JP2013014677A - Composite pigment, electrophotographic photoreceptor using the same, image forming apparatus, and process cartridge for image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite pigment to achieve image-quality enhancement and stabilization enhancement of an electrophotographic apparatus, and to provide an electrophotographic photoreceptor using the same, an image forming method, and an image forming apparatus.SOLUTION: The composite pigment is composed of a hydroxylgallium phthalocyanine obtained by hydrolyzing oxycarbonylgallium phthalocyanine of formula (A), and an azo pigment. In the formula (A), X is an alkyl group which may have a substituent, or the like; R1 to R16 are each independently hydrogen, an alkoxy group or the like; and n is an integer of 1 to 3.

Description

  The present invention relates to a highly stable photoconductor that is highly sensitive, can be used repeatedly, and can stably output an image even in a wide range of temperature and humidity environments and voltage application conditions, and an image forming apparatus using the same.

  In recent years, the development of information processing systems using electrophotography has been remarkable, and laser printers and digital copiers that record information using light by converting information into digital signals have significantly improved print quality and reliability. . Recently, these laser printers and digital copying machines that are rapidly spreading have rapidly increased demands for high speed, high image quality, and high stability.

As an electrophotographic photosensitive member used in an image forming apparatus, an organic photosensitive material using an organic photosensitive material is generally widely applied for reasons such as cost, productivity, and low environmental load.
Various kinds of charge generating materials used in the organic photoreceptor have been developed, and pigments useful as photoreceptor characteristics such as azo pigments and phthalocyanine pigments have been found. Examples of the azo pigment include benzidine-based bisazo pigments described in, for example, Patent Document 1 (Japanese Patent Laid-Open No. 47-37543), Patent Document 2 (Japanese Patent Laid-Open No. 52-55643), and Patent Document 3 ( JP-A-52-8832), stilbene-based bisazo pigments, JP-A-58-222152, diphenylhexatriene-based bisazo pigments, JP-A-58-222152 Diphenylbutadiene bisazo pigments described in JP-A-222153) are known.

  As an example of a phthalocyanine pigment, a titanyl phthalocyanine pigment is described in a saddle type described in Patent Document 6 (Japanese Patent Laid-Open No. 61-239248) and Patent Document 7 (Japanese Patent Laid-Open No. 1-17066). Type Y, Type I described in Patent Document 8 (Japanese Patent Laid-Open No. 61-109056), Type A described in Patent Document 9 (Japanese Patent Laid-Open No. 62-67094), Patent Document 10 (Japanese Patent Laid-Open No. 63-364) and Patent Document 11 (Japanese Patent Laid-Open No. 63-366), Type C, Patent Document 12 (Japanese Patent Laid-Open No. 2005-15682), Type B, Patent Examples include the M type described in Document 13 (Japanese Patent Laid-Open No. 63-198067) and the quasi-amorphous type described in Patent Document 14 (Japanese Patent Laid-Open No. 1-123868). Specific examples of the metal-free phthalocyanine pigment include X-type metal-free phthalocyanine disclosed in Patent Document 15 (US Pat. No. 3,357,989), Patent Document 16 (Japanese Patent Application Laid-Open No. 58-182039). The cage-type metal-free phthalocyanine etc. which are disclosed are mentioned. Specific examples of the hydroxygallium phthalocyanine pigment are disclosed in Patent Document 17 (Japanese Patent Laid-Open No. 5-263007) and Patent Document 18 (Japanese Patent Laid-Open No. 5-279591). As specific examples of the copper phthalocyanine pigment, Patent Document 19 (Japanese Patent Laid-Open No. 58-100134), Patent Document 20 (Japanese Patent Laid-Open No. 61-273994), and Patent Document 21 (Japanese Patent Laid-Open No. 62-62367). ) And the like. Examples of the chlorogallium phthalocyanine pigment are disclosed in Patent Document 22 (Japanese Patent Laid-Open No. 59-44053) and Patent Document 23 (Japanese Patent Laid-Open No. 1-222159). Examples of chloroindium phthalocyanine pigments are disclosed in Patent Document 24 (Japanese Patent Laid-Open No. 60-59355).

  However, the photoreceptors using these single pigments have a narrow wavelength range, so the sensitivity to the light in the long wavelength region transmitted by the semiconductor laser, which is the mainstream of writing light for laser printers and copiers, is low, In addition, there are problems such as fluctuations in the characteristics of the photoconductor depending on the use environment and usage time, which is insufficient as a photoconductor for future high image quality or high-speed copying machines. In order to solve these problems, Patent Document 25 (JP-A-5-301292), Patent Document 26 (JP-A-2001-290296) containing a metal-free phthalocyanine and a fluorenone-based azo pigment, a phthalocyanine compound and an azo pigment Patent Document 27 (Japanese Patent Laid-Open No. 9-127711) containing metal, Patent Document 28 of mixed metal phthalocyanine and perylene pigment (Japanese Patent Laid-Open No. 2002-23399), Patent Document 29 of quinacridone pigment and titanyl phthalocyanine pigment (Japanese Patent Laid-Open No. 2007-2007) No. 334099), and a mixture of two or more pigments such as titanyl phthalocyanine pigment and other phthalocyanine pigment Patent Document 30 (Japanese Patent Laid-Open No. Hei 3-9962) has been proposed, but there is still not enough .

One of the reasons for this is that the pigment mixing method mainly uses mechanical means such as milling, cannot be mixed and combined at the molecular level, and has not been able to fully function as an organic photoconductor. Conceivable. In addition, a method using an acid paste is also proposed, but since concentrated sulfuric acid is used, there are problems in production, and there is a concern about decomposition and the application to pigments is limited. In addition, a phthalocyanine pigment such as a phthalocyanine pigment whose characteristics vary greatly depending on the crystal type, when mixed in an acid paste, the desired crystal type cannot be obtained, and as a result, sufficient photoreceptor characteristics cannot be obtained. It was.
Therefore, in order to realize an electrophotographic photoreceptor that overcomes the conventional drawbacks, a more excellent charge generating material is desired.

  The present invention has been made in view of the above circumstances, and in order to realize high image quality and high stability of an electrophotographic apparatus (an image forming apparatus such as a copying machine or a laser printer), a composite gallium phthalocyanine pigment, and The present invention provides an electrophotographic photosensitive member, an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the inventions described in the following (1) to (24), and have reached the present invention.
(1) “A composite pigment comprising hydroxygallium phthalocyanine obtained by hydrolyzing an oxycarbonylgallium phthalocyanine compound represented by the following general formula (A) and an azo pigment.

(However, in general formula (A), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. An aralkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, which may be an alkoxy group, an alkylthio group, an alkyl group or a halogen atom. , A nitro group, an amino group, an aryl group, a carboxy group, a cyano group, etc. R1 to R16 are each independently hydrogen, alkoxy group, alkylthio group, alkyl group, halogen atom, nitro group, aryl group, Represents a group selected from the group consisting of n is an integer of 1 to 3) ",
(2) “The composite pigment as described in (1) above, wherein the oxycarbonylgallium phthalocyanine compound is represented by the following general formula (B):

(In the general formula (B), Y represents a perfluoroaryl group or a perfluoroalkyl group. N is an integer of 1 to 3.) "
(3) The above (1), wherein the hydroxygallium phthalocyanine is obtained by hydrolysis of an oxycarbonylgallium phthalocyanine compound represented by the general formula (A) after the adsorption treatment with an adsorbent. Or the composite pigment according to (2) ",
(4) “The hydroxygallium phthalocyanine is obtained by hydrolysis of the recrystallized oxycarbonylgallium phthalocyanine compound represented by the general formula (A)”. 3) the composite pigment according to any one of “
(5) The above-mentioned hydroxygallium phthalocyanine is obtained by hydrolyzing the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) in the presence of a basic compound. 1) to the composite pigment according to any one of (4) ",
(6) “The azo pigment is represented by a general formula of A (H) n (sometimes referred to herein as“ general formula (I) ”), and the oxycarbonyl gallium of the general formula (A)” Simultaneously with the hydrolysis of the phthalocyanine compound, the azo pigment A (H) n represented by the general formula (I) is produced from the azo compound represented by the following general formula (II) by a chemical method and / or a thermal method. The composite pigment according to any one of (1) to (5) above, wherein
A (E) n: general formula (II)
(Wherein A is a residue of an azo compound and this residue A is bonded to n E groups by one or more heteroatoms, and these heteroatoms are a group consisting of N and O) And each of the E groups is independently hydrogen or the following group: —C (═O) —O—R1 (wherein R1 is a group having 4 to 10 carbon atoms). Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group.) N is an integer of 1 to 9).
(7) The above-mentioned (1), wherein the azo pigment A (H) n represented by the general formula (I) was present when the oxycarbonylgallium phthalocyanine compound of the general formula (A) was hydrolyzed. ) To (6) any of the composite pigments],
(8) “The hydroxygallium phthalocyanine is present when the azo pigment represented by A (H) n is produced from the azo compound represented by the following general formula (II) by a chemical method and / or a thermal method. The composite pigment according to any one of (1) to (6) above,
A (E) n: general formula (II)
(Wherein A is a residue of an azo compound and this residue A is bonded to n E groups by one or more heteroatoms, and these heteroatoms are a group consisting of N and O) And each of the E groups is independently hydrogen or the following group: —C (═O) —O—R1 (wherein R1 is a group having 4 to 10 carbon atoms). Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group.) N is an integer of 1 to 9).
(9) “A product obtained by simultaneously combining a hydroxygallium phthalocyanine obtained by hydrolysis of an oxycarbonylgallium phthalocyanine compound represented by the general formula (A) and an azo pigment represented by A (H) n The composite pigment according to any one of (1) to (6) above,
(10) An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support and containing at least the composite pigment according to any one of (1) to (9) in the photosensitive layer. "
(11) "Image forming method using the electrophotographic photosensitive member according to (10)",
(12) "Image forming apparatus comprising the electrophotographic photosensitive member according to (10)",
(13) “Process cartridge for an image forming apparatus comprising the electrophotographic photosensitive member according to (10)”,
Further, the present invention includes the following aspects.
(14) “A method for producing a composite pigment comprising hydroxygallium phthalocyanine and an azo pigment, comprising a step of hydrolyzing an oxycarbonylgallium phthalocyanine compound represented by the following general formula (A) to obtain the hydroxygallium phthalocyanine: A method for producing a composite pigment comprising hydroxygallium phthalocyanine and an azo pigment.

(However, in general formula (A), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. An aralkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, which may be an alkoxy group, an alkylthio group, an alkyl group or a halogen atom. , A nitro group, an amino group, an aryl group, a carboxy group, a cyano group, etc. R1 to R16 are each independently hydrogen, alkoxy group, alkylthio group, alkyl group, halogen atom, nitro group, aryl group, Represents a group selected from the group consisting of n is an integer of 1 to 3) ",
(15) “The substituent that the group X may have is an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an amino group, an aryl group, a carboxy group, or a cyano group,” The method for producing a composite pigment according to (14) above ”,
(16) “The method for producing a composite pigment according to (14) or (15) above, wherein the oxycarbonylgallium phthalocyanine compound is represented by the following general formula (B):

(In the general formula (B), Y represents a perfluoroaryl group or a perfluoroalkyl group. N is an integer of 1 to 3.) "
(17) The above-mentioned step, wherein the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) is dissolved in an organic solvent, the solution is subjected to adsorption treatment with an adsorbent, and then hydrolyzed. (14) A method for producing a composite pigment according to any one of (16) ",
(18) “Production method according to (17) above, wherein the adsorbent is selected from the group consisting of silica gel, alumina, florisil, activated carbon, activated clay, diatomaceous earth, or perlite” ,
(19) The method according to any one of (14) to (18) above, wherein each step comprises hydrolyzing the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) after recrystallization treatment with an organic solvent. A method for producing a composite pigment according to any one of the following ”
(20) The method according to any one of (14) to (19) above, further comprising a step of hydrolyzing the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) in the presence of a basic compound. Method for producing composite pigment of ",
(21) From the azo compound A (E) n represented by the general formula (II) by the chemical method and / or the thermal method, simultaneously with the hydrolysis of the oxycarbonylgallium phthalocyanine compound of the general formula (A) The method for producing a composite pigment according to any one of the above (14) to (20), which comprises a step of producing an azo pigment A (H) n represented by (I).
A (H) n: general formula (I)
A (E) n: general formula (II)
(Wherein A is a residue of an azo compound and this residue A is bonded to n E groups by one or more heteroatoms, and these heteroatoms are a group consisting of N and O) And each of the E groups is independently hydrogen or the following group: —C (═O) —O—R1 (wherein R1 is a group having 4 to 10 carbon atoms). Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group.) N is an integer of 1 to 9.
(22) “When the azo pigment is represented by A (H) n in the general formula (I) and hydrolyzes the oxycarbonylgallium phthalocyanine compound in the general formula (A), A (H) n The method for producing a composite pigment according to any one of (14) to (21), wherein the azo pigment represented by
(23) “When the azo pigment A (H) n of the general formula (I) is produced from the azo compound A (E) n represented by the general formula (II) by a chemical method and / or a thermal method The composite pigment according to any one of (14) to (22), wherein hydroxygallium phthalocyanine obtained by hydrolyzing the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) is present. Production method",
(24) “A composite pigment produced by the production method according to any one of (14) to (22)”.

