JP5204945B2 - Method for producing phthalocyanine compound, electrophotographic photosensitive member, electrophotographic photosensitive member cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to a method for producing a phthalocyanine compound, and an electrophotographic photoreceptor, an electrophotographic photoreceptor cartridge, and an image forming apparatus using the phthalocyanine compound produced by the production method.

Phthalocyanine compounds are very useful materials as dyes, pigments, printing inks, catalysts, electronic materials and the like. In particular, in recent years, it has been extensively studied as a material for an electrophotographic photoreceptor, an optical recording material, and a photoelectric conversion material, and some of them have been put into practical use.
In general, phthalocyanine compounds are known to exhibit various crystal forms depending on the production route, production conditions, and treatment method. Moreover, when a phthalocyanine compound is used as a photoelectric conversion material, it is also known that the photoelectric conversion characteristics vary greatly depending on the crystal type (see, for example, Non-Patent Document 1).

  In electrophotographic photoreceptors that are photoelectric conversion devices, phthalocyanine compounds have been found to be very useful. For example, metal free phthalocyanine, oxytitanium phthalocyanine, chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, chloroindium phthalocyanine, hydroxyindium phthalocyanine, dichlorotin phthalocyanine, dihydroxysilicon phthalocyanine, etc. Various crystal types have been reported. In particular, phthalocyanine compounds having a phthalocyanine molecular structure having a shuttlecock structure are known to have excellent electrophotographic photoreceptor characteristics (hereinafter, simply referred to as “photoreceptor characteristics”), and are particularly vigorously studied. Has been done. For example, Patent Document 1 mentions chlorogallium phthalocyanine as an example of a phthalocyanine compound having a trivalent central metal and a shuttlecock structure.

  Conventionally, as a method for producing chlorogallium phthalocyanine, a method of reacting gallium trichloride and 1,3-diiminoisoindoline without solvent (see, for example, Non-Patent Document 2), gallium trichloride and phthalonitrile are reacted. A method of reacting without solvent (for example, see Patent Document 2), a method of reacting gallium trichloride and phthalonitrile in butyl cellosolve using 1,8-diazabicyclo [5.4.0] -7-undecene as a catalyst (for example, Patent Reference 3), a method of reacting gallium trichloride and phthalonitrile in quinoline (for example, see Non-patent Document 3), and reacting gallium trichloride and 1,3-diiminoisoindoline in an aprotic polar solvent. (For example, see Patent Document 4), gallium trichloride and 1,3-diiminoisoindoline are converted to dimethylsulfo A method of reacting in a sid and dropping a hypochlorous acid solution after the reaction (see, for example, Patent Document 5), reacting phthalonitrile or 1,3-diiminoisoindoline with gallium trichloride in α-chloronaphthalene A method (see Patent Document 6) is known.

Japanese Patent Laid-Open No. 5-98181 Japanese Patent Publication No. 3-30854 Japanese Patent Laid-Open No. 1-222159 Japanese Patent Laid-Open No. 7-252429 JP-A-11-217512 JP 2000-344778 A The Journal of Electrophotographic Society, 1990, VOL. 29, NO. 3,250-258 pages D. C. R. Acad. Sci. , 1956, 242, 1026 Inorg. Chem. 1980, 19, 3131

  However, when a phthalocyanine compound is produced by carrying out the reaction under a solvent-free condition, a by-product is generated, so that the product becomes a mixture of various products, which is not preferable. For example, as described in Patent Document 2, when chlorogallium phthalocyanine is produced under solvent-free conditions, chlorination occurs in the phthalocyanine ring, and the product becomes a mixture with various halogen-substituted compounds. When the produced phthalocyanine compound is used for an electrophotographic photoreceptor, preferred photoreceptor characteristics are difficult to obtain.

  On the other hand, even when the reaction is carried out using a solvent, the characteristics of the photoreceptor when the obtained phthalocyanine compound is used for an electrophotographic photoreceptor are greatly affected by the solvent and the synthesis conditions during the production of the phthalocyanine compound. For example, in the case of producing chlorogallium phthalocyanine in a quinoline solvent, it is necessary to control the temperature rise of the reaction system in order to obtain a desired product, so that the operation becomes complicated (for example, JP-A-7-207171). No. publication).

  Further, as described in Patent Document 1, in the method of reacting gallium trichloride and 1,3-diiminoisoindoline in a quinoline solvent, a phthalocyanine compound produced thereby is used for an electrophotographic photoreceptor. Although there was no problem in the characteristics of the photoconductor, the variation among the production lots was very large. For this reason, in order to eliminate the above-described variation, it is necessary to precisely control the manufacturing process.

  Furthermore, as described in Patent Document 4, in the method of reacting gallium trichloride and 1,3-diiminoisoindoline in a dimethyl sulfoxide solvent, dimethyl sulfoxide is very unstable in a high temperature environment. A decomposition reaction occurs during the high temperature reaction, and dimethyl mercaptan and dimethyl sulfide are produced as by-products. In order to remove this by-product and to increase safety during production, a post-reaction treatment as described in Patent Document 5 is required, and the production process is complicated.

Further, as described in Patent Document 6, in the method of reacting phthalonitrile or 1,3-diiminoisoindoline and gallium trichloride in α-chloronaphthalene, a substance that forms a phthalocyanine ring during production (phthalophthalene). Nitrile or 1,3-diiminoisoindoline) and the difference in the charging ratio of the metal salt, the characteristics of the electrophotographic photoreceptor using the produced phthalocyanine compound, and the yield of the produced phthalocyanine compound It has fluctuated greatly. Therefore, it is necessary to precisely set the raw material charging ratio at the time of manufacture.
Furthermore, the phthalocyanine compound obtained by the conventional production method is not sufficiently satisfactory in the photoreceptor characteristics when used in an electrophotographic photoreceptor.

  The present invention was devised in view of the above problems, and a phthalocyanine compound that exhibits particularly excellent photoreceptor characteristics, such as initial chargeability and sensitivity, when used in an electrophotographic photoreceptor can be easily obtained. It is an object of the present invention to provide a method for producing a phthalocyanine compound that can be produced, and an electrophotographic photosensitive member, an electrophotographic photosensitive member cartridge, and an image forming apparatus using the same.

  The inventor of the present invention has intensively studied to solve the above-mentioned problems. As a result, the present invention can be applied to an electrophotographic photoreceptor by a simple method of reacting a compound capable of forming a phthalocyanine ring with a trivalent metal salt in a nitro compound. The present inventors have found that a phthalocyanine compound exhibiting excellent photoreceptor characteristics can be produced when it is present.

That is, the gist of the present invention, phthalonitriles, and 1,3-diisopropyl and amino isoindoline compound or Ranaru compound capable of forming at least one phthalocyanine ring selected from the group, and a gallium trichloride, nitrobenzenes in characterized in that the reaction consists in the production method of the chlorogallium phthalocyanine compound (claim 1).

Another gist of the present invention resides in an electrophotographic photoreceptor comprising a photosensitive layer containing a chlorogallium phthalocyanine compound produced by the above production method (claim 2 ).
Furthermore, another gist of the present invention is the above-described electrophotographic photosensitive member, a charging unit for charging the electrophotographic photosensitive member, an exposure unit for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, An electrophotographic photosensitive device comprising: a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member; and a cleaning unit that removes the developer from the photosensitive member. It exists in a body cartridge (Claim 3 ).

Still another subject matter of the present invention is the above-described electrophotographic photosensitive member, a charging unit for charging the electrophotographic photosensitive member, and an exposure unit for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image. When, characterized by comprising a developing unit for developing an electrostatic latent image formed on the electrophotographic photosensitive member, it lies in the image forming apparatus (claim 4).

  According to the method for producing a phthalocyanine compound of the present invention, it is possible to easily produce a phthalocyanine compound that exhibits particularly excellent photoreceptor characteristics such as initial chargeability and sensitivity when used in an electrophotographic photoreceptor. Can do. In addition, by using a phthalocyanine compound produced by this production method, an electrophotographic photoreceptor having particularly excellent photoreceptor characteristics, such as initial chargeability and sensitivity, and an electrophotographic photoreceptor using the same A cartridge and an image forming apparatus can be obtained.

Hereinafter, the present invention will be described in detail with reference to embodiments. However, the present invention is not limited to the following embodiments, and may be arbitrarily modified without departing from the gist of the present invention. it can.
[I. Method for producing phthalocyanine compound]
The method for producing the phthalocyanine compound of the present invention (hereinafter, appropriately referred to as “the method of the present invention”) includes a compound capable of forming a phthalocyanine ring (hereinafter, appropriately referred to as “phthalocyanine ring-forming compound”), a trivalent metal salt, Is reacted in a nitro compound to obtain a phthalocyanine compound.

