature in the system during the dropping was less than 50 ° C., and the temperature at the end was 40 ° C.

Next, the precipitated crystals are separated by filtration, washed with distilled water until the conductivity of the filtrate is less than ²⁰ μS / m ² , and the obtained wet cake is dried under vacuum at 50 ° C. for 48 hours. 19 parts by weight of hydroxygallium phthalocyanine crystals were obtained. FIG. 14 shows a powder X-ray diffraction diagram of the obtained hydroxygallium phthalocyanine crystal.

Further, in the same manner as in Example 1, the grain shape of the obtained crystal was observed with a transmission electron microscope. The obtained electron micrograph is shown in FIG. It was confirmed that the obtained hydroxygallium phthalocyanine crystal was a non-uniform crystal containing coarse particles having a particle size of 0.7 μm or more, and the average particle size was 0.5 μm.

Comparative Example 4 (Solvent treatment of hydroxygallium phthalocyanine) The procedure of Example 3 was repeated except that the hydroxygallium phthalocyanine crystal obtained in Example 3 was replaced by 10 parts by weight of the hydroxygallium phthalocyanine crystal obtained in Example 3. 4
Was carried out in the same manner as described above to obtain 9.0 parts by weight of hydroxygallium phthalocyanine crystal. FIG. 16 shows a powder X-ray diffraction pattern of the obtained hydroxygallium phthalocyanine crystal.

When the grain shape of the obtained crystal was observed with a transmission electron microscope in the same manner as in Example 1,
It was confirmed that the obtained hydroxygallium phthalocyanine crystal was a non-uniform crystal containing coarse particles having a particle size of 0.5 μm or more, and the average particle size was 0.3 μm.

(Preparation of Electrophotographic Photoreceptor and Electrophotographic Apparatus) An electrophotographic photoreceptor and an electrophotographic apparatus were prepared in the same manner as in Example 2 except that the thus obtained hydroxygallium phthalocyanine crystal was used. Then, a charging characteristic evaluation test and a 10,000-sheet print test were performed. Table 1 shows the obtained results.

Comparative Example 5 Hydroxygallium phthalocyanine was synthesized in the same manner as in Comparative Example 3 except that the 1,2-di (oxogallium phthalocyaninyl) ethane concentration in the pigment solution was changed to 3.2% by weight. The diffraction peak in the powder X-ray diffraction pattern of the obtained hydroxygallium phthalocyanine was similar to that of Comparative Example 3.

When the grain shape of the obtained crystal was observed by a transmission electron microscope in the same manner as in Example 1, the obtained hydroxygallium phthalocyanine crystal had a particle size of 0.1 mm.
It was confirmed that the crystal was a non-uniform crystal containing coarse particles of 7 μm or more, and the average particle size was 0.5 μm.

Comparative Example 6 (Solvent treatment of hydroxygallium phthalocyanine) Example 10 was repeated except that the hydroxygallium phthalocyanine crystal obtained in Example 3 was replaced with 10 parts by weight of the hydroxygallium phthalocyanine crystal obtained in Example 3. 4
Was carried out in the same manner as described above to obtain 9.0 parts by weight of hydroxygallium phthalocyanine crystal. The diffraction peak of the obtained hydroxygallium phthalocyanine in the powder X-ray diffraction pattern was similar to that of Comparative Example 4.

Further, when the grain shape of the obtained crystal was observed with a transmission electron microscope in the same manner as in Example 1,
It was confirmed that the obtained hydroxygallium phthalocyanine crystal was a non-uniform crystal containing coarse particles having a particle size of 0.5 μm or more, and the average particle size was 0.28 μm.

(Preparation of Electrophotographic Photoreceptor and Electrophotographic Apparatus) An electrophotographic photoreceptor and an electrophotographic apparatus were prepared in the same manner as in Example 2 except that the hydroxygallium phthalocyanine crystal thus obtained was used. Then, a charging characteristic evaluation test and a 10,000-sheet print test were performed. Table 1 shows the obtained results.

[0099]

[Table 1]

As shown in Table 1, the electrophotographic photoreceptors obtained in Examples 2 and 4 exhibited excellent charging characteristics, and the electrophotographic apparatus using these electrophotographic photoreceptors produced black spots. Was obtained, and a good image quality was sufficiently suppressed.