  By including the composite pigment of the present invention in the photosensitive layer on the conductive support, an electrophotographic photosensitive member capable of outputting a high-quality print without image deterioration over a long period of time in a wide range of temperature and humidity environments and voltage application conditions. An image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus have been provided.

It is a figure explaining an example of a structure of the electrophotographic photosensitive member of this invention. It is a figure explaining another example of composition of an electrophotographic photosensitive member of the present invention. It is a figure explaining another example of a structure of the electrophotographic photosensitive member of this invention. It is a figure explaining another example of a structure of the electrophotographic photosensitive member of this invention. 1 is a schematic diagram for explaining an electrophotographic process and an image forming apparatus of the present invention. 1 is a conceptual diagram illustrating an example of a charging unit used in an image forming apparatus of the present invention. 1 is a schematic view for explaining an example of a tandem-type full-color electrophotographic apparatus of the present invention. It is a conceptual diagram which shows an example of the process cartridge of this invention.

[Composite pigments and their production methods]
The composite pigment of the present invention and the production method thereof will be described.
The oxycarbonyl gallium phthalocyanine compound of the general formula (A) of the present invention (hereinafter also simply referred to as “gallium phthalocyanine compound”) is synthesized by reacting a halogenated gallium phthalocyanine or hydroxygallium phthalocyanine with a carboxylic acid derivative in an organic solvent. be able to. Examples of the halogenated gallium phthalocyanine include chlorogallium phthalocyanine, bromogallium phthalocyanine, iodine gallium phthalocyanine, and the like, which can be synthesized by a known method. For example, chlorogallium phthalocyanine is disclosed in D.C. C. Acad. Sci. , (1965), 242, 1026, and the method of reacting gallium trichloride with diiminoisoindoline. Bromogallium phthalocyanine can be synthesized by a method of reacting gallium tribromide and phthalonitrile described in JP-A-59-133551 of Patent Document 6. Iodine gallium phthalocyanine can be synthesized by a method of reacting gallium triiodide and phthalonitrile described in JP-A-60-59354 of Patent Document 7. Hydroxygallium phthalocyanine can be obtained by hydrolyzing the above-mentioned gallium halide phthalocyanine. Hydrolysis may be acid hydrolysis or alkaline hydrolysis. Regarding acid hydrolysis, see, for example, Bull. Soc. Chim. France, 23 (1962), and can be obtained by a method of hydrolyzing chlorogallium phthalocyanine using sulfuric acid. Regarding alkaline hydrolysis, Inlog. Chem. (19), 3131, (1980) can be obtained by the decomposition method using ammonia.
Subsequently, the gallium phthalocyanine compound of the general formula (A) can be synthesized by reacting the obtained gallium halide phthalocyanine or hydroxygallium phthalocyanine with a carboxylic acid compound. Can be used. As described above, this is due to the production method, and in the production method of hydroxygallium phthalocyanine, the formation of decomposition products is unavoidable when the acid hydrolysis treatment using acid or alkali is performed.
In contrast, halogenated gallium phthalocyanine can be produced without providing a hydrolysis step, and therefore, in the present invention, there is no generation of a decomposition product as a raw material for synthesis, and there are few production steps. Gallium phthalocyanine can be used favorably.
As the carboxylic acid compound of the present invention, any compound having a carboxyl group in its molecular structure, such as generally known organic fatty acids, high acid value resins or copolymers, can be used.
For example, pentafluorobenzoic acid, tetrafluorobenzoic acid, cyclohexanecarboxyl acid, cyclopentylacetic acid, cyclopentanecarboxyl acid, cyclohexylacetic acid, cyclopentylmalonic acid, cyclohexene-1,2-dicarboxyl acid 3-cyclohexene-1-carboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 3-trifluoromethylbenzoic acid, 3,5-bistrifluoromethylbenzoic acid 4-methylbenzoic acid, 3-methylbenzoic acid, 4-methoxybenzoic acid, 4- Trobenzoic acid, 4-cyanobenzoic acid, picolinic acid, nicotinic acid, isonicotinic acid, 2,3-pyridinedicarboxylic acid, nonadecafluorodecanoic acid, hexadecafluorosebasic acid, Hexafluoroglutaric acid, chlorodifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, trifluoroacetic acid, difluoroacetic acid, fluoroacetic acid, dichloroacetic acid, acrylic acid, methacrylic acid, Pivalic acid, nonafluorovaleric acid, n-valeric acid, pentafluoropropionic acid, heptafluo Butyric acid, undecafluorohexanoic acid, tert-butylacetic acid, 2,2-dimethylbutyric acid, tridecafluoroheptanoic acid, pentadecafluorooctanoic acid, heptadecafluorononanoic acid 1,2,3-propanetricarboxylic acid, trimesic acid, 1,9-nonanecarboxylic acid, adipic acid, azelaic acid, dodecanedioic acid, eicosangioic acid, glutaric acid , Heptadecanedic acid, hexadecanedic acid, malonic acid, nonadecanedic acid, octadecanedic acid, pentadecanedic acid , Pimelic acid, sebacic acid, suberic acid, succinic acid, tetradecandioic acid, tridecandioic acid, and their acid anhydrides, acid halides, and the like.
The amount ratio between the halogenated gallium phthalocyanine or hydroxygallium phthalocyanine and the carboxylic acid derivative is as follows. Is about 1/3 mole. When n in the general formula (A) is 1 (general formula (II)), the carboxylic acid derivative is preferably equimolar or more, and it varies depending on the reactivity of the carboxylic acid derivative used, but is 1.1-fold to 500-fold. Mole is suitable.
Further, when the carboxylic acid derivative is liquid at the reaction temperature, it may be used as a reaction solvent.
Examples of the organic solvent used here include dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, 2-butanone, cyclohexanone, monochlorobenzene, dichlorobenzene, toluene, xylene, anisole, Examples thereof include nitrobenzene, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyl acetate, butyl acetate, dichloroethane, trichloroethane, pyridine, picoline or quinoline.
It can be synthesized by reacting at a reaction temperature of 0 to 200 ° C., preferably 20 to 150 ° C. for 30 minutes to 50 hours.

The hydrolysis of the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) will be described.
The hydrolysis may be basic hydrolysis or acidic hydrolysis. Further, no solvent or an organic solvent may be used. Basic hydrolysis using an organic solvent is suitable for producing high purity hydroxygallium phthalocyanine.
Suitable organic solvents are, for example, ether solvents such as tetrahydrofuran or dioxane, or glycol ether solvents such as ethylene glycol methyl ether, ethylene glycol ethyl ether or acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, Examples include dimethyl sulfoxide, ethyl cellosolve (registered trademark), ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, toluene, xylene, nitrobenzene, pyridine, picoline or quinoline.
Suitable bases as catalysts are, for example, alkali metals: sodium, potassium, etc., and their hydroxides and carbonates, or alkali metal amides, sodium amides, potassium amides, and alkali metal hydrides, such as Examples include lithium hydride.
Ammonia is also useful. Organic aliphatic, aromatic or heterocyclic N-bases include diazabicyclooctene, diazabicycloundecene, 4-dimethylaminopyridine, dimethylpyridine, pyridine, triethylamine, diethylamine, ethylamine, methylamine, dimethylamine , Trimethylamine, propylamine, butylamine, dibutylamine, cyclohexylamine, benzylamine, allylamine and the like can be used.
The amount of water used for hydrolysis may be equimolar or more with respect to the gallium phthalocyanine compound represented by formula (A). In consideration of the complexation at the molecular level, it is preferable to react in a dissolved state, and the water for reducing the solubility is preferably 10 wt% or less with respect to the solvent.
The reaction temperature varies depending on the hydrolyzability of the gallium phthalocyanine compound represented by the general formula (A) and the presence or absence of a catalyst, but is 0 to 300 ° C, preferably 20 to 250 ° C, and the heating time is 30 minutes to 20 hours. Is desirable.

In the present invention, adsorption treatment or recrystallization treatment can be performed for the purpose of increasing the purity of the gallium phthalocyanine compound represented by the general formula (A).
Adsorption treatment is performed by dissolving the gallium phthalocyanine compound of the general formula (A) in an organic solvent and adding an adsorbent such as silica gel, alumina, florisil, activated carbon, activated clay, diatomaceous earth, or pearlite during column chromatography, room temperature or heating. There is a way to do it.
Examples of the organic solvent used here include ether solvents such as tetrahydrofuran or dioxane, glycol ether solvents such as ethylene glycol methyl ether and ethylene glycol ethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, Dimethyl sulfoxide, ethyl cellosolve, ethyl acetate, butyl acetate, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, monochlorobenzene, dichlorobenzene, toluene, xylene, anisole, n-hexane, cyclohexane, cyclohexanone, nitrobenzene, pyridine, picoline or quinoline And mixed solvents thereof.

In the recrystallization treatment, heating is performed using the above-described organic solvent, followed by cooling, and the produced compound may be collected by filtration. By combining adsorption treatment and recrystallization, a gallium phthalocyanine compound represented by the general formula (A) having a high purity can be produced more efficiently.
In performing these adsorption treatments and recrystallization treatments, the gallium phthalocyanine compound needs to be dissolved in an organic solvent or the like. This solubility can be controlled by X in the general formula (A). Particularly, in the case of a perfluoroaryl group or a perfluoroalkyl group, the solubility in an organic solvent is excellent, and an adsorption treatment and a recrystallization treatment are easy. Can be done. Here, examples of the perfluoroaryl group include a trifluorophenyl group, a tetrafluorophenyl group, and a pentafluorophenyl group. Examples of the perfluoroalkyl group include CF ₃ — (CF ₂ ) n — (n is 0 to 8), or — (CF ₂ ) n — (n is 2 to 8).
In the present invention, for the purpose of reducing and homogenizing the particle size of hydroxygallium phthalocyanine, it is effective to use a method of mixing dispersion media during the reaction or a microreactor that performs the reaction in a minute space. is there.

  Further, as the azo compound represented by the general formula (II) of the present invention, those described in JP-A-2009-7523 can be used, and this is decarboesterified by a chemical method and / or a thermal method. Thus, the azo pigment A (H) n represented by the general formula (I) can be produced.

As a chemical method for performing decarboesterification, there is a method of reacting a catalyst such as an acid or a base, and an acid can be preferably used. Examples of the acid include acetic acid, trifluoroacetic acid, propionic acid, acrylic acid, benzoic acid, hydrochloric acid, sulfuric acid, boric acid, p-toluenesulfonic acid, salicylic acid and the like.
As a thermal method for carrying out decarboesterification, there is a method of heating to 50 to 300 ° C. in a solvent, and preferably heating conditions of 70 to 250 ° C. can be used. The heating time is preferably 30 minutes to 20 hours.
Examples of the organic solvent used herein include ether solvents such as tetrahydrofuran and dioxane, glycol ether solvents such as ethylene glycol methyl ether and ethylene glycol ethyl ether, butanol, N, N-dimethylformamide, N, N- Examples thereof include dimethylacetamide, ethyl cellosolve, ethyl acetate, butyl acetate, monochlorobenzene, dichlorobenzene, toluene, xylene, anisole, cyclohexanone, nitrobenzene, pyridine, picoline or quinoline.
By combining the chemical method and thermal method for decarboesterification, an azo pigment represented by A (H) n can be produced more efficiently. It becomes possible to produce a composite pigment.
The residue A of the azo compound and azo pigment used in the present invention is represented by the following general formula (2).

（ただし、Ｂはアゾ化合物の主骨格を示し、Ｃｐはカップラー成分残基であり、ｍは２又は３の整数を表わす。）

(B represents the main skeleton of the azo compound, Cp represents a coupler component residue, and m represents an integer of 2 or 3.)

  More preferably, Cp in the general formula (2) is a coupler component residue represented by at least one of the following general formulas (3) to (11).

In the general formulas (3) to (6), X, Y ¹ , Z, p and q each represent the following.
X: -OH, -N (R1) (R2) or -NHSO2-R3.
(Where R1 and R2 represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R3 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)
Y ¹ : a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxy group, a sulfone group, a substituted or unsubstituted sulfamoyl group, or —CON (R4) (Y2). [R4 represents a hydrogen atom, an alkyl group or a substituted product thereof, or a phenyl group or a substituted product thereof, and Y2 represents a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or -N = C (R5) ( R6) (wherein R5 represents a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof or a styryl group or a substituted product thereof, R6 represents a hydrogen atom, an alkyl group, a phenyl group or a substituted product thereof, or R5 and R6 may form a ring together with the carbon atom bonded to them). ]
Z: A hydrocarbon ring or a substituted product thereof, or a heterocyclic ring or a substituted product thereof.
p: an integer of 1 or 2.
q: An integer of 1 or 2.