[1. Phthalocyanine compound]
As for the phthalocyanine compound that can be produced by the production method of the present invention (hereinafter referred to as “the phthalocyanine compound of the present invention” as appropriate), any phthalocyanine compound can be produced as long as the valence of the central metal is trivalent. is there.
Examples of the phthalocyanine compound whose central metal is trivalent include a phthalocyanine compound having a group 13 element in the long-period periodic table at the center of the phthalocyanine ring. Specific examples thereof include phthalocyanine compounds in which a halogen atom is bonded to a central metal such as chloroaluminum phthalocyanine, chlorogallium phthalocyanine, chloroindium phthalocyanine, bromoaluminum phthalocyanine, bromogallium phthalocyanine, bromoindium phthalocyanine; methoxyaluminum phthalocyanine, methoxygallium phthalocyanine, Examples thereof include phthalocyanine having an alkoxy group bonded to a central metal such as ethoxygallium phthalocyanine and methoxyindium phthalocyanine. Of these, chlorogallium phthalocyanine, chloroindium phthalocyanine, and methoxygallium phthalocyanine, which can exhibit excellent photoreceptor characteristics when used in an electrophotographic photoreceptor, are preferable. Moreover, at the time of manufacture, 1 type of phthalocyanine compound may be manufactured independently, and 2 or more types may be manufactured by arbitrary combinations and a ratio.

[2. Nitro compounds]
The nitro compound used in the production method of the present invention functions as a reaction medium for the reaction between a phthalocyanine ring-forming compound and a trivalent metal salt. There is no other limitation as long as it is a compound containing a nitro group, and any compound can be used. Specific examples thereof include aliphatics such as nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, 1-nitrobutane, 3-nitro-2-butanol, 1-nitropentane, and 3-nitro-2-pentanol. Aromatic nitro compounds such as nitro compounds, nitrobenzene, dinitrobenzene and the like can be mentioned. The nitro compound may have an arbitrary substituent as long as the above reaction is not adversely affected.

  Among these, a nitro compound having a boiling point of 130 ° C. or higher is preferable from the viewpoint of securing appropriate reaction conditions during the synthesis of the phthalocyanine compound. Further, since the phthalocyanine ring-forming compound is an aromatic compound, it is preferable to use an aromatic nitro compound in consideration of the affinity between the nitro compound as a reaction medium and the phthalocyanine ring-forming compound. Examples of preferred aromatic nitro compounds include nitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrotoluene, o-nitroanisole, m-nitroanisole, p-nitroanisole, o-nitrochlorobenzene, m-chloronitrobenzene, p -Unsubstituted, monosubstituted, disubstituted nitrobenzenes such as chloronitrobenzene, 1,2-dimethoxy-4-nitrobenzene, nitro-o-xylene, 2-nitrodiphenyl ether, 4-nitrobenzophenone, 1-nitronaphthalene, 2- And nitronaphthalenes such as nitronaphthalene.

Further, in consideration of handling at the time of production, the nitro compound is preferably in a liquid state at room temperature, more specifically, at 20 ° C. and atmospheric pressure, and at least at the temperature and atmospheric pressure when synthesizing the phthalocyanine compound. It is preferably a liquid. Further, as the nitro compound, those having a boiling point of usually 100 ° C. or higher are used, preferably those having a boiling point of 130 ° C. or higher, more preferably those having a boiling point of 200 ° C. or higher. Specific examples include nitrobenzenes such as nitrobenzene, o-nitrotoluene, m-nitrotoluene, o-nitroanisole, m-nitroanisole, and nitro-o-xylene.
In consideration of production costs, nitrobenzene, o-nitrotoluene, and o-nitroanisole are more preferable.

  In addition, a nitro compound may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Furthermore, you may mix and use the well-known solvent used with the manufacturing method of another phthalocyanine compound by arbitrary combinations and a ratio.

[3. Phthalocyanine ring-forming compound]
The phthalocyanine ring-forming compound used in the production method of the present invention is not particularly limited as long as it is a compound that can form a phthalocyanine ring by reaction, and any compound can be used.

  Specific examples thereof include phthalonitriles such as phthalonitrile, 4-methylphthalonitrile, 4-fluorophthalonitrile, 3-nitrophthalonitrile; 1,3-diiminoisoindoline, 1,3-diimino-5-methyl. 1,3-diiminoisoindolines such as isoindoline, 1,3-diimino-4-nitroisoindoline, 1,3-diimino-5-fluoroisoindoline; 4-methylphthalic anhydride, 3-nitrophthalic anhydride Examples thereof include phthalic anhydrides such as acid and 4-fluorophthalic anhydride; phthalimides such as 3-methylphthalimide, 4-nitrophthalimide and 4-fluorophthalimide. Among these, phthalonitriles, 1,3-diiminoisoindolines, and phthalic anhydrides are preferable from the viewpoint of reactivity when forming a phthalocyanine ring. Furthermore, since the photoreceptor characteristics when the obtained phthalocyanine compound of the present invention is used for an electrophotographic photoreceptor greatly depend on the production route, considering the influence of the production route on the photoreceptor characteristics, phthalonitriles, 1 1,3-diiminoisoindolines are more preferred.

  Moreover, the phthalocyanine ring forming compound may have a substituent. The type of the substituent is arbitrary, but a group that is inert to the reaction for forming a phthalocyanine ring is preferable. From this viewpoint, specific examples of the substituent include alkyl groups such as methyl group, ethyl group, isopropyl group, tertiary-butyl group and benzyl group; aryl groups such as phenyl group and naphthyl group; fluorine atom, chlorine atom, bromine Halogen atoms such as atoms and iodine atoms; nitro groups; alkoxy groups such as methoxy groups, ethoxy groups, isopropyl groups, tertiary-butoxy groups and benzyloxy groups; aryloxy groups such as phenoxy groups and naphthoxy groups; methylthio groups and ethylthio groups Thioalkyl groups such as isopropylthio group, tertiary-butylthio group, and benzylthio group; thioaryl groups such as phenylthio group and naphthylthio group are preferable.

  Further, when the phthalocyanine compound of the present invention is used for an electrophotographic photoreceptor, carbon such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is considered in consideration of the influence of substituents on the photoreceptor characteristics of the electrophotographic photoreceptor. A C 1-3 alkyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a nitro group is preferred. Among these, C1-C3 alkyl groups, such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, are more preferable.

  In the case of producing a phthalocyanine compound by reacting a phthalocyanine ring-forming compound with a trivalent metal salt in the presence of a nitro compound, the reason for this is not clear, but the effect of the present invention appears remarkably. The ring-forming compound preferably has a substituent. In addition, 1 substituent may be substituted independently and 2 or more may be substituted by arbitrary combinations and ratios. Moreover, a phthalocyanine ring formation compound may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[4. Metal salt]
There is no restriction | limiting in the trivalent metal salt used in the manufacturing method of this invention, Arbitrary metal salts can be used if the valence of a metal is trivalent. Specific examples thereof include metal chlorides such as aluminum trichloride, gallium trichloride and indium trichloride; metal bromides such as aluminum bromide, gallium tribromide and indium tribromide; aluminum triiodide and gallium triiodide. Metal iodides such as indium triiodide; metal alkoxide compounds such as aluminum trimethoxide, gallium trimethoxide, indium trimethoxide, aluminum triethoxide, gallium triethoxide, indium triethoxide; gallium triacetylacetate And metal acetylacetonate compounds such as indium triacetylacetonate. Among them, due to the versatility of the reagent, aluminum trichloride, gallium trichloride, indium trichloride, aluminum tribromide, gallium tribromide, indium tribromide, aluminum trimethoxide, gallium trimethoxide, indium trimethoxide, Aluminum triethoxide, gallium triethoxide, indium triethoxide, etc. are preferable, and considering the characteristics of the photoreceptor when the obtained phthalocyanine compound is used in an electrophotographic photoreceptor, aluminum trichloride, gallium trichloride, indium trichloride Etc. are more preferable.
In addition, a metal salt may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[5. Reaction conditions]
In the production method of the present invention, the specific reaction conditions are not limited as long as a phthalocyanine ring-forming compound and a trivalent metal salt can be reacted in a nitro compound.
Therefore, the charging ratio at the time of reaction of the phthalocyanine ring-forming compound and the trivalent metal salt is arbitrary, but considering the dispersibility during the reaction of the resulting phthalocyanine compound, the phthalocyanine ring-forming compound is a trivalent metal salt. On the other hand, the number of moles is usually 2.0 times or more, and if the metal salt is too much, the purity of the phthalocyanine compound is lowered, so 3.0 times or more is preferable. In consideration of the yield of the obtained phthalocyanine compound, it is usually 6.0 times or less, and 5.0 times or less is preferable in consideration of production cost.

  Further, the amount of the nitro compound used in the reaction is arbitrary, but if it is too small, impurities are easily taken into the obtained phthalocyanine compound, and therefore usually 2 parts by weight or more with respect to 1 part by weight of the phthalocyanine ring-forming compound. In view of dispersibility of the resulting phthalocyanine compound, 3 parts by weight or more is preferable. The reaction for forming a phthalocyanine ring is a condensation reaction, and the yield may decrease when the concentration of the phthalocyanine ring-forming compound in the reaction system decreases. The amount is not more than parts by weight, and if the solvent (reaction medium) is excessively used during the reaction, the productivity may be lowered.