[0101]

As described above, according to the production method of the present invention, it is possible to efficiently and surely obtain hydroxymetal phthalocyanine having a sufficiently small and uniform average particle size. Accordingly, the production method of the present invention and the hydroxymetal phthalocyanine of the present invention obtained thereby,
Further, the electrophotographic photosensitive member, the process cartridge and the electrophotographic apparatus using the same can achieve sufficient light sensitivity and sufficient durability, and can obtain stable image quality for a long period without causing image quality defects. Very useful in that respect.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a preferred embodiment of an electrophotographic photoreceptor of the present invention.

FIG. 2 is a schematic sectional view showing a preferred embodiment of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic sectional view showing a preferred embodiment of the electrophotographic photoreceptor of the present invention.

FIG. 4 is a schematic sectional view showing a preferred embodiment of the electrophotographic photosensitive member of the present invention.

FIG. 5 is a schematic sectional view showing a preferred embodiment of the electrophotographic photosensitive member of the present invention.

FIG. 6 is a schematic configuration diagram showing a preferred embodiment of the electrophotographic apparatus of the present invention.

FIG. 7 is a powder X-ray diffraction diagram of hydroxygallium phthalocyanine obtained in Example 1.

FIG. 8 is a powder X-ray diffraction diagram of hydroxygallium phthalocyanine obtained in Example 2.

FIG. 9 is a powder X-ray diffraction chart of hydroxygallium phthalocyanine obtained in Example 3.

FIG. 10 is an electron micrograph of hydroxygallium phthalocyanine obtained in Example 3.

FIG. 11 is a powder X-ray diffraction chart of hydroxygallium phthalocyanine obtained in Example 4.

FIG. 12 is a powder X-ray diffraction chart of hydroxygallium phthalocyanine obtained in Comparative Example 1.

13 is a powder X-ray diffraction chart of hydroxygallium phthalocyanine obtained in Comparative Example 2. FIG.

14 is a powder X-ray diffraction chart of hydroxygallium phthalocyanine obtained in Comparative Example 3. FIG.

FIG. 15 is an electron micrograph of hydroxygallium phthalocyanine obtained in Comparative Example 3.

FIG. 16 is a powder X-ray diffraction diagram of hydroxygallium phthalocyanine obtained in Comparative Example 4.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photoreceptor, 2 ... Conductive support, 3 ... Photosensitive layer,
4 ... undercoat layer, 5 ... charge generation layer, 6 ... charge transport layer, 7 ...
Protective layer, 8 single-layer type photosensitive layer, 9 support, 10 charging means, 11 image input means, 12 developing means, 13 transfer means, 14 image fixing means, 15 cleaning means.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Katsumi Nukata 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (Reference) 2H068 AA19 BA39 EA05 FA27

Claims (5)

[Claims] 1. Metal phthalocyanine having no hydroxyl group bonded to a central metal, based on the total amount of the pigment solution.
Producing a hydroxymetal phthalocyanine, comprising: dissolving in an acid so as to be 0% by weight or less to obtain a pigment solution; and adding the pigment solution to a predetermined solvent to precipitate hydroxymetal phthalocyanine. Method. 2. A hydroxymetal phthalocyanine obtained by the production method according to claim 1 and having an average particle size of 0.18 μm or less. 3. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer disposed on the conductive support, wherein the photosensitive layer contains the hydroxymetal phthalocyanine according to claim 2. An electrophotographic photoreceptor, comprising: 4. An electrophotographic photosensitive member according to claim 3, charging means for charging said electrophotographic photosensitive member, and a toner image formed by developing an electrostatic latent image formed on said electrophotographic photosensitive member with toner. And a cleaning means for removing toner remaining on the surface of the electrophotographic photoreceptor. 5. An electrophotographic photosensitive member according to claim 3, charging means for charging said electrophotographic photosensitive member, image input means for forming an electrostatic latent image on said electrophotographic photosensitive member, and said electronic device. Developing means for developing the electrostatic latent image formed on the photographic photoreceptor with toner to form a toner image; transfer means for transferring the toner image to a transfer-receiving body; remaining on the surface of the electrophotographic photoreceptor An electrophotographic apparatus comprising: a cleaning unit that removes the removed toner.