(In the above formula, R ⁷ represents a substituted or unsubstituted hydrocarbon group, and X is as defined above.)

(In the above formula, A is a heterocycle containing a divalent aromatic hydrocarbon group or a nitrogen atom necessary for forming an N-containing heterocycle together with the two N atoms described in formula (8). Represents an atom-containing divalent group (these rings may be substituted or unsubstituted. X is as defined above.)

(In the above formula, R ⁸ represents an alkyl group, a carbamoyl group, a carboxy group or an ester thereof, Ar ¹ represents a hydrocarbon ring group or a substituent thereof, and X is the same as described above.)

(In the formula (10) and (11), R ⁹ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, Ar ² represents a hydrocarbon ring group or a substitution product thereof. However, at the same time R ⁹ is hydrogen It is an atom and Ar ² does not become a cycloalkyl group or a cycloalkenyl group.

  More preferably, B in the general formula (2) is an azo compound represented by the following general formulas (12) to (14). Since these azo compounds generally exhibit n-type characteristics, when combined with a gallium phthalocyanine compound, a pn junction can be formed, which is very effective.

(In the above formula, R ¹¹ and R ¹² independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, or an ester thereof.)

(In the above formula, R ¹⁹ and R ²⁰ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.)

(In the above formula, R ₁₄ , R ₁₅ and R ₁₆ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group and esters thereof.)

  As the azo pigment and azo compound of the present invention, formulas (12-1) to (12-14) in which the main skeleton of the azo compound is general formula (12), and the main skeleton of the azo compound is general formula (13). Formulas (13-1) to (13-5) are formulas (14-1) to (14-5) in which the main skeleton of the azo compound is general formula (14).

  Specific examples of the azo compound represented by the general formula (II) of the present invention are shown below. In the structure of the specific example, the group E is hydrogen or a carboester group: —C (═O) —O—R1 (wherein R1 is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group having 4 to 10 carbon atoms) Represents a cycloalkyl group, a cycloalkenyl group, or an aralkyl group.

  The compound of the formula (II) having the carboester group is described in, for example, the aforementioned Japanese Patent Application Laid-Open No. 2009-7523, European Patent No. 648770, European Patent No. 648817, and Japanese Translation of PCT International Publication No. 2001-513119. For example, in an aprotic organic solvent in the presence of a base as a catalyst, at a temperature of 0 to 150 ° C., preferably at a temperature of 10 to 100 ° C., for 30 minutes to 20 hours, the above general formula (2) And those represented by the following formula (15) can be synthesized at an appropriate molar ratio.

(Wherein R ₀ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group having 4 to 10 carbon atoms.)

In each case, the molar ratio depends on the number of E introduced. Preferably, the pyrocarbonic acid diester is used in a slight excess.
Suitable aprotic organic solvents include, for example, ether solvents such as tetrahydrofuran or dioxane, or glycol ether solvents such as ethylene glycol methyl ether and ethylene glycol ethyl ether, or acetonitrile, N, N-dimethylformamide, N, N- Examples include dimethylacetamide, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, toluene, xylene, nitrobenzene, pyridine, picoline or quinoline. Preferred solvents are pyridine, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide.
Suitable bases as catalysts are, for example, alkali metals: sodium, potassium, etc., and their hydroxides and carbonates, or alkali metal amides, sodium amides, potassium amides, and alkali metal hydrides, such as Examples include lithium hydride.
As the organic aliphatic, aromatic or heterocyclic N-bases, diazabicyclooctene, diazabicycloundecene, 4-dimethylaminopyridine, dimethylpyridine, pyridine, triethylamine and the like can be used. Preferred are organic N-bases such as 4-dimethylaminopyridine, dimethylpyridine and pyridine.
The pyrocarbonic acid diester represented by the above formula (15) can be produced by a generally known method. It is also commercially available. R ₀ is as described above, and a branched alkyl group is preferable from the viewpoint of surprisingly improved solubility.

The composite pigment of the present invention will be further described. The composite ratio of the hydroxygallium phthalocyanine obtained by hydrolyzing the oxycarbonylgallium phthalocyanine compound of the general formula (A) and the azo compound represented by the general formula (II) can be arbitrarily selected according to the purpose. When the purpose is to further draw out the characteristics of the gallium phthalocyanine compound, 0.1 to 300 parts of the azo compound is suitable for 100 parts of hydroxygallium phthalocyanine.
When the amount is less than 0.1 part, the effect of complexation is not clear, and when the amount is more than 300 parts, the characteristics of hydroxygallium phthalocyanine are not sufficiently developed. Conversely, when the purpose is to further draw out the characteristics of the azo compound, 0.1 to 300 parts of hydroxygallium phthalocyanine is suitable for 100 parts of the azo compound. When the amount is less than 0.1 part, the effect of compounding is not clear. When the amount is more than 300 parts, the characteristics of the azo compound are not sufficiently exhibited.

As the organic solvent used in producing the composite pigment, the above-mentioned organic solvents can be used. For example, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, 2-butanone, Examples include cyclohexanone, monochlorobenzene, dichlorobenzene, toluene, xylene, anisole, nitrobenzene, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyl cellosolve, ethyl acetate, butyl acetate, trichloroethane, picoline, or quinoline.
The heating temperature for producing the composite pigment is 0 to 300 ° C., preferably 20 to 250 ° C., and the heating time is preferably 30 minutes to 20 hours.

The method for producing the composite pigment of the present invention can be roughly divided into four methods as described in the items (6) to (9) and the items (17) to (23).
That is, in the cases described in the items (6) and (21), hydrolysis of the oxycarbonylgallium phthalocyanine compound of the general formula (A) and decarboxylation of the azo compound A (E) n represented by the general formula (II) The composite pigment of the present invention can be produced by simultaneously performing the conversion.
In the method for producing the composite pigment, the oxycarbonyl gallium phthalocyanine compound of the general formula (A) and the azo compound A (E) n represented by the general formula (II) are reacted in a dissolved state at the molecular level. Can be combined.
As specific solvents, those having good solubility in both are suitable, and in particular, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, monochlorobenzene, dichlorobenzene, picoline, quinoline and the like can be mentioned. It is done.
As mentioned above, the hydrolysis reaction of the gallium phthalocyanine compound of the general formula (A) is more suitable for the basic, while the decarboesterification reaction of the azo compound A (E) n represented by the general formula (II) Is more acidic. Therefore, in the method for producing the composite pigment, a method for controlling the reaction temperature can be used favorably, and the reaction temperature is preferably in the range of 130 to 300 ° C.

  Specifically, the gallium phthalocyanine compound of the general formula (A) is reacted with the oxycarbonyl gallium phthalocyanine compound of the general formula (A) and the azo compound A (E) n in the presence of the above solvent and water. A composite pigment of the present invention comprising hydroxygallium phthalocyanine obtained by hydrolysis and azo pigment A (H) n can be produced.

In the cases described in the items (7) and (22), the oxycarbonylgallium phthalocyanine compound of the general formula (A) is hydrolyzed in the presence of the azo pigment A (H) n represented by the general formula (I). The composite pigment of the present invention can be produced.
The azo pigment A (H) n used here can be subjected to a mechanical pulverization process such as ball milling in advance in order to efficiently combine it. As the solvent for this reaction, the above-mentioned solvents can be used.
As described above, the basic reaction is more suitable for the hydrolysis reaction of the gallium phthalocyanine compound of the general formula (A). Therefore, in the method for producing this composite pigment, it is better to use the above-mentioned basic catalyst in order to advance the reaction efficiently.
Specifically, by reacting the gallium phthalocyanine compound of the general formula (A) with the azo pigment represented by A (H) n at 20 to 250 ° C. in the presence of the above-mentioned solvent and water and optionally a basic catalyst. A composite pigment of the present invention comprising a hydroxygallium phthalocyanine obtained by hydrolyzing a gallium phthalocyanine compound of the general formula (A) and an azo pigment represented by A (H) n can be produced.

In the case of (8) and (23), the azo compound represented by the general formula (II) in the presence of hydroxygallium phthalocyanine compound obtained by hydrolyzing the oxycarbonyl gallium phthalocyanine compound represented by the general formula (A). The composite pigment of the present invention can be produced by decarboesterifying compound A (E) n.
The decarboxyesterification reaction of the azo compound A (E) n represented by the general formula (II) is more suitable for the acidity. However, since hydroxygallium phthalocyanine may react with the acidic catalyst to be used, in the method for producing this composite pigment, a method for controlling the reaction temperature can be favorably used, and the reaction temperature is 130 to 300. A range of ° C is used favorably.
As the solvent used here, a solvent having good solubility of an azo compound is suitable, and examples thereof include dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, monochlorobenzene and dichlorobenzene.

  Specifically, hydroxygallium phthalocyanine obtained by hydrolyzing the oxycarbonylgallium phthalocyanine compound of the general formula (A) and the azo compound A (E) n represented by the general formula (II) are present in the presence of the above-mentioned solvent. By reacting below, the composite pigment of the present invention consisting of hydroxygallium phthalocyanine and an azo pigment represented by A (H) n can be produced.

In the case of (9) and (24), hydroxygallium phthalocyanine obtained by hydrolyzing the gallium phthalocyanine compound represented by general formula (A) and azo compound A (E) represented by general formula (II) The composite pigment of the present invention can be produced by simultaneously combining n.
The compounding treatment used here can be selected from conventionally known methods. For example, a gallium phthalocyanine compound represented by the general formula (A) and an azo pigment represented by A (H) n together with a binder resin as necessary. The composite pigment of the present invention can be produced by dispersing in a suitable solvent using a known dispersion method such as ball mill, attritor, sand mill, or ultrasonic wave.

[Electrophotographic photoconductor]
Next, the configuration of the electrophotographic photoreceptor will be described in detail below with reference to the drawings. As shown in FIG. 1, the photoreceptor (1) of the present invention comprises, on a conductive support (2), a charge generation layer (3) containing a charge generation material as a main component and a charge transport material as a main component. The charge transport layer (4) to be stacked is laminated.
As shown in FIG. 2, the photoreceptor (1) of the present invention has an undercoat layer (6) or an intermediate layer between the conductive support (2) and the charge generation layer (3). It may be formed.
In the photoreceptor (1) of the present invention, a protective layer (5) may be formed on the charge transport layer (4) as shown in FIG.
Further, as shown in FIG. 4, the photoreceptor (1) of the present invention has a single photosensitive layer (7) containing a charge generation substance and a charge transport substance on a conductive support (2). You may make the aspect of a layer type photoreceptor.

<Conductive support>
Examples of the conductive support include those having a volume resistance of 10 ¹⁰ Ω · cm or less, such as metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, and platinum, tin oxide, and indium oxide. Metal oxide coated by film or cylindrical plastic or paper by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel, etc. After the conversion, a tube subjected to surface treatment such as cutting, superfinishing or polishing can be used. Endless nickel belts and endless stainless steel belts can also be used as the conductive support.
In addition, the conductive support dispersed in an appropriate binder resin on the support can be used as the conductive support of the present invention.
Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done.
The binder resin used at the same time includes polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine Thermoplastic, thermosetting resin or photo-curing resin such as resin, urethane resin, phenol resin, alkyd resin and the like can be mentioned.
Such a conductive layer can be provided by dispersing and applying these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.
Furthermore, a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and polytetrafluoroethylene-based fluororesin on a suitable cylindrical substrate. Those provided with a conductive layer can be used favorably as the conductive support of the present invention.

<Photosensitive layer>
Next, the photosensitive layer will be described. The laminated photosensitive layer is constituted by sequentially laminating at least a charge generation layer and a charge transport layer.

<Charge generation layer>
The charge generation layer is a layer containing a charge generation material. The charge generation material contains at least the composite pigment used in the present invention.
The charge generation material may be used by mixing the composite pigment of the present invention and a conventionally known charge generation material.
Examples of conventionally known charge generating materials include azo pigments such as monoazo pigments, disazo pigments, asymmetrical disazo pigments, trisazo pigments, phthalocyanine pigments such as titanyl phthalocyanine, copper phthalocyanine, vanadyl phthalocyanine, hydroxygallium phthalocyanine, and metal-free phthalocyanine, Examples include perylene pigments, perinone pigments, indigo pigments, pyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, quinone condensed polycyclic compounds, and squalium pigments.
Binder resins used in the charge generation layer include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly-N-vinylcarbazole, polyacrylamide. , Polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulose resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone and the like. The amount of the binder resin is preferably 0 to 500 parts by mass and more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the charge generation material.
The charge generation layer disperses the charge generation material in a suitable solvent together with a binder resin as necessary using a known dispersion method such as a ball mill, an attritor, a sand mill, or an ultrasonic wave. Alternatively, it is formed by applying on an undercoat layer or an intermediate layer and drying. The binder resin may be added before or after the charge generating material is dispersed.
Examples of the solvent used for forming the charge generation layer include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, ligroin. Although generally used organic solvents such as ketone solvents, ketone solvents, ester solvents, and ether solvents are particularly preferable. These may be used alone or in combination of two or more.
The coating solution for forming the charge generation layer is mainly composed of a charge generation material, a solvent and a binder resin, and includes any additive such as a sensitizer, a dispersant, a surfactant, and silicone oil. May be included.
As a method for coating the charge generation layer using the coating solution, known methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used.
The thickness of the charge generation layer is preferably from 0.01 to 5 μm, more preferably from 0.1 to 2 μm. After coating, it is heated and dried in an oven or the like. The drying temperature of the charge generation layer in the present invention is preferably 50 ° C. or higher and 160 ° C. or lower.