  Furthermore, the reaction temperature is arbitrary, but if it is too low, the reaction for forming a phthalocyanine ring is slowed, and therefore it is usually 100 ° C. or higher, and 130 ° C. or higher is preferable in consideration of the yield of the resulting phthalocyanine compound. In addition, since a nitro compound is used as a reaction solvent, the reaction at an excessively high temperature is usually 230 ° C. or less, considering that the nitro compound becomes unstable. If the reaction temperature is too high, the reaction becomes complicated. Since there is a possibility that the purity of the phthalocyanine compound obtained may be lowered, 210 ° C. or lower is preferable. Furthermore, considering the photoreceptor characteristics when the phthalocyanine compound obtained is used in an electrophotographic photoreceptor, 180 ° C. or lower is more preferable.

  Further, when the phthalocyanine ring-forming compound and the trivalent metal salt are reacted, the reaction may be performed in the presence of another substance in the nitro compound for the purpose of improving the yield and promoting the reaction. Examples of coexisting substances include catalysts used in known methods for producing phthalocyanine compounds, such as quaternary ammonium salts, urea, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU). You may let them.

  Furthermore, some metal salts that are raw materials for phthalocyanine compounds are decomposed by moisture in the air, and the decomposition products may adversely affect the characteristics of the photoreceptor when the phthalocyanine compound is used for an electrophotographic photoreceptor. Therefore, for the purpose of preventing the decomposition, it is preferable to carry out the above reaction in the presence of an inert gas or under an inert gas flow.

[6. Washing]
As described above, the phthalocyanine compound of the present invention can be obtained by reacting a phthalocyanine ring-forming compound with a trivalent metal salt in a nitro compound. The obtained phthalocyanine compound is usually obtained in a crystalline state.
When the phthalocyanine compound is taken out from the nitro compound, the target phthalocyanine compound is usually removed from the reaction system by cooling to room temperature after completion of the reaction and filtering, or by filtering at a temperature of 200 ° C. or lower while hot. Can be sorted.

  However, since the phthalocyanine compound usually contains impurities in the reaction system at the stage of fractionation, it is desirable to remove the impurities. Any method can be used to remove the impurities. For example, the impurities can be removed by washing the collected phthalocyanine compound with some liquid. Although the liquid used for washing | cleaning is arbitrary, an organic solvent, aqueous solution, water etc. can be used, for example.

  Specific examples of organic solvents used for washing include aromatic solvents such as benzene, toluene, xylene, anisole, dimethoxybenzene, tetrahydronaphthalene (tetralin), methylnaphthalene, diphenylmethane; methyl formate, ethyl acetate, n-butyl acetate, etc. Ester solvents; chain or cyclic ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone; chain or cyclic ethers such as diethyl ether, dibutyl ether, tetrahydrofuran; methanol, ethanol, isopropanol, butanol, ethylene glycol, benzyl alcohol, etc. Alcohol solvents; aprotic such as N, N-dimethylformamide, sulfolane, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, N-methyl-2-pyrrolidone Such as sexual solvents.

Specific examples of the aqueous solution used for washing include a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium hydrogen carbonate aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, ammonia water, an ammonium chloride aqueous solution, an acetic acid aqueous solution, a trifluoroacetic acid aqueous solution, Examples include aqueous hydrochloric acid, aqueous sulfuric acid, aqueous nitric acid, and aqueous phosphoric acid.
In addition, the liquid used for washing | cleaning of said organic solvent, aqueous solution, water, etc. may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

[7. Refinement]
Usually, the phthalocyanine compound obtained by the above reaction is obtained in the form of particles. The particle size of the phthalocyanine compound may be too large for use as an electrophotographic photoreceptor. In such a case, refinement is performed in order to obtain a phthalocyanine compound having a desired particle size.
The particle size of the phthalocyanine compound is arbitrary depending on the application, but for example, when used for forming a laminated photosensitive layer, it is usually 1.0 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less. It is desirable. When used for a single-layer type photosensitive layer, it is usually 0.5 μm or less, preferably 0.3 μm or less.

The method of miniaturization is arbitrary, but, for example, a mechanical treatment method such as a grinding method that applies a mechanical force to make the material fine, a chemical method such as an acid pasting method, an acid slurry method, etc. A chemical treatment method for miniaturization can be performed. In addition, the above-described miniaturization method may be performed alone or in any combination of two or more.
Furthermore, after finer processing, it is possible to convert the phthalocyanine compound into a specific crystal form by subjecting the obtained phthalocyanine compound particles to a solvent treatment as described later.

Hereinafter, the grinding method will be described as a specific example of the miniaturization method. When refining by the grinding method, grinding may be performed by a dry method, or grinding may be performed by a wet method in the presence of a solvent.
First, the dry grinding method will be described. As an apparatus to be used, for example, apparatuses such as an automatic mortar, a planetary mill, a vibrating ball mill, a CF mill, a roller mill, a sand mill, and a kneader can be used, but are not limited thereto. It is not a thing. Moreover, there is no restriction | limiting in the grinding media used when refinement | miniaturizing by grinding, Although arbitrary things can be used, For example, glass beads, steel beads, alumina beads, zirconia beads, silicon carbide beads, silicon nitride beads Any grinding media such as boron nitride beads can be used. Furthermore, it is also possible to carry out by using a grinding aid such as sodium chloride and sodium nitrate which can be easily removed after grinding in addition to the grinding media during grinding.
In addition, a grinding media and a grinding aid may each be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  In addition, in the case of miniaturization by a dry grinding method, after grinding, the phthalocyanine compound is separated from the grinding media, and the phthalocyanine compound is subjected to a solvent treatment using a solvent, whereby the phthalocyanine compound is converted into a desired crystal form. Can be converted. The solvent used for the conversion of the crystal form is not limited, but for example, chain and cyclic saturated aliphatic solvents such as pentane, hexane, octane, nonane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc .; toluene, xylene, trimethylbenzene, naphthalene Aromatic solvents such as chlorobenzene, dichlorobenzene, and chloronaphthalene; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, and benzyl alcohol; and aromatic solvents such as methylnaphthalene, diphenylmethane, diphenylethane, and anisole; Aliphatic polyhydric alcohols such as glycerin, ethylene glycol, and polyethylene glycol; chain and cyclic ketone solvents such as acetone, cyclohexanone, and methyl ethyl ketone; methyl formate, ethyl acetate Ester solvents such as n-butyl acetate; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane; diethyl ether, dibutyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, methyl cellosolve Chain solvents such as ethyl cellosolve and butyl cellosolve; dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, γ-butyrolactone, dimethyl sulfoxide, sulfolane, hexa Aprotic polar solvents such as methylphosphoric triamide; nitrogen-containing compounds such as n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine; mineral oil such as ligroin; Water etc. are mentioned.

Among these, in consideration of operability during the conversion of the crystal form, saturated aliphatic solvents, aromatic solvents, alcohol solvents, chain and cyclic ketone solvents, ester solvents, chain and cyclic ether solvents An aprotic polar solvent, water and the like are preferable.
In addition, the solvent used for the solvent process for crystal form conversion may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Furthermore, the treatment temperature at the time of the solvent treatment can be from the freezing point of the solvent to be used or the mixed solvent to the boiling point or less, but from the viewpoint of safety, it is usually from 10 ° C. to 200 ° C.
The amount of the solvent used in the solvent treatment is arbitrary, but it is usually 0.1 parts by weight or more, preferably 1 part by weight or more, and usually 500 parts by weight with respect to 1 part by weight of the phthalocyanine compound. In consideration of productivity, it is preferable to carry out in a range of 250 parts by weight or less.

  On the other hand, when miniaturization is performed by a wet grinding method, as a device to be used, for example, a ball mill, an attritor, a roll mill, a sand mill, a homomixer, or the like can be used, but is not limited thereto. Moreover, the grinding media to be used are the same as those in the dry type, and a grinding aid may be used as in the dry type.

  Furthermore, there is no limitation on the solvent used for wet grinding, and any solvent can be used. For example, linear and cyclic saturated aliphatic solvents such as pentane, hexane, octane, nonane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Aromatic solvents such as toluene, xylene, trimethylbenzene, naphthalene, methylnaphthalene, diphenylmethane, diphenylethane, and anisole; halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, and chloronaphthalene; methanol, ethanol, isopropanol, n- Alcohol solvents such as butanol and benzyl alcohol; Aliphatic polyhydric alcohols such as glycerin, ethylene glycol and polyethylene glycol; Chains and rings such as acetone, cyclohexanone and methyl ethyl ketone Ketone solvents; ester solvents such as methyl formate, ethyl acetate, n-butyl acetate; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane; diethyl ether, dibutyl ether, dimethoxyethane, tetrahydrofuran, Chain and cyclic ether solvents such as 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve; dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, γ -Aprotic polar solvents such as butyrolactone, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide; n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine, etc. Nitrogen-containing compounds; mineral oil such as ligroin; water and the like.