<Charge transport layer>
Next, the charge transport layer will be described. The charge transport layer is formed by applying and drying a coating liquid in which a charge transport material and a binder resin are dissolved or dispersed in a solvent. Moreover, you may add additives, such as a plasticizer, a leveling agent, antioxidant, a lubricant, etc. individually or in 2 types or more to the coating liquid of a charge transport layer as needed.
Examples of the charge transport material include a hole transport material and an electron transport material. Examples of the hole transport material include poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, etc., bisstilbene derivatives, enamine derivatives, etc. Other known materials may be mentioned. These charge transport materials may be used alone or in combination of two or more.
Examples of the electron transporting material include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives.
These charge transport materials may be used alone or in combination of two or more. The content of the charge transport material is usually 20 to 300 parts by weight and preferably 40 to 150 parts by weight with respect to 100 parts by weight of the binder resin.
Binder resins include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, poly Vinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly (N-vinylcarbazole), acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, Examples thereof include thermoplastic or thermosetting resins such as phenol resins and alkyd resins.
As the solvent, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone or the like is used. Among them, the use of a non-halogen solvent is desirable for the purpose of reducing the environmental load. Specifically, cyclic ethers such as tetrahydrofuran, dioxolane and dioxane, aromatic hydrocarbons such as toluene and xylene, and derivatives thereof are preferably used. Two or more of these may be used in combination.
The film thickness of the charge transport layer is preferably 10 to 50 μm, more preferably 15 to 35 μm, from the viewpoint of resolution and responsiveness.
As a coating method, known methods such as a dip coating method, a spray coating method, a bead coating method, a nozzle coating method, a spinner coating method, and a ring coating method can be used, but the charge transport layer has a certain thickness. Since it is necessary to apply thickly, it is preferable to apply the dip coating method with a highly viscous liquid.
The charge transport layer after coating is heated and dried by a thermal means used in the charge generation layer. Although drying temperature changes also with the solvent contained in a coating liquid, it is preferable that it is 80-200 degreeC, and 110-170 degreeC is more preferable. The drying time is preferably 10 minutes or more, more preferably 20 minutes or more.

<Single layer>
Next, the case where the photosensitive layer has a single layer structure will be described. This is a photoreceptor in which the above-described charge generation material and charge transport material are dispersed or dissolved in a binder resin to realize a charge generation function and a charge transport function in one layer.
In the photosensitive layer, a charge generating substance, a charge transporting substance and a binder resin are dissolved or dispersed in a solvent such as tetrahydrofuran, dioxane, dichloroethane, methyl ethyl ketone, cyclohexane, cyclohexanone, toluene, xylene, etc., and this is dip coating, spray coating, bead coating. It can be formed by coating using a conventionally known method such as ring coating.
The charge transport material preferably contains both the hole transport material and the electron transport material described above. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.
Regarding the charge generating substance, charge transporting substance, binder resin, organic solvent and various additives used in the single photosensitive layer, any material contained in the above-described charge generating layer and charge transporting layer should be used. Is possible.
As the binder resin, in addition to the binder resin previously mentioned in the charge transport layer, the binder resin mentioned in the charge generation layer may be mixed and used. The amount of the charge generating material with respect to 100 parts by mass of the binder resin is preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass.
The amount of the charge transport material is preferably 0 to 190 parts by mass, and more preferably 50 to 150 parts by mass. Further, the film thickness of the photosensitive layer is preferably 5 to 40 μm, more preferably 10 to 30 μm.

<Underlayer>
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, in consideration of applying a photosensitive layer using a solvent thereon, such a resin is a resin having high solvent resistance to a general organic solvent. Preferably there is. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resins, phenol resins, alkyd-melamine resins, and isocyanates. And curable resins that form a three-dimensional network structure, such as epoxy resins.
Further, a fine powder pigment of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, or indium oxide may be added to the undercoat layer in order to prevent moire and reduce residual potential.
Moreover, it can form using a solvent and a coating method similarly to the above-mentioned charge generation layer and charge transport layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer.

<Protective layer>
In the present invention, a protective layer can be provided on the outermost surface of the photoreceptor in order to improve wear resistance. As the protective layer, a polymer charge transport material type obtained by polymerizing a charge transport component and a binder component, a filler dispersion type containing a filler, a curable type obtained by curing a constituent material having a reactive functional group, and the like are known. However, in the present invention, any conventionally known protective layer can be used.

[Image forming apparatus]
Next, the electrophotographic method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 5 is a schematic view for explaining the electrophotographic process and the image forming apparatus of the present invention, and the following examples also belong to the category of the present invention.
As shown in FIG. 5, the photoconductor (1) has a drum shape, but may be a sheet or an endless belt. For charging roller (12), pre-transfer charger (15), transfer charger (18), separation charger (19), pre-cleaning charger (21), in addition to corotron, scorotron, solid state charger (solid state charger) A roller-shaped charging member or a brush-shaped charging member is used, and all known means can be used.
As the charging member, a non-contact charging method such as corona charging or a contact charging method using a charging member using a roller or a brush is generally used, and any of them can be used effectively in the present invention. In particular, the charging roller can significantly reduce the amount of ozone generated compared to corotron, scorotron, etc., and is effective in stability and prevention of image quality deterioration when the photoreceptor is used repeatedly.
However, due to the contact between the photoconductor and the charging roller, the charging roller is contaminated by repeated use, which affects the photoconductor and contributes to the occurrence of abnormal images and reduced wear resistance. It was.
In particular, when a photoconductor having high wear resistance is used, it is difficult to perform reface due to surface wear, and therefore it is necessary to reduce contamination of the charging roller.

Therefore, as shown in FIG. 6, the charging roller (12) is provided with a gap forming member (12a) and is disposed close to the photoreceptor (1) via the gap, so that contaminants adhere to the charging roller. It is difficult or easy to remove, and the influence thereof can be reduced.
In this case, the gap between the photosensitive member and the charging roller is preferably small, for example, 100 μm or less is preferable, and 50 μm or less is more preferable.
However, by making the charging roller non-contact, discharge may become non-uniform and charging of the photoreceptor may become unstable. Such a problem is caused by maintaining the charging stability by superimposing the alternating current component on the direct current component, thereby making it possible to simultaneously reduce the influence of ozone, the charging roller contamination and the charging effect. .

On the other hand, the light source such as the image exposure unit (13) and the charge removal lamp (11) shown in FIG. 5 includes a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), All luminescent materials such as electroluminescence (EL) can be used. Among these, a semiconductor laser (LD) and a light emitting diode (LED) are mainly used.
Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The light source or the like provides the photosensitive member (1) with light by providing a transfer step, a static elimination step, a cleaning step, or a pre-exposure step using light irradiation. However, the exposure of the photoreceptor (1) in the charge eliminating step is greatly affected by fatigue on the photoreceptor 1, and may cause a decrease in charge and an increase in residual potential. Therefore, there is a case where it is possible to eliminate static electricity by applying a reverse bias in the charging process or cleaning process instead of static elimination by exposure, which may be effective from the viewpoint of enhancing the durability of the photoreceptor.

When the electrophotographic photosensitive member (1) is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner. A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.
As the transfer means, the above-described charger can be generally used. However, as shown in FIG. 5, a combination of the transfer charger (18) and the separation charger (19) is effective.
Further, the toner image is directly transferred from the photosensitive member to the paper using such a transfer unit. In the present invention, the toner image on the photosensitive member is once transferred to the intermediate transfer member, and then from the intermediate transfer member to the paper. An intermediate transfer method for transferring the toner to the photoconductor is more preferable for enhancing the durability or improving the image quality of the photoreceptor.
Among the contaminants that adhere to the surface of the photoconductor, discharge substances generated by charging and external additives contained in the toner are easy to pick up the effects of humidity and cause abnormal images. Paper powder is one of the causative substances, and when they adhere to the photoreceptor, abnormal images are more likely to occur, as well as a tendency to reduce wear resistance and cause uneven wear. Is seen. Therefore, it is more preferable from the viewpoint of high image quality that the photoconductor and the paper are not in direct contact for the above reason.
The intermediate transfer method is particularly effective for image forming apparatuses capable of full-color printing, and controls the prevention of color misregistration by forming a plurality of toner images on the intermediate transfer member and then transferring them to the paper at once. It is easy and effective for high image quality. However, the intermediate transfer method requires four scans to obtain one full-color image, so that the durability of the photoconductor has been a big problem. The photoconductor of the present invention is particularly effective and useful since it is easy to use in combination with an intermediate transfer type image forming apparatus because image blurring hardly occurs even without a drum heater. The intermediate transfer member includes various materials or shapes such as a drum shape and a belt shape. In the present invention, any conventionally known intermediate transfer member can be used. It is effective and useful for achieving high quality or high image quality.

The toner developed on the photosensitive member (1) by the developing unit (14) shown in FIG. 5 is transferred to the transfer paper (17), but not all of the toner is transferred to the photosensitive member (1). The toner remaining in the toner is also generated.
Such toner is removed from the photoreceptor (1) by the fur brush (22) or the cleaning blade (23). This cleaning process may be performed only with a cleaning brush or may be performed in combination with a blade, and known cleaning brushes such as a fur brush and a mag fur brush are used. As described above, the cleaning is a process of removing toner remaining on the photosensitive member (1) after the transfer. However, the photosensitive member (1) is repeatedly rubbed by the cleaning blade (23) or the fur brush (22). As a result, wear of the photoconductor (1) is promoted, or an abnormal image may be generated due to scratches.
In addition, if the surface of the photoconductor is contaminated due to poor cleaning, it not only causes an abnormal image, but also significantly reduces the life of the photoconductor.
In particular, in the case of a photoconductor with a protective layer on the outermost layer to improve wear resistance, it is difficult to remove contaminants adhering to the surface of the photoconductor, which promotes the generation of filming and abnormal images. Will do. Therefore, improving the cleaning property of the photoconductor is very effective for improving the durability and image quality of the photoconductor.

As means for improving the cleaning property of the photosensitive member, a method of reducing the coefficient of friction on the surface of the photosensitive member is known. Methods for reducing the coefficient of friction on the surface of the photoreceptor are classified into a method in which various lubricants are contained in the photoreceptor surface and a method in which the lubricant is supplied to the photoreceptor surface from the outside. The former is advantageous for small-diameter photoreceptors because of the high degree of freedom in layout around the engine, but the coefficient of friction increases remarkably with repeated use, and there remains a problem in its sustainability. On the other hand, the latter needs to be provided with a component for supplying a lubricating substance, but is effective for enhancing the durability of the photoreceptor because of high stability of the friction coefficient. Among them, the method of adhering to the photoreceptor during development by incorporating a lubricant into the developer is not restricted by the layout around the engine, and the effect of reducing the friction coefficient on the photoreceptor surface is high. Therefore, it is a very effective means for improving the durability and image quality of the photoreceptor.
These lubricants include lubricating fluids such as silicone oil and fluorine oil, various fluorine-containing resins such as PTFE, PFA and PVDF, silicone resins, polyolefin resins, silicone grease, fluorine grease, paraffin wax, fatty acid esters , Fatty acid metal salts such as zinc stearate, lubricating liquids such as graphite and molybdenum disulfide, solids, powders, and the like. Zinc has little adverse effect and can be used very effectively. When the zinc stearate powder is contained in the toner, it is necessary to consider the balance and the influence on the toner, and the content is preferably 0.01 to 0.5% by mass with respect to the toner. 3 mass% is more preferable.
The photoconductor according to the present invention can be applied to a small-diameter photoconductor because high photosensitivity and high stability are realized. Accordingly, as an image forming apparatus or method using the above photoreceptor more effectively, each developing unit corresponding to a plurality of colors of toner is provided with a plurality of corresponding photoreceptors, thereby performing parallel processing. It is very effectively used in a so-called tandem type image forming apparatus. The tandem image forming apparatus includes at least four color toners of yellow (C), magenta (M), cyan (C), and black (K) required for full-color printing and a developing unit that holds them. Further, by providing at least four photoconductors corresponding to them, full-color printing can be performed at a very high speed as compared with a conventional image forming apparatus capable of full-color printing.