Among them, in consideration of operability during the conversion of the crystal form described later, the solvents used in the wet grinding method are saturated aliphatic solvents, aromatic solvents, alcohol solvents, chain and cyclic ketone solvents, ester solvents. Preferred are chain and cyclic ether solvents, aprotic polar solvents, water and the like.
In addition, a solvent may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Furthermore, the treatment temperature during the wet grinding treatment can be carried out at a temperature not lower than the freezing point of the solvent and not higher than the boiling point.
The amount of the solvent used is arbitrary, but is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, and usually 200 parts by weight or less based on 1 part by weight of the phthalocyanine compound. In consideration of productivity, it is desirable to carry out at 100 parts by weight or less.

Further, after wet grinding, the phthalocyanine compound can be converted into a desired crystal form by subjecting the phthalocyanine compound to a solvent treatment in the same manner as in the dry grinding method. The kind and amount of the solvent used for the solvent treatment, and the treatment temperature are the same as those in the solvent treatment after dry grinding. Further, in the solvent treatment performed after wet grinding, milling may be performed using a known grinding media such as glass beads, alumina beads, steel beads or the like, if necessary.
In addition, the phthalocyanine compound obtained as a wet cake after grinding or after solvent treatment is appropriately dried by using a known method such as room temperature drying, reduced pressure drying, hot air drying, freeze drying, etc. It can be obtained as a phthalocyanine compound having a structure.

[8. Others]
The production method of the present invention has been described above, but the production method of the present invention is not limited as long as it has a step of reacting a phthalocyanine ring-forming compound and a trivalent metal salt in a nitro compound. You may perform processes other than the washing | cleaning, refinement | miniaturization, and solvent processing which were mentioned above.
The use of the phthalocyanine compound produced by the production method of the present invention is arbitrary, but it is suitable for use as a photoconductive material of an electrophotographic photoreceptor.

[II. Electrophotographic photoreceptor]
Hereinafter, an electrophotographic photoreceptor produced by using the phthalocyanine compound of the present invention as a photoconductive material (hereinafter referred to as “the electrophotographic photoreceptor of the present invention” as appropriate) will be described.
The electrophotographic photoreceptor of the present invention includes a photosensitive layer containing a phthalocyanine compound produced by the production method of the present invention. That is, the phthalocyanine compound of the present invention is contained in the photosensitive layer in an electrophotographic photoreceptor having a photosensitive layer.

[1. Conductive support]
There is no particular limitation on the conductive support, but for example, metal materials such as aluminum, aluminum alloy, stainless steel, copper and nickel, and conductive powder such as metal, carbon and tin oxide are mixed to impart conductivity. A resin material, a resin, glass, paper, or the like on which a conductive material such as aluminum, nickel, or ITO (indium tin oxide alloy) is deposited or applied on its surface is mainly used. Moreover, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. Further, as the shape, for example, a drum shape, a sheet shape, a belt shape or the like is used. Alternatively, a conductive material made of a metal material coated with a conductive material having an appropriate resistance value may be used for controlling conductivity and surface properties or for covering defects.

Further, when a metal material such as an aluminum alloy is used as the conductive support, it may be used after anodizing. In addition, when anodizing is performed, it is desirable to perform sealing by a known method.
The anodizing treatment can be carried out by any method, but is usually carried out by energizing in an acidic bath using the conductive support as an electrode. Although there is no restriction | limiting in particular about an acidic bath, For example, acidic baths, such as chromic acid, a sulfuric acid, an oxalic acid, a boric acid, sulfamic acid, are mentioned. Of these, anodizing in sulfuric acid gives the best results.

For example, in the case of anodizing the conductive support made of aluminum in sulfuric acid, the sulfuric acid concentration is 100 g / l to 300 g / l, and the dissolved aluminum concentration is 2 g / l to 15 g / l. l, the liquid temperature is preferably set to 15 ° C. to 30 ° C., the electrolysis voltage is set to 10 V to 20 V, and the current density is preferably set within the range of 0.5 A / dm ^{2 to 2} A / dm ² . However, the processing conditions during the anodizing treatment are not limited to this.
By performing the anodizing treatment in this way, an anodized film is formed on the surface of the conductive support.

  It is desirable to subject the anodic oxide film thus formed to a sealing treatment. The sealing treatment can be carried out by any method, but is usually carried out by immersing the conductive support in an aqueous sealing agent solution containing a sealing agent. A typical example is a low-temperature sealing treatment in which a conductive support is immersed in a sealant aqueous solution at a low temperature, or a high-temperature sealing in which a conductive support is immersed in a sealant aqueous solution at a high temperature. Processing.

As described above, the low temperature sealing treatment is performed by immersing the conductive support in an aqueous sealing agent solution at a low temperature.
In the low temperature sealing treatment, nickel fluoride is usually used as a main component as a sealing agent.
At this time, the concentration of the sealing agent in the sealing agent aqueous solution used in the case of the low temperature sealing treatment is arbitrary, but it is usually most effective to carry out in the range of 3 g / l to 6 g / l. is there.
The treatment temperature is arbitrary, but is usually 25 ° C. or higher, preferably 30 ° C. or higher, and usually 40 ° C. or lower, preferably 35 ° C. or lower, in order to facilitate the sealing treatment.

Further, the pH of the aqueous sealant solution is also arbitrary, but is usually 4.5 or more, preferably 5.5 or more, and usually 6.5 or less, preferably 6.0 or less. In addition, there is no restriction | limiting in the pH regulator used when adjusting pH, Although arbitrary things can be used, For example, oxalic acid, boric acid, formic acid, acetic acid, sodium hydroxide, sodium acetate, aqueous ammonia etc. are used. be able to.
Further, the treatment time is arbitrary, but it is preferable to carry out the treatment usually within a range of 1 minute to 3 minutes per 1 μm of film thickness.

In addition, the sealing agent aqueous solution may contain substances other than the sealing agent. For example, in order to further improve the physical properties of the film, a metal salt such as cobalt fluoride, cobalt acetate, or nickel sulfate, a surfactant, or the like may be mixed in the sealing agent aqueous solution.
After the immersion, washing with water and drying are performed to finish the low temperature sealing treatment.

On the other hand, the high temperature sealing treatment is performed by immersing the conductive support in an aqueous sealing agent solution at a high temperature.
In the high-temperature sealing treatment, a metal salt such as nickel acetate, cobalt acetate, lead acetate, nickel acetate-cobalt, and barium nitrate can be used as the sealing agent, but usually nickel acetate is used as a main component.

At this time, the concentration of the sealing agent in the aqueous sealing agent solution used in the case of the high-temperature sealing treatment is arbitrary, but it is usually most effective to carry out in the range of 5 g / l to 20 g / l. is there.
The treatment temperature is arbitrary, but is usually 80 ° C. or higher, preferably 85 ° C. or higher, and usually 100 ° C. or lower, preferably 98 ° C. or lower, in order to smoothly proceed with the sealing treatment.

Furthermore, the pH of the aqueous sealing agent solution is also arbitrary, but is usually 5.0 or more and usually 6.0 or less. In addition, there is no restriction | limiting in the pH adjuster used when adjusting pH, Although arbitrary things can be used, For example, the thing similar to the case of a low temperature sealing process can be used.
The treatment time is also arbitrary, but it is usually 1 minute to 3 minutes per film thickness of 1 μm, and it is usually 10 minutes or more, preferably 20 minutes or more.

As in the case of the low temperature sealing treatment, the sealing agent aqueous solution may contain a substance other than the sealing agent in the high temperature sealing treatment. For example, in order to further improve the film properties, sodium acetate, organic carboxylic acid, anionic or nonionic surfactant, etc. may be mixed in the sealing agent aqueous solution.
After the immersion, the high-temperature sealing treatment is completed by washing with water and drying.

  However, when the average film thickness of the coating is thick, usually, a strong sealing condition is required due to a high concentration of the sealing liquid and high temperature / long time treatment. Therefore, productivity is reduced and surface defects such as spots, dirt, and dusting are likely to occur on the coating surface. From the viewpoint of preventing such harmful effects, the average film thickness of the anodized film is usually 20 μm or less, preferably 7 μm or less.

  The support surface may be smooth, or may be roughened by using a special cutting method or by performing a polishing process. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support. In order to reduce the cost, it is possible to use the drawing tube as it is without performing the cutting process. In particular, when a non-cutting aluminum substrate such as drawing, impact processing, and ironing is used as a support, the above-described treatment eliminates dirt and foreign matter adhering to the surface, small scratches, and the like. This is preferable because a clean substrate can be obtained.

[2. Undercoat layer]
An undercoat layer may be provided between the conductive support and the photosensitive layer described later for improving adhesion and blocking properties. As the undercoat layer, a resin or a resin in which particles such as a metal oxide are dispersed is used.

  Examples of the metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium titanate and barium titanate. One kind of these particles may be used alone, or two or more kinds of particles may be mixed and used in an arbitrary combination and ratio.

Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable.
The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicone. In addition, the process performed to a titanium oxide particle may be one type, and may perform two or more types of processes by arbitrary combinations and grades.

Further, as the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. In addition, the titanium oxide particles may have only one crystal type, or two or more crystal types may be included in any combination and ratio.
In addition, various particle diameters of the metal oxide particles can be used. Among them, the average primary particle diameter is usually 10 nm or more from the viewpoint of the characteristics of the binder resin as a raw material for the undercoat layer and the stability of the liquid. Further, it is usually 100 nm or less, preferably 50 nm or less.

  The undercoat layer is preferably formed in a form in which the metal oxide particles are dispersed in a binder resin. The type of binder resin used for the undercoat layer is arbitrary, but specific examples include epoxy resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, Polycarbonate resin, polyurethane resin, polyimide resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, polyacrylic acid resin, polyacrylamide resin, polyvinyl pyrrolidone resin, polyvinyl pyridine resin, water-soluble polyester Resin, cellulose ester resin such as nitrocellulose, cellulose ether resin, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, zirconium chelate compound Zirconium alkoxide compounds such as organic zirconium compounds of titanyl chelate compounds, organic titanyl compounds such as titanyl alkoxide compounds, such as known binder resin such as a silane coupling agent can be used.

  In addition, binder resin may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamide, modified polyamide, and the like are preferable because they exhibit good dispersibility and coating properties.

  The mixing ratio of the metal oxide particles to the binder resin used in the undercoat layer can be arbitrarily selected, but it is usually preferable to use in the range of 10 wt% or more and 500 wt% or less. Usually, the undercoat layer is formed by applying a dispersion obtained by dissolving or dispersing metal oxide particles and a binder resin in an appropriate solvent or dispersion medium to the support surface, and the mixing ratio is within the above range. As a result, the stability and coating properties of the dispersion can be improved. In addition, the kind of the solvent and dispersion medium used when forming the undercoat layer is arbitrary.

Furthermore, the thickness of the undercoat layer can be arbitrarily selected, but is usually 0.01 μm or more, preferably from the viewpoint of improving the photoreceptor characteristics of the electrophotographic photoreceptor and the coating properties of the dispersion during production. The thickness is 0.1 μm or more, usually 30 μm or less, preferably 20 μm or less.
The undercoat layer may contain pigment particles, resin particles, and the like for the purpose of preventing image defects.

[3. Photosensitive layer]
Next, the photosensitive layer formed on the conductive support (on the undercoat layer when an undercoat layer is provided) will be described.
The photosensitive layer is a layer containing the phthalocyanine compound of the present invention as a charge generating material. The type may be a single layer structure in which the charge generation material and the charge transport material are present in the same layer and dispersed in a binder resin (hereinafter referred to as “single layer type” as appropriate) It has a layered structure (hereinafter referred to as “laminated type” as appropriate) in which a charge generating layer in which a generating material is dispersed in a binder resin and a charge transporting layer in which a charge transporting material is dispersed in a binder resin. May be. In addition, as the laminated photosensitive layer, a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and a charge transport layer and a charge generation layer are laminated in this order. There are reverse laminated type photosensitive layers, and any of them can be adopted.

[3-1. Multilayer type photosensitive layer]
In the multilayer photosensitive layer, the charge generation layer is composed of a charge generation material containing the phthalocyanine compound of the present invention as at least one of the charge generation materials and a binder resin. That is, the charge generation layer is composed of at least the phthalocyanine compound of the present invention and a binder resin, may contain any charge generation material other than the phthalocyanine compound of the present invention, and appropriately contains other components. May be.

  In the multilayer photoreceptor, the method for producing the charge generation layer is arbitrary, but usually the charge generation material containing at least one phthalocyanine compound of the present invention is dispersed in a solution in which a binder resin is dissolved in a solvent or the like. This is formed by preparing a coating solution, applying the coating solution on a conductive support, and binding the fine particles of the charge generating material with various binder resins.

  As the charge generation material, the phthalocyanine compound of the present invention may be used alone or in combination with other known charge generation materials (dyes, pigments, etc.). When other charge generating materials are used in combination, they may be used in a mixed / dispersed state or in a co-crystal state.

  Examples of charge generation materials that can be used in combination with the phthalocyanine compound of the present invention include phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium pigments), quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, Examples thereof include benzimidazole pigments. Of these, phthalocyanine pigments and azo pigments are preferably used from the viewpoint of photosensitivity.

  Here, when the phthalocyanine compound of the present invention is used in combination with another charge generation material, the phthalocyanine compound of the present invention and another charge generation material may be mixed in the form of powder or dispersion, You may mix in the manufacturing process (Including various processing processes, such as pigmentation and crystallization) of the phthalocyanine compound of an invention, and another charge generation material. As described above, acid paste treatment, grinding treatment, solvent treatment, and the like are known as methods of mixing at each production stage. In particular, in order to produce a co-crystal state in the charge generating material, as described in JP-A-10-48859, after mixing two types of crystals, they are mechanically ground and made amorphous, and then subjected to solvent treatment. A method of converting to a specific crystal state is mentioned.

  There is no restriction | limiting in binder resin used for the electric charge generation layer in a laminated type photoreceptor, Arbitrary resin can be used. Specific examples thereof include polyvinyl butyral resins, polyvinyl formal resins, polyvinyl acetal resins such as partially acetalized polyvinyl butyral resins partially modified with formal, acetal, etc., polyarylate resins, polycarbonate resins, polyester resins. , Modified ether 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, cellulose resin, polyurethane Resin, epoxy resin, silicon resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, casein, vinyl chloride-vinyl acetate copolymer, hydroxy-modified vinyl chloride -Vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer such as vinyl chloride-vinyl acetate-maleic anhydride copolymer, styrene-butadiene copolymer, chloride Insulating resins such as vinylidene-acrylonitrile copolymers, styrene-alkyd resins, silicon-alkyd resins, phenol-formaldehyde resins, and organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinyl anthracene, and polyvinyl perylene. It is done. In addition, binder resin may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Moreover, there is no restriction | limiting in particular in the solvent and dispersion medium which melt | dissolve binder resin and are used for preparation of a coating liquid, Arbitrary solvents and dispersion media can be used. However, when an undercoat layer is provided on the electrophotographic photosensitive member, a solvent and a dispersion medium that do not dissolve the undercoat layer are preferably used.

  In the charge generation layer of the multilayer photoreceptor, the blending ratio (weight) of the binder resin and the charge generation material is arbitrary, but is usually 10 parts by weight or more, preferably 30 parts by weight or more with respect to 100 parts by weight of the binder resin. Also, it is usually 1000 parts by weight or less, preferably 500 parts by weight or less. If the ratio of the charge generation material is too high, the stability of the coating solution is reduced due to aggregation of the charge generation material, and on the other hand, if it is too low, the sensitivity as a photoreceptor may be reduced. It is preferable to use it. When the phthalocyanine compound of the present invention is used in combination with another charge generation material as a charge generation material, the total of the charge generation material used in combination and the phthalocyanine compound of the present invention is within the above range.

The thickness of the charge generating layer of the multilayer photoreceptor is not particularly limited, but is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 10 μm or less, preferably 5 μm or less.
Furthermore, as a method for dispersing the charge generation material in the dispersion medium, a known dispersion method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be arbitrarily used. When dispersing, it is effective to reduce the particle size of the charge generating material to a particle size of usually 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.

  On the other hand, the charge transport layer contains a charge transport material and usually contains a binder resin and other components used as necessary. Specifically, such a charge transport layer is prepared by, for example, preparing a coating solution by dissolving or dispersing a charge transport material and a binder resin in a solvent or a dispersion medium. It can be obtained by coating and drying on the generation layer, or in the case of a reverse lamination type photosensitive layer, on a conductive support (or on the undercoat layer when an undercoat layer is provided). Moreover, the solvent or dispersion medium used in this case is arbitrary.

  In the charge transport layer, the binder resin is used for securing the film strength of the charge transport layer. There is no limitation on the type, and a known resin can be used arbitrarily. For example, butadiene resin, styrene resin, vinyl acetate resin, vinyl chloride resin, acrylic ester resin, methacrylic ester resin, vinyl alcohol resin, ethyl alcohol Polymers and copolymers of vinyl compounds such as vinyl ether, polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal, polycarbonate resin, polyester resin, polyarylate resin, polyamide resin, polyurethane resin, cellulose ester resin, phenoxy resin, silicon Examples thereof include resins, silicon-alkyd resins, poly-N-vinylcarbazole resins and the like. Of these, polycarbonate resins and polyarylate resins are particularly preferable. These can also be used by crosslinking with an appropriate curing agent by heat, light or the like. Moreover, 1 type of binder resin may be used independently, and 2 or more types may be used together by arbitrary combinations and a ratio.

  The charge transport material is not particularly limited, and a known charge transport material can be arbitrarily used. Examples of charge transport materials include aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, electron withdrawing materials such as quinone compounds such as diphenoquinone, carbazole derivatives, indoles Derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, thiadiazole derivatives, heterocyclic compounds such as benzofuran derivatives, aniline derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives and multiple types of these compounds bind Or an electron donating substance such as a polymer having a group consisting of these compounds in the main chain or side chain. Among these, carbazole derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and those in which a plurality of these compounds are bonded are preferable. In addition, a charge transport substance may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  Specific examples of suitable structures of the charge transport material are shown below. However, these specific examples are shown for illustration, and any known charge transport material may be used as long as it is not contrary to the gist of the present invention. In the following structural formulas, Me represents a methyl group, and Bu represents a butyl group.