FIG. 7 is a schematic diagram for explaining the tandem-type full-color electrophotographic apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 7, photoconductors (1C) (cyan), (1M) (magenta), (1Y) (yellow), and (1K) (black) are drum-like photoconductors (1), and these photoconductors. (1C), (1M), (1Y), (1K) rotate in the direction of the arrow in the figure, and charging members (12C), (12M), (12Y), (12K), Developing members (14C), (14M), (14Y), (14K), and cleaning members (15C), (15M), (15Y), (15K) are arranged.
The charging members (12C), (12M), (12Y), and (12K) constitute a charging device for uniformly charging the surface of the photoreceptor (1). From the back side of the photoreceptor (1) between the charging members (12C), (12M), (12Y), (12K) and the developing members (14C), (14M), (14Y), (14K). Then, laser beams (13C), (13M), (13Y), and (13K) from an exposure member (not shown) are irradiated, and electrostatic latent images are formed on the photoreceptors (1C), (1M), (1Y), and (1K). Is to be formed.
Then, the four image forming elements (10C), (10M), (10Y), and (10K) centering on such photoconductors (1C), (1M), (1Y), and (1K) serve as transfer materials. It is juxtaposed along the transfer and transport belt (25) which is a transport means. The transfer conveyance belt (25) includes developing members (14C), (14M), (14Y), and (14K) of the image forming units (elements) (10C), (10M), (10Y), and (10K), Between the cleaning members (15C), (15M), (15Y), and (15K), the photosensitive members (1C), (1M), (1Y), and (1K) are in contact with the transfer conveyance belt (25). Transfer brushes (26C), (26M), (26Y), and (26K) for applying a transfer bias are disposed on a surface (back surface) that is in contact with the back side of the photoconductor (1). Each of the image forming elements (10C), (10M), (10Y), and (10K) is different in the color of the toner inside the developing device, and the others are the same in configuration.
In the color electrophotographic apparatus having the configuration shown in FIG. 7, the image forming operation is performed as follows. First, in each of the image forming elements (10C), (10M), (10Y), (10K), the photoconductors (1C), (1M), (1Y), (1K) are in the direction indicated by the arrows (photoconductor (1)). Exposure unit (not shown) which is charged by charging members (12C), (12M), (12Y) and (12K) which rotate in the rotation direction and then arranged outside the photoreceptor (1). Thus, an electrostatic latent image corresponding to each color image to be created is formed by the laser beams (13C), (13M), (13Y), and (13K).
Next, the latent image is developed by developing members (14C), (14M), (14Y), and (14K) to form a toner image. Development members (14C), (14M), (14Y), and (14K) are development members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively. The toner images of the respective colors produced on the two photoconductors (1C), (1M), (1Y), and (1K) are superimposed on the transfer paper. The transfer paper (17) is fed out from the tray by the paper feed roller (24), and is temporarily stopped by the pair of registration rollers (16). Sent.

The transfer paper (17) held on the transfer / conveying belt (25) is conveyed, and each color at the contact position (transfer portion) with each photoconductor (1C), (1M), (1Y), (1K). The toner image is transferred.
The toner image on the photoconductor includes the transfer bias applied to the transfer brushes (26C), (26M), (26Y), and (26K) and the photoconductors (1C), (1M), (1Y), and (1K). The image is transferred onto the transfer paper (17) by an electric field formed from the potential difference. Then, the recording paper (17) on which the four color toner images are passed through the four transfer portions is conveyed to the fixing device (27), where the toner is fixed, and is discharged to a paper discharge portion (not shown). The Further, the residual toner remaining on each of the photoconductors (1C), (1M), (1Y), and (1K) without being transferred by the transfer unit is removed from the cleaning devices (15C), (15M), (15Y), ( 15K).
In the example of FIG. 7, the image forming elements are arranged in the order of C (cyan), M (magenta), Y (yellow), and K (black) from the upstream side to the downstream side in the transfer paper conveyance direction. However, it is not limited to this order, and the color order is arbitrarily set. Further, when a black-only document is created, it is particularly effective to use the present invention to provide a mechanism that stops the image forming elements (10C), (10M), and (10Y) other than black.
Further, although the charging member is in contact with the photosensitive member in FIG. 7, by using a charging mechanism as shown in FIG. 6, an appropriate gap (about 10 to 200 μm) is provided between them. In addition, the wear amount of the both can be reduced, and toner filming on the charging member can be reduced and the toner can be used satisfactorily.

The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge.
The process cartridge includes the photoelectric conversion element of the present invention, and further includes at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit, and is detachable from the image forming apparatus. Device (parts).
An example of the process cartridge is shown in FIG. 8, but the neutralizing means is not described here.
The above-described tandem image forming apparatus can transfer a plurality of toner images at a time, so that high-speed full-color printing is realized.
However, since at least four photoconductors are required, an increase in the size of the apparatus is unavoidable, and depending on the amount of toner used, there is a difference in the wear amount of each photoconductor, thereby reproducing the color. There are many problems such as a decrease in performance and occurrence of abnormal images.
On the other hand, the photosensitive member according to the present invention can be applied to a small-diameter photosensitive member by realizing high photosensitivity and high stability, and the influence of increase in residual potential, sensitivity deterioration, etc. is reduced. Even if the amount of the photoconductor used is different, the difference in residual potential and sensitivity over time is small, and a full color image having excellent color reproducibility can be obtained even when used repeatedly for a long time.

  Hereinafter, the present invention will be described in more detail based on examples, but these examples are intended to facilitate understanding of the present invention and are not intended to limit the present invention. In each example, “part” represents “part by mass” unless otherwise specified.

(Synthesis example)
First, synthesis examples of chlorogallium phthalocyanine and hydroxygallium phthalocyanine, which are raw materials for the gallium phthalocyanine compound represented by the general formula (A), are shown. In the following description, “part” means “part by weight”.

[Synthesis example of chlorogallium phthalocyanine]
After adding 30 parts of 1,3-diiminoisoindoline and 8 parts of gallium trichloride to 200 parts of dehydrated dimethyl sulfoxide and reacting at 150 ° C. for 12 hours under an Ar stream, the produced chlorogallium phthalocyanine is filtered off. did. The wet cake was washed with methyl ethyl ketone and N, N-dimethylformamide and then dried to obtain 22 parts (70.3%) of chlorogallium phthalocyanine crystals.

[Synthesis example of hydroxygallium phthalocyanine]
The above-mentioned 5 parts of chlorogallium phthalocyanine was dissolved in 150 parts of concentrated ice-cooled sulfuric acid, and this sulfuric acid solution was gradually added dropwise to 500 parts of ice-cooled ion-exchanged water to precipitate hydroxygallium phthalocyanine crystals. After the crystals were separated by filtration, the wet cake was washed with 500 parts of 2 wt% ammonia water, and then thoroughly washed with ion-exchanged water. By drying, 4.6 parts of hydroxygallium phthalocyanine crystals were obtained.

[Synthesis Example A1 (i); Synthesis of gallium phthalocyanine compound of general formula (A) (1)]
Next, a synthesis example of a gallium phthalocyanine compound represented by the general formula (A) and a hydroxygallium phthalocyanine obtained by hydrolyzing the compound will be shown.
To 100 parts of chlorobenzene, 0.62 part of chlorogallium phthalocyanine and 23 parts of trifluoroacetic acid were added, heated to 90 ° C. and reacted for 5 hours. After cooling, about 10 parts of distilled water was added and stirred at room temperature for 1 hour. The obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.64 parts (93%) of gallium phthalocyanine compound crystals.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration was observed. Furthermore, m / z: 694.04 (theoretical value is 694.06: C34H16F3GaN8O2) was recognized by MALDI-TOFMS (negative). The results of further elemental analysis are shown in the table below.

これらの結果より、下記式（Ｃ）のガリウムフタロシアニン化合物であることを確認した。

From these results, it was confirmed that it was a gallium phthalocyanine compound of the following formula (C).

[Synthesis Example A1 (ii); hydrolysis of gallium phthalocyanine compound of general formula (A) (1)]
1.39 parts of the gallium phthalocyanine compound of the formula (C), 1.0 part of 4-dimethylaminopyridine and 0.1 part of ion-exchanged water are added to 150 parts of N, N-dimethylformamide and heated to 100 ° C. for 8 hours. Reacted. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.04 parts (87%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A2; hydrolysis of gallium phthalocyanine compound of general formula (A) (2)]
1.39 parts of the gallium phthalocyanine compound of the formula (C) obtained in Synthesis Example A1 (i) and 0.45 part of aqueous ammonia are added to 150 parts of N, N-dimethylformamide, heated to 100 ° C. and reacted for 7 hours. I let you. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.16 parts (97%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A3; hydrolysis of gallium phthalocyanine compound of general formula (A) (3)]
1.39 parts of the gallium phthalocyanine compound of the formula (C) obtained in Synthesis Example A1 (i), 1.0 part of 4-dimethylaminopyridine and 0.1 part of ion-exchanged water are added to 100 parts of dimethyl sulfoxide, and 100 ° C. And allowed to react for 7 hours. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.14 parts (95%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A4; hydrolysis of gallium phthalocyanine compound of general formula (A) (4)]
1.39 parts of the gallium phthalocyanine compound of the formula (C) obtained in Synthesis Example 1 (i) and 0.45 part of aqueous ammonia were added to 150 parts of tetrahydrofuran, heated to 65 ° C. and reacted for 5 hours. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.12 parts (93%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A5 (i); Synthesis Example (2) of Gallium Phthalocyanine Compound of General Formula (A)]
2.47 parts of chlorogallium phthalocyanine and 25.2 parts of pentadecafluorooctanoic acid hydrate were added to 300 parts of dimethyl sulfoxide, heated to 110 ° C. and reacted for 22 hours. After cooling to room temperature, 50 parts of silica gel for column chromatography (Wakogel C300, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 3 hours for adsorption treatment. Silica gel was removed by filtration, and 50 parts of distilled water was added to the obtained filtrate under cooling, followed by stirring at room temperature for 2 hours. The produced crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 2.67 parts (67%) of gallium phthalocyanine compound crystals. A part of this was further recrystallized and purified with dimethyl sulfoxide and subjected to the following analysis.
As a result of analysis by infrared absorption spectrum (KBr tablet method), absorption at 1732 cm ⁻¹ based on C═O stretching vibration was observed. The results of further elemental analysis are shown in the table below. (Calculated value is C40H16F15GaN8O2)
From these results, it was confirmed that the compound was a gallium phthalocyanine compound represented by the following formula (D).

[Synthesis Example A5 (ii); hydrolysis of gallium phthalocyanine compound of general formula (A) (5)]
Add 1.00 part of the gallium phthalocyanine compound of formula (D), 1.0 part of 4-dimethylaminopyridine and 0.1 part of ion-exchanged water to 100 parts of N, N-dimethylformamide, and warm to 100 ° C. for 6 hours. Reacted. After cooling, the obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.55 part (92%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A6; hydrolysis of gallium phthalocyanine compound of general formula (A) (6)]
2.00 parts of the gallium phthalocyanine compound of the formula (D) obtained in Synthesis Example A5 (i) and 0.45 part of aqueous ammonia are added to 130 parts of N, N-dimethylformamide, heated to 80 ° C. and reacted for 5 hours. I let you. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.14 parts (95%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A7; hydrolysis of gallium phthalocyanine compound of general formula (A) (7)]
2.00 parts of the gallium phthalocyanine compound of the formula (D) obtained in Example 5, 5.0 parts of pyridine and 0.1 part of ion-exchanged water are added to 100 parts of dimethyl sulfoxide, heated to 100 ° C. and reacted for 7 hours. I let you. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.03 parts (86%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A8 (i); Synthesis Example (3) of Gallium Phthalocyanine Compound of General Formula (A)]
To 100 parts of chlorobenzene, 1.24 parts of chlorogallium phthalocyanine and 17.1 parts of heptafluorobutyric acid were added, heated to 90 ° C. and reacted for 12 hours. After cooling, about 50 parts of distilled water was added and stirred at room temperature for 1 hour. The obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 2.82 parts (89%) of a gallium phthalocyanine compound crystal. A part of this was subjected to column purification with Florisil (for chromatography, manufactured by Kishida Chemical) / dimethyl sulfoxide, and the following analysis was performed.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1730 cm ⁻¹ based on C═O stretching vibration was observed.
The results of further elemental analysis are shown in the table below. (Calculated value is C37H16F9GaN8O2)
From these results, it was confirmed that it was a gallium phthalocyanine compound of the following formula (E).