  The ratio of the binder resin and the charge transport material is arbitrary, but the charge transport material is usually used at a ratio of 20 parts by weight or more with respect to 100 parts by weight of the binder resin. Among these, 30 parts by weight or more is preferable from the viewpoint of residual potential reduction, and 40 parts by weight or more is more preferable from the viewpoint of stability and charge mobility when repeatedly used. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, the charge transport material is usually used at a ratio of 150 parts by weight or less. Among them, 120 parts by weight or less is preferable from the viewpoint of compatibility between the charge transport material and the binder resin, 100 parts by weight or less is more preferable from the viewpoint of printing durability, and 80 parts by weight or less is particularly preferable from the viewpoint of scratch resistance.

  In the multilayer photoreceptor, the thickness of the charge transport layer is not particularly limited, but is usually 5 μm or more, preferably 10 μm or more, and usually 50 μm from the viewpoint of long life, image stability, and high resolution. Hereinafter, it is preferably 45 μm or less, more preferably 30 μm or less.

  The photosensitive layer or each layer (charge generation layer, charge transport layer, etc.) constituting the photosensitive layer may contain other components. For example, well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds, leveling agents for the purpose of improving film-forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. Further, additives such as a visible light shielding agent may be contained.

[3-2. Single-layer type photosensitive layer]
The single-layer type photosensitive layer has a structure in which a charge generating substance is further dispersed in the charge transport medium having the above-described mixing ratio. That is, the single-layer type photosensitive layer is formed using a binder resin in order to ensure film strength, in the same manner as the charge transport layer of the multilayer photoreceptor, in addition to the charge generation material and the charge transport material. Specifically, a charge generation material, a charge transport material, and various binder resins are dissolved or dispersed in a solvent or dispersion medium to prepare a coating liquid, and the coating liquid is formed on a conductive support (when an undercoat layer is provided). It can be obtained by coating and drying on the undercoat layer.

  The types of the charge transport material and the binder resin and the use ratios thereof are the same as those described for the charge transport layer of the multilayer photoreceptor. Moreover, the solvent or dispersion medium used for preparation of a coating liquid is arbitrary. Usually, a charge generation material is further dispersed in a charge transport medium comprising a charge transport material and a binder resin.

  The charge generation material contains at least the phthalocyanine compound of the present invention as described for the charge generation layer of the multilayer photoreceptor, and can be used in combination with any known charge generation material. However, in the case of a photosensitive layer of a single-layer type photoreceptor, it is desirable to sufficiently reduce the particle size of the charge generating material. Specifically, the range is usually 1 μm or less, preferably 0.5 μm or less.

If the amount of the charge generating material dispersed in the single-layer type photosensitive layer is too small, sufficient sensitivity cannot be obtained, but if it is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. It is usually used in the range of 0.1% by weight or more, preferably 1% by weight or more, and usually 50% by weight or less, preferably 20% by weight or less based on the whole layer type photosensitive layer.
The film thickness of the single-layer type photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100 μm or less, preferably 50 μm or less.

Furthermore, the use ratio of the binder resin and the charge generating material in the single-layer type photosensitive layer is such that the charge generating material is usually 0.1 parts by weight or more, preferably 1 part by weight or more, based on 100 parts by weight of the binder resin. It is 30 parts by weight or less, preferably 10 parts by weight or less.
Further, as in the case of the laminated photosensitive layer, the photosensitive layer may contain other components.

[4. Other layers]
In both the multilayer type photoreceptor and the single-layer type photoreceptor, the above-mentioned photosensitive layer may be the uppermost layer, that is, the surface layer, but another layer may be provided on the photosensitive layer, and this may be used as the surface layer.
For example, a protective layer may be provided for the purpose of preventing the photosensitive layer from being worn out or preventing or reducing the deterioration of the photosensitive layer due to discharge products generated from a charger or the like.

The protective layer is formed by containing a conductive material in a suitable binder resin, or charge transporting ability such as a triphenylamine skeleton as described in JP-A-9-190004 and JP-A-10-252377. It can form using the copolymer using the compound which has this.
There is no restriction | limiting in the electroconductive material used for a protective layer. For example, aromatic amino compounds such as TPD (N, N′-diphenyl-N, N′-bis- (m-tolyl) benzidine), antimony oxide, indium oxide, tin oxide, titanium oxide, tin oxide-antimony oxide, Metal oxides such as aluminum oxide and zinc oxide can be used, but are not limited thereto.

  Moreover, there is no restriction | limiting also about binder resin used for a protective layer, Although arbitrary resin can be used, For example, a polyamide resin, a polyurethane resin, a polyester resin, an epoxy resin, a polyketone resin, a polycarbonate resin, a polyvinyl ketone resin, a polystyrene resin In addition, known resins such as polyacrylamide resin and siloxane resin can be used, and charge transporting ability such as triphenylamine skeleton as described in JP-A-9-190004 and JP-A-10-252377 can be used. A copolymer of the skeleton having the above resin can also be used.

Further, the protective layer is preferably configured so that the electric resistance is usually 10 ⁹ Ω · cm or more and 10 ¹⁴ Ω · cm or less. If the electric resistance is higher than the above range, the residual potential may increase and an image with much fog may be formed. On the other hand, if it is lower than the above range, there is a risk that the image is blurred and the resolution is lowered. Further, it is desirable that the protective layer is configured so as not to substantially prevent transmission of light irradiated for image exposure.

  In addition, for the purpose of reducing frictional resistance and wear on the surface of the photoconductor, and increasing the transfer efficiency of toner from the photoconductor to the transfer belt and paper, the surface layer is made of fluorine resin, silicon resin, polyethylene resin, or the like. Particles made of this resin or inorganic compound particles may be contained in the surface layer. Alternatively, a layer containing these resins and particles may be newly formed as a surface layer.

[5. Formation method of each layer]
The formation method of each layer (including the photosensitive layer and the undercoat layer) constituting the above-described photoreceptor is arbitrary, but usually a coating solution obtained by dissolving or dispersing a substance to be contained in a solvent or a dispersion medium. Are formed by repeating the coating / drying step sequentially for each layer using a known coating method.
The type and amount of the solvent or dispersion medium used in this case are not particularly limited, but considering the purpose of each layer and the properties of the selected solvent / dispersion medium, the physical properties such as the solid content concentration and viscosity of the coating liquid are in a desired range. It is preferable to adjust as appropriate.

  Examples of usable solvents or dispersion media include saturated aliphatic solvents such as pentane, hexane, octane and nonane, aromatic solvents such as toluene, xylene and anisole, and halogenated solvents such as chlorobenzene, dichlorobenzene and chloronaphthalene. Aromatic solvents, amide solvents such as dimethylformamide and N-methyl-2-pyrrolidone, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and benzyl alcohol, aliphatic polyhydric alcohols such as glycerin and polyethylene glycol , Chain solvents such as acetone, cyclohexanone, methyl ethyl ketone, and cyclic ketone solvents, ester solvents such as methyl formate, ethyl acetate, n-butyl acetate, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane Solvent Aprotic polar solvents such as chain ethers such as tilether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, and cyclic ether solvents, acetonitrile, dimethyl sulfoxide, sulfolane, hexamethylphosphate triamide, etc. , N-butylamine, isopropanolamine, diethylamine, triethanolamine, nitrogen-containing compounds such as ethylenediamine, triethylenediamine and triethylamine, mineral oil such as ligroin, and water. In addition, a solvent and a dispersion medium may each be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

Furthermore, the concentration and viscosity of the coating solution used for forming each layer are arbitrary, and may be determined to an appropriate value according to the layer to be formed.
For example, in the case of a single layer type photoreceptor and a charge transport layer of a laminated type photoreceptor, the solid content concentration of the coating solution is usually 5% by weight or more, preferably 10% by weight or more, and usually 40% by weight or less, Preferably it is 35 weight% or less of range. Further, the viscosity of the coating solution is usually in the range of 10 cps or more, preferably 50 cps or more, and usually 500 cps or less, preferably 400 cps or less.

  In the case of a charge generating layer of a multilayer photoreceptor, the solid content concentration of the coating solution is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 15% by weight or less, preferably 10% by weight. % Or less. The viscosity of the coating solution is usually 0.01 cps or more, preferably 0.1 cps or more, and usually 20 cps or less, preferably 10 cps or less.

  Furthermore, there is no restriction | limiting in the coating method of a coating liquid, A well-known coating method can be used arbitrarily. Specific examples include dip coating, spray coating, spinner coating, bead coating, wire bar coating, blade coating, roller coating, air knife coating, curtain coating, etc. A known coating method can also be used.

  Furthermore, the drying method of the coating solution is also arbitrary. For example, after touch-drying at room temperature, it is usually dried in a temperature range of 30 ° C. or higher and usually 200 ° C. or lower for 1 minute to 2 hours with no wind or air blowing. Can be dried. The heating temperature may be constant or the heating may be performed while changing the temperature during drying.