[Synthesis Example A8 (ii); hydrolysis of gallium phthalocyanine compound of general formula (A) (8)]
0.80 part of the gallium phthalocyanine compound of the formula (E) obtained above, 4.0 part of 4-picoline and 0.1 part of ion-exchanged water are added to 80 parts of N, N-dimethylformamide and heated to 90 ° C. And allowed to react for 7 hours. After cooling, the obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.55 part (92%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1730 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A9 (i); Synthesis Example (4) of Gallium Phthalocyanine Compound of General Formula (A)]
To 100 parts of methyl ethyl ketone, 0.60 part of hydroxygallium phthalocyanine and 2.0 parts of pivalic acid were added and reacted under reflux for 6 hours. The obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.60 part (88%) of a gallium phthalocyanine compound crystal.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the product, absorption at about 3480 cm ⁻¹ derived from OH group disappeared, and absorption at 1655 cm ⁻¹ based on C═O stretching vibration was observed. Further, MALDI-TOFMS (negative) confirmed m / z: 682.25 (theoretical value was 682.14: C37H25GaN8O2). The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that it was a gallium phthalocyanine compound of the following formula (F).

[Synthesis Example A9 (ii); hydrolysis of gallium phthalocyanine compound of general formula (A) (9)]
0.68 parts of the gallium phthalocyanine compound of the formula (F) obtained above, 4.0 parts of 4-picoline and 0.1 part of ion-exchanged water are added to 80 parts of N, N-dimethylformamide and heated to 90 ° C. And allowed to react for 7 hours. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.54 parts (90%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1655 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3480 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A10 (i); Synthesis Example (5) of Gallium Phthalocyanine Compound of General Formula (A)]
To 100 parts of xylene, 0.62 part of chlorogallium phthalocyanine and 16 parts of pentafluoropropionic acid were added, heated to 100 ° C. and reacted for 15 hours. After cooling, about 10 parts of distilled water was added and stirred at room temperature for 1 hour.
The obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.61 part (82%) of a gallium phthalocyanine compound crystal. A portion of this was recrystallized and purified with N, N-dimethylformamide and subjected to the following analysis.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1724 cm ⁻¹ based on C═O stretching vibration was observed. Furthermore, m / z: 744.17 (theoretical value is 744.06: C35H16F5GaN8O2) was recognized by MALDI-TOFMS (negative). The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that it was a gallium phthalocyanine compound of the following formula (G).

[Synthesis Example A10 (ii); hydrolysis of gallium phthalocyanine compound of general formula (A) (10)]
1.49 parts of the starting gallium phthalocyanine compound obtained above and 0.45 part of aqueous ammonia were added to 150 parts of N, N-dimethylformamide, heated to 100 ° C. and reacted for 7 hours. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.16 parts (97%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1724 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3490 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A11 (i); Synthesis Example (6) of Gallium Phthalocyanine Compound of General Formula (A)]
To 100 parts of methyl ethyl ketone, 0.60 part of hydroxygallium phthalocyanine and 1.3 parts of 3,5-bis (trifluoromethyl) benzoic acid were added and reacted under reflux for 8 hours. The obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.73 part (87%) of a gallium phthalocyanine compound crystal.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the product, absorption at about 3480 cm ⁻¹ derived from OH group disappeared, and absorption at 1670 cm ⁻¹ based on C═O stretching vibration was observed. Further, MALDI-TOFMS (negative) confirmed m / z: 838.01 (theoretical value was 838.08: C41H19F6GaN8O2). The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that it was a gallium phthalocyanine compound of the following formula (H).

[Synthesis Example A11 (ii); hydrolysis of gallium phthalocyanine compound of general formula (A) (11)]
0.84 parts of the gallium phthalocyanine compound of the formula (H) obtained above, 5.0 parts of 4-dimethylaminopyridine and 0.1 part of ion-exchanged water are added to 100 parts of N, N-dimethylformamide, and the mixture is heated to 100 ° C. Warmed and allowed to react for 7 hours. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.54 parts (90%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1670 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3480 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A12 (i); Synthesis Example (7) of Gallium Phthalocyanine Compound of General Formula (A)]
To 100 parts of methyl ethyl ketone, 0.60 part of hydroxygallium phthalocyanine and 1.6 parts of trichloroacetic acid were added and reacted under reflux for 7 hours. The obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.68 part (91%) of a gallium phthalocyanine compound crystal.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the product, absorption at about 3480 cm ⁻¹ derived from OH group disappeared, and absorption at 1714 cm ⁻¹ based on C═O stretching vibration was observed.
The results of further elemental analysis are shown in the table below. (Calculated value is C34H16Cl3GaN8O2)
From these results, it was confirmed that it was a gallium phthalocyanine compound of the following formula (J).

[Synthesis Example A2 (ii); water content of gallium phthalocyanine compound of general formula (A) (12)]
1.89 parts of the gallium phthalocyanine compound of the formula (J) obtained above and 0.65 part of aqueous ammonia were added to 130 parts of ethyl acetate, heated to 80 ° C. and reacted for 5 hours. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.11 parts (93%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1714 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption near 3480 cm ⁻¹ based on hydroxyl group was observed. It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A13 (i); Synthesis Example (8) of Gallium Phthalocyanine Compound of General Formula (A)]
To 100 parts of methyl ethyl ketone, 0.60 part of hydroxygallium phthalocyanine and 2.9 parts of tribromoacetic acid were added, and the reaction was carried out under reflux for 7 hours. The obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.64 part (73%) of a gallium phthalocyanine compound crystal.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the product, absorption at about 3480 cm ⁻¹ derived from OH group disappeared, and absorption at 1680 cm ⁻¹ based on C═O stretching vibration was observed.
The results of further elemental analysis are shown in the table below. (Calculated value is C34H16Br3GaN8O2)
From these results, it was confirmed that it was a gallium phthalocyanine compound of the following formula (K).

[Synthesis Example A13 (ii); water content of gallium phthalocyanine compound of general formula (A) (13)]
1.76 parts of the gallium phthalocyanine compound of the formula (K) obtained above, 0.1 part of ion-exchanged water and 10 parts of triethylamine are added to 130 parts of N, N-dimethylformamide, heated to 100 ° C. and reacted for 10 hours. I let you. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.14 parts (95%) of hydroxygallium phthalocyanine.
Analysis by infrared absorption spectrum of this product (KBr tablet method), absorption and disappearance of the 1680 cm ^-1 based on the C = O stretching vibration was observed in the starting material, observed absorption around 3480cm ^-1 based on hydroxyl group It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

[Synthesis Example A14 (i); Synthesis Example (9) of Gallium Phthalocyanine Compound of General Formula (A)]
To 100 parts of methyl ethyl ketone, 0.60 part of hydroxygallium phthalocyanine and 0.12 part of hexafluoroglutamate were added, and the reaction was carried out under reflux for 9.5 hours. The obtained crystal was washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 0.31 part (44%) of a gallium phthalocyanine compound crystal.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the product, absorption at about 3480 cm ⁻¹ derived from OH group disappeared, and absorption at 1720 cm ⁻¹ based on C═O stretching vibration was observed.
The results of further elemental analysis are shown in the table below. (Calculated value is C69H32F6Ga2N16O4)
From these results, it was confirmed that it was a gallium phthalocyanine compound of the following formula (L).

[Synthesis Example A14 (ii); water content of gallium phthalocyanine compound of general formula (A) (14)]
1.40 parts of the gallium phthalocyanine compound of the formula (L) obtained above and 0.65 part of aqueous ammonia were added to 130 parts of N, N-dimethylformamide, heated to 90 ° C. and reacted for 7 hours. After cooling, the obtained crystals were washed with methyl ethyl ketone and ion-exchanged water and then dried to obtain 1.03 parts (86%) of hydroxygallium phthalocyanine.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1720 cm ⁻¹ based on C═O stretching vibration observed in the starting material disappeared, and absorption around 3480 cm ⁻¹ based on hydroxyl group was observed It was.
From this result, it was confirmed that it was hydroxygallium phthalocyanine.

<Synthesis Example of Azo Compound Having Carboester Group in the Present Invention>
Next, an azo compound having a carboester group represented by the general formula (II) of the present invention is synthesized by the method described in JP-A-2009-7523. An example of this is shown below.

[Synthesis Example E1; Synthesis of Exemplified Compound (12-2)]
1.61 grams of a precursor of an azo compound having a carboester group represented by the structural formula (12-2) [all E groups in the structural formula (12-2) are H (hydrogen atoms)], Disperse 4.3 g (10 moles) of pyrocarboxylic acid di-tert-butyl ester in 50 ml of dehydrated pyridine and 200 ml of dehydrated N, N-dimethylformamide, stir at room temperature for 15 minutes, and then warm to about 50 ° C. The reaction was performed for 2 hours. Gradually reddish and a homogeneous solution was obtained. After returning to room temperature, the solvent was removed, and about 100 ml of ethyl acetate was added to obtain 2.24 grams (yield: 93%) of a red powder.
The results of elemental analysis of the obtained powder are shown in Table 11 below.
The calculated values (%) of each element in Table 11 below are based on the assumption that the carboester group (E group) represented by the structural formula (12-2) is C5H9O2, and the chemical formula of the azo compound Is calculated as C68H63N6O13Cl.

As a result of analysis by infrared absorption spectrum (KBr tablet method) of the product, absorption derived from a substituent, i.e., absorption based on saturated hydrocarbons 2980cm ^-1, C = O stretching vibration of carbonate to 1760 cm ^-1 Absorption based on was observed.
From this result, it was confirmed that the product was an azo compound represented by the structural formula (12-2).
Similarly, the azo compound represented by the structural formula (12-3), the azo compound represented by the structural formula (12-4), the azo compound represented by the structural formula (13-1), and the structural formula (14) The azo compound shown by -5) was synthesized and the product was confirmed.

<Synthesis of composite pigment>
[Synthesis Example 1 of Composite Pigment]
1.04 parts of a gallium phthalocyanine compound of the formula (C), 0.92 parts of a precursor of an azo compound having a carboester group represented by the structural formula (12-3), and 0.1 part of ion-exchanged water are mixed with N, The reaction was carried out at 150 ° C. for 7 hours in 100 parts of N-dimethylformamide. The obtained crystals were washed 3 times with about 100 parts of N, N-dimethylformamide, once with about 100 parts of methyl ethyl ketone and twice with about 100 parts of ion-exchanged water, and then dried to obtain 1.45 parts (95 %) Composite pigment crystals.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration based on carboxylic acid ester group of the gallium phthalocyanine compound of formula (C) disappears, similarly The absorption of 2980 cm ⁻¹ based on the saturated hydrocarbon of the azo compound having a carboester group represented by the structural formula (12-3) and the absorption of 1760 cm ⁻¹ based on the C═O stretching vibration of the carbonate disappear, and the azo pigment 1724 cm ^-1 based on the carbonyl group, and 1676cm ^-1 based on the amide group absorption was observed in.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (12-3) were H (hydrogen atom).

[Synthesis Example 2 of Composite Pigment]
1.19 parts of a gallium phthalocyanine compound of the formula (E), 0.91 part of a precursor of an azo compound having a carboester group represented by the structural formula (12-2), and 0.1 part of ion-exchanged water are mixed with N, The reaction was carried out at 150 ° C. for 7 hours in 100 parts of N-dimethylformamide. The obtained crystals were washed with about 100 parts of N, N-dimethylformamide three times, once with about 100 parts of methyl ethyl ketone and twice with about 100 parts of ion-exchanged water, and then dried to obtain 1.40 parts (93% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1730 cm ⁻¹ based on C═O stretching vibration based on carboxylic acid ester group of the gallium phthalocyanine compound of formula (E) disappears, similarly , disappeared absorption of 1765cm ^-1 based on the absorption and C = O stretching vibration of carbonate of 2980cm ^-1 based on a saturated hydrocarbon of the azo compound having a carboxy ester group represented by the structural formula (12-2), azo pigments 1724 cm ^-1 based on the carbonyl group, and 1676cm ^-1 based on the amide group absorption was observed in.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (12-2) were H (hydrogen atom).

[Synthesis Example 3 of Composite Pigment]
1.12 parts of a gallium phthalocyanine compound of the formula (part), 0.89 part of a precursor of an azo compound having a carboester group represented by the structural formula (12-4), and 0.3 part of ion-exchanged water are mixed with N, The reaction was carried out at 150 ° C. for 6 hours in 100 parts of N-dimethylformamide. The obtained crystals were washed 3 times with about 100 parts of N, N-dimethylformamide, once with about 100 parts of methyl ethyl ketone and twice with about 100 parts of ion-exchanged water, and then dried to obtain 1.38 parts (93% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1724 cm ⁻¹ based on C═O stretching vibration based on the carboxylic acid ester group of the gallium phthalocyanine compound of the formula (part) disappeared, similarly The absorption of 2980 cm ⁻¹ based on the saturated hydrocarbon of the azo compound having a carboester group represented by the structural formula (12-4) and the absorption of 1760 cm ⁻¹ based on the C═O stretching vibration of the carbonate disappear, and the azo pigment 1724 cm ^-1 based on the carbonyl group, and 1672cm ^-1 based on the amide group absorption was observed in.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (12-4) were H (hydrogen atom).

[Synthesis Example 4 of Composite Pigment]
1.32 parts of a gallium phthalocyanine compound of the formula (K), 1.01 part of a precursor of an azo compound having a carboester group represented by the structural formula (13-1), and 0.1 part of ion-exchanged water are mixed with N, The reaction was carried out at 150 ° C. for 6 hours in 100 parts of N-dimethylformamide. The obtained crystals were washed 3 times with about 100 parts of N, N-dimethylformamide, once with about 100 parts of methyl ethyl ketone and twice with about 100 parts of ion-exchanged water, and then dried to obtain 1.49 parts (93% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1680 cm ⁻¹ based on C═O stretching vibration based on carboxylic acid ester group of gallium phthalocyanine compound of formula (K) disappears, similarly The absorption of 2980 cm ⁻¹ based on the saturated hydrocarbon of the azo compound having a carboester group represented by the structural formula (13-1) and the absorption of 1760 cm ⁻¹ based on the C═O stretching vibration of the carbonate disappear, and the azo pigment Absorption of 1674 cm ⁻¹ , based on the amide group, was observed.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (13-1) were H (hydrogen atom).

[Synthesis Example 5 of Composite Pigment]
1.04 parts of a gallium phthalocyanine compound of the formula (C), 1.24 parts of an azo pigment in which all E groups in the structural formula (12-3) are H (hydrogen atoms), 1.0 of 4-dimethylaminopyridine And 0.1 part of ion-exchanged water were reacted in 100 parts of N, N-dimethylformamide for 6.5 hours at 100 ° C. The obtained crystals were washed 3 times with about 100 parts of N, N-dimethylformamide, once with about 100 parts of methyl ethyl ketone and twice with about 100 parts of ion-exchanged water, and then dried to obtain 2.03 parts (95% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration based on carboxylic acid ester group of gallium phthalocyanine compound of formula (C) disappeared, and azo pigment 1724 cm ^-1 based on the carbonyl group, and 1676cm ^-1 based on the amide group absorption was observed in.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (12-3) were H (hydrogen atom).

[Synthesis Example 6 of composite pigment]
1.00 parts of a gallium phthalocyanine compound of the formula (D), 0.64 parts of an azo pigment in which all E groups in the structural formula (12-2) are H (hydrogen atoms), 1.0 part of pyridine, and ion exchange The reaction was carried out at 110 ° C. for 9 hours in 60 parts of N, N-dimethylformamide with 1.0 part of water. The obtained crystals were washed 3 times with about 60 parts of N, N-dimethylformamide, once with about 60 parts of methyl ethyl ketone and twice with about 60 parts of ion-exchanged water, and then dried to obtain 1.19 parts (96% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1732 cm ⁻¹ based on C═O stretching vibration based on carboxylic acid ester group of gallium phthalocyanine compound of formula (D) disappeared, and azo pigment 1724 cm ^-1 based on the carbonyl group, and 1676cm ^-1 based on the amide group absorption was observed in.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (12-2) were H (hydrogen atom).

[Composite Pigment Synthesis Example 7]
0.74 part of a gallium phthalocyanine compound of the formula (J), 0.16 part of an azo pigment in which all E groups in the structural formula (12-2) are H (hydrogen atom), 3.0 of 4-dimethylaminopyridine And 1.0 part of ion-exchanged water were reacted in 130 parts of N, N-dimethylformamide for 9 hours at 130 ° C. The obtained crystals were washed 3 times with about 60 parts of N, N-dimethylformamide, once with about 60 parts of methyl ethyl ketone and twice with about 60 parts of ion-exchanged water, and then dried to give 0.68 parts (90% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1714 cm ⁻¹ based on C═O stretching vibration based on carboxylic acid ester group of gallium phthalocyanine compound of formula (J) disappeared, and azo pigment 1724 cm ^-1 based on the carbonyl group, and 1676cm ^-1 based on the amide group absorption was observed in.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (12-2) were H (hydrogen atom).

[Synthesis Example 8 of Composite Pigment]
1.40 parts of a gallium phthalocyanine compound of the formula (K), 0.40 part of an azo pigment in which all E groups in the structural formula (13-1) are H (hydrogen atoms), and 1.0 part of aqueous ammonia The reaction was carried out in 100 parts of N, N-dimethylformamide at 100 ° C. for 7 hours. The obtained crystals were washed 3 times with about 100 parts of N, N-dimethylformamide, once with about 100 parts of methyl ethyl ketone and twice with about 100 parts of ion-exchanged water, and then dried to obtain 1.42 parts (89% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption at 1720 cm ⁻¹ based on C═O stretching vibration based on carboxylic acid ester group of gallium phthalocyanine compound of formula (K) disappears, and azo pigment Absorption of 1674 cm ⁻¹ , based on the amide group, was observed.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (13-1) were H (hydrogen atom).

[Synthesis Example 9 of Composite Pigment]
Precursor 1 of an azo compound having 0.90 part of hydroxygallium phthalocyanine synthesized by hydrolysis of the gallium phthalocyanine compound of formula (F) in Synthesis Example 9 and a carboester group represented by the structural formula (12-2) The reaction was carried out at 170 ° C. for 7 hours in 100 parts of dimethyl sulfoxide. The obtained crystals were washed 3 times with about 100 parts of N, N-dimethylformamide, once with about 100 parts of methyl ethyl ketone and twice with about 100 parts of ion-exchanged water, and then dried to obtain 1.84 parts (87% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption of 2980 cm ⁻¹ based on saturated hydrocarbon of azo compound having a carboester group represented by Structural Formula (12-2) and C═ of carbonate absorption of 1765cm ^-1 based on O stretching vibration disappeared, 1724 cm ^-1 based on the carbonyl group of azo pigments, and 1676cm ^-1 based on the amide group absorption was observed in.
From this, it was confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (12-2) were H (hydrogen atom).

[Composite Pigment Synthesis Example 10]
Precursor 1 of an azo compound having 0.90 part of hydroxygallium phthalocyanine synthesized by hydrolysis of the gallium phthalocyanine compound of the formula (H) in the synthesis example 11 and a carboester group represented by the structural formula (14-5) The reaction was carried out at 160 ° C. for 7 hours in 100 parts of N, N-dimethylacetamide. The obtained crystals were washed 3 times with about 100 parts of N, N-dimethylformamide, once with about 100 parts of methyl ethyl ketone and twice with about 100 parts of ion-exchanged water, and then dried to obtain 1.85 parts (88% ) Composite pigment crystals were obtained.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, absorption of 2980 cm ⁻¹ based on saturated hydrocarbon of an azo compound having a carboester group represented by the structural formula (14-5) and C═ of carbonate Absorption at 1765 cm ⁻¹ based on O stretching vibration disappeared, and absorption at 1676 cm ⁻¹ based on the amide group of the azo pigment was observed.
This confirmed that it was a composite pigment composed of hydroxygallium phthalocyanine and an azo pigment in which all of the E groups in the structural formula (14-5) were H (hydrogen atom).

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited by these Examples. All parts are parts by weight.
After coating on a 2 mm thick aluminum plate (for electrophotographic characteristic evaluation) and 346 mm long, φ40 mm aluminum cylinder (for actual machine evaluation) using an intermediate layer coating solution having the following composition, it is dried at 130 ° C. for 20 minutes. And an intermediate layer of about 3.5 μm was formed. Subsequently, the coating solution for the charge generation layer having the following composition was subjected to vibration mill dispersion for 6 hours together with zirconia balls having a diameter of 2 mm. After coating using this coating solution, drying was performed at 100 ° C./30 minutes, and the coating solution was about 0.3 μm. A charge generation layer was formed.
Furthermore, after coating using a coating solution for charge transport layer having the following composition, drying was performed at 130 ° C./20 minutes to form a charge transport layer of about 25 μm, and an electrophotographic photoreceptor of Example 1 was produced. For coating, a blade coating method (for electrophotographic characteristic evaluation) and a dip coating method (for actual machine evaluation) were used.

(Intermediate layer coating solution)
Titanium oxide CR-EL (manufactured by Ishihara Sangyo Co., Ltd.): 50 parts alkyd resin Beckolite M6401-50 (solid content 50% by weight, manufactured by Dainippon Ink & Chemicals, Inc.): 15 parts melamine resin L-145-60 (solid content 60) % By weight, manufactured by Dainippon Ink & Chemicals, Inc.): 8 parts 2-butanone: 120 parts

(Coating solution for charge generation layer)
Composite pigment obtained in Synthesis Example 1: 3.0 parts polyvinyl butyral (“XYHL” manufactured by UCC): 2 parts methyl ethyl ketone: 150 parts

(Coating liquid for charge transport layer)
Polycarbonate Z Polyca (manufactured by Teijin Chemicals Ltd .; Panlite TS-2050): 10 parts Charge transporting compound represented by the following structural formula: 7 parts Tetrahydrofuran: 80 parts Silicone oil (KF50-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.): 0 .002 copies

  An electrophotographic photosensitive member of Example 2 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 2.

  An electrophotographic photosensitive member of Example 3 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 3.

  An electrophotographic photosensitive member of Example 4 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 4.

  An electrophotographic photosensitive member of Example 5 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 5.

  An electrophotographic photoreceptor of Example 6 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 6.

  An electrophotographic photoreceptor of Example 7 was produced in the same manner as in Example 6 except that the recrystallization purification treatment of the gallium phthalocyanine compound of the formula (D) used in Example 6 was omitted.

  An electrophotographic photoreceptor of Example 8 was produced in the same manner as in Example 6 except that the adsorption treatment of the gallium phthalocyanine compound of the formula (D) used in Example 6 was omitted.

  An electrophotographic photoreceptor of Example 9 was produced in the same manner as in Example 6 except that the adsorption treatment and recrystallization purification treatment of the gallium phthalocyanine compound of formula (D) used in Example 6 were omitted.

  An electrophotographic photoreceptor of Example 10 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 7.

  An electrophotographic photosensitive member of Example 11 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 8.

  An electrophotographic photosensitive member of Example 12 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 9.

  An electrophotographic photoreceptor of Example 13 was produced in the same manner as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to that of Synthesis Example 10.

An electrophotographic photosensitive member of Example 14 was produced in the same manner as in Example 1 except that the charge generation layer coating solution used in Example 1 was changed as follows.
(Coating solution for charge generation layer)
Hydroxygallium phthalocyanine obtained in Synthesis Example 14: 1.6 parts Azo pigment in which all E groups in the structural formula (13-5) are H (hydrogen atoms): 1.4 parts polyvinyl butyral (“XYHL” “UCC): 2 parts methyl ethyl ketone: 150 parts

An electrophotographic photoreceptor of Example 15 was produced in the same manner as in Example 1 except that the charge generation layer coating solution used in Example 1 was changed as follows.
(Coating solution for charge generation layer)
Hydroxygallium phthalocyanine obtained in Synthesis Example 1: 1 part Azo pigment in which all E groups in the structural formula (14-2) are H (hydrogen atoms): 2 parts polyvinyl butyral (“XYHL” manufactured by UCC) : 2 parts methyl ethyl ketone: 150 parts

[Comparative Example 1]
An electrophotographic photosensitive member of Comparative Example 1 was produced in the same manner as in Example 1 except that the charge generation layer coating solution used in Example 1 was changed as follows.
(Coating solution for charge generation layer)
Hydroxygallium rusocyanine obtained in Synthesis Example 1: 3 parts polyvinyl butyral (manufactured by “XYHL” UCC): 2 parts methyl ethyl ketone: 150 parts

[Comparative Example 2]
An electrophotographic photosensitive member of Comparative Example 2 was produced in the same manner as in Example 1 except that the charge generation layer coating solution used in Example 1 was changed as follows.
(Coating solution for charge generation layer)
Azo pigment in which all E groups in the structural formula (14-2) are H (hydrogen atoms): 3 parts Polyvinyl butyral (“XYHL” manufactured by UCC): 2 parts Methyl ethyl ketone: 150 parts

[Comparative Example 3]
Comparative Example 3 as in Example 1 except that the composite pigment of the coating solution for charge generation layer used in Example 1 was changed to 3.0 parts of Y-type titanyl phthalocyanine (manufactured by Toyo Ink Co., Ltd .; Riophoton-TOPA). An electrophotographic photoreceptor was prepared.