[III. Image forming apparatus]
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention (hereinafter referred to as “image forming apparatus of the present invention” as appropriate) will be described. The image forming apparatus of the present invention is described above. As long as the electrophotographic photosensitive member is provided, there is no other limitation, and the present invention is not limited to the following embodiments, and can be modified as appropriate.
As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device (charging unit) 2, an exposure device (exposure unit) 3, and a developing device (developing unit) 4. Accordingly, a transfer device 5, a cleaning device (cleaning unit) 6 and a fixing device 7 are provided.

  The electrophotographic photosensitive member 1 is not particularly limited as long as it is an electrophotographic photosensitive member using the above-described phthalocyanine compound of the present invention. In FIG. 1, as an example, the above-described photosensitive member is applied to the surface of a cylindrical conductive support. 2 shows a drum-shaped photoreceptor on which layers are formed. The photoreceptor 1 is driven to rotate at a predetermined peripheral speed in the direction of the arrow in the figure. Further, along the outer peripheral surface of the electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, a developing device 4, a transfer device 5 and a cleaning device 6 are arranged.

The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. As the charging device, a corona charging device such as corotron or scorotron, a direct charging device (contact type charging device) in which a direct charging member to which voltage is applied is brought into contact with the surface of the photosensitive member and charged is often used. Examples of direct charging means include contact chargers such as charging rollers and charging brushes. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2.
As the direct charging means, either charging with air discharge or injection charging without air discharge is possible. Furthermore, as the voltage applied at the time of charging, in the case of only a DC voltage, it is also possible to use an AC superimposed on a DC.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. As a specific example, a halogen lamp, a fluorescent lamp, a laser (semiconductor, He—Ne), LED, an optical shutter array, a photoconductor internal exposure method, and the like are used for exposure, but as a digital electrophotographic method, a laser, LED, It is preferable to use an optical shutter array or the like. The wavelength of light at the time of exposure is arbitrary, but exposure can be performed with, for example, monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a short wavelength of 380 nm to 500 nm. That's fine.

  The developing device 4 is not particularly limited as long as it can develop the electrostatic latent image formed on the electrophotographic photosensitive member 1, and includes cascade development, one-component insulating toner development, and one-component conductive toner development. Any apparatus such as a dry development system such as a two-component magnetic brush development or a wet development system can be used. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and stores toner T as a developer inside the developing tank 41. It has become. Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

  The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicon resin, a urethane resin, a fluorine resin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary.

  The developing roller 44 is disposed between the electrophotographic photoreceptor 1 and the supply roller 43 and is in contact with the electrophotographic photoreceptor 1 and the supply roller 43, respectively. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown). The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photosensitive member 1.

  The regulating member 45 is formed of a resin blade such as silicon resin or urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such a metal blade with resin. The regulating member 45 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

  The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.

  As the toner, in addition to the pulverized toner, chemical toners such as suspension granulation, suspension polymerization, and emulsion polymerization aggregation can be used. In particular, in the case of chemical toners, those having a small particle size of about 4 to 8 μm are used, and those having a shape close to a sphere, and those outside a sphere such as a potato or rugby ball can also be used. . The polymerized toner is excellent in charging uniformity and transferability, and is preferably used for high image quality.

  The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like disposed so as to face the electrophotographic photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a recording paper (paper, medium) P. Is.

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 scrapes the residual toner adhering to the photosensitive member 1 with a cleaning member and removes it from the surface of the electrophotographic photosensitive member, and collects the removed residual toner. If there is little or almost no residual toner, the cleaning device 6 may be omitted.

  The fixing device 7 is not particularly limited, and a fixing device that uses any fixing method such as heat roller fixing, flash fixing, oven fixing, pressure fixing, IH fixing, belt fixing, and IHF fixing can be used. In addition, these fixing methods may be used alone or in combination with a plurality of fixing methods.

  In the present embodiment, the fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. In the fixing device 7, when the toner T transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner T is heated to a molten state. Then, the toner is fixed on the recording paper P after being cooled.

  As the upper and lower fixing members 71 and 72, a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, a fixing sheet, or the like is known. A heat fixing member can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

  In the electrophotographic apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is uniformly charged to a predetermined negative potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.

  Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

  The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.

When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner T which is not transferred and remains on the photosensitive surface of the photoreceptor 1 is removed by the cleaning device 6.
After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.
The recording paper P to which the image has been transferred is printed out of the apparatus.

In addition to the above-described configuration, the image forming apparatus may have a configuration capable of performing, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.
The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.

  The electrophotographic photosensitive member 1 is combined with one or more of the charging device 2, the exposure device 3, the developing device 4, the transfer device 5, the cleaning device 6, and the fixing device 7 to form an integrated cartridge ( The electrophotographic photosensitive member cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. In this case, for example, when the electrophotographic photosensitive member 1 and other members are deteriorated, the electrophotographic photosensitive member cartridge is removed from the main body of the image forming apparatus, and another new electrophotographic photosensitive member cartridge is mounted on the main body of the image forming apparatus. This facilitates maintenance and management of the image forming apparatus.

  Hereinafter, the present invention will be described with reference to examples. However, the examples shown below are shown to explain the present invention in detail, and the present invention is limited to the following examples without departing from the gist thereof. Is not to be done. In this specification, “parts” means “parts by weight” unless otherwise specified.

[Example 1]
25.2 parts of 1,3-diimino-5-fluoroisoindoline shown in the following structure and 7.5 parts of gallium trichloride were placed in 160 parts of nitrobenzene, which is a nitro compound, and reacted at 165 ° C. for 5 hours. After the reaction, the product was separated by filtration, washed with N-methyl-2-pyrrolidone, toluene, pure water, and methanol, and then dried to obtain 15.6 parts of tetrafluorochlorogallium phthalocyanine crystal as a phthalocyanine compound. Obtained (yield 59%).

The powder X-ray diffraction pattern of the obtained tetrafluorochlorogallium phthalocyanine crystal is shown in FIG. Moreover, in Examples 1-4 and Comparative Examples 1-2, the measurement conditions of an X-ray diffraction spectrum are as follows.
Powder X-ray diffractometer: PANalytical PW1700
X-ray tube: Cu
Scanning axis: θ / 2θ
Measurement range: 3.0 ° to 40.0 °
Scanning speed: 3.0 ° / min

[Example 2]
Except for replacing nitrobenzene in Example 1 with o-nitrotoluene, the same procedure as in Example 1 was performed to obtain 20.3 parts of tetrafluorochlorogallium phthalocyanine crystal as a phthalocyanine compound (76% yield). . FIG. 3 shows a powder X-ray diffraction pattern of the obtained tetrafluorochlorogallium phthalocyanine crystal.

[Example 3]
19.5 parts of tetrafluorochlorogallium phthalocyanine crystals were obtained as a phthalocyanine compound by performing the same operation as in Example 1 except that nitrobenzene in Example 1 was replaced with o-nitroanisole (yield: 73%). ). The powder X-ray diffraction pattern of the obtained tetrafluorochlorogallium phthalocyanine crystal is shown in FIG.

[Example 4]
22.6 parts of 4-fluorophthalonitrile and 7.5 parts of gallium trichloride were placed in 100 parts of o-nitroanisole, which is a nitro compound, and reacted at 200 ° C. for 6 hours. After the reaction, filtration, washing, and drying were performed in the same manner as in Example 1 to obtain 13.2 parts of tetrafluorochlorogallium phthalocyanine crystal as a phthalocyanine compound (yield 49%). FIG. 5 shows a powder X-ray diffraction pattern of the obtained tetrafluorochlorogallium phthalocyanine crystal.

[Comparative Example 1]
10.2 parts of tetrafluorochlorogallium phthalocyanine crystals were obtained in the same manner as in Example 1 except that the nitrobenzene in Example 1 was replaced with sulfolane, which is an aprotic polar solvent (yield 38 %). The powder X-ray diffraction pattern of the obtained tetrafluorochlorogallium phthalocyanine crystal is shown in FIG.

[Comparative Example 2]
26.7 parts of 4-fluorophthalonitrile and 7.5 parts of gallium trichloride were placed in 100 parts of 1-chloronaphthalene and reacted at 200 ° C. for 4 hours. After the reaction, 18.4 parts (69%) of tetrafluorochlorogallium phthalocyanine crystals were obtained by filtering, washing and drying in the same manner as in Example 1. A powder X-ray diffraction pattern of the obtained tetrafluorochlorogallium phthalocyanine crystal is shown in FIG.

[Comparative Example 3]
30 parts of phthalonitrile and 12.5 parts of titanium tetrachloride were put in 200 parts of nitrobenzene and reacted at 200 ° C. for 4 hours. After the reaction, the reaction solution was filtered, but there was no solid separated by filtration, and the target substance dichlorotitanyl phthalocyanine was not obtained.

[Photoconductor characteristics evaluation]
[Application Example 1]
Using a conductive support in which an aluminum vapor-deposited film (thickness 70 nm) is formed on the surface of a biaxially stretched polyethylene terephthalate resin film (thickness 75 μm), the following coating solution for charge generation layer is placed on the vapor-deposited layer of the support. The charge generation layer was formed by coating with a coater such that the film thickness after drying was 0.4 μm and drying.

Coating solution for charge generation layer:
To 4 parts of tetrafluorochlorogallium phthalocyanine which is the phthalocyanine compound obtained in Example 1, 30 parts of 4-methyl-4-methoxy-pentanone-2 and 270 parts of 1,2-dimethoxyethane were added, and sand grind was added. The mixture was pulverized for 2 hours in a mill and subjected to a fine particle treatment. Thereafter, 1 part of polyvinyl butyral (“Denkabutyral # 6000C” manufactured by Denki Kagaku Kogyo Co., Ltd.) as a binder resin and 1 part of phenoxy resin (“PKHH” manufactured by Union Carbide Co., Ltd.) were added. A charge generation layer coating solution was prepared by grinding for a period of time.

  Separately, 50 parts by weight of a compound represented by the following formula (1) as a charge transport material, and 2,2-bis (4-hydroxy-3-methylphenyl) propane represented by the following formula (2) as an aromatic diol as a binder resin A terminal structure derived from pt-butylphenol, comprising 51 mol% of repeating units as components and 49 mol% of repeating units having 1,1-bis (4-hydroxyphenyl) -1-phenylethane as an aromatic diol component A charge transport layer coating solution was prepared by dissolving 100 parts by weight of a polycarbonate resin having an amount of 0.03 part by weight of silicone oil as a leveling agent in 640 parts by weight of a tetrahydrofuran / toluene (weight ratio 8/2) mixed solvent. . The charge transport layer coating solution is applied onto the charge generation layer with a film applicator so that the film thickness after drying is 25 μm, and dried to form a charge transport layer, whereby a laminated photosensitive layer is formed. An electrophotographic photosensitive member was prepared.

The photoreceptor characteristics of the obtained electrophotographic photoreceptor were measured by a static method using a photoreceptor evaluation apparatus (Cynthia 55, manufactured by GENTEC).
First, in a dark place, a scorotron charger discharges so that the surface potential of the electrophotographic photosensitive member becomes about −700 V, passes through the electrophotographic photosensitive member at a constant speed (125 mm / sec), and charges the charged voltage. Was measured, and the initial band voltage V0 (-V) was determined. Thereafter, the potential drop DD (−V) when measured for 2.5 seconds was measured. Next, irradiation with 780 nm monochromatic light having an intensity of 1.0 μW / cm ² and half exposure energy E _1/2 (μJ / cm ² ) required until the photoreceptor surface potential is changed from −550 V to −275 V, The residual potential Vr (−V) 10 seconds after irradiation was determined. Further, the voltage applied to the scorotron charger in order to charge the surface potential of the photoreceptor to about −700 V was defined as Vg (V). The results are shown in Table 1.

[Application Examples 2 to 4 and Comparative Application Examples 1 and 2]
Similar to Application Example 1, as Application Examples 2 to 4 and Comparative Application Examples 1 and 2, the phthalocyanine compounds obtained in Examples 2 to 4 and Comparative Examples 1 and 2 were used in place of tetrafluorochlorogallium phthalocyanine, respectively. Thus, an electrophotographic photoreceptor was prepared in the same manner as described above, and the photoreceptor characteristics of each electrophotographic photoreceptor were measured in the same manner as described above. The results are shown in Table 1.

  For application examples 1 to 4 and comparative application example 1, the initial charging voltage V0 could be charged to about −700 V, but the electrophotographic photosensitive member of comparative application example 2 using the phthalocyanine compound of comparative example 2 was used. With respect to, the maximum voltage (-900 V) that can be applied to the scorotron charger was applied by the measuring machine, but it could not be charged to about -700 V. For this reason, in the electrophotographic photosensitive member of Comparative Application Example 2, the initial charging voltage V0 was set to the maximum charging voltage (−478V).

As can be seen from Table 1, the electrophotographic photoreceptors of application examples 1 to 4 have a larger initial charging voltage V0 than the electrophotographic photoreceptors of comparative application examples 1 and 2, and have a chargeability superior to that of the prior art. confirmed.
In addition, it was confirmed that the electrophotographic photoreceptors of the application examples 1 to 4 have a smaller potential drop DD than the electrophotographic photoreceptors of the comparative application examples 1 and 2, and the dark attenuation is smaller than that of the conventional examples.
Furthermore, it was confirmed that the electrophotographic photoreceptors of the application examples 1 to 4 have a half exposure energy E1 _{/ 2} smaller than that of the electrophotographic photoreceptor of the comparative application example 1, and have good light attenuation characteristics (sensitivity). . Although the exposure energy E1 _/ 2 of the electrophotographic photosensitive member of Comparative Application Example 2 is very small, the exposure voltage E1 _{/ 2} is about −− even though the maximum voltage (−900 V) that can be applied to the scorotron charger is applied by the measuring machine. Considering that it could not be charged to 700 V, it is considered that the overall performance as an electrophotographic photoreceptor is not practical.

  As described above, in Examples 1 to 4, a phthalocyanine compound produced by a simple production method of synthesizing a phthalocyanine compound in a nitro compound is used as a charge generation material for an electrophotographic photosensitive member. It has been clarified that an electrophotographic photoreceptor excellent in photoreceptor characteristics such as dark decay and light decay characteristics can be obtained.

[Image formation test]
[Application Example 5]
The coating solution for charge generation layer obtained in Application Example 1 is applied to an aluminum cylinder (conductive support) having a diameter of 3 cm, a length of 250 cm, and a wall thickness of 0.75 mm, which is anodized and sealed. The charge generation layer was provided so that the film thickness after dip coating was 0.3 g / m ² (about 0.3 μm) after drying. Then, the charge transport layer coating solution obtained in Application Example 1 is dip-coated on the charge generation layer, and the charge transport layer is provided so that the film thickness after drying is 18 μm. Obtained.

  The obtained photosensitive drum was mounted on a drum cartridge (electrophotographic photosensitive member cartridge) of a monolithic laser printer (LP2400 manufactured by Seiko Epson Corporation) modified machine (exposure light amount increased), and a test image was printed out. The printed out image was a good image with no dark and clear fog.

[Comparative Application Example 3]
A test image was printed out by performing the same operation as in Application Example 5 except that the charge generation layer coating solution was changed to the charge generation layer coating solution obtained in Comparative Application Example 1. The printed image was an image having a low density of the entire image.

  From the results of Application Example 5 and Comparative Application Example 3, it is clear that an electrophotographic photosensitive member cartridge and an image forming apparatus excellent in image characteristics can be provided by using the phthalocyanine compound produced by the production method of the present invention. became.

  The present invention can be carried out in any field that requires an electrophotographic photosensitive member, and is suitable for use in, for example, a copying machine, a printer, a printing machine, and the like.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention. It is a powder X-ray-diffraction figure of the phthalocyanine compound manufactured in Example 1 of this invention. It is a powder X-ray-diffraction figure of the phthalocyanine compound manufactured in Example 2 of this invention. It is a powder X-ray-diffraction figure of the phthalocyanine compound manufactured in Example 3 of this invention. It is a powder X-ray-diffraction figure of the phthalocyanine compound manufactured in Example 4 of this invention. 2 is a powder X-ray diffraction pattern of the phthalocyanine compound produced in Comparative Example 1. FIG. 3 is a powder X-ray diffraction pattern of a phthalocyanine compound produced in Comparative Example 2. FIG.

Explanation of symbols

1 Photoconductor (Electrophotographic photoconductor)
2 Charging device (charging roller; charging unit)
3 Exposure equipment (exposure section)
4 Development device (development unit)
5 Transfer device 6 Cleaning device (cleaning part)
7 Fixing Device 41 Developing Tank 42 Agitator 43 Supply Roller 44 Developing Roller 45 Regulating Member 71 Upper Fixing Member (Fixing Roller)
72 Lower fixing member (fixing roller)
73 Heating device T Toner P Recording paper (paper, medium)

Claims (4)

Phthalonitriles, and a 1,3-diiminoisoindoline or Ranaru compound capable of forming at least one phthalocyanine ring selected from the group, and a gallium trichloride, and wherein the reaction is carried out in nitrobenzene in And a method for producing a chlorogallium phthalocyanine compound . An electrophotographic photoreceptor comprising a photosensitive layer containing a chlorogallium phthalocyanine compound produced by the production method according to claim 1 . The electrophotographic photosensitive member according to claim 2 ,
A charging unit for charging the electrophotographic photosensitive member, an exposure unit for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and a developing unit for developing the electrostatic latent image formed on the electrophotographic photosensitive member And an electrophotographic photosensitive member cartridge, comprising: at least one of cleaning units for removing the developer from the photosensitive member. The electrophotographic photosensitive member according to claim 2 ,
A charging unit for charging the electrophotographic photosensitive member;
Exposing the charged electrophotographic photoreceptor to form an electrostatic latent image; and
An image forming apparatus comprising: a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member.

Images