[Comparative Example 4]
An electrophotographic photosensitive member of Comparative Example 4 was produced in the same manner as in Example 1 except that the charge generation layer coating solution used in Example 1 was changed as follows.
(Coating solution for charge generation layer)
Gallium phthalocyanine compound of the following formula (C) obtained in Synthesis Example 1: 1.9 parts Azo pigment in which all E groups in the structural formula (12-3) are H (hydrogen atoms): 1.1 Parts polyvinyl butyral ("XYHL" manufactured by UCC): 2 parts methyl ethyl ketone: 150 parts

[Comparative Example 5]
An electrophotographic photoreceptor of Comparative Example 5 was prepared in the same manner as in Example 1 except that the composite pigment of the charge generation layer coating solution used in Example 1 was changed to the following.
(Coating solution for charge generation layer)
Hydroxygallium phthalocyanine obtained by the acid paste method: 1.8 parts Azo pigment in which all E groups in the structural formula (12-3) are H (hydrogen atoms): 1.2 parts polyvinyl butyral (“XYHL” “UCC): 2 parts methyl ethyl ketone: 150 parts

<Electrophotographic characteristic evaluation>
Corona of -5 KV in the dark using a commercially available electrostatic charge test apparatus (EPA8100 type manufactured by Kawaguchi Electric Mfg. Co., Ltd.) for the photoreceptors of Examples 1-12 and Comparative Examples 1-5 produced on an aluminum plate. After charging for 20 seconds, the surface potential Vm (−V) of the electrophotographic photosensitive member was measured, and after being left in a dark place for 20 seconds, the surface potential V0 (−V) of the electrophotographic photosensitive member was set. The dark decay rate V0 / Vm was determined. Next, after irradiating with 780 nm monochromatic light having a light amount of 5 μW / cm ^{2 on} the surface of the electrophotographic photosensitive member for 30 seconds, the surface potential V30 (−V) of the electrophotographic photosensitive member was measured. Further, as the sensitivity, the exposure amount required for halving V0 was measured as E1 / 2 (μJ / cm ² ). The results are shown in Table 12.
After obtaining the initial characteristics in this way, the fatigue characteristics were measured as follows. Using an electrostatic charge test device, tungsten light irradiation and corona charging are performed simultaneously, and charging exposure is performed for 2 hours while adjusting the amount of light and the corona discharge voltage so that the surface potential of the photoconductor is −800 V and the charging current is 7 μA. It was. Vm (−V), V0 (−V), V0 / Vm, V30 (−V), and E1 / 2 (μJ / cm ² ) were measured for this sample in the same manner as the initial characteristics. The results are shown in Table 13.

<Evaluation of actual machine>
As shown in FIG. 8, the previously prepared photoreceptors of Examples 1 to 12 and Comparative Examples 1 to 5 were mounted on the process cartridge from which the lubricant application member was removed, and the writing LD wavelength was 780 nm. It was mounted on an imgioMPC5000 (Ricoh's digital full-color multifunction peripheral) that was modified as described above.
As a process condition at the time of the test, the applied voltage to the charging member was set so that the charged potential of the unexposed portion was −800V. The development bias was set to -600V. As a sheet passing condition, 40,000 sheets were printed using a chart with a writing rate of 6% (characters equivalent to 6% as an image area are written on the entire A4 surface). The test environment is normal temperature and humidity as temperature: 23 ° C., relative humidity: 55%, high temperature and high humidity environment as temperature: 30 ° C., relative humidity: 80%, and low temperature and low humidity environment as temperature: 10 ° C., relative humidity: 15%. The same printing test was conducted under the three environmental conditions.
The image evaluation was performed before and after the printing of 100,000 images. 5-2 was output, and the image density, resolution, and color color reproducibility were evaluated. These image evaluations were carried out in four stages. Very good ones were indicated by ◎, good ones were indicated by ○, slightly inferior ones by Δ, and bad ones by x. The results are shown in Table 14. Further, before the printing test, the applied voltage of the charging member at which the charged potential of the unexposed portion becomes −500V and the developing bias were set to −300V, and the same image evaluation as described above was performed. The results are shown in Table 15.

  From the above specific results, the electrophotographic photosensitive member using the composite gallium phthalocyanine pigment in the present invention is an electrophotographic apparatus (an image forming apparatus such as a copying machine or a laser printer), an image forming method, and a process cartridge for an image forming apparatus. It is understood that high image quality and high stability are suitably realized, and high-quality prints without image deterioration can be output over a long period of time in a wide range of temperature and humidity environments and voltage application conditions.

DESCRIPTION OF SYMBOLS 1 Photoconductor 1C, 1M, 1Y, 1K Photoconductor 2 Conductive support 3 Charge generation layer 4 Charge transport layer 5 Protective layer 6 Undercoat layer 7 Single layer type photosensitive layer 10C, 10M, 10Y, 10K Image forming element 11 Static elimination Lamp 12 Charging roller 12a Gap forming member 12C, 12M, 12Y, 12K Charging member 13 Image exposure unit 13C, 13M, 13Y, 13K Laser beam 14 Developing unit 14C, 14M, 14Y, 14K Developing member 15 Pre-transfer charger 15C, 15M, 15Y, 15K Cleaning member 16 Registration roller 17 Transfer paper 18 Transfer charger 19 Separation charger 20 Separation claw 21 Charger before cleaning 22 Fur brush 23 Cleaning blade 24 Feed roller 25 Transfer conveyance belts 26C, 26M, 26Y, 26K Transfer brush 27 Fixing device

JP 47-37543 A JP 52-55643 A JP-A-52-8832 JP 58-222152 A JP 58-222153 A Japanese Patent Laid-Open No. 61-239248 JP-A-1-17066 Japanese Patent Laid-Open No. 61-109056 JP-A 62-67094 Japanese Unexamined Patent Publication No. 63-364 JP-A-63-366 Japanese Patent Laid-Open No. 2005-15682 Japanese Unexamined Patent Publication No. 63-198067 JP-A-1-123868 US Pat. No. 3,357,989 JP 58-18239 A Japanese Patent Laid-Open No. 5-263007 Japanese Patent Laid-Open No. 5-279591 JP-A-58-100134 JP 61-273994 A JP-A-62-62367 JP 59-44053 A Japanese Patent Laid-Open No. 1-222159 JP 60-59355 A JP-A-5-301292 JP 2001-290296 A Japanese Patent Laid-Open No. 9-127711 JP 2002-23399 A JP 2007-334099 A Japanese Patent Laid-Open No. 3-9962

Claims (24)

A composite pigment comprising hydroxygallium phthalocyanine obtained by hydrolyzing an oxycarbonylgallium phthalocyanine compound represented by the following general formula (A) and an azo pigment.

(However, in general formula (A), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. An aralkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, which may be an alkoxy group, an alkylthio group, an alkyl group or a halogen atom. , A nitro group, an amino group, an aryl group, a carboxy group, a cyano group, etc. R1 to R16 are each independently hydrogen, alkoxy group, alkylthio group, alkyl group, halogen atom, nitro group, aryl group, Represents a group selected from the group consisting of n is an integer of 1 to 3). The composite pigment according to claim 1, wherein the oxycarbonylgallium phthalocyanine compound is represented by the following general formula (B).

(In the general formula (B), Y represents a perfluoroaryl group or a perfluoroalkyl group. N is an integer of 1 to 3.)   The said hydroxygallium phthalocyanine is obtained by hydrolysis of the oxycarbonyl gallium phthalocyanine compound shown by the said general formula (A) after the adsorption process by adsorption agent, The claim 1 or 2 characterized by the above-mentioned. Composite pigment.   The hydroxygallium phthalocyanine is obtained by hydrolysis of the recrystallized oxycarbonylgallium phthalocyanine compound represented by the general formula (A). Composite pigments.   5. The hydroxygallium phthalocyanine obtained by hydrolyzing the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) in the presence of a basic compound. The composite pigment according to any one of the above. The azo pigment is represented by the general formula (I) of A (H) n, and simultaneously with the hydrolysis of the oxycarbonylgallium phthalocyanine compound of the general formula (A), the azo pigment represented by the general formula (I) The pigment A (H) n is produced from an azo compound represented by the following general formula (II) by a chemical method and / or a thermal method. The composite pigment described.
A (E) n: general formula (II)
(Wherein A is a residue of an azo compound and this residue A is bonded to n E groups by one or more heteroatoms, and these heteroatoms are a group consisting of N and O) And each of the E groups is independently hydrogen or the following group: —C (═O) —O—R1 (wherein R1 is a group having 4 to 10 carbon atoms). Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group.) N is an integer of 1 to 9.)   The azo pigment A (H) n represented by the general formula (I) was present when the oxycarbonylgallium phthalocyanine compound of the general formula (A) was hydrolyzed. A composite pigment according to claim 1. The hydroxygallium phthalocyanine was present when the azo pigment represented by A (H) n was produced from the azo compound represented by the following general formula (II) by a chemical method and / or a thermal method. The composite pigment according to any one of claims 1 to 6, characterized in that:
A (E) n: general formula (II)
(Wherein A is a residue of an azo compound and this residue A is bonded to n E groups by one or more heteroatoms, and these heteroatoms are a group consisting of N and O) And each of the E groups is independently hydrogen or the following group: —C (═O) —O—R1 (wherein R1 is a group having 4 to 10 carbon atoms). Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group.) N is an integer of 1 to 9.)   The hydroxygallium phthalocyanine obtained by hydrolysis of the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) and the azo pigment represented by A (H) n are obtained by simultaneous complexation treatment. The composite pigment according to any one of claims 1 to 6, characterized in that:   An electrophotographic photosensitive member, comprising at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains at least the composite pigment according to claim 1.   An image forming method using the electrophotographic photosensitive member according to claim 10.   An image forming apparatus comprising the electrophotographic photosensitive member according to claim 10. A process cartridge for an image forming apparatus, comprising the electrophotographic photosensitive member according to claim 10. A method for producing a composite pigment comprising hydroxygallium phthalocyanine and an azo pigment, comprising a step of hydrolyzing an oxycarbonylgallium phthalocyanine compound represented by the following general formula (A) to obtain the hydroxygallium phthalocyanine: A method for producing a composite pigment comprising hydroxygallium phthalocyanine and an azo pigment.

(However, in general formula (A), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. An aralkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, which may be an alkoxy group, an alkylthio group, an alkyl group or a halogen atom. , A nitro group, an amino group, an aryl group, a carboxy group, a cyano group, etc. R1 to R16 are each independently hydrogen, alkoxy group, alkylthio group, alkyl group, halogen atom, nitro group, aryl group, Represents a group selected from the group consisting of n is an integer of 1 to 3.)   The substituent that the group X may have is an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an amino group, an aryl group, a carboxy group, or a cyano group. The manufacturing method of the composite pigment as described in above. The method for producing a composite pigment according to claim 14 or 15, wherein the oxycarbonylgallium phthalocyanine compound is represented by the following general formula (B).

(In the general formula (B), Y represents a perfluoroaryl group or a perfluoroalkyl group. N is an integer of 1 to 3.)   The oxycarbonyl gallium phthalocyanine compound represented by the general formula (A) is dissolved in an organic solvent, the solution is subjected to adsorption treatment with an adsorbent, and then hydrolyzed. A method for producing a composite pigment according to any one of the above.   The production method according to claim 17, wherein the adsorbent is selected from the group consisting of silica gel, alumina, florisil, activated carbon, activated clay, diatomaceous earth, or perlite.   The composite pigment according to any one of claims 14 to 18, further comprising hydrolyzing the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) after recrystallization treatment with an organic solvent. Manufacturing method.   The method for producing a composite pigment according to any one of claims 14 to 19, further comprising a step of hydrolyzing the oxycarbonylgallium phthalocyanine compound represented by the general formula (A) in the presence of a basic compound. The oxycarbonyl gallium phthalocyanine compound of the general formula (A) is hydrolyzed and simultaneously converted from the azo compound A (E) n represented by the general formula (II) by the chemical method and / or the thermal method to the general formula (I). The method for producing a composite pigment according to any one of claims 14 to 20, further comprising a step of producing the azo pigment A (H) n shown.
A (H) n: general formula (I)
A (E) n: general formula (II)
(Wherein A is a residue of an azo compound and this residue A is bonded to n E groups by one or more heteroatoms, and these heteroatoms are a group consisting of N and O) And each of the E groups is independently hydrogen or the following group: —C (═O) —O—R1 (wherein R1 is a group having 4 to 10 carbon atoms). Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group.) N is an integer of 1 to 9.)   The azo pigment is represented by A (H) n of the general formula (I), and when the oxycarbonyl gallium phthalocyanine compound of the general formula (A) is hydrolyzed, the azo pigment is represented by A (H) n. The method for producing a composite pigment according to any one of claims 14 to 21, wherein an azo pigment is present.   When the azo pigment A (H) n of the general formula (I) is produced from the azo compound A (E) n represented by the general formula (II) by a chemical method and / or a thermal method, the general formula The method for producing a composite pigment according to any one of claims 14 to 22, wherein hydroxygallium phthalocyanine obtained by hydrolyzing the oxycarbonylgallium phthalocyanine compound represented by (A) is present.   A composite pigment produced by the production method according to claim 14.

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